Ah i see. Well since you tried user1 to user2 i believe they may be in a distribution group of some sort on the pop3 box. Do you have a login/control panel you can check this on?
Also has this ever happened when receiving from a totally different domain? If not then that would support my theory about distribution groups

Also are the pop3 connectors on the mail box direct to each users mailbox? or do u have any addresses taht are distributed to a group?
Thanks
EDIT: i just re-read what u wrote. Did you as the admin send the users an email from the SBS server? because that would indicate a problem on the SBSbox config for sure, rather than any sort of configuration at the external providers end