Knowledge-based probabilistic representations of branching ratios in chemical networks

AbstractWe present the use of Nested Dirichlet distributions to represent uncertain branching ratios in chemical networks. The interest is twofold: (1) to preserve the structure of experimental data by imposing sum-to-one representations; and (2) to be able to introduce totally unknown subsets of branching ratios (missing data). These points are central to sound uncertainty propagation and sensitivity analysis in complex chemical networks

Characterization of aromaticity in analogues of titan's atmospheric aerosols with two-step laser desorption ionization mass spectrometry

The role of polycyclic aromatic hydrocarbons (PAH) and Nitrogen containing PAH (PANH) as intermediates of aerosol production in the atmosphere of Titan has been a subject of controversy for a long time. An analysis of the atmospheric emission band observed by the Visible and Infrared Mapping Spectrometer (VIMS) at 3.28 micrometer suggests the presence of neutral polycyclic aromatic species in the upper atmosphere of Titan. These molecules are seen as the counter part of negative and positive aromatics ions suspected by the Plasma Spectrometer onboard the Cassini spacecraft, but the low resolution of the instrument hinders any molecular speciation. In this work we investigate the specific aromatic content of Titan's atmospheric aerosols through laboratory simulations. We report here the selective detection of aromatic compounds in tholins, Titan's aerosol analogues, produced with a capacitively coupled plasma in a N2:CH4 95:5 gas mixture. For this purpose, Two-Step Laser Desorption Ionization Time-of-Flight Mass Spectrometry (L2DI-TOF-MS) technique is used to analyze the so produced analogues. This analytical technique is based on the ionization of molecules by Resonance Enhanced Multi-Photon Ionization (REMPI) using a {\lambda}=248 nm wavelength laser which is selective for aromatic species. This allows for the selective identification of compounds having at least one aromatic ring. Our experiments show that tholins contain a trace amount of small PAHs with one to three aromatic rings. Nitrogen containing PAHs (PANHs) are also detected as constituents of tholins. Molecules relevant to astrobiology are detected as is the case of the substituted DNA base adenine

Nitrogen isotopic fractionation during abiotic synthesis of organic solid particles

The formation of organic compounds is generally assumed to result from abiotic processes in the Solar System, with the exception of biogenic organics on Earth. Nitrogen-bearing organics are of particular interest, notably for prebiotic perspectives but also for overall comprehension of organic formation in the young solar system and in planetary atmospheres. We have investigated abiotic synthesis of organics upon plasma discharge, with special attention to N isotope fractionation. Organic aerosols were synthesized from N2-CH4 and N2-CO gaseous mixtures using low-pressure plasma discharge experiments, aimed at simulating chemistry occurring in Titan s atmosphere and in the protosolar nebula, respectively. Nitrogen is efficiently incorporated into the synthesized solids, independently of the oxidation degree, of the N2 content of the starting gas mixture, and of the nitrogen speciation in the aerosols. The aerosols are depleted in 15N by 15-25 permil relative to the initial N2 gas, whatever the experimental setup is. Such an isotopic fractionation is attributed to mass-dependent kinetic effect(s). Nitrogen isotope fractionation upon electric discharge cannot account for the large N isotope variations observed among solar system objects and reservoirs. Extreme N isotope signatures in the solar system are more likely the result of self-shielding during N2 photodissociation, exotic effect during photodissociation of N2 and/or low temperature ion-molecule isotope exchange. Kinetic N isotope fractionation may play a significant role in the Titan s atmosphere. We also suggest that the low delta15N values of Archaean organic matter are partly the result of abiotic synthesis of organics that occurred at that time

Simulating Titan's upper atmosphere and its photochemistry in the vacuum ultra-violet (VUV)

International audienceTitan, the largest moon of Saturn, has a dense atmosphere whose upper layers are mainly composed of methane (CH4) and molecular nitrogen (N2). The Cassini mission revealed that the interaction between those molecules and the solar VUV radiation, as well as the electrons from Saturn’s magnetosphere, leads to a complex chemistry above an altitude of 800km.Cassini instruments such as INMS or CAPS revealed that this naturally ionized environment contains heavy organic molecules like benzene (C6H6) even at altitudes higher than 900 k

