What is the purpose of the extra wheel on the XB-70 main gear?
It is a sensing wheel that is part of the antiskid braking system. It contains an electronic sensor to measure the true groundspeed of the airplane. See NASA Technical Note D-4836, Landing Loads and Accelerations of the XB-70-1 Airplane (1968), bottom of page 3 of the document (page 5 on the PDF):