It's difficult to say. The histogram on photo 1 is not the same histogram as photo 2, so I can't tell you very much. Are you certain that nothing has been done to the photo after you brought it into PS. Also the color cast of the images is quite different. Are you sure that your color settings in PS are sRGB?
Which version of PS are you using?
As far as Canon histograms go, they have always seemed quite accurate to me. I use the 20D. I calibrated my histogram to the one in Photoshop so that I would know what offset difference there would be. But by an large, for a JPG image, the two histograms should look the same, but may be offset to different locations. If you have anything that would be pure white in the image or a specular, then you would expect to see a spike on the extreme right.
Try drawing and oval around the face with a selection tool and then check the histogram and see if it still has the spike.
Cheers,
rfs
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