Simultaneous determination of neonicotinoid insecticides and metabolites in rice by dispersive solid–liquid microextraction based on an in situ acid–base effervescent reaction and solidification of a floating organic droplet
A sensitive and rapid method named dispersive solid–liquid microextraction combining in situ acid–base reaction-based effervescence and solidification of a floating organic droplet was developed for the simultaneous determination of eight neonicotinoid insecticides and two metabolites in rice by ultra-performance liquid chromatography-tandem mass spectrometry. The samples were extracted with sodium citrate monobasic-modified acetonitrile by vortexing and purified by primary secondary amine, and then a mixture of 1-undecanol and sodium carbonate aqueous solution was rapidly injected. An acid–base reaction and carbon dioxide bubbles were generated in situ, which promoted the dispersion of 1-undecanol droplets and subsequent transfer of the analytes from the acidified acetonitrile extract to 1-undecanol. The 1-undecanol phase was easily retrieved by centrifugation and solidification in an ice bath. This novel dispersive solid–liquid microextraction fully utilized the advantages of the effervescent reaction and floating droplet solidification, which was carried out in a tube and did not require stepwise analysis for a solid matrix. Under the optimized conditions, the average recoveries of the analytes ranged from 77.8 to 97.1% with relative standard deviations less than 7.3. The limits of detection varied between 0.01 and 0.1 μg kg−1, and enrichment factors were 42–55. The proposed method provides a quantitative, sensitive, and convenient analytical tool applicable for routine monitoring of neonicotinoids in rice.
KeywordsDispersive solid–liquid microextraction In situ acid–base effervescent reaction Solidification of a floating organic droplet Neonicotinoid insecticides and metabolites Rice
This work was partly supported by the National Natural Science Foundation of China (41807490), the Natural Science Research Project of Higher Education of Anhui (KJ2018A0128), and the University Youth Science Foundation of Anhui Agricultural University (2017zd04).
Compliance with ethical standards
Conflict of interest
The authors declare that they have no conflicts of interest.
- 5.EU insecticides database (2016). http://ec.europa.eu/sanco_insecticides/public/index.cfm. 03/01/2016.
- 13.Jiao WT, Xiao Y, Qian XS, Tong MM, Hu YZ, Hou RY, et al. Optimized combination of dilution and refined QuEChERS to overcome matrix effects of six types of tea for determination eight neonicotinoid insecticides by ultra performance liquid chromatography-electrospray tandem mass spectrometry. Food Chem. 2016;210:26–34.CrossRefGoogle Scholar
- 15.Campillo N, Viñas P, Férez-Melgarejo G, Hernández-Córdoba M. Liquid chromatography with diode array detection and tandem mass spectrometry for the determination of neonicotinoid insecticides in honey samples using dispersive liquid-liquid microextraction. J Agric Food Chem. 2013;61:4799–805.CrossRefGoogle Scholar
- 17.Pastor-Belda M, Garrido I, Campillo N, Viñas P, Hellín P, Flores P, et al. Determination of spirocyclic tetronic/tetramic acid derivatives and neonicotinoid insecticides in fruits and vegetables by liquid chromatography and mass spectrometry after dispersive liquid-liquid microextraction. Food Chem. 2016;202:389–95.CrossRefGoogle Scholar
- 18.Jovanov P, Guzsvány V, Franko M, Lazić S, Sakač M, Šarić B, et al. Multi-residue method for determination of selected neonicotinoid insecticides in honey using optimized dispersive liquid-liquid microextraction combined with liquid chromatography-tandem mass spectrometry. Talanta. 2013;111:125–33.CrossRefGoogle Scholar
- 19.Martín J, Santos JL, Aparicio I, Alonso E. Determination of hormones, a plasticizer, preservatives, perfluoroalkylated compounds, and a flame retardant in water samples by ultrasound-assisted dispersive liquid-liquid microextraction based on the solidification of a floating organic drop. Talanta. 2015;143:335–43.CrossRefGoogle Scholar
- 21.Vera-Avila LE, Rojo-Portillo T, Ovarrubias-Herrera R, Peña-Alvarez A. Capabilities and limitations of dispersive liquid-liquid microextraction with solidification of floating organic drop for the extraction of organic pollutants from water samples. Anal Chim Acta. 2013;805:60–9.CrossRefGoogle Scholar
- 23.Wang HZ, Hu L, Liu XY, Yin SJ, Lu RH, Zhang SB, et al. Deep eutectic solvent-based ultrasound-assisted dispersive liquid-liquid microextraction coupled with high-performance liquid chromatography for the determination of ultraviolet filters in water samples. J Chromatogr A. 2017;1516:1–8.CrossRefGoogle Scholar
- 24.Shalash M, Makahleh A, Salhimi SM, Saad B. Vortex-assisted liquid-liquid-liquid microextraction followed by high performance liquid chromatography for the simultaneous determination of fourteen phenolic acids in honey, iced tea and canned coffee drinks. Talanta. 2017;174:428–35.CrossRefGoogle Scholar
- 34.Yang MY, Wu XL, Jia YH, Xi XF, Yang XL, Lu RH, et al. Use of magnetic effervescent tablet-assisted ionic liquid dispersive liquid-liquid microextraction to extract fungicides from environmental waters with the aid of experimental design methodology. Anal Chim Acta. 2016;906:118–27.CrossRefGoogle Scholar
- 36.Wang P, Yang X, Wang J, Cui J, Dong AJ, Zhao HT, et al. Multi-residue method for determination of seven neonicotinoid insecticides in grains using dispersive solid-phase extraction and dispersive liquid-liquid micro-extraction by high performance liquid chromatography. Food Chem. 2012;134:1691–8.CrossRefGoogle Scholar
- 40.Wen YY, Li JH, Yang FF, Zhang WW, Li WR, Liao CY, et al. Salting-out assisted liquid-liquid extraction with the aid of experimental design for determination of benzimidazole fungicides in high salinity samples by high-performance liquid chromatography. Talanta. 2013;106:119–26.CrossRefGoogle Scholar
- 43.Zheng SL, Wu HZ, Li ZG, Wang JM, Zhang H, Qian MR. Ultrasound/microwave-assisted solid-liquid-solid dispersive extraction with high-performance liquid chromatography coupled to tandem mass spectrometry for the determination of neonicotinoid insecticides in Dendrobium officinale. J Sep Sci. 2015;38:121–7.CrossRefGoogle Scholar