アイテム詳細

要旨

Experience of differential atmospheric absorption spectroscopy (DOAS) shows that a spectral shift between measurement and reference spectrum is frequently required in order to achieve optimal fit results, while the straight forward calculation of the optical density proves inferior. The shift is often attributed to temporal instabilities of the instrument, but implicitly solved the problem of the "tilt-effect" discussed/explained in this paper. Spectral positions of Fraunhofer and molecular absorption lines are systematically shifted for different measurement geometries due to an overall slope – or "tilt" – of the intensity spectrum. The phenomenon has become known as "tilt effect" for limb satellite observations, where it is corrected for in a first order approximation, whereas the remaining community is less aware of its cause and consequences. It is caused by the measurement process because atmospheric absorption and convolution in the spectrometer do not commute. Highly resolved spectral structures in the spectrum first will be modified by absorption and scattering processes in the atmosphere. before they are recorded with a spectrometer, which convolves it with a specific instrument function. In the DOAS spectral evaluation process, however, the polynomial (or other function used for this purpose) accounting for broadband absorption is applied after the convolution is performed. In this paper, we derive that changing the order of the two modifications of the spectra leads to different results. Assuming typical geometries for the observations of scattered sunlight and a spectral resolution of 0.6 nm, this effect can be interpreted as a spectral shift of up to 1.5 pm, which is confirmed in actual the analysis of the ground based measurements of scattered sunlight as well as in numerical radiative transfer simulations. If no spectral shift is allowed by the fitting routine, residual structures of up to 2.5 × 10−3 peak-to-peak are observed. Thus, this effect needs to be considered for DOAS application aiming at RMS of the residual of 10−3 and below.