If you bought it via 3G (from the Kindle, while connected via 3G), it should not be downloaded to your PC. It might be in the PC app's archives, though.
Not sure how Archives work on the newer Kindles, but if it is on your Kindle, it very well might be greyed out in Archives, because it is already downloaded.
I think jocampo means the 'Sync and Check for New Items' option on the Kindle.
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