Thanks for the reply Ray.
I'm currently running the latest version of the Swerts-Knudsen SpamAssassin & ClamAV installs, and using the RBL functionality through his Server Manager page. This has gotten rid of several regular offenders, but not these three. I am also unable to block executable content as several of the users regularly get sent scripts and small executable applications - retraining the users is not a viable option (under a management directive). [Read this as the boss of the small firm is technology illiterate, and has a hard enough time as it is, without changing the way he and his staff do things]
I have reported the emails to the ISP, SpamCop, etc but rather than wait any longer for the IP to be added to an RBL, I want to be able to manually add IP addresses myself.
After reviewing the SA documentation, it should be possible to do it that way, so now it's just a case of working out the finer details. If I can work out a viable solution before someone can provide an answer, I'll post it here.
FWIW it seems that the compromised PCs owners' were all attendees of a recent school reunion, and had their email addresses published on a public website in good faith. We only tracked this down because several of the spam emails contained addresses remarkably similar to those of other attendees, and the ISPs & locations seem to match up too well to be coincidence. Pity that none of these folk seem to respond to emails either...