Laboratory reflection spectra for the determination of chemical composition of icy bodies

The visible (0.3 to 1.03 μm) spectral reflectances of H₂O, NH₃, H₂S, and NH₄HS frosts and mixtures of these frosts and their uv irradiated products have been measured. These spectra are compared with the spectra of the Galilean satellites of Jupiter, Saturn's rings and Saturn's satellites to place limits on their surface composition.     

New upper limits for atmospheric constituents on Io

A spectrum of the satellite of Jupiter, Io, from 0.86 to 2.7 μm at a resolution of 3.36 cm^?1 and a signal to rms noise ratio of 120 is presented. No absorptions due to any atmospheric constituents on Io could be found on the spectrum. Upper limits of 0.12 cm-atm for NH₃, 0.12cm-atm for CH₄, 0.4cm-atm for N₂O, and 24cm-atm for H₂S were determined. Laboratory spectra of ammonia frosts as a function of temperature were compared with the spectrum of Io and showed as a frost not to be present at the surface of Io. A search for possible resonance lines of carbon, silicon, and sulfur as well as the 1.08μm line of helium proved negative and upper emission limits of 60, 18, 27, and 60 kilorayleighs, respectively, were established for these lines.     

Infrared measurements of the chemical composition of C/2006 P1 McNaught

C/2006 P1 McNaught is a dynamically new comet from the Oort cloud that passed very close to the Sun, driving overall volatile production rates up to about 10³¹ molecules s⁻¹. Post-perihelion observations were obtained in a target-of-opportunity campaign using the CSHELL instrument at the NASA Infrared Telescope Facility atop Mauna Kea, Hawaii, on UT 2007 January 27 and 28. Eight parent volatiles (H₂O, CH₄, C₂H₂, C₂H₆, HCN, CO, NH₃, H₂CO) and two daughter fragments (OH and NH₂) were detected, enabling the determination of a rotational temperature and production rate for H₂O on UT January 27 and absolute and relative production rates for all the detected parent species on UT January 28. The chemical composition measured in the coma suggests that this close perihelion passage stripped off processed outer surface layers, likely exposing relatively fresh primordial material during these observations. The post-perihelion abundances we measure for CO and CH₄ (relative to H₂O) are slightly depleted while C₂H₂, NH₂ and possibly NH₃ are enhanced when compared to the overall comet population. Measured abundances for other detected molecular species were within the range typically observed in comets.     

Monte Carlo modeling of neutral gas and dust in the coma of Comet 1P/Halley

The neutral gas environment of a comet is largely influenced by dissociation of parent molecules created at the surface of the comet and collisions of all the involved species. We compare the results from a kinetic model of the neutral cometary environment with measurements from the Neutral Mass Spectrometer and the Dust Impact Detection System onboard the Giotto spacecraft taken during the fly-by at Comet 1P/Halley in 1986. We also show that our model is in good agreement with contemporaneous measurements obtained by the International Ultraviolet Explorer, sounding rocket experiments, and various ground based observations.The model solves the Boltzmann equation with a Direct Simulation Monte Carlo technique (Tenishev, V., Combi, M., Davidsson, B. [2008]. Astrophys. J. 685, 659-677) by tracking trajectories of gas molecules and dust grains under the influence of the comet’s weak gravity field with momentum exchange among particles modeled in a probabilistic manner. The cometary nucleus is considered to be the source of dust and the parent species (in our model: H₂O, CO, H₂CO, CO₂, CH₃OH, C₂H₆, C₂H₄, C₂H₂, HCN, NH₃, and CH₄) in the coma. Subsequently our model also tracks the corresponding dissociation products (H, H₂, O, OH, C, CH, CH₂, CH₃, N, NH, NH₂, C₂, C₂H, C₂H₅, CN, and HCO) from the comet’s surface all the way out to 10⁶ km.As a result we are able to further constrain cometary the gas production rates of CO (13%), CO₂ (2.5%), and H₂CO (1.5%) relative to water without invoking unknown extended sources.     

