Estimation of the amount of tropospheric ozone in a cloudy sky by ground-based Fourier-transform infrared emission spectroscopy

The problem of retrieving minor concentrations of constituents by ground-based Fourier-transform infrared emission spectroscopy is addressed by means of the concept of differential optical emission spectroscopy in analogy to the concept of differential optical absorption spectroscopy. Using the prominent ν3 ozone feature at 1043 cm-1, we show that the strength of the spectral signature depends not only on the amount of ozone but also on the atmospheric thermal structure. This dependence can be described by a rather accurate approximation, which was used to construct a simple diagram to estimate the amount of column ozone between the instrument site and a cloud deck as well as to determine the detection limit. The detection limit is shown to depend on cloud base height. For a given thermal lapse rate it was found that the lower the detection limit, the higher the cloud base altitude. However, as shown in a case study with variable cloud base height, the concept fails for semitransparent clouds. Multiple scattering of the emitted radiation within the clouds yielded a path enhancement that simulated an enhanced amount of constituent. The path enhancement was estimated to be 2.4–4 km at 1000 cm-1 for low-level clouds, equivalent to an enhancement factor of 6–21. The multiple scattering effect has considerable consequences for ground-based as well as for nadir satellite retrieval techniques in cloudy skies.