This issue can occur when inactive users are added in 'Approval Step 1' of the Approval Process.
Note: This can also happen if the User record of the affected user has the "Receive Approval Request Emails" field set to "Never." To check, go to:
In Salesforce Classic: Setup | Manage Users | Users
In Lightning Experience: gear icon | Setup | Users | Users
After following the above information, it might be necessary to request the email logs to see if Salesforce is sending the emails out. If the emails are being sent from Salesforce, work with your internal IT team with the message IDs to investigate further.
000387402

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