still kinda tough to discern what you're asking for, but this code searches through every used cell in every worksheet for a "valid" email address (code for IsEmailValid found here: http://www.vbaexpress.com/kb/getarticle.php?kb_id=281 , commented out several of the validation checks since your emails appear to all have a "," at the end making them invalid...) and if it is valid, searches through column A of Sheet1 to try to find it. Assuming that address is not found, it is added to the end of column A in Sheet1. End result was 7,281 unique email addresses listed in Column A of Sheet1.
As in the attached.
For future reference, it is probably better to use fake data - make up fake email addresses etc... these look like real people and they may not appreciate your having provided their addresses for all the world to see.
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