You can:
1) Use ClientCredentials=Windows on the binding (if client/service host on are the same AD/Network). Then, you would use impersonation or set Windows Credentials on the client, and not use the built in Users table from Config Service at all (still would be using ConfigService, but not using Users table for authentication--on Win Server 2003/2008, you are then using full Kerberos security built into Windows).
2) If you want to pass in username/password from an external net, and use ClientCredentials=UserName, then you could swap out logic in the base CustomUserNameValidator class provided and instead of looking up user in the Config DB Users table, you would use logic to lookup using .NET against AD. Here is an article with some example code for using .NET to perform a lookup against an AD store:
http://www.15seconds.com/issue/020730.htm
-Greg