QuEChERS-气相色谱-质谱法检测鱼肉中19种氯酚类化合物  

Determination of 19 chlorophenols in fish by QuEChERS-gas chromatography-mass spectrometry

作　　者：穆应花 邢家溧 沈坚 应璐 毛玲燕 徐晓蓉 娄永江[1] 吴希 MU Yinghua;XING Jiali;SHEN Jian;YING Lu;MAO Lingyan;XU Xiaorong;LOU Yongjiang;WU Xi(College of Food and Pharmaceutical Sciences, Ningbo University, Ningbo 315211, China;Ningbo Academy of Product and Food Quality Inspection (Ningbo Fibre Inspection Institute), Ningbo 315048, China)

机构地区：[1]宁波大学食品与药品学院,浙江宁波315211 [2]宁波市产品食品质量检验研究院(宁波市纤维所),浙江宁波315048

出　　处：《色谱》2022年第5期477-487,共11页Chinese Journal of Chromatography

基　　金：国家市场监管总局科技计划项目(2020MK117);浙江省市场监管系统科技计划项目(20210140);浙江省基础公益研究计划项目(LGC20C200003);宁波市自然科学基金项目(202003N4196,2019A610438,2019A610437);宁波市泛3315创新团队项目(2018B-18-C);宁波市高新精英创新团队项目(甬高科[2018]63);宁波市公益类科技计划项目(2021S194);宁波市重大科技攻关项目(2021ZDYF020179).

摘　　要：大量含氯农药、次氯酸消毒水以及水产品杀虫剂和杀菌剂的广泛使用,使鱼类容易受到氯酚类化合物的污染,因而建立鱼肉中氯酚类化合物的检测方法十分重要。建立了QuEChERS结合气相色谱-质谱法同时检测鱼肉中19种氯酚类化合物的分析方法。19种氯酚类化合物选用DB-5MS毛细管色谱柱(30 m×0.25 mm×0.25μm),载气流速1 mL/min进行分离,可以得到很好的峰形。前处理采用改良的QuEChERS方法,通过对提取剂的种类和剂量、净化剂的种类和剂量,以及衍生条件中的衍生温度、衍生时间和衍生剂用量等进行优化,确定最优的前处理方法。选择10 mL乙酸乙酯作为提取剂,500 mg的C_(18)作为净化剂,加入3 g氯化钠和5 g无水硫酸镁,过0.22μm的有机滤膜,加入50μL的硅烷化衍生剂在45℃条件下衍生30 min,用EI源测定,选择离子监测模式,以外标法定量。19种氯酚类化合物在0.4~10μg/L范围内具有良好的线性关系,相关系数R^(2)大于0.998,方法定量限为0.04~0.16μg/kg。空白基质不同加标水平的回收率为70.6%~115.0%,相对标准偏差为2.6%~10.5%。将建立的方法应用于实际样品的检测分析,结果显示,各种鱼肉中均有不同程度的氯酚类化合物检出,其中,黄花鱼检出的氯酚类化合物总量最大,为8.74μg/kg;其次为鲫鱼7.59μg/kg;米鱼的检出量最少,为1.59μg/kg。所建立的方法简化了样品的前处理步骤,操作简单,方法灵敏度高、重复性好,可满足鱼肉中19种氯酚类化合物的高通量检测要求,能显著提高氯酚类化合物的检测效率。With the increasing use of chlorine-containing pesticides,hypochlorous acid disinfection water as well as aquatic product insecticides and fungicides are widely used in the cultivation of fish.This has led to the contamination of fish by chlorophenol compounds.However,currently,there is no standard method for the simultaneous determination of 19 chlorophenol compounds in fish.In this study,the optimum chromatography and mass spectrometry conditions were determined by investigating the instrument parameters.The 19 chlorophenol compounds were well separated using the DB-5MS capillary chromatographic column(30 m×0.25 mm×0.25μm)with a carrier gas flow rate of 1 mL/min.Under this condition,the chromatographic peak was sharp and symmetric.An analytical method was developed for the simultaneous determination of the 19 chlorophenol compounds in fish using gas chromatography-mass spectrometry coupled with QuEChERS pretreatment.The improved QuEChERS method was used in sample preparation.The 19 chlorophenol compounds were extracted with organic solvents and purified with purifying agents.During the experiment,the effect of the kinds and volumes of the extraction solvent,as well as the types and dosages of the purifying agent,on the recoveries of the 19 chlorophenol compounds were investigated.Moreover,the temperature and time of derivatization,as well as the dosage of the derivatization agent,were optimized.All aforementioned analyses were conducted with the aim of determining the optimal pretreatment method.Finally,the optimized gas chromatography-mass spectrometry conditions were employed for the quantitative determination of 19 chlorophenol compounds in fish samples.Based on the experimental results,the best extraction method was determined to be the one where the extraction agent(10 mL ethyl acetate)was added to 3 g sodium chloride and 5 g anhydrous magnesium sulfate in the test tube,followed by ultrasonication for 15 min.The sample was centrifuged at 4500 r/min for 5 min,and 500 mg C 18 was selected as the purifying

关 键 词：气相色谱-质谱 QUECHERS 氯酚类化合物 鱼肉 

分 类 号：O658[理学—分析化学]