See also klange's resume: https://github.com/klange/resume. Resume pdf that's also a valid ISO 9660, bootable toaru OS image.
On the other hand, it is possible to make a completely valid PDF and bootable ISO. The first 32KB of an ISO is officially "unused", which is probably why GRUB decided to put itself there, but that can be relocated somewhere else --- the El Torito boot descriptor will need to be updated to point to it --- and the PDF signature (which can be a valid one) and as many objects as will fit can be put in that area, with the rest anywhere else. The xref table can be moved to the very end and the offsets updated to point to the objects.