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.     

Temperature effect on the photodissociation rates in the atmospheres of Mars and Venus

The available solar flux at a given altitude in the atmospheres of Mars and Venus is attenuated mainly by CO₂ (molecular absorption and Rayleigh scattering) with an extra contribution due to SO₂ on Venus. The dissociation cross section of CO₂ depends on temperature. At temperatures appropriate for these atmospheres (～250°K), the cross sections are about 15% lower than those at room conditions (Y.L. Yung and W.B. De More, 1982, Icarus, 51, 199). It is shown that this temperature effect cannot be neglected in the evaluation of photolysis rates. Calculations of the photodissociation coefficients of CO₂, SO₂, HCl, and H₂O are presented. For example, at the surface of Mars, the coefficient of H₂O is nearly multiplied by a factor of 10!     

Heliocentric evolution of the degradation of polyoxymethylene: Application to the origin of the formaldehyde (H2CO) extended source in Comet C/1995 O1 (Hale-Bopp)

The H₂CO production rates measured in Comet C/1995 O1 (Hale-Bopp) from radio wavelength observations [Biver, N., and 22 colleagues, 2002a. Earth Moon Planets 90, 5-14] showed a steep increase with decreasing heliocentric distance. We studied the heliocentric evolution of the degradation of polyoxymethylene (formaldehyde polymers: (CH₂O)_n, also called POM) into gaseous H₂CO. POM decomposition can indeed explain the H₂CO density profile measured in situ by Giotto spacecraft in the coma of Comet 1P/Halley, which is not compatible with direct release from the nucleus [Cottin, H., Bénilan, Y., Gazeau, M.-C., Raulin, F., 2004. Icarus 167, 397-416]. We show that the H₂CO production curve measured in Comet C/1995 O1 (Hale-Bopp) can be accurately reproduced by this mechanism with a few percents by mass of solid POM in grains. The steep heliocentric evolution is explained by the thermal degradation of POM at distances less than 3.5 AU. This study demonstrates that refractory organics present in cometary dust can significantly contribute to the composition of the gaseous coma. POM, or POM-like polymers, might be present in cometary grains. Other molecules, like CO and HNC, might also be produced by a similar process.     

H2O on Io? IR spectra of SO2/H2O mixed ices in the 5000-450 cm−1 region

Laboratory transmission IR spectra of relatively thick films (up to 500 m) of mixed H₂O and SO₂ ices were measured at several temperatures between 10 and 130 K in the range 5000-450 cm^–1. In addition to the strong features due to crystalline SO₂ the spectra reveal bands at 3668 cm^–1, 3634 cm^–1 (with some structure) and 3300 cm^–1 which are identified with H₂O in SO₂ environment. Also, there is no overlap between any of the H₂O bands with the 3584 cm^–1 band of SO₂ at any temperature in the above range. The implication of this result is that H₂O, if present on Io, must be far less than 1 part in 10⁵ SO₂.     

Chemistry of atmospheres formed during accretion of the Earth and other terrestrial planets

We used chemical equilibrium and chemical kinetic calculations to model chemistry of the volatiles released by heating different types of carbonaceous, ordinary and enstatite chondritic material as a function of temperature and pressure. Our results predict the composition of atmospheres formed by outgassing during accretion of the Earth and other terrestrial planets. Outgassing of CI and CM carbonaceous chondritic material produces H₂O-rich (steam) atmospheres in agreement with the results of impact experiments. However, outgassing of other types of chondritic material produces atmospheres dominated by other gases. Outgassing of ordinary (H, L, LL) and high iron enstatite (EH) chondritic material yields H₂-rich atmospheres with CO and H₂O being the second and third most abundant gases. Outgassing of low iron enstatite (EL) chondritic material gives a CO-rich atmosphere with H₂, CO₂, and H₂O being the next most abundant gases. Outgassing of CV carbonaceous chondritic material gives a CO₂-rich atmosphere with H₂O being the second most abundant gas. Our results predict that the atmospheres formed during accretion of the Earth and Mars were probably H₂-rich unless the accreted material was dominantly CI and CM carbonaceous chondritic material. We also predict significant amounts of S, P, Cl, F, Na, and K in accretionary atmospheres at high temperatures (1500-2500 K). Finally, our results may be useful for interpreting spectroscopic observations of accreting extrasolar terrestrial planets.     

