If you have NT 4 Enterprise and Exchange Enterprise then you can go to 16 TB for your Private information store.
However there is no limit to the size of a mailbox. The larger it gets the more resources it will take from your machine. Unless you are lucky and have one huge kickass server. You can also set the max size of the each mailbox.
I would really recommend smaller mailbox's 10 meg per user seems reasonable. Hope this Helps
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