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At least 127 records · Page 7

Direct Deoxygenation of Phenol over Fe-Based Bimetallic Surfaces Using On-the-Fly Surrogate Models

We present an accelerated nudged elastic band (NEB) study of phenol direct deoxygenation (DDO) on Fe-based bimetallic surfaces using a recently developed Gaussian process regression (GPR) calculator. Our test calculations demonstrate that the GPR calculator achieves up to 3 times speedup compared to conventional density functional theory calculations while maintaining high accuracy, with energy barrier errors below 0.015 eV. Using GPR-NEB, we systematically examine the DDO mechanism on pure Fe(110) and surfaces modified with Co and Ni in both top and subsurface layers. Our results show that subsurface Co and Ni substitutions preserve favorable thermodynamics and kinetics for both C–O bond cleavage and C–H bond formation, comparable to those on the pure Fe(110) surface. In contrast, top-layer substitutions generally increase the C–O bond cleavage barrier, render the step endothermic, and result in significantly higher reverse reaction rates, making DDO unfavorable on these surfaces. This work demonstrates the effectiveness of GRR-accelerated transition state searches for complex surface reactions and provides insights into rational design of bimetallic catalysts for selective deoxygenation.

Aromatic compounds↗

What would we miss if we characterized the Moon and Mars with just planetary meteorites, remote mapping, and robotic landers?

Exploration of the Moon and planets began with telescopic studies of their surfaces, continued with orbiting spacecraft and robotic landers, and will culminate with manned exploration and sample return. For the Moon and Mars we also have accidental samples provided by impacts on their surfaces, the lunar and martian meteorites. How much would we know about the lunar surface if we only had lunar meteorites, orbital spacecraft, and robotic exploration, and not the Apollo and Luna returned samples? What does this imply for Mars? With martian meteorites and data from Mariner, Viking, and the future Pathfinder missions, how much could we learn about Mars? The basis of most of our detailed knowledge about the Moon is the Apollo samples. They provide ground truth for the remote mapping, timescales for lunar processes, and samples from the lunar interior. The Moon is the foundation of planetary science and the basis for our interpretation of the other planets. Mars is similar to the Moon in that impact and volcanism are the dominant processes, but Mars' surface has also been affected by wind and water, and hence has much more complex surface geology. Future geochemical or mineralogical mapping of Mars' surface should be able to tell us whether the dominant rock types of the ancient southern highlands are basaltic, anorthositic, granitic, or something else, but will not be able to tell us the detailed mineralogy, geochemistry, or age. Without many more martian meteorites or returned samples we will not know the diversity of martian rocks, and therefore will be limited in our ability to model martian geological evolution.

Lindstrom, M. M.↗

New AFM Techniques for Investigating Molecular Growth Mechanisms of Protein Crystals

Atomic Force Microscopy (AFM) has emerged as a powerful technique for investigating protein crystal growth. Earlier AFM studies were among the first to demonstrate that these crystals grew by dislocation and 2D nucleation growth mechanisms [1]. These investigations were restricted to the micron range where only surface features, such as dislocation hillocks and 2D islands are visible. Most AFM instruments can scan at higher resolutions and have the potential to resolve individual protein molecules at nanometer ranges. Such scans are essential for determining the molecular packing arrangements on crystal faces and for probing the growth process at the molecular level. However, at this resolution the AFM tip influences the image produced, with the resulting image being a convolution of the tip shape and the surface morphology [2]. In most studies this problem is resolved by deconvoluting the image to obtain the true surface morphology. Although deconvolution routines work reasonably well for simple one- dimensional shapes, for complex surfaces this approach does not produce accurate results. In this study we devised a new approach which takes advantage of the precise molecular order of crystal surfaces, combined with the knowledge of individual molecular shapes from the crystallographic data of the protein and the AFM tip shape. This information is used to construct expected theoretical AFM images by convoluting the tip shape with the constructed crystal surface shape for a given surface packing arrangement. By comparing the images from actual AFM scans with the constructed ones for different possible surface packing arrangements, the correct packing arrangement can be conclusively determined. This approach was used in this study to determine the correct one from two possible packing arrangements on (I 10) faces of tetragonal lysozyme crystals. Another novel AFM technique was also devised to measure the dimension of individual growth units of the crystal faces. Measuring these units was not attempted before and most studies have assumed that the growth unit consisted of individual protein molecules. The linescan mode of AFM instruments allows the crystal surface to be scanned along a single line. By scanning across a growth step an image showing the motion of the step is obtained. Normally such an image shows a straight line for continuous and constant step velocity. In this study by increasing the scan rate and by decreasing the step velocity (by decreasing the supersaturation), we were able to capture images of individual growth events, shown by jump discontinuities in the step line. By suitable integration of the image the growth unit dimension in the scanned direction can be obtained. Since multiple units can be involved in the growth process it is necessary to collect a statistically relevant sample before drawing conclusions about the growth mechanism. This technique was successfully employed to obtain the dimensions of growth units for the (110) face, showing that they consisted of various aggregates corresponding to the 43 helices in the crystal structure.

