Answer: fourth option, the crystals phosphoresced when they were exposed to light, exposing the film.
Justification:
Becquerel experiment was developed to study the phosphoresence: the materials exposed to sunlight are able to emit that absorbed light when the exposition ends and they glow in the dark.
That effect is what he was expecting, predicted and obtained.
Nevertheless, further experimentation, one day in which the samples (crystals) were not exposed to the sunlight, they still were able to emitt light (exposing the film), so he concluded that the crystals were radiactive (emitted radiation per se)