Various Solar System objects are covered in layers of ice that are dominated by H ₂O, CH ₄, and N ₂ and in which complex chemical processes take place. In this work, the influence of composition and irradiation duration on the volatile irradiation products of mixed CH ₄:N ₂, CH ₄:H ₂O, and CH ₄:H ₂O:N ₂ ices after electron irradiation are studied. The ices were irradiated for 2 or 4 h with 5 keV electrons, followed by a temperature programmed desorption, where the desorption of the volatile irradiation products was observed. The formation of C ₂H _x and C ₃H _x is observed in all ices and for both irradiation times. For the ices containing H ₂O, molecules as large as tentatively identified C ₄H _x and C ₅H _x are observed to co-desorb with water, whereas for CH ₄:N ₂ a continuous desorption signal is observed instead of a sharp desorption peak. A decrease in signal intensity from the 2 to the 4 h irradiation is observed for most m/z signals in CH ₄:H ₂O and CH ₄:H ₂O:N ₂ ices, whereas the opposite is recorded for CH ₄:N ₂, where in general larger signal for longer irradiation duration is seen. The addition of nitrogen to the CH ₄:H ₂O ice did not lead to clear identification of different molecules, but instead to a decrease of the observed signal for complex molecules, suggesting that the addition of nitrogen to the CH ₄:H ₂O mixture primarily leads to a more effective incorporation of material in an organic residue. The analysis of the residue will be subject of future work to complement the findings in this study.

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Spectroscopic instruments were a part of payloads on orbiter and lander missions and delivered vast data sets to explore minerals, elements and molecules on air-less rocky planets, asteroids and comets on global and local scales. To answer current space science questions, the chemical composition of planetary rocks and soils at grain scale is required, as well as measurements of element (isotope) concentrations down to the part per million or lower. Only mass spectrometric methods equipped with laser sampling ion sources can deliver the necessary information. Laser sampling techniques can reduce the dimensions of the investigated sample material down to micrometre scale, allowing for the composition analysis of grain-sized objects or thin mineral layers with sufficiently high spatial resolution, such that important geological processes can be recognised and studied as they progressed in time. We describe the performance characteristics, when applied to meteorite and geological samples, of a miniaturised laser ablation/ionisation mass spectrometer (named LMS) system that has been developed in our group. The main advantages of the LMS instrument over competing techniques are illustrated by examples of high spatial (lateral and vertical) resolution studies in different meteorites, terrestrial minerals and fossil-like structures in ancient rocks for most elements of geochemical interest. Top-level parameters, such as dimension, weight, and power consumption of a possible flight design of the LMS system are presented as well.

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In the search for extraterrestrial life, biosignatures (e.g., organic molecules) play an important role, of which lipids are one considerable class. If detected, these molecules can be strong indicators of the presence of life, past or present, as they are ubiquitous in life on Earth. However, their detection is challenging, depending on, e.g., instrument performance, as well as the selected site. In this contribution, we demonstrate that, using laser desorption ionization mass spectrometry, detection of lipids is feasible. Using our space prototype instrument designed and built in-house, six representative lipids were successfully detected: cholecalciferol, phylloquinone, menadione, 17α-ethynylestradiol, α-tocopherol, and retinol, both as pure substances and as mixtures additionally containing amino acids or polycyclic aromatic hydrocarbons. Observed limits of detection for lipids already meet the requirements stated in the Enceladus Orbilander mission concept. The current performance of our LDI-MS system allows for the simultaneous identification of lipids, amino acids, and polycyclic aromatic hydrocarbons, using a single instrument. We therefore believe that the LDI-MS system is a promising candidate for future space exploration missions devoted to life detection.

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Recent and past observations of chemical and physical peculiarities in the atmosphere of Venus have renewed speculations about the existence of life in its clouds. To find signs of Venusian life, a dedicated astrobiological space exploration mission is required, and for this reason the Venus Life Finder mission is currently being prepared. A Venus Life Finder mission will require dedicated and specialized instruments to hunt for biosignatures and habitability indicators. In this contribution, we present the ORIGIN space instrument, a laser desorption/laser ablation ionization mass spectrometer. This instrument is designed to detect large, non-volatile molecules, specifically biomolecules such as amino acids and lipids. At the same time, it can also be used in ablation mode for elemental composition analysis. Recent studies with this space prototype instrument of amino acids, polycyclic aromatic hydrocarbons, lipids, salts, metals, sulphur isotopes, and microbial elemental composition are discussed in the context of studies of biosignatures and habitability indicators in Venus’s atmosphere. The implementation of the ORIGIN instrument into a Venus Life Finder mission is discussed, emphasizing the low weight and low power consumption of the instrument. An instrument design and sample handling system are presented that make optimal use of the capabilities of this instrument. ORIGIN is a highly versatile instrument with proven capabilities to investigate and potentially resolve many of the outstanding questions about the atmosphere of Venus and the presence of life in its clouds.

