The role of organic haze in Titan's atmospheric chemistry: I. Laboratory investigation on heterogeneous reaction of atomic hydrogen with Titan tholin

In Titan's atmosphere consisting of N₂ and CH₄, large amounts of atomic hydrogen are produced by photochemical reactions during the formation of complex organics. This atomic hydrogen may undergo heterogeneous reactions with organic aerosol in the stratosphere and mesosphere of Titan. In order to investigate both the mechanisms and kinetics of the heterogeneous reactions, atomic deuterium is irradiated onto Titan tholin formed from N₂ and CH₄ gas mixtures at various surface-temperatures of the tholin ranging from 160 to 310 K. The combined analyses of the gas species and the exposed tholin indicate that the interaction mechanisms of atomic deuterium with the tholin are composed of three reactions; (a) abstraction of hydrogen from tholin resulting in gaseous HD formation (HD recombination), (b) addition of D atom into tholin (hydrogenation), and (c) removal of carbon and/or nitrogen (chemical erosion). The reaction probabilities of HD recombination and hydrogenation are obtained as ηabst=1.9(±0.6)×¹⁰⁻³×exp(−300/T) and ηhydro=2.08(±0.64)×exp(−1000/T), respectively. The chemical erosion process is very inefficient under the conditions of temperature range of Titan's stratosphere and mesosphere. Under Titan conditions, the rates of hydrogenation > HD recombination ? chemical erosion. Our measured HD recombination rate is about 10 times (with an uncertainty of a factor of 3-5) the prediction of previous theoretical model. These results imply that organic aerosol can remove atomic hydrogen efficiently from Titan's atmosphere through the heterogeneous reactions and that the presence of aerosol may affect the subsequent organic chemistry.     

The photochemical formation of a titan haze analog. Structural analysis by x-ray photoelectron and infrared spectroscopy

The photochemical flow reactor (D.W. Clarke et al., 2000, Icarus 147, 282-291) has been modified to minimize the incorporation of oxygen and other impurities in the photoproducts. A mixture of gases that approximate their mixing ratios on Titan (N₂, CH₄, H₂, C₂H₂, C₂H₄, and HC₃N) (0.98, 0.018, 0.002, 3.5 × 10⁻⁴, 3 × 10⁻⁴, 1.7 × 10⁻⁵, respectively) was irradiated in the flow photochemical reactor using a 185-nm source to give a Titan haze analog as a solid product. X-ray photoelectron spectroscopy (XPS) gave a composition of 93.3% C, 5.3% N, and 1.4% O. Of the 93.3% carbon, high-resolution XPS revealed that 81.2% was present as CH, CC, and CC groups, 12.1% may be CO, CN, CN, CN, and/or CN groups, 5.3% as a CN group. The peak for N was symmetrical and was assigned to the CN while that for oxygen was assigned to the CO and/or the CO group. Some of these assignments were confirmed by FTIR spectroscopy. The polymeric product had a C:N ratio of 17.6, which is significantly greater than that for Titan haze analogs prepared in discharge reactions. When the polymer was exposed to air for seven days the oxygen content increased by 6% along with an increase in the infrared absorption at 1710 cm⁻¹ assigned to the CO group of a ketone. The oxidation is attributed to the reaction of oxygen with free radicals trapped in the polymer matrix. It is proposed that the photochemical initiation of Titan haze formation from compounds formed from starting materials formed high in Titan’s atmosphere is a more plausible model than haze formed in reactions initiated by solely by discharges. These data will be helpful in the interpretation of the data returned from the Huygens probe of the Cassini mission.     

Latitudinal transport by barotropic waves in Titan's stratosphere.: II. Results from a coupled dynamics-microphysics-photochemistry GCM

We present a 2D general circulation model of Titan's atmosphere, coupling axisymmetric dynamics with haze microphysics, a simplified photochemistry and eddy mixing. We develop a parameterization of latitudinal eddy mixing by barotropic waves based on a shallow-water, longitude-latitude model. The parameterization acts locally and in real time both on passive tracers and momentum. The mixing coefficient varies exponentially with a measure of the barotropic instability of the mean zonal flow. The coupled GCM approximately reproduces the Voyager temperature measurements and the latitudinal contrasts in the distributions of HCN and C₂H₂, as well as the main features of the zonal wind retrieved from the 1989 stellar occultation. Wind velocities are consistent with the observed reversal time of the North-South albedo asymmetry of 5 terrestrial years. Model results support the hypothesis of a non-uniform distribution of infrared opacity as the cause of the Voyager temperature asymmetry. Transport by the mean meridional circulation, combined with polar vortex isolation may be at the origin of the latitudinal contrasts of trace species, with eddy mixing remaining restricted to low latitudes most of the Titan year. We interpret the contrasts as a signature of non-axisymmetric motions.     

