Team or department mergers before they were announced? Yep, I've caught those. Secret mailing lists for internal projects? Check who's a member and you can ferret out what's going on. Bonus if the list mail address gives some of it away.
`ldapsearch' is good if you know your way around LDAP. Apache LDAP Studio is a great UI tool if you just want to explore.
Everyone should know enough about LDAP to build a login service that binds against it for internal apps. You can exploit the groups the sys admins maintain to control permissions in your app. It's very powerful and an easy way to get up an running in no time.