Titan haze: structure and properties of cyanoacetylene and cyanoacetylene-acetylene photopolymers

The structure and morphological properties of polymers produced photochemically from the UV irradiation of cyanoacetylene and cyanoacetylene mixtures have been examined to evaluate their possible contribution to the haze layers found on Titan. A structural analysis of these polymers may contribute to our understanding of the data returned from the Huygens probe of the Cassini mission that will pass through the atmosphere of Titan in the year 2004. Infrared analysis, elemental analysis, and thermal methods (thermogravimetric analysis, thermolysis, pyrolysis) were used to examine structures of polycyanoacetylenes produced by irradiation of the gas phase HC3N at 185 and 254 nm. The resulting brown to black polymer, which exists as small particles, is believed to be a branched chain of conjugated carbon-carbon double bonds, which, on exposure to heat, cyclizes to form a graphitic structure. Similar methods of analysis were used to show that when HC3N is photolyzed in the presence of Titan's other atmospheric constituents (CH4, C2H6, C2H2, and CO), a copolymer is formed in which the added gases are incorporated as substituents on the polymer chain. Of special significance is the copolymer of HC3N and acetylene (C2H2). Even in experiments where C2H2 was absorbing nearly all of the incident photons, the ratio of C2H2 to HC3N found in the resulting polymer was only 2:1. Scanning electron microscopy was used to visually examine the polymer particles. While pure polyacetylene particles are amorphous spheres roughly 1 micrometer in diameter, polycyanoacetylenes appear to be strands of rough, solid particles slightly smaller in size. The copolymer of HC3N and C2H2 exhibits characteristics of both pure polymers. This is particularly important as pure polyacetylenes do not match the optical constants measured for Titan's atmospheric hazes. The copolymers produced by the incorporation of other minor atmospheric constituents, like HC3N, into the polyacetylenes are expected to have optical constants more comparable to those of the Titan haze.     

Hardening of Titan's aerosols by their charging

Titan's haze consists of long chain polymers of pure and N-mixed hydrocarbons (Coustenis et al., 1989, Icarus 80, 54-76, 1991, Icarus 89, 152-167). These polymers have regularly alternating (i.e., conjugated) double/single and triple/single bonds, which open either spontaneously (free aging) or under the action of some external factors (forced aging), the latter being very diverse, e.g., charging, photolysis, radiolysis, thermolysis, chemical effect of environment, etc. An essential of free aging was examined previously (Dimitrov and Bar-Nun, 2002, Icarus 156, 530-538). The main distinction between free and any forced aging is that both of them possess the same thermodynamics while different kinetics, the forced aging in any case being faster, proceeding in different pathways than the free aging. The more extensive is the list of the external effects and the more intensive they are, the faster and more variably the forced aging proceeds. In this paper we quantified the kinetics of forced aging, considering charging of Titan's aerosol population. It was found that forced aging proceeds approximately hundred times faster as compared to the free aging. Various physico-chemical properties of Titan's aerosol material, including coagulation coefficients, depending on particle size and medium conditions, were defined. The comparison of the aging rate, rate of sedimentation and rate of the particle increase proves that Titan's aerosol domain can be subdivided conditionally into two big subdomains. The upper one contains minor portion (<5%) of the total aerosol bulk, unannealed aerosol particles being fine and sticky. The lower subdomain contains the major portion (>95%) of aerosol bulk, which is completely aged, coarsely dispersed particles. We established the border between these subdomains at the altitude Z∼620 km.     

PAMPRE: A dusty plasma experiment for Titan's tholins production and study

Organic aerosols play a significant role in the properties and evolution of Titan's atmosphere. But our knowledge of them and their physico-chemical mechanisms of formation and evolution are currently limited to a few data obtained by Titan observations from the Earth or from space probes. For this reason, laboratory experiments are developed to simulate the atmospheric chemistry and produce analogues of these aerosols in order to understand better their properties and how they are formed. The plasma discharges are the most efficient devices for the production of such analogues. However, the existing plasmas simulations introduce experimental biases compared with the conditions of aerosols production in Titan's atmosphere: chemistry is induced by electrons instead of photons; the solid analogues are produced and deposited on solid surfaces; direct analysis of the particles inside the reactive chamber is not easy. In order to avoid some of these experimental problems, we have developed another method of production of Titan's aerosols analogues. It is based on a capacitively coupled radio-frequency (RF) cold plasma system at low pressure in a N₂-CH₄ gaseous mixture. In this plasma, solid particles produced from the gas phase are in levitation, thus preventing any wall effect on their production, and allowing the study of the formation and growth of the particles directly in the plasma. Moreover, the electron energy distribution of this plasma can be compared with the solar spectrum. This article describes the RF plasma experiment and presents the first results obtained with an initial N₂-CH₄ (90:10) gaseous mixture which produced our first studied analogues of Titan's aerosols.     

