Excited-state absorption spectroscopy and ionization threshold measurements for coumarin 314 (C314) adsorbed to the surface of NaCl aerosols characterize the chemical environment of the particle surface as a function of relative humidity (RH). An atmospheric pressure flow of aerosol passes through an ionization cell where two-photon laser ionization of the adsorbed molecules produces a net charge on the particle. Monitoring this charge as a function of the laser wavelength produces either the absorption spectrum of the S(1) <-- S(0) transition or the ionization threshold. The wavelength of maximum absorption for the S(1) excited-state shifts from 448 nm for RH < 5% to 441 nm for RH = 60%, indicating that adsorbed water decreases the polarity of the surface. Similarly, the ionization threshold increases from 5.10 to 5.27 eV over a similar range of RH. The decrease in polarity is attributable to changes in the local electric field experienced by C314, which is on the order of 1 x 10(7) V/cm, and is correlated with changes in the surface topography. Using a continuum model, we estimate the contributions to the measured thresholds of the polarization response of the surface ions and the electric field and calculate an effective dielectric constant for the adsorbed water film. For a multilayer water coverage (RH = 65%), the effective dielectric constant is approximately 2.4. These results demonstrate that the changes in surface topography with adsorbed water are as important as direct water-solute interactions in determining the solvent character of the surface.