Bo LIU Dawei WANG Yuhang GUO Xuehua WANG Lei WANG Yajuan SONG
Abstract The QuEChERS extraction technique is a pretreatment technique that has been rapidly applied in recent years and is widely used in the field of pesticide residues with many advantages.This technique is based on solid phase extraction (SPE), which uses the interaction between adsorbent and impurities in the matrix to achieve the purpose of purification. The method has easier operation and better purification effect than SPE. In this paper, the research progress of the QuEChERS technique in pesticide residue detection in different fields in recent years and its future development were reviewed, hoping to provide reference for further development and utilization of the QuEChERS technique in pesticide residue detection in the future.
Key words QuEChERS; Pretreatment; Pesticide residues; Research progress
DOI:10.19759/j.cnki.2164-4993.2024.02.004
Food safety is an important issue that all countries in the world attach great importance to, and the detection of pesticide residues in food is the main content of food quality and safety detection. When detecting pesticide residues in food, it is necessary to pretreat samples to be detected first. There are many traditional sample pretreatment methods, most of which often require a large amount of extractants and a long extraction time, and their purification steps are also very complicated. It is difficult for traditional methods to achieve better extraction and analysis of large quantities of pesticides at the same time, so that the extraction efficiency is relatively low. However, the development of QuEChERS technique has solved this problem. It provides some technical support for food safety supervision. Based on its value, many scholars began to apply and study it. On the basis of previous development, many scholars have continuously studied and improved the QuEChERS method according to the characteristics and functions of different pesticides. The QuEChERS method using a sodium acetate buffer salt system for extraction developed by Lehotay[1] is suitable for the extraction of atrazine, chlorothalonil, chlorpyrifos, dichlorvos and other drugs in grapes, lettuce and oranges. Simin et al.[2] used the QuEChERS method using a sodium citrate buffer salt system for extraction to analyze and detect 80 kinds of pesticides in Chinese cabbage, and the recovery of the 80 kinds of target pesticides could reach 78.5%-111.3%.
Introduction of QuEChERS Method
The QuEChERS (Quick, Easy, Cheap, Effective, Rugged, Safe) pretreatment technique is a new sample treatment technique based on the rapid sample treatment technique of matrix solid-phase dispersion (MSPD). From the perspective of principle, the QuEChERS method is similar to solid-phase extraction (SPE), and both of them purify samples through the interaction of adsorbents and various impurities in matrixes, but the QuEChERS method is simpler than SPE. The original purpose of establishing this method is to develop a rapid sample pretreatment technique for detecting agricultural plant products such as fruits and vegetables. Nowadays, the QuEChERS technique has become the global standard sample preparation technique for detecting pesticide residues in vegetables and fruits. In recent years, its development field has been increasingly extensive, involving the detection of meat, blood samples, drugs, deep-processed foods and environmental samples.
It is found that the extractant acetonitrile in the QuEChERS method can be replaced by methyl dipropylene, which can be widely used in GC/NPD, FPD or ECD detection. Compared with traditional methods, the QuEChERS method has following advantages: ① high recovery (the recovery of a large number of polar and volatile pesticides is more than 85%), ② high accuracy (reproducibility less than 5%, corrected by the internal standard method), ③ short analysis time (six pre-weighed samples can be determined within 30-40 min), ④ less solvent consumption, less pollution and no chloride-containing solvent, and ⑤ simple operation (it can be completed well without good training and higher skills)[3].
Research Progress in Application of QuEChERS Method in Recent Years
Application of QuEChERS method in detection of pesticide residues in vegetables and fruits
The QuEChERS extraction method was used for the treatment of fruits and vegetables at the beginning of its establishment, and now its development in this field has basically matured. Ferracane et al.[4] applied the QuEChERS extraction method and flow modulation-integrated two-dimensional gas chromatography-triple quadrupole mass spectrometry to determine multiple pesticide residues in tomatoes, cucumbers, sweet red peppers and iceberg lettuce. The results showed that the recovery of pesticide residues in different substrates could reach 53%-160%, and the coefficients of variation were in the range of 1%-28%. Yu et al.[5] established a method for rapid determination of eight organochlorine pesticides in green leafy vegetables by dispersive liquid-liquid microextraction-GC-MS/MS based on QuEChERS modified by Fe3O4 magnetic nanoparticles (Fe3O4-MNPs). The experiment used 1 ml of extract obtained in the QuEChERS process as dispersant and 40 μl of chloroform as extractant, and then, 4 ml of water was added. After mixing evenly, dispersive liquid-liquid microextraction was carried out. The results showed that replacing expensive GCB with carbon black in the experiment would not reduce the recovery efficiency. The recovery in the experiment ranged from 78.6% to 107.7%, and the RSD was not more than 7.5%. The method can be successfully used to detect organic pesticide residues in green leafy vegetables. Tang et al.[6] established a UPLC-MS/MS method for simultaneous determination of six pesticides in pak choi. The results showed that the experiment is helpful to determining the maximum amount of residue and is of great significance to evaluate food safety.