Heavy ion formation in Titan's ionosphere: Magnetospheric introduction of free oxygen and a source of Titan's aerosols?

Discovery by Cassini's plasma instrument of heavy positive and negative ions within Titan's upper atmosphere and ionosphere has advanced our understanding of ion neutral chemistry within Titan's upper atmosphere, primarily composed of molecular nitrogen, with ~2.5% methane. The external energy flux transforms Titan's upper atmosphere and ionosphere into a medium rich in complex hydrocarbons, nitriles and haze particles extending from the surface to 1200 km altitudes. The energy sources are solar UV, solar X-rays, Saturn's magnetospheric ions and electrons, solar wind and shocked magnetosheath ions and electrons, galactic cosmic rays (GCR) and the ablation of incident meteoritic dust from Enceladus’ E-ring and interplanetary medium. Here it is proposed that the heavy atmospheric ions detected in situ by Cassini for heights >950 km, are the likely seed particles for aerosols detected by the Huygens probe for altitudes <100 km. These seed particles may be in the form of polycyclic aromatic hydrocarbons (PAH) containing both carbon and hydrogen atoms C_nH_x. There could also be hollow shells of carbon atoms, such as C₆₀, called fullerenes which contain no hydrogen. The fullerenes may compose a significant fraction of the seed particles with PAHs contributing the rest. As shown by Cassini, the upper atmosphere is bombarded by magnetospheric plasma composed of protons, H₂⁺ and water group ions. The latter provide keV oxygen, hydroxyl and water ions to Titan's upper atmosphere and can become trapped within the fullerene molecules and ions. Pickup keV N₂⁺, N⁺ and CH₄⁺ can also be implanted inside of fullerenes. Attachment of oxygen ions to PAH molecules is uncertain, but following thermalization O+ can interact with abundant CH₄ contributing to the CO and CO₂ observed in Titan's atmosphere. If an exogenic keV O+ ion is implanted into the haze particles, it could become free oxygen within those aerosols that eventually fall onto Titan's surface. The process of freeing oxygen within aerosols could be driven by cosmic ray interactions with aerosols at all heights. This process could drive pre-biotic chemistry within the descending aerosols. Cosmic ray interactions with grains at the surface, including water frost depositing on grains from cryovolcanism, would further add to abundance of trapped free oxygen. Pre-biotic chemistry could arise within surface microcosms of the composite organic-ice grains, in part driven by free oxygen in the presence of organics and any heat sources, thereby raising the astrobiological potential for microscopic equivalents of Darwin's “warm ponds” on Titan.     

Reflectance spectra and chemical structure of Titan's tholins: Application to the analysis of Cassini-Huygens observations

Titan's tholins are used as analogs of Titan's aerosols and N-rich organic solids present on many icy surfaces. However, it is not clear whether or not they are relevant analogs, and which kind of tholins should be used among a wide set available in literature. This paper presents reflectance spectral data of two tholins selected as end-members of a series of samples covering a very wide range of continuous chemical and optical properties. These samples were formed under experimental conditions fairly consistent with Titan's stratosphere. A general framework for using these laboratory data to the analysis of spectral observation of Titan's surface or other objects is suggested. Furthermore, the study reports the first in situ unambiguous identification of aromatics compounds and evidences variations in the sp² carbon structure, which controls the absorption properties in the visible/NIR. These results also point out it is very unlikely to derive quantitative chemical information (e.g., N content, sp²/sp³ ratio) from remote sensing reflectance data.     

