Cosmic Dust Grains Research Articles

Astrochemical effect of the fundamental grain surface processes

Context. Thermal diffusion is one of the basic processes for the mobility and formation of species on cosmic dust grains. The rate of thermal diffusion is determined by the grain surface temperature, a pre-exponential factor, and an activation energy barrier for diffusion. Due to the lack of laboratory measurements on diffusion, prior astrochemical models usually assume that the diffusion pre-exponential factor is the same as that for desorption. This oversimplification may lead to an uncertainty in the model predictions. Recent laboratory measurements have found that the diffusion pre-exponential factor can differ from that for desorption by several orders of magnitude. However, the newly determined pre-exponential factor has not been tested in astrochemical models so far. Aims. We aim to evaluate the effect of the newly experimentally measured diffusion pre-exponential factor on the chemistry under cold molecular cloud conditions. Methods. We ran a set of parameters with different grain temperatures and diffusion barrier energies using the NAUTILUS astro-chemical code and compared the molecular abundance between the models with the abundance obtained using the experimentally determined pre-exponential factor for diffusion and with the abundance obtained using the values commonly adopted in prior models. Results. We found that statistically, more than half of the total gas-phase and grain surface species are not affected by the new pre-exponential factor after a chemical evolution of 105 yr. The most abundant gas-phase CO and grain surface water ice are not affected by the new pre-exponential factor. For the grain surface species that are affected, compared to the commonly adopted value of the pre-exponential factor for diffusion used in the chemical models, they could be either overproduced or underproduced with the lower diffusion pre-factor used in this work. The former case applies to radicals and the species that serve as reactants, while the latter case applies to complex organic molecules (COMs) on the grain and the species that rarely react with other species. Gas-phase species could also be affected due to the desorption of the grain surface species. The abundance of some gas-phase COMs could be varied by over one order of magnitude depending on the adopted grain surface temperature and/or the ratio of diffusion to desorption energy in the model. Key species whose diffusion pre-exponential factor significantly affects the model predictions were also evaluated, and these species include CH3OH, H2CO, and NO. Conclusions. The results presented in this study show that the pre-exponential factor is one of the basic and important parameters in astrochemical models. It strongly affects the chemistry and should be determined carefully. More experiments to determine the diffusion of grain surface species are helpful for constraining their properties.

Linking meteorites to their asteroid parent bodies: The capabilities of dust analyzer instruments during asteroid flybys

AbstractLinking meteorites to their asteroid parent bodies remains an outstanding issue. Space‐based dust characterization using impact ionization mass spectrometry is a proven technique for the compositional analysis of individual cosmic dust grains. Here we investigate the feasibility of determining asteroid compositions via cation mass spectrometric analyses of their dust ejecta clouds during low (7–9 km s−1) velocity spacecraft flybys. At these speeds, the dust grain mass spectra are dominated by easily ionized elements and molecular species. Using known bulk mineral volume abundances, we show that it is feasible to discriminate the common meteorite classes of carbonaceous chondrites, ordinary chondrites, and howardite–eucrite–diogenite achondrites, as well as their subtypes, relying solely on the detection of elements with ionization efficiencies of ≤700 or ≤800 kJ mol−1, applicable to low (~7 km s−1) and intermediate (~9 km s−1) flyby speed scenarios, respectively. Including the detection of water ion groups enables greater discrimination between certain meteorite types, and flyby speeds ≥10 km s−1 enhance the diagnostic capabilities of this technique still further. Although additional terrestrial calibration is required, this technique may allow more unequivocal asteroid‐meteorite connections to be determined by spacecraft flybys, emphasizing the utility of dust instruments on future asteroid missions.

New measurement of the diffusion of carbon dioxide on non-porous amorphous solid water

The diffusion of molecules on interstellar grain surfaces is one of the most important driving forces for the molecular complexity in the interstellar medium. Due to the lack of laboratory measurements, astrochemical modeling of grain surface processes usually assumes a constant ratio between the diffusion energy barrier and the desorption energy. This over-simplification inevitably causes large uncertainty in model predictions. We present a new measurement of the diffusion of CO 2 molecules on the surface of non-porous amorphous solid water (np-ASW), an analog of the ice mantle that covers cosmic dust grains. A small coverage of CO 2 was deposited onto an np-ASW surface at 40 K, the subsequent warming of the ice activated the diffusion of CO 2 molecules, and a transition from isolated CO 2 to CO 2 clusters was seen in the infrared spectra. To obtain the diffusion energy barrier and pre-exponential factor simultaneously, a set of isothermal experiments were carried out. The values for the diffusion energy barrier and pre-exponential factor were found to be 1300 ± 110 K and 10 7.6 ± 0.8 s − 1 . A comparison with prior laboratory measurements on diffusion is discussed.

