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The zeta potential of human enamel is of physiological importance for interactions between enamel surfaces and the surrounding aqueous medium of saliva. The zeta potentials of both enamel and hydroxyapatite (HA) have been examined previously by various techniques. In this study, we examined the zeta potential of human enamel and HA using the Coulter DELSA 440, which, by a laser, makes independent Doppler shift measurements of moving particles in an electric field at 4 different angles, providing advantages over previous techniques. The enamel and HA particles were suspended directly in different phosphate buffers, or first incubated for 2 hrs in parotid (PS) or whole saliva (HWS) and then suspended in the same buffers. The enamel and HA particles exhibited an overall net surface potential of -15 to -30 mV, depending on the buffer content. Incubation in PS and HWS gave less negative potentials of -8 to -14 mV. In our previous studies, the salivary micelle-like structures (SMSs), seen in TEM of parotid saliva, were observed to have a zeta potential of -9 mV (Rykke et al., 1996). The zeta potential determinations in this study support the concept of an adsorption of mostly SMSs to the enamel surfaces, with a change of the zeta potential of the enamel and HA toward that of the SMSs.