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.     

New experimental constraints on the composition and structure of tholins

Powdered samples of carbon-nitrogen-hydrogen “tholins” that mimic Titan's atmosphere aerosols were produced under levitation conditions in the laboratory with a dusty plasma (PAMPRE experiment) using different initial N₂:CH₄ gas mixtures and studied using UV Raman and infrared spectroscopy, X-ray diffraction and high resolution transmission electron microscopy (HRTEM). Comparison between the tholins produced in the PAMPRE experiments and samples prepared by other techniques reveal that they form a fairly homogeneous family of hydrogenated carbon nitride materials. Wall effects during the PAMPRE deposition experiments and other were found to have little effect on the chemical structure of tholins. The first-order UV Raman bands of the disordered carbonaceous materials point to a large contribution of sp² clusters present compared with olefinic CN or CC groupings, whereas features at 690 and 980 cm⁻¹ suggest C₃N₃ rings are present as a species inserted in the macromolecular network. Diffraction techniques do not indicate the presence of large polyaromatic species in any of the tholins studied, whatever their nitrogen concentration, in disagreement with certain previous observations. This precludes the idea that the nature and degree of absorption in the visible range is controlled by the size of polyaromatic species, as has been observed in series of carbon-based materials obtained via thermal processing. Infrared spectroscopy analysis of the tholins has confirmed earlier identifications of chemical groups present including primary amines, nitriles, and alkyl moieties such as CH₂/CH₃, but has ruled out CH₂/CH₃ branches appearing on secondary or tertiary amines. Similar analyses were also performed on a polymeric (HCN)_x material, which was found to present several similarities with the tholins, hence suggesting similar polymerization processes.     

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.     

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.     

Carbon isotopic enrichment in Titan's tholins? Implications for Titan's aerosols

Since the discovery of the main composition of Titan's atmosphere, many laboratory experiments have been carried out to reproduce its chemical evolution, particularly the formation of organic haze particles found throughout this atmosphere. Some of these simulations have produced solid products—referred to as Titan's tholins—that are assumed to have properties similar to those of Titan's aerosols. In the present work, we focus on the possible isotopic fractionation of carbon during the processes involved in the formation of Titan's tholins. Initial ¹²C/¹³C isotopic ratios measured on tholins made in the laboratory using cold plasma discharges are presented. Measurements of isotopic enhancement in ¹³C (δ¹³C), both on tholins and on the initial gas mixture (N₂:CH₄ (98:2)) used to produce them do not show any clear deficit or enrichment in ¹³C relative to ¹²C in the lab-made tholins compared to the initial gas mixture. Preliminary data recovered from the Aerosol Collector Pyrolyzer (ACP) experiment of the Huygens probe suggests that Titan's aerosols may also be exempt of carbon isotopic enrichment. This observation creates possibilities for deeper analysis of ACP experiment data.     

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.     

Laboratory studies of methane and ethane adsorption and nucleation onto organic particles: Application to Titan's clouds

Titan, Saturn's largest moon, has a thick nitrogen/methane atmosphere. The temperature and pressure conditions in Titan's atmosphere are such that the methane vapor should condense near the tropopause to form clouds. Several ground-based measurements have observed sparse cloud-like features in Titan's atmosphere, while the Cassini mission to Saturn has provided large scale images of the clouds. However, Titan's cloud formation conditions remain poorly constrained. Heterogeneous nucleation (from the vapor phase onto a solid or liquid aerosol surface) greatly enhances cloud formation relative to homogeneous nucleation. In order to elucidate the cloud formation mechanism near the tropopause, we have performed laboratory measurements of the adsorption of methane and ethane onto solid organic particles (tholins) representative of Titan's photochemical haze. We find that monolayers of methane adsorb onto tholin particles at saturation ratios less than unity. We also find that solid methane nucleates onto the adsorbed methane at a saturation ratio of S=1.07±0.008. This implies that Titan's methane clouds should form easily. This is consistent with recent measurements of the column of methane ruling out excessive methane supersaturation. In addition, we find ethane adsorbs onto tholin particles in a metastable phase prior to nucleation. However, ethane nucleation onto the adsorbed ethane occurs at a relatively high saturation ratio of S=1.36±0.08. These findings are consistent with the recent report of polar ethane clouds in Titan's lower stratosphere.     

