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Two hitherto neglected mechanisms, which occur at the interface between insulating liquids and metal electrodes under high electrical fields, are considered and shown to be significant for the initiation of breakdown. One involves the Lippmann effect in which the electrical fields of the double layers at the electrodes reduce the interfacial tension and lead to the generation of low-density microcavities on the electrode surfaces. The other is the Auger effect in which non-radiative recombination of electrons and positive holes across the large energy gap between these states leads to secondary electrons of high energy. The coupling between these two mechanisms is expected to be highly conducive to streamer initiation at the electrodes.