|#1 – BREAKTHROUGHS in CARBON CHEMISTRY in CIRCUMSTELLAR ENVELOPES (CSEs)
Breakthroughs in our current understanding on the formation of carbonaceous dust and complex molecules in the circumstellar envelopes (CSEs) of AGB stars and the interstellar medium (ISM).
Production and analysis of carbon dust seeds in conditions resembling those in the dust formation zones of CSEs contrasting to all previous experiments in the field.
|Innovative experimental methodology
1 – Production of carbon dust seeds at the Stardust Machine using exclusively gas-phase carbon atoms and molecular hydrogen in a ratio close to that in the atmospheres of AGB stars under ultra-high vacuum (UHV) conditions.
2 – Expansion of the previous study to investigate the interaction of atomic carbon and diatomic carbon with acetylene.
3 – First use of the sputtering gas aggregation source (SGAS) in Laboratory Astrophysics to generate small clusters of nanometre-sized particles by gas-phase aggregation of individual atoms in a weakly ionized environment, thus resembling what happens in the dust formation zones of CSEs.
4 – Full experimental analysis: atomic force microscopy (AFM), scanning tunnel microscopy (STM), transmission electron microscopy (TEM), optical emission spectroscopy (OES), infrared spectroscopy in transmission geometry and quadrupole mass spectrometry (QMS) at the Stardust Machine. Ex-situ laser desorption ionization/mass spectrometry (LDI-MS) in the AROMA machine that resembles the reactions on the surfaces of dust grains.
1) From experiment 1. Efficient production of carbonaceous nanometre-sized grains, nanometer-sized small amorphous carbon clusters, acetylene (C2H2), along with fragments of ethylene (C2H4), ethane (C2H6) and larger aliphatic molecules, saturated aliphatic species and marginal detection of aromatic species (benzene, small PAHs like naphthalene) and no fullerenes. We reproduce the abundances of the acetylene and ethylene found in CSEs around AGB stars.
2) From experiment 2. Production of a non-negligible amount of pure and hydrogenated carbon clusters as well as aromatics with aliphatic substitutions, both being a direct consequence of the addition of atomic carbon
Our experiments, that closely resemble the chemistry involved in the CSEs, do not favour the formation of aromatic species (PAHs and fullerenes), which can account for up to 18% of the total carbon species in the interstellar medium. We also show that aromatics with aliphatic substitutions as well as pure and hydrogenated carbon clusters can be produced as a direct consequence of the addition of atomic carbon.
1) SGAS, a technique not previously used in laboratory astrophysics, can be a very valuable tool to gain information on the chemistry operating in CSEs and the interstellar medium.
2) PAHs might not be efficiently formed during gas-phase growth in CSEs.
3) New theoretical plausible scenario: Thermal processing of aliphatic species deposited on dust grains in CSEs could lead to the formation of larger molecules or aromatic species. Such a temperature rise happens in later stages of stellar evolution (protoplanetary nebula PPNe) when the star emits UV radiation that leads to photo-processing of the carbon dust. Indeed, aromatic infrared bands, the signature for PAHs, are not convincingly detected in AGBs, but are observed at these later stages.
4) Unveiling of chemical routes: these results could unveil chemical routes leading to the formation of acetylene-based molecular species in the external layers of AGB stars and in PPNe, and to foster the search for alkyl-substituted aromatics in these environments.
– Prevalence of non-aromatic carbonaceous molecules in the inner regions of circumstellar envelopes (L. Martínez et al., Nature Astronomy, volume 4, pages 97–105, 2020), DOI link. EPMC link.
– A new take on circumstellar carbon chemistry (M. Gatchell, News and Views, Nature Astronomy, volume 4, pages 21 – 22, 2020), share link).
– The Chemistry of Cosmic Dust Analogs from C, C2, and C2H2 in C-rich Circumstellar Envelopes (G. Santoro et al., The Astrophysical Journal, volume 895, number 2, 2020). DOI link. EPMC link.
|Discovery of molecular species in IRC+10216
|Methyl silane (CH3SiH3) and silyl cyanide (SiH3CN, first time in Space)
|We propose a formation mechanism through catalytic reactions on the surface of dust grains by hydrogenation of silicon-carbon species in the inner dust formation zone
|Formation of SiC dust in C-rich AGBs
|SiC2, CS, SiO and SiS gas-phase precursors of dust
|Decline in the abundances of these molecular species with increasing density in the envelopes of C-rich AGB stars. Important constraints for Stardust experiments on SiC dust formation.
|Formation of dust in O-rich AGBs
|SiO and SO gas-phase precursors of dust
|Decline in the abundances of these molecular species with increasing density in the envelopes of O-rich AGB stars
|Discovery of molecular species in the Interstellar Medium
|7 molecules, including one protonated form and isotopologs (2 of them, first time in Space)
|See dedicated descriptions below (under construction)
NANOCOSMOS has performed several key observations of the circumnuclear envelopes -CSEs- of AGB stars with the IRAM 30m radio telescope and the ALMA interferometer. These observations are mandatory to foster the study of the gas-phase precursors of dust in these envelopes. We have made fruitful efforts in the study of the Si-C chemistry in these objects.
