Ooookay, ask the chemical geek, eh?
Firstly, even with the even of awakened critters spitting flame, et all, most _dangerous_ poisonous creatures have either an Irritant poison, a tissue-bound compound or an injectile delivery system.
Having an irritant posion that suddenly makes your face melt off, although rather cool, is best left to man-made goodies as mother nature has found stuff like that will simply take up too much of the animal's "system resources" to replentish, maintain and deliver.
Cases:
1: The (Reef) Stonefish, happily hoovering up small fish and crustacea in shallow reef areas. This thing belongs to the
Scorpaenidae, which also includes the Lionfish, Red Scorpion Fish, The Bearded Ghoul... Well, you get the idea. They tend to be spiky, put it that way. The usual way to get envemomated by these suckers is to walk on one of the 13 strongly-anchored dorsal spines, breaking a protein sheath and literally injecting yourself with what's described as "Purified, distilled, hatefull agony from the lake of fire".
So, why the spines, and the "ouch-maker" poison?
Defence. When alarmed, it erects the spines, and hides under the nearest shelter (usually the other foot.) while the stung beastie runs away as fast as it can. And dies. (Out of interest, the
Scorpaenidae family are great eating(Yes, I have.), the Red Scorpionfish also known as "Poorman's Lobster.")
Code: 8S, same damage in stun. Yes. It's that bad.
2: Coneshells. These happy, carnivorous shells with strikingly beautiful patterns (The Geographical Coneshell is prized by collectors.) have an inbuilt poisoned harpoon in their probiscus (Including a magazine of extra rounds!), which they use on anything that comes in reach (10-30 cm, maybe more for other species.) These little suckers kill 8-19 ignorant divers a year. So, why such a horribly-potent neurotoxin? Simple, things in the sea need to eat, and if dinner's dead before you extend your probiscus around it, you feed with less risk. BTW - handle only with BBQ tongs,
IF you must. They can easily hit anything (360 degrees) including faces of interested fellow divers.
Code: 5-8D. (Breathing stops in about 2-9 seconds. Yep.
Seconds. So drop the pretty thing and start CPR.)
3: Box Jellyfish. Similar deliver to the coneshells, but have thousands of limited-range "one-shot" barbs. Agony, yes, Extensive tissue and nerve damage, oh yes. Reason? Feeding. Stealthy because it needs to sneak up to prey, not to ruin a holiday.
Code: Hell, 5M Stun, 2L Physical. Depends on amount and area affected. (Delivery by nanite is about the closest thing to mimic the natural effects, so stick with the cynaide, eh? This was only an example.)
4: Cane Toads: An irritant caustic posion (The previous examples being active protein compounds.) that makes things trying to eat it spit it out in a damn hurry. The posionglands are behind the toad's head and DO NOT spray out. (Except when hit by a golfclub.) Basically, when alarmed it will "sweat" this milky-white crap and not be eaten.
3-5M Stun. It
really hurts kids! Try not to get it into your eyes, either.(Will blind)
I could go into TTX, which causes the Sailfish (about the only thing stupid enough to eat pufferfish apart from Japanese consumers) to get "drunk", but treat it at a 9D when injected, harmless when ingested.
So, if you are wanting a natural poison, stick with what mankind has cooked up in the labs. A concentrated nitric acid solution will cause more pain faster than some home-brewed toxin factory, and you can etch your name in people if you're bored, too.
L.