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That is because the first page (Admin user list page) display Roles as "roll-up" from the Groups a user belongs to. The User page shows the individual settings for the user. Best practices is to not set any individual Roles but instead using Groups.
Thanks to the feedback this will be changing in September. The "roll-up" of Privileges and Knowledge Bases will be displayed on the User page. It will only be possible to select (or deselect) Groups on the User page, we think this will encourage best-practices usage of Groups/KBs/Roles.
With the new update there will also be a new first page for the Admin tab - it will show "All Groups". There will be a new layout on that and the "All Users" page. The columns will also be sortable.
/Carl
There will be no way to add Explicit Role or KB to a user, it all has to go though groups - so the answer is no. For the existing instances that uses this there will be a process of moving to groups where explicit settings has been used.
This should make user management and security much easier to manage.