An investigation of Titan's aerosols using microwave analog measurements and radiative transfer modeling

A combination of laboratory experiments, theoretical modeling, and spacecraft observations is employed to characterize the aerosols in the atmosphere of Titan. The scattering properties of model aerosols were measured using the Microwave Analog Light Scattering Facility at the University of Florida and complemented with theoretical modeling of single scattering characteristics and radiative transfer in Titan's atmosphere. This study compares these modeling results with photopolarimetric observations made over a range of phase angles by the Pioneer 11 and Voyagers 1 and 2 spacecraft. Important results of this work include a survey of the scattering properties of different particle morphologies and compositions necessary to accurately interpret these observations without introducing non-physical assumptions about the particles or requiring additional free parameters to the radiative transfer models. Previous studies use calculation methods which, due to computing memory and processing time requirements, a priori exclude much of the parameter space that the microwave analog laboratory is ideal for exploring. The goal of the present work, to directly constrain aerosol physical characteristics, is addressed by studying in a consistent manner how a variety of particle morphologies and refractive indices affect the polarization and intensity reflected by Titan's atmosphere. Based on comparisons of model results to spacecraft observations, many model morphologies are excluded from further consideration. The most plausible physical particle models suggest that a combination of Rayleigh-like single particles and aggregates that are larger than those previously suggested and investigated [West, R.A., Smith, P.H., 1991. Evidence for aggregate particles in the atmospheres of Titan and Jupiter. Icarus 90, 330-333; Rannou, P., Cabane, M., Botet, R., Chassefière, E., 1997. A new interpretation of scattered light measurements at Titan's limb. J. Geophys. Res. 102, 10997-11013] provide the best fit to the existing data. Additional laboratory experiments and more refined modeling awaits the results of the new rich observational dataset from the Cassini/Huygens encounter with Titan.     

Laboratory experiments of Titan tholin formed in cold plasma at various pressures: implications for nitrogen-containing polycyclic aromatic compounds in Titan haze

Titan, the largest satellite of Saturn, has a thick nitrogen/methane atmosphere with a thick global organic haze. A laboratory analogue of Titan's haze, called tholin, was formed in an inductively coupled plasma from nitrogen/methane=90/10 gas mixture at various pressures ranging from 13 to 2300 Pa. Chemical and optical properties of the resulting tholin depend on the deposition pressure in cold plasma. Structural analyses by IR and UV/VIS spectroscopy, microprobe laser desorption/ionization mass spectrometry, and Raman spectroscopy suggest that larger amounts of aromatic ring structures with larger cluster size are formed at lower pressures (13 and 26 Pa) than at higher pressures (160 and 2300 Pa). Nitrogen is more likely to incorporate into carbon networks in tholins formed at lower pressures, while nitrogen is bonded as terminal groups at higher pressures. Elemental analysis reveals that the carbon/nitrogen ratio in tholins increases from 1.5-2 at lower pressures to 3 at 2300 Pa. The increase in the aromatic compounds and the decrease in C/N ratio in tholin formed at low pressures indicate the presence of the nitrogen-containing polycyclic aromatic compounds in tholin formed at low pressures. Tholin formed at high pressure (2300 Pa) consists of a polymer-like branched chain structure terminated with CH₃, NH₂, and CN with few aromatic compounds. Reddish-brown tholin films formed at low pressures (13-26 Pa) shows stronger absorptions (almost 10 times larger k-value) in the UV/VIS range than the yellowish tholin films formed at high pressures (160 and 2300 Pa). The tholins formed at low pressures may be better representations of Titan's haze than those formed at high pressures, because the optical properties of tholin formed at low pressures agree well with that of Khare et al. (1984a, Icarus 60, 127-137), which have been shown to account for Titan's observed geometric albedo. Thus, the nitrogen-containing polycyclic aromatic compounds we find in tholin formed at low pressure may be present in Titan's haze. These aromatic compounds may have a significant influence on the thermal structure and complex organic chemistry in Titan's atmosphere, because they are efficient absorbers of UV radiation and efficient charge exchange intermediaries. Our results also indicate that the haze layers at various altitudes might have different chemical and optical properties.     

