超高效液相色谱-串联质谱法测定丁氟螨酯和联苯肼酯在柑橘上的残留及膳食风险评估

Determination of Residues of Cyflumetofen and Bifenazate on Citrus and Dietary Risk Assessment by Ultra-High-Performance Liquid Chromatography-Tandem Mass Spectrometry

  • 摘要: 本研究建立了超高效液相色谱-串联质谱法测定柑橘中丁氟螨酯和联苯肼酯及其代谢物残留。柑橘样品用乙腈提取,盐析分层,以甲醇和0.1%甲酸水溶液为流动相,在ACQUITY UPLC® BEH C18色谱柱上分离,采用电喷雾正、负离子同时扫描模式和多反应监测模式进行质谱检测,外标法定量。结果表明,在0.005~0.5 mg/L浓度范围内,各化合物的线性关系良好,相关系数均大于0.997 4;在3种不同浓度的回收实验中,丁氟螨酯、2-三氟甲基苯甲酸、联苯肼酯、联苯肼酯-二氮烯的平均回收率分别为76.4%~96.4%、91.6%~108.5%、84.0%~107.0%、94.2%~112.0%,相对标准偏差分别为2.0%~5.0%、1.3%~7.0%、0.5%~8.8%、0~4.1%;这4种化合物的定量限均为0.01 mg/kg。通过测定12个地区采收后14天和21天的柑橘果肉和全果样品,丁氟螨酯、2-三氟甲基苯甲酸、丁氟螨酯+2-三氟甲基苯甲酸(以丁氟螨酯计)的残留量分别为<0.080、<0.01、<0.10 mg/kg;联苯肼酯、联苯肼酯+联苯肼酯-二氮烯(以联苯肼酯计)的残留量分别为<0.16、<0.37 mg/kg。膳食风险评估表明,普通人群丁氟螨酯的国家估算每日摄入总量为0.0279 mg,风险熵为0.4%;联苯肼酯的每日摄入总量为0.119 mg,风险熵为18.9%,柑橘中丁氟螨酯和联苯肼酯残留对一般人群健康不会产生不可接受的风险。

     

    Abstract: Cyflumetofen and bifenazate are widely used as high-efficiency agents in citrus cultivation. Their residues and metabolic patterns are closely related to food safety and human health. Therefore, establishing accurate and sensitive residue detection methods is essential for agricultural product quality monitoring. In this study, an ultra-high performance liquid chromatography tandem mass spectrometry (UPLC-MS/MS) method was developed for the simultaneous determination of residues of the two acaricides (2-trifluoromethylbenzoic acid, bifenazate-diazene) and their metabolites in citrus fruits. The samples were extracted with acetonitrile, and purified by salt precipitation. Chromatographic separation was performed an ACQUITY UPLC® BEH C18 column using a mobile phase consisting of methanol and 0.1% formic acid aqueous solution with gradient elution. Mass spectrometric detection was performed under both positive and negative ion modes with multiple reaction monitoring, and quantitative analysis was performed using the external standard method. The results showed that the target analytes and their metabolites exhibit good linearity within the range of 0.005-0.5 mg/L (R2>0.997 4). At low, medium and high spiked concentration levels, the average recoveries of cyflumetofen, 2-trifluoromethylbenzoic acid, bifenazate and bifenazate-diazene are 76.4%-96.4%, 91.6%-108.5%, 84.0%-107.0%, 94.2%-112.0%, while their relative standard deviations are 2.0%-5.0%, 1.3%-7.0%, 0.5%-8.8% and 0%-4.1%, respectively. The limit of quantification (LOQ) for all four species is 0.01 mg/kg. This method was applied for the analysis citrus pulp and whole-fruit samples collected from 12 major citrus-producing regions in China at 14 and 21 days after harvesting. The results indicated that the residual concentration of cyflumetofen and 2-trifluoromethylbenzoic acid, and the total residue concentration of cyflumetofen and 2-trifluoromethylbenzoic acid (calculated as cyflumetofen) are <0.080, <0.01, and <0.10 mg/kg, respectively, and the residual concentration of bifenazate and the total residue level of bifenazate and binfenazate-diazene (calculated as bifenazate) are <0.16 and <0.37 mg/kg, respectively. Dietary risk assessment showed that the national estimated daily intake (NEDI) and risk entropy (RQ) for the general population are 0.0279 mg and 0.4% for cyflumetofen, and 0.119 mg and 18.9% for bifenazate. This result indicates that the residues of cyflumetofen and bifenazate in citrus poses no unacceptable risks to humans.

     

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