Li, Huayu↗

Theoretical study of the HCS + –H 2 van der Waals complex: potential energy surface, rovibrational bound states, and rotationally inelastic collisional cross sections

An accurate ground-state intermolecular potential energy surface (PES) was calculated for the HCS + –H 2 complex. The surface was constructed from 3023 ab initio energies, computed with explicitly correlated coupled-cluster theory, CCSD(T)-F12b, with extrapolation to the complete basis set limit (VTZ-F12/VQZ-F12). The new 4D PES was used to compute rovibrational energies, rota- tional constants, and close-coupling quantum scattering calculations at low collision energies. A symmetry-adapted Lanczos algorithm was used to variationally compute the low-lying rovibrational bound states. Rotational constants for states of two isomers were determined from the energy levels and reported in hopes of motivating experiments. The rotationally inelastic state-to-state cross sections of HCS + by collision with para- and ortho-H 2 were computed and compared, and trends and propensities are discussed.

74 ATOMIC AND MOLECULAR PHYSICS↗

A computational pipeline to generate a synthetic dataset of metal ion sorption to oxides for AI/ML exploration

The charged mineral/electrolyte interfaces are ubiquitous in the surface and subsurface–including the surroundings of the geological disposal sites for radioactive waste. Therefore, understanding how ions interact with charged surfaces is critically important for predicting radionuclide mobility in the case of waste leakage. At present, the Surface Complexation Models (SCMs) are the most successful thermodynamic frameworks to describe ion retention by mineral surfaces. SCMs are interfacial speciation models that account for the effect of the electric field generated by charged surfaces on sorption equilibria. These models have been successfully used to analyze and interpret a broad range of experimental observations including potentiometric and electrokinetic titrations or spectroscopy. Unfortunately, many of the current procedures to solve and fit SCM to experimental data are not optimal, which leads to a non-transferable or non-unique description of interfacial electrostatics and consequently of the strength and extent of ion retention by mineral surfaces. Recent developments in Artificial Intelligence (AI) offer a new avenue to replace SCM solvers and fitting algorithms with trained AI surrogates. Unfortunately, there is a lack of a standardized dataset covering a wide range of SCM parameter values available for AI exploration and training–a gap filled by this study. Here, we described the computational pipeline to generate synthetic SCM data and discussed approaches to transform this dataset into AI-learnable input. First, we used this pipeline to generate a synthetic dataset of electrostatic properties for a broad range of the prototypical oxide/electrolyte interfaces. The next step is to extend this dataset to include complex radionuclide sorption and complexation, and finally, to provide trained AI architectures able to infer SCMs parameter values rapidly from experimental data. Here, we illustrated the AI-surrogate development using the ensemble learning algorithms, such as Random Forest and Gradient Boosting. These surrogate models allow a rapid prediction of the SCM model parameters, do not rely on an initial guess, and guarantee convergence in all cases.

