Zinc oxide nanoparticles are widely used in sunscreen products because of their chemical stability and capability of blocking harmful ultraviolet rays. However, zinc oxide nanoparticles can also generate reactive species under ultraviolet irradiation. Because nitrite can form reactive nitrogen species under oxidative stress and because it exists in perspiration and cosmetics, we studied the effects of nitrites on the photocatalytic damage of zinc oxide nanoparticles (50 nm and 90 nm) to bovine serum albumin and human keratinocyte cells under ultraviolet irradiation (365 nm and 254 nm). The results indicate that nitrite plays an enhancing role in photocatalytic damage by breaking amino acid residues and promoting protein oxidation and nitration. The concentrations of zinc oxide and nitrite, the irradiation light and duration, and the pH of the medium are important factors influencing this photocatalytic damage. Size effects of ZnO nanoparticles on bovine serum albumin and keratinocyte cells are different. It is speculated that the extent of photo-damage is partially dependent on the aggregation of zinc oxide. These findings may be valuable for understanding potential risks of applying zinc oxide nanoparticle-containing sunscreens to human skin under sunlight exposure. (C) 2012 Elsevier B.V. All rights reserved.