The surface composition of an Au-62at%Pd alloy has been studied by means of a catalytic atom probe (CAP) before and after exposures to nitric oxide (NO) at temperatures ranging from 300 to 573K for 20min. Subsequent CAP analysis at 100K revealed a considerable surface enrichment in Pd (to approximately 80at%) after exposure at 573K. This is correlated with the occurrence of NO dissociation, and the formation of strong Pd-O bonds at the surface. Blank experiments in ultra-high vacuum reflect the surface composition of the bulk material, in excellent agreement with electron microprobe analysis. At 573K, no detectable surface segregation occurs in the absence of NO adsorption for the times and temperatures studied. However, classical Metropolis Monte-Carlo simulations performed with a semi-empirical potential on the Au(40)Pd(60) (111), (110) and (100) systems show surface enrichment of gold at equilibrium. This suggests that the temperatures of the clean surface segregation experiments are too low to reach equilibrium within times of the order of hours.