Surface Ices Research Articles

Sublimation and infrared spectral properties of ammonium cyanide

The ammonium ion (NH4+) has been suggested to be present in interstellar ices and has been observed on the surfaces of planetary bodies using infrared (IR) spectroscopy as the primary means of identification. Evidence for several ammonium salts has also been found in the dust and surface ices of comet 67P/Churyumov-Gerasimenko. Here we present a laboratory study of ammonium cyanide (NH4CN) and report on several properties of this compound, measured with higher accuracy than in previous reports, including its IR band strengths and optical constants for use in quantifying its abundance in interstellar and planetary ices. We also report the first measurements since 1882 of NH4CN vapor pressures, sublimation fluxes, and sublimation enthalpy measured at temperatures relevant to subliming cometary ices (134–155 K). The density and refractive index of NH4CN at 125 K and the sublimation enthalpy and vapor pressures of NH3 at ~100 K are also reported.

Use of geothermal energy to prevent road pavement icing and damage in cold climate areas

In cold climate or alpine regions, freezing temperatures and snow can result into road icing, with consequent threat of the circulation security (Figure 1(a)). When the road surface temperature goes below zero, not only the road surface ices, but also the soil below the pavement can undergo freezing. The phenomenon of soil freezing is complex due to the multi-phase and porous nature of the soil itself. Generally speaking, as ice expands in the soil pores, the soil volume increases (of about 9%, depending on the soil porosity and water saturation). This can induce frost heaving, with consequent damage of the road pavement. In this framework, the possibility to use geothermal energy systems embedded in tunnel linings for road pavement de-icing has rarely been investigated. In such systems, the concrete tunnel lining is equipped with a circuit of pipes, in which a heat carrier fluid circulates and exchanges heat with the ground. As the rock or soil around the tunnel is generally hotter than the external air temperature, heat is extracted from the rock or soil to the fluid, transported through the pipes circuit outside the tunnel, and used to de-ice the pavement road.
 The objective of this study is to go a step forward in the investigation of this innovative application, for both road de-icing and prevention of frost heave. A portion of a geothermally activated tunnel and its connection to a road pipe circuit was simulated numerically (Figure 1 (b)). Appropriate climatic conditions were considered as boundary conditions at the surface level and inside the tunnel, according to available data. The efficiency of the technology was investigated under different climatic and exploitation scenarios. Figure 1 (c) shows as an example the thermal field obtained after the activation of the geothermal plant. The evolution of temperature on the road pavement surface and at the road pipes depth (30 cm from the road pavement surface) are presented on Figure 2 (a), together with the evolution of the external air and tunnel temperature, imposed as boundary conditions according to the monitored climatic conditions in the city of Oslo [1].
 The geothermal system was activated after two years of simulation, by changing the fluid pipes velocity from 0 (non active system) to 0.9 m/s (purple curve on the right axis on Figure 2 (a)). The results show that the road temperature increases thanks to the activation of the system (i.e. when the fluid pipes velocity is imposed to 0.9 m/s).
 Furthermore, a recently developed thermo-hydro-mechanical constitutive model for frozen soils [2] was used to quantify the soil heave due to freezing, with and without the activation of the geothermal system. For this purpose, a similar numerical model has been developped where a column of saturated soil below the road and the tunnel were modelled. The phreatic water table is at the ground surface level and gravity as well as the geostatic stress conditions are considered. The soil is a clay with a low hydraulic conductivity of Kw=4.1×10-10 m/s and a thermal conductivity of Γ=2.35 W/m/K. The other soil properties are: soil stiffness E=100 MPa, Poisson’s ratio ν=0.3, porosity n=0.25, solid grain thermal volumetric expansion coefficient αs=3.4×10-4 K-1. The same soil surface climatic conditions used in the first part were applied. The temperature evolution obtained in the road from the previously mentioned analyses (Figure 2 (a)) was imposed to reproduce the effect of the geothermal activation on the road behaviour. Furthermore, the soil surface is free of stress to study the soil swelling and settlement. The bottom limit of the soil column is hydraulically drained and allows heat flux (at constant liquid pressure and temperature). The lateral far field boundaries are thermally adiabatic, hydraulically impervious, and with oedometric conditions. The results were firstly compared with the case without geothermal activation to quantify the effects in terms of road heave and settlement (Figure 2 (b)). Swelling and settlement are due to thermal expansion and compression of the soil under positive temperature (T>0°C) and to frost heave and thaw settlement under negative temperature (T<0°C). The liquid pressure at the road surface is also depicted (Figure 2 (b)). These results and comparisions allowed understanding the performance of the technology in reducing road mechanical damage induced by freezing.

