Both copper sulfate and lime sulfur can be irritating to the skin and eyes, so it is very important to wear gloves, long sleeves, and goggles when you spray them -- especially because you are spraying up into a tree, so it's likely to drift. The dormant oil is very low toxicity. Copper sulfate is approved for use by certified organic growers.
See our separate article--Are Dormant Sprays Organic?