Li, Chunhui↗

Benefits Assessment for Tactical Runway Configuration Management Tool

The Tactical Runway Configuration Management (TRCM) software tool was developed to provide air traffic flow managers and supervisors with recommendations for airport configuration changes and runway usage. The objective for this study is to conduct a benefits assessment at Memphis (MEM), Dallas Fort-Worth (DFW) and New York's John F. Kennedy (JFK) airports using the TRCM tool. Results from simulations using the TRCM-generated runway configuration schedule are compared with results using historical schedules. For the 12 days of data used in this analysis, the transit time (arrival fix to spot on airport movement area for arrivals, or spot to departure fix for departures) for MEM departures is greater (7%) than for arrivals (3%); for JFK, there is a benefit for arrivals (9%) but not for departures (-2%); for DFW, arrivals show a slight benefit (1%), but this is offset by departures (-2%). Departure queue length benefits show fewer aircraft in queue for JFK (29%) and MEM (11%), but not for DFW (-13%). Fuel savings for surface operations at MEM are seen for both arrivals and departures. At JFK there are fuel savings for arrivals, but these are offset by increased fuel use for departures. In this study, no surface fuel benefits resulted for DFW. Results suggest that the TRCM algorithm requires modifications for complex surface traffic operations that can cause taxi delays. For all three airports, the average number of changes in flow direction (runway configuration) recommended by TRCM was many times greater than the historical data; TRCM would need to be adapted to a particular airport's needs, to limit the number of changes to acceptable levels. The results from this analysis indicate the TRCM tool can provide benefits at some high-capacity airports. The magnitude of these benefits depends on many airport-specific factors and would require adaptation of the TRCM tool; a detailed assessment is needed prior to determining suitability for a particular airport.

Oseguera-Lohr, Rosa↗

Macroscopic and microscopic behaviors of Mn(II) (ad)sorption to goethite with the effects of dissolved carbonates under anoxic conditions

Manganese and its compounds have been extensively researched because of their far-reaching roles in a wide range of biogeochemical processes in natural systems. The (ad)sorption behavior of Mn(II), however, is poorly understood despite its important role as the primary reaction step for surface-catalyzed Mn(II) oxidation that is the principal abiotic process forming various Mn (oxyhydr)oxides in nature. Here, we systematically examined Mn(II) (ad)sorption to one of the most common natural sorbents, goethite, in oxygen- and carbonate-free systems. Traditional sorption edge and isotherm experiments were conducted by varying sorbate-to-sorbent ratio (0.027–15 μmol∙m -2 ) and solution pH (pH 5.0–9.0). The effects of dissolved carbonates on Mn(II) sorption were also assessed in a range of naturally prevalent concentrations (0.5–10 mM NaHCO 3 ). The Mn(II) uptake on goethite followed a typical Langmuir isotherm in the absence of dissolved carbonates, with increasing maximum adsorption capacities (Γ max ) from 0.19 at pH 6.5 to 3.4 μmol∙m -2 at pH 9.0. The presence of dissolved carbonates raised the extent of Mn(II) adsorption, which appeared to be directly correspondent to that of the adsorption of dissolved carbonates. Extended X-ray absorption fine structure (EXAFS) analysis indicated that Mn(II) predominantly formed inner-sphere binuclear bidentate surface complexes. Mn(II) uptake became deviated from the Langmuir model and showed a clear indication of surface precipitation when the Mn(II) sorption density (Γ) exceeded a threshold value in a given solution composition. This secondary Mn(II) phase was identified as rhodochrosite using X-ray diffraction (XRD) and transmission electron microscope (TEM). Furthermore, it would be plausible that a minor fraction of adsorbed Mn(II) coexisted with the secondary rhodochrosite according to a linear combination fitting (LCF) of the X-ray absorption near edge structure (XANES) spectra of Mn reference and samples. These systematic investigations of the macroscopic and microscopic behaviors of Mn(II) (ad)sorption to goethite provide a critical avenue for disentangling surface-catalytic Mn(II) oxidation processes, which ultimately lead to the formation of diverse Mn (oxyhydr)oxides in the environment.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Effect of Adsorbed Carboxylates on the Dissolution of Boehmite Nanoplates in Highly Alkaline Solutions

