As a solo canoeist, (just found out that canoe-er is not a word. thank you spell check!), I do think about personal safety in the same way that I worry about cuts and scrapes, being thirsty or hungry, or getting sunburnt, and therefore take steps to mediate. I don't really worry about 2-legged "critters" when I'm out, though we have our share of backwoods/backwater meth labs around here. Avoidance is a good technique there... "don't tempt fate". I thought about "the danger", and my greatest threating life form is water moccasins. I generally carry a revolver with snake shot in 3 chambers, and 3 more of solid shot, for critters... hogs are not all that aggressive, but when they are, you need more than bear spray to stop them. Since LA doesn't have the most relaxed gun laws, I can't legally cover my weapon up without a permit. However, even if I could, I'd continue to use what I use, and that's an "Alaskan Guide" chest rig. It's there when/if I need it, I can sleep in my hammock with it on, it won't get too muddy (hopefully) if I go overboard, I can wear a backpack over the rig without strap interference, and it's right there in plain sight for the game wardens/rangers/police to see.
I also like being able to reach out a little farther, and if I'm canoeing during a valid small-game season, I sometimes carry the appropriate firearm (.22 or shotgun) in case I happen to run across br'er squirrel or br'er rabbit. I leave the waterfowl alone... costs too much for the extra licenses (state and federal waterfowl stamps) to be worth the trouble/cost vs the amount of meat I'd get, and I'm a terrible shotgunner at hunting distances.
Guns will most certainly fire when wet... mud in the barrel may be an issue, but a bore brush, a piece of strong cord, and an oily rag in a ziplock bag will generally take care of most cleaning problems for any trip.
Regarding hunting, yes, you do occasionally see people hunting from canoes. In many places, it's illegal to take a big-game animal from a powered boat, but canoes are legal for that (again, I'm speaking in generalities... local game laws vary widely). A deer swimming across a river is kind of in a weak position, hence the positioning of hunting blinds near them. I have an uncle who, in his younger days, would spend a couple weeks up the Oswegatchie with a group of friends each Fall, deer hunting, and they brought their harvest out by canoe due to the areas inaccessibility by other means. And I know at least one forum member here hunts/has hunted that same area by going in through Low's Lake.