Most likely you can combine them and they will run at the slower speed. Memory compatibility is so bizzare these days that you'll just have to try it, just make sure the pairs are in the corrct, matching dual channel slots. Be sure to create an ERD or do a system restore point before trying in case Windows gets corrupted. Also be aware that mixing up ram like that can lead to some bizzare, random events....especially on a dual channel system.
Personally, I doubt the added benefit of the extra ram will out weigh the sheer speed of the PC3200, unless he's always working with HUGE files like video editing. Your talking about going from 400MHz DDR down to 266MHz, significantly slower.
Good Luck!