The role of subsurface ice in sustaining bacteria in continental and maritime glaciers

In supraglacial environments, surface and subsurface ices are two distinct and connected microhabitats in terms of physicochemical and biological aspects. At the frontline of climate change, glaciers lose tremendous ice masses to downstream ecosystems, serving as crucial sources of both biotic and abiotic materials. In this study, we studied the disparities and relationships of microbial communities between surface and subsurface ices collected from a maritime and a continental glacier during summer. The results showed that surface ices had significantly higher nutrients and were more physiochemically different than subsurface ices. Despite lower nutrients, subsurface ices had higher alpha-diversity with more unique and enriched operational taxonomic units (OTUs) than surface ices, indicating the potential role of subsurface as a bacterial refuge. Sorensen dissimilarity between bacterial communities in surface ices and subsurface ices was mainly contributed by the turnover component, suggesting strong species replacement from surface to subsurface ices due to large environmental gradients. For different glaciers, the maritime glacier had significantly higher alpha-diversity than the continental glacier. The difference between surface and subsurface communities was more pronounced in the maritime glacier than in the continental glacier. The network analysis revealed that surface-enriched and subsurface-enriched OTUs formed independent modules, with surface-enriched OTUs having closer interconnections and greater importance in the network of the maritime glacier. This study highlights the important role of subsurface ice as a bacterial refuge and enriches our knowledge of microbial properties in glaciers.

Io’s Volcanic Activity and Atmosphere

Driven by tidal heating, Io’s extreme volcanism has created a young, impact crater–free surface dominated by hundreds of active volcanic centres. From these volcanoes erupt voluminous, low-viscosity, high-temperature silicate lavas. Volcanic plumes, from venting gas and mobilised surface ices (primarily SO2 and S), contribute to Io’s thin atmosphere. Away from volcanoes, SO2 ice on the surface alternately sublimes during the daytime and condenses during eclipses and at night, resulting in a strong day/night atmospheric dichotomy. Sunlight and radiation bombardment at high altitude breaks the gas molecules apart, leading to the formation of SO, O, O2, S, K, Na, and Cl. These atoms reside as both neutral and charged particles in clouds that are found along Io’s orbit around Jupiter.

Vacuum-UV Photodesorption from Compact Amorphous Solid Water: Photon Energy Dependence, Isotopic and Temperature Effects

Photodesorption from water-rich interstellar ice mantles is known to play an important role on the gas-to-ice ratio in stars and planet formation regions. Quantitative determination of the photodesorption yields in the laboratory is crucial to astrochemical models. This study presents for the first time, the photon-energy dependence of the photodesorption yields from water ice samples in the vacuum-UV (VUV) range. Experiments have been performed with the Surface Processes and ICES (SPICES) setup coupled to the DESIRS beamline at the SOLEIL synchrotron facility (St. Aubin, France). Thick (20–100 ML) compact amorphous solid water ices (H2O and D2O) grown onto a cold Au substrate have been irradiated at sample temperatures ranging from 15 to 110 K. Photodesorption yields of water and photoproducts have been obtained by mass-spectrometry from 7 to 13.5 eV. In interstellar conditions, average H2O photodesorption yields are (5 ± 2) × 10–4 molecule/photon at low temperature (15 K) whereas, lower yields, by a factor of ∼6–9 on average, were found for D2O. This strong isotopic effect can be explained by a differential chemical recombination between OH (OD) and H (D) photofragments at the surface of the samples. In addition, an enhancement of the yields above (70 ± 10) K suggests a thermally induced ice restructuration at this threshold temperature.

