Elimination by insect family and chemical ecology:
Buprestid (jewel) beetles are wood-boring insects with no known defensive toxin of medicinal relevance. Chafer beetles (Scarabaeidae) are plant and root feeders without a comparable defensive chemical. Pulse beetles (Bruchidae) are stored-grain pests, again with no such toxin.
Only members of the family Meloidae, the blister beetles, secrete cantharidin, historically called "Spanish fly", as a haemolymph-based defensive compound that causes blistering on contact.
By elimination of the other three beetle groups, the source is the Blister Beetle.