Outgassing of ordinary chondritic material and some of its implications for the chemistry of asteroids, planets, and satellites

We used chemical equilibrium calculations to model thermal outgassing of ordinary chondritic material as a function of temperature, pressure, and bulk composition and use our results to discuss outgassing on asteroids and the early Earth. The calculations include ∼1000 solids and gases of the elements Al, C, Ca, Cl, Co, Cr, F, Fe, H, K, Mg, Mn, N, Na, Ni, O, P, S, Si, and Ti. The major outgassed volatiles from ordinary chondritic material are CH₄, H₂, H₂O, N₂, and NH₃ (the latter at conditions where hydrous minerals form). Contrary to widely held assumptions, CO is never the major C-bearing gas during ordinary chondrite metamorphism. The calculated oxygen fugacity (partial pressure) of ordinary chondritic material is close to that of the quartz-fayalite-iron (QFI) buffer. Our results are insensitive to variable total pressure, variable volatile element abundances, and kinetic inhibition of C and N dissolution in Fe metal. Our results predict that Earth's early atmosphere contained CH₄, H₂, H₂O, N₂, and NH₃; similar to that used in Miller—Urey synthesis of organic compounds.     

New Molecular Species in Comet C/1995 O1 (Hale-Bopp) Observed with the Caltech Ssubmillimeter Observatory

We present millimeter-wave observations of HNCO, HC₃N, SO, NH₂CHO, H¹³CN, and H₃O⁺ in comet C/1995 O1 (Hale-Bopp)obtained in February–April, 1997 with the Caltech Submillimeter Observatory (CSO). HNCO, first detected at the CSO in comet C/1996B2 (Hyakutake), is securely confirmed in comet Hale-Bopp via observations of three rotational transitions. The derived abundance with respect to H₂O is (4-13) × 10^-4. HC₃N, SO, and NH₂CHO are detected for the first time in a comet. The fractional abundance of HC₃N based on observations of three rotational lines is (1.9 ± 0.2) × 10^-4. Four transitions of SO are detected and the derived fractional abundance, (2-8) ×10^-3, is higher than the upper limits derived from UV observations of previous comets. Observations of NH₂CHO imply a fractional abundance of (1-8) × 10^-4. H₃O is detected for the first time from the ground. The H¹³CN (3-2)transition is also detected and the derived HCN/H¹³CN abundance ratio is 90 ± 15, consistent with the terrestrial¹²C/¹³C ratio. In addition, a number of other molecular species are detected, including HNC, OCS, HCO⁺, CO⁺, and CN(the last two are first detections in a comet at radio wavelengths). This revised version was published online in July 2006 with corrections to the Cover Date.     

The molecular composition of Comet C/2007 W1 (Boattini): Evidence of a peculiar outgassing and a rich chemistry

We measured the chemical composition of Comet C/2007 W1 (Boattini) using the long-slit echelle grating spectrograph at Keck-2 (NIRSPEC) on 2008 July 9 and 10. We sampled 11 volatile species (H₂O, OH^∗, C₂H₆, CH₃OH, H₂CO, CH₄, HCN, C₂H₂, NH₃, NH₂, and CO), and retrieved three important cosmogonic indicators: the ortho-para ratios of H₂O and CH₄, and an upper-limit for the D/H ratio in water. The abundance ratios of almost all trace volatiles (relative to water) are among the highest ever observed in a comet. The comet also revealed a complex outgassing pattern, with some volatiles (the polar species H₂O and CH₃OH) presenting very asymmetric spatial profiles (extended in the anti-sunward hemisphere), while others (e.g., C₂H₆ and HCN) showed particularly symmetric profiles. We present emission profiles measured along the Sun-comet line for all observed volatiles, and discuss different production scenarios needed to explain them. We interpret the emission profiles in terms of release from two distinct moieties of ice, the first being clumps of mixed ice and dust released from the nucleus into the sunward hemisphere. The second moiety considered is very small grains of nearly pure polar ice (water and methanol, without dark material or apolar volatiles). Such grains would sublimate only very slowly, and could be swept into the anti-sunward hemisphere by radiation pressure and solar-actuated non-gravitational jet forces, thus providing an extended source in the anti-sunward hemisphere.     

