Modeling the distribution of H_2O and HDO in the upper atmosphere of Venus

The chemical and dynamical processes in the upper atmosphere of Venus are poorly known. Recently obtained vertical profiles of trace species from the Venus Express mission, such as HCl, H_2O, and HDO, provide new information to constrain these processes. Here, we simulate these profiles, using the model we have developed and described in a related paper by Yung et al. (2008), with special emphasis on the modeling of H_2O and HDO. A new mechanism, the photo-induced isotopic fractionation effect (PHIFE) of H_2O and HCl, is incorporated into our model. The observed enhancement of HDO could be attributed to (1) preferential destruction of H_2O relative to HDO via PHIFE and (2) escape of hydrogen that enhances the abundance of D and hence its parent molecule HDO. Over a wide range of the sensitivity of the results to the changes of the two mechanisms, we find that the observed profiles of HDO and H2O profiles cannot be explained satisfactorily by current knowledge of chemical and dynamical processes in this region of the atmosphere. Several conjectures to tackle the problems are discussed

Sources of the oxygen isotopic anomaly in atmospheric N_2O

One-dimensional and two-dimensional models are used to investigate the isotopic composition of atmospheric N_2O. The sources of N_2O in the atmosphere are based on recent laboratory measurements of the N_2O quantum yield in the mixture of O_3/O_2/N_2 (Estupiñán et al., 2002). Two recently proposed pathways (Estupiñán et al., 2002; Prasad, 2005) are evaluated in the model. We find that the new atmospheric sources constitute a few percent of the total N_2O source, but can account for ∼50–100% of the Δ^(17)O anomaly observed in N_2O. The essence of the mechanism is to transfer a heavy oxygen atom originally in O_3 to N_2O. The magnitude of Δ^(17)O in N_2O is a linear function of the strength of these new N_2O sources. Laboratory and atmospheric measurements are proposed to confirm the chemical pathways. The potential of Δ^(17)O in N_2O for providing a new tool to probe ozone levels in paleoatmospheres is discussed

A Born-Oppenheimer photolysis model of N_2O fractionation

The isotopically light N_2O produced by microbial activity is thought to be balanced by the return of heavy stratospheric nitrous oxide. The Yung and Miller [1997] method that first explained these trends yields photolytic fractionation factors ∼half those observed by experiment or predicted quantum mechanically, however. To address these issues, we present here a Born-Oppenheimer photolysis model that uses only commonly available spectroscopic data. The predicted fractionations quantitatively reproduce laboratory data, and have been incorporated into zonally averaged atmospheric simulations. Like McLinden et al. [2003] , who employ a three-dimensional chemical transport model with cross sections scaled to match laboratory data, we find excellent agreement between predictions and stratospheric measurements; additional processes that contribute to the mass independent anomaly in N_2O can only account for a fraction of its global budget

Oxygen isotopic composition of carbon dioxide in the middle atmosphere

The isotopic composition of long-lived trace molecules provides a window into atmospheric transport and chemistry. Carbon dioxide is a particularly powerful tracer, because its abundance remains >100 parts per million by volume (ppmv) in the mesosphere. Here, we successfully reproduce the isotopic composition of CO2 in the middle atmosphere, which has not been previously reported. The mass-independent fractionation of oxygen in CO2 can be satisfactorily explained by the exchange reaction with O(1D). In the stratosphere, the major source of O(1D) is O3 photolysis. Higher in the mesosphere, we discover that the photolysis of 16O17O and 16O18O by solar Lyman-{alpha} radiation yields O(1D) 10–100 times more enriched in 17O and 18O than that from ozone photodissociation at lower altitudes. This latter source of heavy O(1D) has not been considered in atmospheric simulations, yet it may potentially affect the "anomalous" oxygen signature in tropospheric CO2 that should reflect the gross carbon fluxes between the atmosphere and terrestrial biosphere. Additional laboratory and atmospheric measurements are therefore proposed to test our model and validate the use of CO2 isotopic fractionation as a tracer of atmospheric chemical and dynamical processes