Experimental impact shock chemistry on planetary icy satellites

We present new experimental results on impact shock chemistry into icy satellites of the outer planets. Icy mixtures of pure water ice with CO₂, Na₂CO₃, CH₃OH, and CH₃OH/(NH₄)₂SO₄ at 77 K were ablated with a powerful pulsed laser—a new technique used to simulate shock processes which can occur during impacts. New products were identified by GC-MS and FTIR analyses after laser ablation. Our results show that hydrogen peroxide is formed in irradiated H₂O/CO₂ ices with a final concentration of 0.23%. CO and CH₃OH were also detected as main products. The laser ablation of frozen H₂O/Na₂CO₃ generates only CO and CO₂ as destruction products from the salt. Pulsed irradiation of water ice containing methanol leads also to the formation of CO and CO₂, generates methane and more complex molecules containing carbonyl groups like acetaldehyde, acetone, methyl formate, and a diether, dimethyl formal. The last three compounds are also produced when adding ammonium sulfate to H₂O/CH₃OH ice, but acetone is more abundant. The formation of two hydrocarbons, CH₄ and C₂H₆ is observed as well as the production of three nitrogen compounds, nitrous oxide, hydrogen cyanide, and acetonitrile.     

Carbon dioxide on planetary bodies: Theoretical and experimental studies of molecular complexes

An absorption band at ∼4.26 μm wavelength attributed to the asymmetric stretching mode of CO in CO₂ has been found on two satellites of Jupiter and several satellites of Saturn. The wavelength of pure CO₂ ice determined in the laboratory is 4.2675 μm, indicating that the CO₂ on the satellites occurs either trapped in a host material, or in a chemical or physical complex with other materials, resulting in a blue shift of the wavelength of the band. In frequency units, the shifts in the satellite spectra range from 3.7 to 11.3 cm⁻¹. We have performed ab initio quantum chemical calculations of CO₂ molecules chemically complexed with one, two, and more H₂O molecules and molecules of CH₃OH to explore the possibility that the blue shift of the band is caused by chemical complexing of CO₂ with other volatile materials. Our computations of the harmonic and anharmonic vibrational frequencies using high levels of theory show a frequency shift to the blue by 5 cm⁻¹ from pure CO₂ to CO-H₂O, and an additional 5 cm⁻¹ from CO₂-H₂O to CO₂-2H₂O. Complexing with more than two H₂O molecules does not increase the blue shift. Complexes of CO₂ with one molecule of CH₃OH and with one CH₃OH plus one H₂O molecule produce smaller shifts than the CO₂-2H₂O complex. Laboratory studies of CO₂:H₂O in a solid N₂ matrix also show a blue shift of the asymmetric stretching mode.     

Ion irradiation of H2O ice on top of sulfurous solid residues and its relevance to the Galilean satellites

In this paper we present the results of new experiments of ion irradiation of water ice deposited on top of a solid sulfurous residue to study the potential formation of SO₂ at the interface ice/refractory material and discuss the possibility that this mechanism accounts for the sulfur dioxide ice detected on the surfaces of the Galilean satellites. In situ infrared spectroscopy was the used experimental technique. We have irradiated a thin film of H₂O frost on a sulfurous layer with 200 keV of He⁺ at 80 K. The used sulfurous residue was obtained by irradiation of frozen SO₂ at 16 K and it is used as a template of sulfur bearing solid materials. We have not found evidences of the efficient formation of SO₂ after irradiation of H₂O ice on top of the sulfurous residue. An upper limit to the production yield of SO₂, of interface area for each 100 eV of energy absorbed in 1 cm³ of ice-covered residue, has been estimated. These results have relevance in the context of the surfaces of the icy Galilean satellites in which SO₂ was detected. Our results show that radiolysis of mixtures of water ice and refractory sulfurous materials is not the primary formation mechanism responsible for the SO₂ present on the surfaces of the Galilean satellites.     