Photochemical processes on Titan: Irradiation of mixtures of gases that simulate Titan's atmosphere

Photochemical reaction pathways in Titan's atmosphere were investigated by irradiation of the individual components and the mixture containing nitrogen, methane, hydrogen, acetylene, ethylene, and cyanoacetylene. The quantum yields for the loss of the reactants and the formation of products were determined. Photolysis of ethylene yields mainly saturated compounds (ethane, propane, and butane) while photolysis of acetylene yields the same saturated compounds as well as ethylene and diacetylene. Irradiation of cyanoacetylene yields mainly hydrogen cyanide and small amounts of acetonitrile. When an amount of methane corresponding to its mixing ratio on Titan was added to these mixtures the quantum yields for the loss of reactants decreased and the quantum yields for hydrocarbon formation increased indicative of a hydrogen atom abstraction from methane by the photochemically generated radicals. GC/MS analysis of the products formed by irradiation of mixtures of all these gases generated over 120 compounds which were mainly aliphatic hydrocarbons containing double and triple bonds along with much smaller amounts of aromatic compounds like benzene, toluene and phenylacetylene. The reaction pathways were investigated by the use of ¹³C acetylene in these gas mixtures. No polycyclic aromatic compounds were detected. Vapor pressures of these compounds under conditions present in Titan's atmosphere were calculated. The low molecular weight compounds likely to be present in the atmosphere and aerosols of Titan as a result of photochemical processes are proposed.     

Laboratory simulations of Titan's atmosphere: organic gases and aerosols

Titan, the main satellite of Saturn, has been observed by remote sensing for many years, both from interplanetary probes (Pioneer and Voyager's flybys) and from the Earth. Its N2 atmosphere, containing a small fraction of CH4 (approximately 2%), with T approximately 90 K and P approximately 1.5 bar at the ground level, is irradiated by solar UV photons and deeply bombarded by energetic particles, i.e. Saturn mangetospheric electrons and protons, interplanetary electrons and cosmic rays. The resulting energy deposition, which takes place mainly below 1000 km, initiates chemical reactions which yield gaseous hydrocarbons and nitriles and, through polymerisation processes, solid aerosol particles which grow by coagulation and settle down to the ground. At the present time, photochemical models strongly require the results of specific laboratory studies. Chemical rate constants are not well known at low temperatures, charged-particle-induced reactions are difficult to model and laboratory simulations of atmospheric processes are therefore of great interest. Moreover, the synthesis of organic compounds which have not been detected to date provides valuable information for future observations. The origin and chemical composition of aerosols depend on the nature of chemical and energy sources. Their production from gaseous species may be monitored in laboratory chambers and their optical or microphysical properties compared to those deduced from the observations of Titan's atmosphere. The development of simulation chambers of Titan's extreme conditions is necessary for a better understanding of past and future observations. Space probes will sound Titan's atmosphere by remote sensing and in situ analysis in the near future (Cassini-Huygens mission). It appears necessary, as a preliminary step to test on-board experiments in such chambers, and as a final step, when new space data have been acquired, to use them for more general scientific purposes.     

Transition from Gaseous Compounds to Aerosols in Titan's Atmosphere

We investigate the chemical transition of simple molecules like C₂H₂ and HCN into aerosol particles in the context of Titan's atmosphere. Experiments that synthesize analogs (tholins) for these aerosols can help illuminate and constrain these polymerization mechanisms. Using information available from these experiments, we suggest chemical pathways that can link simple molecules to macromolecules, which will be the precursors to aerosol particles: polymers of acetylene and cyanoacetylene, polycyclic aromatics, polymers of HCN and other nitriles, and polyynes. Although our goal here is not to build a detailed kinetic model for this transition, we propose parameterizations to estimate the production rates of these macromolecules, their C/N and C/H ratios, and the loss of parent molecules (C₂H₂, HCN, HC₃N and other nitriles, and C₆H₆) from the gas phase to the haze. We use a one-dimensional photochemical model of Titan's atmosphere to estimate the formation rate of precursor macromolecules. We find a production zone slightly lower than 200 km altitude with a total production rate of 4×10⁻¹⁴ g cm⁻² s⁻¹ and a C/N?4. These results are compared with experimental data, and to microphysical model requirements. The Cassini/Huygens mission will bring a detailed picture of the haze distribution and properties, which will be a great challenge for our understanding of these chemical processes.     

