The role of submicrometer aerosols and macromolecules in H2 formation in the titan haze

Previous studies of the photochemistry of small molecules in Titan’s atmosphere found it difficult to have hydrogen atoms removed at a rate sufficient to explain the observed abundance of unsaturated hydrocarbons. One qualitative explanation of the discrepancy nominated catalytic aerosol surface chemistry as an efficient sink of hydrogen atoms, although no quantitative study of this mechanism was attempted. In this paper, we quantify how haze aerosols and macromolecules may efficiently catalyze the formation of hydrogen atoms into H₂. We describe the prompt reaction model for the formation of H₂ on aerosol surfaces and compare this with the catalytic formation of H₂ using negatively charged hydrogenated aromatic macromolecules. We conclude that the PRM is an efficient mechanism for the removal of hydrogen atoms from the atmosphere to form H₂ with a peak formation rate of ∼ 70 cm⁻³ s⁻¹ at 420 km. We also conclude that catalytic H₂ formation via hydrogenated anionic macromolecules is viable but much less productive (a maximum of ∼ 0.1 cm⁻³ s⁻¹ at 210 km) than microphysical aerosols.     

High-altitude charged aerosols in the atmosphere of Titan

Observations by several instruments onboard the Cassini spacecraft revealed the existence of heavy hydrocarbon and nitrile species with masses of several thousand atomic mass units in the ionosphere of Titan. These very large molecules are in fact aerosols. The goal of this paper is to compute the concentrations of the charged aerosols in the upper atmosphere (950-1200 km) of Titan. The charging of these aerosols has been studied using the charge balance equations, where positive ions, negative ions, electrons, neutral and charged aerosols are included. Number concentrations of charged aerosols are compared with those observed by the Cassini instruments. The present work estimates the aerosol mass density as 1-10 kg/m³, which is within the predicted range. The results show that the aerosols must be smaller than 10 nm in order to have reasonable agreement with observations by the Cassini Plasma Spectrometer.     

Negative ion chemistry in Titan's upper atmosphere

The Electron Spectrometer (ELS), one of the sensors making up the Cassini Plasma Spectrometer (CAPS) revealed the existence of numerous negative ions in Titan's upper atmosphere. The observations at closest approach (∼1000 km) show evidence for negatively charged ions up to ∼10,000 amu/q, as well as two distinct peaks at 22±4 and 44±8 amu/q, and maybe a third one at 82±14 amu/q. We present the first ionospheric model of Titan including negative ion chemistry. We find that dissociative electron attachment to neutral molecules (mostly HCN) initiates the formation of negative ions. The negative charge is then transferred to more acidic molecules such as HC₃N, HC₅N or C₄H₂. Loss occurs through associative detachment with radicals (H and CH₃). We attribute the three low mass peaks observed by ELS to CN⁻, C₃N⁻/C₄H⁻ and C₅N⁻. These species are the first intermediates in the formation of the even larger negative ions observed by ELS, which are most likely the precursors to the aerosols observed at lower altitudes.     

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.     

HST spectral imaging of Titan's haze and methane profile between 0.6 and 1 μm during the 2000 opposition

We report on the analysis of high spatial resolution visible to near-infrared spectral images of Titan at Ls=240° in November 2000, obtained with the Space Telescope Imaging Spectrograph instrument on board the Hubble Space Telescope as part of program GO-8580. We employ a radiative transfer fractal particle aerosol model with a Bayesian parameter estimation routine that computes Titan's absolute reflectivity per pixel for 122 wavelengths by modeling the vertical distribution of the lower atmosphere haze and tropospheric methane. Analysis of these data suggests that Titan's haze concentration in the lower atmosphere varies in strength with latitude. We find Titan's tropospheric methane profile to be fairly consistent with latitude and longitude, and we find evidence for local areas of a CH₄-N₂ binary saturation in Titan's troposphere. Our results suggest that a methane and haze profile at one location on Titan would not be representative of global conditions.     

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.     

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.     

