Research in atmospheric chemistry and transport

The carbon monoxide cycle was studied by incorporating the known CO sources and sinks in a tracer model which used the winds generated by a general circulation model. The photochemical production and loss terms, which depended on OH radical concentrations, were calculated in an interactive fashion. Comparison of the computed global distribution and seasonal variations of CO with observations was used to yield constraints on the distribution and magnitude of the sources and sinks of CO, and the abundance of OH radicals in the troposphere

Kinetic conversion of CO to CH4 in the Solar System

Some of the most interesting chemistry in the Solar System involves changes in the oxidation state of the simple 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. This is surprising in view of the importance of the reduction process in the chemistry of the Solar System. Recently we investigated the chemical kinetics of a hitherto unsuspected reaction. It is argued that the formation of the methoxy radical (CH3O) from H+H2CO may play an essential role in the reduction of CO to CH4. The rate coefficient for this reaction has been estimated using the approximate theory of J. Troe and transition state theory. We will discuss the implications of this reaction for the chemistry of CO on Jupiter, in the solar nebula, for interpreting the laboratory experiments of A. Bar-Nun and A. Shaviv and A. Bar-Nun and S. Chang, and for organic synthesis in the prebiotic terrestrial atmosphere. The possible relation of CO reduction in the solar nebula and polyoxymethylene observed in comet Halley will be discussed

An updated hydrocarbon photochemical model for the Jovian atmosphere from the troposphere through the homopause: A prelude to Galileo

A photochemical model for the atmosphere of Jupiter, including 1-D vertical eddy diffusive transport, was developed. It extends from the upper troposphere through the homopause. The hydrocarbon chemistry involves species containing up to four carbon atoms (and polyynes through C8H2). The calculations show that a large fraction of photochemical carbon may be contained in molecules with more than two carbon atoms. At the tropopause, C2H6 is the major photochemical species and C2H2, C3H8, and C4H10 are of comparable abundance and down from C2H6 by a factor of ten. These species may be detectable with the mass spectrometer of the Galileo Probe. The vertical distributions of the photochemical species are sensitive to the magnitude of eddy diffusive mixing in the troposphere and stratosphere and the details of the interface region

Evolution of the atmosphere of Venus

The photochemistry of the stratosphere of Venus was modeled using an updated and expanded chemical scheme, and the results of recent laboratory studies. The model satisfactorily accounts for the observations of CO, O2, (1) and SO2 in the stratosphere. Oxygen, derived from CO2 photolysis, is primarily consumed by CO2 recombination and oxidation of SO2 to H2SO4. Photolysis of HCl in the upper stratosphere provides a major source of odd hydrogen radicals essential for the catalytic oxidation of CO. Oxidation of SO2 by O occurs in the lower stratosphere, with the O-O bond broken by S + O2 and SO + HO2. The sensitivity of stratospheric chemistry to ambient H2 abundance was studied and the model prefers the high value (1 10 ppm) recently inferred from the Pioneer Venus ionospheric measurements. The importance of the photochemical production of S2O, (SO)2, S2, H2S2O2 and H2S2O3 is speculated. A number of previously unsuspected similarities between the chemistry of the stratospheres of Venus and the Earth, presented and discussed

Atmospheric pressure as a natural climate regulator for a terrestrial planet with a biosphere

Lovelock and Whitfield suggested in 1982 that, as the luminosity of the Sun increases over its life cycle, biologically enhanced silicate weathering is able to reduce the concentration of atmospheric carbon dioxide (CO_2) so that the Earth's surface temperature is maintained within an inhabitable range. As this process continues, however, between 100 and 900 million years (Ma) from now the CO_2 concentration will reach levels too low for C_3 and C_4 photosynthesis, signaling the end of the solar-powered biosphere. Here, we show that atmospheric pressure is another factor that adjusts the global temperature by broadening infrared absorption lines of greenhouse gases. A simple model including the reduction of atmospheric pressure suggests that the life span of the biosphere can be extended at least 2.3 Ga into the future, more than doubling previous estimates. This has important implications for seeking extraterrestrial life in the Universe. Space observations in the infrared region could test the hypothesis that atmospheric pressure regulates the surface temperature on extrasolar planets

Remote sensing of tropical tropopause layer radiation balance using A-train measurements