Investigation of Dust Grains by Optical Tweezers for Space Applications

Cosmic dust plays a dominant role in the universe, especially in the formation of stars and planetary systems. Furthermore, the surface of cosmic dust grains is the benchwork where molecular hydrogen and simple organic compounds are formed. We manipulate individual dust particles in a water solution by contactless and noninvasive techniques such as standard optical and Raman tweezers, to characterize their response to mechanical effects of light (optical forces and torques) and to determine their mineral compositions. Moreover, we show accurate optical force calculations in the T-matrix formalism highlighting the key role of composition and complex morphology in the optical trapping of cosmic dust particles. This opens perspectives for future applications of optical tweezers in curation facilities for sample-return missions or in extraterrestrial environments.

Radical Recombination during the Phase Transition of Interstellar CO Ice

Complex organic molecules (COMs) can be produced efficiently in ice mixtures that simulate the ice mantle on cosmic dust grains, according to prior experimental studies. However, the mechanism that brings the reactive species together in the ice has been debated. Thermal diffusion, which is widely regarded as the main mechanism to bring reactants together, is inefficient at a typical dense cloud temperature of 10 K. A recent experimental study found that the transition of a thin CO ice film from the amorphous to crystalline phase happens at about 10 K. When a small fraction of CO2 was mixed with CO, the CO2 molecules can separate and form clusters during CO phase transition. It was further proposed that the separation of minor species in the CO ice during phase transition may be an important mechanism to form interstellar COMs without the need for thermal diffusion. In this study, we try to verify this new mechanism through laboratory experiments. An ice mixture of CH3OH and CO, which is an analog of the outer layer of the ice mantle on cosmic dust grains, was exposed to UV irradiation to produce radicals such as HCO and CH2OH, whose concentration was monitored during the subsequent warm-up of the ice. We find clear evidence that during the CO phase transition, most of the radicals recombine to form other molecular species, therefore supporting the recently proposed mechanism of COM formation via CO phase transition.

Formation of Complex Organic and Prebiotic Molecules in H2O:NH3:CO2 Ices at Temperatures Relevant to Hot Cores, Protostellar Envelopes, and Planet-Forming Disks.

Photochemistry in H2O:NH3:CO2 cosmic ice analogues was studied at temperatures of 75, 120, and 150 K, relevant to hot cores and warmer regions in protostellar envelopes and planet-forming disks. A combination of two triggers of surface chemistry in cosmic ice analogues, heat and UV irradiation, compared to using either just heat or UV irradiation, leads to a larger variety and an increased production of complex organic molecules, including potential precursors of prebiotic molecules. In addition to complex organic molecules detected in previous studies of H2O:NH3:CO2 ices, ammonium carbamate, carbamic acid, ammonium formate and formamide, we detected acetaldehyde, urea, and, tentatively, glycine, the simplest amino acid. Water ice hampers reactions at low temperature (75 K) but allows the parent molecules, CO2 and NH3, to stay in the solid state and react at higher temperatures (120 and 150 K, above their desorption temperatures). The experiments were performed on the surface of KBr substrates and amorphous silicate grains, analogs of cosmic silicate dust. The production of complex molecules on the silicate surface is decreased compared to KBr. This result suggests that the larger surface area and/or surface properties of the silicate grains play a role in controlling the chemistry, preventing it taking place to the same extent as on the flat KBr substrate. This is further evidence of the fact that cosmic dust grains play an important role in the chemistry taking place on their surface.

