Yes, but it becomes a casual thing to fire off a pepper round or hit the canister for a spray. It's should be used instead of firing a live round, not as a routine crowd control measure which is what has happened.

Ask the girl from Northeastern doing nothing wrong who got hit with a pepper round by an officer looking to disperse a crowd after the Red Sox won the ALCS this year. Oh that's right, you can't. It hit her in the eye and she died.

Such cases may be rare but they're not unheard of. The way these weapons are marketed and used is as if they were water balloons.