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You could open up the preference file at:

~/Library/Preferences/com.omnigroup.OmniWeb5.plist

and add your black list entries this way. They black list is kept in the "OWAddressesToFilter" key.

You'll need a plist editor to edit this. One comes with the Apple Developer Tools or you could get PlistEdit Pro:

http://homepage.mac.com/bwebster/plisteditpro.html