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I think Epic tier bugs are the ones. You can get them from Soul Destroyer Forest. Legendary Bugs will increase by 5 and Epic will increase by 1
You'll need to deal with the reduced HP/MP or offset it with Herbs from Soul Destroyer Forest.
You can also trade Poison Characters for a Toxicology book for + 3 or 5 Toxicology but there are only a few of those.
if you are trying to do the plant sect quest then just get the lady in chuliang city in your team, you do not need to have the skills yourself anyone in your team having the skill is enough.
Meeting Miao Caidie also gives you +25 Toxicology and 1 Epic Bug.
She also has a Legendary Bug, 9 Epic Bugs, and a Epic Toxicology book (+10 Toxicology but need 100+ Toxicology to use)
Jiang Ziyan (Lady in Chuxiang City Inn as mentioned above) also has a Blue Toxicology Book (+5 Toxicology but need 5+ Toxicology to use).
She also gives you an accessory that boosts the chances to get both Epic(+150%) and Legendary Bugs(+50%) if you want to get the 200+ and 500+ Toxicology Achievements/Traits
If you are under 100.
Miao Caidie can try Gu. (You need to be in the tribe)