ta2.11 – Europlanet Society

22-EPN3-053: Proton Processing of Phenanthrene Ice Mixtures for Application to Titan’s Lower Atmosphere

April 26, 2024

22-EPN3-053: Proton Processing of Phenanthrene Ice Mixtures for Application to Titan’s Lower Atmosphere

Visit by Alessandra Candian and Annemieke Petrignani (University of Amsterdam, Netherlands) to TA2.11 Atomki Ice Chamber for Astrophysics / Astrochemistry (ICA) (Hungary).
Dates of visit: 4-8 March 2024

Report Summary: During this TNA visit, the three-ring PAH phenanthrene (C₁₄H₁₀), acetonitrile (CH₃CN) and their 1:1 mixture were irradiated using 10 KeV protons. The subsequent products of this processing were then measured using infrared spectroscopy (5000-700 cm-1) and a quadrupole mass spectrometer.

The aim of these experiments was to investigate 1) if energetic processing can modify the structure of solid hydrocarbons and 2) if proton irradiation could trigger the formation of new species. During the visit to Atomki, the team collected infrared spectra of at different proton fluences and then following this, infrared spectra during temperature-programmed desorption (TPD). They also obtained the residues after TPD for ex-situ analysis. The preliminary results show a) the puckering of phenanthrene solid, b) the formation of ethanimine (C₂H₅N) in acetonitrile solid, c) a complex behaviour of the 1:1 mixture, with puckering and formation of new hydrocarbon species.

Full scientific report published by kind permission of Alessandra Candian and Annemieke Petrignani.

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22-EPN3-091: Evolution Under Radiation of Organics Pertaining to Europa

Visit by Alexis Bouquet (Aix-Marseilles University, France) to TA2.11 Atomki Ice Chamber for Astrophysics / Astrochemistry (ICA) (Hungary).
Dates of visit: 19-24 February 2024

Report Summary: Several of the icy moons of Jupiter possess a liquid water ocean under a thick icy crust. In the especially promising case of Europa, a young surface (>100 Myr), and likely recent cryovolcanicactivity (within the last 8 years) imply the presence of ocean material on the surface. Therefore, observations performed by space missions could determine the ocean’s composition, and derive indications on its potential habitability (presence of chemical gradients providing metabolic energy, quantity and composition of available organic matter…). Characterising Europa’s ocean and its possible habitability requires to understand processes that alter organic and inorganic molecules in this environment. These processes include the processing by energetic ions coming from Jupiter’s magnetosphere and hitting the surface.

In this project, Alexis Bouquet visited the Atomki facility to study the effect of sulfur ion bombardment on methanol, a species that could be indicative of key characteristics of the ocean, pure and within an ice matrix. The alteration of the sample was followed using infrared spectroscopy, and the resulting complex organic residues were retrieved for ultra-high resolution mass spectrometry.

Full scientific report published by kind permission of Alexis Bouquet.

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20-EPN2-090 – A Search for Thiols Formation Pathways Under Space-Relevant Conditions

Visit by Zuzana Kaňuchová (Astronomical Institute of the Slovak Academy of Sciences, Slovakia) and Tom Field (Queen’s University Belfast, UK) TA2.11 Atomki Ice Chamber for Astrophysics / Astrochemistry (ICA) (Hungary).
Dates of visit: 27 November – 8 December 2023

Report Summary: Despite being only the tenth most abundant element in space, sulfur is a component of several biomolecules, making it a key subject for astrochemistry studies. Sulfur containing molecules were observed in the solid phase on the surfaces of icy moons and in the icy mantles of interstellar grains. Despite the seemingly ubiquitous detection of sulfur-bearing species in space, the sulfur budget is still puzzling the scientific community. To address this, Zuzana Kaňuchová and Tom Field conducted an exploratory series of irradiation experiments to determine if species with thiol (-SH) groups may be formed in hydrocarbon-rich ices at temperatures relevant to interstellar matter, the surfaces of Solar System icy satellites, and Kuiper Belt objects.