Application of QuEChERS method in the detection of pesticide residues in drugs
Huang et al.[7] applied QuEChERS combined with GC-MS/MS to detect 63 kinds of agricultural residues in Lycopus lucidus. The experimental results showed that the average recovery of each pesticide compound was 71.5%-120.4% at three addition levels (0.05, 0.25 and 0.75 mg/kg). Five kinds of pesticide residues, including permethrin, propiconazole, isazofos, benalaxyl and trifloxystrobin, were detected in L. lucidus from different habitats to varying degrees. Li et al.[8] simultaneously detected 74 pesticide residues in Panax notoginseng established by the combined application of the QuEChERS technique and GC-MS/MS, so as to analyze the data of 20 batches of P. notoginseng samples in the market. The average recovery was controlled between 70% and 120%, and the RDS was less than 20%. The results showed that nine pesticides were detected, and quinene exceeded foreign standards. This method can be successfully applied to the detection of pesticide residues in 20 samples from markets in China. In addition, the QuEChERS method can also be used for pretreatment of environmental samples. In 2019, Siti et al.[9] determined pesticide residues in rice soil and water by the combined application of the QuEChERS method and UPLC-MS/MS. The recovery of the method was controlled in 74%-11% in soil and 77%-117% in water.
Application of QuEChERS method in detection of pesticide residues in meat
Chen et al.[10] applied QuEChERS combined with GC-MS/MS to detect 34 kinds of pesticide residues in poultry. During the experiment, the main purification object of meat samples extracted by acetonitrile was lipid. At present, there are two kinds of materials known to be mainly used for purifying lipid: C18 and EMR degreasing purification tube. The authors of the study adopted a QuEChERS purification tube with more stable recovery (that is, a C18-contianing purification tube) after experimental comparison. Thirty four kinds of pesticide residues in poultry meat were detected by this method. The average recovery of adding standard pesticides was about 78.22%-118.79%, and the relative standard deviations were about 0.27%-9.23%. Shen et al.[11] used QuEChERS combined with the 96-well solid-phase extraction (SPE) plate method to extract vancomycin and norvancomycin from fish samples, and analyzed them by UPLC-MS/MS/MS. The recovery of the experiment was between 86.7% and 98.6%. The results showed that the method could meet daily monitoring requirements of vancomycin and norvancomycin, and could be successfully applied to polluted and randomly collected samples.
Conclusions
The QuEChERS method is a relatively new pretreatment technique, but it has developed rapidly with a series of advantages such as high recovery, wide analysis range, fast detection speed and little environmental pollution. After nearly 20 years of development, it has been relatively mature in the fields of vegetables and fruits, medicines, and pesticide residues in deeply-processed products and so on. The continuously improved QuEChERS method can be used with various analyzers and detect a large number of pesticides at the same time, which provides very important help for pesticide residue analysts to carry out experiments. During experiments, scholars and analysts found that the QuEChERS purifying agents used in experiments also have a certain adsorption effect on purification targets, which greatly affects the recovery of pesticides. Therefore, it will be the focus of future research and improvement of the QuEChERS method to develop purifying agents that have obvious purification effect on sample impurities but weakly adsorb or even do not adsorb the targets.
References
[1] LEHOTAY SJ. Determination of pesticide residues in foods by acetonitrile extraction and partitioning with magnesium sulfate: Collaborative study[J]. Journal of AOAC International, 2007, 90(2): 485-520.
[2] CHEN SM, LIN TY, LI N, et al. Detection of 80 pesticide residues in cabbage by QuEChERS combined with gas chromatography triple quadrupole mass spectrometry[J]. Journal of Food Safety and Quality, 2020(11): 5428-5439. (in Chinese).
[3] HU XZ, CHENG YB, HU DJ. Introduce of quick, easy, cheap, effective, rugged and safe (QuEchERS) approach for determining pesticide residues[J]. Modern Agrochemicals, 2006(4): 24-29, 44. (in Chinese).
[4] FERRACANE A, ZOCCALI M, CACCIOLA F, et al. Determination of multi-pesticide residues in vegetable products using a "reduced-scale" Quechers method and flow-modulated comprehensive two-dimensional gas chromatography-triple quadrupole mass spectrometry[J]. Journal of Chromatography A, 2021(5): 1645-1649.
[5] YU L, GUO GQ, ZHAO J, et al. Determination of organochlorine pesticides in green leafy vegetable samples via Fe3O4 magnetic nanoparticles modified QuEChERS integrated to dispersive liquid-liquid microextraction coupled with gas chromatography-mass spectrometry[J]. Journal of analytical methods in chemistry, 2021(8): 658-667
[6] TANG HX, MA L, HUANG JQ, et al. Residue behavior and dietary risk assessment of six pesticides in pak choi using QuEChERS method coupled with UPLC-MS/MS[J]. Ecotoxicology and Environmental Safety, 2021(16): 213-218.
[7] HUANG XL, ZHOU XD, HE XF, et al. Determination of 63 kinds of pesticide residues in Lycopus lucidus by QuEChERS-GC-MS/MS[J]. China Brewing, 2021(40): 170-176. (in Chinese).
[8] LI HJ, WU JS, CHEN C, et al. Simultaneous determination of 74 pesticide residues in Panax notoginseng by QuEChERS coupled with gas chromatography tandem mass spectrometry[J]. Food Science and Human Wellness, 2021, 10(2): 241-250.
[9] SITI ZZ, YU BH, HAZWANEE H, et al. Improved QuEChERS and solid phase extraction for multi-residue analysis of pesticides in paddy soil and water using ultra-high performance liquid chromatography tandem mass spectrometry[J]. Microchemical Journal, 2019(145): 614-621.
[10] CHEN YM, CHEN LX, YU CX, et al. Determination of 34 pesticide residues in poultry meat by QuEChERS-GC-MS/MS[J]. Modern Food, 2021(5): 182-188. (in Chinese).
[11] SHEN Q, ZHU XF, ZHAO QL, et al. QuEChERS and 96-wellplate solid phase extraction for determination of vancomycin and norvancomycin in fish meat by UPLC-MS/MS[J]. Food Chemistry, 2021(342): 128326.
推荐访问:QuEChERS Pretreatment Research