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In Outlook Express, take
File>>Identities>>Manage Identities..

In the following screen click on the
New button.

Now, type the name of the new
Identity. And tick mark the "Require a password"
check box. Now you will be asked for a new password. Give the
password and click on OK.

Now, the new Identity is created,
and if you want to switch over to the new Identity, click on the
"Yes" button in the following screen. Now you need to
re-configure your POP3 account.

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