They implanted 200 keV S+ ions in methane (CH4), ethane (C2H6), ethene (C₂H₄), and ethyne (C₂H₂) ices at 20 K and 60 K. Formation (and destruction) of species was monitored via FTIR spectroscopy and quadrupole mass spectrometry. Based on preliminary analysis performed during the TA they decided to conduct one extra (supplementary) experiment to explore the possibility of forming carbon and sulfur-bearing molecules by implanting high-energy carbon (750 keV) ions into hydrogen sulfide (H₂S).
The preliminary analysis does not indicate the formation of thiols in the investigated hydrocarbon ices as a result of high-energy sulfur ions implantation. However, several new absorption bands appeared in the
spectra of all irradiated hydrocarbons, indicating the formation of various alkanes and alkenes. The emergence of a prominent band around ~1600 cm-1 could suggest the presence of carbon in an amorphous form.

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22-EPN3-028 – Energetic Ion Processing of Pyrene Ice

Visit by Alicja Domaracka (CIMAP-CNRS, France) and Anna Bychkovato (Normandie Université, France) TA2.11 Atomki Ice Chamber for Astrophysics / Astrochemistry (ICA) (Hungary).
Dates of visit: 16-20 October 2023

Report Summary: Over the last decades it became clear that we live in a “molecular universe”. Carbon forms the basis of the majority of the molecular species that so far have been identified in space. Although small carbon-based molecules, like CO and CO2, are some of the most abundant molecules in space, only a small fraction of the carbon is expected to be locked up in such species. It was proposed that a large portion of the interstellar carbon, up to 20%, is built in polycyclic aromatic hydrocarbons (PAHs) and fullerenes. There is a clear lack of information about interaction of energetic ions with pyrene in the solid phase.

In January 2022, Alicja Domaracka (CIMAP-CNRS, France) and Anna Bychkovato (Normandie Université) performed irradiations of pure pyrene 20 K by protons and carbon ions at the ATOMKI facility. Within the present TA, they studied pure pyrene ice at 20K irradiated with 6.4 MeV S³⁺, 4 MeV S²⁺, 2,4 MeV C²⁺, 400 KeV He⁺, 800 keV He⁺ and 800 keV H⁺ ion beams, respectively. In particular, we are interested in learning how the pyrene destruction cross sections depend on the projectile parameters (atomic number, energy).

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20-EPN2-070: Formation of Glycine and Alanine Upon Ion Irradiation of Space-Relevant Ices

June 3, 2023

20-EPN2-070: Formation of Glycine and Alanine Upon Ion Irradiation of Space-Relevant Ices

Visit by Alejandra Traspas Muina, Queen Mary University of London (UK), to TA2.11 Atomki Ice Chamber for Astrophysics / Astrochemistry (ICA) (Hungary).
Dates of visit: 20 March – 2 April 2023

Report Summary: The experiments initially proposed aimed to investigate the formation and chemical evolution of both glycine and alanine under space relevant conditions. Following a systematic approach, the TA was divided into three projects carried out by a multidisciplinary group of scientist (chemists, biologists, astrophysicists and engineers): looking at (i) experimental insights into the microphysics of molecule destruction and sputtering of CO₂ exposed to cosmic rays analogues; (ii) the formation of methyl formate and its isomers (glycolaldehyde and acetic acid) through the systematic irradiation of H₂ CO:CO, H₂ CO:CH₄ , and H₂ CO:CH₃ OH ice mixtures with 1 MeV and 200 keV H⁺ ; (iii) and 1 MeV H⁺ irradiation of pure Glycine and Glycine:CH₄ interstellar relevant ice mixtures, exploring the survivability and stability of this amino acid in astrophysical relevant environments.

The three projects were designed with incremental molecular complexity to investigate the chemistry of many precursors of simple amino acids. Moreover, the sub-projects were designed to be connected to other awarded TAs either at ICA or AQUILA (PIs: Ivlev, Ioppolo, and Hopkinson) in a synergic manner. For instance, the work of H₂ CO completes the systematic study on methyl formate and its isomers, started at this Europlanet facility 2 years ago, trying to improve the understanding of the standing dichotomy on the formation of glycolaldehyde, methyl formate, and acetic acid. All these species are detected in space in star-forming regions and are considered prebiotic molecules.

