ABSTRACT A professional dark sky assessment normally requires the numerical modelling of light propagation from ground-based sources into the atmosphere. The spectral power distribution (SPD) of light escaping from an artificial source is one of the key parameters needed in predicting models to simulate the optical signatures of the night sky as a function of distance. SPD at zero distance is due to a non-trivial superposition of light beams, but does not necessarily coincide with the weighted SPD of individual lights. This is because most photons can be removed by obstacles or can interact with many surfaces before being directed into the atmosphere. We have developed an experimental and theoretical method for obtaining the initial SPD from ground-based spectroscopy of the night sky. The method is applicable to distant sources of light and is demonstrated in field measurements conducted on the light dome of Chicago with a new sky glow spectrometer. We show that the method requires analysing the relative impact of local light sources scattered around the measuring site on the radiance of the light dome. Our theoretical method along with ground-based spectroscopy represents a new approach to characterizing light-pollution sources which are otherwise difficult to study due to lack of information on either light-source inventory or a heterogeneous 3D structure of light-emitting and blocking environments.