Impact of aerosols present in Titan's atmosphere on the CASSINI radar experiment

Simulations of Titan's atmospheric transmission and surface reflectivity have been developed in order to estimate how Titan's atmosphere and surface properties could affect performances of the Cassini radar experiment. In this paper we present a selection of models for Titan's haze, vertical rain distribution, and surface composition implemented in our simulations. We collected dielectric constant values for the Cassini radar wavelength (∼2.2 cm) for materials of interest for Titan: liquid methane, liquid mixture of methane-ethane, water ice, and light hydrocarbon ices. Due to the lack of permittivity values for Titan's haze particles in the microwave range, we performed dielectric constant (ε_r) measurements around 2.2 cm on tholins synthesized in laboratory. We obtained a real part of ε_r in the range of 2-2.5 and a loss tangent between 10⁻³ and 5×10⁻². By combining aerosol distribution models (with hypothetical condensation at low altitudes) to surface models, we find the following results: (1) Aerosol-only atmospheres should cause no loss and are essentially transparent for Cassini radar, as expected by former analysis. (2) However, if clouds are present, some atmospheric models generate significant attenuation that can reach −50 dB, well below the sensitivity threshold of the receiver. In such cases, a 13.78 GHz radar would not be able to measure echoes coming from the surface. We thus warn about possible risks of misinterpretation if a “wet atmosphere” is not taken into account. (3) Rough surface scattering leads to a typical response of ∼−17 dB. These results will have important implications on future Cassini radar data analysis.     

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.     

Heat balance in Titan's atmosphere

The recent measurements of the vertical distribution and optical properties of haze aerosols as well as of the absorption coefficients for methane at long paths and cold temperatures by the Huygens entry probe of Titan permit the computation of the solar heating rate on Titan with greater certainty than heretofore. We use the haze model derived from the Descent Imager/Spectral Radiometer (DISR) instrument on the Huygens probe [Tomasko, M.G., Doose, L., Engel, S., Dafoe, L.E., West, R., Lemmon, M., Karkoschka, E., See, C., 2008a. A model of Titan's aerosols based on measurements made inside the atmosphere. Planet. Space Sci., this issue, doi:10.1016/j.pss.2007.11.019] to evaluate the variation in solar heating rate with altitude and solar zenith angle in Titan's atmosphere. We find the disk-averaged solar energy deposition profile to be in remarkably good agreement with earlier estimates using very different aerosol distributions and optical properties. We also evaluated the radiative cooling rate using measurements of the thermal emission spectrum by the Cassini Composite Infrared Spectrometer (CIRS) around the latitude of the Huygens site. The thermal flux was calculated as a function of altitude using temperature, gas, and haze profiles derived from Huygens and Cassini/CIRS data. We find that the cooling rate profile is in good agreement with the solar heating profile averaged over the planet if the haze structure is assumed the same at all latitudes. We also computed the solar energy deposition profile at the 10°S latitude of the probe-landing site averaged over one Titan day. We find that some 80% of the sunlight that strikes the top of the atmosphere at this latitude is absorbed in all, with 60% of the incident solar energy absorbed below 150 km, 40% below 80 km, and 11% at the surface at the time of the Huygens landing near the beginning of summer in the southern hemisphere. We compare the radiative cooling rate with the solar heating rate near the Huygens landing site averaging over all longitudes. At this location, we find that the solar heating rate exceeds the radiative cooling rate by a maximum of 0.5 K/Titan day near 120 km altitude and decreases strongly above and below this altitude. Since there is no evidence that the temperature structure at this latitude is changing, the general circulation must redistribute this heat to higher latitudes.     

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 from 0 to 400 km. Ionization due to both galactic cosmic rays and electron precipitation from the Saturnian magnetosphere is considered. This ionization results in free electrons and the primary ions N₂⁺ and N⁺ which are then rapidly converted into secondary ions such as H₂CN⁺ and NH₄⁺ which in turn form ion clusters such as H₂CN⁺(HCN)_n and NH₄⁺(NH₃)_m. In contrast to the atmospheres of Venus and Earth, we find no species in the Titan atmosphere that lead to the formation of appreciable concentrations of negative ions. Consequently, the predicted conductivity is quite different in that a substantial concentration of electrons exists all the way to the surface of Titan. The ubiquitous aerosols observed in the Titan atmosphere also play an important role in determining the charge distribution in the atmosphere. At altitudes above 100 km and for aerosol concentrations above approximately 10/cc, the recombination of electrons and positive ions is controlled by the recombination on the surface of the aerosols rather than by the gas-kinetic recombination rate. For small aerosol concentrations, the ratio of the number of charges per particle to the radius of the particle is approximately 30, for radii in microns. This value is similar to that obtained by previous investigators for terrestrial noctilucent clouds. Because the aerosol particles are highly charged, coagulation is inhibited, particle sizes are smaller, and their settling rates are reduced. As a consequence, the optical depth of the atmosphere is much higher than it would be if the particles were uncharged.     

