Chemical kinetics and modeling of planetary atmospheres

A unified overview is presented for chemical kinetics and chemical modeling in planetary atmospheres. The recent major advances in the understanding of the chemistry of the terrestrial atmosphere make the study of planets more interesting and relevant. A deeper understanding suggests that the important chemical cycles have a universal character that connects the different planets and ultimately link together the origin and evolution of the solar system. The completeness (or incompleteness) of the data base for chemical kinetics in planetary atmospheres will always be judged by comparison with that for the terrestrial atmosphere. In the latter case, the chemistry of H, O, N, and Cl species is well understood. S chemistry is poorly understood. In the atmospheres of Jovian planets and Titan, the C-H chemistry of simple species (containing 2 or less C atoms) is fairly well understood. The chemistry of higher hydrocarbons and the C-N, P-N chemistry is much less understood. In the atmosphere of Venus, the dominant chemistry is that of chlorine and sulfur, and very little is known about C1-S coupled chemistry. A new frontier for chemical kinetics both in the Earth and planetary atmospheres is the study of heterogeneous reactions. The formation of the ozone hole on Earth, the ubiquitous photochemical haze on Venus and in the Jovian planets and Titan all testify to the importance of heterogeneous reactions. It remains a challenge to connect the gas phase chemistry to the production of aerosols

Photochemical production of H2SO4 aerosols on Venus

The quantum yields for producing O2(a (1 delta g)) and O2(b(1 sigma g +)) for the reaction, O + ClO yields Cl + O2, are summarized. Also included are results for other simple reactions capable of producing the singlet oxygen states. An episodic injection of SO2 into the upper atmosphere of Venus is considered as a possible explanation for the airglow values

Photochemical and thermal modeling in the early atmosphere of the earth

The simplest carbon compounds, present in the terrestrial and planetary atmospheres, exhibit a wide range of oxidation states, carbon dioxide and methane being the most oxidized and the most reduced form of carbon, respectively. The question arises as to the origin and the interconversion among the carbon species. The chemical pathways for the conversion of CH4 to CO and CO2 are for the most part known. The reverse process, the reduction of CO to CH4 is however, poorly understood. A new reaction is proposed, H2CO + H + M yields CH3O + M, which might play a fundamental role in the reduction of CO or CH4. An update is presented of nitrile photochemistry on Titan

Attractor Landscapes and Information Processing by Convective Obstacle Flows

We present recent results concerning the attractor landscape, memory, hysteresis and computation that can emerge in simple convective obstacle flows. In these systems a single phase fluid is heated from below and cooled from above. Small obstacles (one or two) are placed on the horizontal mid plane of the system and extract some fraction of the fluid’s horizontal or vertical momentum. Horizontal momentum sinks tend to attract convection plumes. Vertical momentum sinks are bistable; the obstacle will either align with a convection cell centre or convection plume depending on initial conditions and the history of the system. The resulting attractor landscape can be exploited to produce a single bit memory or even elementary Boolean logic

Surface Mapping of Earth-like Exoplanets using Single Point Light Curves

Spatially resolving exoplanet features from single-point observations is essential for evaluating the potential habitability of exoplanets. The ultimate goal of this protocol is to determine whether these planetary worlds harbor geological features and/or climate systems. We present a method of extracting information from multi-wavelength single-point light curves and retrieving surface maps. It uses singular value decomposition (SVD) to separate sources that contribute to light curve variations and infer the existence of partially cloudy climate systems. Through analysis of the time series obtained from SVD, physical attributions of principal components (PCs) could be inferred without assumptions of any spectral properties. Combining with viewing geometry, it is feasible to reconstruct surface maps if one of the PCs are found to contain surface information. Degeneracy originated from convolution of the pixel geometry and spectrum information determines the quality of reconstructed surface maps, which requires the introduction of regularization. For the purpose of demonstrating the protocol, multi-wavelength light curves of Earth, which serves as a proxy exoplanet, are analyzed. Comparison between the results and the ground truth is presented to show the performance and limitation of the protocol. This work provides a benchmark for future generalization of exoplanet applications