Simulations of Titan's brightness by a two-dimensional haze model

We have used a 2-D microphysics model to study the effects of atmospheric motions on the albedo of Titan's thick haze layer. We compare our results to the observed variations of Titan's brightness with season and latitude. We use two wind fields; the first is a simple pole-to-pole Hadley cell that reverses twice a year. The second is based on the results of a preliminary Titan GCM. Seasonally varying wind fields, with horizontal velocities of about 1 cm sec-1 at optical depth unity, are capable of producing the observed change in geometric albedo of about 10% over the Titan year. Neither of the two wind fields can adequately reproduce the latitudinal distribution of reflectivity seen by Voyager. At visible wavelengths, where only haze opacity is important, upwelling produces darkening by increasing the particle size at optical depth unity. This is due to the suspension of larger particles as well as the lateral removal of smaller particles from the top of the atmosphere. At UV wavelengths and at 0.89 micrometers the albedo is determined by the competing effects of the gas the haze material. Gas is bright in the UV and dark at 0.89 micrometers. Haze transport at high altitudes controls the UV albedo and transport at low altitude controls the 0.89 micrometers albedo. Comparisons between the hemispheric contrast at UV, visible, and IR wavelengths can be diagnostic of the vertical structure of the wind field on Titan.     

The influence of methane, acetylene and carbon dioxide on the crystallization of supercooled ethane droplets in Titan's clouds

Spectroscopic studies of the homogeneous and heterogeneous crystallization of supercooled ethane aerosol droplets performed under conditions representative of those in Titan's lower atmosphere are presented. Pure ethane aerosols and both internally- and externally-mixed ensembles of ethane/acetylene and ethane/carbon dioxide aerosols were generated in a bath gas cooling cell and their freezing dynamics monitored using infrared absorption spectroscopy. A detailed overview of the spectroscopic signatures of pure ethane and mixed ethane/acetylene and ethane/carbon dioxide aerosols and their phase-dependence is provided. The ice-nucleating efficiencies of acetylene and carbon dioxide aerosols were compared, as were the efficiencies of freezing via an immersion or contact freezing mechanism. The spectral data provided will be of significant use for remote sensing applications, while the nucleation studies have important consequences for models of Titan's ethane clouds.     

The detached haze layer in Titan's mesosphere

By comparing observations from the Cassini imaging system, UV spectrometer, and Huygens atmospheric structure instrument, we determine an apparent radius of ∼40 nm, an imaginary index <0.3 at 187.5 nm and a number density of ∼30 particles cm⁻³ for the detached haze layer at 520 km in Titan's mesosphere. We point out that the detached haze layer is coincident with a local maximum in the measured temperature profile and show that the temperature maximum is caused by absorption of sunlight in the detached haze layer. This rules out condensation as the source of the layer. The derived particle size is in good agreement with that estimated for the size of the monomers in the aggregate particles that make up the main haze layer. Calculations of the sedimentation velocity of the haze particles coupled with the derived number density imply a mass flux , which is approximately equal to the mass flux required to explain the main haze layer. Because the aerosol size and mass flux derived for the detached layer agree with those determined for the main layer, we suggest that the main haze layer in Titan's stratosphere is formed primarily by sedimentation and coagulation of particles in the detached layer. This implies that high-energy radical and ion chemistry in the thermosphere is the main source of haze on Titan.     

Predictions of the electrical conductivity and charging of the aerosols in Titan's atmosphere

The electrical conductivity and electrical charge on the aerosols in atmosphere of Titan are computed for altitudes between 0 and 400 km. Ionization of methane and nitrogen due to galactic cosmic rays (GCR) is important at night where these ions are converted to ion clusters such as CH⁺₅CH₄, C₇H⁺₇, C₄H⁺₇, and H₄C₇N⁺. The ubiquitous aerosols observed also play an important role in determining the charge distribution in the atmosphere. Because polycyclic aromatic hydrocarbons (PAHs) are expected in Titan's atmosphere and have been observed in the laboratory and found to be electrophilic, we consider the formation of negative ions. During the night, the very smallest molecular complexes accept free electrons to form negative ions. This results in a large reduction of the electron abundance both in the region between 150 and 350 km over that predicted when such aerosols are not considered. During the day time, ionization by photoemission from aerosols irradiated by solar ultraviolet (UV) radiation overwhelms the GCR-produced ionization. The presence of hydrocarbon and nitrile minor constituents substantially reduces the UV flux in the wavelength band from the cutoff of CH₄ at 155 to 200 nm. These aerosols have such a low ionization potential that the bulk of the solar radiation at longer wavelengths is energetic enough to produce a photoionization rate sufficient to create an ionosphere even without galactic cosmic ray (GCR) bombardment. At altitudes below 60 km, the electron and positive ion abundances are influenced by the three-body recombination of ions and electrons. The addition of this reaction significantly reduces the predicted electron abundance over that previously predicted. Our calculations for the dayside show that the peaks of the charge distributions move to larger values as the altitude increases. This variation is the result of the increased UV flux present at the highest altitudes. Clearly, the situation is quite different than that for the night where the peak of the distribution for a particular size is nearly constant with altitude when negative ions are not present. The presence of very small aerosol particles (embryos) may cause the peak of the distribution to decrease from about 8 negative charges to as little as one negative charge or even zero charge. This dependence on altitude will require models of the aerosol formation to change their algorithms to better represent the effect of charged aerosols as a function of altitude. In particular, the charge state will be much higher than previously predicted and it will not be constant with altitude during the day time. Charging of aerosol particles, whether on the dayside or nightside, has a major influence on both the electron abundance and electrical conductivity. The predicted conductivities are within the measurement range of the HASI PWA instrument over most but not all, of the altitude range sampled.     