NANOCOSMOS has discovered methyl silane, CH3SiH3 and silyl cyanide (SiH3CN) in the envelope of the C-rich AGB star IRC +10216. We suggest that both are formed in the inner zones of the circumstellar envelope through catalytic reactions on the surface of dust grains by hydrogenation of silicon-carbon species.
We have also performed two molecular surveys with the IRAM facility, one to study the envelopes of 25 C-rich AGB stars to search for emission lines of SiC2, SiC, Si2C, CS, SiO and SiS and another one with a sample of 30 O-rich AGB stars to investigate the potential role of SiO, CS, SiS, SO, and SO2 in the formation of dust in these environments.
Our results show strong evidences that the observed decline in the molecular abundances of these species with increasing density in the envelopes are due to their incorporation to the solid phase. Furthermore, we establish that SiC2, CS, SiO and SiS (tentatively) are very likely gas-precursors of SiC dust in C-rich envelopes of AGB stars and SiO and SO (tentatively) in O-rich AGB stars.
Finally, the team has detected 7 molecules in the Interstellar Medium, some of them of key importance to constrain chemical models. These are the c-C3D isotopologs, the metastable and polar isomer isocyanogen (CNCN), the isocyanate radical NCO, the thioformyl radical (HCS) and its metastable isomer HSC, all of them in the dark cold cloud core L483, which contains a low-mass protostar. We have also detected ethyl formate (CH3CH2OCOH) and NS+ in the young protostellar system Barnard 1b with ALMA and IRAM respectively.
The Nanocosmos team published in October 21, 2019, at Nature Astronomy (available free at Europe PubMed Central), the results of a set of laboratory experiments showing that gas-phase chemistry, under conditions similar to those of a red giant star environment, can produce very efficiently small amorphous carbon grains and carbon chains similar to those found in oil.
Stardust, an ultra-high vacuum machine built in the ERC Nanocosmos project (a Synergy project funded by the European Research Council), was specifically conceived to simulate, with a high level of control, the complex conditions of stardust formation and processing in the environment of evolved stars. In addition, the AROMA setup was built to analyse the molecular content of the samples synthesized by Stardust.
In the words of José Ángel Martín-Gago (Institute of Materials Science of Madrid, ICMM-CSIC, Spain), responsible for the Stardust instrument, “Mimicking the conditions of the envelope of an evolved star, laboratory experiments allow scientists to follow, step by step, the formation process of dust grains, from atoms to simple molecules and their growth to more complex clusters of molecules.”
For José Cernicharo (Institute of Fundamental Physics, IFF-CSIC, Spain), lead co-investigator of the project together with Martín-Gago and Christine Joblin (Institut de Recherche en Astrophysique et Planétologie, IRAP-CNRS, France), “That process is important because those grains of dust, which emerge from the final stages of the evolution of medium-sized stars like our Sun will provide the fundamental pieces needed for the birth of the planets and the main ingredients for the onset of life once injected into the interstellar medium.”
This is why it is essential to develop experiments combining laboratory astrophysics, surface science and astronomical observations to unveil the chemical routes that operate in the inner layers of the envelope of evolved stars.
The results obtained show the formation of amorphous carbon nanograins and aliphatic carbon clusters with traces of aromatic species and no fullerenes. This shows that the latter species cannot form effectively by gas-phase condensation at these temperatures in the zone of the evolved star where the dust is formed, a region that extends up to a few stellar radii.
Carbon dust analogues were produced in Stardust and analysed with several characterization techniques including Scanning Tunneling Microscopy and mass spectrometry with the AROMA setup. To produce them only gas carbon atoms and molecular hydrogen were used in a ratio close to that in the atmospheres of AGB stars.
The results showed two types of products: amorphous carbonaceous nanograins – the most abundant, considered to be the main component of carbonaceous star dust – and aliphatic carbon groups. But almost no aromatic molecules were found in the analysis.
According to Joblin, “Polycyclic aromatic hydrocarbons (PAHs) are widespread in massive star-forming regions and in carbon-rich protoplanetary and planetary nebulae. Large carbonaceous molecules like buckminsterfullerene C60 have also been detected in some of these environments. But it seems that they need different conditions to be formed”.
One possible pathway could be through thermal processing of aliphatic material on the surface of dust, which could take place as a result of the significant rise in the temperature of nanograins that occurs in highly UV-irradiated environments. Those results give us new insights into the chemistry of carbonaceous stardust seed formation and foster new observations in order to constrain the physical and chemical conditions in the inner shells of the envelops of evolved stars.
About the ERC
The European Research Council, set up by the European Union in 2007, is the premier European funding organisation for excellent frontier research. Every year it selects and funds the very best, creative researchers of any nationality and age to run projects based in Europe. The ERC has three grant schemes for individual principal investigators – Starting Grants, Consolidator Grants, and Advanced Grants – and Synergy Grants for small groups of excellent researchers.
