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Some tree frogs have a kind of secretion on their skin as well. I remember as a kid handling one and not washing my hands before I happened to touch my lips. Boy did they burn. Not sure what all species you have near you but if licking them brings on that kind of reaction I'd be concerned. What if it's not just short term effects but has some kind of cumulative effect? Or what if it's toxic in large enough amounts. Don't think you have Cane toads in that area but they are deadly toxic.
As for why the dog would do it, she probably chased a frog a few times because of the movement and then found out the effect of licking them. Guess she enjoys her high.
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