CO Abundance Research Articles

VIRA: An exoplanet atmospheric retrieval framework for JWST transmission spectroscopy

Abstract JWST observations are leading to important new insights into exoplanetary atmospheres through transmission spectroscopy. In order to harness the full potential of the broad spectral range and high sensitivity of JWST, atmospheric retrievals of exoplanets require a high level of robustness and accuracy in the underlying models. We present the VIRA retrieval framework which implements a range of modelling and inference capabilities motivated by early JWST observations of exoplanet transmission spectra. This includes three complementary approaches to modelling atmospheric composition, three atmospheric aerosol models, including a physically-motivated Mie scattering approach, and consideration of correlated noise. VIRA enables a cascading retrieval architecture involving a sequence of retrievals with increasing sophistication. We demonstrate VIRA using a JWST transmission spectrum of the hot Saturn WASP-39 b in the ∼1–5 μm range. In addition to confirming prior chemical inferences, we retrieve molecular abundances for H2O, CO, CO2, SO2 and H2S, resulting in super-solar elemental abundances of log(O/H) = −2.0 ± 0.2, log(C/H) = −2.1 ± 0.2 and log(S/H) = −3.6 ± 0.2, along with C/O and S/O ratios of $0.83^{+0.05}_{-0.07}$ and $0.029^{+0.012}_{-0.009}$, respectively, in the free chemistry case. The abundances correspond to $20.1^{+10.5}_{-8.1}\times$, $28.2^{+16.3}_{-12.1}\times$ and $20.8^{+10.3}_{-7.5}\times$ solar values for O/H, C/H and S/H, respectively, compared to C/H =8.67 ± 0.35 × solar for Saturn. Our results demonstrate how JWST transmission spectroscopy combined with retrieval frameworks like VIRA can measure multi-elemental abundances for giant exoplanets and enable comparative characterisation with solar system planets.

Deciphering Photoinduced Catalytic Reaction Mechanisms in Natural and Artificial Photosynthetic Systems on Multiple Temporal and Spatial Scales Using X-ray Probes.

Utilization of renewable energies for catalytically generating value-added chemicals is highly desirable in this era of rising energy demands and climate change impacts. Artificial photosynthetic systems or photocatalysts utilize light to convert abundant CO2, H2O, and O2 to fuels, such as carbohydrates and hydrogen, thus converting light energy to storable chemical resources. The emergence of intense X-ray pulses from synchrotrons, ultrafast X-ray pulses from X-ray free electron lasers, and table-top laser-driven sources over the past decades opens new frontiers in deciphering photoinduced catalytic reaction mechanisms on the multiple temporal and spatial scales. Operando X-ray spectroscopic methods offer a new set of electronic transitions in probing the oxidation states, coordinating geometry, and spin states of the metal catalytic center and photosensitizers with unprecedented energy and time resolution. Operando X-ray scattering methods enable previously elusive reaction steps to be characterized on different length scales and time scales. The methodological progress and their application examples collected in this review will offer a glimpse into the accomplishments and current state in deciphering reaction mechanisms for both natural and synthetic systems. Looking forward, there are still many challenges and opportunities at the frontier of catalytic research that will require further advancement of the characterization techniques.

High-precision Atmospheric Characterization of a Y Dwarf with JWST NIRSpec G395H Spectroscopy: Isotopologue, C/O Ratio, Metallicity, and the Abundances of Six Molecular Species

The launch of the James Webb Space Telescope (JWST) marks a pivotal moment for precise atmospheric characterization of Y dwarfs, the coldest brown dwarf spectral type. In this study, we leverage moderate spectral resolution observations (R ∼ 2700) with the G395H grating of the Near-Infrared Spectrograph (NIRSpec) on board JWST to characterize the nearby (9.9 pc) Y dwarf WISEPA J182831.08+265037.8. With the NIRSpec G395H 2.88–5.12 μm spectrum, we measure the abundances of CO, CO2, CH4, H2S, NH3, and H2O, which are the major carbon-, nitrogen-, oxygen-, and sulfur-bearing species in the atmosphere. Based on the retrieved volume mixing ratios with the atmospheric retrieval framework CHIMERA, we report that the C/O ratio is 0.45 ± 0.01, close to the solar C/O value of 0.458, and the metallicity is +0.30 ± 0.02 dex. Comparison between the retrieval results and the forward modeling results suggests that the model bias for C/O and metallicity could be as high as 0.03 and 0.97 dex, respectively. We also report a lower limit of the 12CO/13CO ratio of >40, being consistent with the nominal solar value of 90. Our results highlight the potential for JWST to measure the C/O ratios down to percent-level precision and characterize isotopologues of cold planetary atmospheres similar to WISE 1828.

