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I'd like to save the details (headers and contents) of all messages that are rejected when sent out from our server, so I can figure out why they might have been rejected.

Is there any way for postfix to save a message somewhere when it has been rejected?

Forwarding a copy to the root mail account would be fine.

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Add bounce to your notify_classes directive in main.cf. This will send a copy of all of the message headers to postmaster. (For privacy reasons, Postfix truncates the message body on the copy sent to postmaster.)

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