Latitudinal transport by barotropic waves in Titan's stratosphere.: I. General properties from a horizontal shallow-water model

We present a numerical study of barotropic waves in Titan's stratosphere based on a shallow-water model. The forcing of the zonal flow by the mean meridional circulation is represented by a relaxation towards a barotropically unstable wind profile. The relaxation profile is consistent with observations and with previous results from a 3D general circulation model. The time constant of the forcing that best matches the northward eddy-transport of zonal momentum from the 3D model is τ∼5 Titan days. The eddy wind field is a zonal wavenumber-2 wave with a peak amplitude about 10% of the mean wind speed. The latitudinal transport of angular momentum by the wave tends to keep the flow close to marginal stability by carrying momentum upgradient, from the core of the jets into the low latitudes. Although the strongest eddy motions occur at the latitudes of the wind maxima, the strongest mixing takes place at the barotropically unstable regions, close to ±30° and spanning about 30° in latitude. An eddy-mixing time constant of the order of 1 Titan day is inferred within these regions, and of a few tens of days within regions of stable flow. Horizontal gradients in transient tracer fields are less than 10% of the latitudinal gradient of the meridional tracer profile. Cassini's detection of such waves could provide a direct observation of wind speeds at stratospheric levels.     

The role of organic haze in Titan's atmospheric chemistry: II. Effect of heterogeneous reaction to the hydrogen budget and chemical composition of the atmosphere

One of the key components controlling the chemical composition and climatology of Titan's atmosphere is the removal of reactive atomic hydrogen from the atmosphere. A proposed process of the removal of atomic hydrogen is the heterogeneous reaction with organic aerosol. In this study, we investigate the effect of heterogeneous reactions in Titan's atmospheric chemistry using new measurements of the heterogeneous reaction rate [Sekine, Y., Imanaka, H., Matsui, T., Khare, B.N., Bakes, E.L.O., McKay, C.P., Sugita, S., 2008. Icarus 194, 186-200] in a one-dimensional photochemical model. Our results indicate that 60-75% of the atomic hydrogen in the stratosphere and mesosphere are consumed by the heterogeneous reactions. This result implies that the heterogeneous reactions on the aerosol surface may predominantly remove atomic hydrogen in Titan's stratosphere and mesosphere. The results of our calculation also indicate that a low concentration of atomic hydrogen enhances the concentrations of unsaturated complex organics, such as C₄H₂ and phenyl radical, by more than two orders in magnitude around 400 km in altitude. Such an increase in unsaturated species may induce efficient haze production in Titan's mesosphere and upper stratosphere. These results imply a positive feedback mechanism in haze production in Titan's atmosphere. The increase in haze production would affect the chemical composition of the atmosphere, which might induce further haze production. Such a positive feedback could tend to dampen the loss and supply cycles of CH₄ due to an episodic CH₄ release into Titan's atmosphere.     

Ozone abundance on Mars from infrared heterodyne spectra: II. Validating photochemical models

Ozone is an important observable tracer of martian photochemistry, including odd hydrogen (HO_x) species important to the chemistry and stability of the martian atmosphere. Infrared heterodyne spectroscopy with spectral resolution ?¹⁰⁶ provides the only ground-based direct access to ozone absorption features in the martian atmosphere. Ozone abundances were measured with the Goddard Infrared Heterodyne Spectrometer and the Heterodyne Instrument for Planetary Wind and Composition at the NASA Infrared Telescope Facility on Mauna Kea, Hawai'i. Retrieved total ozone column abundances from various latitudes and orbital positions (LS=40°, 74°, 102°, 115°, 202°, 208°, 291°) are compared to those predicted by the first three-dimensional gas phase photochemical model of the martian atmosphere [Lefèvre, F., Lebonnois, S., Montmessin, F., Forget, F., 2004. J. Geophys. Res. 109, doi:10.1029/2004JE002268. E07004]. Observed and modeled ozone abundances show good agreement at all latitudes at perihelion orbital positions (LS=202°, 208°, 291°). Observed low-latitude ozone abundances are significantly higher than those predicted by the model at aphelion orbital positions (LS=40°, 74°, 115°). Heterogeneous loss of odd hydrogen onto water ice cloud particles would explain the discrepancy, as clouds are observed at low latitudes around aphelion on Mars.     