CMB as thermal radiation from cosmic dust grains in equilibrium with the redshifted starlight

This paper suggests that the cosmic microwave background radiation (CMB) arises from thermalized cosmic dust grains both in the interstellar medium (ISM) and in the intergalactic medium (IGM) in electron density zones equal to 0.5 el/m3. Otherwise, the thermalization is characterized by higher temperatures in the observed range 15-27 K. Considering that a black body spectrum requires an absorber/re-emitter to take place, starting from the radiative transfer equation, the calculation method applied determines the diameter of the targets in equilibrium with the redshifted starlight necessary to produce a thermal radiation at 2.725 K. The calculated value of the diameter can only correspond to cosmic dust grains in nature with their specific mass density and to nothing else. It is fully consistent with the observed size range of extra-terrestrial cosmic dust within 10-1000 μm. Furthermore, the carbon composition of the grains is capable to describe a black body behaviour as well as the metal composition is in a position to feature the polarization CMB map under the influence of galactic magnetic fields. The results of this inquiry are valid for any observer in the Cosmos.

Modelling the cold dust in nearby spiral galaxies with radiative transfer

Cosmic dust grains are one of the fundamental ingredients of the interstellar medium (ISM). In spite of their small contribution to the total mass budget, dust grains play a significant role in the physical and chemical evolution of galaxies. Over the past decades, a plethora of multi-wavelength data, from UV to far-infrared, has increased substantially our knowledge on the dust properties of nearby galaxies. Nevertheless, one regime of the spectrum, the mm range, remains relatively unexplored. Thanks to the new, high-resolution data in the mm range observed with the NIKA2 instrument and our radiative transfer framework, we aim to firmly characterise the physical properties of the very cold dust (<15K), and to quantify the importance of different emission mechanisms in the mm. So far, we have developed a methodology to use dust radiative transfer modelling and applied it to a small group of face-on spiral galaxies. The combination of the new NIKA2 data with our radiative transfer techniques would provide the right conditions to generate an accurate model of the interplay between starlight and dust in a sizeable sample of spatiallyresolved nearby galaxies.

Synthesis of magnesiowüstite nanocrystallites embedded in an amorphous silicate matrix via low energy multiple ion implantations

A synthesis process is presented for experimentally simulating modifications in cosmic dust grains using sequential ion implantations or irradiations followed by thermal annealing. Cosmic silicate dust analogues were prepared via implantation of 20–80 ​keV Fe−, Mg−, and O− ions into commercially available p-type silicon (100) wafers. The as-implanted analogues are amorphous with a Mg/(Fe ​+ ​Mg) ratio of 0.5 tailored to match theoretical abundances in circumstellar dusts. Before the ion implantations were performed, Monte-Carlo-based ion-solid interaction codes were used to model the dynamic redistribution of the implanted atoms in the silicon substrate. 600 ​keV helium ion irradiation was performed on one of the samples before thermal annealing. Two samples were thermally annealed at a temperature appropriate for an M-class stellar wind, 1000 ​K, for 8.3 ​h in a vacuum chamber with a pressure of 1 ​× ​10−7 torr. The elemental depth profiles were extracted utilizing Rutherford Backscattering Spectrometry (RBS) in the samples before and after thermal annealing. X-ray diffraction (XRD) analysis was employed for the identification of various phases in crystalline minerals in the annealed analogues. Transmission electron microscopy (TEM) analysis was utilized to identify specific crystal structures. RBS analysis shows redistribution of the implanted Fe, Mg, and O after thermal annealing due to incorporation into the crystal structures for each sample type. XRD patterns along with TEM analysis showed nanocrystalline Mg and Fe oxides with possible incorporation of additional silicate minerals.

Behavior of Hydroxyl Radicals on Water Ice at Low Temperatures.

