According to Apple’s own support forum:
Podcasts which were recently added to the Store, or which recently changed their image, are experiencing delays in the appearance of those images. Once the issue has been resolved, podcasts with valid images will display correctly.
In the meantime, the best action to take is to ensure that the image in the podcast, and the itunes:image tag, are present and valid in the feed. More information is available here:
http://www.apple.com/itunes/store/podcaststechspecs.html#image
Le Sigh.
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