Determination Of Sulfonylurea,Aniline And Organophosphorus Herbicides In Food By Liquid Chromatography Tandem Mass Spectrometry

The application of sulfonylurea herbicides are playing an important role in the modernization of agricultural production.However,the herbicide residues also cause many negative impacts on the ecological environment and agricultural products.Sulfonylurea herbicides are extremely water-soluble and easy to enter the soil,then causing water pollution.Through the water circulation,it can inhibit the growth of plants in surrounding,reducing the reproductive rate of aquatic organisms,destroying the ecological environment and harming human beings through the enrichment of the food chain.In view of this,the application of chlorsulfuron,metsulfuron and triasulfuron has been banned in China.As selective bud pretreatment agent,aniline herbicides are occupying a high proportion in the application of herbicides because of the advantages of broad-spectrum,high efficiency and low toxicity.Soil has a strong adsorption effect on aniline herbicides,and the residue will cause phytotoxicity for the following crops.Studies show that aniline herbicides can poison cells,damage DNA and cause rectal cancer and lung cancer.Organicphosphorus herbicides are widely used in agriculture as efficient and broad-spectrum herbicides.In recent years,organicphosphorus herbicides have the teratogenic,carcinogenic and mutagenic effects,damaging the body’s immune system in a number of studies.Due to high sensitivity and high accuracy,liquid chromatography tandem mass spectrometry(LC-MS/MS)has been widely used in food safety testing.In this paper,the physical and chemical properties,toxicity mechanism,domestic and international limit standards and common detection methods are described for sulfonylurea,aniline and organophosphorus herbicides.Ultrasound-assisted extraction and LC-MS/MS are used to detect the sulfonylurea herbicides in rice flour and eight treasure porridge,the aniline herbicides in radish,corn and peanut,the organicphosphorus herbicides in pollen and wine.The results are as follows:1.A LC-MS/MS method is developed for detecting 32 kinds of sulfonylurea herbicides in rice flour and eight treasure porridge.The 32 kinds of sulfonylurea herbicides could be separated well within 16 minutes under gradient elution with 0.1%formic acid aqueous solution-acetonitrile as the mobile phase.The mixed solution of acetonitrile and ethyl acetate(V:V,4:1)is used as extraction agent.Under ultrasonic-assisted extraction and dispersive solid phase extraction purification,32 kinds of sulfonylurea herbicides are detected by LC-MS/MS with ESI+source under multiple reaction monitoring(MRM)mode.Good linearities of the 32 herbicides are observed and the correlation coefficients(r)are above 0.9995.The limit of detection(LOD)ranges from 0.01 to 1.14 μg·kg-1,the limit of quantitation(LOQ)ranges from 0.03 to 3.80 μg·kg-1.The recoveries of sulfonylurea herbicides in spiked samples range from 68.01%to 108.97%and the relative standard deviations(RSD)range from 0.33%to 9.95%.The method can satisfy the rapid detection requirements of 32 sulfonylurea herbicides in rice flour and eight treasure porridge because of simple and rapid advantages.2.The qualitative and quantitative methods for the determination of 9 kinds of aniline herbicides in radish,peanut and corn are established by using LC-MS/MS.After dispersive solid phase extraction purification,the 9 kinds of aniline herbicides were determined by LC-MS/MS with ESI+under MRM mode and external standard method by using acetonitrile as extraction agent.Good linear relations are obtained and the correlation coefficients(r)are above 0.9995.The LOD and LOQ range from 0.02 to 1.20 μg·kg-1 and 0.07 to 4.00 μg·kg-1,respectively.The recoveries of aniline herbicides at three different spiked levels range from 68.10%to 98.60%and the RSD range from 0.35%to 9.98%.The results showed that the method is simple and accurate.3.The pretreatment methods and the parameters of mass spectrometry and chromatograph were optimized in this experiment.After ultrasonic assisted extraction and dispersive solid phase extraction purification,the 5 kinds of organicphosphorus herbicides are determined by LC-MS/MS with ESI+under MRM mode using ethyl acetate as extraction agent.The 5 kinds of organicphosphorus herbicides can be separated well within 5 min with 0.1%formic acid solution and methanol as mobile phase.The results showed that the excellent linear relations are achieved in the range of 1～200 ng·mL-1 and the correlation coefficients(r)are above 0.9995.The LOD and LOQ range from 0.01 to 0.05μg·kg-1 and from 0.03 to 0.16 μg·kg-1,respectively.The recoveries of organicphosphorus herbicides in spiked samples range from 69.29%to 99.25%and RSD range from 1.94%to 9.45%.The method can simultaneously meet the detection needs of organicphosphorus herbicides in bee pollens and wine.