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You can add a user more than once, because a user may be a part of the team for different time frames. In other words users may be entering and leaving a team from time to time. But you can't add a user to the team two times with intersecting start and end times. If you try to add you will receive an error which states "User is already a member of the team for this period".
Removing a User From the Team
To remove a user press the "Delete" link corresponding to the membership. A delete dialog will be displayed. Simply press the Delete button to delete the user, or press cancel if you don't want to delete membership.