This paper describes recent advances in the study of self-generated emission of vacuum ultraviolet (VUV) radiation which is produced during the early time period leading to high voltage breakdown at atmospheric pressure. Previous studies of air breakdown showed the presence of 121.5 nm radiation which is spontaneously emitted by excited hydrogen atoms, HI. Since this Lyman-α line is self-absorbed, it enabled inferring various plasma parameters from recording emission spectra from 115-135 nm for species of HI and NI. For instance, measurements in H2/N2 mixtures have revealed that the highest amount of absorption via HI atoms occurs in the high field region near the anode, implying that significant H2 dissociation for radiation-trapping is occurring in this zone. Selective spatial measurements further showed that the apparent VUV emission centers (i.e. streamer heads) move away from the anode and the mechanisms leading to line broadening (i.e. Stark effect from space charge) are a function of streamer position. The presented self-absorption mechanisms are essential in quantitatively understanding the role of VUV radiation transport via absorption for photo-ionization during streamer breakdown, in which re-absorption of high energy photons is inherently a requirement.