Dust emission from comets at large heliocentric distances

Possible mechanisms for the production of the extended dust coma observed in comet Bowell (1980b) at the large heliocentric distance of 7.17 AU are considered. It is concluded that a plausible mechanism is electrostatic blow-off of fine, loose dust from an electrically charged H₂O dominated nucleus, as recently proposed by Mendiset al. (1981). Of all the other processes considered, dust entrainment by a chemical species more volatile than H₂O is considered the most plausible. However, the non-observation of prominent CO⁺ lines of theA ²-X ² band, seems to mitigate against a CO dominated nucleus, particularly if its radius is 1 km. A CO₂ dominated nucleus, however, cannot be ruled out by this non-observation unless its radius is considerably larger ( 5 km). The electrostatic blow-off process predicts that the dust grains in the coma of comet Bowell at 7.17 AU must be very small (r _g0.4 ), with a total mass 4×10⁸ g, and a spatial extension 10⁵ km, which is consistent with the observations (observed coma diameter 6×10⁴ km). Both the size and spatial distribution of the dust given by electrostatic blow-off and the gas entrainment processes are shown to be different, and this would be a way of discriminating between the two processes. However, the present observations do not have the resolution to do so.Department of Physics.Department of Electrical Engineering and Computer Sciences.     

Global atmospheric monitoring with SCIAMACHY

SCIAMACHY (SCanning Imaging Absorption spectrometer for Atmospheric CHartographY) is a space based spectrometer designed to measure sunlight transmitted, reflected and scattered by the Earth atmosphere or surface. It is a contribution to the Envisat-1 satellite to be launched in late 1999.SCIAMACHY measurements will provide amounts and distribution of 0₃, BrO, OCl0, ClO, S0₂, H₂CO, N0₂, CO, CO₂, CH₄, H₂O, N₂0, pressure, temperature, aerosol, radiation, cloud cover and cloud top height from atmospheric measurements in nadir, limb and occultation geometry.By the combination of the near simultaneous limb and nadir observations SCIAMACHY is one of a limited number of instruments which is able to detect tropospheric column amounts of 0₃, N0₂, CO, CH₄, H₂O, N₂0, S0₂, H₂CO, and BrO down to the planetary boundary layer under cloud free conditions.     

Prebiotic organic synthesis in early Earth and Mars atmospheres: Laboratory experiments with quantitative determination of products formed in a cold plasma flow reactor

The goal of this study was to explore prebiotic chemistry in a range of plausible early Earth and Mars atmospheres. To achieve this laboratory continuous flow plasma irradiation experiments were performed on N₂/H₂/CO/CO₂ gas mixtures chosen to represent mildly reducing early Earth and Mars atmospheres derived from a secondary volcanic outgassing of volatiles in chemical equilibrium with magmas near present day oxidation state. Under mildly reducing conditions (91.79% N₂, 5.89% H₂, 2.21% CO, and 0.11% CO₂), simple nitriles are produced in the gas phase with yield (G in molecules per 100 eV), for the key prebiotic marker molecule HCN at G∼1×¹⁰⁻³ (0.1 nmol J⁻¹). In this atmosphere localized HCN concentrations possibly could approach the 10⁻² M needed for HCN oligomerization. Yields under mildly oxidizing conditions (45.5% N₂, 0.1% H₂, 27.2% CO, 27.2% CO₂) are significantly less as expected, with HCN at G∼3×¹⁰⁻⁵ (). Yields in a Triton atmosphere which can be plausibly extrapolated to represent what might be produced in trace CH₄ conditions (99.9% N₂, 0.1% CH₄) are significant with HCN at G∼1×¹⁰⁻² (1 nmol J⁻¹) and tholins produced. Recently higher methane abundance atmospheres have been examined for their greenhouse warming potential, and higher abundance hydrogen atmospheres have been proposed based on a low early Earth exosphere temperature. A reducing (64.04% N₂, 28.8% H₂, 3.60% CO₂, and 3.56% CH₄), representing a high CH₄ and H₂ abundance early Earth atmosphere had HCN yields of G∼5×¹⁰⁻³ (0.5 nmol J⁻¹). Tholins generated in high methane hydrogen gas mixtures is much less than in a similar mixture without hydrogen. The same mixture with the oxidizing component CO₂ removed (66.43% N₂, 29.88% H₂, 0% CO₂, and 3.69% CH₄) had HCN yields of G∼1×¹⁰⁻³ (0.1 nmol J⁻¹) but more significant tholin yields.     