Ozone production in electron irradiated CO2:O2 ices.

The detection of ozone (O3) in the surface ices of Ganymede, Jupiter's largest moon, and of the Saturnian moons Rhea and Dione, has motivated several studies on the route of formation of this species. Previous studies have successfully quantified trends in the production of O3 as a result of the irradiation of pure molecular ices using ultraviolet photons and charged particles (i.e., ions and electrons), such as the abundances of O3 formed after irradiation at different temperatures or using different charged particles. In this study, we extend such results by quantifying the abundance of O3 as a result of the 1 keV electron irradiation of a series of 14 stoichiometrically distinct CO2:O2 astrophysical ice analogues at 20 K. By using mid-infrared spectroscopy as our primary analytical tool, we have also been able to perform a spectral analysis of the asymmetric stretching mode of solid O3 and the variation in its observed shape and profile among the investigated ice mixtures. Our results are important in the context of better understanding the surface composition and chemistry of icy outer Solar System objects, and may thus be of use to future interplanetary space missions such as the ESA Jupiter Icy Moons Explorer and the NASA Europa Clipper missions, as well as the recently launched NASA James Webb Space Telescope.

Dust Outburst Dynamics and Hazard Assessment for Close Spacecraft–Comet Encounters

Abstract Using the gas drag by sublimating cometary surface ices for the acceleration of dust particles and deceleration by the gravity field of the nucleus combined with basic laws of mechanics, the sizes, velocities, and number densities of escaping particles are calculated and evaluated with respect to the hazard assessment of comet–spacecraft flybys and encounters. We find good agreement between our analytical method and the more elaborate and precise DSMC calculations, but, being simpler, our method can more easily be used to explore a wide range of cometary conditions and can be more easily scaled to specific comets with different nucleus sizes, masses, and gravity potentials and various gas and dust production rates. Our analytical method is applied to outbursts expanding into a cone of ∼60°, where the gas density falls off with height from the surface rather than radial distance from the center of a uniformly outgassing nucleus. In this scenario, larger dust particles can be ejected and attain ballistic trajectories, go into orbit, or escape from the nucleus, thus being potentially more hazardous to a spacecraft. Sample calculations are carried out for potential dust outbursts for the highly active Centaur/Comet 29P/Schwassmann-Wachmann 1 for various assumed active areas and dust particle size distributions. Particle velocity ranges for ballistic trajectories, orbiting particles, and particles escaping into the coma are presented. These calculations are used to estimate the coma particle number densities during outbursts to get an assessment of the hazards and required mitigation for a flyby or orbiting space mission.

FUV Observations of the Inner Coma of 46P/Wirtanen

Abstract Far-ultraviolet observations of comets yield information about the energetic processes that dissociate the sublimated gases from their primitive surfaces. Understanding which emission processes are dominant, their effects on the observed cometary spectrum, and how to properly invert the spectrum back to the composition of the presumably pristine surface ices of a comet nuclei are all critical components for proper interpretation and analysis of comets. The close approach of comet 46P/Wirtanen in 2018–2019 provided a unique opportunity to study the innermost parts of a cometary coma with the Hubble Space Telescope Cosmic Origins Spectrograph, rarely accessible with remote observations, at length scales (hundreds of kilometers) and wavelengths (900–1430 Å) previously probed only by the European Space Agency’s Rosetta spacecraft. Our observations show a complex picture for the inner coma; atomic production rates for H and O that show water is the dominant source of both, an abundance of atomic sulfur that is difficult to explain with the lifetimes of common sulfur parent molecules, and a density distribution that is poorly fit with both Haser and vectorial models.