Representative abundances of a few positive ions in the innermost coma of comet Halley

The production rate of H₂O molecules at a heliocentric distance of 1 AU for comet Halley and the abundance ratio with respect to water (H₂O) of parent molecules at the cometary nucleus from the paper of Yamamoto (1987) have been used to compute the number densities of positive ions viz. H₃O⁺, H₃S⁺, H₂CN⁺, H₃CO⁺, CH₃OH ₂ ⁺ and NH ₄ ⁺ at various cometocentric distances within 600 kms from the nucleus.The role of proton transfer reactions in producing major ionic species is discussed. A major finding of the present investigation is that NH ₄ ⁺ ion which may be produced through proton transfer reactions is the most abundant ion near the nucleus of a comet unless the abundance of NH₃ as a parent is abnormally low. Using the quoted value of Q(NH₃)/Q(H₂O) for comet Halley and the life times of NH₃ and H₂O molecules, the abundance ratio N(NH₃)/N(H₂O) is found to be one-third of that used in the present paper. The consequent proportionate decrease in the NH ₄ ⁺ ions does not, however, affect its superiority in number density over other ions near the nucleus.The number density of the next most abundant ion viz. H₃O⁺ is found to be 4 × 10⁴ cm^-3 at the nucleus of comet Halley and decreases by a factor of two only upto a distance of 600 K ms from the nucleus. The ionic mass peak recorded by VEGA and GIOTTO spacecrafts atm/q = 18 is most probably composite of the minor ionic species H₂O⁺, as its number density = 10² cm^-3 remains virtually constant in the inner coma and of NH ₄ ⁺ , the number density of which at large cometocentric distances may add to the recorded peak atmlq = 18. The number densities of other major ions produced through proton transfer from H₃O⁺ are also discussed in the region within 600 K ms from the nucleus of comet Halley.     

A theoretical study of Comet Halley's spectrum in the infrared range

Synthetic spectra of Comet Halley between 2.5 and 15 μm are calculated on the basis of current cometary models. This study shows that molecules which are most likely detectable in the infrared range include H₂O, CO, CO₂, CH₄, NH₃, N₂H₄, and H₂CO. The flux emitted by these molecules, mostly due to resonant scattering, should be sufficient for detection by a flyby mission.     

Martian dust particles as condensation nuclei: A preliminary assessment of mineralogical factors

Condensation of frosts on Mars should depend not only on temperature and degree of vapor supersaturation but also on the nature of dust particles that would act as condensation nuclei. For a given particle size, the favorability of a condensate nucleator is determined by (1) degree of crystallographic misfit, or disregistry (δ), between substrate and condensate, (2) chemical-bond compatibility between substrate and condensate, and (3) abundance of substrate surface defects that would encourage assembly of condensate atoms or molecules. New data on ice-forming characteristics of candidate Martian materials, obtained by differential scanning calorimetry, confirmed previous evidence for systematic variations in ice-nucleation temperature, T_in, among geologic materials. By considering individual types of minerals separately, factors (2) and (3) can be held relatively constant and differences in nucleation effectiveness can be estimated by computation of (1). Both calorimetry data and cloud-chamber (literature) data indicate that T_in varies inversely with minimum absolute value of disregistry, /δ/. On Mars, H₂OIc might be an important form of water ice whereas H₂OIh is the common form on Earth. Phase H₂OIc offers the lowest overall /δ/ values for heterogeneous nucleation of other condensates, including H₂OIh, solid CO₂, and CO₂ hydrate, suggesting that the best overall mineral nuclei might be those that most effectively nucleate H₂OIc. Based on /δ/ values, good nucleators of H₂OIc should include nonexpandable clay minerals (e.g., kaolinite, chlorite), certain zeolites (e.g., clinoptilolite), goethite, and bassanite. Although goethite might preferentially nucleate H₂OIc, hematite should preferentially nucleate H₂OIh. Cryptocrystalline mineraloids (e.g., palagonite) should be generally poor nucleators and nucleating abilities of expandable clay minerals (e.g., nontronite, montmorillonite) should vary significantly with degree of c-axis expansion, as controlled by degree of interlayer hydration.     

