I tried vinegar and in some cases it simply doesn't show much visible reaction to determine if the rock has any calcium carbonate in it. I thought many of the rocks I have in the aquarium are "safe" since they passed the vinegar test, but when I read about using the #1 bottle of ammonia test (apparently also HCl), I tried and half of what I have in the tank was bubbling! I took some out and left some in since my water is super soft, but that goes to show that vinegar may not catch all rocks.
HCl, when diluted, should be very safe for aquariums... (or even for human for that matter).