Complex Refractive Index of Titan's Aerosol Analogues in the 200-900 nm Domain

The main gas-phase constituents of Titan's upper atmosphere, N₂ and CH₄, are photolyzed and radiolyzed by solar photons and magnetospheric electrons, respectively. The primary products of these chemical interactions evolve to heavier organic compounds that are likely to associate into the particles of haze layers that hide Titan's surface. The different theories and models that have been put forward to explain the characteristics and properties of the haze composites require a knowledge of their optical properties, which are determined by the complex refractive index. We present a new set of values for refractive index n and extinction coefficient k calculated directly from the transmittance and reflectance curves exhibited by a laboratory analogue of Titan's aerosols in the 200-900 nm range. Improvements in the aerosol analogue quality have been made. The effects of variables such as the uncertainty in sample thickness, aerosol porosity, and amount of scattered light on the final n and k values are assessed and discussed. Within the studied wavelength domain, n varies from 1.53 to 1.68 and k varies from 2.62×10⁻⁴ to 2.87×10⁻². These final n and k values should be considered as a new reference to modelers who compute the properties of Titan's aerosols in trying to explain the atmospheric dynamics and surface characteristics.     

Titan's atmospheric chemistry: Photolysis of gas mixtures containing hydrogen cyanide and carbon monoxide at 185 and 254 nm

The formation of organic compounds in the atmosphere of Titan is an ongoing process of the generation of complex organics from the simplest hydrocarbon, methane. Solar radiation and magnetosphere electrons are the main energy sources that drive the reactions in Titan's atmosphere. Since energy from solar radiation is 200 times greater than that from magnetosphere electrons, we have investigated the products formed by the action of UV radiation (185 and 254 nm) on a mixture of gases containing nitrogen, methane, hydrogen, acetylene, ethylene, and cyanoacetylene, the basic gas mixture (BGM) that simulates aspects of Titan's atmosphere using a flow reactor [Tran, B.N., Ferris, J.P., Chera, J.J., 2003a. Icarus 162, 114-124; Tran, B.N., Joseph, J.C., Force, M., Briggs, R.G., Vuitton, V., Ferris, J.P., 2005. Icarus 177, 106-115]. The present research extends these studies by the addition of carbon monoxide and hydrogen cyanide to the BGM. Quantum yields for the loss of reactants and the formation of volatile products were determined and compared with those measured in the absence of the hydrogen cyanide and carbon monoxide. The GCMS analyses of the volatile photolysis products from the BGM, with added hydrogen cyanide, had a composition similar to that of the BGM while the photolysis products of the BGM with added carbon monoxide contained many oxygenated compounds. The infrared spectrum of the corresponding solid product revealed the absorption band of a ketone group, which was probably formed from the reaction of carbon monoxide with the free radicals generated by photolysis of acetylene and ethylene. Of particular interest was the observation that the addition of HCN to the gas mixture only resulted in a very small change in the C/N ratio and in the intensity of the CN frequency at 2210 cm⁻¹ in the infrared spectrum suggesting that little HCN is incorporated into the haze analog. The C/N ratio of the haze analogs was found to be in the 10-12 range. The UV spectra of the solid products formed when HCN or CO added to the BGM is similar to the UV absorption formed from the BGM alone. This result is consistent with absence of additional UV chromophores to the solid product when these mixtures are photolyzed. The following photoproducts, which were not starting materials in our photochemical studies, have been observed on Titan: acetonitrile, benzene, diacetylene, ethane, propene, propane, and propyne.     

