When you use a remote ErrorDocument URL like http://mysite.com/my_404.php Apache will send a redirect to that URL to the client, that's why you can't get the URL that causes the 404 from $_SERVER'REQUEST_URI' like Matt Bridges suggested. You might want to try using a local ErrorDocument (no scheme and servername), like this.
This is likely already being done in your Apache log file. You could just parse the data rather than recording it twice.
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