Ion chemistry and N-containing molecules in Titan's upper atmosphere

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.     

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.     

Optical properties of Titan and early Earth haze laboratory analogs in the mid-visible

Scattering and absorption of sunlight by aerosols are integral to understanding the radiative balance of any planetary atmosphere covered in a haze, such as Titan and possibly the early Earth. One key optical parameter of an aerosol is its refractive index. We have simulated both Titan and early Earth organic haze aerosols in the laboratory and measured the real and imaginary portion of their refractive index at λ = 532 nm using cavity ringdown aerosol extinction spectroscopy. This novel technique allows analysis on freely-floating particles minutes after formation. For our Titan analog particles, we find a real refractive index of n = 1.35 ± 0.01 and an imaginary refractive index k = 0.023 ± 0.007, and for the early Earth analog particles we find n = 1.81 ± 0.02 and k = 0.055 ± 0.020. The Titan analog refractive index has a smaller real and similar imaginary refractive index compared to most previous laboratory measurements of Titan analog films, including values from Khare et al. (Khare, B.N., Sagan, C., Arakawa, E.T., Suits, F., Callcott, T.A., Williams, M.W. [1984]. Icarus 60, 127-137). These newly measured Titan analog values have implications for spacecraft retrievals of aerosol properties on Titan. The early Earth analog has a significantly higher real and imaginary refractive index than Titan analogs reported in the literature. These differences suggest that, for a given amount of aerosol, the early Earth analog would act as a stronger anti-greenhouse agent than the Titan analog.     

Inverse radiation modeling of Titan's atmosphere to assimilate solar aureole imager data of the Huygens probe

During the descent of the Huygens probe through Titan's atmosphere in January 2005, the Descent Imager/Spectral Radiometer (DISR) will perform upward and downward looking measurements at various spectral ranges and spatial resolutions. This internal radiation density could be estimated by radiative transfer calculations for Titan's atmosphere. However, to do this, the optical properties—i.e. volume extinction coefficient, single scattering albedo and scattering phase function—have to be prescribed at every altitude, and these are apriori not known. Herein, an inverse approach is investigated, which retrieves the single scattering albedo and the phase function of the aerosols from DISR observations. The method uses data from a DISR subinstrument, the Solar Aureole imager (SA), to estimate the optical properties of the atmospheric layer between two successive observation altitudes. A unique solution for one layer can in principle be calculated directly from a linear system of equations, but due to the sparseness of the data and the unavoidable noise in the measurements, the inverse problem is ill-posed. The problem is stabilized by the regularization method requiring smoothness of the resultant solution. A consistent set of solutions for all layers is obtained by iterating several times downward and upward through the layers. The method is tested in a simulated radiation density scenario for Titan, which is based on a microphysical aerosol model for the haze layer. Within this scenario, the expected coverage of SA data allows a reconstruction of the angular dependence of the scattering phase function with an explained variance better than 90%.     

Investigation of energetic proton penetration in Titan's atmosphere using the Cassini INCA instrument

Saturn's largest moon, Titan, provides an interesting opportunity to study how dense atmospheres interact with the surrounding plasma environment. Without an intrinsic magnetic field, this satellite's nitrogen-rich atmosphere is relatively unprotected from plasma interactions. Therefore, the energy-deposition rate is important for understanding chemistry and dynamics in Titan's atmosphere. Since the plasma environment can vary significantly we focus here on the T18 Titan encounter using in-situ data from instruments on board the Cassini spacecraft. These instruments cannot provide in-situ information below the spacecraft closest approach altitude (∼>960 km) so we use the Cassini magnetospheric imaging instrument (MIMI) ion-neutral camera (INCA) to remotely image energetic hydrogen particle fluxes (20-80 keV) at altitudes below Titan closest approach. We also use the MIMI low-energy magnetosphere measurements system (LEMMS) to measure the incident ion fluxes as the spacecraft approaches Titan and combine these data sets with an atmospheric model to first reproduce INCA images. We then use this model to calculate the energy-deposition profiles for the observed incident proton flux. Our model is able to reproduce the INCA observations and give the energy density deposited vs. altitude in Titan's atmosphere; however, we find that the incident fluxes and energy-deposition profiles vary significantly during the encounter.     

