We examine the applicability of the assumption that nighttime ozone is in photochemical equilibrium. The analysis is based on calculations with a 3‐D chemical transport model. These data are used to determine the ratio of correct (calculated) O3 density to its equilibrium value for the conditions of the nighttime mesosphere depending on the altitude, latitude, and month in the annual cycle. The results obtained demonstrate that the retrieval of O and H distributions using the assumption of photochemical ozone equilibrium may lead to a significant error below 81–87 km depending on season. Possible modifications of the currently used approach that allow improving the quality of retrieval of O and H mesospheric distributions from satellite‐based observations are discussed.

Abstract. For the retrieval of atomic oxygen via ozone observations in the extended mesopause region under sunlight conditions, two assumptions are used: first, the photochemical equilibrium of ozone and, second, that the ozone losses are dominated by ozone's dissociation from solar UV radiation, silently ignoring the O 3 destruction by atomic hydrogen. We verify both by 3-D modeling. We found that ozone approaches photochemical equilibrium at 75-100 km for daytime conditions. Hence, the first assumption is valid. However, the reaction of ozone with atomic hydrogen was found to be an important loss process and should not be omitted in retrieving atomic oxygen.

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In this work, we compare the values of 15 convective indices obtained from radiosonde and microwave temperature and water vapor profiles simultaneously measured over Nizhny Novgorod (56.2°N, 44°E) during 5 convective seasons of 2014–2018. A good or moderate correlation (with coefficients of ~0.7–0.85) is found for most indices. We assess the thunderstorm prediction skills with a lead time of 12 h for each radiosonde and microwave index. It is revealed that the effectiveness of thunderstorm prediction by microwave indices is much better than by radiosonde ones. Moreover, a good correlation between radiosonde and microwave values of a certain index does not necessarily correspond to similar prediction skills. Eight indices (Showalter Index, Maximum Unstable Convective Available Potential Energy (CAPE), Total Totals index, TQ index, Jefferson Index, S index, K index, and Thompson index) are regarded to be the best predictors from both the true skill statistics (TSS) maximum and Heidke skill score (HSS) maximum points of view. In the case of radiosonde data, the best indices are the Jefferson Index, K index, S index, and Thompson index. Only TSS and HSS maxima for these indices are close to the microwave ones, whereas the prediction skills of other radiosonde indices are essentially worse than in the case of microwave data. The analysis suggests that the main possible reason of this discrepancy is an unexpectedly low quality of radiosonde data.

Abstract. This Technical Note presents a statistical approach to evaluating simultaneous measurements of several atmospheric components under the assumption of photochemical equilibrium. We consider simultaneous measurements of OH, HO 2 , and O 3 at the altitudes of the mesosphere as a specific example and their daytime photochemical equilibrium as an evaluating relationship. A simplified algebraic equation relating local concentrations of these components in the 50-100 km altitude range has been derived. The parameters of the equation are temperature, neutral density, local zenith angle, and the rates of eight reactions. We have performed a one-year simulation of the mesosphere and lower thermosphere using a 3-D chemical-transport model. The simulation shows that the discrepancy between the calculated evolution of the components and the equilibrium value given by the equation does not exceed 3-4 % in the full range of altitudes independent of season or latitude. We have developed a statistical Bayesian evaluation technique for simultaneous measurements of OH, HO 2 , and O 3 based on the equilibrium equation taking into account the measurement error. The first results of the application of the technique to MLS/Aura data (Microwave Limb Sounder) are presented in this Technical Note. It has been found that the satellite data of the HO 2 distribution regularly demonstrate lower altitudes of this component's mesospheric maximum. This has also been confirmed by model HO 2 distributions and comparison with offline retrieval of HO 2 from the daily zonal means MLS radiance.

In this study, the criterion for validity of the nighttime ozone chemical equilibrium assumption in the mesopause region is applied to Sounding of the Atmosphere using Broadband Emission Radiometry data for the year 2004 to define the boundary of this equilibrium. We demonstrate that the boundary varies within the range of 77–86 km depending on season and latitude and the retrieval of atomic oxygen from the equilibrium assumption below this boundary leads to significant (up to 5–8 times) underestimation of this component's concentration in the range of 80–85 km. However, this fact does not influence the subsequent atomic hydrogen retrieval.

Ground-based microwave radiometers are increasingly used in operational meteorology and nowcasting. These instruments continuously measure the spectra of downwelling atmospheric radiation in the range 20–60 GHz used for the retrieval of tropospheric temperature and water vapor profiles. Spectroscopic uncertainty is an important part of the retrieval error budget, as it leads to systematic bias. In this study, we analyze the difference between observed and simulated microwave spectra obtained from more than four years of microwave and radiosonde observations over Nizhny Novgorod (56.2° N, 44° E). We focus on zenith-measured and elevation-scanning data in clear-sky conditions. The simulated spectra are calculated by a radiative transfer model with the use of radiosonde profiles and different absorption models, corresponding to the latest spectroscopy research. In the case of zenith-measurements, we found a systematic bias (up to ~2 K) of simulated spectra at 51–54 GHz. The sign of bias depends on the absorption model. A thorough investigation of the error budget points to a spectroscopic nature of the observed differences. The dependence of the results on the elevation angle and absorption model can be explained by the basic properties of radiative transfer and by cloud contamination at elevation angles.

The mechanism of the generation of reaction-diffusion waves in the mesopause region (80-90 km) has been studied analytically. These waves are the propagating phase fronts arising in the oscillations of O, O 3 , H, OH, and HO 2 concentrations. They appear in the presence of horizontal eddy diffusion in zonal direction when mesospheric photochemistry responds subharmonically (with a period of 2 days) to diurnal variations of solar radiation. The photochemical system in the mesopause region is a nonlinear oscillator which can be roughly described by a system of two differential nonautonomous equations with power law nonlinearity which was derived in our earlier papers. To model the wave propagation, we have considered a continuous chain of oscillators with diffusion coupling and with the phase of external periodic forcing depending linearly on spatial coordinates. It was found that the reaction-diffusion waves are caused by specific "wind" type transport appearing in the equations for the amplitudes of 2-day photochemical oscillations of O and H concentrations due to the zonal inhomogeneity of the external forcing. The obtained expression for the wave propagation velocity fully confirmed the earlier numerical results that the magnitude of the velocity is proportional to the diffusion coefficient and the gradient of the external forcing phase. The wave propagation direction is determined by the definite phase relations specified by internal parameters of the system only.