The spectroscopic characteristics of the polarization of 129Xe nuclei in Xe gas by spin exchange with optically pumped Rb atoms is examined in high magnetic field. The high field Zeeman effect provides the spectral dispersion necessary to separate the effects of different light polarizations and incident wavelengths on the pumping cycle. Indirect detection of the D1 line in Rb using 129Xe nuclear magnetic resonance in combination with direct optical detection indicates that conventional container construction significantly decreases the efficiency of the 129Xe polarization. The decreased pumping efficiency is due to randomly polarized photons that can be eliminated by using containers with good optical quality windows. Study of these effects is facilitated by the large Zeeman shifts obtained with multi-tesla fields which resolve the D1 multiplet structure even in the presence of the significant pressure-broadening incells with typical gas pressures of 0⋅1-1 atm.