液相色谱—串联质谱对果蔬中农药残留测定的研究

发布时间：2018-02-15 05:40

本文关键词： 农药残留液相色谱-串联质谱固相萃取样品稀释基质效应　出处：《山东大学》2017年硕士论文　论文类型：学位论文

【摘要】：农药残留检测已经成为全球食品安全和环境监测中的重要组成部分。许多国家和国际组织都制定了严格的限量标准,规定了农产品中农药最大残留限量(MRLs),保证食品安全及进出口贸易。随着农药残留的广泛重视,许多分析方法已经报道过。其中,液相色谱-串联质谱因其高选择性、高灵敏度而受到广泛关注,是农药残留分析中的有力检测技术。根据以上分析,本研究利用液相色谱-串联质谱对果蔬中的强极性农药和农药多残留测定进行了研究。本论文共分为三章:第一章为绪论,概述了农药残留分析中常用的前处理方法及检测技术,详细介绍了固相萃取及QuEChERS净化方法,以及液相色谱-质谱联用的检测技术,主要包括液相色谱分离、低分辨串联质谱和高分辨质谱的介绍。第二章利用液相色谱-串联质谱(LC-MS/MS)检测技术,对6种样品中(苹果、黄瓜、番茄、丝瓜、甘蓝和茄子)的两种高度亲水性氨基糖苷类物质春雷霉素和井冈霉素-A进行了研究。使用乙腈和含有0.1%甲酸的水作为流动相,结果表明,ReproSil100C18色谱柱能够用于强极性物质的保留,得到的良好峰形和响应值。甲醇和水混合溶剂(70:30,v/v,pH = 5.5)作为提取剂。HLB-SCX串联固相萃取得到的基质效应在-12.6-6.11%之间,平均回收率在81.7-108%之间,并且RSDs低于13%。按照欧盟SANTE 11945/2015标准进行方法验证。结果证明,该方法适合复杂水果和蔬菜样品中的春雷霉素和井冈霉素-A的测定。第三章采用简化的QuEChERS提取方法与超高效液相色谱-串联质谱(UPLC-MS/MS)相结合,快捷、准确地对甘蓝、生菜、番茄和甜椒四种蔬菜中的16种农药进行检测。分析过程中采用超高效液相色谱,16种农药在10 min内能够完全洗脱。样品经0.2%甲酸乙腈(0.2:99.8,v/v)提取后,提取剂用甲醇/水(50:50,v/v)1:1稀释后用于UPLC-MS/MS定量分析。在添加回收实验中,添加水平为4,20,40 μg/kg,每个加标水平平行做五次。该方法的回收率为72.2-119%,相对标准偏差(RSDs)均小于17%,实现了农药多残留测定。该方法适合蔬菜中农药多残留测定。
[Abstract]:Pesticide residue detection has become an important part of global food safety and environmental monitoring. Many countries and international organizations have established strict limit standards. The maximum pesticide residue limit (MRLsN) in agricultural products is stipulated to ensure food safety and import and export trade. With the extensive attention paid to pesticide residues, many analytical methods have been reported. Among them, liquid chromatography-tandem mass spectrometry (LC-MS) is characterized by its high selectivity. High sensitivity and widespread concern, is a pesticide residue analysis of the force detection technology. According to the above analysis, In this study, the determination of strong polar pesticides and multi-residues in fruits and vegetables by liquid chromatography-tandem mass spectrometry (LC-MS) was studied. The methods of pretreatment and detection in pesticide residue analysis were summarized. The methods of solid phase extraction (SPE) and QuEChERS purification, as well as the detection techniques by liquid chromatography-mass spectrometry (LC-MS) were introduced in detail, including liquid chromatographic separation. Introduction of low Resolution tandem Mass Spectrometry and High Resolution Mass Spectrometry. In Chapter 2, six samples (apple, cucumber, tomato, loofah, luffa) were detected by liquid chromatography-tandem mass spectrometry (LC-MS / MS). Two highly hydrophilic aminoglycoside substances, vermilycin and Jinggangmycin A, were studied in cabbage and eggplant. Acetonitrile and water containing 0.1% formic acid were used as mobile phase. The results showed that ReproSil100C18 column could be used for the retention of highly polar substances. The results showed that the matrix effect of methanol / water mixed solvent 70: 30 v / v / v / v = 5.5) was -12.6-6.11%, and the average recovery was 81.7-108%, which was used as extractant. HLB-SCX was used as extractant in series solid-phase extraction, and the results showed that the matrix effect was in the range of -12.6-6.11%, and the average recovery was between 81.7-108%. And the RSDs is lower than 13. The method is verified according to the EU SANTE 11945/2015 standard. The result shows that, This method is suitable for the determination of vermicycin and Jinggangmycin A in complex fruit and vegetable samples. In Chapter 3, a simplified QuEChERS extraction method is combined with UPLC-MS / MS to rapidly and accurately determine cabbage and lettuce. Sixteen kinds of pesticides in tomato and sweet pepper vegetables were detected. In the process of analysis, 16 kinds of pesticides could be completely eluted in 10 min. The samples were extracted by acetonitrile 0.2% formate (0.2: 99.8 v / v). The extractant was diluted with methanol / water 50: 50 v / v / v / 1 for quantitative analysis of UPLC-MS/MS. The addition level was 40 渭 g 路kg ~ (-1) and each standard level was used for five times. The recovery rate of the method was 72.2-119, and the relative standard deviation (RSDs) was less than 17. The method was suitable for the determination of multi-residue pesticide in vegetables.
【学位授予单位】：山东大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：TS255.7;O657.63

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