I was just reading about the environment.2da thing last night. For weather presets in the toolset, that's what you'd want to edit. AFAIK, that's all environment.2da is for. Never messed with it, myself.
The weather does appear to be hardcoded, at least in the respect that fx_rain, fx_snow and fx_lightning01 are all referenced directly in nwmain.exe. You can edit those models though, but it's going to change the effect everywhere.
If you want to play around with making custom weather effects, like new types of rain, maybe experiment with VFX first instead of placeables?. Rain is just an illusion. When it's raining, it's not raining everywhere in a level. Just on the player.
Here is a link to a modified fx_rain.mdl which should allow you to see more clearly how rain really works. It has been modified quite a bit to exaggerate the beahvior of what rain does and how it's applied. Just pop it into your override and go into a rainy area.
Change the camera orientation, move around, etc. See what I mean?
I'm not sure how well this would actually translate over to VFX or what kind of gotchas are hiding there or, perhaps, in multiplayer situations. Might be easiest to start there, though.