There are sometimes cases where third party services are single username/password that only one user in the company needs access to (or it is registered in their email).
They would put it in their personal password store rather than elsewhere (we can debate the merits of this another time?!)
It would be great as an admin if we can have the option to view a user's passwords, but, with full auditing/warning that comes with it in the logs to make it clear this has happened.