CO2 Ice Research Articles

Experimental study on the competition between carbon dioxide hydrate and ice below the freezing point

As climate change and industrial requirements intensify, the potential of CO2 hydrates for carbon storage has attracted increasing attention. However, despite continuous progress, the subzero phase behavior of the CO2-H2O system is not well understood and merits further research. To investigate the competing and coexisting growth mechanisms of CO2 gas hydrate and ice below the quadruple point, we conducted experiments at both the micrometer-scale and mesoscale scales. The growth morphology of hydrate and ice at large and small subcooling temperatures was observed in situ in a high-pressure optical cell, and the thermodynamic behavior of the competitive process after hydrate formation was investigated in a high-pressure reactor with sands. When hydrates and ice are formed together at small subcooling temperatures, preferential hydrate formation leads to ice dissolution or even disappearance. At large subcooling temperatures, ice forms first, and the hydrate mainly forms a fibrous envelope. A small decrease in the subzero temperature after hydrate formation partially decomposes the hydrates owing to ice formation, followed by more rapid hydrate production. This study provides a thorough and expanded understanding of the competition between ice and hydrates by connecting the evolution of crystal frameworks with the thermodynamic features of the process.

Sulfur Ion Implantations Into Condensed CO2: Implications for Europa

AbstractThe ubiquity of sulfur ions within the Jovian magnetosphere has led to suggestions that the implantation of these ions into the surface of Europa may lead to the formation of SO2. However, previous studies on the implantation of sulfur ions into H2O ice (the dominant species on the Europan surface) have failed to detect SO2 formation. Other studies concerned with similar implantations into CO2 ice, which is also known to exist on Europa, have offered seemingly conflicting results. In this letter, we describe the results of a study on the implantation of 290 keV S+ ions into condensed CO2 at 20 and 70 K. Our results demonstrate that SO2 is observed after implantation at 20 K, but not at the Europa‐relevant temperature of 70 K. We conclude that this process is likely not a reasonable mechanism for SO2 formation on Europa, and that other mechanisms should be explored instead.

On a radiolytic origin of red organics at the surface of the Arrokoth Trans-Neptunian Object

The classical Kuiper Belt Object (KBO) Arrokoth was surveyed by the New Horizons spacecraft on 1st January 2019, revealing a small bilobed object with a red surface, whose spectral slope lies in the average of the whole KBOs population. This red color has been assigned to reddish organic materials, either inherited from the protosolar disk during accretion, or formed through radiolytic processes in the surface due to exposure to solar or interstellar photons, Solar Wind, Solar Energetic Particles or Galactic Cosmic Rays. We report here a study investigating the radiolytic scenario, based on numerical calculations and experimental simulations run with swift heavy ions (74.8 MeV 136Xe19+ and 33.06 MeV 58Ni9+), and low-energy 105 keV 18O6+ ions on CH3OH ice, the only molecule identified at Arrokoth’s surface. Calculations show that sputtering is essentially controlled by Solar Wind (H and He), and that the sputtering rate depends on the nature of the material: erosion thickness over 4.55 Gyr are a few micrometers for amorphous carbon (as an analog of red organics) and a ∼240μm to around ∼10 mm for H2O and CO ice, respectively. Chemistry within the subsurface is essentially controlled by Galactic Cosmic rays (H and He), which penetrate deep down to several tens of meters and deliver an electronic dose higher than 1 eV.atom−1 in the first meter. The electronic and elastic doses delivered by Solar Wind ions are limited to the first 10s nm of the top surface, but Solar Energetic Particles deliver high electronic doses in the first 100μm of the surface (up to 200 eV.atom−1). Experimental simulations show that irradiating methanol ice with a dose consistent with that in planetary conditions, results in the formation of reddish organic materials made of aliphatic, conjugated and unconjugated olefinic, acetylinic, carbonyl and hydroxyl groups. A similarity with irradiated simple polymers (e.g. polyethyleneglycol) and materials formed through cold plasma experiments (tholins) is observed. There is little dependence with the nature and energy of the ion. The residue recovered at room temperature was analyzed with High Resolution Mass Spectrometry (Orbitrap), revealing a complex composition with around 6596 chemical formulas and likely several tens of thousands of molecules. Altogether, these analyses support active polymerization mechanisms similar to those observed in irradiated polymers, as bond-breaking, cross-linking or formation of olefinic bonds through recombination of radicals in adjacent carbon atoms. Considering both sputtering and radiolysis, as well as material ablation due to dust bombardment reported in literature, a scenario is taking shape as the production of reddish organics deep in the subsurface, and the settling of an organic crust at the top surface through volatiles removal. The presence of methanol and absence of water, inconsistent with sputtering fractionation, remains unexplained.