Studies of proton-irradiated cometary-type ice mixtures

Radiation synthesis has been proposed as a mechanism for changing the nature of the outer few meters of ice in a comet stored 4.6 billion years in the Oort cloud and may explain some of the differences observed between new and more evolved comets. Cometary-type ice mixtures were studied in a laboratory experiment designed to approximately simulate the expected temperature, pressure, and radiation environment of the interstellar Oort cloud region. The 2.5- to 15-μm infrared absorption features of thin ice films were analyzed near 20°K before and after 1 MeV proton irradiation. Various ice mixtures included the molecules H₂O, NH₃, CH₄, N₂, C₃H₈, CO, and CO₂. All experiments confirm the synthesis of new molecular species in solid phase mixtures at 20°K. The synthesized molecules, identified by their infrared signatures, are C₂H₆, CO₂, CO, N₂O, NO, and CH₄ (weak). Synthesized molecules, identified by gas chromatographic (GC) analysis of the volatile fraction of the warmed irradiated ice mixture, are C₂H₄ or C₂H₆, and C₃H₈. When CH₄ is present in the irradiated ice mixture, long-chained volatile hydrocarbons and CO₂ are synthesized along with high-molecular-weight carbon compounds present in the room temperature residue. Irradiated mixtures containing CO and H₂O synthesize CO₂ and those CO₂ and H₂O synthesize CO. Due to radiation synthesis, ～1% of the ice was converted into a nonvolatile residue containing complicated carbon compounds not present in blank samples. These results suggest that irrespective of the composition of newly accreted comets, initial molecular abundances can be altered and new species created as a result of radiation synthesis. Irradiated mixtures exhibited thermoluminescence and pressure enhancements during warming; these phenomena suggest irradiation synthesis of reactive species. Ourbursts in new comets resulting from similar radiation induced exothermic activity would be expected to occur beginning at distances of the order of 100 AU.     

Analysis of Cassini/CIRS limb spectra of Titan acquired during the nominal mission: I. Hydrocarbons, nitriles and CO2 vertical mixing ratio profiles

Observations of the Composite InfraRed Spectrometer (CIRS) during the entire nominal Cassini mission (2004-2008) provide us with an accurate global view of composition and temperature in the middle atmosphere of Titan (between 100 and 500 km). We investigated limb spectra acquired at resolution at nine different latitudes between 56°S and 80°N, with a better sampling in the northern hemisphere where molecular abundances and temperature present strong latitudinal variations. From this limb data acquired between February 2005 and May 2008, we retrieved the vertical mixing ratio profiles of C₂H₂, C₂H₄, C₂H₆, C₃H₈, CH₃C₂H, C₄H₂, C₆H₆, HCN, HC₃N and CO₂. We present here for the first time, the latitudinal variations of the C₂H₆, C₃H₈, CO₂, C₂H₄ and C₆H₆ vertical mixing ratios profiles. Some molecules, such as C₂H₆ or C₃H₈ present little variations above their condensation level. The other molecules (except CO₂) show a significant enhancement of their mixing ratios poleward of 50°N. C₂H₄ is the only molecule whose mixing ratio decreases with height at latitudes below 46°N. Regions depleted in C₂H₂, HCN and C₄H₂ are observed around 400 km (0.01 mbar) and 55°N. We also inferred a region enriched in CO₂ located between 30 and 40°N in the 2-0.7 mbar pressure range. At 80°N, almost all molecules studied here present a local minimum of their mixing ratio profiles near 300 km (∼0.07 mbar), which is in contradiction with Global Circulation Models that predict constant-with-height vertical profiles due to subsidence at the north pole.     