A model of Titan's aerosols based on measurements made inside the atmosphere

The descent imager/spectral radiometer (DISR) instrument aboard the Huygens probe into the atmosphere of Titan measured the brightness of sunlight using a complement of spectrometers, photometers, and cameras that covered the spectral range from 350 to 1600 nm, looked both upward and downward, and made measurements at altitudes from 150 km to the surface. Measurements from the upward-looking visible and infrared spectrometers are described in Tomasko et al. [2008a. Measurements of methane absorption by the descent imager/spectral radiometer (DISR) during its descent through Titan's atmosphere. Planet. Space Sci., this volume]. Here, we very briefly review the measurements by the violet photometers, the downward-looking visible and infrared spectrometers, and the upward-looking solar aureole (SA) camera. Taken together, the DISR measurements constrain the vertical distribution and wavelength dependence of opacity, single-scattering albedo, and phase function of the aerosols in Titan's atmosphere.Comparison of the inferred aerosol properties with computations of scattering from fractal aggregate particles indicates the size and shape of the aerosols. We find that the aggregates require monomers of radius 0.05 μm or smaller and that the number of monomers in the loose aggregates is roughly 3000 above 60 km. The single-scattering albedo of the aerosols above 140 km altitude is similar to that predicted for some tholins measured in laboratory experiments, although we find that the single-scattering albedo of the aerosols increases with depth into the atmosphere between 140 and 80 km altitude, possibly due to condensation of other gases on the haze particles. The number density of aerosols is about 5/cm³ at 80 km altitude, and decreases with a scale height of 65 km to higher altitudes. The aerosol opacity above 80 km varies as the wavelength to the −2.34 power between 350 and 1600 nm.Between 80 and 30 km the cumulative aerosol opacity increases linearly with increasing depth in the atmosphere. The total aerosol opacity in this altitude range varies as the wavelength to the −1.41 power. The single-scattering phase function of the aerosols in this region is also consistent with the fractal particles found above 60 km.In the lower 30 km of the atmosphere, the wavelength dependence of the aerosol opacity varies as the wavelength to the −0.97 power, much less than at higher altitudes. This suggests that the aerosols here grow to still larger sizes, possibly by incorporation of methane into the aerosols. Here the cumulative opacity also increases linearly with depth, but at some wavelengths the rate is slightly different than above 30 km altitude.For purely fractal particles in the lowest few km, the intensity looking upward opposite to the azimuth of the sun decreases with increasing zenith angle faster than the observations in red light if the single-scattering albedo is assumed constant with altitude at these low altitudes. This discrepancy can be decreased if the single-scattering albedo decreases with altitude in this region. A possible explanation is that the brightest aerosols near 30 km altitude contain significant amounts of methane, and that the decreasing albedo at lower altitudes may reflect the evaporation of some of the methane as the aerosols fall into dryer layers of the atmosphere. An alternative explanation is that there may be spherical particles in the bottom few kilometers of the atmosphere.     

Laboratory light-scattering measurements with Titan's aerosols analogues produced by a dusty plasma

The chemistry leading to the formation of solid aerosols (tholins) in Titan's atmosphere is simulated by a capacitively coupled plasma in a N₂-CH₄ gas mixture. The solid grains are produced in volume directly in the gas phase and studied ex-situ by SEM imaging and by light scattering on clouds of particles. The scattered light properties depend on the physical properties of the particles (morphologies, size distribution), as well as on the phase angle and the wavelength of the light. The particles may be aggregated or agglomerated grains. The grains size distribution is studied as a function of plasma parameters such as initial methane concentration introduced into the discharge, gas flow, absorbed RF power and plasma duration. The average grain size increases when the amount of CH₄ increases, when the gas flow decreases, and when the plasma duration increases up to a limit for each production condition.For all the samples, the absorption decreases with increasing wavelength in the visible domain. As usually found for irregular particles, the polarization phase curves have a bell-shaped positive branch and a shallow negative branch. The maximum of polarization (P_max) increases when the average grain size decreases (sub-μm-sized grains). To obtain P_max values within the range of those measured in Titan's atmosphere; the average grains diameter has to be smaller than 100 nm, in agreement with the space observations results. In the light-scattering experiment, the size of the agglomerates in the clouds is in the 40-80 μm range in equivalent diameter. As a consequence P_max increases with decreasing wavelength due to the increasing absorption, in agreement with observations of Titan from outside the atmosphere.     

