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Are they getting the following error on your Authorize.Net payment form?
Error 11: A duplicate transaction has been submitted.
If this is the case, you might consider suggesting your customers wait two minutes before submitting a new form entry (to bypass Authorize.Net duplicate transaction time frame), or use another credit card for the second entry.
There is Duplicate Transaction tracking mechanism on Authorize.Net, it has two minutes time frame by default. You can find more information in their documentation:
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