Full scientific report published by kind permission of Alejandra Traspas Muina

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20-EPN-049: The Irradiation of Oxygen-Bearing Ices on Top of Pure Elemental Sulphur Layers

20-EPN-049: The Irradiation of Oxygen-Bearing Ices on Top of Pure Elemental Sulphur Layers (former title: Millimetre-Wave Polarimetry of Space Relevant Ices Exposed to Energetic Ions)

Virtual visit by Olivier Auriacombe, Chalmers University of Technology (Sweden), to TA2.11 Atomki Ice Chamber for Astrophysics / Astrochemistry (ICA) (Hungary).
Dates of visit: 20 June – 4 September 2022

Report Summary: The chemistry of sulphur in icy extra-terrestrial settings such as the dense interstellar medium and the outer Solar System remains poorly constrained. In particular, the chemical routes towards the formation of SO₂ ice (and other volatile sulphur-bearing species) is not completely understood, despite the detection of this species in interstellar icy grain mantles, on the surface of Europa, and on comets. We have therefore explored the possibility of forming SO₂ ice as a result of the irradiation of oxygen-bearing ices (including O₂, CO, CO₂, H₂O, and CH₃OH) deposited on top of pure elemental sulphur layers, both of which are known to exist in the dense interstellar medium and the outer Solar System where radiation chemistry may be engendered by galactic cosmic rays or the solar wind.

Our results demonstrate that SO₂ may indeed be produced after the 1 MeV He⁺ ion irradiation of O₂ and CO₂ ices deposited on top of elemental sulphur, but not as a result of similar irradiations conducted using CO, H₂O, or CH₃OH ices. Other volatile radiation product species incorporating sulphur, such as CS₂, OCS, and H₂SO₄, were also detected in different experiments. Our work should therefore contribute to a better understanding of solid-phase sulphur astrochemistry and the role of elemental sulphur in the formation of volatile sulphur-bearing species in icy extra-terrestrial settings.

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20-EPN2-045: Irradiation Effects of Energetic H+ and S+ Ion Implantation in Salts and Minerals Relevant to the Surface of Europa

20-EPN2-045: Irradiation Effects of Energetic H⁺ and S⁺ Ion Implantation in Salts and Minerals Relevant to the Surface of Europa

Virtual visit by Duncan Mifsud, University of Kent (UK) to TA2.11 Atomki Ice Chamber for Astrophysics / Astrochemistry (ICA) (Hungary).
Dates of visit: 21-29 November 2022 and 18-20 January 2023

Report Summary: The surface of Europa is host to a rich radiation environment, in which ions from the giant Jovian magnetosphere drive physico-chemical transformations of surface ices and minerals. Although a number of previous studies have looked into the irradiation of surface ice analogues in order to better constrain the chemistry occurring on Europa, considerably fewer studies have investigated the radiation chemistry of plausible mineral analogues.

Therefore, in this study, we have irradiated four mineral species (halite, fayalite, epsomite, and berthierine) using 1 MeV H⁺ and 1 MeV S⁺ ions to better understand the dissociation pathways of these minerals and the associated radiolysis products. Our preliminary results have shown that irradiation brings about significant changes in the appearances of the minerals that signify alterations in the structures and chemical compositions. Further infrared, visible, and ultraviolet spectroscopic analyses of retained mineral samples (both irradiated and pristine) are planned for the near future.

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20-EPN-025: Radioresistance of aromatic complex organic molecules

20-EPN-025: Radioresistance of aromatic complex organic molecules (nucleobases)

Virtual visit by Alicja Domaracka and Anna Bychkova, CIMAP-CNRS (France) to TA2.11 Atomki Ice Chamber for Astrophysics / Astrochemistry (ICA) (Hungary).
Dates of visit: 17-28 January 2022

Report Summary: Over the last decades it became clear that we live in a “molecular universe”. Carbon forms the basis of the majority of the molecular species that so far have been identified in space. Although small carbon-based molecules, like CO and CO₂, are some of the most abundant molecules in space, only a small fraction of the carbon is expected to be locked up in such species. It was proposed that a large portion of the interstellar carbon, up to 20%, is built in polycyclic aromatic hydrocarbons (PAHs) and fullerenes. Several laboratory studies were carried out to investigate the effects of vacuum ultraviolet photolysis on PAH:H₂O ices. However, data about interaction energetic ions with PAH ices are very scare.

We therefore studied the radiolysis of the pure pyrene ice and mixed pyrene- water ices at different concentrations at 20 K with 200 keV and 2 MeV H⁺ and 2 MeV C²⁺ beams at Atomki. The preliminary analysis of water-pyrene ices irradiated 200 keV H⁺ (with pyrene concentration from about 5 to 100% of pyrene) indicates that pyrene is more radio-resistant at high concentrations. The results are preliminary and analysis is ongoing.

