I would imagine the most scaleable method would be to store an fingerprint with each image. Then when a new image is added, it's a simple case of SELECT id FROM photos where id='uploaded_image_id' to check for duplicates (or fingerprinting all the images, then doing a query for duplicate
Obviously a simple file-hash wouldn't work as the actual content differs..
Acoustic fingerprinting/this paper may be a good start on the concept, as there are many implementations of this. Here is a paper on image fingerprinting.
That said, you may be able to get away with something simpler. Something as basic as resizing the image to equal width or height, subtracting image_a from image_b, and summing the difference. If the total difference is below a threshold, the image is a duplicate.
The problem with this is you need to compare every image to every other. The time required will exponentially increase..