Laboratory predictions for the night-side surface ice glow of Europa

Europa’s surface continuously experiences high fluxes of charged particles due to the presence of Jupiter’s strong magnetic field. These high-energy charged particles, including electrons, interact with the ice- and salt-rich surface, resulting in complex physical and chemical processes. Here, we report that Europa ice analogues emit characteristic spectral signatures in the visible region when exposed to high-energy electron radiation. The strongest emission (ice glow) we observed was centred at ~525 nm. We found that the presence of sodium chloride and carbonate strongly quenched, while epsomite enhanced, the radiation-induced ice glow. These emission characteristics could be used to determine the chemical composition of Europa’s surface during night-time low-altitude fly-bys of spacecraft such as the Europa Clipper. We estimate that the Europa Clipper Wide Angle Camera could record between 500 and 280,000 counts per second through different colour filters, depending on the chemical composition of Europa’s surface. Though we focus here on Europa, our study may be relevant to other bodies exposed to high doses of ionizing radiation, such as Io and Ganymede. With its extreme radiation environment, rich surface geology and compositional diversity, the radiation-induced ice glow on Europa could enable more precise surface characterization and provide unique night-time views. Based on laboratory experiments and predictions, the Europa Clipper mission is expected to detect the surface ices on the night side of Jupiter’s moon Europa glowing in the dark, with an intensity that can be used to determine their composition.

Low-temperature synthesis of polycyclic aromatic hydrocarbons in Titan's surface ices and on airless bodies.

Titan's equatorial dunes represent the most monumental surface structures in our Solar System, but the chemical composition of their dark organics remains a fundamental, unsolved enigma, with solid acetylene detected near the dunes implicated as a key feedstock. Here, we reveal in laboratory simulation experiments that aromatics such as benzene, naphthalene, and phenanthrene-prospective building blocks of the organic dune material-can be efficiently synthesized via galactic cosmic ray exposure of low-temperature acetylene ices on Titan's surface, hence challenging conventional wisdom that aromatic hydrocarbons are formed solely in Titan's atmosphere. These processes are also of critical importance in unraveling the origin and chemical composition of the dark surfaces of airless bodies in the outer Solar System, where hydrocarbon precipitation from the atmosphere cannot occur. This finding notably advances our understanding of the distribution of carbon throughout our Solar System such as on Kuiper belt objects like Makemake.

New Horizons Observations of the Atmosphere of Pluto

New Horizons data provide a snapshot of the current state of Pluto's atmosphere. Winds are slow and mostly controlled by sublimation of surface ices. Molecular nitrogen is the primary constituent below 1,800 km, while methane and carbon monoxide are important minor species. Photolysis of these gases leads to a thin haze that encompasses Pluto from the surface up to >500-km altitude and is important in heating and cooling the atmosphere. A cold (∼70 K) upper atmosphere curtails the escape of Pluto's molecular nitrogen to space, although there is substantial escape of methane (∼5 × 1025 molecules s−1), coincidentally about equal to its loss by photochemistry. It is unknown if the current atmosphere is representative of its long-term average state. From the inferred rapid rate of haze settling, it seems that Pluto's atmosphere must occasionally undergo collapse to allow time for radiation processing of the colorless haze material into the dark deposits found on the surface. ▪ This article outlines what has been gleaned about Pluto's atmosphere in the years since the New Horizons flyby. ▪ Pluto's atmosphere is most similar to Titan's—with the photochemistry of supervolatile nitrogen and hydrocarbons resulting in a kind of factory for cold haze production. ▪ Much has been learned about Pluto's atmosphere, but many new questions have arisen, and these will likely remain unanswered until there is a follow-up mission—no doubt a long time from now.

Prebiotic Chemistry of Pluto.