Retrieving C and O Abundance of HR 8799 c by Combining High- and Low-resolution Data

Abstract The formation and evolution pathway for the directly imaged multiplanetary system HR 8799 remains mysterious. Accurate constraints on the chemical composition of the planetary atmosphere(s) are key to solving the mystery. We perform a detailed atmospheric retrieval on HR 8799 c to infer the chemical abundances and abundance ratios using a combination of photometric data along with low- and high-resolution spectroscopic data (R ∼ 20–35,000). We specifically retrieve [C/H], [O/H], and C/O and find them to be 0.55 − 0.39 + 0.36 , 0.47 − 0.32 + 0.31 , and 0.67 − 0.15 + 0.12 at 68% confidence. The superstellar C and O abundances, yet a stellar C/O ratio, reveal a potential formation pathway for HR 8799 c. Planet c, and likely the other gas giant planets in the system, formed early on (likely within ∼1 Myr), followed by further atmospheric enrichment in C and O through the accretion of solids beyond the CO ice line. The enrichment either preceded or took place during the early phase of the inward migration to the current planet locations.

Survey of Ices toward Massive Young Stellar Objects. I. OCS, CO, OCN−, and CH3OH

An important tracer of the origin and evolution of cometary ices is the comparison with ices found in dense clouds and toward young stellar objects (YSOs). We present a survey of ices in the 2–5 μm spectra of 23 massive YSOs, taken with the NASA InfraRed Telescope Facility SpeX spectrometer. The 4.90 μm absorption band of OCS ice is detected in 20 sight lines, more than 5 times the previously known detections. The absorption profile shows little variation and is consistent with OCS embedded in CH3OH-rich ices, and proton-irradiated H2S or SO2-containing ices. The OCS column densities correlate well with those of CH3OH and OCN−, but not with H2O and apolar CO ice. This association of OCS with CH3OH and OCN− firmly establishes their formation location deep inside dense clouds or protostellar envelopes. The median composition of this ice phase toward massive YSOs, as a percentage of H2O, is CO:CH3OH:OCN−:OCS = 24:20:1.53:0.15. CS, due to its low abundance, is likely not the main precursor to OCS. Sulfurization of CO is likely needed, although the source of this sulfur is not well constrained. Compared to massive YSOs, low-mass YSOs and dense clouds have similar or somewhat lower CO and CH3OH ice abundances, but less OCN− and more apolar CO, while OCS awaits detection. Comets tend to be underabundant in carbon-bearing species, but this does not appear to be the case for OCS, perhaps signalling OCS production in protoplanetary disks.

LIDA: The Leiden Ice Database for Astrochemistry

Context. High-quality vibrational spectra of solid-phase molecules in ice mixtures and for temperatures of astrophysical relevance are needed to interpret infrared observations toward protostars and background stars. Such data are collected worldwide by several laboratory groups in support of existing and upcoming astronomical observations. Over the last 25 yr, the Laboratory for Astrophysics at Leiden Observatory has provided more than 1100 (high-resolution) spectra of diverse ice samples. Aims. In time with the recent launch of the James Webb Space Telescope, we have fully upgraded the Leiden Ice Database for Astrochemistry (LIDA) adding recently measured spectra. The goal of this paper is to describe what options exist regarding accessing and working with a large collection of infrared (IR) spectra, and the ultraviolet-visible (UV/vis) to the mid-infrared refractive index of H2O ice. This also includes astronomy-oriented online tools to support the interpretation of IR ice observations. Methods. This ice database is based on open-source Python software, such as Flask and Bokeh, used to generate the web pages and graph visualization, respectively. Structured Query Language (SQL) is used for searching ice analogs within the database and Jmol allows for three-dimensional molecule visualization. The database provides the vibrational modes of molecules known and expected to exist as ice in space. These modes are characterized using density functional theory with the orca software. The IR data in the database are recorded via transmission spectroscopy of ice films condensed on cryogenic substrates. The real UV/vis refractive indices of H2O ice are derived from interference fringes created from the simultaneous use of a monochromatic HeNe laser beam and a broadband Xe-arc lamp, whereas the real and imaginary mid-IR values are theoretically calculated. LIDA not only provides information on fundamental ice properties, but it also offers online tools. The first tool, SPECFY, is directly linked to the data in the database to create a synthetic spectrum of ices towards protostars. The second tool allows the uploading of external files and the calculation of mid-infrared refractive index values. Results. LIDA provides an open-access and user-friendly platform to search, download, and visualize experimental data of astrophysically relevant molecules in the solid phase. It also provides the means to support astronomical observations; in particular, those that will be obtained with the James Webb Space Telescope. As an example, we analysed the Infrared Space Observatory spectrum of the protostar AFGL 989 using the resources available in LIDA and derived the column densities of H2O, CO and CO2 ices.