The Impact of Cometary “Impacts” on the Chemistry, Climate, and Spectra of Hot Jupiter Atmospheres

Impacts from icy and rocky bodies have helped shape the composition of Solar System objects; for example, the Earth–Moon system, or the recent impact of comet Shoemaker–Levy 9 with Jupiter. It is likely that such impacts also shape the composition of exoplanetary systems. Here, we investigate how cometary impacts might affect the atmospheric composition/chemistry of hot Jupiters, which are prime targets for characterization. We introduce a parameterized cometary impact model that includes thermal ablation and pressure driven breakup, which we couple with the 1D “radiative-convective” atmospheric model ATMO, including disequilibrium chemistry. We use this model to investigate a wide range of impactor masses and compositions, including those based on observations of Solar System comets, and interstellar ices (with JWST). We find that even a small impactor (R = 2.5 km) can lead to significant short-term changes in the atmospheric chemistry, including a factor >10 enhancement in H2O, CO, and CO2 abundances, as well as atmospheric opacity more generally, and the near-complete removal of observable hydrocarbons, such as CH4, from the upper atmosphere. These effects scale with the change in atmospheric C/O ratio and metallicity. Potentially observable changes are possible for a body that has undergone significant/continuous bombardment, such that the global atmospheric chemistry has been impacted. Our works reveals that cometary impacts can significantly alter or pollute the atmospheric composition/chemistry of hot Jupiters. These changes have the potential to mute/break the proposed link between atmospheric C/O ratio and planet formation location relative to key snowlines in the natal protoplanetary disk.

Insight into the mechanism of helium enrichment in natural gas from the Bohai Bay basin, China: Chemical and isotopic composition perspectives

Helium (He) is an important societal resource, yet its enrichment mechanism is unclear in the Bohai Bay Basin, despite the presence of He-rich (He > 0.1% v/v) gas. A comprehensive analysis of 112 sets of chemical and isotopic data from natural gases in the literature was conducted to further elucidate the source and accumulation mechanism of He in this basin. Natural gas is categorized into five groups based on CO2 and N2 abundances: N2 gas (CO2+N2 ≥ 95%, CO2 < N2), high-purity CO2 gas (CO2+N2 ≥ 95%, CO2 > N2), low-purity CO2 gas (50 ≤ CO2+N2 < 95%, CO2 > N2), low-purity HC gas (15 ≤ CO2+N2 < 50%) and high-purity HC gas (CO2+N2 < 15%). δ13C–CO2 (−8.3 to −3.0‰) and 3He/4He (1.66–6.45 Ra, where Ra is the atmospheric 3He/4He) suggest a mantle origin of CO2 in N2 and CO2 gases. The δ13C–CO2 of N2 gas (−8.3‰) is lighter than that of high-purity CO2 gas (−6.2 to −3.4‰), indicating CO2 dissolution and mineralization. A positive correlation between He and CH4 content in the N2 and high-purity CO2 gases suggests water-derived CH4 capture during CO2 migration. Similarly, the positive correlation between He and N2 content across all samples indicates water-derived N2 capture during gas migration. A mixture of mantle and crust-derived He is indicated by 3He/4He ratio (0.06–6.45 Ra). Two distinct types of He-rich gas were identified: He-rich N2 gas (3He/4He = 3.1–3.2 Ra) and He-rich HC gas (3He/4He = 0.36–0.48 Ra). He enrichment in N2 gas is attributed to water-derived He capture and concurrent loss of CO2 during mantle-derived CO2 migration. He-rich HC gas formation results from He-rich N2 gas dilution with hydrocarbons. The findings provide theoretical support for exploring He-rich natural gas in this basin and offer valuable insights into He enrichment mechanisms in comparable sedimentary basins globally.

