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I know of a site that had some information that was updated about 4 months ago. The site has both HTML and PDF versions of the information. Both were updated on the site the very same day. However, for Google results, the HTML version has updated in the SERPs many months ago, but the PDF version in the SERPs still comes up for the old search terms and the cache still has the old copy.
Google can also see inside Microsoft Word Docs and Rich Text Format stuff, as well as a few others.