Understanding the dissolution of boehmite in highly alkaline solutions is important to the processing of the complex nuclear wastes stored at the Hanford (WA) and Savannah River (SC) sites. Here, we report the adsorption of model carboxylate anions on boehmite nanoplates in alkaline solutions and their effects on subsequent boehmite dissolution in 3 M NaOH at 80 °C. Although expectedly lower than at circumneutral pH, adsorption of oxalate at pH 13 at room temperature was significant and remained so through a linear decrease to 3 M NaOH conditions with no evidence for the appearance of new phases. Modeling of the adsorption data and rate were consistent with the formation of outer-sphere surface complexes. By using these conditions to preload the boehmite nanoplates with oxalate, and separately acetate, we measured and compared their dissolution behavior at 80 °C and observed a clear suppression of the dissolution rate for the case of adsorbed oxalate by 23% and for adsorbed acetate by 10% compared to pure solids. Ex situ scanning electron microscopy (SEM) and transmission electron microscopy (TEM) characterization revealed no detectable difference in the morphologic evolution of the dissolving boehmite materials. In conclusion, we nonetheless conclude that pre-adsorbed carboxylate anions, even as nominally weakly bound outer-sphere complexes, can persist on the surface through highly alkaline conditions, decreasing the density of dissolution-active sites and thereby adding an extrinsic control on the dissolution rate.

Adsorption kinetics↗

Off-Equilibrium Reactivity of Boron-Enriched Metal Diboride Surfaces in Electroreduction Conditions

Boron-based materials, featuring B-dependent reactivity and diverse phases, are emerging as promising catalyst systems. However, the catalytic mechanism on many borides remains poorly understood due to complex surface reconstructions under reaction conditions. Here, we investigate the MoB 2 surface in conditions of hydrogen evolution reaction in acidic media, using grand canonical global optimization, grand canonical density functional theory, ab initio molecular dynamics, free energy surface sampling, and an analytical model for electrochemical barrier evaluation. We propose a boron-enrichment strategy to tune the surface reactivity of the hexagonal face of MoB 2 . We reveal the dynamic nature of the B-enriched surface under H coverage and kinetic trapping of the system in the metastable regime with an extensive examination of the deactivation pathways. The metastable center B site on B-enriched surfaces, featuring buckled-up configuration and a usual relaxation effect, is found to be highly active toward HER via the Volmer–Heyrovsky mechanism. In conclusion, this work demonstrates how off-equilibrium behaviors can arise from the interplay between adsorbate coverage and surface reconstruction on a seemingly simple surface, and we present a theoretical framework and computational workflows to address these behaviors, along with other realistic complexities, in kinetics simulations.

Adsorption↗

A Multiple Filter Based Neural Network Approach to the Extrapolation of Adsorption Energies on Metal Surfaces for Catalysis Applications

Computational catalyst discovery involves the development of microkinetic reactor models based on estimated parameters determined from density functional theory (DFT). For complex surface chemistries, the number of reaction intermediates can be very large, and the cost of calculating the adsorption energies by DFT for all surface intermediates even for one active site model can become prohibitive. In this paper, we have identified appropriate descriptors and machine learning models that can be used to predict a significant part of these adsorption energies given data on the rest of them. Furthermore, our investigations also included the case when the species data used to train the predictive model are of different size relative to the species the model tries to predict—this is an extrapolation in the data space which is typically difficult with regular machine learning models. Due to the relative size of the available data sets, we have attempted to extrapolate from the larger species to the smaller ones in the current work. Here, we have developed a neural network based predictive model that combines an established additive atomic contribution based model with the concepts of a convolutional neural network that, when extrapolating, achieves a statistically significant improvement over the previous models.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Numerical Estimation of the Curvature of Biological Surfaces

Many biological systems may profitably be studied as surface phenomena. A model consisting of isotropic growth of a curved surface from a flat sheet is assumed. With such a model, the Gaussian curvature of the final surface determines whether growth rate of the surface is subharmonic or superharmonic. These properties correspond to notions of convexity and concavity, and thus to local excess growth and local deficiency of growth. In biological models where the major factors controlling surface growth are intrinsic to the surface, researchers thus gained from geometrical study information on the differential growth undergone by the surface. These ideas were applied to an analysis of the folding of the cerebral cortex, a geometrically rather complex surface growth. A numerical surface curvature technique based on an approximation to the Dupin indicatrix of the surface was developed. A metric for comparing curvature estimates is introduced, and considerable numerical testing indicated the reliability of this technique.