A Subsolar Metallicity on the Ultra-short-period Planet HIP 65Ab

Studying and understanding the physical and chemical processes that govern hot Jupiters gives us insights on the formation of these giant planets. Having a constraint on the molecular composition of their atmosphere can help us pinpoint their evolution timeline. Namely, the metal enrichment and carbon-to-oxygen ratio can give us information about where in the protoplanetary disk a giant planet may have accreted its envelope, and, subsequently, indicate if it went through migration. Here we present the first analysis of the atmosphere of the hot Jupiter HIP 65Ab. Using near-infrared high-resolution observations from the IGRINS spectrograph, we detect H2O and CO absorption in the dayside atmosphere of HIP 65Ab. Using a high-resolution retrieval framework, we find a CO abundance of log(CO) = −3.85−0.36+0.33 , which is slightly underabundant with expectation from solar composition models. We also recover a low-water abundance of log(H2O) = −4.42 ± 0.18, depleted by 1 order of magnitude relative to a solar-like composition. Upper limits on the abundance of all other relevant major carbon- and oxygen-bearing molecules are also obtained. Overall, our results are consistent with a sub-stellar metallicity but slightly elevated C/O. Such a composition may indicate that HIP 65Ab accreted its envelope from beyond the water snowline and underwent a disk-free migration to its current location. Alternatively, some of the oxygen on HIP 65Ab could be condensed out of the atmosphere, in which case the observed gas-phase abundances would not reflect the true bulk envelope composition.

Radial gradients of CO absorptions and abundance ratios in the bulge of M31

We present new H- and K-band spectroscopy for the bulge of M31, taken with the LUCI spectrograph at the Large Binocular Telescope (LBT). We studied radial trends of CO absorption features (namely and ) in the bulge of M31, out to a galactocentric distance of $ 380$ pc). We find that most COs do not exhibit a strong radial gradient, despite the strong metallicity gradient inferred from the optical spectral range, except for showing a steep increase in the center. We compared the observed line strengths to predictions of different state-of-the-art stellar population models, including an updated version of EMILES models, which also uses the extended IRTF spectral library. The observed COs are close to models' predictions, but in some models they turn out to be underestimated. We find that the lack of radial gradients is due to the combination of increasing CO strength with metallicity and C abundance, and decreasing CO strength with IMF slope and O abundance. We speculate that the steep gradient of might be due to Na overabundance. Remarkably, we were able to fit, at the same time, optical indices and all the NIR COs (except for CO1.68) leaving abundance ratios (i.e. and ) as free-fitting parameters, imposing age and metallicity constraints from the optical spectral range with no significant contribution from intermediate-age populations ($ 1$ Gyr-old). For the majority of the bulge, we find 0.15$ dex larger than (by $ 0.1$ dex), and C abundance consistent with that of Mg. In the central (few arcsec) region, we still find an enhancement of O and Mg, but significantly lower . We find that the COs' line strengths of the bulge are significantly lower than those of massive galaxies, possibly because of a difference in carbon abundance, as well as, to some extent, total metallicity.

A Formally Motivated Retrieval Framework Applied to the High-resolution Transmission Spectrum of HD 189733 b

Ground-based high-resolution spectra provide a powerful tool for characterizing exoplanet atmospheres. However, they are greatly hampered by the dominating telluric and stellar lines, which need to be removed prior to any analysis. Such removal techniques (“preparing pipelines”) deform the spectrum; hence, a key point is to account for this process in the forward models used in retrievals. We develop a formal derivation on how to prepare froward models for retrievals, in the case where the telluric and instrumental deformations can be represented as a matrix multiplied element-wise with the data. We also introduce the notion of a “bias pipeline metric,” which can be used to compare the bias potential of preparing pipelines. We use the resulting framework to retrieve simulated observations of 1D and 3D exoplanet atmospheres and to reanalyze high-resolution ( R≈80,400 ) near-infrared (0.96–1.71 μm) CARMENES transit data of HD 189733 b. We compare these results with those obtained from a cross-correlation function analysis. With our fiducial retrieval, we find a blueshift of the absorption features of −5.51−0.53+0.66 km s−1. In addition, we retrieve a H2O log10(VMR) of −2.39−0.16+0.12 and a temperature of 660−11+6 K. We are also able to put upper limits for the abundances of CH4, CO, H2S, HCN, and NH3, consistent with a subsolar-metallicity atmosphere enriched in H2O. We retrieve a broadened line shape, consistent with rotation- and wind-induced line broadening. Finally, we find a lower limit for the pressure of an opaque cloud consistent with a clear atmosphere, and we find no evidence for hazes.