ConspectusBecause chemical reactions on/in cosmic ice dust grains covered by amorphous solid water (ASW) play important roles in generating a variety of molecules, many experimental and theoretical studies have focused on the chemical processes occurring on the ASW surface. In laboratory experiments, conventional spectroscopic and mass-spectrometric detection of stable products is generally employed to deduce reaction channels and mechanisms. However, despite their importance, the details of chemical reactions involving reactive species (i.e., free radicals) have not been clarified because of the absence of experimental methods for in situ detection of radicals. Because OH radicals can be easily produced in interstellar conditions by not only the photolysis and/or ion bombardments of H2O but also the reaction of H and O atoms, they are thought to be one of the most abundant radicals on ice dust. In this context, the development of a close monitoring method of OH radicals on the ASW surface may help to elucidate the chemical reactions occurring on the ASW surface.Recently, to detect OH radicals adsorbed on the ASW surface, we applied our developed method to sensitively and selectively detect surface adsorbates with a combination of photostimulated desorption and resonance-enhanced multiphoton ionization techniques. Using this method, we showed that an OH radical on the ASW surface can be desorbed upon one-photon absorption at 532 nm, at which wavelength both the OH radical and H2O molecule are transparent. Theoretical calculations addressing an OH radical adsorbed on water clusters indicated that the valence A-X transition of an OH radical significantly red-shifts by ∼2 eV when the OH radical is strongly adsorbed to ice through three hydrogen bonds. With this method, the number density of surface OH can be monitored as a snapshot so that the behaviors of OH radicals, such as surface diffusion, can be studied. Moreover, the development of a system for studying the wavelength dependence of photodesorption may establish a foundation for future research investigating the absorption spectra of surface adsorbed species.Owing to the large electron affinity of OH radicals on ice, they are expected to easily become OH- by electron attachment on the ASW surface. We characterized the behavior of OH- on ASW at low temperatures, which may be relevant not only to physicochemical processes on cosmic ice dust and planetary atmosphere but also to understanding the electrochemical properties of ice. A negative constant current was found when ASW at temperatures below 50 K was exposed to both UV photons and electrons. It was demonstrated that the negative current is initiated by the formation of OH- ions on the ASW surface, and they are transported to the bulk via the proton-hole transfer mechanism, which was predicted 100 years ago as a mirror image of proton transfer known as the Grotthuss mechanism. These results indicate that OH- ions are readily transported to the bulk ice and further induce reactions, even at low temperatures where thermal diffusion is negligible. Therefore, in-mantle chemical processes that have been considered inactive at low temperatures are worth reevaluating.

INFRA-ICE: An ultra-high vacuum experimental station for laboratory astrochemistry.

Laboratory astrochemistry aims at simulating, in the laboratory, some of the chemical and physical processes that operate in different regions of the universe. Amongst the diverse astrochemical problems that can be addressed in the laboratory, the evolution of cosmic dust grains in different regions of the interstellar medium (ISM) and its role in the formation of new chemical species through catalytic processes present significant interest. In particular, the dark clouds of the ISM dust grains are coated by icy mantles and it is thought that the ice-dust interaction plays a crucial role in the development of the chemical complexity observed in space. Here, we present a new ultra-high vacuum experimental station devoted to simulating the complex conditions of the coldest regions of the ISM. The INFRA-ICE machine can be operated as a standing alone setup or incorporated in a larger experimental station called Stardust, which is dedicated to simulate the formation of cosmic dust in evolved stars. As such, INFRA-ICE expands the capabilities of Stardust allowing the simulation of the complete journey of cosmic dust in space, from its formation in asymptotic giant branch stars to its processing and interaction with icy mantles in molecular clouds. To demonstrate some of the capabilities of INFRA-ICE, we present selected results on the ultraviolet photochemistry of undecane (C11H24) at 14 K. Aliphatics are part of the carbonaceous cosmic dust, and recently, aliphatics and short n-alkanes have been detected in situ in the comet 67P/Churyumov-Gerasimenko.

Dust/ice mixing in cold regions and solid-state water in the diffuse interstellar medium

Whether ice in cold cosmic environments is physically separated from the silicate dust or mixed with individual silicate moieties is not known. However, different grain models give very different compositions and temperatures of grains. The aim of the present study is to compare the mid-infrared spectra of laboratory silicate grain/water ice mixtures with astronomical observations to evaluate the presence of dust/ice mixtures in interstellar and circumstellar environments. The laboratory data can explain the observations, assuming reasonable mass-averaged temperatures for the protostellar envelopes and protoplanetary disks, demonstrating that a substantial fraction of water ice may be mixed with silicate grains. On the basis of the combination of laboratory data and infrared observations, we provide evidence of the presence of solid-state water in the diffuse interstellar medium. Our results have implications for future laboratory studies investigating cosmic dust grain analogues and for future observations trying to identify the structure, composition and temperature of grains in different astrophysical environments. Laboratory spectra of dust/ice aggregates are comparable to those observed in astrophysical environments, questioning the traditional onion-like layered ice model. According to observational spectra, such icy mixtures could harbour water ice in the diffuse interstellar medium, as well as in low-temperature circumstellar environments.