Corona-like atmospheric escape from KBOs: II. The behavior of aerosols

In Levi and Podolak (Levi, A., Podolak, M. [in press] Icarus) we applied the theory of coronal expansion to gas escape from a small, cold, object such as those found in the Kuiper belt. Here we extend the theory to include aerosols that are lifted off the surface by the escaping gas. Aerosols carried by the gas but still gravitationally bound, tend to be lifted to a height above the surface that is dependent on the aerosol radius, so that in steady state the variation of aerosol radius with height is well-defined. We develop an extension of Parker’s coronal flow theory to include the effect of aerosols carried along by the gas and use this to estimate the optical depth of such an atmosphere. For KBOs with CO evaporation from the surface and with radii in the range 245-334 km, line-of-site optical depths through the atmosphere can exceed one at heights of a few hundred kilometers above the surface. Such aerosol layers should be observable, and might be used to infer the flow proprieties of the escaping gas.     

The jovian anticyclone BA: II. Circulation and interaction with the zonal jets

In this second part of our study of the large jovian anticyclone BA we present detailed measurements of its internal circulation and numerical models of its interaction with the zonal jets and nearby cyclonic regions. We characterized the flow using high-resolution observations obtained by the Cassini spacecraft in December 2000 (9 months after the genesis of BA as a result of the merger of two large White Ovals), by the ACS camera onboard HST in January 2005 and April 2006 and by the New Horizons spacecraft in February 2007. Cloud motions were derived from high-resolution images using an automatic correlator that provides a large sampling of the motions in images separated by short time intervals (30 min-2 h). The internal wind structure did not change when the oval changed its color reddening in late 2005-early 2006 and all four datasets from 2000 to 2007 consistently show a similar wind regime: an asymmetric intense anticyclonic vortex with faster winds in its Southern portion with mean speeds of 110 m/s and peak velocities of 135 m/s. These speeds are slightly higher than those measured in the three White Ovals predecessors of BA by the Voyagers [Mitchell, J.L., Beebe, R.F., Ingersoll, A.P., Garneau, G.W., 1981. J. Geophys. Res. 86, 8751-8757] and Galileo [Vasavada, A.R., and 13 colleagues, 1998. Icarus 135, 265-275] but not as much as it has been recently reported [Simon-Miller, A.A., Chanover, N.J., Orton, G.S., Sussman, M., Tsavaris, I.G., Karkoschka, E., 2006. Icarus 185, 558-562; Cheng, A.F., and 14 colleagues, 2008. Astronom. J. 135, 2446-2452]. The asymmetry of the velocities in the vortex is a consequence of the interaction of BA with the zonal circulation and emerges as a natural result in high-resolution simulations of the vortex dynamics using the EPIC model.     

The jovian anticyclone BA: III. Aerosol properties and color change

A study of the vertical cloud structure of oval BA and its red color change is presented in this third part of our complete analysis. A large interest in Jupiter’s anticyclone BA was created by its reddening that occurred between 2005 and 2006. In this work we quantify the color change in oval BA by using images taken with the Advanced Camera for Surveys (ACS) onboard the Hubble Space Telescope (HST) in six filters from the near ultraviolet (F250W) to the deep methane band in the near infrared (F892N). Reflectivity changes are noteworthy in nadir viewing geometry at the ultraviolet and blue wavelengths (F250W, F330W and F435W filters) but almost undetectable or inside error bars in the rest of filters (F550M, F658N and F892N). The observed reflectivity variations are discussed in terms of a commonly accepted vertical cloud structure model for jovian anticyclones in order to explore some causes for the color alteration. Our models of the observed reflectivity variation show that the vortex clouds did not change its vertical extension (top pressure) or its optical depth. We find that a change occurred in the absorbing properties of the particles populating the upper aerosols (single scattering albedo and imaginary refractive index). A discussion on the thermo-physical and dynamical properties of the vortex that could be in the origin of the color change is also presented.     

