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Visible emission from Rb optical pumping cells was characterized under a range of conditions relevant to the production of laserpolarized xenon (including temperature, partial pressures, and D1-resonant 795 nm laser power). Bright 421 nm (6P --> 5S) emission was consistent with energy-pooling processes of the type: Rb*(5P1/2) + Rb*(5P1/2,3/2) --> Rb*(6P1/2,3/2) + Rb(5S1/2), with processes transiting through 5D states likely contributing at higher temperatures/lower N2 partial pressures. Under such conditions a number of Rb lines may be observed, indicating population of Rb states to P9D (~31822 cm^-1). Such energies exceed those required for efficient production of laser-induced plasma.