Interaction dust-plasma in Titan's ionosphere: feedbacks on the gas phase composition

Titan's organic aerosols are formed in the ionosphere, a layer ionized by solar VUV photons and energetic particles from the magnetosphere of Saturn, forming a natural N2-CH4-H2 plasma. Previous works showed some chemical evolution processes: VUV photons slightly alter the aerosols nitrile bands, hydrogen atoms tend to hydrogenate their surface and carbon-containing species participate to the growth of the aerosols. This work investigates the effect of the other plasma species, namely the N2-H2 derived ions, radicals and excited states. Industrial plasmas often use N2-H2 discharges to form ammonia-based fertilizers, for metal nitriding, and to erode organic surfaces. Consequently, these are likely to affect Titan's organic aerosols. We therefore developed the THETIS experiment to study the interactions between analogues of Titan's aerosols (tholins) and the erosive N2-H2 plasma species found in Titan's ionosphere. Following a first paper on the evolution of the solid phase by Scanning Electron Microscopy and IR transmission spectroscopy (Chatain et al., Icarus, 2020), this paper focuses on evolution of the gas phase composition, by neutral and ion mass spectrometry. Newly formed HCN, NH3-CN and C2N2 are extracted from the tholins as well as some other carbon-containing species and their derived ions. On the other hand, the production of ammonia strongly decreases, probably because the H, NH and N radicals are rather used for the production of HCN at the surface of tholins. Heterogeneous processes are suggested: chemical processes induced by radicals at the surface would modify and weaken the tholin structure, while ion sputtering would desorb small molecules and highly unsaturated ions. The effect of plasma erosion on aerosols in Titan's ionosphere could therefore lead to the formation of CN bonds in the aerosol structure and the production of HCN or R-CN species in the gas phase.Comment: This paper has been accepted in Icarus (February 2023). The current version in arXiv is the submitted versio

Chemistry under EUV Irradiation of H2_2-CO-N2_2 Gas Mixtures: Implications for Photochemistry in the Outer CSE of Evolved Stars

{CircumStellar Envelopes (CSEs) of stars are complex chemical objects for which theoretical models encounter difficulties in elaborating a comprehensive overview of the occurring chemical processes. Along with photodissociation, ion-neutral reactions and dissociative recombination might play an important role in controlling molecular growth in outer CSEs. The aim of this work is to provide experimental insights into pathways of photochemistry-driven molecular growth within outer CSEs to draw a more complete picture of the chemical processes occurring within these molecule-rich environments. A simplified CSE environment was therefore reproduced in the laboratory through gas-phase experiments exposing relevant gas mixtures to an Extreme UltraViolet (EUV) photon source. This photochemical reactor should ultimately allow us to investigate chemical processes and their resulting products occurring under conditions akin to outer CSEs. We used a recently developed EUV lamp coupled to the APSIS photochemical cell to irradiate CSE relevant gas mixtures of H$_2$, CO and N$_2$, at one wavelength, 73.6 nm. The detection and identification of chemical species in the photochemical reactor was achieved through in-situ mass spectrometry analysis of neutral and cationic molecules. We find that exposing CO-N$_2$-H$_2$ gas mixtures to EUV photons at 73.6 nm induces photochemical reactions that yield the formation of complex, neutral and ionic species. Our work shows that N$_2$H$^+$ can be formed through photochemistry along with highly oxygenated ion molecules like HCO$^+$ in CSE environments. We also observe neutral N-rich organic species including triazole and aromatic molecules. These results confirm the suitability of our experimental setting to investigate photochemical reactions and provide fundamental insights into the mechanisms of molecular growth in the outer CSEs

Characterization of a DC glow discharge in N2-H2 with electrical measurements and neutral and ion mass spectrometry

