Comparative Evaluation of Chemical and Photolytic Denitrosation Methods for Chemiluminescence Detection of Total N -Nitrosamines in Wastewater Samples.

N -Nitrosamines form as byproducts during oxidative water treatment and occur as impurities in consumer and industrial products. To date, two methods based on chemiluminescence (CL) detection of nitric oxide liberated from N -nitrosamines via denitrosation with acidic triiodide (HI 3 ) treatment or ultraviolet (UV) photolysis have been developed to enable the quantification of total N -nitrosamines (TONO) in environmental water samples. In this work, we configured an integrated experimental setup to compare the performance of HI 3 -CL and UV-CL methods with a focus on their applicability for TONO measurements in wastewater samples. With the use of a large-volume purge vessel for chemical denitrosation, the HI 3 -CL method achieved signal stability and detection limits comparable to those achieved by the UV-CL method which utilized a microphotochemical reactor for photolytic denitrosation. Sixty-six structurally diverse N -nitroso compounds (NOCs) yielded a range of conversion efficiencies relative to N -nitrosodimethylamine (NDMA) regardless of the conditions applied for denitrosation. On average, TONO measured in preconcentrated raw and chloraminated wastewater samples by the HI 3 -CL method were 2.1 ± 1.1 times those measured by the UV-CL method, pointing to potential matrix interferences as further confirmed by spike recovery tests. Overall, our comparative assessment of the HI 3 -CL and UV-CL methods serves as a basis for addressing methodological gaps in TONO analysis.