Yuk L. Yung

Photochemistry of the atmosphere of Titan - Comparison between model and observations

The photochemistry of simple molecules containing carbon, hydrogen, nitrogen, and oxygen atoms in the atmosphere of Titan has been investigated using updated chemical schemes and our own estimates of a number of key rate coefficients. Proper exospheric boundary conditions, vertical transport, and condensation processes at the tropopause have been incorporated into the model. It is argued that he composition, climatology, and evolution of Titans atmosphere are controlled by five major processes: (a) photolysis and photosensitized dissociation of CH4; (b) conversion of H to H2 and escape of hydrogen; (c) synthesis of higher hydrocarbons; (d) coupling between nitrogen and hydrocarbons; (e) coupling between oxygen and hydrocarbons. Starting with N2, CH4, and H2O, and invoking interactions with ultraviolet sunlight, energetic electrons, and cosmic rays, the model satisfactorily accounts for the concentrations of minor species observed by the Voyager IRIS and UVS instruments. Photochemistry is responsible for converting the simpler atmospheric species into more complex organic compounds, which are subsequently condensed at the tropopause and deposited on the surface. Titan might have lost 5.6 x 10(4), 1.8 x 10(3), and 4.0 g cm-2, or the equivalent of 8, 0.25, and 5 x 10(-4) bars of CH4, N2, and CO, respectively, over geologic time. Implications of abiotic organic synthesis on Titan for the origin of life on Earth are briefly discussed.

Greenhouse Effects due to Man-Made Perturbations of Trace Gases

Nitrous oxide, methane, ammonia, and a number of other trace constituents in the earths atmosphere have infrared absorption bands in the spectral region 7 to 14 �m and contribute to the atmospheric greenhouse effect. The concentrations of these trace gases may undergo substantial changes because of mans activities. Extensive use of chemical fertilizers and combustion of fossil fuels may perturb the nitrogen cycle, leading to increases in atmospheric N2O, and the same perturbing processes may increase the amounts of atmospheric CH4 and NH3. We use a one-dimensional radiative-convective model for the atmospheric thermal structure to compute the change in the surface temperature of the earth for large assumed increases in the trace gas concentrations; doubling the N2O, CH4, and NH3 concentrations is found to cause additive increases in the surface temperature of 0.7�, 0.3�, and 0.1�K, respectively. These systematic effects on the earths radiation budget would have substantial climatic significance. It is therefore important that the abundances of these trace gases be accurately monitored to determine the actual trends of their concentrations.

Water vapour in the atmosphere of a transiting extrasolar planet

Water is predicted to be among the most abundant (if not the most abundant) molecular species after hydrogen in the atmospheres of close-in extrasolar giant planets (‘hot Jupiters’). Several attempts have been made to detect water on such planets, but have either failed to find compelling evidence for it or led to claims that should be taken with caution. Here we report an analysis of recent observations of the hot Jupiter HD 189733b (ref. 6) taken during the transit, when the planet passed in front of its parent star. We find that absorption by water vapour is the most likely cause of the wavelength-dependent variations in the effective radius of the planet at the infrared wavelengths 3.6 μm, 5.8 μm (both ref. 7) and 8 μm (ref. 8). The larger effective radius observed at visible wavelengths may arise from either stellar variability or the presence of clouds/hazes. We explain the report of a non-detection of water on HD 189733b (ref. 4) as being a consequence of the nearly isothermal vertical profile of the planet’s atmosphere.

Ethane ocean on Titan

It is proposed that Saturns satellite Titan is covered by an ocean one to several kilometers deep consisting mainly of ethane. If the ocean is in thermodynamic equilibrium with an atmosphere of 3 percent (mole fraction) methane, then its composition is roughly 70 percent ethane, 25 percent methane, and 5 percent nitrogen. Photochemical models predict that ethane is the dominant end product of methane photolysis so that the evolving ocean is both the source and sink for continuing photolysis. The coexisting atmosphere is compatible with Voyager data.

Atmospheric bromine and ozone perturbations in the lower stratosphere

The role of bromine compounds in the photochemistry of the natural and perturbed stratosphere has been reexamined using an expanded reaction scheme and the results of recent laboratory studies of several key reactions. The most important finding is that through the reaction BrO + CIO → Br + Cl + O2, there is a synergistic effect between bromine and chlorine which results in an efficient catalytic destruction of ozone in the lower stratosphere. One-dimensional photochemical model results indicate that BrO is the major bromine species throughout the stratosphere, followed by BrONO2, HBr, HOBr and Br. We show from the foregoing that bromine is more efficient than chlorine as a catalyst for destroying ozone, and discuss the implications for stratospheric ozone of possible future growth in the industrial and agricultural use of bromine. Bromine concentrations of 20 pptv (2 × 10^−11), as suggested by recent observations, can decrease the present-day integrated ozone column density by 2.4%, and can enhance ozone depletion from steady-state chlorofluoromethane release at 1973 rates by a factor of 1.1–1.2.

