If you send an e-mail message that cannot be delivered (for example you use the wrong address), typically the mail message will be forwarded to the postmaster of your machine. There is usually no account called postmaster, postmaster is a mail alias.
When the mail delivery program gets mail for postmaster it will not be able to find a matching username. Instead it will look up a specific file, under Linux /etc/aliases. This file will typically have an entry like postmaster: root
This tells the delivery program that anything addressed postmaster should actually be delivered to the user root. Take a look at the /etc/aliases file on your system for other aliases.
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