A new "Bayesian" minimization algorithm for the retrieval of the diurnal variation of UV/vis absorbing radicals (O₃, NO₂, BrO, OClO and HONO) from balloon-borne limb scattered skylight observations is discussed. The method evaluates spectroscopic measurements in combination with radiative transfer calculations to drive a mathematical inversion on a discrete time and height grid. Here, the proposed method is applied to data obtained during two deployments of the mini-DOAS instrument on different balloon payloads in northern Brazil in June 2005. The retrieval is tested by comparing the inferred profiles to in-situ ozone sounding data and to measurements of the ENVISAT/SCIAMACHY satellite instrument performed during a collocated overpass. The comparison demonstrates the strength and validity of our approach. In particular for time-varying radical concentrations, photochemical corrections due to temporal mismatch of the corresponding observations are rendered dispensable. Thus, limb scanning UV/vis spectrometry from balloon platforms offers a more direct and concise approach for satellite validation of radical measurements than solar occultation measurements. Furthermore, monitoring of the diurnal variation of stratospheric radicals allows us to constrain photochemical parameters which are critical for stratospheric ozone chemistry, such as the photolysis frequency of N₂O₅ by observations of the diurnal variation of NO₂.