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The ability to effectively detect N-nitrosamine compounds by liquid chromatography–tandem mass spectrometry presents a challenge due to the problems of high detection limits and difficulty in simultaneous N-nitrosamine compound detection. In order to overcome these limitations, this study reduced the detection limit of N-nitrosamine compounds by applying n-hexane pre-treatment to remove non-polar impurities before the conventional process of column extraction. In addition, ammonium acetate was used as the mobile phase to enhance the retention of nitrosamine target substances on the chromatographic column, with formic acid added to the mobile phase to improve the ionization level of N-nitrosodiphenylamine, to achieve the simultaneous detection of multiple N-nitrosamine compounds. Applying these modifications to the established detection method allowed the rapid and accurate detection of N-nitrosamine in water within 12 min. The linear relationship, detection limit, quantification limit and sample spiked recovery rate of nine types of nitrosamine compound were investigated, showing that the correlation coefficient ranged from 0.9985–0.9999, while the detection limits of the instrument and the method were 0.280–0.928 µg·L⁻¹ and 1.12–3.71 ng·L⁻¹, respectively. The spiked sample recovery rate ranged from 64.2–83.0%, with a standard deviation of 2.07–8.52%, meeting the requirements for trace analysis. The method was applied to the detection of N-nitrosamine compounds in nine groundwater samples in Wuhan, China, and showed that the concentrations of N-nitrosodimethylamine and NDEA were relatively high, highlighting the need to monitor water bodies with very low levels of pollutants and identify those requiring treatment. Full article