The zeta potential of microbubbles, generated by injecting pressurised air into water and then releasing the pressure, was determined in the absence and presence of different polyacrylamides. Air was dissolved in either water or solutions of cationic, anionic, amphoteric or nonionic polymers at a constant pressure of four atmospheres. The charge of the bubbles at the shear-zeta plane was measured using a modified microelectrophoresis glass cell, held at a stationary level, at varying pH (2.0-12.0). Known practical problems with this technique were solved, and these solutions are described in detail. The anionic, amphoteric and nonionic polymers increased the negative charge of the bubbles, but the isoelectric point (iep) remained constant at about pH 2.0. Conversely, in the presence of the cationic polymer, the bubbles exhibited positive surface charges between pH 2.0 and 8.0 and an iep of pH 8.0. The results revealed the existence of an important interaction mechanism between air bubbles and polymeric macromolecules; neither this mechanism nor its practical implications have been reported in the literature to date, especially in the treatment of wastewater by flocculation followed by dissolved air flotation (DAF). (C) 2010 Elsevier B.V. All rights reserved.