Saturn's Titan: Surface change, ammonia, and implications for atmospheric and tectonic activity

Titan is known to have a young surface. Here we present evidence from the Cassini Visual and Infrared Mapping Spectrometer that it is currently geologically active. We report that changes in the near-infrared reflectance of a 73,000 km² area on Titan (latitude 26° S, longitude 78° W) occurred between July 2004 and March of 2006. The reflectance of the area increased by a factor of two between July 2004 and March-April 2005; it then returned to the July 2004 level by November 2005. By late December 2005 the reflectance had surged upward again, establishing a new maximum. Thereafter, it trended downward for the next three months. Detailed spectrophotometric analyses suggest these changes happen at or very near the surface. The spectral differences between the region and its surroundings rule out changes in the distribution of the ices of reasonably expected materials such as H₂O, CO₂, and CH₄ as possible causes. Remarkably, the change is spectrally consistent with the deposition and removal of NH₃ frost over a water ice substrate. NH₃ has been proposed as a constituent of Titan's interior and has never been reported on the surface. The detection of NH₃ frost on the surface might possibly be explained by episodic effusive events occur which bring juvenile ammonia from the interior to the surface. If so, its decomposition would feed nitrogen to the atmosphere now and in the future. The lateral extent of the region exceeds that of active areas on the Earth (Hawaii) or Io (Loki).     

Simulation of Titan haze formation using a photochemical flow reactor: The optical constants of the polymer

Solar UV is the principal energy source impinging the atmosphere of Titan while the energy from the electrons in Saturn's magnetosphere is less than 0.5% of the UV light. Titan haze analogs were prepared by the photolysis of a mixture of gases that simulate the composition of its atmosphere (nitrogen, methane, hydrogen, acetylene, ethylene, and cyanoacetylene). The real (n) and imaginary (k) parts of the complex refractive index of haze analogs formed from four different gas mixtures were calculated from the spectral properties of the solid polymer in UV-visible, near infrared and infrared wavelength spectral regions. The value of n was constant at 1.6±0.1 throughout the 0.2-2.5 μm region. The variation of k with wavelength for the values derived for Titan has a lower error than the absolute values of k so the more significant comparisons are with the slopes of the k(λ) plots in the UV-VIS region. Three of the photochemical Titan haze analogs had slopes comparable to those derived for Titan from the Voyager data (Rages and Pollack, 1980, Icarus 41, 119-130; McKay and Toon, 1992, in: Proceedings of the Symposium on Titan, in: ESA SP, Vol. 338, pp. 185-190). The slopes of the k(λ) plots for haze analogs prepared by spark discharge (Khare et al., 1984, Icarus 60, 127-137) and plasma discharge (Ramirez et al., 2002, Icarus 156, 515-529) were also comparable to Titan's. These finding show that the k(λ) plots do not differentiate between different laboratory simulations of atmospheric chemistry on Titan in the UV-VIS near IR region (0.2-2.5 microns). There is a large difference between the k(λ) in the infrared between the haze analogs prepared photochemically and analogs prepared using a plasma discharges (Khare et al., 1984, Icarus 60, 127-137; Coll et al., 1999, Planet. Space Sci. 47, 1331-1340; Khare et al., 2002, Icarus 160, 172-182). The C/N ratio in the haze analog prepared by discharges is in the 2-11 range while that of the photochemical analogs is in the 18-24 range. The use of discharges and UV light for initiating the chemistry in Titan's atmosphere is discussed.     

Water sorption on martian regolith analogs: Thermodynamics and near-infrared reflectance spectroscopy

The near-infrared reflectance spectra of the martian surface present strong absorption features attributed to hydration water present in the regolith. In order to characterize the relationships between this water and atmospheric vapor and decipher the physical state of water molecules in martian regolith analogs, we designed and built an experimental setup to measure near-IR reflectance spectra under martian atmospheric conditions. Six samples were studied that cover part of the diversity of Mars surface mineralogy: a hydrated ferric oxide (ferrihydrite), two igneous samples (volcanic tuff, and dunite sand), and three potential water rich soil materials (Mg-sulfate, smectite powder and a palagonitic soil, the JSC Mars-1 regolith stimulant). Sorption and desorption isotherms were measured at 243 K for water vapor pressure varying from 10⁻⁵ to ∼0.3 mbar (relative humidity: 10⁻⁴ to 75%). These measurements reveal a large diversity of behavior among the sample suite in terms of absolute amount of water adsorbed, shape of the isotherm and hysteresis between the adsorption and desorption branches. Simultaneous in situ spectroscopic observations permit a detailed analysis of the spectral signature of adsorbed water and also point to clear differences between the samples. Ferric (oxy)hydroxides like ferrihydrite or other phases present in palagonitic soils are very strong water adsorbent and may play an important role in the current martian water cycle by allowing large exchange of water between dust-covered regions and atmosphere at diurnal and seasonal scales.     