Direct Monte Carlo and multifluid modeling of the circumnuclear dust coma: Spherical grain dynamics revisited

This paper describes the first computations of dust distributions in the vicinity of an active cometary nucleus, using a multidimensional Direct Simulation Monte Carlo Method (DSMC). The physical model is simplistic: spherical grains of a broad range of sizes are liberated by H₂O sublimation from a selection of nonrotating sunlit spherical nuclei, and submitted to the nucleus gravity, the gas drag, and the solar radiation pressure. The results are compared to those obtained by the previously described Dust Multi-Fluid Method (DMF) and demonstrate an excellent agreement in the regions where the DMF is usable. Most importantly, the DSMC allows the discovery of hitherto unsuspected dust coma properties in those cases which cannot be treated by the DMF. This leads to a thorough reconsideration of the properties of the near-nucleus dust dynamics. In particular, the results show that (1) none of the three forces considered here can be neglected a priori, in particular not the radiation pressure; (2) hitherto unsuspected new families of grain trajectories exist, for instance trajectories leading from the nightside surface to the dayside coma; (3) a wealth of balistic-like trajectories leading from one point of the surface to another point exist; on the dayside, such trajectories lead to the formation of “mini-volcanoes.” The present model and results are discussed carefully. It is shown that (1) the neglected forces (inertia associated with a nucleus rotation, solar tidal force) are, in general, not negligible everywhere, and (2) when allowing for these additional forces, a time-dependent model will, in general, have to be used. The future steps of development of the model are outlined.     

Navier-Stokes and direct Monte-Carlo simulations of the circumnuclear gas coma: III. Spherical, inhomogeneous sources

We pursue our program of comparative simulations of the cometary gas coma by the two most advanced techniques available: (1) numerical solution of Navier-Stokes equations coupled to the Boltzman equation in the surface boundary layer, and (2) direct Monte-Carlo simulation. Here, we consider two different spherical but compositionally inhomogeneous nuclei, at three very different levels of gas production. The results show the same excellent agreement between the two methods in a domain adjacent to the surface as found precedingly, practically down to free-molecular conditions. A wealth of coma density patterns with non-intuitive structure is obtained. Some of these structures appear even under free-molecular effusion from the surface. The physical origin of all structures is discussed, and their evolution with changing gas production is studied. The computed comae are compared to those computed by various authors precedingly. Intercomparison of the present results demonstrates that differing inhomogeneity patterns may lead to similar structures in the gas coma. Comparison between these structures and those created by homogeneous, aspherical surfaces shows that it is not possible to guess from empirical rules which one of the two processes is responsible for the creation of a given structure. The implications for the interpretation of future high resolution images, or of future in situ mass spectrometric samplings of the near-nucleus gas coma are discussed.     

The jovian anticyclone BA: I. Motions and interaction with the GRS from observations and non-linear simulations

A study of the dynamics of the second largest anticyclone in Jupiter, Oval BA, and its red colour change that occurred in late 2005 is presented in a three part study. The first part, this paper, deals with its long-term kinematical and dynamical behaviour monitored since its formation in 2000 to September 2008 using ground-based observations archived at the public International Outer Planet Watch (IOPW) database. The vortex changed its zonal drift velocity from 1.8 m s⁻¹ in the period 2000-2002 to 0.8 m s⁻¹ in 2002-2003, and to 2.5 m s⁻¹ since late 2003. It also migrated southwards by 1.0 ± 0.5° in latitude between 2000 and 2004, remaining afterwards at an almost fixed latitude position. During the period 2000-2007, the oval also changed its triangular-like shape to a more symmetrical one. No latitudinal change was found in the months before the development of a red annulus in its interior. The colour change took place in less than 5 months in 2005-2006 and no red colour feature was observed to have been present or entrained by BA months before the annulus development. After detailed examination of the four encounters between BA and GRS that took place during this 9 year period, we did not detect any noticeable change in its drift rate or in apparent structure associated with the encounters at cloud level. Also, the area of BA did not significantly change in this period. Additionally, we found that BA displays a long-term oscillation of ∼160 days in its longitude position with peak to peak amplitude of 1.2°. Numerical experiments using the global circulation model EPIC reproduce accurately the shape, connecting it to its latitude migration, and morphology of the oval and confirm that no strong interaction between BA and the GRS is possible at least in the current situation.     

