I have two thoughts. The first is that your difference may have to do with the subjects relationship with the background. In the shot of your daughter, she seems to be separated from the backgound more than your son. For your daughters case the cameras exposure took less account of the backgound and gave a different exposure. The fact that your son was standing closer to the background made the camera take it more into consideration.
The other thing I have noticed about cloudy days is that if the clouds are patchy you can move into and out of very different lighting situations very quickly, and you don't even realize it's happened.
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Mike McCarty
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