It appears interbase has no easy way to SQL populate a guid field. Therefore the solution is to create your own UDF function in the database to create a random guid. It then becomes a three step process:
Add the field to the table
ALTER TABLE IBUSERS ADD IBUSERSPK VARCHAR(32) NOT NULL
Populate the new field using the UDF:
UPDATE IBUSERS SET IBUSERSPK = GETGUID()
Add primary key constraint if it is such:
ALTER TABLE IBUSERS ADD CONSTRAINT PK_IBUSERS PRIMARY KEY (IBUSERSPK)
The nice thing about this is that then this function can be used anytime/anywhere in the database.