Already invited a user but need to change the email address? Or need to update an existing user account's email?
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As a Super Admin (what are the different access rights?), you can head to 'Add / Edit Company',

Click 'View Users',

Click 'Edit Access' for the selected User Account,

Finally click 'Remove Access'. 

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Now that the existing account has been removed, you can navigate back to the Employee's Profile (Profiles - Employee Listing - Select and Edit a Profile), to input the new email address, then click 'Create and send invite'.