Ultraviolet Photoprocessing of Glycine Adsorbed on Various Space-Relevant Minerals

The discovery of amino acids such as glycine on meteorites and comets confirms the role of small bodies as transport and delivery vehicles of building blocks of life on Earth and possibly on other planetary bodies of our Solar System. Glycine is quite interesting because it is the simplest of the 20 biogenic amino acids, from which complex organic molecules might have originated in our evolved Solar System. To investigate the possible chemical evolution of this molecule in space, it is important to consider how the interaction with mineral matrices influences its photostability. Indeed, the presence of minerals can mediate the effects of electromagnetic radiation, catalyzing photoreactions, or protecting molecules against degradation. Such interactions are responsible for the preservation/degradation mechanisms of organic molecules in space environments. Laboratory simulations of UV processing may provide key insights into the survival of organic molecules in space environment and rocky surfaces, which is of particular relevance for current missions of sample return from asteroids, such as NASA OSIRIS-REx and JAXA Hayabusa 2, and in particular, upcoming space exploration missions on planetary surfaces, such as ESA-Roscosmos ExoMars 2022 and NASA Mars 2020. In this article, we report a laboratory study of UV irradiation of glycine adsorbed on various space relevant minerals: forsterite, antigorite, spinel, and pyrite. We monitored possible changes of glycine functional groups due to UV irradiation through in situ infrared (IR) spectroscopic analysis. Results show that degradation of glycine occurs with a half-life of 0.5–2 h depending on the mineral substrate. Appearance of new IR bands suggests the occurrence of catalytic reactions mediated by minerals and UV

Photoprocessing of formamide ice: route towards prebiotic chemistry in space

Aims. Formamide (HCONH2) is the simplest molecule containing the peptide bond first detected in the gas phase in Orion-KL and SgrB2. In recent years, it has been observed in high temperature regions such as hot corinos, where thermal desorption is responsible for the sublimation of frozen mantles into the gas phase. The interpretation of observations can benefit from information gathered in the laboratory, where it is possible to simulate the thermal desorption process and to study formamide under simulated space conditions such as UV irradiation. Methods. Here, two laboratory analyses are reported: we studied formamide photo-stability under UV irradiation when it is adsorbed by space relevant minerals at 63 K and in the vacuum regime. We also investigated temperature programmed desorption of pure formamide ice in the presence of TiO2 dust before and after UV irradiation. Results. Through these analyses, the effects of UV degradation and the interaction between formamide and different minerals are compared.We find that silicates, both hydrates and anhydrates, offer molecules a higher level of protection from UV degradation than mineral oxides. The desorption temperature found for pure formamide is 220 K. The desorption temperature increases to 250 K when the formamide desorbs from the surface of TiO2 grains. Conclusions. Through the experiments outlined here, it is possible to follow the desorption of formamide and its fragments, simulate the desorption process in star forming regions and hot corinos, and constrain parameters such as the thermal desorption temperature of formamide and its fragments and the binding energies involved. Our results offer support to observational data and improve our understanding of the role of the grain surface in enriching the chemistry in space.Comment: In press Astronomy and Astrophysics, 13 pages, 12 figure

Life detection in Martian returned samples: correlation between analytical techniques and biological signatures

As soon as samples collected from Mars will be brought back to Earth, the samples will be placed inside a receiving facility to check for the presence of life. There is a large number of approaches that were proposed on the techniques to be used to investigate the presence of life and any biological risk in the returned samples. Another interesting approach was reported by Kminek in which suggestions were provided on how to organize the sample analysis sequence within the facility. Finally, another study suggested a long list of techniques capable of measuring biological signatures based on their general characteristics: global, morphological, mineralogical, organic, molecular and biochemical, isotopic analysis. Despite the effort of the cited studies, there is still the need of a critical approach to make an actual comparison between the techniques, with the aim to find a ranking. In this work, we focused on the construction of a correlation matrix with which to correlate biosignatures to analytical techniques. It is known that a number of techniques can detect biological signatures and, at the same time, each technique can be applied to multiple biological signatures. Using this method, it is possible to summarize all this information to be easily consulted, but also to define in a quantitative way how strong each correlation is

The photochemical evolution of polycyclic aromatic hydrocarbons and nontronite clay on early Earth and Mars