Characteristics of Titan's stratospheric aerosols and condensate clouds from Cassini CIRS far-infrared spectra

Four broad spectral features were identified in far-infrared limb spectra from the Cassini Composite Infrared Spectrometer (CIRS), two of which have not been identified before. The features are broader than the spectral resolution, which suggests that they are caused by particulates in Titan's stratosphere. We derive here the spectral properties and variations with altitude for these four features for six latitudes between 65° S and 85° N. Titan's main aerosol is called Haze 0 here. It is present at all wavenumbers in the far-infrared and is found to have a fractional scale height (i.e., the aerosol density scale height divided by the atmospheric density scale height) between 1.5 and 1.7 with a small increase in opacity in the north. A second feature around 140 cm⁻¹ (Haze A) has similar spatial properties to Haze 0, but has a smaller fractional scale height of 1.2-1.3. Both Haze 0 and Haze A show an increase in retrieved abundance below 100 km. Two other features (Haze B around 220 cm⁻¹ and Haze C around 190 cm⁻¹) have a large maximum in their density profiles at 140 and 90 km, respectively. Haze B is much more abundant in the northern hemisphere compared to the southern hemisphere. Haze C also shows a large increase towards the north, but then disappears at 85° N.     

Photometric properties of Titan''s surface from Cassini VIMS: Relevance to titan''s hemispherical albedo dichotomy and surface stability

The Visual and Infrared Mapping Spectrometer (VIMS) instrument on the Cassini Saturn Orbiter returned spectral imaging data as the spacecraft undertook six close encounters with Titan beginning 7 July, 2004. Three of these flybys each produced overlapping coverage of two distinct regions of Titan's surface. Twenty-four points were selected on approximately opposite hemispheres to serve as photometric controls. Six points were selected in each of four reflectance classes. On one hemisphere each control point was observed at three distinct phase angles. From the derived phase coefficients, preliminary normal reflectances were derived for each reflectance class. The normal reflectance of Titan's surface units at 2.0178 μm ranged from 0.079 to 0.185 for the most absorbing to the most reflective units assuming no contribution from absorbing haze. When a modest haze contribution of τ=0.1 is considered these numbers increase to 0.089–0.215. We find that the lowest three reflectance classes have comparable normal reflectance on either hemisphere. However, for the highest brightness class the normal reflectance is higher on the hemisphere encompassing longitude 14–65° compared to the same high brightness class for the hemisphere encompassing 122–156° longitude. We conclude that an albedo dichotomy observed in continental sized units on Titan is due not only to one unit having more areal coverage of reflective material than the other but the material on the brighter unit is intrinsically more reflective than the most reflective material on the other unit. This suggests that surface renewal processes are more widespread on Titan's more reflective units than on its less reflective units.

We note that one of our photometric control points has increased in reflectance by 12% relative to the surrounding terrain from July of 2004 to April and May of 2005. Possible causes of this effect include atmospheric processes such as ground fog or orographic clouds; the suggestion of active volcanism cannot be ruled out.

Several interesting circular features which resembled impact craters were identified on Titan's surface at the time of the initial Titan flyby in July of 2004. We traced photometric profiles through two of these candidate craters and attempted to fit these profiles to the photometric properties expected from model depressions. We find that the best-fit attempt to model these features as craters requires that they be unrealistically deep, approximately 70 km deep. We conclude that despite their appearance, these circular features are not craters, however, the possibility that they are palimpsests cannot be ruled out.

We used two methods to test for the presence of vast expanses of liquids on Titan's surface that had been suggested to resemble oceans. Specular reflection of sunlight would be indicative of widespread liquids on the surface; we found no evidence of this. A large liquid body should also show uniformity in photometric profile; we found the profiles to be highly variable. The lack of specular reflection and the high photometric variability in the profiles across candidate oceans is inconsistent with the presence of vast expanses of flat-lying liquids on Titan's surface. While liquid accumulation may be present as small, sub-pixel-sized bodies, or in areas of the surface which still remain to be observed by VIMS, the presence of large ocean-sized accumulations of liquids can be ruled out.

The Cassini orbital tour offers the opportunity for VIMS to image the same parts of Titan's surface repeatedly at many different illumination and observation geometries. This creates the possibility of understanding the properties of Titan's atmosphere and haze by iteratively adapting models to create a best fit to the surface reflectance properties.     

