two things to consider here...
for your network part... i would encourage you to use Locations. I have a location for home and location for work. At each location I have it set to join "A specific network". this way when i'm at home it won't join my neighbors access point by accident. locations can be easily changed on the fly from the Apple menu > Locations.
now for Mail the way that you have it worded is a little confusing to me. do you mean that you have one eMail address - xero@loopback.edu for example - and you can send mail from two different SMTP servers as that address? meaning that your work domain is loopback.edu but you go home and connect to (SBC, BellSouth, Comcast - whoever) and you can send mail using their SMTP servers as loopback.edu? if this is the case, then someone is running an unsecured mail server... you shouldn't be able to do that unless you are authorized for relaying. (thought to self: maybe they allow relaying for their scope of IPs?)




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