If your dog is a curious one, chances are he/she will have an encounter with a skunk sooner or later. Although very smelly, being sprayed by a skunk is in no way harmful to a dog. It may even cause temporary blindness, but a quick flush of the eyes with water should eliminate that.
Here is a police dog handler's special formula for getting rid of that skunky smell:
1 QRT Hydrogen peroxide (3% solution)
2 TBSP Dawn liquid dish soap
1/4 CUP Baking soda
Mix well and use solution to shampoo dog.
Be careful to avoid the eyes.