Todd, P. H.↗

Potential Advantages of Conducting Short Duration Visits to the Martian Surface

Recent NASA concepts for human missions to Mars, including the Evolvable Mars Campaign and Design Reference Architecture 5.0, have focused on the conduct of missions with long duration stays on the Martian surface. The decision to focus on long duration missions (typically to a single site) is driven by a desire to increase the perceived sustainability of the human Mars campaign, predicated on the assumption that sustainability is best achieved by maximizing the level of activity on the surface, providing for continuous growth in operations, and promoting pioneering of Mars. However, executing a series of long duration missions to a single site is not the only option for human exploration of Mars that has been proposed. Other architectures have been evaluated that focus on missions with short duration surface stays, with each mission visiting a separate site on the surface. This type of architecture is less efficient in that elements are not typically reused from one mission to the next but requires a far less complex surface architecture. There are potentially valid arguments to be made that a short duration, multiple site approach could result in different types of advantages when compared to the long duration, single site approach to Mars exploration, particularly for initial human missions to Mars. These arguments revolve around four areas: Achieved Value, Risk Mitigation, Developmental Affordability, and Operational Affordability & Flexibility. The question of Achieved Value relates to the prioritization of goals for Martian exploration. As discussed, goals related to pioneering and expanding human presence are often referenced as justifications for the long duration approach. However, there are other competing goals, including science and exploration. While there is not a clear consensus among planetary scientists, many have argued that the value of being able to visit multiple sites could outweigh the value of continually visiting a single site. Risk Mitigation is a major concern for initial human missions to Mars. There are a number of hazards related to operating on the Martian surface that are not well characterized. It may be desirable to conduct a series of short duration missions to better understand the nature of these risks prior to committing to a long duration mission. Developmental Affordability relates to the ability of NASA and its partners to develop and deploy the proposed architecture. Any human missions to Mars will be among the most complex endeavors ever undertaken. The capabilities that must be developed to enable any human Mars missions are extremely challenging. The total design, development, test, and evaluation (DDT&E) budget required to develop just the essential capabilities alone will be substantial. If additional surface capabilities are required to support long duration surface stays, the development effort could be unaffordable. Operational Affordability & Flexibility relates to the continued costs to execute the Mars campaign. Long duration missions, even with some amount of in-situ resource utilization, require a significant level of resupply for every mission. This requires additional launches and in-space transportation assets, increasing the operational complexity and total operational cost. This paper will explore each of the four potential advantages of short duration missions in detail. The authors will present comparisons between proposed long duration and short duration architectures through an evaluation of relevant performance, cost, and risk metrics.

Stromgren, Chel↗

Synergistic Enhancement of Lead and Selenate Uptake at the Barite (001)–Water Interface

The interactions of heavy metals with minerals influence the mobility and bioavailability of toxic elements in natural aqueous environments. The sorption of heavy metals on covalently bonded minerals is generally well described by surface complexation models (SCMs). However, understanding sorption on sparingly soluble minerals is challenging because of the dynamically evolving chemistry of sorbent surfaces. The interpretation can be even more complicated when multiple metal ions compete for sorption. In the present study, we observed synergistically enhanced uptake of lead and selenate on the barite (001) surface through two sorption mechanisms: lattice incorporation that dominates at lower coverages and two-dimensional monolayer growth that dominates at higher coverages. Further, we also observed a systematic increase in the sorption affinity with increasing co-sorbed ion coverages, different from the assumption of invariant binding constants for individual adsorption processes in classical SCMs. Computational simulations showed thermodynamically favorable co-incorporation of lead and selenate by simultaneously substituting for barium and sulfate in neighboring sites, resulting in the formation of molecular clusters that locally match the net dimension of the substrate lattice. These results emphasize the importance of ion–ion interactions at mineral–water interfaces that control the fate and transport of contaminants in the environment.

54 ENVIRONMENTAL SCIENCES↗

Morphological growth of sputtered MoS2 films

Sputtered MoS2 films from 300 A to 20,000 A thick were deposited on metal and glass surfaces. The substrate effects such as surface temperature, finish, pretreatment and chemistry as they affect the film formation characteristics were investigated by optical, electron transmission, electron diffraction, and scanning electron microscopy. Substrate temperature and surface chemistry were found to be the prime variables as to the formation of a crystalline or amorphous film. The friction characteristics are strictly influenced by the type of film formed. Surface chemistry and surface pretreatment account for compound formation and corresponding grain growth, which directly affect the adhesion characteristics, resulting in poor adherence. The type of surface finish (topography) as related to scratches, impurities, inhomogeneities, etc., are favorable nucleation sites for the growth of isolated and complex nodules within the film, and various complex surface overgrowths on the film. These nodular growth features have progressively more undesirable effects on the film behavior as the film thickness increases.

