摘要
建立了固相萃取-超高效液相色谱-串联质谱法(SPE-UHPLC-MS/MS)测定动物源食品中氯苯胺灵残留的分析方法。动物源食品经乙腈溶液提取、正己烷脱脂、ProElut PLS固相萃取柱富集净化,采用C18色谱柱进行分离,以0.2%(v/v)甲酸水溶液和乙腈为流动相进行梯度洗脱,采用电喷雾电离、正离子模式扫描,多反应监测模式(MRM)检测,基质匹配标准曲线外标法定量。研究通过对不同填料的固相萃取柱的考察,最终选择了ProElut PLS固相萃取柱,其能对动物源食品复杂基质中的氯苯胺灵进行有效富集和净化;通过考察3种规格的C18柱对氯苯胺灵的保留能力和出峰效果,选择了Agilent ZORBAX SB-C18(150 mm×2.1 mm,5μm)作为氯苯胺灵的分离色谱柱;通过考察氯苯胺灵在正负两种质谱电离模式下的响应情况,选择了正离子模式,确定氯苯胺灵一级质谱准分子离子和相应的碎片离子。结果表明:氯苯胺灵在0.5~100.0μg/L范围内呈良好的线性关系,相关系数(r^(2))均不低于0.9929;方法定量限(LOQ)为3μg/kg(S/N≥10);以猪肉、牛奶、牛肉、鸡肉、鸭肉、鸡蛋、鸡胗、鸭蛋、猪腰、猪肝、牛肝、羊肉、鸭胗共13种动物源食品为基质,在0.003、0.006、0.060 mg/kg添加水平下,氯苯胺灵的平均回收率为74.9%~97.6%,相对标准偏差(RSD)为2.9%~9.5%(n=6)。本方法前处理简便易行、基质干扰小、灵敏度高、准确性高,适用于多种动物源食品中氯苯胺灵的定性和定量检测。
Chlorpropham is a plant growth regulator and a herbicide. It is commonly used in the post-harvest treatment of potato to inhibit germination. It can also be used for flower thinning and fruit thinning of fruit trees, and for controlling annual gramineous weeds and a few broad-leaved weeds. Improper or excessive use of chlorpropham in crop cultivation will affect the safety of animal-derived food and impair human health through the food chain and water cycle. Therefore, accurate quantification of chlorpropham is imperative for risk assessment and mitigating risks to food safety. A method based on solid phase extraction and ultra-high performance liquid chromatography-tandem mass spectrometry(SPE-UHPLC-MS/MS) was established for the determination of chlorpropham in animal-derived food. First, the pretreatment conditions were optimized. To purify the samples and remove impurities, SPE column cartridges with different packing materials such as PXC, PXA, Florisil, and PLS were investigated. Based on the retention of chlorpropham, the ProElut PLS SPE column was selected as the pretreatment purification column. The washing solution and eluents were then optimized. When water was used as the washing solution, chlorpropham remained adsorbed on the SPE column and was not eluted along with other water-soluble substances. When the proportion of acetonitrile exceeded 40%, chlorpropham adsorbed on the filler of the SPE column could be gradually washed down. Acetonitrile-water solution(30∶70, v/v) was used for washing the SPE column. The elution ability of seven eluents for chlorpropham on the SPE column was then investigated. Among them, pure methanol, pure acetonitrile, and 1%(v/v) formic acid-methanol showed better elution effect. Considering that acetonitrile was used in the sample extraction, it was chosen as the mobile phase eluent. Subsequently, the chromatographic conditions and MS parameters were optimized. By examining the ionization cracking of chlorpropham, the quasimolecular ions and corresponding fragmentations in the chlorpropham primary MS were determined. The separation effect of three C18 columns was investigated. Based on the retention ability and peak effect of chlorpropham on the column, the Agilent ZORBAX SB-C18(150 mm×2.1 mm, 5 μm) column was used for chlorpropham separation. The response of chlorpropham in the positive and negative ionization modes was investigated and optimized. The results showed that the response was better in the positive ion mode than that in the negative ion mode. After optimizing the chromatographic conditions and MS parameters, the sensitivity of the method was improved. Finally, the analytes were separated on the Agilent ZORBAX SB-C18(150 mm×2.1 mm, 5 μm) under a gradient elution program using acetonitrile and 0.2%(v/v) formic acid aqueous solution as the mobile phases. The analytes were detected in the multiple reaction monitoring(MRM) mode under positive electrospray ionization(ESI;) conditions.The standard curve solutions were prepared using the matrix solution and quantified by the external standard method. The results showed a good linear relationship in the range of 0. 5-100. 0 μg/L,with correlation coefficients(r2)greater than 0. 992 9. The limit of quantification(LOQ)of this method was 3 μg/kg(S/N ≥ 10). At three spiked levels(0. 003,0. 006,and0. 060 mg/kg)in 13 animal-derived foods(pork,milk,beef,chicken,duck,egg,chicken gizzard,duck egg,pork kidney,pork liver,beef liver,mutton,duck gizzard),the average recoveries were in the range of 74. 9% to 97. 6%,and the RSDs were in the range of 2. 9% to 9. 5%(n= 6). Sixty batches of animal-derived food available on the market were analyzed by the developed method,and chlorpropham was not detected in any of these foods. The developed method is rapid,sensitive,and accurate,and it is suitable for the qualitative and quantitative detection of chlorpropham in a variety of animal-derived foods.
作者
杨丽霞
黄小贝
曾希珂
易姿
YANG Lixia;HUANG Xiaobei;ZENG Xike;YI Zi(Changsha Institute for Food and Drug Control, Changsha 410036, China;National Alcohol Products Quality Supervision and Inspection Center, Changsha 410036, China)
出处
《色谱》
CAS
CSCD
北大核心
2022年第1期41-47,共7页
Chinese Journal of Chromatography
基金
湖南省市场监督管理局科技计划项目(2020KJJH13).
关键词
超高效液相色谱-串联质谱
固相萃取
氯苯胺灵
动物源食品
残留
ultra-high performance liquid chromatography-tandem mass spectrometry(UHPLC-MS/MS)
solid phase extraction(SPE)
chlorpropham
animal derived foods
residues
