Evidence from the limb infrared monitor of the stratosphere for nonlocal thermodynamic equilibrium in the nu2 mode of mesospheric water vapour and the nu3 mode of stratospheric nitrogen dioxide

Data from the 6.9-micron H2O channel and the 6.2-micron NO2 channel of the Nimbus 7 Limb Infrared Monitor of the Stratosphere (LIMS) have been used to investigate the daytime enhancement to H2O; the high concentration of H2O sometimes observed in the polar night mesosphere; and the high ratio of daytime to nighttime NO2 in the upper stratosphere. These three phenomena deviate noticeably from the predictions of photochemical theory. The 20 to 30 percent diurnal variation in stratospheric H2O apparent in LIMS data cannot be reconciled with a photochemical lifetime in excess of four months. This is attributed to departure from local thermodynamic equilibrium of daytime emission which had not been accounted for in retrievals. Speculative possibilities of NLTE emission from the H2O nu2 and NO2 nu3 hot bands are discussed. It is found that the nonthermal emission from NO2 significantly affects retrieval of H2O in the polar nighttime and NO2 in the daytime stratosphere at low latitudes.