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20-EPN-084: Converting one amino acid to the other containing sulfur via ion irradiation: Implication to chemical evolution on Europa surface ices

January 6, 2022

20-EPN-084: Converting one amino acid to the other containing sulfur via ion irradiation : Implication to chemical evolution on Europa surface ices

Visit by Rahul Kumar Kushwaha, Physical Research Laboratory, Ahmedabad (India) to TA2.11 Atomki Ice Chamber for Astrophysics / Astrochemistry (ICA) (Hungary).
Dates of visit: 8-19 December 2021

Report Summary: The non-equilibrium chemistry driven by the charged particle and photon irradiation processes are responsible for the rich chemistry on the surfaces of icy satellites. Among the icy satellites of the Jovian and Saturnian planetary systems, a few satellites such as Ganymede, Europa, Dione, Rhea, Callisto and Titan that are embedded in their respective planetary magnetospheres were observed to undergo rich chemical processes due to the bombardment of a wide range of energetic atomic and molecular ions that are present in their planet’s magnetospheres, which processes the icy surfaces of satellites by irradiation and implantation. Magnetospheres also help in bringing new species from one satellite to the other. Especially in the Jupiter system of icy satellites, sulfur transfer from Io to the other satellites is quite likely. The sulfur ions from Io are picked up by the magnetosphere and are accelerated towards the other icy satellites; Europa being the closest neighbour to Io will be implanted with sulfur ions. The Jovian satellites, due to the presence of the Jupiter’s magnetosphere, are subjected to highly energetic S ion irradiation which leads to a range of chemical activity on their surfaces. In this project, we have studied the effect of S ion irradiation on Aspartic acid for a range of energies at two different temperatures (100 K, 20 K), where the 100 K experiments are aimed to mimic the conditions of Europa. The irradiated residue was then analysed using an optical microscope, scanning electron microscope and liquid chromatography mass spectrometry.

Full scientific report published by kind permission of Rahul Kumar Kushwaha

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20-EPN-016: Formation and fate of methyl formate isomers in space

September 29, 2021

20-EPN-016: Formation and fate of methyl formate isomers in space

Virtual visit by Dr Sergio Ioppolo (Queen Mary University of London, UK) to TA2.11 Atomki Ice Chamber for Astrophysics / Astrochemistry (ICA) (Hungary).
Dates of visit: 12 October 2020 – 31 March 2021

Report Summary: All isomers of C₂H₄O₂, i.e. glycolaldehyde (HCOCH₂OH), acetic acid (CH₃COOH) and methyl formate (HCOOCH₃), have been observed abundantly around the Galactic center, in dark clouds, and hot cores of the interstellar medium (ISM), as well as in some minor ice objects of the Solar System. However, their exact gas-grain formation and destruction pathway is still under debate. According to El-Abd et al. (2019), the observed column densities of methyl formate and acetic acid are well-correlated, and are likely simply tracking the relative total gas mass in star forming regions. Methyl formate and glycolaldehyde, however, display a stark dichotomy in their relative column densities. The latter findingsuggests that different formation/destruction routes are at play for the three isomers. To date, there is a strong laboratory evidence for an efficient production of glycolaldehyde, methyl formate, and acetic acid in the ISM (Gerakines et al. 1996; Bennett and Kaiser 2007; Modica et al. 2012).

During the TA 20-EPN-016 at the ion accelerator facility Atomki in Debrecen (Hungary), we have performed a systematic set of experiments using the novel ultrahigh vacuum ICA end station to investigate the formation and destruction pathways of C₂H₄O₂ isomers and a variety of other interstellar complex organic molecules. The experimental campaign revealed to be successful as all the planned experiments were performed. Results aided the design of new potential key experiments that will be included in a future follow-up beamtime bid at the facility.

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20-EPN-005: Cosmic-ray-induced chemistry in pure ices

September 5, 2021

20-EPN-005: Cosmic-ray-induced chemistry in pure ices

Virtual visit by Alexei Ivlev, Max Planck Institute for Extraterrestrial Physics (MPE) (Germany) to TA2.11 Atomki Ice Chamber for Astrophysics / Astrochemistry (ICA) (Hungary).
Dates of visit: 23 February – 05 July 2021

Report Summary: The principal aim of the project was a dedicated study of generic effects induced in pure astrophysical ice analogs due to their bombardment by cosmic rays with energies E in the vicinity of the maximum of electronic stopping power. It is known that the energy of ejected electrons, which are produced in primary ionization events, has a significant dependence on E in this energy range.

