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Yes. In fact, psylocibin is produced as a result of the fungi metabolism, so if you see mycellium you see psylocibin. Some people extract the compound directly from cakes (without mushrooms)... well i find it not worthing, some might disagree.
As for your 2nd question, if the contaminant is toxic and it's absorved by the mycellium, you'll end up with contaminated mushrooms, well, wich contaminant is toxic ? Good question!! The next step is easy, just don't eat.