Determining the level of zero net radiative heating (LZH) is critical to understanding parcel trajectory in the Tropical Tropopause Layer (TTL) and associated stratospheric hydration processes. Previous studies of the TTL radiative balance have focused on using radiosonde data, but remote sensing measurements from polar-orbiting satellites may provide the relevant horizontal and vertical information for assessing TTL solar heating and infrared cooling rates, especially across the Pacific Ocean. CloudSat provides a considerable amount of vertical information about the distribution of cloud properties relevant to heating rate analysis. The ability of CloudSat measurements and ancillary information to constrain LZH is explored. We employ formal error propagation analysis for derived heating rate uncertainty given the CloudSat cloud property retrieval algorithms. Estimation of the LZH to within approximately 0.5 to 1 km is achievable with CloudSat, but it has a low-altitude bias because the radar is unable to detect thin cirrus. This can be remedied with the proper utilization of Cloud-Aerosol Lidar and Infrared Pathfinder Satellite Observations (CALIPSO) lidar backscatter information. By utilizing an orbital simulation with the GISS data set, we explore the representativeness of non-cross-track scanning active sounders in terms of describing the LZH distribution. In order to supplement CloudSat, we explore the ability of Atmospheric Infrared Sounder (AIRS) and Advanced Microwave Scanning Radiometer-EOS (AMSR-E) to constrain LZH and find that these passive sounders are useful where the cloud top height does not exceed 7 km. The spatiotemporal distributions of LZH derived from CloudSat and CALIPSO measurements are presented which suggest that thin cirrus have a limited effect on LZH mean values but affect LZH variability

Convective flow in the presence of a small obstacle: Symmetry breaking, attractors, hysteresis, and information

This work explores the stability and hysteresis effects that occur when a small sink of momentum is introduced into a heat-driven, two-dimensional convective flow. As per standard fluid mechanical intuition, the system minimizes work generation and dissipation when one component of momentum is extracted. However, when the sink absorbs all incoming momentum, the system configures itself such that one of the convection plumes aligns directly with the sink. This state is the most hydrodynamically stable, but it maximizes, rather than minimizes extracted mechanical work. Furthermore, in the case of only vertical momentum extraction, there are two attractors, with different stabilities. Numerical experiments involving slow variations of the horizontal momentum extraction show a clear history dependence. This hysteresis preserves information about the system's past states, and hence represents a primitive memory. The momentum sink can also be used to manipulate the horizontal position of the flow field, with potential applications in microfluidics and laminar convection systems. This simple system exhibits the phenomena of autocatalysis (during the initial growth of the convection plumes), negative feedback (the attractors are either fully or quasistable), memory, and elementary computation

Triton: Topside ionosphere and nitrogen escape

The principal ion in the ionosphere of Triton is N^+. Energetic electrons of magnetospheric origin are the primary source of ionization, with a smaller contribution due to photoionization. To explain the topside plasma scale height, we postulate that N^+ ions escape from Triton. The loss rate is 3.4 × 10^7 cm^(−2) s^(−1) or 7.9 × 10^(24) ions s^(−1). Dissociative recombination of N^+_2 produces neutral exothermic fragments that can escape from Triton. The rate is estimated to be 8.6 × 10^6 N cm^(−2) s^(−1) or 2.0 × 10^(24) atoms s^(−1). Implications for the magnetosphere of Neptune and Triton's evolution are discussed

On the Insignificance of Photochemical Hydrocarbon Aerosols in the Atmospheres of Close-in Extrasolar Giant Planets

The close-in extrasolar giant planets (CEGPs) reside in irradiated environments much more intense than that of the giant planets in our solar system. The high UV irradiance strongly influences their photochemistry and the general current view believed that this high UV flux will greatly enhance photochemical production of hydrocarbon aerosols. In this letter, we investigate hydrocarbon aerosol formation in the atmospheres of CEGPs. We find that the abundances of hydrocarbons in the atmospheres of CEGPs are significantly less than that of Jupiter except for models in which the CH$_4$ abundance is unreasonably high (as high as CO) for the hot (effective temperatures $\gtrsim 1000$ K) atmospheres. Moreover, the hydrocarbons will be condensed out to form aerosols only when the temperature-pressure profiles of the species intersect with the saturation profiles--a case almost certainly not realized in the hot CEGPs atmospheres. Hence our models show that photochemical hydrocarbon aerosols are insignificant in the atmospheres of CEGPs. In contrast, Jupiter and Saturn have a much higher abundance of hydrocarbon aerosols in their atmospheres which are responsible for strong absorption shortward of 600 nm. Thus the insignificance of photochemical hydrocarbon aerosols in the atmospheres of CEGPs rules out one class of models with low albedos and featureless spectra shortward of 600 nm.Comment: ApJL accepte