Thus, by selecting pairs of beam energies on both sides of the Bragg peak, such that the corresponding stopping-power values are equal, we were able to probe the effect of electron-impact excitations of ice molecules. We selected CO films as the best irradiation target, for which the biggest variety of radiolysis products was expected and the most detailed predictions of chemical models were available.

We found that the first radiolysis products, detected at the astrophysically relevant values of ion fluence, are very different from predictions of chemical models. At the same time, the reaction kinetics shows no statistically significant difference between ion beams of same stopping power. This rules out the importance of electron-impact excitation in radiolysis chemistry of CO, and suggests that this process may generally be negligible compared to the chemistry driven by CR heating (determined by the stopping power value). On the other hand, by comparing the sputtering yields measured for beams of same stopping power, we discovered a significant asymmetry, with the yield at lower energies being up to a factor of two larger that at higher energies.

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20-EPN-043: A Systematic Study of Sulfur Ion Radiolysis of Simple Oxide Ices

20-EPN-043: A Systematic Study of Sulfur Ion Radiolysis of Simple Oxide Ices.

Visit by Zuzana Kanuchova (virtual participation), Astronomical Institute od Slovak Academy of Sciences (Slovakia) and Duncan Mifsud (in-person participation), University of Kent (UK) to TA2.11 Atomki Ice Chamber for Astrophysics / Astrochemistry (ICA) (Hungary).
Dates of visit: 30 November – 4 December 2020 and 25-29 January 2021

Report Summary: We have implanted 290 keV S⁺ ions in a variety of simple oxide ices, including CO, CO₂, H₂O, N₂O, O₂, and CO:N₂O at 20 K, as well as CO₂ and H₂O at 70 K. Our aim was to determine whether such implantations could result in the formation of sulfur-bearing product molecules, particularly SO₂which has been detected at the surfaces of several icy Solar System moons.

The performed experiments suffered from initial setbacks in the form of unexpected and significant sputtering of the astrophysical ice analogues during irradiation. In order to mitigate this sputtering, we made use of two different experimental techinques; (i) via simultaneous deposition and irradiation of the ice analogue in cases where we knew gas phase chemistry to be negligible, and (ii) via creation of a very thick (~3-5 μm) ice and a slow rate of implantation. Once these initial problems were solved, we were able to successfully carry out implantations into the six ices mentioned above.

Our work has indicated that although sulfur-bearing molecules (such as OCS and H₂SO₄ hydrates) may form as a result of such implantations, SO₂ formation was not detected in most experiments, except at high fluence (~1016 ions/cm²) implantations in CO. Such results have important implications for the icy Galilean satellites of Jupiter, suggesting that the SO₂ present there may be formed by endogenic processes at the lunar surfaces.

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20-EPN-032: Radioresistance of aromatic complex organic molecules

20-EPN-032: Radioresistance of aromatic complex organic molecules: nucleobases.

Virtual visit by Hermann Rothard, CIMAP (Caen, F) CNRS (France) to TA2.11 Atomki Ice Chamber for Astrophysics / Astrochemistry (ICA) (Hungary).
Dates of visit: 17 May – 02 July 2021

Report Summary: Complex molecules (including amino acids and nucleobases) can be formed in cold space environments conditions (e.g. dense molecular clouds, outer solar system) by e.g. UV irradiation and ion bombardment of ices containing simple molecules. Consequently, the radiation resistance of such complex molecules in order to determine their survival times in space should be investigated. We therefore studied the radiolysis and radio-resistance of the purine nucleobase (Adenine, two aromatic rings) in solid phase as a function of temperature (20-300 K) with H (0.8 MeV) and He (3.2 MeV) beams at ATOMKI. This first systematic study of the influence of the temperature revealed that Adenine is found to be significantly (of the order of 50%) more radio-resistant at high temperatures. At low temperatures T < 50K, Adenine is more radiosensitive (higher cross sections).

The results are preliminary and analysis is ongoing. Furthermore, we found that the destruction cross sections scales with the electronic stopping stopping following a power law with a stronger than linear dependence.

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