When someone responsible for a particular approval role leaves the company or changes roles, then you need to change his approval role on PPO, by replacing him with a new approver. That change is only effective to new projects going forward because the projects which are already in PPO, will keep the previous incumbent in that approval role even in appending approvals. I think PPO should be designed in such a way that it is able to synchronise the approval requests with the applicable approval rules.
In that way PPO will be able to pick up that when the project was loaded Mr X was responsible for a particular approval role, but now Mr Y is responsible for that approval role. I think such synchronisation can be applied throughout PPO even in other entities.