Well there are around 175 species and while many are extremely poisonous (the most deadly, the golden poison frog has enough poison to kill 20 men!) others are noticeably less so.
They do secrete the posion onto their skin yes, and it appears as ‘sweat’ so the animal doens’t have to sting or bite you to poison you. However I’m not so sure how quickly the poison acts, it couold be seconds, but that all depends where you get the posion – if you swallowed it, or got it in your eye it would obviously act much faster!
It seems to be more lethal if you have an open wound of eat it raw and it will act faster if it gets into the bloodstream, it is not a very nice way to die!
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