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to get a poison barb in Pokemon emerald(*1), first get a Pokemon that knows the move THIEF(*2). next you go into the desert sand in route 111, (the sand acts like grass so wild Pokemon will appear while in it) there is a chance that a wild cacnea will attack you. if you are super lucky(*3) the cacnea will be holding a poison barb which is used for increasing the power of poison type moves like ACID.

Hope it helps, from Pokemon emerald trainer: Coolguy

(*1) wild roslia also hold it in ruby or Sapphire

(*2) it is also a TM that you can get in slateport city

(*3) there is a 5% chance it will hold a poison barb

(*4) I am sorry for any misspellings I may have made

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