Remobilization of carbon in the lithospheric mantle during decratonization

The sub-continental lithosphere mantle (SCLM) contains considerable amounts of carbon and is responsible for significant CO2 emissions via magmatism during major heating and rifting events. However, the role of SCLM in Earth's carbon cycle during other geological processes, such as decratonization, a process of major removal and replacement of cratonic SCLM, remains poorly understood. The North China Craton is an archetype of Archean craton having been decratonized during the Mesozoic with extensive magmatism developed. Here we show that the primary melt of Early Cretaceous Yixian basalts contained abundant CO2 (0.6 wt%), through investigating melt inclusions trapped in olivine crystals. The melt inclusions are alkalic and chemically distinct from their sub-alkalic host basalts, which could be explained by that the primary alkalic melt was reactively modified during magma ascent in the SCLM. The primary melt has geochemical characteristics consistent with partial melting of a veined carbon-rich amphibole clinopyroxenite source in the SCLM formed metasomatically during circum-craton subduction events. The findings highlight that the carbon introduced into the cratonic SCLM during subduction could be subsequently reactivated and transferred to the crust and atmosphere through decratonization-related magmatism, which might represent a major process regarding the SCLM in regulating the terrestrial carbon cycle.

Possible Hycean conditions in the sub-Neptune TOI-270 d

The JWST has ushered in a new era in atmospheric characterisations of temperate low-mass exoplanets with recent detections of carbon-bearing molecules in the candidate Hycean world K2-18 b. We investigated JWST observations of the TOI-270 system, with two sub-Neptunes simultaneously transiting the nearby M dwarf during the visit. We report our atmospheric characterisation of the outer planet TOI-270 d, a candidate Hycean world, with JWST transmission spectroscopy using the NIRSpec G395H instrument in the 2.7–5.2 μm range, combined with previous observations obtained with the HST WFC3 spectrograph (1.1–1.6 μm). The spectrum reveals strong signatures of CH4 and CO2 at 3.8–4.9σ and 2.9–3.9σ confidence, respectively, and no evidence of NH3. The abundant CH4 and CO2, at ∼0.1–1% mixing ratios, and the non-detection of NH3 are similar to the findings reported for K2-18 b and consistent with predictions for a Hycean world with a planet-wide ocean under a H2-rich atmosphere. We also report evidence of CS2 at a 2.3–3.0σ confidence and a potential inference of H2O at 1.6–4.4σ, depending on the data analysis approach, and discuss possible interpretations of these results. The spectrum does not provide strong constraints on the presence of clouds or hazes in the observable atmosphere, nor any evidence for the effects of stellar heterogeneities, which is consistent with previous studies. For the smaller inner planet TOI-270 b, we find that the spectrum is inconsistent with a featureless spectrum at ∼3σ, showing some preference for an H2-rich atmosphere in a super-Earth. We discuss the implications of our findings and future prospects.

Hydrogenation of CO2 into Value-added Chemicals Using Solid-Supported Catalysts.

Reducing CO2 emissions is an urgent global priority. In this context, several mitigation strategies, including CO2 tax and stringent legislation, have been adopted to halt the deterioration of the natural environment. Also, carbon recycling procedures undoubtedly help reduce net emissions into the atmosphere, enhancing sustainability. Utilizing Earth's abundant CO2 to produce high-potential green chemicals and light fuels opens new avenues for the chemical industry. In this context, many attempts have been devoted to converting CO2 as a feedstock into various value-added chemicals, such as CH4, lower methanol, light olefins, gasoline, and higher hydrocarbons, for numerous applications involving various catalytic reactions. Although several CO2-conversion methods have been used, including electrochemical, photochemical, and biological approaches, the hydrogenation method allows the reaction to be tuned to produce the targeted compound without significantly altering infrastructure. This review discusses the numerous hydrogenation routes and their challenges, such as catalyst design, operation, and the combined art of structure-activity relationships for the various product formations.

