The positive column of dc excited atmospheric pressure glow discharges in a metal pin–water electrode system is investigated in air, N2, He, Ar, N2O, CO2 and He–N2 mixtures. The electric field and the plasma temperatures in the positive column are measured and the effect of the filling gas on the optical emission is examined. Estimates of the electron temperature and density and the observed emission properties indicate that the formation processes of the excited dissociation fragments of H2O are due to recombination processes rather than direct electron excitation. Deviation from a Boltzmann rotational population distribution of OH(A) is observed in all gases due to the formation process of OH(A). In the case of He the non-Boltzmann behavi...