Simultaneous determination of triazine herbicides in rice by high-performance liquid chromatography coupled with high resolution and high mass accuracy hybrid linear ion trap-orbitrap mass spectrometry

A method was developed for the simultaneous determination of 10 triazine herbicides (cyanazine, simazine, simetryn, metribuzin, atrazine, ametryn, terbuthylazine, prometryn, terbutryn, and dimethametryn) in rice samples by high resolution and high mass accuracy hybrid linear ion trap-Orbitrap mass spectrometer. After extraction with acetonitrile and evaporation, the herbicides were redissolved in n-hexane and purified on a Florisil solid-phase extraction column. All compounds were separated within 12 min, producing more than 11 data points for each herbicide and high mass accuracy quantified ions which the mass errors of absolute value were less than 1.9 ppm in pure solution and 2.1 ppm in the matrix-matched standards solution. The method was validated in terms of the limits of detection and the limits of quantification. The linearity was satisfactory, with a correlation coefficient of >0.9975. Precision and recovery studies were evaluated at three concentration levels for Japonica, Indica, and Glutinous rice matrix. The mean recoveries obtained for all analytes in spiked Xiushui 03, Liangyoupeijiu, and Taihunuo rice samples were 83.3–99.0%, 82.0–99.7%, and 84.2–99.4%, respectively, with relative standard deviation in range 1.7–10.6%, 1.2–10.7%, and 1.9–11.6% for spiked rice samples, respectively. The intra-day precision (n = 5) for the 10 herbicides in rice samples spiked at an intermediate level was between 2.8% and 7.9%, and the inter-day precision over 10 days (n = 10) was between 5.5% and 15.9%.

The high-resolution extracted ion chromatograms of standard cyanazine in data dependent scan mode at the resolving powers of 15 000 (a) and 30 000 (b) in CID MS/MS scan.Figure optionsDownload as PowerPoint slideHighlights
► The study reported an analytical method for triazine herbicides quantification.
► Analytes were quantified in rice matrix by LC LTQ-Orbitrap MS.
► The different resolution resulted a different scan data points.
► Exact precursor ion and exact product ion were monitored in the data dependent mode.
► Mass accuracies were similar between the matrix-matched and the pure-solution.