A systematic mid-infrared spectroscopic study of thermally processed SO2 ices.

The use of mid-infrared spectroscopy to characterise the chemistry of icy interstellar and Solar System environments will be exploited in the near future to better understand the chemical processes and molecular inventories in various astronomical environments. This is, in part, due to observational work made possible by the recently launched James Webb Space Telescope as well as forthcoming missions to the outer Solar System that will observe in the mid-infrared spectroscopic region (e.g., the Jupiter Icy Moons Explorer and the Europa Clipper missions). However, such spectroscopic characterisations are crucially reliant upon the generation of laboratory data for comparative purposes. In this paper, we present an extensive mid-infrared characterisation of SO2 ice condensed at several cryogenic temperatures between 20 and 100 K and thermally annealed to sublimation in an ultrahigh-vacuum system. Our results are anticipated to be useful in confirming the detection (and possibly thermal history) of SO2 on various Solar System bodies, such as Ceres and the icy Galilean moons of Jupiter, as well as in interstellar icy grain mantles.

New Signatures of Bio-Molecular Complexity in the Hypervelocity Impact Ejecta of Icy Moon Analogues.

Impact delivery of prebiotic compounds to the early Earth from an impacting comet is considered to be one of the possible ways by which prebiotic molecules arrived on the Earth. Given the ubiquity of impact features observed on all planetary bodies, bolide impacts may be a common source of organics on other planetary bodies both in our own and other solar systems. Biomolecules such as amino acids have been detected on comets and are known to be synthesized due to impact-induced shock processing. Here we report the results of a set of hypervelocity impact experiments where we shocked icy mixtures of amino acids mimicking the icy surface of planetary bodies with high-speed projectiles using a two-stage light gas gun and analyzed the ejecta material after impact. Electron microscopic observations of the ejecta have shown the presence of macroscale structures with long polypeptide chains revealed from LCMS analysis. These results suggest a pathway in which impact on cometary ices containing building blocks of life can lead to the synthesis of material architectures that could have played a role in the emergence of life on the Earth and which may be applied to other planetary bodies as well.

Possible detection of hydrazine on Saturn's moon Rhea.

We present the first analysis of far-ultraviolet reflectance spectra of regions on Rhea's leading and trailing hemispheres collected by the Cassini Ultraviolet Imaging Spectrograph during targeted flybys. In particular, we aim to explain the unidentified broad absorption feature centred near 184 nm. We have used laboratory measurements of the UV spectroscopy of a set of candidate molecules and found a good fit to Rhea's spectra with both hydrazine monohydrate and several chlorine-containing molecules. Given the radiation-dominated chemistry on the surface of icy satellites embedded within their planets' magnetospheres, hydrazine monohydrate is argued to be the most plausible candidate for explaining the absorption feature at 184 nm. Hydrazine was also used as a propellant in Cassini's thrusters, but the thrusters were not used during icy satellite flybys and thus the signal is believed to not arise from spacecraft fuel. We discuss how hydrazine monohydrate may be chemically produced on icy surfaces.

Shock Processing of Amino Acids Leading to Complex Structures-Implications to the Origin of Life.

The building blocks of life, amino acids, are believed to have been synthesized in the extreme conditions that prevail in space, starting from simple molecules containing hydrogen, carbon, oxygen and nitrogen. However, the fate and role of amino acids when they are subjected to similar processes largely remain unexplored. Here we report, for the first time, that shock processed amino acids tend to form complex agglomerate structures. Such structures are formed on timescales of about 2 ms due to impact induced shock heating and subsequent cooling. This discovery suggests that the building blocks of life could have self-assembled not just on Earth but on other planetary bodies as a result of impact events. Our study also provides further experimental evidence for the 'threads' observed in meteorites being due to assemblages of (bio)molecules arising from impact-induced shocks.

Survival of Extremotolerant Bacteria from the Mukundpura Meteorite Impact Crater.

Carbonaceous meteorites provide clues with regard to prebiotic chemistry and the origin of life. Geological Survey of India recorded a carbonaceous chondrite meteorite fall in Mukundpura, India, on June 6, 2017. We conducted a study to investigate the microbial community that survived the meteorite impact. 16S rRNA metagenomic sequencing indicates the presence of Actinobacteria, Proteobacteria, and Acidobacteria in meteorite impact soil. Comparative phylogenetic analysis revealed an intriguing abundance of class Bacilli in the impact soil. Bacillus thermocopriae IR-1, a moderately thermotolerant organism, was isolated from a rock, impacted by the Mukundpura meteorite. We investigated the resilience of B. thermocopriae IR-1 to environmental stresses and impact shock in a Reddy shock tube. Bacillus thermocopriae IR-1 survived (28.82% survival) the effect of shock waves at a peak shock pressure of 300 kPa, temperature 400 K, and Mach number of 1.47. This investigation presents the first report on the effect of impact shock on B. thermocopriae IR-1. The study is also the first report on studying the microbial diversity and isolation of bacteria from impact crater soil immediately after meteorite impact event.