Earth as an Exoplanet. III. Using Empirical Thermal Emission Spectra as an Input for Atmospheric Retrieval of an Earth-twin Exoplanet

In this study, we treat Earth as an exoplanet and investigate our home planet by means of a potential future mid-infrared space mission called the Large Interferometer For Exoplanets (LIFE). We combine thermal spectra from an empirical data set of disk-integrated Earth observations with a noise model for LIFE to create mock observations. We apply a state-of-the-art atmospheric retrieval framework to characterize the planet, assess the potential for detecting the known bioindicators, and investigate the impact of viewing geometry and seasonality on the characterization. Our key findings reveal that we are observing a temperate habitable planet with significant abundances of CO2, H2O, O3, and CH4. Seasonal variations in the surface and equilibrium temperature, as well as in the Bond albedo, are detectable. Furthermore, the viewing geometry and the spatially and temporally unresolved nature of our observations only have a minor impact on the characterization. Additionally, Earth’s variable abundance profiles and patchy cloud coverage can bias retrieval results for the atmospheric structure and trace-gas abundances. Lastly, the limited extent of Earth’s seasonal variations in biosignature abundances makes the direct detection of its biosphere through atmospheric seasonality unlikely. Our results suggest that LIFE could correctly identify Earth as a planet where life could thrive, with detectable levels of bioindicators, a temperate climate, and surface conditions allowing liquid surface water. Even if atmospheric seasonality is not easily observed, our study demonstrates that next generation space missions can assess whether nearby temperate terrestrial exoplanets are habitable or even inhabited.

JWST Observations of K2-18b Can Be Explained by a Gas-rich Mini-Neptune with No Habitable Surface

The James Webb Space Telescope (JWST) recently measured the transmission spectrum of K2-18b, a habitable-zone sub-Neptune exoplanet, detecting CH4 and CO2 in its atmosphere. The discovery paper argued the data are best explained by a habitable “Hycean” world, consisting of a relatively thin H2-dominated atmosphere overlying a liquid water ocean. Here, we use photochemical and climate models to simulate K2-18b as both a Hycean planet and a gas-rich mini-Neptune with no defined surface. We find that a lifeless Hycean world is hard to reconcile with the JWST observations because photochemistry only supports <1 part-per-million CH4 in such an atmosphere while the data suggest about ∼1% of the gas is present. Sustaining percent-level CH4 on a Hycean K2-18b may require the presence of a methane-producing biosphere, similar to microbial life on Earth ∼3 billion years ago. On the other hand, we predict that a gas-rich mini-Neptune with 100× solar metallicity should have 4% CH4 and nearly 0.1% CO2, which are compatible with the JWST data. The CH4 and CO2 are produced thermochemically in the deep atmosphere and mixed upward to the low pressures sensitive to transmission spectroscopy. The model predicts H2O, NH3, and CO abundances broadly consistent with the nondetections. Given the additional obstacles to maintaining a stable temperate climate on Hycean worlds due to H2 escape and potential supercriticality at depth, we favor the mini-Neptune interpretation because of its relative simplicity and because it does not need a biosphere or other unknown source of methane to explain the data.

A Combined Ground-based and JWST Atmospheric Retrieval Analysis: Both IGRINS and NIRSpec Agree that the Atmosphere of WASP-77A b Is Metal-poor

Ground-based high-resolution and space-based low-resolution spectroscopy are the two main avenues through which transiting exoplanet atmospheres are studied. Both methods provide unique strengths and shortcomings, and combining the two can be a powerful probe into an exoplanet’s atmosphere. Within a joint atmospheric retrieval framework, we combined JWST NIRSpec/G395H secondary eclipse spectra and Gemini South/IGRINS pre- and post-eclipse thermal emission observations of the hot Jupiter WASP-77A b. Our inferences from the IGRINS and NIRSpec data sets are consistent with each other, and combining the two allows us to measure the gas abundances of H2O and CO, as well as the vertical thermal structure, with higher precision than either data set provided individually. We confirm WASP-77A b’s subsolar metallicity ([(C+O)/H] = −0.61 −0.09+0.10) and solar C/O ratio (C/O = 0.57 −0.06+0.06) . The two types of data are complementary, and our abundance inferences are mostly driven by the IGRINS data, while inference of the thermal structure is driven by the NIRSpec data. Our ability to draw inferences from the post-eclipse IGRINS data is highly sensitive to the number of singular values removed in the detrending process, potentially due to high and variable humidity. We also search for signatures for atmospheric dynamics in the IGRINS data and find that propagated ephemeris error can manifest as either an orbital eccentricity or a strong equatorial jet. Neither are detected when using more up-to-date ephemerides. However, we find moderate evidence of thermal inhomogeneity and measure a cooler nightside that presents itself in the later phases after secondary eclipse.