Near-infrared Spectroscopy of a Massive Young Stellar Object in the Direction toward the Galactic Center: XCN and Aromatic C–D Features

We report near-infrared (2.5–5 μm) long-slit (∼30″) spectroscopy of a young stellar object in the direction toward the Galactic center with the Infrared Camera on board the AKARI satellite. The present target is suggested to be AFGL 2006 based on its very red color and close location. The spectra show strong absorption features of H2O and CO2 ices, and emission of H i Brα recombination line and the 3.3 μm band, the latter of which originates from polycyclic aromatic hydrocarbons (PAHs) or materials containing PAHs. The spectra show a broad, complex absorption feature at 4.65 μm, which is well explained by a combination of absorption features of CO ice, CO gas, and XCN, and H i Pfβ emission. The spectra also indicate excess emission at 4.4 μm. The characteristics of the spectra suggest that the object is a massive young stellar object. The XCN feature shows a good correlation with the Brα emission, suggesting that the photolysis by ultraviolet photons plays an important role in the formation of the XCN carriers, part of which are attributed to OCN−. The 4.4 μm emission shows a good correlation with the 3.3 μm PAH emission, providing supporting evidence that it comes from the aromatic C–D stretching vibration. The formation of OCN− is of importance for the formation process of prebiotic matter in the interstellar medium (ISM), while the detection of aromatic C–D emission provides valuable information on the deuteration process of PAHs in the ISM and implications on the hiding site of the missing deuterium in the ISM.

Ammonia, carbon dioxide, and the non-detection of the 2152 cm−1 CO band

Context. COa title should be crisp and newspaper-style, and direct questions are to be avoided in scientific writing. Please rephrase your title and take this into account. Your running title may be a good place to start is one of the most abundant ice components on interstellar dust grains. When it is mixed with amorphous solid water (ASW) or located on its surface, an absorption band of CO at 2152 cm−1 is always present in laboratory measurements. This spectral feature is attributed to the interaction of CO with dangling-OH bonds (dOH) in ASW. However, this band is absent in observational spectra of interstellar ices. This raises the question whether CO forms a relatively pure layer on top of ASW or is in close contact with ASW, but not via dangling bonds. Aims. We aim to determine whether the incorporation of NH3 or CO2 into ASW blocks the dOH and therefore reduces the 2152 cm−1 band. Methods. We performed laboratory experiments to simulate the layered structure of the ice mantle, that is, we grew CO ice on top of 1) pure ASW, 2) NH3:H2O=10:100 mixed ice, and 3) CO2:H2O=20:100 mixed ice. Infrared spectra were measured to quantify the strength of the 2152 cm−1 band. In addition, a second set of experiments were performed to determine how the incorporation of NH3 into ASW affects the dOH band. Results. We found that annealing the ice reduces the 2152 cm−1 band and that NH3 blocks the dOH on ASW surface and therefore reduces the 2152 cm−1 band more effectively than CO2. We suggest that this difference between NH3 and CO2 can be ascribed to the polarity of the guest molecule (NH3 is a polar species, whereas CO2 is apolar). The polarity implies that the formation of an H-bond between the N atom of ammonia and the dOH is a barrier-less reaction. We also determined the pore surface area of the ice mixtures as a function of the annealing temperature, and found that the nondetection of 2152 cm−1 band does not necessarily exclude the possibility of a porous ice mantle.