A DHT-Based Multicarrier Modulation System with Pairwise ML Detection

This paper presents a complex-valued discrete multicarrier modulation (MCM) system based on the real-valued discrete Hartley transform (DHT) and its inverse (IDHT). Unlike the conventional discrete Fourier transform (DFT), the DHT cannot diagonalize multipath fading channels due to its inherent properties, and this results in mutual interference between subcarriers of the same mirror-symmetrical pair. We explore this interference pattern in order to seek an optimal solution to utilize channel diversity for enhancing the bit error rate (BER) performance of the system. It is shown that the optimal channel diversity gain can be achieved via pairwise maximum likelihood (ML) detection, taking into account not only the subcarrier's own channel quality but also the channel state information of its mirror-symmetrical peer. Performance analysis indicates that DHT-based MCM can mitigate fast fading effects by averaging channel power gains of each mirror-symmetrical pair of subcarriers. Simulation results show that the proposed scheme has a substantial improvement in BER over the conventional DFT-based MCM system

Evidence for O-atom exchange in the O(^1D) + N_2O reaction as the source of mass-independent isotopic fractionation in atmospheric N_2O

Recent experiments have shown that in the oxygen isotopic exchange reaction for O(^1D) + CO_2 the elastic channel is approximately 50% that of the inelastic channel [Perri et al., 2003]. We propose an analogous oxygen atom exchange reaction for the isoelectronic O(^1D) + N_2O system to explain the mass-independent isotopic fractionation (MIF) in atmospheric N_2O. We apply quantum chemical methods to compute the energetics of the potential energy surfaces on which the O(^1D) + N_2O reaction occurs. Preliminary modeling results indicate that oxygen isotopic exchange via O(^1D) + N_2O can account for the MIF oxygen anomaly if the oxygen atom isotopic exchange rate is 30–50% that of the total rate for the reactive channels

Photolytically generated aerosols in the mesosphere and thermosphere of Titan

Analysis of the Cassini Ultraviolet Imaging Spectrometer (UVIS) stellar and solar occultations at Titan to date include 12 species: N$_{2}$ (nitrogen), CH$_{4}$ (methane), C$_{2}$H$_{2}$ (acetylene), C$_{2}$H$_{4}$ (ethylene), C$_{2}$H$_{6}$ (ethane), C$_{4}$H$_{2}$ (diacetylene), C$_{6}$H$_{6}$ (benzene), C$_{6}$N$_{2}$ (dicyanodiacetylene), C$_{2}$N$_{2}$ (cyanogen), HCN (hydrogen cyanide), HC$_{3}$N (cyanoacetylene), and aerosols distinguished by a structureless continuum extinction (absorption plus scattering) of photons in the EUV. The introduction of aerosol particles, retaining the same refractive index properties as tholin with radius $\sim$125 \AA and using Mie theory, provides a satisfactory fit to the spectra. The derived vertical profile of aerosol density shows distinct structure, implying a reactive generation process reaching altitudes more than 1000 km above the surface. A photochemical model presented here provides a reference basis for examining the chemical and physical processes leading to the distinctive atmospheric opacity at Titan. We find that dicyanodiacetylene is condensable at $\sim$650 km, where the atmospheric temperature minimum is located. This species is the simplest molecule identified to be condensable. Observations are needed to confirm the existence and production rates of dicyanodiacetylene.Comment: A typo in Table 1 was made in the previous version. The corrected tholin abundance is 4.6x10^11. ApJL in press. Will be published on June 1st, or May 21 onlin

Reply to comment by Röckmann and Kaiser on "Evidence for O-atom exchange in the O(^1D) + N_2O reaction as the source of mass-independent isotopic fractionation in atmospheric N_2O"

Based upon the authors’ questioning of the existence of the C_(2v) intermediate, we have reviewed our evidence for the existence of this state. It now appears that this state was in fact an artifact of our calculation [Yung et al., 2004], and was a saddle point rather than a true minimum. Our desire to provide a timely response to this criticism has kept us from determining exactly what minimum structure will be obtained by a full minimization at the level of theory employed. However, it is clear that the C_(2v) symmetry of the compound is broken in such a way that the two N-O bonds are no longer equivalent. We are grateful to the authors for helping us resolve this issue

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