We present the case for the presence of complex organic molecules, such as amino acids and nucleobases, formed by abiotic processes on the surface and in near-subsurface regions of Pluto. Pluto's surface is tinted with a range of non-ice substances with colors ranging from light yellow to red to dark brown; the colors match those of laboratory organic residues called tholins. Tholins are broadly characterized as complex, macromolecular organic solids consisting of a network of aromatic structures connected by aliphatic bridging units (e.g., Imanaka et al., 2004; Materese et al., 2014, 2015). The synthesis of tholins in planetary atmospheres and in surface ices has been explored in numerous laboratory experiments, and both gas- and solid-phase varieties are found on Pluto. A third variety of tholins, exposed at a site of tectonic surface fracturing called Virgil Fossae, appears to have come from a reservoir in the subsurface. Eruptions of tholin-laden liquid H2O from a subsurface aqueous repository appear to have covered portions of Virgil Fossae and its surroundings with a uniquely colored deposit (D.P. Cruikshank, personal communication) that is geographically correlated with an exposure of H2O ice that includes spectroscopically detected NH3 (C.M. Dalle Ore, personal communication). The subsurface organic material could have been derived from presolar or solar nebula processes, or might have formed in situ. Photolysis and radiolysis of a mixture of ices relevant to Pluto's surface composition (N2, CH4, CO) have produced strongly colored, complex organics with a significant aromatic content having a high degree of nitrogen substitution similar to the aromatic heterocycles pyrimidine and purine (Materese et al., 2014, 2015; Cruikshank et al., 2016). Experiments with pyrimidines and purines frozen in H2O-NH3 ice resulted in the formation of numerous nucleobases, including the biologically relevant guanine, cytosine, adenine, uracil, and thymine (Materese et al., 2017). The red material associated with the H2O ice may contain nucleobases resulting from energetic processing on Pluto's surface or in the interior. Some other Kuiper Belt objects also exhibit red colors similar to those found on Pluto and may therefore carry similar inventories of complex organic materials. The widespread and ubiquitous nature of similarly complex organic materials observed in a variety of astronomical settings drives the need for additional laboratory and modeling efforts to explain the origin and evolution of organic molecules. Pluto observations reveal complex organics on a small body that remains close to its place of origin in the outermost regions of the Solar System.

Observational constraints on the cometary impact flux on Mars and Earth

While dynamical models indicate that both cometary and asteroid collisions likely contribute to the population of bodies that impact the inner solar system, the distinction between the craters produced by the two populations remains uncertain. Although cometary impacts larger than 10 km in diameter are rare, dynamical studies cannot confidently eliminate their possible contribution to the total impact population at levels lower than ~10%. Due to the speed and volatile content of comets, their impact should couple more energy with a planetary atmosphere and result in observable signatures. The tenuous atmosphere of Mars makes the planet an ideal location to recognize such signatures. Here we use computational simulations and laboratory experiments to model both asteroid and cometary impacts on Mars. We explore the relationship between such impacts and enigmatic radial streaks that form around certain impact craters due to high-speed, long-duration winds. While lower speed asteroid impacts into thick (500 m) surface ices also can produce intense outward winds, the global distribution of craters with impact-generated wind streaks limits this mode of origin to just a few candidates; the rest are likely cometary. Based on the occurrence and relatively young age of these craters, we conclude that ~1% of the impactors on Mars over the last 2 Ga resulted from Long-Period cometary impacts, which should be about 6 times higher on Earth. Inclusion of Jupiter-Family and Haley-type comets (but not including cometary asteroids) then predicts that ~ 16% of all terrestrial impacts, with important implications for future impact hazards on Earth.

