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The photo above was taken by a group of high school students in Spain who got a camera 100,000 ft in to the atmosphere on a balloon and were able to take photos. Full article is here.
The second article I wanted to share are photos of the shuttle Atlantis approaching the Hubble Space Telescope silhouetted against the sun.
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There are more pictures and information available on the photographer's website here: including pictures of the shuttle Endeavour docked to the ISS.