The first computational model of solid-phase chemistry in cometary nuclear ices is presented. An astrochemical kinetics model, MAGICKAL, is adapted to trace the chemical evolution in multiple layers of cometary ice, over a representative period of 5 Gyr. Physical conditions are chosen appropriate for "cold storage" of the cometary nucleus in the outer Solar System, prior to any active phase. The chemistry is simulated at a selection of static temperatures in the range 5 - 60 K, while the ice is exposed to the interstellar radiation field, inducing a photochemistry in the outer ice layers that produces significant formation of complex organic molecules. A treatment for the chemistry resulting from cosmic-ray bombardment of the ices is also introduced into the model, along with a new formulation for low-temperature photochemistry. Production of simple and complex molecules to depth on the order of 10~m or more is achieved, with local fractional abundances comparable to observed values in many cases. The production of substantial amounts of O$_2$ (and H$_2$O$_2$) is found, suggesting that long-term processing by high-energy cosmic rays of cometary ices in situ, over a period on the order of 1 Gyr, may be sufficient to explain the large observed abundances of O$_2$, if the overall loss of material from the comet is limited to a depth on the order of 10 m. Entry into the inner solar system could produce a further enhancement in the molecular content of the nuclear ices that may be quantifiable using this modeling approach.
Comets provide unique information about the physical and chemical properties of the environment in which the Solar system was formed. Understanding how cometary dust and ice evolve under the effect of sunlight is essential for constraining nuclear structure and triggering mechanism of comet activity. In this paper, we first study rotational disruption of dust grains lifted by outgassing from comet nuclei by radiative torques (RATs). We find that composite grains could be rapidly disrupted into small fragments by the Radiative Torque Disruption (RATD) mechanism. We then study rotational desorpt…
The gas-driven dust activity of comets is still an unresolved question in cometary science. In the past, it was believed that comets are dirty snowballs and that the dust is ejected when the ice retreats. However, thanks to the various space missions to comets, it has become evident that comets have a much higher dust-to-ice ratio than previously thought and that most of the dust mass is ejected in large particles. Here we report on new comet-simulation experiments dedicated to the study of the ejection of dust aggregates caused by the sublimation of solid water ice. We find that dust ejection…
[Abridged] The detection of abundant O$_{2}$ ice at 1-10% with respect to H$_{2}$O ice in the comae of comets 1P/Halley and 67P/Churyumov-Gerasimenko motivated attempts to explain the origin of the high O$_{2}$ ice abundance. Recent chemical modelling of the outer, colder regions of a protoplanetary disk midplane has shown production of O$_{2}$ ice at the same abundance as that measured in the comet. An updated chemical kinetics code is utilised here to evolve chemistry under pre-Solar nebula midplane conditions. Four different chemical starting conditions, and the effects of various chemical …
Context. Cometary dust particles are subjected to various forces after being lifted off the nucleus. These forces define the dynamics of dust, trajectories, alignment, and fragmentation, which, in turn, have a significant effect on the particle distribution in the coma. Aims. We develop a numerical thermophysical model that is applicable to icy cometary dust to study the forces attributed to the sublimation of ice. Methods. We extended the recently introduced synoptic model for ice-free dust particles to ice-containing dust. We introduced an additional source term to the energy balance equatio…
Comets are small bodies thought to contain the most pristine material in the solar system. However, since their formation 4.5 Gy ago, they have been altered by different processes. While not exposed to much electromagnetic radiation, they experience intense particle radiation. Galactic cosmic rays and solar energetic particles have a broad spectrum of energies and interact with the cometary surface and subsurface; they are the main source of space weathering for a comet in the Kuiper Belt or in the Oort cloud; and also affect the ice prior to the comet agglomeration. While low energy particles…
To date, at least three comets -- 2I/Borisov, C/2016 R2 (PanSTARRS), and C/2009 P1 (Garradd) -- have been observed to have unusually high CO concentrations compared to water. We attempt to explain these observations by modeling the effect of drifting solid (ice and dust) material on the ice compositions in protoplanetary disks. We find that, independent of the exact disk model parameters, we always obtain a region of enhanced ice-phase CO/H2O that spreads out in radius over time. The inner edge of this feature coincides with the CO snowline. Almost every model achieves at least CO/H2O of unity…