Identification of a new band system of isotopic CO2 near 3.3 μm: Implications for remote sensing of biomarker gases on Mars

We present the discovery of a new vibrational band system of isotopic CO₂ (carbon dioxide) near 3.3 μm, with multiple strong P, Q and R lines in the prime spectral region used to search for Mars CH₄ (methane). The band system was discovered on Mars using high-resolution spectrometers (λ/δλ>40,000, CSHELL and NIRSPEC) at telescopes (NASA-IRTF and Keck-2) atop Mauna Kea, HI. The observed line intensities and frequencies agree very well with values predicted by a vibrational band model that we developed using known parameters for the molecular levels involved. Using this model, we synthesized spectra for different observing conditions (from Space and ground-based telescopes) and for different spectral resolving powers (5000 to 40,000). Although the total atmospheric burden on Mars is more than 150 times smaller than on Earth, the greater mixing ratio of CO₂ ensures that its column abundance on Mars is almost 20 times greater than on Earth. Thus, weak telluric CO₂ band systems appear much stronger on Mars. Many molecules of possible biological and geothermal interest have strong signatures at these wavelengths, in particular hydrocarbons owing to their strong ro-vibrational CH stretching modes. For example, the new isotopic CO₂ band-system encompasses lines of CH₄, C₂H₆ (ethane), CH₃OH (methanol) and H₂O (water). Implications for previous and future searches of biomarker gases are presented.     

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.     

Volatile compounds in shergottite and nakhlite meteorites

Abstract— Vacuum pyrolysis and quadrupole mass spectrometry were used to measure evolved-gas profiles and total concentrations of H₂O, CO₂, CO, SO₂, S₂, H₂S, HCl, Cl, and hydrocarbons in both exterior and interior samples of shergottites (ALHA77005, EETA79001, and Shergotty), a nakhlite (Nakhla), and eucrites (ALHA81001, EETA79004, and Pasamonte). Eucrites were analyzed as control samples to monitor effects of terrestrial weathering and contamination, relative to properties sought for the shergottite-nakhlite parent body. In contrast with eucrites, shergottites and Nakhla contain large proportions of their sulfur as oxidized sulfur compounds. Sulfate occurs in all shergottite and Nakhla samples and carbonate was confirmed in EETA79001 and Nakhla. Carbonate and sulfate abundances are inversely correlated but total chlorine abundance varies directly with fractional sulfate abundance. Most of the volatile compounds seem to be anhydrous, based on low bulk water contents in the meteorites (<0.1% H₂O), although Nakhla might contain significant water that is chemically associated with chlorine. Traces of saturated and unsaturated hydrocarbons in some samples are most likely terrestrial contaminants. The indigenous volatile compounds indicate that the shergottite-nakhlite parent body was highly oxidizing and supported aqueous geochemistry during at least part of its history.     

An Improved Optical Model for the Non-LTE Problem for the CO2 Molecule in the Atmosphere of Mars: Nighttime Populations of Vibrational States and the Rate of Radiative Cooling of the Atmosphere