Theoretical study of the infrared frequencies of crystalline methyl acetate under interstellar medium conditions.

Identification of methyl acetate in the interstellar medium (ISM) and its spectroscopic studies have prompted us to investigate the structure of crystalline methyl acetate using numerical calculations. Here, we present a theoretical study of the structure of crystalline methyl acetate and its isotopologues and compare the calculated infrared (IR) spectra with the available experimental data. The optimized structure and vibrational properties were calculated using SIESTA software at 0 K. In the optimization process, the Perdew-Burke-Ernzerhof functional and conjugate gradient methods were used with double zeta polarization basis functions. After optimization of the periodic structure, the vibrational frequencies and normal modes were calculated within the harmonic approximation. Using the calculated results, we refine the mode assignments of experimental work on crystalline methyl acetate and determine the low frequency modes (below 650 cm(-1)). To investigate the accuracy of the pseudopotential and confirm the IR frequencies, we performed molecular calculations using a periodic model of methyl acetate and its isotopologues using SIESTA and compared them with results obtained from Gaussian 09 (all electron method) calculations. Finally, we assigned the vibrational modes of crystalline CD3-COO-CH3 and CH3-COO-CD3, for which experimental data are not available in the crystalline phase under ISM conditions. For all of the calculation methods, the IR vibrational modes of molecular and crystalline methyl acetate and its isotopologues were in good agreement with the available experimental data and predict the unavailable values.

Communication: vacuum ultraviolet photoabsorption of interstellar icy thiols.

Following the recent identification of ethanethiol in the interstellar medium (ISM) we have carried out Vacuum UltraViolet (VUV) spectroscopy studies of ethanethiol (CH3CH2SH) from 10 K until sublimation in an ultrahigh vacuum chamber simulating astrochemical conditions. These results are compared with those of methanethiol (CH3SH), the lower order thiol also reported to be present in the ISM. VUV spectra recorded at higher temperature reveal conformational changes in the ice and phase transitions whilst evidence for dimer production is also presented.

Ozone and carbon trioxide synthesis by low energy ion implantation onto solid carbon dioxide and implications to astrochemistry.

Ion implantation experiments were carried out on amorphous (30 K) and crystalline (80 K) solid CO2 using both reactive (D(+), H(+)) and non-reactive (He(+)) ions, simulating different irradiation environments on satellite and dust grain surfaces. Such ion irradiation synthesized several new species in the ice including ozone (O3), carbon trioxide (CO3), and carbon monoxide (CO) the main dissociation product of carbon dioxide. The yield of these products was found to be strongly dependent upon the ion used for irradiation and the sample temperature. Ion implantation changes the chemical composition of the ice with recorded infrared spectra clearly showing the coexistence of D3h and C2v isomers of CO3, for the first time, in ion irradiated CO2 ice.

Morphological study into the temperature dependence of solid ammonia under astrochemical conditions using vacuum ultraviolet and Fourier-transform infrared spectroscopy.

The authors present the results of a morphological study of solid ammonia using both Fourier-transform infrared and vacuum ultraviolet (VUV) spectroscopy. Dramatic changes in the VUV and infrared spectra at temperatures between 65 and 85 K provide a deeper insight into the structure of ammonia ice particularly with the observation of an exciton transition at 194 nm (6.39 eV) in the VUV spectrum, revealing a structure that is composed of crystallites. A complementary structure is observed in the IR spectrum at 1100 cm(-1) which is assigned to the symmetric deformation of ammonia molecules at the surfaces of the crystallites. Such spectral signatures may be used to identify the environment within which the ammonia ice is formed and provide a new route for obtaining information on the physical and chemical conditions occurring within the interstellar medium, on the surfaces of planetary bodies, and in Kuiper belt objects.

VUV spectroscopy and photo-processing of astrochemical ices: an experimental study.

In order to understand much of the chemistry that underpins astronomical phenomena (e.g. star and planet formation) it is essential to probe the physico-chemistry of ice surfaces under astronomical conditions. The physical properties and chemical reactivity of such icy surfaces depends upon its morphology. Thus it is necessary to explore how the morphology of astrochemical ices is influenced by their local environment (e.g. temperature and pressure) and the mechanisms by which they are processed. In this paper we report the results of a series of experiments to explore the morphology of a variety of molecular ices using VUV spectroscopy. Spectral signatures are found that may allow the morphology of such ices to be identified.