Origin and evolution of planetary atmospheres

Spacecraft and groundbased observations of the atmospheres of solar system objects have provided a definition of their present characteristics and have yielded clues about their past history. Table 1 presents a summary of our current knowledge of the atmospheric properties of all the planets, except Pluto, and several satellites. The masses of these atmospheres range from the very miniscule values for the Moon, Mercury, and Io, to the more substantial values for the Earth, Venus, Mars, and Titan, to the very large values for the giant planets, where the atmosphere constitutes a significant fraction of the total planetary mass. The compositions of these atmospheres encompass ones dominated by rare gases (the Moon and Mercury), ones containing highly oxidized compounds of carbon, nitrogen, and sulfur (the outer three terrestrial planets and Io), and ones with highly reduced gases (Titan and the giant planets). What factors account for this enormous diversity in properties

Helium Atmospheres on Warm Neptune- and Sub-Neptune-Sized Exoplanets and Applications to GJ 436 b

Warm Neptune- and sub-Neptune-sized exoplanets in orbits smaller than Mercury's are thought to have experienced extensive atmospheric evolution. Here we propose that a potential outcome of this atmospheric evolution is the formation of helium-dominated atmospheres. The hydrodynamic escape rates of Neptune- and sub-Neptune-sized exoplanets are comparable to the diffusion-limited escape rate of hydrogen, and therefore the escape is heavily affected by diffusive separation between hydrogen and helium. A helium atmosphere can thus be formed -- from a primordial hydrogen-helium atmosphere -- via atmospheric hydrodynamic escape from the planet. The helium atmosphere has very different abundances of major carbon and oxygen species from those of a hydrogen atmosphere, leading to distinctive transmission and thermal emission spectral features. In particular, the hypothesis of a helium-dominated atmosphere can explain the thermal emission spectrum of GJ 436 b, a warm Neptune-sized exoplanet, while also consistent with the transmission spectrum. This model atmosphere contains trace amounts of hydrogen, carbon, and oxygen, with the predominance of CO over CH4 as the main form of carbon. With our atmospheric evolution model, we find that if the mass of the initial atmosphere envelope is 1E-3 planetary mass, hydrodynamic escape can reduce the hydrogen abundance in the atmosphere by several orders of magnitude in ~10 billion years. Observations of exoplanet transits may thus detect signatures of helium atmospheres and probe the evolutionary history of small exoplanets.Comment: ApJ, accepte

Use of high-resolution measurements for the retrieval of temperature and gas-concentration profiles from outgoing infrared spectra in the presence of cirrus clouds

We explore ways in which high-spectral-resolution measurements can aid in the retrieval of atmospheric temperature and gas-concentration profiles from outgoing infrared spectra when optically thin cirrus clouds are present. Simulated outgoing spectra that contain cirrus are fitted with spectra that do not contain cirrus, and the residuals are examined. For those lines with weighting functions that peak near the same altitude as the thin cirrus, unique features are observed in the residuals. These unique features are highly sensitive to the resolution of the instrumental line shape. For thin cirrus these residual features are narrow (≤0.1 cm-1), so high spectral resolution is required for unambiguous observation. The magnitudes of these unique features are larger than the noise of modern instruments. The sensitivities of these features to cloud height and cloud optical depth are also discussed. Our sensitivity studies show that, when the errors in the estimation of temperature profiles are not large, the dominant contribution to the residuals is the misinterpretation of cirrus. An analysis that focuses on information content is also presented. An understanding of the magnitude of the effect and of its dependence on spectral resolution as well as on spectral region is important for retrieving spacecraft data and for the design of future infrared instruments for forecasting weather and monitoring greenhouse gases

Chemistry and transport in a multi-dimensional model

The focus of our research program is the achievement of a quantitative understanding of the spatial distribution and temporal variation of chemical species in the terrestrial middle atmosphere, with emphasis on ozone. Although not directed at assessments of anthropogenic impacts, our activities contribute to a refinement of model descriptions of chemical and dynamical processes that are needed for assessment tasks. A unique feature of our research effort is a close interaction with the chemical kinetics group at JPL and the field measurement groups at JPL. The principal tools used in our investigations are l-D and 2-D photochemical models. The advective component of the meridional transport in these models is approximated by the diabatic circulation, which is derived diagnostically from the net radiative heating rates. We are developing accurate radiative transfer algorithms to find the net heating rates and the diabatic circulation for use in the 2-D model