Titan's atmospheric engine: an overview

Heating occurs in Titan's stratosphere from the absorption of incident solar radiation by methane and aerosols. About 10% of the incident sunlight reaches Titan's surface and causes heating there. Thermal radiation redistributes heat within the atmosphere and cools to space. The resulting vertical temperature profile is stable against convection and a state of radiative equilibrium is established. Equating theoretical and observed temperature profiles enables an empirical determination of the vertical distribution of thermal opacity. A uniformly mixed aerosol is responsible for most of the opacity in the stratosphere, whereas collision-induced absorption of gases is the main contributor in the troposphere. Occasional clouds are observed in the troposphere in spite of the large degrees of methane supersaturation found there. Photochemistry converts CH₄ and N₂ into more complex hydrocarbons and nitriles in the stratosphere and above. Thin ice clouds of trace organics are formed in the winter and early spring polar regions of the lower stratosphere. Precipitating ice particles serve as condensation sites for supersaturated methane vapor in the troposphere below, resulting in lowered methane degrees of supersaturation in the polar regions. Latitudinal variations of stratospheric temperature are seasonal, and lag instantaneous response to solar irradiation by about one season for two reasons: (1) an actual instantaneous thermal response to a latitudinal distribution of absorbing gases, themselves out of phase with the sun by about one season, and (2) a sluggish dynamical response of the stratosphere to the latitudinal transport of angular momentum, induced by radiative heating and cooling. Mean vertical abundances of stratospheric organics and aerosols are determined primarily by atmospheric chemistry and condensation, whereas latitudinal distributions are more influenced by meridional circulations. In addition to preferential scavenging by precipitating ice particles from above, the polar depletion of supersaturated methane results from periodic scavenging by short-lived tropospheric clouds, coupled with the steady poleward march of the continuously drying atmosphere due to meridional transport.     

Two formation regions for Titan's hazes: indirect clues and possible synthesis mechanisms

It is suggested that aerosol particles forming the detached and main haze layers of Titan's atmosphere do not originate in the same atmospheric levels. Particles present above approximately 350 km could be formed of polyacetylenes synthetized in the 500-800 km altitude range through successive insertion reactions involving the C2H radical under the action of solar ultraviolet photons (Yung et al., Astrophys. J. Suppl. 55, 465, 1984). They might contain C-N oligomers in comparable amounts, as well as C-H-N oligomers synthetized at high altitude (900-1000 km) by the action of suprathermal Saturn plasma electrons. Physically, they are expected to consist of fluffy aggregates of density approximately 0.01-0.1 g cm-3. Their mass production rate is small (10(-15)-10(-14) kg m-2 s-1), that is typically 10% or less of the main haze production rate. Due to their low fall velocity, they are very sensitive to large scale horizontal motions and one substantial part of them may be swept away by meridional circulation at the detached haze level. The altitude range where these aerosols are created is well above the range proposed by Cabane et al. (Planet. Space Sci. 41, 257, 1993) for aerosols of the main haze layer, on the basis of a new fractal microphysical modeling of Titan's aggregates, that is approximately 350-400 km. A natural outcome of this apparent discrepancy is to suppose that there is a second formation region, below approximately 400 km altitude, giving rise to the main haze layer. The aim of the present paper is to review the different possible formation mechanisms of this main haze layer and assess their ability to account for the observed characteristics of the haze. Several conditions are established. The first one, called "condition A", concerns the formation altitude range imposed by fractal modeling. Possible chemical and energy sources are examined. Two additional constraints, relative to the minimum gas mass ("condition B") and input energy ("condition C") required for efficient conversion of gas into aerosols, are defined. By comparing the production rates of the haze, as derived from microphysical models, and of gaseous chemical species, as derived from photochemical models, five possible source constituents are identified: N2, CH4, C2H2, C2H6 and HCN. Polymerization of C2H2 into (C2H2)n through action of solar ultraviolet photons is shown to be rather improbable (condition A is hardly satisfied). From both our current knowledge of the gaseous phase photochemistry, through modeling and laboratory experiments, and existing models of the interaction between Saturn magnetosphere and Titan atmosphere, the formation of C-H-N polymers through action of Saturn magnetospheric energetic particles (E approximately 100 keV), is proposed as the basic polymerization mechanism in the lower formation region (conditions A,B and C are jointly satisfied).