Precision requirements for space-based XCO 2 data

Precision requirements are determined for space-based column-averaged CO_2 dry air mole fraction (X_(CO)_2) data. These requirements result from an assessment of spatial and temporal gradients in (X_(CO)_2) the relationship between (X_(CO)_2) precision and surface CO_2 flux uncertainties inferred from inversions of the (X_(CO)_2) data, and the effects of (X_(CO)_2) biases on the fidelity of CO_2 flux inversions. Observational system simulation experiments and synthesis inversion modeling demonstrate that the Orbiting Carbon Observatory mission design and sampling strategy provide the means to achieve these (X_(CO)_2) data precision requirements.

Photochemistry of the stratosphere of Venus: Implications for atmospheric evolution☆☆☆

The photochemistry of the stratosphere of Venus was modeled using an updated and expanded chemical scheme, combined with the results of recent observations and laboratory studies. We examined three models, with H2 mixing ratio equal to 2 × 10^(−5), 5 × 10^(−7), and 1 × 10^(−13), respectively. All models satisfactorily account for the observations of CO, O_2, O_2(^1Δ), and SO_2 in the stratosphere, but only the last one may be able to account for the diurnal behavior of mesospheric CO and the uv albedo. Oxygen, derived from CO_2 photolysis, is primarily consumed by CO_2 recombination and oxidation of SO_2 to H_2SO_4. Photolysis of HCl in the upper stratosphere provides a major source of odd hydrogen and free chlorine radicals, essential for the catalytic oxidation of CO. Oxidation of SO_2 by O occurs in the lower stratosphere. In the high-H_2 model (model A) the O-O bond is broken mainly by S + O_2 and SO + HO_2. In the low-H_2 models additional reactions for breaking the O-O bond must be invoked: NO + HO_2 in model B and ClCO + O_2 in model C. It is shown that lightning in the lower atmosphere could provide as much as 30 ppb of NO_x in the stratosphere. Our modeling reveals a number of intriguing similarities, previously unsuspected, between the chemistry of the stratosphere of Venus and that of the Earth. Photochemistry may have played a major role in the evolution of the atmosphere. The current atmosphere, as described by our preferred model, is characterized by an extreme deficiency of hydrogen species, having probably lost the equivalent of 10^2–10^3 times the present hydrogen content.

The Atmospheric Trace Molecule Spectroscopy (ATMOS) Experiment: Deployment on the ATLAS space shuttle missions

The ATMOS Fourier transform spectrometer was flown for a fourth time on the Space Shuttle as part of the ATLAS-3 instrument payload in November 1994. More than 190 sunrise and sunset occultation events provided measurements of more than 30 atmospheric trace gases at latitudes 3–49°N and 65–72°S, including observations both inside and outside the Antarctic polar vortex. The instrument configuration, data retrieval methodology, and mission background are described to place in context analyses of ATMOS data presented in this issue.

MOLECULAR SIGNATURES IN THE NEAR-INFRARED DAYSIDE SPECTRUM OF HD 189733b

We have measured the dayside spectrum of HD 189733b between 1.5 and 2.5 μm using the NICMOS instrument on the Hubble Space Telescope. The emergent spectrum contains significant modulation, which we attribute to the presence of molecular bands seen in absorption. We find that water (H2O), carbon monoxide (CO), and carbon dioxide (CO2) are needed to explain the observations, and we are able to estimate the mixing ratios for these molecules. We also find temperature decreases with altitude in the ~0.01 < P< ~1 bar region of the dayside near-infrared photosphere and set an upper limit to the dayside abundance of methane (CH4) at these pressures.

WATER, METHANE, AND CARBON DIOXIDE PRESENT IN THE DAYSIDE SPECTRUM OF THE EXOPLANET HD 209458b

Using the NICMOS instrument on the Hubble Space Telescope, we have measured the dayside spectrum of HD 209458b between 1.5 and 2.5 μm. The emergent spectrum is dominated by features due to the presence of methane (CH4) and water vapor (H2O), with smaller contributions from carbon dioxide (CO2). Combining this near-infrared spectrum with existing mid-infrared measurements shows the existence of a temperature inversion and confirms the interpretation of previous photometry measurements. We find a family of plausible solutions for the molecular abundance and detailed temperature profile. Observationally resolving the ambiguity between abundance and temperature requires either (1) improved wavelength coverage or spectral resolution of the dayside emission spectrum or (2) a transmission spectrum where abundance determinations are less sensitive to the temperature structure.