The estimates of the population of excited vibrational states of the CO₂ molecule and of the rate of radiative cooling of the atmosphere in the 15-m CO₂ band are given for the nighttime mesosphere and thermosphere of Mars. For the first time, these estimates are made (1) with allowance for the overlap of lines in the 15-m band; (2) for a wide set of vibrational states of seven isotopes of the CO₂ molecule, which was used earlier in the solution of a similar terrestrial problem; and (3) using the rate constant for quenching of the CO₂(01¹0) state in collisions with oxygen atoms, which has been recently measured for low temperatures by Khvorostovskaya et al. (2002). The main results are as follows. 1. The approximation of isolated lines provides a satisfactory accuracy of determining the radiative cooling rate and overestimates vibrational temperatures of the states of the ₂ mode by no more than 3 K for the ¹²C¹⁶O₂ molecule and by no more than 2 K for low-abundant isotopes of the CO₂ molecule. 2. A reasonably high accuracy of estimating the cooling rate can be achieved by taking into account only fundamental vibrational transitions in ¹²C¹⁶O₂, ¹³C¹⁶O₂, ¹⁶O¹²C¹⁸O, and ¹⁶O¹²C¹⁷O molecules and the hot transitions 2_{2 2} and 3₂ 2₂ in the ¹²C¹⁶O₂ molecule. 3. The vertical profile of the total rate of radiative cooling displays two peaks. The maximum near a height of 130 km is very sensitive to temperature and to the ratio of the mixture for oxygen in the atmosphere.     

Photochemistry of the stratosphere of Venus: Implications for atmospheric evolution

The photochemistry of the stratosphere of Venus was modeled using an updated and expanded chemical scheme, combined with the results of recent observations and laboratory studies. We examined three models, with H₂ mixing ratio equal to 2 × 10^?5, 5 × 10^?7, and 1 × 10^?13, respectively. All models satisfactorily account for the observations of CO, O₂, O₂(¹Δ), and SO₂ in the stratosphere, but only the last one may be able to account for the diurnal behavior of mesospheric CO and the uv albedo. Oxygen, derived from CO₂ photolysis, is primarily consumed by CO₂ recombination and oxidation of SO₂ to H₂SO₄. Photolysis of HCl in the upper stratosphere provides a major source of odd hydrogen and free chlorine radicals, essential for the catalytic oxidation of CO. Oxidation of SO₂ by O occurs in the lower stratosphere. In the high-H₂ model (model A) the OO bond is broken mainly by S + O₂ and SO + HO₂. In the low-H₂ models additional reactions for breaking the OO bond must be invoked: NO + HO₂ in model B and ClCO + O₂ in model C. It is shown that lightning in the lower atmosphere could provide as much as 30 ppb of NO_x in the stratosphere. Our modeling reveals a number of intriguing similarities, previously unsuspected, between the chemistry of the stratosphere of Venus and that of the Earth. Photochemistry may have played a major role in the evolution of the atmosphere. The current atmosphere, as described by our preferred model, is characterized by an extreme deficiency of hydrogen species, having probably lost the equivalent of 10²–10³ times the present hydrogen content.     

Energy balance of the Deep Impact experiment

We present results on the energy balance of the Deep Impact experiment based on analysis of 180 infrared spectra of the ejecta obtained by the Deep Impact spacecraft. We derive an output energy of 16.5 (+9.1/−4.1) GJ. With an input energy of 19.7 GJ, the error bars are large enough so that there may or may not be a balance between the kinetic energy of the impact and that of outflowing materials. Although possible, no other source of energy other than the impactor or the Sun is needed to explain the observations. Most of the energy (85%) goes into the hot plume in the first few seconds, which only represents a very small fraction (<0.01%) of the total ejected mass. The hot plume contains 190 (+263/−71) kg of H₂O, 1.6 ± 0.5 kg of CO₂, 8.2 (+11.3/3.1) kg of CO (assuming a CO/H₂O ratio of 4.3%), 27.9 (+25.0/−8.9) kg of organic material and 255 ± 128 kg of dust, while the ejecta contains ∼10⁷ kg of materials. About 12% of the energy goes into the ejecta (mostly water) and 3% to destroy the impactor. Volatiles species other than H₂O (CO₂, CO or organic molecules) contribute to <7% of the energy balance. In terms of physical processes, 68% of the energy is used to accelerate grains (kinetic energy), 16% to heat them, 6% to sublimate or melt them and 10% (upper limit) to break and compress dust and/or water ice aggregates into small micron size particles. For the hot plume, we derive a dust/H₂O ratio of 1.3 (+1.9/−1.0), a CO₂/H₂O ratio of 0.008 (+0.009/−0.006), an organics/H₂O ratio of 0.15 (+0.29/−0.11) and an organics/dust ratio of 0.11 (+0.30/−0.07). This composition refers to the impact site and is different from that of the bulk nucleus, consistent with the idea of layers of different composition in the nucleus sub-surface. Our results emphasize the importance of laboratory impact experiments to understand the physical processes involved at such a large scale.     