Magnesium and silicon in interstellar dust: X-ray overview

Context.The dense Galactic environment is a large reservoir of interstellar dust. Therefore, this region represents a perfect laboratory to study the properties of cosmic dust grains. X-rays are the most direct way to detect the interaction of light with dust present in these dense environments.Aims.The interaction between the radiation and the interstellar matter imprints specific absorption features on the X-ray spectrum. We study them with the aim of defining the chemical composition, the crystallinity, and structure of the dust grains that populate the inner regions of the Galaxy.Methods.We investigated the magnesium and the silicon K-edges detected in theChandra/HETG spectra of eight bright X-ray binaries, distributed in the neighbourhood of the Galactic centre. We modelled the two spectral features using accurate extinction cross-sections of silicates, which we measured at the synchrotron facility Soleil, France.Results.Near the Galactic centre, magnesium and silicon show abundances similar to the solar ones and they are highly depleted from the gas phase (δMg> 0.90 andδSi> 0.96). We find that amorphous olivine with a composition of MgFeSiO4is the most representative compound along all lines of sight according to our fits. The contribution of Mg-rich silicates and quartz is low (less than 10%). On average we observe a percentage of crystalline dust equal to 11%. For the extragalactic source LMC X-1, we find a preference for forsterite, a magnesium-rich olivine. Along this line of sight we also observe an under-abundance of siliconASi∕ALMC= 0.5 ± 0.2.

Ice Coverage of Dust Grains in Cold Astrophysical Environments.

Surface processes on cosmic solids in cold astrophysical environments lead to gas-phase depletion and molecular complexity. Most astrophysical models assume that the molecular ice forms a thick multilayer substrate, not interacting with the dust surface. In contrast, we present experimental results demonstrating the importance of the surface for porous grains. We show that cosmic dust grains may be covered by a few monolayers of ice only. This implies that the role of dust surface structure, composition, and reactivity in models describing surface processes in cold interstellar, protostellar, and protoplanetary environments has to be reevaluated.

Atomistic simulations of the aggregation of small aromatic molecules in homogenous and heterogenous mixtures.

The relatively weak London dispersion forces are the only interactions that could cause aggregation between simple aromatic molecules. The use of molecular dynamics and high-level ab initio computer simulations has been used to describe the aggregation and interactions between molecular systems containing benzene, naphthalene and anthracene. Mixtures containing one type of molecule (homogenous) and more than one type of molecule (heterogenous) were considered. Our results indicate that as molecular weight increases so does the temperature at which aggregation will occur. In all simulations, the mechanism of aggregation is through small clusters coalescing into larger clusters. The structural analysis of the molecules within the clusters reveals that benzene will orient itself in T-shaped and parallel displaced configurations. Molecules of anthracene prefer to orient themselves in a similar manner to a bulk crystal with no T-shaped configuration observed. The aggregation of these aromatic molecules is discussed in the context of astrochemistry with particular reference to the dust formation region around stars.

The Photolysis of Aromatic Hydrocarbons Adsorbed on the Surfaces of Cosmic Dust Grains

The work is devoted to the adaptation of the results of laboratory studies of the laser-induced dissociation of molecules of benzene adsorbed on a quartz substrate to the conditions of the interstellar medium. Adsorption was performed under conditions of low temperature and deep vacuum. The difference between the photolysis of adsorbed molecules and molecules in the gas phase is identified. Significance of process of photolytic desorption in the interstellar conditions is analyzed, in particular, in the conditions of photodissociation regions. It is shown that the efficiency and dissociation channels of photolysis of adsorbed and gas phase benzene differ substantially. It is concluded that the photolysis of aromatic hydrocarbons adsorbed on the interstellar dust grains contributes a negligible fraction to the abundance of small hydrocarbons in the interstellar medium.

