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It's a classic [[Sam ]] expression, used to expression show a range of feelings from extreme displeasure to bemusement.

The term "Sturgeon Face" arose from the expression's resemblance to the underside of a sturgeon, a connection popularized by an internet meme which defines it as "turning down one’s corners that traces the origin to places outside of mouth so that it forms an excessive frown"Supernatural fandom.[http://knowyourmeme.com/memes/sturgeon-face source].