Formation of c-C6H5CN Ice Using the SPACE TIGER Experimental Setup

Benzonitrile (c-C6H5CN) has been recently detected in cold and dense regions of the interstellar medium, where it has been used as a signpost of a rich aromatic organic chemistry that might lead to the production of polycyclic aromatic hydrocarbons. One possible origin of this benzonitrile is interstellar ice chemistry involving benzene (c-C6H6) and nitrile molecules (organic molecules containing the −C≡N group). We have addressed the plausibility of this c-C6H5CN formation pathway through laboratory experiments using our new setup SPACE TIGER. The SPACE TIGER experimental setup is designed to explore the physics and chemistry of interstellar ice mantles using laser-based ice processing and product detection methods. We have found that c-C6H5CN is formed upon irradiation of c-C6H6:CH3CN binary ice mixtures with 2 keV electrons and Lyα photons at low temperatures (4−10 K). Formation of c-C6H5CN was also observed when c-C6H6 and CH3CN were embedded in a CO ice matrix, but it was efficiently quenched in a H2O ice matrix. The results presented in this work imply that interstellar ice chemistry involving benzene and nitrile molecules could contribute to the formation of the observed benzonitrile only if these species are present on top of the ice mantles or embedded in the CO-rich ice layer, instead of being mixed into the H2O-rich ice layer.

Unraveling sulfur chemistry in interstellar carbon oxide ices

Formyl radical (HCO•) and hydroxycarbonyl radical (HOCO•) are versatile building blocks in the formation of biorelevant complex organic molecules (COMs) in interstellar medium. Understanding the chemical pathways for the formation of HCO• and HOCO• starting with primordial substances (e.g., CO and CO2) is of vital importance in building the complex network of prebiotic chemistry. Here, we report the efficient formation of HCO• and HOCO• in the photochemistry of hydroxidooxidosulfur radical (HOSO•)–a key intermediate in SO2 photochemistry–in interstellar analogous ices of CO and CO2 at 16 K through hydrogen atom transfer (HAT) reactions. Specifically, 266 nm laser photolysis of HOSO• embedded in solid CO ice yields the elusive hydrogen‑bonded complexes HCO•···SO2 and HOCO•···SO, and the latter undergoes subsequent HAT to furnish CO2···HOS• under the irradiation conditions. Similar photo-induced HAT of HOSO• in solid CO2 ice leads to the formation of HOCO•···SO2. The HAT reactions of HOSO• in astronomical CO and CO2 ices by forming reactive acyl radicals may contribute to understanding the interplay between the sulfur and carbon ice-grain chemistry in cold molecular clouds and also in the planetary atmospheric chemistry.

The cosmic-ray induced sputtering process on icy grains

ABSTRACT In molecular cloud cores, the cosmic ray (CR) induced sputtering via CR ion-icy grain collision is one of the desorption processes for ice molecules from mantles around dust grains. The efficiency of this process depends on the incident CR ion properties as well as the physicochemical character of the ice mantle. Our main objective is the examination of the sputtering efficiency for H2O and CO ices found in molecular cloud cores. In the calculation routine, we consider a multidimensional parameter space that consists of 30 CR ion types, 5 different CR ion energy flux distributions, 2 separate ice mantle components (pure H2O and CO), 3 ice formation states, and 2 sputtering regimes (linear and quadratic). We find that the sputtering behaviour of H2O and CO ices is dominated by the quadratic regime rather than the linear regime, especially for CO sputtering. The sputtering rate coefficients for H2O and CO ices show distinct variations with respect to the adopted CR ion energy flux as well as the grain-size-dependent mantle depth. The maximum radius of the cylindrical latent region is quite sensitive to the effective electronic stopping power. The track radii for CO ice are much bigger than H2O ice values. In contrast to the H2O mantle, even relatively light CR ions (Z ≥ 4) may lead to a track formation within the CO mantle, depending on Se,eff. We suggest that the latent track formation threshold can be assumed as a separator between the linear and the quadratic regimes for sputtering.

Transport of Water Into the Polar Regions of Mars Through Scavenging by CO2 Snowfall

AbstractThe Martian water cycle is tightly coupled to the polar regions, where water in the residual polar caps exchanges with the atmosphere on seasonal and multi‐annual timescales. It is thus crucial to understand the mechanisms that control water exchange in the polar regions in order to understand the water cycle as a whole. One such mechanism is CO2 snowfall, which previous studies have shown is frequent in the poles and provides a pathway for material to move from the atmosphere to the surface. We hypothesize that water ice particles that form in the wintertime atmosphere above the polar region act as condensation nuclei (CN) for the CO2 ice particles and are deposited onto the polar caps during the CO2 snowfall process. A significant amount of water may thus be contributed to the polar caps in winter through CO2 snowfall. In this study we use atmospheric retrievals of temperature, pressure, and CO2 ice cloud opacity from the Mars Climate Sounder on board NASA's Mars Reconnaissance Orbiter coupled with a simple cloud settling model to determine sedimentation rates of CO2 ice in the polar winter. We then use these snowfall rates to quantify the amount of water ice deposited to the seasonal polar caps as CN and analyze spatial and temporal patterns in its distribution. We find a lower limit on the average mass of water scavenged every winter on the order of 109–1010 kg in the north and 108–109 kg in the south.