Structure and Properties of Nanosilicates with Olivine (Mg2SiO4)N and Pyroxene (MgSiO3)N Compositions

Magnesium-rich silicates are ubiquitous both terrestrially and astronomically, where they are often present as small particles. Nanosized Mg-rich silicate particles are likely to be particularly important for understanding the formation, processing, and properties of cosmic dust grains. Although astronomical observations and laboratory studies have revealed much about such silicate dust, our knowledge of this hugely important class of nanosolids largely rests on top-down comparisons with the properties of bulk silicates. Herein, we provide a foundational bottom-up study of the structure and properties of Mg-rich nanosilicates based on carefully procured atomistic models. Specifically, we employ state-of-the-art global optimization methods to search for the most stable structures of silicate nanoclusters with olivine (Mg2SiO4)N and pyroxene (MgSiO3)N compositions with N = 1–10. To ensure the reliability of our searches, we develop a new interatomic potential that has been especially tuned for nanosilicates. Subsequently, we refine these searches and calculate a range of physicochemical properties of the most stable nanoclusters using accurate density functional theory based electronic structure calculations. We report a detailed analysis of structural and energy properties, charge distributions, and infrared vibrational spectra, where in all cases we compare our finding for nanosilicates with those of the corresponding bulk silicate crystals. For most properties considered, we find large differences with respect to the bulk limit, underlining the limitations of a top-down approach for describing these species. Overall, our work provides a new platform for an accurate and detailed understanding of nanoscale silicates.

Evidence of Surface Catalytic Effect on Cosmic Dust Grain Analogs: The Ammonia and Carbon Dioxide Surface Reaction

Abstract Surface chemistry on cosmic dust grains plays an important role in the formation of molecules at low temperatures in the interstellar and circumstellar environments. For the first time, we experimentally put in evidence the catalytic role of dust surfaces using the thermal reaction CO2 + 2NH3 → NH2COO−, which is also a proxy of radical–radical reactions. Nanometer-sized amorphous silicate and carbon grains produced in our laboratory were used as grain analogs. Surface catalysis on grains accelerates the kinetics of the reaction studied at a temperature of 80 K by a factor of up to 3 compared to the reaction occurring in the molecular solid. The evidence of the catalytic effect of grain surfaces opens a door for experiments and calculations on the formation of interstellar and circumstellar molecules on dust. Ammonium carbamate on the surface of grains or released intact into protostellar or protoplanetary disk phases can give start to a network of prebiotic reactions. Therefore, there should be a great interest to search for ammonium carbamate and its daughter molecule, carbamic acid, in interstellar clouds, protostellar envelopes, and protoplanetary disks.

High‐Speed Drag Measurements of Aluminum Particles in Free Molecular Flow

AbstractHigh‐speed drag in a free molecular flow is still poorly understood despite playing an important role in a variety of physical situations, including meteor ablation in the upper atmosphere, the orbits of satellites, and the dynamics of cosmic dust grains. To measure drag at high speeds, small aluminum spheres 0.1–2.1 μm in radius were shot at 1–10 km/s into air, N2, Ar, and CO2 using an electrostatic dust accelerator. The measured drag coefficient in air is Γ = 1.29 ± 0.13, with similar values for the other gases. The measurement constrains the heating coefficient to Λ = 0.58 ± 0.37 in air assuming the gas molecules reflect diffusely from the particles' surfaces. The drag appears to be independent of the molecular structures of the four gases tested but has a slight dependence on molecular mass. The drag is also higher than frequently assumed, which has implications for the modeling of high‐speed objects in free molecular flows.

Synthesis of crystalline phases in space silicate analogues with helium ion irradiation

Silicate minerals such as “Mg-Fe-Si-O” compounds, are found in asteroids, planets, and cosmic dust grains in the interstellar medium. As the silicate dust grains traverse regions of space, they are irradiated by energetic ions, such as alpha particles, which can modify the crystalline phase of the mineral dust. Silicate dust grain analogues were synthesized using multiple low energy (<60 keV) ion (Fe−, Mg−, O−) implantations into a silicon wafer. The low energy ion beam as-implanted samples were cut into several smaller sections. Some of these low-energy as-implanted samples were further irradiated with a 600 keV helium ion beam at varying current densities (ions/unit area/unit time) and subsequent furnace annealed at 1000 °C temperature in Ar gas environment. The crystalline phases of the post annealed samples were monitored and reported as a function of current densities using x-ray diffraction (XRD). The XRD results showed an increase in the crystalline phases of olivine by the high-energy helium ion irradiation processing with a beam of current density of 500 nA/cm2. This work is relevant for space weathering processes as well as solid material evolution in astrophysical environments, especially asymptotic giant branch stars with an oxygen rich outflow.