Boosting CO2 transport in mixed matrix membranes by chitosan-MOF networks

The chitosan (CS)-grafted UiO-66-NH2 (U6N) (CSGUN) was synthesized and incorporated into Pebax matrix to fabricate mixed matrix membranes (MMMs) for boosting CO2 transport. The excellent CO2 separation performance was exhibited for MMMs due to the following reasons: U6N with the suitable porosity and abundant CO2 transport carriers can provide a unique “expressway” for CO2 to boost CO2 transport through MMMs. The grafting CS in CSGUN can connect Pebax (regular roads) and U6N (expressway), acting as an “on-ramp” between them to enrich CO2 and guide CO2 through U6N in an orderly manner. Thus, the constructed “on-ramp” and “expressway” in MMMs can improve CO2 separation performance. Furthermore, the CS-MOF networks were formed in MMMs through using CS molecular chains to connect U6N for enhancing CO2 separation performance of MMMs. Therefore, Pebax/CSGUN MMMs exhibited the excellent CO2 separation performance with the CO2 permeability of 558 ± 7 Barrer and the CO2/CH4 selectivity of 37.5 ± 0.7. The study indicated that MMMs with CS-MOF bridged networks had great potential for boosting CO2 transport by combining “expressways” and “on-ramp”.

Titanium carbide-based nanocomposite: A promising reinforcing material for enzymatic CO2 conversion

Enzymatic conversion of CO2 to formate is a highly significant pathway for CO2 utilization, but current level of conversion efficiency remains unsatisfactory due to low solubility of CO2 under mild conditions. CO2-philic materials can significantly augment the reaction by raising local concentration of substrate. Herein, the intercalated Ti3C2Tx, nano-silica (SiO2) and carbon nitride (CN) with abundant CO2 adsorption sites were introduced to fabricate Ti3C2Tx based nanocomposites, Ti3C2Tx/SiO2/CN (TSCN), for the first time. As the controls, binary composites including Ti3C2Tx/SiO2 (TS), Ti3C2Tx/CN (TCN) and SiO2/CN (SCN) were also studied. For each kind of material, the composition, structure, morphology, and application performance in the enzymatic CO2 conversion were characterized and influencing factors were investigated. Among these composites, TSCN exhibited the best application performance and the enzyme reaction was accelerated up to 23.9 times that of the blank system. The value could reach as high as 35.3 after polyethyleneimine (PEI) modification. Following that, PEI modified composites were used as carrier of formate dehydrogenase (FDH) and apparent specific activity was up to 2.8 times that of free enzyme, which could retain 88.2% of the initial value after 10 cycles associated with the structural integrity. This work provides new impetus to CO2 capture and conversion in a clean and mild way that shows bright application prospects.

Enhancing DMC Production from CO2: Tuning Oxygen Vacancies and In Situ Water Removal

The direct synthesis of dimethyl carbonate (DMC) from methanol and CO2 presents an attractive route to turn abundant CO2 into value-added chemicals. However, insufficient DMC yields arise due to the inert nature of CO2 and the limitations of reaction equilibrium. Oxygen vacancies are known to facilitate CO2 activation and improve catalytic performance. In this work, we have demonstrated that tuning oxygen vacancies in catalysts and implementing in situ water removal can enable highly efficient DMC production from CO2. CexZryO2 nanorods with abundant oxygen vacancies were synthesized via a hydrothermal method. In liquid-phase DMC synthesis, the Ce10Zr1O2 nanorods exhibited a 1.7- and 1.4-times higher DMC yield compared to CeO2 nanoparticles and undoped CeO2 nanorods, respectively. Zr doping yielded a CeZr solid solution with increased oxygen vacancies, promoting CO2 adsorption and activation. In addition, adding 2-cyanopyridine as an organic dehydrating agent achieved an outstanding 87% methanol conversion and &gt;99% DMC selectivity by shifting the reaction equilibrium to the desired product. Moreover, mixing CeO2 nanoparticles with hydrophobic fumed SiO2 in gas-phase DMC synthesis led to a doubling of DMC yield. This significant increase was attributed to the faster diffusion of water molecules away from the catalyst surface, facilitated by the hydrophobic SiO2. This study illustrates an effective dual strategy of enhancing oxygen vacancies and implementing in situ water removal to boost DMC production from CO2. The strategy can also be applied to other reactions impacted by water accumulation.