Clouds, haze, and CH4, CH3D, HCN, and C2H2 in the atmosphere of Titan probed via 3 μm spectroscopy

Using synthetic spectra derived from an updated model atmosphere together with a continuum model that includes contributions from haze, cloud and ground, we have re-analyzed the recently published (Geballe et al., 2003, Astrophys. J. 583, L39-L42) high-resolution 3 μm spectrum of Titan which contains newly-detected bands of HCN (in emission) and C₂H₂ and CH₃D (in absorption), in addition to previously detected bands of CH₄. In the 3.10-3.54 μm interval the analysis yields strong evidence for the existence of a cloud deck or optically thick haze layer at about the 10 mbar (∼ 100 km) level. The haze must extend well above this altitude in order to mask the strong CH₄ lines at 3.20-3.50 μm. These cloud and haze components must be transparent at 2.87-2.92 μm, where analysis of the CH₃D spectrum demonstrates that Titan's surface is glimpsed through a second cloud deck at about the 100 mbar (∼ 50 km) level. Through a combination of areal distribution and optical depth this cloud deck has an effective transmittance of ∼ 20%. The spectral shape of Titan's continuum indicates that the higher altitude cloud and haze particles responsible for suppressing the CH₄ absorptions have a largely organic make-up. The rotational temperature of the HCN ranges from 140 to 180 K, indicating that the HCN emission occurs over a wide range of altitudes. This emission, remodeled using an improved collisional deactivation rate, implies mesospheric mixing ratio curves that are consistent with previously predictions. The stratospheric and mesospheric C₂H₂ mixing ratios are ∼¹⁰⁻⁵, considerably less than previous model predictions (Yung et al., 1984), but approximately consistent with recent observational results. Upper limits to mixing ratios of HC₃N and C₄H₂ are derived from non-detections of those species near 3.0 μm.     

Rain and dewdrops on titan based on in situ imaging

The Descent Imager/Spectral Radiometer (DISR) of the Huygens probe was in an excellent position to view aspects of rain as it descended through Titan's atmosphere. Rain may play an important part of the methane cycle on Titan, similar to the water cycle on Earth, but rain has only been indirectly inferred in previous studies. DISR detected two dark atmospheric layers at 11 and 21 km altitude, which can be explained by a local increase in aerosol size by about 5-10%. These size variations are far smaller than those in rain clouds, where droplets grow some 1000-fold. No image revealed a rainbow, which implies that the optical depth of raindrops was less than ∼0.0002/km. This upper limit excludes rain and constrains drizzle to extremely small rates of less than 0.0001 mm/h. However, a constant drizzle of that rate over several years would clear the troposphere of aerosols faster than it can be replenished by stratospheric aerosols. Hence, either the average yearly drizzle rate near the equator was even less (<0.1 mm/yr), or the observed aerosols came from somewhere else. The implied dry environment is consistent with ground-based imaging showing a lack of low-latitude clouds during the years before the Huygens descent. Features imaged on Titan's surface after landing, which might be interpreted as raindrop splashes, were not real, except for one case. This feature was a dewdrop falling from the outermost baffle of the DISR instrument. It can be explained by warm, methane-moist air rising along the bottom of the probe and condensing onto the cold baffle.     

Aging of Titan's Aerosols

Titan's haze is composed of aerosols containing long chain polymers of acetylene with some hydrogen cyanide. These polymers have alternating double/single and triple/single bonds, which can open spontaneously or under the action of UV radiation or particle impact. Once opened, they can induce the opening of a double or triple bond in an adjacent chain and link to it. This cross-linking and chain elongation hardens or “ages” the polymer particles, making them less sticky. As observed experimentally and calculated theoretically, newly formed polymer particles grow by collecting other polymer chains and by complete merging into symmetrical spheres. However, when aged, they merely adhere to each other and do not merge. Eventually, when hard enough, they do not even adhere to each other. In this paper we calculate the spontaneous aging process as applied to Titan's atmospheric conditions and find that the surface tension and viscosity of the aerosols below H∼570 km are one order of magnitude harder than when the aerosols formed. Furthermore, UV irradiation and particle impacts reduce both viscosity and surface tension by an additional factor of 10-100. Thus, the aerosol particles expected to be encountered by the descending Huygens probe will, most likely, be quite hard.