Radiolysis of sulfuric acid, sulfuric acid monohydrate, and sulfuric acid tetrahydrate and its relevance to Europa

We report laboratory studies on the 0.8 MeV proton irradiation of ices composed of sulfuric acid (H₂SO₄), sulfuric acid monohydrate (H₂SO₄·H₂O), and sulfuric acid tetrahydrate (H₂SO₄·4H₂O) between 10 and 180 K. Using infrared spectroscopy, we identify the main radiation products as H₂O, SO₂, (S₂O₃)_x, H₃O⁺, , and . At high radiation doses, we find that H₂SO₄ molecules are destroyed completely and that H₂SO₄·H₂O is formed on subsequent warming. This hydrate is significantly more stable to radiolytic destruction than pure H₂SO₄, falling to an equilibrium relative abundance of 50% of its original value on prolonged irradiation. Unlike either pure H₂SO₄ or H₂SO₄·H₂O, the loss of H₂SO₄·4H₂O exhibits a strong temperature dependence, as the tetrahydrate is essentially unchanged at the highest irradiation temperatures and completely destroyed at the lowest ones, which we speculate is due to a combination of radiolytic destruction and amorphization. Furthermore, at the lower temperatures it is clear that irradiation causes the tetrahydrate spectrum to transition to one that closely resembles the monohydrate spectrum. Extrapolating our results to Europa’s surface, we speculate that the variations in SO₂ concentrations observed in the chaotic terrains are a result of radiation processing of lower hydration states of sulfuric acid and that the monohydrate will remain stable on the surface over geological times, while the tetrahydrate will remain stable in the warmer regions but be destroyed in the colder regions, unless it can be reformed by other processes, such as thermal reactions induced by diurnal cycling.     

Models of the cometary coma in which abundances are calculated for various heliocentric distances

One-dimensional radial models of the chemistry in cometary comae have been constructed for heliocentric distances ranging from 2 to 0.125 AU. The coma's opacity to solar radiation is included and photolytic reaction rates are calculated. A parent volatile mixture similar to that found in interstellar molecular clouds is assumed. Profiles through the coma of number density and column density are presented for H₂O, OH, O, CN, C₂, C₃, CH, and NH₂. Whole-coma abundances are presented for NH₂, CH, C₂, C₃, CN, OH, CO⁺, H₂O⁺, CH⁺, N₂⁺, and CO₂⁺.     

Methane rich models of Uranus

A series of models of Uranus is computed assuming that Uranus consists of a core of rocky material sorrounded by a convecting envelope rich in H₂O, NH₃, and CH₄. It is found that good fits are obtained to the observed parameters when the CH₄: H₂ ratio is of the order of 0.1. It is suggusted that the rotational period of Uranus is roughly 18 hours.     

Detectability of minor constituents in the martian atmosphere by infrared and submillimeter spectroscopy