Inferring the CO2 Abundance in Comet 45P/Honda-Mrkos-Pajdušáková from [O i] Observations: Implications for the Source of Icy Grains in Cometary Comae

The study of cometary composition is important for understanding our solar system's early evolutionary processes. Carbon dioxide (CO2) is a common hypervolatile in comets that can drive activity but is more difficult to study than other hypervolatiles owing to severe telluric absorption. CO2 can only be directly observed from space-borne assets. Therefore, a proxy is needed to measure CO2 abundances in comets using ground-based observations. The flux ratio of the [O i] λ5577 line to the sum of the [O i] λ6300 and [O i] λ6364 lines (hereafter referred to as the [O i] line ratio) has, with some success, been used in the past as such a proxy. We present an [O i] line ratio analysis of comet 45P/Honda-Mrkos-Pajdušáková (HMP), using data obtained with the Tull Coudé Spectrograph on the 2.7 m Harlan J. Smith Telescope at McDonald Observatory, taken from UT 2017 February 21–23, when the comet was at heliocentric distances of 1.12–1.15 au. HMP is a hyperactive Jupiter-family comet (JFC). Icy grains driven out by CO2 sublimation have been proposed as a driver of hyperactivity, but the CO2 abundance of HMP has not been measured. From our [O i] line ratio measurements, we find a CO2/H2O ratio for HMP of 22.9% ± 1.4%. We compare the CO2/H2O ratios to the active fractions of the nine comets (including HMP) in the literature that have data for both values. We find no correlation. These findings imply that CO2 sublimation driving out icy grains is not the only factor influencing active fractions for cometary nuclei.

Disentangling CO Chemistry in a Protoplanetary Disk Using Explanatory Machine-learning Techniques

Molecular abundances in protoplanetary disks are highly sensitive to the local physical conditions, including gas temperature, gas density, radiation field, and dust properties. Often multiple factors are intertwined, impacting the abundances of both simple and complex species. We present a new approach to understanding these chemical and physical interdependencies using machine learning. Specifically, we explore the case of CO modeled under the conditions of a generic disk and build an explanatory regression model to study the dependence of CO spatial density on the gas density, gas temperature, cosmic-ray ionization rate, X-ray ionization rate, and UV flux. Our findings indicate that combinations of parameters play a surprisingly powerful role in regulating CO abundance compared to any singular physical parameter. Moreover, in general we find the conditions in the disk are destructive toward CO. CO depletion is further enhanced in an increased cosmic-ray environment and in disks with higher initial C/O ratios. These dependencies uncovered by our new approach are consistent with previous studies, which are more modeling intensive and computationally expensive. Our work thus shows that machine learning can be a powerful tool not only for creating efficient predictive models, but also for enabling a deeper understanding of complex chemical processes.

Relative Abundances of CO2, CO, and CH4 in Atmospheres of Earth-like Lifeless Planets

Carbon is an essential element for life on Earth, and the relative abundances of major carbon species (CO2, CO, and CH4) in the atmosphere exert fundamental controls on planetary climate and biogeochemistry. Here we employed a theoretical model of atmospheric chemistry to investigate diversity in the atmospheric abundances of CO2, CO, and CH4 on Earth-like lifeless planets orbiting Sun-like (F-, G-, and K-type) stars. We focused on the conditions for the formation of a CO-rich atmosphere, which would be favorable for the origin of life. Results demonstrated that elevated atmospheric CO2 levels trigger photochemical instability of the CO budget in the atmosphere (i.e., CO runaway) owing to enhanced CO2 photolysis relative to H2O photolysis. Higher volcanic outgassing fluxes of reduced C (CO and CH4) also tend to initiate CO runaway. Our systematic examinations revealed that anoxic atmospheres of Earth-like lifeless planets could be classified in the phase space of CH4/CO2 versus CO/CO2, where a distinct gap in atmospheric carbon chemistry is expected to be observed. Our findings indicate that the gap structure is a general feature of Earth-like lifeless planets with reducing atmospheres orbiting Sun-like (F-, G-, and K-type) stars.