“Methane on Mars: A product of H2O photolysis in the presence of CO”: Response to V.A. Krasnopolsky

The detection of CH₄ in the martian atmosphere, at a mixing ratio of about 10 ppb, prompted Krasnopolsky et al. [Krasnopolsky, V.A., Maillard, J.P., Owen, T.C., 2004. Icarus 172, 537-547] and Krasnopolsky [Krasnopolsky, V.A., 2006. Icarus 180, 359-367] to propose that the CH₄ is of biogenic origin. Bar-Nun and Dimitrov [Bar-Nun, A., Dimitrov, V., 2006. Icarus 181, 320-322] proposed that CH₄ can be formed in the martian atmosphere by photolysis of H₂O in the presence of CO. We based our arguments on a clear demonstration that CH₄ is formed in our experiments, and on thermodynamic equilibrium calculations, which show that CH₄ formation is favored even in the presence of oxygen at a mixing ratio 1.3×¹⁰⁻³, as observed on Mars. In the present comment, Krasnopolsky [Krasnopolsky, V.A., 2007. Icarus, in press (this issue)] presents his arguments against the suggestion of Bar-Nun and Dimitrov [Bar-Nun, A., Dimitrov, V., 2006. Icarus 181, 320-322], based on the effect of O₂ on CH₄ formation, the absence of kinetic pathways for CH₄ formation and on the inadequacy of thermodynamic equilibrium calculations to describe the martian atmosphere. In this rebuttal we demonstrate that experiments with molecular oxygen at a ratio of O₂/CO₂=(8.9-17)×¹⁰⁻³, exceeding the martian ratio, still form CH₄. Thermodynamic equilibrium calculations replicate the experimental CH₄ mixing ratio to within a factor of 1.9 and demonstrate that CH₄ production is favored in the martian atmosphere, which is obviously not in thermodynamic equilibrium. Consequently, we do not find the presence of methane to be a sign of biological activity on Mars.     

Analysis of Cassini/CIRS limb spectra of Titan acquired during the nominal mission: I. Hydrocarbons, nitriles and CO2 vertical mixing ratio profiles

Observations of the Composite InfraRed Spectrometer (CIRS) during the entire nominal Cassini mission (2004-2008) provide us with an accurate global view of composition and temperature in the middle atmosphere of Titan (between 100 and 500 km). We investigated limb spectra acquired at resolution at nine different latitudes between 56°S and 80°N, with a better sampling in the northern hemisphere where molecular abundances and temperature present strong latitudinal variations. From this limb data acquired between February 2005 and May 2008, we retrieved the vertical mixing ratio profiles of C₂H₂, C₂H₄, C₂H₆, C₃H₈, CH₃C₂H, C₄H₂, C₆H₆, HCN, HC₃N and CO₂. We present here for the first time, the latitudinal variations of the C₂H₆, C₃H₈, CO₂, C₂H₄ and C₆H₆ vertical mixing ratios profiles. Some molecules, such as C₂H₆ or C₃H₈ present little variations above their condensation level. The other molecules (except CO₂) show a significant enhancement of their mixing ratios poleward of 50°N. C₂H₄ is the only molecule whose mixing ratio decreases with height at latitudes below 46°N. Regions depleted in C₂H₂, HCN and C₄H₂ are observed around 400 km (0.01 mbar) and 55°N. We also inferred a region enriched in CO₂ located between 30 and 40°N in the 2-0.7 mbar pressure range. At 80°N, almost all molecules studied here present a local minimum of their mixing ratio profiles near 300 km (∼0.07 mbar), which is in contradiction with Global Circulation Models that predict constant-with-height vertical profiles due to subsidence at the north pole.     

Saturn’s icy satellites investigated by Cassini-VIMS: II. Results at the end of nominal mission

