I checked out some of the ideas posed here, and would like to share the results:
View > Proof Colors would change the appearance onscreen, but would not change the RGB values in the Info Panel.
If it's on one Layer, Paint Bucket Blend Mode would not change the color and rgb values without another layer to interact with.
Paint Bucket Opacity reduced from 100% would darken the colors and change the RGB values.
So it looks to be in the Paint bucket tool, unless he is getting the same results with other tools like the Brush Tool.
Alt + backspace would also fill his document with the Foreground color and we can see if the results are the same.