Toronto is pretty good about separating it's storm and sanitary systems, except for the numerous CSO's around the downtown core.
Like others said, if you find the end of a drain going into a river or stream, it's either a storm drain or a CSO, the latter of which should be dry-ish unless the combined sewer connected to it is overflowing... in which case you shouldn't be out draining anyways.
Personally, I've drained in hiking boots, rain boots, and sandals without issue, and generally I carry two flashlights minimum when exploring, along with my camera gear, and just follow general rules (same for when I explore old mines)... if anyone starts to feel headaches, disoriented, or nausea, we assume we've hit bad air and GTFO.
If you or catdog want to hit some of the Toronto drains, let me know (I've only done a few myself and I'm meaning to get out more), but be warned that I work a very erratic work schedule and my days off are all over the map.