Figuratively speaking JPA is just interface, Hibernate/TopLink - class (i.e. interface implementation).
You must have interface implementation to use interface. But you can use class through interface, i.e. Use Hibernate through JPA API or you can use implementation directly, i.e. use Hibernate directly, not through pure JPA API.
Good book about JPA is "High-Performance Java Persistence" of Vlad Mihalcea.