Single crystal sapphire substrates were lithographically patterned with a system of parallel platinum electrodes, which were used to manipulate 1.58μm silica particles inplane, in the presence of an aqueous solution. Observation of the motion of these particles revealed the adhesion of some of them to the sapphire surface near the platinum working electrode, even in the range of pH where the zeta potentials of silica and sapphire are of the same sign. This phenomenon suggests the existence of localized differences in pH, attributable to the presence of potential determining ions produced in the faradaic processes occurring at the electrodes during the electrophoretic manipulation of silica particles. Atomic force microscopy (AFM) was used to corroborate this hypothesis, measuring the forces between a silica particle and a sapphire substrate in the presence of an applied field. The resultant force-distance curves demonstrate a change in the interaction forces between particle and substrate as a function of distance from the electrode. Variations in this interaction correspond to localized differences in the zeta potential of the substrate, which, in turn, are related to localized differences in pH. Quantification of these spatial variations in pH as a function of time yields further information about the diffusion of these faradaically produced potential determining ions across the substrate.