All rocks are 'safe', as long as they have no metallic veins in them, but some will dissolve over time and increase the hardness and/or pH of your water.
You can try the vinegar test, although vinegar isn't really a strong enough acid. If you can lay your hands on some rust remover, that's the ideal stuff to test rocks with.
Scrubbing with very hot water is all the prep you need do; no boiling or baking in the oven! As Ninj says, that's very dangerous!