In situ research on cometary chemistry began when measurements from the Giotto mission at comet 1P/Halley revealed the presence of complex organics in the coma. New telescopes and space missions have provided detailed remote and in situ measurements of the composition of cometary volatiles. Recently, the Rosetta mission to comet 67P/Churyumov-Gerasimenko more than doubled the number of parent species and the number of isotopic ratios known in comets. 39 of the 66 parent species have also been detected in pre- and proto-stellar clouds, making the similarities of cometary ices with pre-stellar m…
The composition of cometary ices provides key information on the thermal and chemical properties of the outer parts of the protoplanetary disk where they formed 4.6 Gy ago. This chapter reviews our knowledge of composition of cometary comae based on remote spectroscopy and in-situ investigations techniques. Cometary comae can be dominated by water vapour, CO or CO2. The abundances of several dozen of molecules, with a growing number of complex organics, have been measured in comets. Many species that are not directly sublimating from the nucleus ices have also been observed and traced out into…
Comets likely formed in the outer regions of the protosolar nebula where they incorporated and preserved primitive presolar materials, volatiles resident in the outer disk, and more refractory materials from throughout the disk. The return of a sample of volatiles (i.e., ices and entrained gases), along with other components of a cometary nucleus, will yield numerous major scientific opportunities. We are unaccustomed to thinking of ices through a mineralogical/petrological lens, but at cryogenic temperatures, ices can be regarded as mineral components of rocky material like any other. This is…
Interstellar ice mantles on the surfaces of dust grains are thought to have a bi-layered structure, with a H2O-rich polar layer, covered by a CO-rich apolar layer that probably harbors H2 and other volatiles such as N2. In this work, we explore the chemistry induced by 2 keV electrons and Ly-alpha photons in H2:CO:15N2 ice analogs of the CO-rich layer when exposed to similar fluences to those expected from the cosmic-ray-induced secondary electrons and UV photons during the typical lifetime of dense clouds. Six products were identified upon 2 keV electron irradiation: CO2, C2O (and other carbo…
Periodic comets of different dynamical groups with orbits at 2 - 5 AU still occasionally active. The observed dust activity of such objects can be connected with processes of water ice sublimation (MBCs) or crystallization of amorphous water ice (QHCs) as well as with external causes. No connections of cometary flares with cyclic variations of solar activity indexes were found. But some individual solar flares can affect the brightness of comets. Cometary objects in the main asteroid belt have a lower statistic of flares than comets at orbits like quasi-Hilda objects.
The modelling of molecular excitation and dissociation processes relevant to astrochemistry requires the validation of theories by comparison with data generated from laboratory experimentation. The newly commissioned Ice Chamber for Astrophysics-Astrochemistry (ICA) allows for the study of astrophysical ice analogues and their evolution when subjected to energetic processing, thus simulating the processes and alterations interstellar icy grain mantles and icy outer Solar System bodies undergo. ICA is an ultra-high vacuum compatible chamber containing a series of IR-transparent substrates upon…
(abridged) Data and results from the WISH key program are summarized, designed to provide a legacy data set to address its physics and chemistry. WISH targeted ~80 sources along the two axes of luminosity and evolutionary stage: from low- to high-mass protostars and from pre-stellar cores to protoplanetary disks. Lines of H2O, HDO, OH, CO and [O I] were observed with the HIFI and PACS instruments, complemented by molecules that probe UV, X-ray or grain chemistry. Most of the far-infrared water emission from protostars is found to be compact, originating from warm outflowing and shocked gas at …
Grain surfaces play a central role in the formation and desorption of molecules in space. To form molecules on a grain surface, adsorbed species trapped in binding sites must be mobile and migrate to adjacent sites. Thermal hopping is a popular mechanism for the migration of adsorbed species when the grain surface is warmed up by stellar radiation. However, previous studies disregarded the fact that grains can be spun-up to suprathermal rotation by radiative torques (RATs) during grain heating process. To achieve an accurate model of surface astrochemistry, in this paper, we study the effect o…
Interstellar Simulations Using A Unified Microscopic-Macroscopic Monte Carlo Model with a full Gas-Grain Network including Bulk Diffusion in Ice Mantles
Cometary studies suggest that the organic composition of the early Solar Nebula was rich in complex nitrile species such a CH$_3$CN. Recent ALMA detections in protoplanetary disks suggest that these species may be common during planet and comet formation, but connecting gas phase measurements to cometary abundances first requires constraints on formation chemistry and distributions of these species. We present here the detection of seven spatially resolved transitions of CH$_3$CN in the protoplanetary disk around the T-Tauri star TW Hya. Using a rotational diagram analysis we find a disk-avera…