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Rationale: Femtosecond (fs) laser ablation ion sources have allowed for improved measurement capabilities and figures of merit of laser ablation based spectroscopic and mass spectrometric measurement techniques. However, in comparison to longer pulse laser systems, the ablation plume from fs lasers is observed to be colder, which favors the formation of polyatomic species. Such species can limit the analytical capabilities of a system due to isobaric interferences. In this contribution, a double-pulse femtosecond (DP-fs) laser ablation ion source is coupled to our miniature Laser Ablation Ionization Mass Spectrometry (LIMS) system and its impact on the recorded stoichiometry of the generated plasma is analyzed in detail. Methods: A DP-fs laser ablation ion source (temporal delays of +300 to – 300 ps between pulses) is connected to our miniature LIMS system. The first pulse is used for material removal from the sample surface and the second for post-ionization of the ablation plume. To characterize the performance, parametric double- and single-pulse studies (temporal delays, variation of the pulse energy, voltage applied on detector system) were conducted on three different NIST SRM alloy samples (SRM 661, 664 and 665). Results: At optimal instrument settings for both the double-pulse laser ablation ion source and the detector voltage, relative sensitivity coefficients were observed to be closer (factor of ~2) to 1 compared with single-pulse measurements. Furthermore, the optimized settings worked for all three samples, meaning no further optimization was necessary when changing to another alloy sample material during this study. Conclusions: The application of a double-pulse femtosecond laser ablation ion source resulted in the recording of improved stoichiometry of the generated plasma using our LIMS measurement technique. This is of great importance for the quantitative chemical analysis of more complex solid materials, e.g., geological samples or metal alloys, especially when aiming for standard-free quantification procedures for the determination of the chemical composition.

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Accurate isotope ratio measurements are of high importance in various scientific fields, ranging from radio isotope geochronology of solids to studies of element isotopes fractionated by living organisms. Instrument limitations, such as unresolved isobaric inferences in the mass spectra, or cosampling of the material of interest together with the matrix material may reduce the quality of isotope measurements. Here, we describe a method for accurate isotope ratio measurements using our laser ablation ionization time-of-flight mass spectrometer (LIMS) that is designed for in situ planetary research. The method is based on chemical depth profiling that allows for identifying micrometer scale inclusions embedded in surrounding rocks with different composition inside the bulk of the sample. The data used for precise isotope measurements are improved using a spectrum cleaning procedure that ensures removal of low quality spectra. Furthermore, correlation of isotopes of an element is used to identify and reject the data points that, for example, do not belong to the species of interest. The measurements were conducted using IR femtosecond laser irradiation focused on the sample surface to a spot size of ~12 μm. Material removal was conducted for a predefined number of laser shots, and time-of-flight mass spectra were recorded for each of the ablated layers. Measurements were conducted on NIST SRM 986 Ni isotope standard, trevorite mineral, and micrometer-sized inclusions embedded in aragonite. Our measurements demonstrate that element isotope ratios can be measured with accuracies and precision at the permille level, exemplified by the analysis of B, Mg, and Ni element isotopes. The method applied will be used for in situ investigation of samples on planetary surfaces, for accurate quantification of element fractionation induced by, for example, past or present life or by geochemical processes.

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For the last four decades space exploration missions have searched for molecular life on planetary surfaces beyond Earth. Often pyrolysis gas chromatography mass spectrometry has been used as payload on such space exploration missions. These instruments have relatively low detection sensitivity and their measurements are often undermined by the presence of chloride salts and minerals. Currently, ocean worlds in the outer Solar System, such as the icy moons Europa and Enceladus, represent potentially habitable environments and are therefore prime targets for the search for biosignatures. For future space exploration missions, novel measurement concepts, capable of detecting low concentrations of biomolecules with significantly improved sensitivity and specificity are required. Here we report on a novel analytical technique for the detection of extremely low concentrations of amino acids using ORIGIN, a compact and lightweight laser desorption ionization – mass spectrometer designed and developed for in situ space exploration missions. The identified unique mass fragmentation patterns of amino acids coupled to a multi-position laser scan, allows for a robust identification and quantification of amino acids. With a detection limit of a few fmol mm−2, and the possibility for sub-fmol detection sensitivity, this measurement technique excels current space exploration systems by three orders of magnitude. Moreover, our detection method is not affected by chemical alterations through surface minerals and/or salts, such as NaCl that is expected to be present at the percent level on ocean worlds. Our results demonstrate that ORIGIN is a promising instrument for the detection of signatures of life and ready for upcoming space missions, such as the Europa Lander.@en

Rationale: Laser ablation combined with mass spectrometry forms a promising tool for chemical depth profiling of solids. At irradiations near the ablation threshold, high depth resolutions are achieved. However, at these conditions, a large fraction of ablated species is neutral and therefore invisible to the instrument. To compensate for this effect, an additional ionization step can be introduced. Methods: Double-pulse laser ablation is frequently used in material sciences to produce shallow craters. We apply double-pulse UV femtosecond (fs) Laser Ablation Ionization Mass Spectrometry to investigate the depth profiling performance. The first pulse energy is set to gentle ablation conditions, whereas the second pulse is applied at a delay and a pulse energy promoting the highest possible ion yield. Results: The experiments were performed on a Cr/Ni multi-layered standard. For a mean ablation rate of ~3 nm/pulse (~72 nJ/pulse), a delay of ~73 ps provided optimal results. By further increasing the energy of the second pulse (5–30% higher with respect to the first pulse) an enhancement of up to 15 times the single pulse intensity was achieved. These conditions resulted in mean depth resolutions of ~37 and ~30 nm for the Cr and Ni layers, respectively. Conclusions: It is demonstrated on the thin-film standard that the double-pulse excitation scheme substantially enhances the chemical depth profiling resolution of LIMS with respect to the single-pulse scheme. The post-ionization allows for extraordinarily low ablation rates and for quantitative and stoichiometric analysis of nm-thick films/coatings.

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