Spectroscopic remote sensing in the infrared and (sub)millimeter range is a powerful technique that is well suited for detecting minor species in planetary atmospheres (Planet Space Sci. 43(1995) 1485). Yet, only a handful of molecules in the Mars atmosphere (CO₂, CO and H₂O along with their isotopic species, O_3, and more recently H₂O₂ and CH₄) have been detected so far by this method. New high performance spectroscopic instruments will become available in the future in the infrared and (sub)millimeter range, for observations from the ground (infrared spectrometers on 8 m class telescopes, large millimeter and submillimeter interferometers) and from space, in particular the Planetary Fourier Spectrometer (PFS) aboard Mars Express (MEx), and the Heterodyne Instrument for the Far-Infrared (HIFI) aboard the Herschel Space Observatory (HSO). In this paper we will present results of a study that determines detectability of minor species in the atmosphere of Mars, taking into account the expected performance of the above spectroscopic instruments. In the near future, a new determination of the D/H value is expected with the PFS, especially during times of maximum H₂O abundance in the martian atmosphere. PFS is also expected to place constraints on the abundance of several minor species (H₂O₂,CH₄,CH₂O, SO₂, H₂S, OCS, HCl) above any local outgassing sources, the hot spots. It will be possible to obtain complementary information on some minor species (O₃,H₂O₂, CH₄) from ground-based infrared spectrometers on large telescopes. In the more distant future, HIFI will be ideally suited for measuring the isotopic ratios with unprecedented accuracy. Moreover, it should be able to observe O₂, which has not yet been detected spectroscopically in the IR/submm range, as well as H₂O₂. HIFI should also provide upper limits for several species that have not yet been detected (HCl, NH₃, PH₃) in the atmosphere of Mars. Some species (SO, SO₂,H₂S, OCS, CH₂O) that may be observable from the ground could be searched for with present single-dish antennae and arrays, and in the future with the Atacama Large Millimeter Array (ALMA) submillimeter interferometer.     

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).     

Spectral comparison of heavily hydrated salts with disrupted terrains on Europa

Hydrated magnesium sulfate salts have been proposed as major components of the disrupted, reddish terrains on the surface of Europa. This is based on near-infrared reflectance spectra which contain distorted and asymmetric water absorption features typical of moderately hydrated materials such as hexahydrite (MgSO₄⋅6H₂O) and epsomite (MgSO₄⋅7H₂O). Hydrated magnesium sulfates having many waters of hydration could produce improved spectral matches. Here we present cryogenic laboratory spectra of highly hydrated sulfur-bearing salts, including hexahydrite, epsomite, bloedite (Na₂Mg(SO₄)₂⋅4H₂O), mirabilite (Na₂SO₄⋅10H₂O), sodium sulfide nonahydrate (Na₂S⋅9H₂O), supersaturated MgSO₄, NaHCO₃, and Na₂SO₄ brines, and magnesium sulfate dodecahydrate (MgSO₄⋅12H₂O). All have been measured under conditions of pressure and temperature appropriate to the surface environment of Europa. Novel methods for preparation, verification and analysis of MgSO₄⋅12H₂O, which is not stable at standard temperature and pressure (STP), are described. At 100 K, all of these materials exhibit distorted and asymmetric absorption features similar to those in the Europa observations, as well as several weaker, narrow absorptions having widths ranging from 15 to 80 nm. While the agreement with Galileo NIMS observations of dark terrains on Europa is indeed better for highly hydrated salts than for salts of lower hydration states, we conclude that none of these materials alone can account for all of the observed spectral character. As previously suggested, Europa's reddish material appears to be a complex mixture of sulfate hydrates and other materials.     

Electronic Sputtering Analysis of Astrophysical Ices

Experimental results on fast ion collision with icy surfaces having astrophysical interest are presented. ²⁵²Cf fission fragments projectiles were used to induce ejection of ionized material from H₂O, CO₂, CO, NH₃, N₂, O₂ and Ar ices; the secondary ions were identified by time-of-flight mass spectrometry. It is observed that all the bombarded frozen gas targets emit cluster ions which have the structure X_nR^±, where X is the neutral ice molecule and R^± is either an atomic or a molecular ion. The shape of the positive or negative ion mass spectra is characterized by a decreasing yield as the emitted ion mass increases and is generally described by the sum of two exponential functions. The positive ion water ice spectrum is dominated by the series (H₂O)_nH₃O⁺ and the negative ion spectrum by the series (H₂O)_nOH⁻ and (H₂O)_nO⁻. The positive ion CO₂ ice spectrum is characterized by R⁺ = C⁺, O⁺, CO⁺, O₂⁺ or CO₂⁺ and the negative one by R⁻ = CO₃⁻. The dominant series for ammonia ice correspond to R⁺ = NH₄⁺ and to R⁻ = NH₂⁻. The oxygen series are better described by (O₃)_nO_m⁺ secondary ions where m = 1, 2 or 3. Two positive ion series exist for N₂ ice: (N₂)_nN₂⁺ and (N₂)_nN⁺. For argon positive secondary ions, only the (Ar)_nAr⁺ series was observed. Most of the detected molecular ions were formed by one-step reactions. Ice temperature was varied from ∼20 K to complete sublimation.     