Broadband spectroscopy of astrophysical ice analogues

Context. Broadband optical constants of astrophysical ice analogues in the infrared (IR) and terahertz (THz) ranges are required for modeling the dust continuum emission and radiative transfer in dense and cold regions, where thick icy mantles are formed on the surface of dust grains. Such data are still missing from the literature, which can be attributed to the lack of appropriate spectroscopic systems and methods for laboratory studies. Aims. In this paper, the THz time-domain spectroscopy (TDS) and the Fourier-transform IR spectroscopy (FTIR) are combined to study optical constants of CO and CO2 ices in the broad THz-IR spectral range. Methods. The measured ices were grown at cryogenic temperatures by gas deposition on a cold silicon window. We developed a method to quantify the broadband THz-IR optical constants of ices, based on the direct reconstruction of the complex refractive index of ices in the THz range from the TDS data and the use of the Kramers-Kronig relation in the IR range for the reconstruction from the FTIR data. Uncertainties introduced by the Kramers-Kronig relations were eliminated by merging the THz and IR spectra. Finally, the reconstructed THz-IR response was analyzed using classical models of complex dielectric permittivity. Results. The complex refractive index of CO and CO2 ices deposited at the temperature of 28 K was obtained in the range of 0.312.0 THz and fitted using the analytical Lorentz model. Based on the measured dielectric constants, opacities of the astrophysical dust with CO and CO2 icy mantles were computed. Conclusions. The method developed in this work can be used for a model-independent reconstructions of optical constants of various astrophysical ice analogs in a broad THz-IR range. Such data can provide important benchmarks for interpreting broadband observations from existing and future ground-based facilities and space telescopes. The reported results will be useful in modeling sources that exhibit a drastic molecular freeze-out, such as the central regions of prestellar cores and mid-planes of protoplanetary disks, as well as CO and CO2 snow lines in disks.

SimAb: A simple, fast, and flexible model to assess the effects of planet formation on the atmospheric composition of gas giants

Context. The composition of exoplanet atmospheres provides us with vital insight into their formation scenario. Conversely, planet formation processes shape the composition of atmospheres and imprint their specific signatures. In this context, models of planet formation containing key formation processes help supply clues to how planets form. This includes constraints on the metallicity and carbon-to-oxygen ratio (C/O ratio) of the planetary atmospheres. Gas giants in particular are of great interest due to the amount of information we can obtain about their atmospheric composition from their spectra, and also due to their relative ease of observation. Aims. We present a basic, fast, and flexible planet formation model, called Simulating Abundances (SimAb), that forms giant planets and allows us to study their primary atmospheric composition soon after their formation. Methods. In SimAb we introduce parameters to simplify the assumptions about the complex physics involved in the formation of a planet. This approach allows us to trace and understand the influence of complex physical processes on the formed planets. In this study we focus on four different parameters and how they influence the composition of the planetary atmospheres: initial protoplanet mass, initial orbital distance of the protoplanet, planetesimal ratio in the disk, and dust grain fraction in the disk. Results. We focus on the C/O ratio and the metallicity of the planetary atmosphere as an indicator of their composition. We show that the initial protoplanet core mass does not influence the final composition of the planetary atmosphere in the context of our model. The initial orbital distance affects the C/O ratio due to the different C/O ratios in the gas phase and the solid phase at different orbital distances. Additionally, the initial orbital distance together with the amount of accreted planetesimals cause the planet to have subsolar or supersolar metallicity. Furthermore, the C/O ratio is affected by the dust grain fraction and the planetesimal ratio. Planets that accrete most of their heavy elements through dust grains will have a C/O ratio close to the solar C/O ratio, while planets that accrete most of their heavy elements from the planetesimals in the disk will end up with a C/O ratio closer to the C/O ratio in the solid phase of the disk. Conclusions. By using the C/O ratio and metallicity together we can put a lower and upper boundary on the initial orbital distance where supersolar metallicity planets are formed. We show that planetesimals are the main source for reaching supersolar metallicity planets. On the other hand, planets that mainly accrete dust grains will show a more solar composition. Supersolar metallicity planets that initiate their formation farther than the CO ice line have a C/O ratio closer to the solar value.

