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I need one for my competitive team and a black sludge is one of the items I can't find. Can I have some help?

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You have to uses Thief, Covet, Trick or Switcheroo to pinch it off of wild Grimer, Muk, Trubbish, and Garbador. They have a 5% chance of holding a Black Sludge — use the DexNav to search until you find one holding the item.

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Alternatively you can use a Pokémon with Frisk and catch it.