Cometary surface dust layers built out of millimetre-scale aggregates: dependence of modelled cometary gas production on the layer transport properties
Thanks to Rosetta orbiter's and Philae lander's data our knowledge of cometary nuclei composition has experienced a great advancement. The properties of 67P/CG nucleus are discussed and compared with other comets explored in the past by space missions. Cometary nuclei are made by a collection of ices, minerals, organic matter, and salts resulting in very dark and red-colored surfaces. When far from the Sun, exposed water and carbon dioxide ices are found only in few locations of 67P/CG where the exposure of pristine subsurface layers or the recondensation of volatile species driven by the sola…
The chemistry of planet-forming disks sets the exoplanet atmosphere composition and the prebiotic molecular content. Dust traps are of particular importance as pebble growth and transport are crucial for setting the chemistry where giant planets are forming. The asymmetric Oph~IRS~48 dust trap located at 60 au radius provides a unique laboratory for studying chemistry in pebble-concentrated environments in warm Herbig disks with low gas-to-dust ratios down to 0.01. We use deep ALMA Band~7 line observations to search the IRS~48 disk for H$_2$CO and CH$_3$OH line emission, the first steps of com…
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 rep…
The Formation of Uranus and Neptune in Solid-Rich Feeding Zones: Connecting Chemistry and Dynamics
行星形成的核心吸积理论至少有两个基本问题来解释天王星和海王星的起源：（1）跨土星太阳星云的动力学时间很长，核心的增长可能需要超过1500万年，（2）当核心达到10个地球质量时，失控的气体吸积开始发生，这就需要在冰巨人核心达到临界质量时突然停止气体吸积。这两个问题都可以通过允许冰巨星在富含固体的供给区形成后向外迁移来解决，这些供给区的星子表面密度远高于最小质量的太阳星云。我们使用Nice模型（Gomes et al. 2005; Morbidelli et al. 2005; Tsiganis et al. 2005）的初始半长轴分布，对Dodson-Robinson et al.（2009）的富固体盘中天王星和海王星的形成进行了新的模拟，其中一个冰巨星在12 AU形成，另一个在15 AU形成。最里面的冰巨星在380万~ 400万年后达到现在的质量，最外面的冰巨星在530万~ 600万年后达到现在的质量，与以前的一维模拟相比，时间缩短了很多（例如Pollack et al. 1996）。核心质量保持亚临界状态，消除了突然停止气体吸积的需要。我们计算的碳质量分数为22%，与Podolak等人（1995）和Marley等人（1995）的冰巨星内部模型非常一致。基于形成冰巨星的微行星含有>10%质量分数的甲烷冰的要求，我们可以拒绝任何最初将天王星和海王星置于土星轨道内的太阳系形成模型。我们…
Sulfur is the tenth most abundant element in the universe and is known to play a significant role in biological systems. Accordingly, in recent years there has been increased interest in the role of sulfur in astrochemical reactions and planetary geology and geochemistry. Among the many avenues of research currently being explored is the laboratory processing of astrophysical ice analogues. Such research involves the synthesis of an ice of specific morphology and chemical composition at temperatures and pressures relevant to a selected astrophysical setting (such as the interstellar medium or …
Observations have revealed that the elemental abundances of carbon and oxygen in the warm molecular layers of some protoplanetary disks are depleted compared to those is the interstellar medium by a factor of ~10-100. Meanwhile, little is known about nitrogen. To investigate the time evolution of nitrogen, carbon, and oxygen elemental abundances in disks, we develop a one-dimensional model that incorporates dust settling, turbulent diffusion of dust and ices, as well as gas-ice chemistry including the chemistry driven by stellar UV/X-rays and the galactic cosmic rays. We find that gaseous CO i…
C-H-N-O system is central for organic chemistry and biochemistry, and plays a major role in planetary science (dominating the composition of "ice giants" Uranus and Neptune). The inexhaustible chemical diversity of this system at normal conditions explains it as the basis of all known life, but the chemistry of this system at high pressures and temperatures of planetary interiors is poorly known. Using ab initio evolutionary algorithm USPEX, we performed an extensive study of the phase diagram of the C-H-N-O system at pressures of 50, 200, and 400 GPa and temperatures up to 3000 K. Eight novel…
In cold and shielded environments, molecules freeze out on dust grain surfaces to form ices such as H2O, CO, CO2, CH4, CH3OH, and NH3. In protoplanetary disks, the exact radial and vertical ice extension depend on disk mass, geometry, and stellar UV irradiation. The goal of this work is to present a computationally efficient method to compute ice and bare-grain opacities in protoplanetary disk models consistently with the chemistry and to investigate the effect of ice opacities on the physico-chemical state and optical appearance of the disk. A matrix of Mie efficiencies is pre-calculated for …
We develop a simple iterative scheme to include vertical turbulent mixing and diffusion in ProDiMo thermo-chemical models for protoplanetary discs. The models are carefully checked for convergence toward the time-independent solution of the reaction-diffusion equations, as e.g. used in exoplanet atmosphere models. A series of five T Tauri disc models is presented where we vary the mixing parameter α mix from 0 to 0.01 and take into account (a) the radiative transfer feedback of the opacities of icy grains that are mixed upward and (b) the feedback of the changing molecular abundances on the ga…