Interplanetary dust delivery of water to the atmospheres of Pluto and Triton

Context. Both Pluto and Triton possess thin, N2-dominated atmospheres controlled by sublimation of surface ices. Aims. We aim to constrain the influx and ablation of interplanetary dust grains into the atmospheres of both Pluto and Triton in order to estimate the rate at which oxygen-bearing species are introduced into both atmospheres. Methods. We use (i) an interplanetary dust dynamics model to calculate the flux and velocity distributions of interplanetary dust grains relevant for both Pluto and Triton and (ii) a model for the ablation of interplanetary dust grains in the atmospheres of both Pluto and Triton. We sum the individual ablation profiles over the incoming mass and velocity distributions of interplanetary dust grains in order to determine the vertical structure and net deposition of water to both atmospheres. Results. Our results show that <2% of silicate grains ablate at either Pluto or Triton while approximately 75% and >99% of water ice grains ablate at Pluto and Triton, respectively. From ice grains, we calculate net water influxes to Pluto and Triton of ~3.8 kg day−1 (8.5 × 103 H2O cm−2 s−1) and ~370 kg day−1 (6.2 × 105 H2O cm−2 s−1), respectively. The significant difference in total water deposition between Pluto and Triton is due to the presence of Triton within Neptune’s gravity well, which both enhances interplanetary dust particle (IDP) fluxes due to gravitational focusing and accelerates grains before entry into Triton’s atmosphere, thereby causing more efficient ablation. Conclusions. We conclude that water deposition from dust ablation plays only a minor role at Pluto due to its relatively low flux. At Triton, water deposition from IDPs is more significant and may play a role in the alteration of atmospheric and ionospheric chemistry. We also suggest that meteoric smoke and smaller, unablated grains may serve as condensation nuclei for the formation of hazes at both worlds.

Triton’s surface ices: Distribution, temperature and mixing state from VLT/SINFONI observations

Triton, the largest Solar System satellite beyond Saturn, was probably captured from the Transneptunian population by Neptune. It is mainly covered by N2, CO, CO2, CH4 and H2O in solid state and, except for H2O and CO2, these species are also present in gas phase. Sublimation and recondensation of the volatile species may lead to geographical and temporal variation on the surface composition, and could participate to the formation of complex chemical compounds formed from photochemistry occurring in the atmosphere (Krasnopolsky and Cruikshank, 1999) or from irradiation of N2 : CH4 : CO layers (Moore and Hudson, 2003).We present new near-IR observations performed at the VLT-ESO with SINFONI in 2010, 2011 and 2013, from which band depths, areas and positions of the main ice features are determined at different longitudes. We also re-reduce and re-analyze earlier data obtained during the last 20 years. Models based on the Hapke theory (Hapke, 1993) are developed to constrain the abundance, grain size, temperature, and state of mixing of the different ices (N2, CH4, CO, CO2, H2O) as well as attempt to identify other species. For this purpose, we present and use new optical constants of CO2 measured at 35 and 54 K.Our analyses confirm the longitudinal variation of the N2 and CO surface abundances previously evidenced, and suggest additional latitudinal and/or temporal variability of these two species. We confirm the presence of deep N2 layers in which CO and CH4 are diluted. In particular, we demonstrate that CO is present in diluted (as opposed to pure ice) form. In contrast, our models support the presence of small and longitudinally variable amounts of pure CH4 ice, providing an explanation to the enhanced atmospheric CH4/N2 ratio over expectations based on an ideal N2-CH4-CO mixture. They also suggest significant smaller particles of H2O and CO2 than reported previously in Quirico et al. (1999), with CO2 being probably distributed over a large area of the surface. We find that the 2.40 µm band is primarily due to 13CO ice, with a telluric value of the 13CO/12CO ratio, and not to ethane. We infer a N2 ice temperature of 37.5 ± 1K, suggesting that the atmospheric pressure over 2010–2013 was similar to that during the Voyager 1989 epoch.

