Sometimes you run into distros or occasions where Pithos will always asks you for the keyring password upon first boots.
This is usually just the default GPG keyring not unlocking at boot.
Generally, I’ve found just a discrepancy between your system boot password and the gpg keyring password.
Install Seahorse, right click on “Login” and select “change password”. Usually your current password is the same as your system login. You can enter that password as the old, and then just re-enter it twice as the new.
There’s a few solutions on the net that just say to leave the new password fields empty. You can certainly do this, but it opens up a security concern.
In search of a better answer, I’ve found that just re-syncing the old password and the new password works to stop that pesky keyring pop-up.
For whatever reason…
Hope this helps those who may be looking for a solution.