钱建瑞, 张玉芬, 李晓伟, 武亚明, 张学金, 吴迪. QuEChERS-LC-MS/MS测定姜油树脂、姜精油中8种农药残留及膳食风险评估[J]. 质谱学报, 2024, 45(2): 281-291. DOI: 10.7538/zpxb.2023.0064
引用本文: 钱建瑞, 张玉芬, 李晓伟, 武亚明, 张学金, 吴迪. QuEChERS-LC-MS/MS测定姜油树脂、姜精油中8种农药残留及膳食风险评估[J]. 质谱学报, 2024, 45(2): 281-291. DOI: 10.7538/zpxb.2023.0064
QIAN Jian-rui, ZHANG Yu-fen, LI Xiao-wei, WU Ya-ming, ZHANG Xue-jin, WU Di. Determination and Dietary Risk Assessment of 8 Pesticide Residues in Ginger Oleoresin and Ginger Essential Oil by QuEChERS-LC-MS/MS[J]. Journal of Chinese Mass Spectrometry Society, 2024, 45(2): 281-291. DOI: 10.7538/zpxb.2023.0064
Citation: QIAN Jian-rui, ZHANG Yu-fen, LI Xiao-wei, WU Ya-ming, ZHANG Xue-jin, WU Di. Determination and Dietary Risk Assessment of 8 Pesticide Residues in Ginger Oleoresin and Ginger Essential Oil by QuEChERS-LC-MS/MS[J]. Journal of Chinese Mass Spectrometry Society, 2024, 45(2): 281-291. DOI: 10.7538/zpxb.2023.0064

QuEChERS-LC-MS/MS测定姜油树脂、姜精油中8种农药残留及膳食风险评估

Determination and Dietary Risk Assessment of 8 Pesticide Residues in Ginger Oleoresin and Ginger Essential Oil by QuEChERS-LC-MS/MS

  • 摘要: 本研究建立了QuEChERS-液相色谱-串联四极杆质谱(LC-MS/MS)法测定姜油树脂、姜精油样品中噻虫嗪、吡虫啉、噻虫胺等8种农药残留,通过方法优化,选择乙腈-水-正己烷体系提取样品,QuEChERS方法净化提取液,在电喷雾离子源正离子模式下电离,多反应监测(MRM)模式下测定,并采用基质匹配标准曲线内标法进行定量分析。结果表明,8种农药在1~32 μg/L浓度范围内的线性关系良好,相关系数(R2)均大于0.99,方法检出限和定量限分别为0.03~0.16、0.10~0.53 mg/kg;3种不同加标水平下的回收率均在70%~119%之间,相对标准偏差(RSD)均小于20%。采用该方法测定实际样品,其中,噻虫嗪、吡虫啉、噻虫胺阳性样本的检出率较高,分别为56%、58%、52%,残留量大于1 mg/kg的样本量占比分别为12%、16%、10%,最高残留量分别为2.16、1.92、2.01 mg/kg,其他5种农药的检出率均低于20%。基于实际样品中农药残留中位值评估干姜片、姜精油和姜油树脂中噻虫嗪、吡虫啉、噻虫胺的慢性膳食摄入风险,评估结果远小于100%,表明农药残留的慢性摄入风险较小。

     

    Abstract: Ginger (Zingiber officinale Rosc.) is the first batch of medicinal and edible plants announced by the Ministry of Health in China. Ginger oleoresin and ginger essential oil are the products extracted from ginger, widely used as flavours and fragrances, of which the quality has a direct influence on food safety. Due to the complex composition of ginger oleoresin and ginger essential oil, the qualitative and quantitative detection of pesticide residues is challenging. In this study, a liquid-liquid extraction and QuEChERS pretreatment method of 8 pesticide residues in ginger and subsequently analysis of the extracts by liquid chromatography-tandem mass spectrometry (LC-MS/MS) were developed and validated. The sample was extracted by 1% acidic acetonitrile solution, followed by addition of an equal volume of water and a small amount of hexane to the sample. After vortexing and centrifugation, the sample underwent purification via an optimized QuEChERS technique. The purified sample was analyzed by electrospray ionization MS under positive ion mode with multiple reaction monitoring (MRM). Under optimized conditions, the results showed that the calibration curves of the 8 pesticides have good linearity within the range of 1-32 μg/L, with correlation coefficients(R2) higher than 0.99. The limits of detection (LODs) are 0.03-0.16 mg/kg, and the limits of quantification (LOQs) are 0.10-0.53 mg/kg. The recoveries are 70%-119%, and the relative standard deviations (RSDs) are lower than 20% (n=6) at high, medium and low of spiking levels. The method was successfully applied to 20 ginger, 15 oleoresin, and 15 essential oil samples. The results showed that the positive detection rates of thiamethoxam, imidacloprid, and clothianidin are 56%, 58%, 52%, respectively. The detection rates of other five pesticides are lower than 20%. The proportion of residual levels greater than 1 mg/kg were found to be at a rate of 12%, 16% and 10% for thiamethoxam, imidacloprid and clothianidin with maximum levels recorded as 2.16, 1.92 and 2.01 mg/kg, respectively. Dietary exposure risk of the 3 pesticides in ginger, ginger essential oil and ginger oleoresin was evaluated based on the median value of pesticide residues. The evaluation result was far less than 100%, indicating that dietary exposure risk of pesticide residues in ginger oleoresin and ginger essential oil should be acceptable. This study provides not only an efficient and reliable quantitative method for the detection of various pesticide residues in ginger oleoresin and ginger essential oil, but also a practical technical reference for the internal quality control of plant extract enterprises and market supervision of government departments. Moreover, in view of the fact that pesticide residues have been detected in plant extract products, such as ginger oleoresin and ginger essential oil, it is recommended to formulate the maximum residue limit (MRL) standards of various plant extracts according to the acceptable daily intake (ADI) values of pesticides, MRL standards of plant extracts raw materials and extraction concentration factors to regulate the market.

     

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