Optical alteration of complex organics induced by ion irradiation:: 1. Laboratory experiments suggest unusual space weathering trend

Most ion irradiation experiments relevant to primitive outer Solar System objects have been performed on ice and silicate targets. Here we present the first ion irradiation experiments performed on natural complex hydrocarbons (asphaltite and kerite). These materials are very dark in the visible and have red-sloped spectra in the visible and near-infrared. They may be comparable in composition and structure to refractory organic solids on the surfaces of primitive outer Solar System objects. We irradiated the samples with 15-400 keV H⁺, N⁺, Ar⁺⁺, and He⁺ ions and measured their reflectance spectra in the range of 0.3-2.5 μm before ion implantation and after each irradiation step. The results show that irradiation-induced carbonization gradually neutralizes the spectral slopes of these red organic solids. This implies a similar space weathering trend for the surfaces of airless bodies optically dominated by spectrally red organic components. The reduction of spectral slope was observed in all experiments. Irradiation with 30 keV protons, which transfers energy to the target mostly via electronic (inelastic) collisions, showed lower efficiency than the heavier ions. We found that spectral alteration in our experiments increased with increasing contribution of nuclear versus electronic energy loss. This implies that nuclear (elastic) energy deposition plays an important role in changing the optical properties of irradiated refractory complex hydrocarbon materials. Finally, our results indicated that temperature variations from 40 K to room temperature did not influence the spectral properties of these complex hydrocarbon solids.     

The role of organic haze in Titan's atmospheric chemistry: I. Laboratory investigation on heterogeneous reaction of atomic hydrogen with Titan tholin

In Titan's atmosphere consisting of N₂ and CH₄, large amounts of atomic hydrogen are produced by photochemical reactions during the formation of complex organics. This atomic hydrogen may undergo heterogeneous reactions with organic aerosol in the stratosphere and mesosphere of Titan. In order to investigate both the mechanisms and kinetics of the heterogeneous reactions, atomic deuterium is irradiated onto Titan tholin formed from N₂ and CH₄ gas mixtures at various surface-temperatures of the tholin ranging from 160 to 310 K. The combined analyses of the gas species and the exposed tholin indicate that the interaction mechanisms of atomic deuterium with the tholin are composed of three reactions; (a) abstraction of hydrogen from tholin resulting in gaseous HD formation (HD recombination), (b) addition of D atom into tholin (hydrogenation), and (c) removal of carbon and/or nitrogen (chemical erosion). The reaction probabilities of HD recombination and hydrogenation are obtained as ηabst=1.9(±0.6)×¹⁰⁻³×exp(−300/T) and ηhydro=2.08(±0.64)×exp(−1000/T), respectively. The chemical erosion process is very inefficient under the conditions of temperature range of Titan's stratosphere and mesosphere. Under Titan conditions, the rates of hydrogenation > HD recombination ? chemical erosion. Our measured HD recombination rate is about 10 times (with an uncertainty of a factor of 3-5) the prediction of previous theoretical model. These results imply that organic aerosol can remove atomic hydrogen efficiently from Titan's atmosphere through the heterogeneous reactions and that the presence of aerosol may affect the subsequent organic chemistry.     

Comparison between infrared Martian disk spectra and optical properties of terrestrial analogs

Medium spectral resolution (20 cm^?1) infrared measurements of the Martian disk made between 2900 and 5600 cm^?1 from the NASA Lear Airborne Observatory have been successfully compared with predictions derived from a model of the Martian soil and atmosphere. Modeling of the Martian atmosphere permitted the extraction of Martian soil reflectance in the CO₂ bands centered at 3657 cm^?1. Three previously considered acceptable Martian soil analogs, limonite, montmorillonite, and basalt, were analyzed to determine the optical complex indices of refraction in the same range as the airborne observations, for mathematical modeling. A characteristic surface particle size ～1 to 3 μm diameter is indicated. It is concluded that the Martian soil surface near-infrared optical properties are consistent with a soil composition similar to montmorillonite or limonite, mixed with a basalt.     

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.     