Spalvins, T.↗

Turbulent heat transfer from a sparsely vegetated surface - Two-component representation

The conventional calculation of heat fluxes from a vegetated surface involving the coefficient of turbulent heat transfer which increases logarithmically with surface roughness, is inappropriate such highly structured surfaces as desert scrub or open forest. An approach is developed here for computing sensible heat flux from sparsely vegetated surfaces, where the absorption of insolation and the transfer of absorbed heat to the atmosphere are calculated separately for the plants and for the soil. This approach is applied to a desert-scrub surface in the northern Sinai, for which the turbulent transfer coefficient of sensible heat flux from the plants is much larger than that from the soil below, as shown by an analysis of plant, soil, and air temperatures. The plant density is expressed as the sum of products (plant-height) x (plant-diameter) of plants per unit horizontal surface area. The solar heat absorbed by the plants is assumed to be transferred immediately to the airflow. The effective turbulent transfer coefficient k(g-eff) for sensible heat from the desert-scrub/soil surface computed under this assumption increases sharply with increasing solar zenith angle, as the plants absorb a greater fraction of the incoming irradiation. The surface absorptivity (the coalbedo) also increases sharply with increasing solar zenith angle, and thus the sensible heat flux from such complex surfaces is a much broader function of time of day than when computed under constant k(g-eff) and constant albedo assumptions.

Otterman, J.↗

Surface temperature of a magnetized neutron star and interpretation of the ROSAT data. 1: Dipole fields

We model the temperature distribution at the surface of a magnetized neutron star and study the effects on the observed X-ray spectra and light curves. Generalrelativistic effects, i.e., redshift and lensing, are fully taken into account. Atmospheric effects on the emitted spectral flux are not included: we consider only blackbody emission at the local effective temperature. In this first paper we restrict ourselves to dipole fields. General features are studied and compared with the ROSAT data from the pulsars 0833 - 45 (Vela), 0656 + 14, 0630 + 178 (Geminga), and 1055 - 52, the four cases for which there is strong evidence that thermal radiation from the stellar surface is detected. The composite spectra we obtain are not very different from a blackbody spectrum at the star's effective temperature. We conclude that, as far as blackbody spectra are considered, temperature estimates using single-temperature models give results practically identical to our composite models. The change of the (composite blackbody) spectrum with the star's rotational phase is also not very large and may be unobservable inmost cases. Gravitational lensing strongly suppresses the light curve pulsations. If a dipole field is assumed, pulsed fractions comparable to the observed ones can be obtained only with stellar radii larger than those which are predicted by current models of neutron star struture, or with low stellar masses. Moreover, the shapes of the theoretical light curves with dipole fields do not correspond to the observations. The use of magnetic spectra may raise the pulsed fraction sufficiently but will certainly make the discrepancy with the light curve shapes worse: dipole fields are not sufficient to interpret the data. Many neutron star models with a meson condensate or hypersons predict very small radii, and hence very strong lensing, which will require highly nondipolar fields to be able to reproduce the observed pulsed fractions, if possible at all: this may be a new tool to constrain the size of neutron stars. The pulsed fractions obtained in all our models increase with photon energy: the strong decrease observed in Geminga at energies 0.3-0.5 keV is definitely a genuine effect of the magnetic field on the spectrum in contradistinction to the magnetic effects on the surface temperature considered her. Thus, a detailed analysis of thermal emission from the four pulsars we consider will require both complex surface field configurations and the inclusion of magnetic effects in the atmosphere (i.e., on the emitted spectrum).

Page, Dany↗

Cassini radar views the surface of Titan

The Cassini Titan Radar Mapper imaged about 1% of Titan’s surface at a resolution of È0.5 kilometer, and larger areas of the globe in lower resolution modes. The images reveal a complex surface, with areas of low relief and a variety of geologic features suggestive of dome-like volcanic constructs, flows, and sinuous channels. The surface appears to be young, with few impact craters. Scattering and dielectric properties are consistent with porous ice or organics. Dark patches in the radar images show high brightness temperatures and high emissivity and are consistent with frozen hydrocarbons.

Lunine, J.↗