If they are the port settings that are in your Windows Live Mail accounts, then avast can't actually scan them (as they are secure encrypted) connections. So avast would normally throw up an error/notification that it can't scan SSL mail.
If you do want avast to scan those email accounts, you have to uncheck the secure connection bit (sorry I don't use Windows Live Mail) and change the ports to smtp 25 and pop3 110.
Your settings in the avast Mail Shield, Expert settings, SSL Accounts, for those accounts would/should be: smtp 465, Encryption SSL; Pop3 995 Encryption SSL.