N-Nitrosamines are potent mutagens and carcinogens that can be formed during oxidative water treatment. This study describes a novel method for the determination of total N-nitrosamines by UV-photolysis and subsequent chemiluminescence detection of nitric oxide. Denitrosation of N-nitrosamines was accomplished with a microphotochemical reactor consisting of a knitted reaction coil and a low-pressure mercury lamp. The detection limits for differing N-nitrosamines ranged between 0.07 mu M (14 pmol injected) and 0.13 mu M (26 pmol injected). The nitric oxide formation from selected N-nitrosamines was linear (R-2 = 0.98-0.99) from 0.1 to 10 mu M. The small cross-section and volume of the micro photochemical reactor used in this study was optimal to reach a sensitivity level comparable to chemical denitrosation-based methods. In addition, this method had several advantages over other similar methods: (i) compared to chemical denitrosation with copper monochloride or triiodide, the UV-photolysis does not require chemicals and is not affected by interferences of byproducts (e.g., formation of NOI), (ii) the reproducibility of replicates was enhanced compared to the triiodide-based method, and (iii) a commercially available photoreactor and NO analyzer were used. The application of this method for the determination of the N-nitrosamine formation potential of personal care products demonstrates its utility for assessing whether N-nitrosodimethylamine (NDMA) or other specific nitrosamines of current interest are dominant or minor components, respectively, of the total N-nitrosamine pool in technical aquatic systems or biological samples.