Chemical evolution in planet-forming regions with growing grains

Context. Planets and their atmospheres are built from gas and solid material in protoplanetary disks. This solid material grows from smaller micron-sized grains to larger sizes in the disks during the process of planet formation. This solid growth may influence the efficiency of chemical reactions that take place on the surfaces of the grains and in turn affect the chemical evolution that the gas and solid material in the disk undergoes, with implications for the chemical composition of the planets. Aims. Our goal is to model the compositional evolution of volatile ices on grains of different sizes, assuming both time-dependent grain growth and several constant grain sizes. We also examine the dependence on the initial chemical composition. Methods. The custom Walsh chemical kinetics code was used to model the chemical evolution. This code was upgraded to account for the time-evolving sizes of solids. Chemical evolution was modelled locally at four different radii in a protoplanetary disk midplane (with associated midplane temperatures of 120, 57, 25, and 19.5 K) for up to 10 Myr. The evolution was modelled for five different constant grain sizes, and in one model, the grain size changed with time according to a grain-growth model appropriate for the disk midplane. Results. Local grain growth, with conservation of the total grain mass, and assuming spherical grains, acts to reduced the total grain-surface area that is available for ice-phase reactions. This reduces the efficiency of these reactions compared to a chemical scenario with a conventional grain-size choice of 0.1 μm. The chemical evolution modelled with grain growth leads to increased abundances of H2O ice. For carbon in the inner disk, grain growth causes CO gas to overtake CO2 ice as the dominant carrier, and in the outer disk, CH4 ice becomes the dominant carrier. Larger grain sizes cause less change the C/O ratio in the gas phase over time than when 0.1 μm sized grains are considered. Overall, a constant grain size adopted from a grain evolution model leads to an almost identical chemical evolution as a chemical evolution with evolving grain sizes. A constant grain size choice, albeit larger than 0.1 μm, may therefore be an appropriate simplification when modelling the impact of grain growth on chemical evolution.

Characterizing Seasonal and Residual Ices at the South Pole of Mars Using a Universal Set of CRISM Spectral Endmembers

AbstractCurrent maps of compositional variation across south polar ice exposures on Mars do not resolve the meter‐scales at which erosional processes are most active, ultimately limiting our understanding of how the deposits form and evolve and how they can be used to interpret long‐term climate records. In this study, we use k‐means clustering and random forest classification to identify and map a set of universal spectral endmembers across 167 high‐resolution observations acquired during southern summer by the Compact Reconnaissance Imaging Spectrometer for Mars. The 21 endmembers show distinct combinations and strengths of key infrared absorption features reflecting diverse mixtures of CO2 ice, H2O ice, and dust. The resulting compositional framework can be used to characterize the nature of both seasonal CO2 frost and the residual ices it overlies across a variety of terrains. Following the large dust event of Mars Year 28, the residual CO2‐ice deposits (RCD) were covered by an unusually thick or long‐lived deposit of seasonal frost. Within the RCD, low‐albedo material around erosional features display H2O ice absorptions consistent with exposures around the outer margins of the RCD. These peripheral water‐ice deposits show unexpected variation in CO2 ice and dust content. Most notably, regions within several km of the edge of the RCD display spectral contributions from CO2 ice even after seasonal frost has been removed. These results can inform investigations focused on the dynamics of seasonal CO2 deposition, the development of erosional morphologies, and the creation of climate records in south polar stratigraphy.

Key Parameters Controlling the Photodesorption Yield in Interstellar CO Ice Analogs: The Influence of Ice Deposition Temperature and Thickness

The overabundance of gas molecules in the coldest regions of space points to a nonthermal desorption process. Laboratory simulations show the efficient desorption of CO ice that is exposed to ultraviolet radiation, known as photodesorption, which decreases with increasing ice deposition temperature. However, our understanding of this abnormal phenomenon still remains elusive. In this work, we show that the same phenomenon—and, in particular, a dramatic drop in the photodesorption yield—is observed when the deposition temperature is 19 K and higher. Also, the minimum ice thickness that accounts for a constant photodesorption yield of CO ice is dependent on the deposition temperature, an observation that is reported here for the first time. We propose that the key parameters dominating the absorbed photon energy transfer in CO ice, and contributing to the measured photodesorption yields, are the energy transfer length, the desorption yield contributed by a single ice layer, and the relative effective surface area. These parameters should be incorporated into astrophysical models that simulate the photodesorption of the top CO-rich ice layer in icy dust populations, with a size distribution that is related to the ice thickness.

