The totalN‐nitroso content of foods can be measured by chemical denitrosation with hydrogen bromide and chemiluminescence detection of the cleaved nitric oxide radical. The denitrosation reagent itself causes a significant detector response which has limited the application of the technique to trace analysis. A procedure is described in which the errors associated with this interference are minimized. Application of this method to the trace analysis of aqueous and solid samples is reported together with an investigation of the effects of sample size on the accuracy and sensitivity of the assay as applied to aqueous analytes. The magnitude and significance of the false‐positive response from nitrate is discussed in relation to the analysis of cured meats.