To date, the ERC has funded more than 9,000 top researchers at various stages of their careers, and over 50,000 postdoctoral fellows, PhD students and other staff working in their research teams. The ERC strives to attract top researchers from anywhere in the world to come to Europe.
The ERC is led by an independent governing body, the Scientific Council. The ERC current President is Professor Jean-Pierre Bourguignon. The ERC has an annual budget of €2 billion for the year 2019. The overall ERC budget from 2014 to 2020 is more than €13 billion, as part of the Horizon 2020 programme, for which European Commissioner for Research, Innovation and Science Carlos Moedas is currently responsible.
On Monday 23rd of September, Rémi Bérard (center of the picture) presented his PhD thesis entitled Formation and growth by plasma of laboratory stardust analogues : investigation of the role of the c/o ratio and metals”, that was carried out at the IRAP in the framework of the Nanocosmos projet under the direction of Kremena Makasheva (LAPLACE, right side of the picture) and Christine Joblin (IRAP, on the left).
Dust formation is a fundamental topic in both cold plasma physics and astrophysics. This PhD thesis, carried out at the interface between the two fields, aims to better understand the formation of stardust. The problem is treated experimentally in cold plasmas and discussed in the context of the environment of evolved stars.
We observe the formation of successive generations of dust due to pulsed injection of hexamethyldisiloxane (HMDSO: Si2O(CH3)3) in a capacitively-coupled radiofrequency asymmetric plasma sustained in argon. The used molecular precursor contains potential stardust forming elements, like carbon, oxygen, silicon and hydrogen. Our approach involves different steps: study of the dust formation in the plasma, dust collection, characterization of the dust properties and correlation of the plasma parameters with the dust characteristics. We have thus succeeded to identify optimum conditions for the formation of organosilicon dust with typical size of 50 nm.
A major factor impacting dust formation in evolved stars is the variation of the C/O ratio, which is though to determine two large families of stardust, silicates (C/O < 1) and carbonaceous dust (C/O > 1). To explore this effect, we have enriched the Ar/HMDSO mixture with oxygen aiming at a variation of the C/O ratio in the plasma. Above a certain quantity of oxygen, dust is not formed anymore in the plasma. The abundance of oxygen limits dust formation through inhibition of the dust seeds in the gas phase. Instead, deposition of a silica- like matrix is favored.
The role of metals is studied through sputtering of a silver target during organosilicon dust formation. We have demonstrated the formation of dust with composite structure in this case. Dust contains crystalline silver nanoparticles that attach to the amorphous organosilicon dust during their growth phase. Moreover, the presence of silver leads to a large variety of molecules composed of species containing Ag and/or Si and hydrocarbon species. Those molecules reveal a complex chemistry around three competitive processes at molecular scale: dust formation involving molecules such as SiCH3 or SiOCH3, metallic grains with clusters of Agn and aromatic molecules of large size such as C16H10 and C24H12, whose formation path involves radicals and possibly an organometallic chemistry as revealed by AgC5H6 and AgC13H8. The above results demonstrate the undoubted necessity to tackle stardust formation by taking into account the chemical complexity of these media.
AROMA (Astrochemistry Research of Organics with Molecular Analyzer) is a new analytical experimental set-up developed at IRAP/LCAR (Toulouse, France). The main purpose of AROMA is the study and identification, with micro-scale resolution, of the molecular content of cosmic dust analogues, including stardust analogues produced in the Stardust machine and meteoritic samples. AROMA combines laser desorption/ionization (LDI) techniques with a linear ion trap coupled to an orthogonal time of flight mass spectrometer (LQIT-oTOF).
Outstanding publications on our innovative setup
Molecular content of nascent soot: Family characterization using two-step laser desorption laser ionization mass spectrometry (H. Sabbah, M. Commodo, F. Picca, G. de Falco, P. Minutolo, A. D´Anna and C. Joblin). Proceedings of the Combustion Institute, Volume 38, Issue 1, 2021, Pages 1241-1248.
Impact of Metals on (Star)Dust Chemistry: A Laboratory Astrophysics Approach (R. Bérard, K. Makasheva, K. Demyk, A. Simon, D. Nuñez-Reyes, F. Mastrorocco, H. Sabbah and C. Joblin). Frontiers in Astronomy and Space Sciences, 2021 March 21. IRAP Press Release: Role des metaux dans la chimie des poussieres detoiles
Characterization of large carbonaceous molecules in cosmic dust analogues and meteorites (H. Sabbah, M. Carlos and C. Joblin). Proceedings of the International Astronomical Union, 2019 Apr; 15(Suppl 350): 103–106.
Identification of PAH Isomeric Structure in Cosmic Dust Analogues: the AROMA setup (H. Sabbah, A. Bonnamy, D. Papanastasiou, J. Cernicharo, J.-A. Martín-Gago, and C. Joblin). Astrophysical Journal, 2017 Jul 1; 843(1): 34.
Check our posts on the AROMA set-up