The salt rejection by Shirasu porous glass (SPG) membranes having nano-order uniform pores was investigated for understanding the electrokinetic mechanism resulting from the surface charge developed on the membrane when in contact with salt solutions. Due to the dissociation of the hydroxyl groups such as silanol groups on the membrane surface, the membrane was negatively charged over a pH range of 3-10 from electrophoretic measurements. Cross-flow filtration experiments showed that up to 63% of NaCl was rejected by an SPG membrane having a mean pore diameters of 33 nm in a 1 mol m(-3) NaCl solution at pH 7 under a transmembrane pressure of 74 kPa, even though the pore diameter is much larger than the ion diameter. This is a consequence of the electrostatic repulsive interaction between the co-ions (Cl- ions) and the membrane surface. At the same pH, the rejection factor of NaCl decreased with increasing salt concentration due to an increase in the ionic strength. More negative charge on the membrane surface at higher pH resulted in higher rejection factors of NaCl for a fixed salt concentration. Higher rejection factors of NaCl by SPG membranes with smaller pore sizes for a fixed concentration are due to the higher ratio of the thickness of the electric double layer (Debye length) to the pore radius. The SPG membrane showed a salt rejection sequence: Na2SO4, NaCl and CaCl2 at the same pH. This is because divalent anions (SO42-) are more strongly repelled by the negatively charged membrane, while divalent cations (Ca2+) adsorb specifically onto the membrane surface than monovalent cations (Na+). The salt rejection factor increased with increasing permeate volume flux. Due to the stronger acidity of the membrane materials, SPG membranes had a higher rejection factor and a lower isoelectric point (IEP < 3) than ceramic membranes. (c) 2009 Elsevier B.V. All rights reserved.