Reflecting and scattering of acoustic wave from sea ices

In order to build an efficient underwater acoustic sensor network in the Arctic Ocean environment, transmission characteristics of under-ice acoustic channels need comprehensive understanding. The reflecting and scattering of acoustic waves from sea ices have great influences on under-ice acoustic channels. Both topology and structure of sea surface ices are very complex and variable. The physical dimension, acoustic property and interface roughness of sea ices depend not only on local environment, but also on climate and formation time. Therefore, it is of great significance to develop a model of reflecting and scattering of acoustic waves from sea ices for investigating the sound propagation in the under-ice environment. Assuming that sea ices are a multi-layered elastic solid medium and the ice-water interface is rough and satisfies the boundary condition of perturbation, we develop a system of linear equations to solve the coherent reflection coefficient of the incident sound wave from water to sea ice. The coherent reflection coefficient is a function of the frequency of sound wave and incident grazing angle, and is numerically evaluated. The influences of ice thickness and ice-water interface roughness on the coherent reflection coefficient are analyzed. Furthermore, the method of calculating scattering coefficient by using the power spectrum density of the scattering field is introduced. The scattering coefficient as a function of the scattering grazing angle is numerically evaluated. The influences of ice thickness and ice-water interface roughness on scattering coefficient are analyzed. The results show that both the coherent reflection coefficient and the scattering coefficient are dependent on the frequency of acoustic wave, ice thickness and grazing angle. The coherent reflection coefficient is close to 1.0 and the scattering coefficient is less than 0.01 when incident grazing angle is less than 15°. In addition, the frequency of acoustic wave and ice thickness have weak influences on them. However, the frequency of acoustic wave and ice thickness have significant influences on the coherent reflection coefficient and the scattering coefficient when the incident grazing angle is big, say, greater than 30°. In general, the thicker the ice is, the smaller the coherent reflection coefficient and the scattering coefficient are. The coherent reflection coefficient is less than 0.18 when the ice thickness is greater than 10.0 m and the frequency of acoustic waves is greater than 2 kHz. The ice-water interface roughness has great influences on both the coherent reflection coefficient and the scattering coefficient. The rougher of the ice-water interface is, the smaller the coherent reflection coefficient is, and the bigger the scattering coefficient is.

Rosetta observes sublimating surface ices

Cometary Science Comets are “dirty snowballs” made of ice and dust, but they are dark because the ice sublimates away, leaving some of the dust behind on the surface. The Rosetta spacecraft has provided a close-up view of the comet 67P/Churyumov-Gerasimenko as it passes through its closest point to the Sun (see the Perspective by Dello Russo). Filacchione et al. detected the spectral signature of solid CO2 (dry ice) in small patches on the surface of the nucleus as they emerged from local winter. By modeling how the CO2 sublimates, they constrain the composition of comets and how ices generate the gaseous coma and tail. Fornasier et al. studied images of the comet and discovered bright patches on the surface where ice was exposed, which disappeared as the ice sublimated. They also saw frost emerging from receding shadows. The surface of the comet was noticeably less red just after local dawn, indicating that icy material is removed by sunlight during the local day. Science , this issue p. [1563][1], p. [1566][2]; see also p. [1536][3] [1]: /lookup/doi/10.1126/science.aag3161 [2]: /lookup/doi/10.1126/science.aag2671 [3]: /lookup/doi/10.1126/science.aal1964

ICE CHEMISTRY ON OUTER SOLAR SYSTEM BODIES: ELECTRON RADIOLYSIS OF N2-, CH4-, AND CO-CONTAINING ICES.

Radiation processing of the surface ices of outer Solar System bodies may be an important process for the production of complex chemical species. The refractory materials resulting from radiation processing of known ices are thought to impart to them a red or brown color, as perceived in the visible spectral region. In this work, we analyzed the refractory materials produced from the 1.2-keV electron bombardment of low-temperature N2-, CH4-, and CO-containing ices (100:1:1), which simulates the radiation from the secondary electrons produced by cosmic ray bombardment of the surface ices of Pluto. Despite starting with extremely simple ices dominated by N2, electron irradiation processing results in the production of refractory material with complex oxygen- and nitrogen-bearing organic molecules. These refractory materials were studied at room temperature using multiple analytical techniques including Fourier-transform infrared spectroscopy, X-ray absorption near-edge structure (XANES) spectroscopy, and gas chromatography coupled with mass spectrometry (GC-MS). Infrared spectra of the refractory material suggest the presence of alcohols, carboxylic acids, ketones, aldehydes, amines, and nitriles. XANES spectra of the material indicate the presence of carboxyl groups, amides, urea, and nitriles, and are thus consistent with the IR data. Atomic abundance ratios for the bulk composition of these residues from XANES analysis show that the organic residues are extremely N-rich, having ratios of N/C ~ 0.9 and O/C ~ 0.2. Finally, GC-MS data reveal that the residues contain urea as well as numerous carboxylic acids, some of which are of interest for prebiotic and biological chemistries.