Evaluation of the possible presence of clathrate hydrates in Europa's icy shell or seafloor

Several substances besides water ice have been detected on the surface of Europa by spectroscopic sensors, including CO₂, SO₂, and H₂S. These substances might occur as pure crystalline ices, as vitreous mixtures, or as clathrate hydrate phases, depending on the system conditions and the history of the material. Clathrate hydrates are crystalline compounds in which an expanded water ice lattice forms cages that contain gas molecules. The molecular gases that may constitute Europan clathrate hydrates may have two possible ultimate origins: they might be primordial condensates from the interstellar medium, solar nebula, or jovian subnebula, or they might be secondary products generated as a consequence of the geological evolution and complex chemical processing of the satellite. Primordial ices and volatile-bearing compounds would be difficult to preserve in pristine form in Europa without further processing because of its active geological history. But dissociated volatiles derived from differentiation of a chondritic rock or cometary precursor may have produced secondary clathrates that may be present now. We have evaluated the current stability of several types of clathrate hydrates in the crust and the ocean of Europa. The depth at which the clathrates of SO₂, CO₂, H₂S, and CH₄ are stable have been obtained using both the temperatures observed in the surface [Spencer, J.R., Tamppari, L.K., Martin, T.Z., Travis, L.D., 1999. Temperatures on Europa from Galileo photopolarimeter-radiometer: Nighttime thermal anomalies. Science 284, 1514-1516] and thermal models for the crust. In addition, their densities have been calculated in order to determine their buoyancy in the ocean, obtaining different results depending upon the salinity of the ocean and type of clathrate. For instance, assuming a eutectic composition of the system MgSO₄H₂O for the ocean, CO₂, H₂S, and CH₄ clathrates would float but SO₂ clathrate would sink to the seafloor; an ocean of much lower salinity would allow all these clathrates to sink, except that CH₄ clathrate would still float. Many geological processes may be driven or affected by the formation, presence, and destruction of clathrates in Europa such as explosive cryomagmatic activity [Stevenson, D.J., 1982. Volcanism and igneous processes in small icy satellites. Nature 298, 142-144], partial differentiation of the crust driven by its clathration, or the local retention of heat within or beneath clathrate-rich layers because of the low thermal conductivity of clathrate hydrates [Ross, R.G., Kargel, J.S., 1998. Thermal conductivity of Solar System ices, with special reference to martian polar caps. In: Schmitt, B., De Berg, C., Festou, M. (Eds.), Solar System Ices. Kluwer Academic, Dordrecht, pp. 33-62]. On the surface, destabilization of these minerals and compounds, triggered by fracture decompression or heating could result in formation of chaotic terrain morphologies, a mechanism that also has been proposed for some martian chaotic terrains [Tanaka, K.L., Kargel, J.S., MacKinnon, D.J., Hare, T.M., Hoffman, N., 2002. Catastrophic erosion of Hellas basin rim on Mars induced by magmatic intrusion into volatile-rich rocks. Geophys. Res. Lett. 29 (8); Kargel, J.S., Prieto-Ballesteros, O., Tanaka K.L., 2003. Is clathrate hydrate dissociation responsible for chaotic terrains on Earth, Mars, Europa, and Triton? Geophys. Res. 5. Abstract 14252]. Models of the evolution of the ice shell of Europa might take into account the presence of clathrate hydrates because if gases are vented from the silicate interior to the water ocean, they first would dissolve in the ocean and then, if the gas concentrations are sufficient, may crystallize. If any methane releases occur in Europa by hydrothermal or biological activity, they also might form clathrates. Then, from both geological and astrobiological perspectives, future missions to Europa should carry instrumentation capable of clathrate hydrate detection.