Abstract. Methods of UV/VIS absorption spectroscopy to determine the constituents in the Earth's atmosphere from measurements of scattered light are often based on the Beer-Lambert law, like e.g. Differential Optical Absorption Spectroscopy (DOAS). Therefore they are strictly valid for weak absorptions and narrow wavelength intervals (strictly only for monochromatic radiation). For medium and strong absorption (e.g. along very long light-paths like in limb geometry) the relation between the optical depth and the concentration of an absorber is not linear anymore. As well, for large wavelength intervals the wavelength dependent differences in the travelled light-paths become important, especially in the UV, where the probability for scattering increases strongly with decreasing wavelength. However, by taking into account these dependencies, the applicability of the DOAS method can be extended also to cases with medium to strong absorptions and for broader wavelength intervals. Common approaches for this correction are the so called air mass factor modified (or extended) DOAS and the weighting function modified DOAS. These approaches take into account the wavelength dependency of the slant column densities (SCDs), but also require a-priori knowledge for the air mass factor or the weighting function calculation by radiative transfer modelling. We describe an approach that considers the fitting results obtained from DOAS, the SCDs, as a function of wavelength and vertical optical depth and expands this function into a Taylor series of both quantities. The Taylor coefficients are then applied as additional fitting parameters in the DOAS analysis. Thus the variability of the SCD in the fit window is determined by the retrieval itself. This new approach gives a description of the SCD that is as close to reality as desired (depending on the order of the Taylor expansion), and is independent from any assumptions or a-priori knowledge of the considered absorbers. In case studies for simulated and measured spectra in the UV (332–357 nm), we demonstrate the improvement by this approach for the retrieval of vertical profiles of BrO from the SCIAMACHY limb observations. Compared to the standard DOAS approach, the results for BrO obtained from the simulated spectra are closer to the true profile, when applying the new method for the SCDs of ozone. Also for the measured spectra the agreement with validation measurements is improved significantly, especially for cases with strong ozone absorption. While the focus of this article is on the improvement of the BrO profile retrieval from the SCIAMACHY limb measurements, the novel approach may be applied for a wide range of DOAS retrievals.
Averaging kernels for DOAS total-column satellite retrievals
