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Plenty of frogs can be poisonous, but Greening’s frog and Bruno’s casque-headed frog use bony spines on their snouts to break the skin of would-be predators and introduce toxins into their attacker’s bloodstream. This makes them the first species of truly venomous frogs that we know of. And they do it via headbutt.
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Sources:
https://amphibiaweb.org/species/685
https://amphibiaweb.org/species/676
https://www.cell.com/current-biology/fulltext/S0960-9822(15)00788-5
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Images:
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