The chemical nature of Europa surface material and the relation to a subsurface ocean

The surface composition of Europa is of special interest due to the information it might provide regarding the presence of a subsurface ocean. One source of this information is the infrared reflectance spectrum. Certain surface regions of Europa exhibit distorted H₂O vibrational overtone bands in the 1.5 and 2.0 μm region, as measured by the Galileo mission Near Infrared Mapping Spectrometer (NIMS). These bands are clearly the result of highly concentrated solvated contaminants. However, two interpretations of their identity have been presented. One emphasizes hydrated salt minerals and the other sulfuric acid, although each does not specifically rule out some of the other. It has been pointed out that accurate chemical identification of the surface composition must depend on integrating spectral data with geochemical models, and information on the tenuous atmosphere sputtered from the surface. It is also extremely important to apply detailed chemistry when interpreting the spectral data, including knowledge of mineral dissolution chemistry and the subsequent optical signatures of ion solvation in low-temperature ice. We present studies of flash frozen acid and salt mixtures as Europa surface analogs and demonstrate that solvated protons, metal cations and inorganic anions all influence the spectra and must all, collectively, be considered when assigning Europa spectral features. These laboratory data show best correlation with NIMS Europa spectra for multi-component mixtures of sodium and magnesium bearing sulfate salts mixed with sulfuric acid. The data provide a concentration upper bound of 50-mol% for MgSO₄ and 40-mol% for Na₂SO₄. This newly reported higher sodium and proton content is consistent with low-temperature aqueous differentiation and hydrothermal processing of carbonaceous chondrite-forming materials during the formation and early evolution of Europa.     

Near-infrared reflectance spectroscopy of Ca-rich clinopyroxenes and prospects for remote spectral characterization of planetary surfaces

We present results of laboratory near-infrared reflectance studies of a set of calcic pyroxenes with comparable calcium contents (Wo_45-50) but variable iron content and oxidation states. This new dataset complements earlier published data (Cloutis and Gaffey, 1991, J. Geophys. Res. 96, 22809-28826, and references therein). In particular, our new spectra extend the scarce available spectral data on chemically analyzed Fe-rich high-Ca clinopyroxenes. We attempted to interpret the spectral behavior of our samples in terms of chemistry and coordination site occupancies. Tentatively, we conclude that Fe-rich calcic pyroxenes have very low contents of Fe²⁺ in the M2 sites and belong to the spectral type A lacking the 2-μm band. This may be due to high Ca and Mn contents in these pyroxenes. Fe-poor high-Ca pyroxenes are more spectrally variable. In general, they tend to belong to the spectral type B with two major bands near 1 and 2 μm, unless the samples have high Fe³⁺/Fe²⁺ ratios or are rich in Mn and Ca. Some of them (including unusual meteorite Angra dos Reis) are of type B despite very high Ca contents. We applied the Modified Gaussian Model (MGM) to characterize three major Fe²⁺ absorption bands in the 1-μm region of the spectra of Ca-rich pyroxenes. Only the band due to Fe²⁺ in the M1 coordination site near 1.15 μm may be potentially useful to estimate the Fe content in calcic pyroxenes on remotely-sensed surfaces of Solar System bodies. The spectral variability of basaltic meteorites (angrites) that are rich in calcic pyroxenes is also discussed. The presence of spectral type A calcic pyroxenes in these meteorites complicates unambiguous identification of olivine in asteroid spectra.     

Evidence from scanning electron microscopy ofexperimental influences on the morphology of Triton andTitan tholins

To simulate experimentally the production of aerosols in the atmospheres of Titan andTriton, we have studied organic material (tholins) obtained by inductively coupled plasma fromCH₄ : N₂ gas mixtures, with ratios 10 : 90 for Titan simulations and 0.1 : 99.9 for Tritonsimulations. Observation of tholins by high performance scanning electron microscopy showsthat tholin morphology varies with the chemical composition of the initial gas mixture. Althoughthe role of the experimental design (especially the diameter of the discharge chamber) and theflux of matter were not fully investigated, it appears that they have a significant effect not on theoverall morphology of the tholins but on the size distribution of the particles.     

Spectral Models of Kuiper Belt Objects and Centaurs

We present models of the spectral reflectances of groups of outer Solar System objects defined primarily by their colors in the spectral region 0.4–1.2 mu;m, and which have geometric albedo ～0.04 at wavelength 0.55 μm. Our models of the groups with the strongest reflectance gradients (reddest colors) use combinations of organic tholins. We test the hypothesis that metal-reddened igneous rock-forming minerals contribute to the red colors of Centaurs and KBOs by using the space-weathered lunar soil as one of the components of our models. We find that our models can admit the presence of moderate amounts of space-weathered (metal-reddened) minerals, but that they do not require this material to achieve the red colors of the reddest outer Solar System bodies. Our models with organic tholins are consistent with the results of other investigators.