The addition of small amounts of H2 were investigated in a DC glow discharge in N2, at low pressure (~1 mbar) and low power (0.05 to 0.2 W.cm-3). We quantified the electric field, the electron density, the ammonia production and the formation of positive ions for amounts of H2 varying between 0 and 5%, pressure values between 0.5 and 4 mbar, and currents between 10 and 40 mA. The addition of less than 1% H2 has a strong effect on the N2 plasma discharges. Hydrogen quenches the (higher) vibrational levels of N2 and some of its highly energetic metastable states. This leads to the increase of the discharge electric field and consequently of the average electron energy. As a result, higher quantities of radical and excited species are suspected to be produced. The addition of hydrogen also leads to the formation of new species. In particular, ammonia and hydrogen-bearing ions have been observed: N2H+ and NH4+ being the major ones, and also H3+, NH+, NH2+, NH3+, N3H+ and N3H3+. The comparison to a radiofrequency capacitively coupled plasma (RF CCP) discharge in similar experimental conditions shows that both discharges led to similar observations. The study of N2-H2 discharges in the laboratory in the adequate ionization conditions then gives some insights on which plasma species made of nitrogen and hydrogen could be present in the ionosphere of Titan. Here, we identified some protonated ions, which are reactive species that could participate to the erosion of organic aerosols on Titan.Comment: Paper accepted in Plasma Sources Science and Technology in March 2023. The current version on arXiv is the submitted versio

Gaseous chemistry for a Titan's atmospheric plasma experimental simulation

We present the first study of gaseous composition monitoring for the PAMPRE experiment, which simulates Titan's atmospheric chemistry by radio-frequency N 2-CH 4 plasma. Methane consumption is quantified for various N 2-CH 4 gas mixtures. Moreover in situ mass spectrometry (MS) and ex-situ gas chromatography coupled with mass spectrometry (GC-MS) analyses reveal a large dominance of nitrile species in the gas phase chemistry

N2-H2 capacitively coupled radio-frequency discharges at low pressure: II. Modeling results: The relevance of plasma-surface interaction

In this work, we present the results of simulations carried out for N2-H2 capacitively coupled radio-frequency discharges, running at low pressure (0.3-0.9 mbar), low power (5-20 W), and for amounts of H2 up to 5%. Simulations are performed using a hybrid code that couples a two-dimensional time-dependent fluid module, describing the dynamics of the charged particles in the discharge, to a zero-dimensional kinetic module, that solves the Boltzmann equation and describes the production and destruction of neutral species. The model accounts for the production of several vibrationally and electronic excited states, and contains a detailed surface chemistry that includes recombination processes and the production of NH x molecules. The results obtained highlight the relevance of the interactions between plasma and surface, given the role of the secondary electron emission in the electrical parameters of the discharge and the critical importance of the surface production of ammonia to the neutral and ionic chemistry of the discharge.The Portuguese Foundation sponsored this research for Science and Technology (FCT) in the framework of the Strategic Funding UID/FIS/04650/2019

Seasonal riverine inputs may affect diet and mercury bioaccumulation in Arctic coastal zooplankton

Climate change driven increases in permafrost thaw and terrestrial runoff are expected to facilitate the mobilization and transport of mercury (Hg) from catchment soils to coastal areas in the Arctic, potentially increasing Hg exposure of marine food webs. The main aim of this study was to determine the impacts of seasonal riverine inputs on land-ocean Hg transport, zooplankton diet and Hg bioaccumulation in an Arctic estuary (Adventfjorden, Svalbard). The Adventelva River was a source of dissolved and particulate Hg to Adventfjorden, especially in June and July during the river's main discharge period. Stable isotope and fatty acid analyses suggest that zooplankton diet varied seasonally with diatoms dominating during the spring phytoplankton bloom in May and with increasing contributions of dinoflagellates in the summer months. In addition, there was evidence of increased terrestrial carbon utilization by zooplankton in June and July, when terrestrial particles contributed substantially to the particulate organic matter pool. Total (TotHg) and methyl Hg (MeHg) concentrations in zooplankton increased from April to August related to increased exposure to riverine inputs, and to shifts in zooplankton diet and community structure. Longer and warmer summer seasons will probably increase riverine runoff and thus Hg exposure to Arctic zooplankton.Seasonal riverine inputs may affect diet and mercury bioaccumulation in Arctic coastal zooplanktonpublishedVersio