Possible Atmospheric Water Vapor Contribution from Martian Swiss Cheese Terrain

Mars’s south polar residual cap (SPRC) is a several-meters-thick CO2 ice cap with a variety of features, including quasi-circular depressions known as “Swiss cheese” that may expose underlying water ice. Swiss cheese pits have been suggested as a source for the observation of unusually high water vapor during the southern summer of Mars Year (MY) 8 (1969). To evaluate this hypothesis, we map the current extent of Swiss cheese pits to estimate the contribution to atmospheric water vapor from sublimation from the pits. We use data from the Mars Reconnaissance Orbiter Context Camera to map individual features and use the Mars Climate Sounder to obtain surface temperatures to estimate areas of exposed water ice to infer the amount of water vapor sublimated under typical south polar summer atmospheric conditions. We find that there is a negligible impact on atmospheric water vapor from sublimation with the current coverage and temperatures of Swiss cheese terrain (0.2% of the SPRC at an average of ∼161 K). At current typical temperatures, complete removal of residual CO2 from 99% of the SPRC would be required to sublimate enough water vapor to reproduce the MY 8 observation. However, a modest increase in temperature (∼20 K) could lead to a dramatic increase in sublimation rate, such that only water ice over 2.6% of the SPRC area would recreate the MY 8 observation. >180 K surface water ice has been observed on Mars, but such temperatures are likely transient at the south pole over the past ∼30 Mars years.

ALCHEMI Finds a “Shocking” Carbon Footprint in the Starburst Galaxy NGC 253

The centers of starburst galaxies may be characterized by a specific gas and ice chemistry due to their gas dynamics and the presence of various ice desorption mechanisms. This may result in a peculiar observable composition. We analyse the abundances of CO2, a reliable tracer of ice chemistry, from data collected as part of the Atacama Large Millimeter/submillimeter Array large program ALCHEMI, a wide-frequency spectral scan toward the starburst galaxy NGC 253 with an angular resolution of 1.″6. We constrain the CO2 abundances in the gas phase using its protonated form HOCO+. The distribution of HOCO+ is similar to that of methanol, which suggests that HOCO+ is indeed produced from the protonation of CO2 sublimated from ice. The HOCO+ fractional abundances are found to be (1–2) × 10−9 at the outer part of the central molecular zone (CMZ), while they are lower (∼10−10) near the kinematic center. This peak fractional abundance at the outer CMZ is comparable to that in the Milky Way CMZ, and orders of magnitude higher than that in Galactic disk, star-forming regions. From the range of HOCO+/CO2 ratios suggested from chemical models, the gas-phase CO2 fractional abundance is estimated to be (1–20) × 10−7 at the outer CMZ, and orders of magnitude lower near the center. We estimate the CO2 ice fractional abundances at the outer CMZ to be (2–5) × 10−6 from the literature. A comparison between the ice and gas CO2 abundances suggests an efficient sublimation mechanism. This sublimation is attributed to large-scale shocks at the orbital intersections of the bar and CMZ.

Different Degrees of Nitrogen and Carbon Depletion in the Warm Molecular Layers of Protoplanetary Disks

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 in 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 plane-parallel 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 galactic cosmic rays. We find that gaseous CO in the warm molecular layer is converted to CO2 ice and locked up near the midplane via the combination of turbulent mixing (i.e., the vertical cold finger effect) and ice chemistry driven by stellar UV photons. On the other hand, gaseous N2, the main nitrogen reservoir in the warm molecular layer, is less processed by ice chemistry and exists as it is. Then, nitrogen depletion occurs solely through the vertical cold finger effect of N2. As the binding energy of N2 is lower than that of CO and CO2, the degree of nitrogen depletion is smaller than that of carbon and oxygen depletion, leading to higher elemental abundance of nitrogen than that of carbon and oxygen. This evolution occurs within 1 Myr and proceeds further, when the α parameter for the diffusion coefficient is ≳10−3. Consequently, the N2H+/CO column density ratio increases with time. How the vertical transport affects the midplane ice composition is briefly discussed.