Adsorption and Thermal Processing of Glycolaldehyde, Methyl Formate, and Acetic Acid on Graphite at 20 K.

We present the first detailed comparative study of the adsorption and thermal processing of the three astrophysically important C2O2H4 isomers glycolaldehyde, methyl formate, and acetic acid adsorbed on a graphitic grain analogue at 20 K. The ability of the individual molecule to form intermolecular hydrogen bonds is extremely important, dictating the growth modes of the ice on the surface and the measured desorption energies. Methyl formate forms only weak intermolecular bonds and hence wets the graphite surface, forming monolayer, bilayer, and multilayer ices, with the multilayer having a desorption energy of 35 kJ mol(-1). In contrast, glycolaldehyde and acetic acid dewet the surface, forming clusters even at the very lowest coverages. The strength of the intermolecular hydrogen bonding for glycolaldehyde and acetic acid is reflected in their desorption energies (46.8 and 55 kJ mol(-1), respectively), which are comparable to those measured for other hydrogen-bonded species such as water. Infrared spectra show that all three isomers undergo structural changes as a result of thermal processing. In the case of acetic acid and glycolaldehyde, this can be assigned to the formation of well-ordered, crystalline, structures where the molecules form chains of hydrogen-bonded moieties. The data reported here are of relevance to astrochemical studies of hot cores and star-forming regions and can be used to model desorption from interstellar ices during the warm up phase with particular importance for complex organic molecules.

The surface compositions of Pluto and Charon

The surface of Pluto as it is understood on the eve of the encounter of the New Horizons spacecraft (mid-2015) consists of a spatially heterogeneous mix of solid N2, CH4, CO, C2H6, and an additional component that imparts color, and may not be an ice. The known molecular ices are detected by near-infrared spectroscopy. The N2 ice occurs in the hexagonal crystalline β-phase, stable at T>35.6K. Spectroscopic evidence for wavelength shifts in the CH4 bands attests to the complex mixing of CH4 and N2 in the solid state, in accordance with the phase diagram for N2+CH4. Spectra obtained at several aspects of Pluto’s surface as the planet rotates over its 6.4-day period show variability in the distribution of CH4 and N2 ices, with stronger CH4 absorption bands associated with regions of higher albedo, in correlation with the visible rotational light curve. CO and N2 ice absorptions are also strongly modulated by the rotation period; the bands are strongest on the anti-Charon hemisphere of Pluto. Longer term changes in the strengths of Pluto’s absorption bands occur as the viewing geometry changes on seasonal time-scales, although a complete cycle has not been observed. The non-ice component of Pluto’s surface may be a relatively refractory material produced by the UV and cosmic-ray irradiation of the surface ices and gases in the atmosphere, although UV does not generally penetrate the atmospheric CH4 to interact with the surface. Laboratory simulations indicate that a rich chemistry ensues by the irradiation of mixtures of the ices known to occur on Pluto, but specific compounds have not yet been identified in spectra of the planet. Charon’s surface is characterized by spectral bands of crystalline H2O ice, and a band attributed to one or more hydrates of NH3. Amorphous H2O ice may also be present; the balance between the amorphization and crystallization processes on Charon remains to be clarified. The albedo of Charon and its generally spatially uniform neutral color indicate that a component, not yet identified, is mixed in some way with the H2O and NH3·nH2O ices. Among the many known small bodies in the transneptunian region, several share characteristics with Pluto and Charon, including the presence of CH4, N2, C2H6, H2O ices, as well as components that yield a wide variety of surface albedo and color. The New Horizons investigation of the Pluto–Charon system will generate new insight into the physical properties of the broader transneptunian population, and eventually to the corresponding bodies expected in the numerous planetary systems currently being discovered elsewhere in the Galaxy.