The photochemical evolution of polycyclic aromatic hydrocarbons (PAHs), an abundant form of meteoritic organic carbon, is of great interest to early Earth and Mars origin-of-life studies and current organic molecule detection efforts on Mars. Fe-rich clay environments were abundant on early Earth and Mars, and may have played a role in prebiotic chemistry, catalyzing the breakdown of PAHs and freeing up carbon for subsequent chemical complexification. Current Mars is abundant in clay-rich environments, which are most promising for harboring organic molecules and have comprised the main studied features by the Curiosity rover in search of them. In this work we studied the photocatalytic effects of the Fe-rich clay nontronite on adsorbed PAHs. We tested the effect of ultraviolet radiation on pyrene, fluoranthene, perylene, triphenylene, and coronene adsorbed to nontronite using the spike technique, and in situ diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy in a Mars simulation chamber. We studied the infrared vibrational PAH bands with first order reaction kinetics and observed an extensive decrease of bands of pyrene, fluoranthene, and perylene, accompanied by the formation of PAH cations, while triphenylene and coronene remained preserved. We further analyzed our irradiated samples with nuclear magnetic resonance (NMR). Our study showed certain PAHs to be degraded via the (photo)Fenton mechanism, even under a dry, hypoxic atmosphere. Using solar spectra representative of early Earth, early Mars, and current Mars surface illumination up to 400 nm, the processes occurring in our set up are indicative of the UV-induced photochemistry taking place in Fe-rich clay environments on early Earth and Mars

Measuring absolute frequencies beyond the GPS limit via long-haul optical frequency dissemination

Global Positioning System (GPS) dissemination of frequency standards is ubiquitous at present, providing the most widespread time and frequency reference for the majority of industrial and research applications worldwide. On the other hand, the ultimate limits of the GPS presently curb further advances in high-precision, scientific and industrial applications relying on this dissemination scheme. Here, we demonstrate that these limits can be reliably overcome even in laboratories without a local atomic clock by replacing the GPS with a 642-km-long optical fiber link to a remote primary caesium frequency standard. Through this configuration we stably address the 1S0—3P0 clock transition in an ultracold gas of 173Yb, with a precision that exceeds the possibilities of a GPS-based measurement, dismissing the need for a local clock infrastructure to perform beyond-GPS high-precision tasks. We also report an improvement of two orders of magnitude in the accuracy on the transition frequency reported in literature

UV Irradiation and Near Infrared Characterization of Laboratory Mars Soil Analog Samples

The search for molecular biosignatures at the surface of Mars is complicated by an intense irradiation in the mid- and near-ultraviolet (UV) spectral range for several reasons: (i) many astrobiologically relevant molecules are electronically excited by efficient absorption of UV radiation and rapidly undergo photochemical reactions; (ii) even though the penetration depth of UV radiation is limited, aeolian erosion continually exposes fresh material to radiation; and (iii) UV irradiation generates strong oxidants such as perchlorates that can penetrate deep into soils and cause subsurface oxidative degradation of organics. As a consequence, it is crucial to investigate the effects of UV radiation on organic molecules embedded in mineral matrices mimicking the martian soil, in order to validate hypotheses about the nature of the organic compounds detected so far at the surface of Mars by the NASA Mars Science Laboratory’s (MSL) Curiosity rover, as well as organics that will be possibly found by the next rover missions Mars 2020 (NASA) and ExoMars 2022 (ESA-Roscosmos). In addition, studying the alteration of possible molecular biosignatures in the martian environment will help to redefine the molecular targets for life detection missions and devise suitable detection methods. Here we report the results of mid- and near-UV irradiation experiments of Mars soil analog samples obtained adsorbing relevant organic molecules on a clay mineral that is quite common on Mars, i.e. montmorillonite, doped with 1 wt% of magnesium perchlorate. Specifically, we chose to investigate the photostability of a plausible precursor of the chlorohydrocarbons detected on Mars by the Curiosity rover, namely phthalic acid, along with the biomarkers of extant life L-phenylalanine and L-glutamic acid, which are proteomic amino acids, and adenosine 5’-monophosphate, which is a nucleic acid component. We monitored the degradation of these molecules adsorbed on montmorillonite through in situ spectroscopic analysis, investigating the reflectance properties of the samples in the Near InfraRed (NIR) spectral region. Such spectroscopic characterization of molecular alteration products provides support for two upcoming robotic missions to Mars that will employ NIR spectroscopy to look for molecular biosignatures, through the instruments SuperCam on board Mars 2020, ISEM, Ma_Miss and MicrOmega on board ExoMars 2022

Multidisciplinary Analysis of Lermontov Crater on Mercury

We present the geological, age determination, and spectrophotometric analysis of the Lermontov Crater on Mercury

Evolution and alteration of organic material on Ceres, a pathway towards the understanding of complex geological and chemical history of a wet small body

Ceres is the largest object in the Solar System main belt. Clearly, Ceres experienced extensive water-related processes and geochemical differentiation and nowadays it is a body with a complex geological and chemical history. Its surface is characterized by dark materials, phyllosilicates, ammonium-bearing minerals, carbonates, water ice, and salts. In addition to a global presence of carbon bearing chemistry, local concentration of aliphatic organics has been detected by Dawn. In this context, we have started a series of laboratory spectroscopy measurements targeted to study the physicochemical interactions between organic material and minerals possibly present on Ceres. The goal is to understand the transformations induced on these samples by ultraviolet radiation, neutral atoms, and fast ions, under experimental conditions that simulate the environment of Ceres. The spectroscopic data obtained in laboratory experiments allow, through the comparison with the observations of the VIR spectrometer aboard the Dawn mission, to clarify the nature and origin of organic material identified on Ceres