We report the detailed analysis of the spectrophotometric properties of Saturn’s icy satellites as derived by full-disk observations obtained by visual and infrared mapping spectrometer (VIMS) experiment aboard Cassini. In this paper, we have extended the coverage until the end of the Cassini’s nominal mission (June 1st 2008), while a previous paper (Filacchione, G., and 28 colleagues [2007]. Icarus 186, 259-290, hereby referred to as Paper I) reported the preliminary results of this study.During the four years of nominal mission, VIMS has observed the entire population of Saturn’s icy satellites allowing us to make a comparative analysis of the VIS-NIR spectral properties of the major satellites (Mimas, Enceladus, Tethys, Dione, Rhea, Hyperion, Iapetus) and irregular moons (Atlas, Prometheus, Pandora, Janus, Epimetheus, Telesto, Calypso, Phoebe). The results we discuss here are derived from the entire dataset available at June 2008 which consists of 1417 full-disk observations acquired from a variety of distances and inclinations from the equatorial plane, with different phase angles and hemispheric coverage. The most important spectrophotometric indicators (as defined in Paper I: I/F continua at 0.55 μm, 1.822 μm and 3.547 μm, visible spectral slopes, water and carbon dioxide bands depths and positions) are calculated for each observation in order to investigate the disk-integrated composition of the satellites, the distribution of water ice respect to “contaminants” abundances and typical regolith grain properties. These quantities vary from the almost pure water ice surfaces of Enceladus and Calypso to the organic and carbon dioxide rich Hyperion, Iapetus and Phoebe. Janus visible colors are intermediate between these two classes having a slightly positive spectral slope. These results could help to decipher the origins and evolutionary history of the minor moons of the Saturn’s system. We introduce a polar representation of the spectrophotometric parameters as function of the solar phase angle (along radial distance) and of the effective longitude interval illuminated by the Sun and covered by VIMS during the observation (in azimuth) to better investigate the spatial distribution of the spectrophotometric quantities across the regular satellites hemispheres. Finally, we report the observed spectral positions of the 4.26 μm band of the carbon dioxide present in the surface material of three outermost moons Hyperion, Iapetus and Phoebe.     

Bidirectional reflectance spectroscopy: 6. Effects of porosity

It is well known that the bidirectional reflectance of a particulate medium such as a planetary regolith depends on the porosity, in contrast to predictions of models based on the equation of radiative transfer as usually formulated. It is shown that this failure to predict porosity dependence arises from an incorrect treatment of the light that passes between the particles. In this paper a more physically correct treatment that takes account of the necessity of preventing particles from interpenetrating is used together with the two-stream approximation to solve the radiative transfer equation and derive improved expressions for the bidirectional and directional-hemispherical reflectances. It is found that increasing the filling factor (decreasing the porosity) increases the reflectance of low and medium albedo powders, but decreases it for ones with very high albedos. The model agrees qualitatively with measured data.     

Phase II of the Small Main-Belt Asteroid Spectroscopic Survey: The Observations

We present visible-wavelength (0.435-0.925 μm) spectroscopic measurements for 1341 main-belt asteroids observed during the second phase of the Small Main-belt Asteroid Spectroscopic Survey (SMASSII). The purpose of this survey is to provide a new basis for studying the compositional structure of the asteroid belt. Through the large sample size and the relatively high spectral resolution (R∼100) of the SMASSII data, we find that values of the spectral parameters describing these data form more of a continuum than previously realized. Objects with intermediate spectral characteristics are bridging gaps that once separated distinct spectral classes. In some cases, newly revealed small-scale spectral features may be indicative of previously unrecognized mineral constituents. Here we present the data and principal component analyses that describe the SMASSII spectra. A companion paper utilizes these principal component scores, along with other measures of the spectral features, to develop a new taxonomy that takes advantage of the information contained within charge-coupled device spectra.     

Ozone abundance on Mars from infrared heterodyne spectra: I. Acquisition, retrieval, and anticorrelation with water vapor

Observations of ozone on Mars were made using the Goddard Space Flight Center's Infrared Heterodyne Spectrometer and Heterodyne Instrument for Planetary Wind and Composition at the NASA Infrared Telescope Facility. Ozone is an important observable tracer of martian photochemistry. Infrared heterodyne spectroscopy with spectral resolution ?¹⁰⁶ is the only technique that directly measures ozone in the martian atmosphere from the surface of the Earth. Ozone column abundances down to the martian surface were acquired in seven data sets taken between 1988 and 2003 at various orbital positions (LS=40°, 74°, 102°, 115°, 202°, 208°, 291°). Ozone abundances are compared with those retrieved using ultraviolet techniques, showing good agreement. Odd hydrogen (HO_X) chemistry predicts anticorrelation of ozone and water vapor abundances. Retrieved ozone abundances consistently show anticorrelation with corresponding water vapor abundances, providing strong confirmation of odd hydrogen activity. Deviation from strict anticorrelation between the observed total column densities of ozone and water vapor suggests that constituent vertical distribution is an additional, significant factor.