Ion chemistry in the cometary atmosphere

Dirty ice of a second kind (major components, H₂O, CO, and N₂; minor components less than several percents, NH₃, CH₄, and other organic substances such as HCN, CH₃CN etc.) is assumed for the composition of volatiles in the cometary nucleus. The consistency with the observations of molecular ions and daughter molecules in the cometary atmosphere is argued by taking into account various ion-molecular reactions and dissociative recombinations. There is a satisfactory agreement for the second kind of dirty-ice model, but the presence of large amounts of CH₄ and NH₃ is found to be rather in contradiction with observational evidence. A velocity of 8 km s^?1 for the hydrogen atoms, derived from analysis of the hydrogen Lyman-alpha corona around comets, is found from the dissociative recombination of H₃O⁺, the dominant constituent of cometary ionosphere, in accordance with H₃O⁺+e ^?→OH+H+H.     

Spectra of hydrate frosts: Their application to the outer solar system

Reflectance spectra from 1 to 6 microns were taken of CH₄ and CO₂ gas hydrates and were found to be very similar to H₂O frost spectra over the entire wavelength region. H₂O clathrates have a gas to H₂O ratio of about $\text{1}\text{6}$, hence a surface may contain 17% (by number) gas and appear spectroscopically similar to an H₂O frost covered surface. This is important in the pressure-temperature regime of the outer solar system where hydrates, which often have vapor pressures 10^?5 (or less) that of the pure gas component, are marginally stable as solids (e.g., the vapor pressure in Torr at 60 K for CH₄·6H₂O = 10^?8 while for CH₄ = 10^?1). We may conclude that reflectance spectroscopy (especially Earth-based) is useful for positive identification of some components of the surface, but does not set stringent limits for spectroscopically active hydrate forming substances in the presence of water frost.     

Cloud base levels for Jupiter and Venus and the heteromolecular nucleation theory

For purified binary gas mixtures like NH₃H₂O or HClH₂O, partial pressures appreciably greater than the two saturation partial pressures are needed to condense the gas mixture into small solution droplets (“homogeneous hetero-molecular nucleation”). Thus without foreign nuclei, clouds are not as easily formed as in the theories of Lewis; the latter should be valid only if large condensation nuclei are available. We calculate here from classical homogeneous heteromolecular nucleation theory the threshold partial pressures necessary to achieve droplet nucleation for the gas mixtures NH₃H₂O (Jupiter,…), HClH₂O (Venus), H₂SO₄H₂O (Venus), and C₂H₅OHH₂O (laboratory). In the last case, theory and experiment agree satisfactorily. If no “dust” particles are available as condensation nuclei, then we expect in Jupiter's atmosphere the cloud base level to be around 40 km above the 400K level instead of 10–25 km in Lewis' models (1969) (similar upward shifts for the outer Jovian planets). For Venus, our corrections make the formation of HClH₂O clouds less probable for the 60-km layer at 0°C. If H₂SO₄ is formed by (photo-)chemical oxidation of SO₂ and if clouds are formed at that level where the H₂SO₄ production is largest, then the cloud base levels for H₂SO₄H₂O mixture clouds will not be shifted by our nucleation effects. For more reliable predictions, one needs more accurate data on the water vapor content of the planetary atmospheres and laboratory experiments testing the theoretically predicted nucleation behavior of these gaseous mixtures.