色谱

色谱 ›› 2022, Vol. 40 ›› Issue (5): 469-476.DOI: 10.3724/SP.J.1123.2021.11015

• 研究论文 • 上一篇    下一篇

基于多壁碳纳米管改进QuEChERS法结合气相色谱-串联质谱检测茶叶中10种拟除虫菊酯类农药残留

许芮菡1,2, 谢倩文1,2, 李旭军2, 赵红丽3, 刘学彬3, 魏远隆2,3,4,5,*(), 邱爱东1,*()   

  1. 1.成都大学食品与生物工程学院, 四川 成都 610106
    2.四川省中安检测有限公司, 四川 成都 610100
    3.四川茂华食品有限公司博士后创新实践基地, 四川 眉山 620038
    4.四川大学轻工科学与工程学院, 四川 成都 610065
    5.榆林学院化学与化工学院, 陕西 榆林 719000
  • 收稿日期:2021-11-19 出版日期:2022-05-08 发布日期:2022-04-28
  • 通讯作者: 魏远隆,邱爱东

Modified QuEChERS method based on multi-walled carbon nanotubes coupled with gas chromatography-tandem mass spectrometry for the detection of 10 pyrethroid pesticide residues in tea

XU Ruihan1,2, XIE Qianwen1,2, LI Xujun2, ZHAO Hongli3, LIU Xuebin3, WEI Yuanlong2,3,4,5,*(), QIU Aidong1,*()   

  1. 1. College of Food and Biological Engineering, Chengdu University, Chengdu 610106, China
    2. Sichuan Safety Testing Center Co. Ltd., Chengdu 610100, China
    3. Postdoctoral Research & Development Base, Sichuan Maohua Food Co. Ltd., Meishan 620038, China
    4. College of Biomass Science and Engineering, Sichuan University, Chengdu 610065, China
    5. School of Chemistry and Chemical Engineering, Yulin University, Yulin 719000, China
  • Received:2021-11-19 Online:2022-05-08 Published:2022-04-28
  • Contact: WEI Yuanlong, QIU Aidong

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摘要：

利用多壁碳纳米管(MWCNTs)QuEChERS法提取茶叶中拟除虫菊酯类残留农药,采用气相色谱-串联质谱(GC-MS/MS)分析测定,建立了一种灵敏度高、可靠性强的茶叶中农药残留检测方法。比较了单壁碳纳米管(SWCNTs)、MWCNTS、氨基化多壁碳纳米管和石墨烯4种碳纳米材料和其不同用量下的净化效果;采用正交试验设计对前处理最佳实验条件进行筛选,并对实验影响因素进行方差分析。结果表明:提取溶剂、碳纳米材料种类对10种拟除虫菊酯类农药回收率的影响具有极显著统计学差异(p<0.001),提取时间对回收率的影响有统计学差异(p<0.05),碳纳米材料用量对回收率影响不显著(p>0.05);最佳样品前处理条件为以乙腈为提取溶剂,超声提取35 min,净化剂为60 mg MWCNTs、200 mg PSA和200 mg C18。方法学考察表明,10种拟除虫菊酯类农药在0.01~2 mg/L范围内线性良好;检出限(LOD)为0.001~0.01 mg/kg,定量限(LOQ)为0.005~0.04 mg/kg;绿茶样品空白基质加标试验中,10种农药的回收率为91.4%~109.7%,相对标准偏差为0.12%~9.80%(n=6)。对花茶、绿茶、红茶3种茶叶基质进行基质效应(ME)评价,结果发现净化剂中加入MWCNTs在绿茶和红茶基质中能有效降低ME。利用该方法检测了市售120份茶叶中拟除虫菊酯类农药的残留,多个样品中检出目标物,但均未超标。该方法检测灵敏度高,可靠性好,具有良好的回收率和稳定性,能满足茶叶中农药残留快速定量分析的要求。

关键词: 多壁碳纳米管, 气相色谱-串联质谱, 拟除虫菊酯类农药, 茶叶, 基质效应

Abstract:

A modified QuEChERS method, based on multi-walled carbon nanotubes (MWCNTs), was established for the detection of 10 pyrethroid pesticides (cyfluthrin, flucythrinate, fenpropathrin, bifenthrin, cyhalothrin, permethrin, cypermethrin, etofenprox, fenvalerate, deltamethrin) in tea, in combination with gas chromatography-tandem mass spectrometry (GC-MS/MS). The purification effects and dosages of four carbon nanomaterials, viz. single-walled carbon nanotubes (SWCNTs), MWCNTs, amino-modified MWCNTs, and graphene, were compared. An orthogonal experimental design was used to determine the optimal experimental conditions for sample pretreatment. The experimental factors governing the process were analyzed using variance. The results showed that the optimized sample pretreatment parameters were as follows. Acetonitrile was used as the extraction solvent with ultrasonic extraction for 35 min, while 60 mg MWCNTs, 200 mg PSA, and 200 mg C18, were used as purifiers. The effects of the extraction solvent and the carbon nanomaterials used on the recoveries of the 10 pyrethroid pesticides were significantly different (p<0.001), and the effect of extraction time on the recoveries was statistically different (p<0.05). The dosage of carbon nanomaterials had no significant effect on the recoveries (p>0.05). Good linearities were observed for the 10 pyrethroid pesticides in the concentration range of 0.01-2 mg/L. The limits of detection (LODs) and limits of quantification (LOQs) were in the ranges of 0.001-0.01 mg/kg and 0.005-0.04 mg/kg, respectively. The average recoveries of the pyrethroid pesticides spiked into blank samples of green tea were 91.4%-109.7%, and the relative standard deviations were 0.12%-9.80% (n=6). Furthermore, the matrix effects (MEs) of scented green tea, green tea, and black tea were evaluated. It was found that the addition of MWCNTs to the purifier can effectively reduce the matrix effect in green tea and black tea matrices. The developed method and the national standard method were used to detect the residues of the 10 pyrethroid pesticides in 120 tea samples available in the market. The results showed that cyfluthrin, deltamethrin, fenvalerate, permethrin, fenpropathrin, cypermethrin, bifenthrin and cyhalothrin were detected, and the contents obtained with the two methods were similar. Although pyrethroids were detected in most tea samples, the contents of all pesticide residues were below the maximum residue limits (MRLs). Therefore, the developed method is suitable for the rapid quantitative analysis of pesticide residues in tea.

Key words: multi-walled carbon nanotubes (MWCNTs), gas chromatography-tandem mass spectrometry (GC-MS/MS), pyrethroid pesticides, tea, matrix effect (ME)

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