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Chinese Journal of Chromatography logoLink to Chinese Journal of Chromatography
. 2024 Apr 8;42(4):368–379. [Article in Chinese] doi: 10.3724/SP.J.1123.2023.09010

全自动QuEChERS前处理仪结合气相色谱-四极杆-飞行时间质谱法测定橄榄油中222种农药残留

Determination of 222 pesticide residues in olive oil by fully automatic QuEChERS pre-treatment instrument coupled with gas chromatography-quadrupole-time-of-flight mass spectrometry

Yan LIANG 1, Chunni LEI 2, Bo WANG 2, Huan ZHANG 2, Xinchao WANG 2, Xiaoping ZHOU 1,2,*, Zhenzhen QI 2, Mengchen ZHU 3
PMCID: PMC10988571  PMID: 38566426

Abstract

Pesticide residues may be present in olive oil because pesticides are applied to olive trees during their cultivation and growth for pest prevention and some of these pesticides are not easily degraded. Studies on pesticide residues in olive oil have mainly focused on the detection of single types of pesticide residues, and reports on the simultaneous detection of multiple pesticide residues are limited. At present, hundreds of pesticides with different polarities and chemical properties are used in practice.

In this study, an analytical method based on fully automatic QuEChERS pretreatment instrument coupled with gas chromatography-quadrupole time-of-flight mass spectrometry (GC-QTOF-MS) was established for the rapid determination of 222 pesticide residues in olive oil. The effects of acetonitrile acidification concentration, n-hexane volume, oscillation time, centrifugation temperature, and purification agent on the determination of the 222 pesticide residues were investigated. First, ions with good responses and no obvious interference were selected for quantification and characterization. The purification process was then developed by setting the parameters of the fully automatic QuEChERS pretreatment instrument to optimal values. The sample was extracted with acetonitrile containing 2% formic acid, and the supernatant was purified by centrifugation in a centrifuge tube containing 400 mg N-propylethylenediamine (PSA), 400 mg octadecylsilane-bonded silica gel (C18), and 1200 mg anhydrous magnesium sulfate. The purified solution was blown dry with nitrogen and then fixed with ethyl acetate for instrumental analysis. Finally, a matrix standard solution was used for quantification. The method was validated in terms of matrix effects, linear ranges, limits of detection (LODs) and quantification (LOQs), accuracies, and precisions. The results showed that 86.04% of the 222 pesticides had linear ranges of 0.02-2.00 μg/mL, 10.81% had linear ranges of 0.10-2.00 μg/mL, and 3.15% had linear ranges of 0.20-2.00 μg/mL. The pesticide residues showed good relationships within their respective linear ranges, and the correlation coefficients (R2) were greater than 0.99. The LODs of all tested pesticides ranged from 0.002 to 0.050 mg/kg, and their LOQs ranged from 0.007 to 0.167 mg/kg. Among the 222 pesticides determined, 170 pesticides had LOQs of 0.007 mg/kg while 21 pesticides had LOQs of 0.017 mg/kg. At the three spiked levels of 0.2, 0.5, and 0.8 mg/kg, 79.58% of all tested pesticides had average recoveries of 70%-120% while 65.92% had average recoveries of 80%-110%. In addition, 93.54% of all tested pesticides had relative standard deviations (RSDs, n=6)<10% while 98.35% had RSDs (n=6)<20%. The method was applied to 14 commercially available olive oil samples, and seven pesticides were detected in the range of 0.0044-0.0490 mg/kg. The residues of fenbuconazole, chlorpyrifos, and methoprene did not exceed the maximum limits stated in GB 2763-2021. The maximum residual limits of molinate, monolinuron, benalaxyl, and thiobencarb have not been established. The method utilizes the high mass resolution capability of TOF-MS, which can improve the detection throughput while ensuring good sensitivity. In addition, high-resolution and accurate mass measurements render the screening results more reliable, which is necessary for the high-throughput detection of pesticide residues. The use of a fully automatic QuEChERS instrument in the pretreatment step reduces personnel errors and labor costs, especially when a large number of samples must be processed, thereby offering significant advantages over other approaches. Moreover, the method is simple, rapid, sensitive, highly automatable, accurate, and precise. Thus, it meets requirements for the high-throughput detection of pesticide residues in olive oil and provides a reference for the development of detection methods for pesticide residues in other types of oils as well as the automatic pretreatment of complex matrices.

Keywords: fully automatic QuEChERS pre-treatment instrument, gas chromatography-quadrupole-time-of-flight mass spectrometry (GC-QTOF-MS), pesticide residues, olive oil

2008-2020年,我国橄榄油的消费量从1.2万吨增至5.3万吨,是世界公认的橄榄油消费大国,而国内橄榄油产量完全满足不了消费需求,2019-2020年自给率仅达到3.34%,巨大的橄榄油消费缺口只能通过进口来解决[1]。橄榄油是由新鲜油橄榄果实通过物理压榨法冷榨而成,不经加热及其他化学手段处理,保留了最天然的营养成分,因其具有极高的营养价值以及抗氧化、预防癌症、美容、烹饪等功能,被誉为“液体黄金”和“植物油皇后”,是迄今为止最适合人体营养的油脂[2]。国际橄榄理事会(IOC)将橄榄油分为初榨橄榄油、精炼橄榄油和油橄榄果渣油,品质依次递减,初榨橄榄油又分为特级初榨橄榄油、中级初榨橄榄油和初榨油橄榄油[3]。由于油橄榄在种植及生长过程中使用农药来达到预防虫害的目的,且部分农药不易降解,因此橄榄油中可能存在农药残留,其潜在风险不容忽视。

我国是橄榄油主要进口国,2017年中华人民共和国商业部公布:在市面上所抽检的进口欧盟橄榄油中,约53%的橄榄油含一种或多种农药残留[4]。目前国内外学者关于植物油中农药残留的检测方法已有报道,如蔡燕斌等[5]测定了食用植物油中7种农药残留;Iosif等[6]测定了橄榄油中39种农药残留等,其中橄榄油农药残留的研究主要集中于一种或一类农药残留的检测,针对数百种不同极性、不同化学性质的多种农药残留的检测报道较少。实现农业长远健康发展必须不断加大对农产品质量的检测检验工作,农药残留是农产品质量把控的重要内容,定期、及时的开展农药残留监测十分必要,通过建立橄榄油中快速、高效并同时实现高通量筛查的多农药残留检测方法,以有效保证橄榄油质量安全、保护进出口公司利益,为提高口岸风险监测效率、加强监管力度提供技术支撑。

橄榄油或植物油样品中农药残留的前处理方法主要有固相萃取法(SPE)[7]、凝胶渗透色谱法(GPC)[8]、分散-液液微萃取法(DLLME)[9]、QuEChERS法[10]等。QuEChERS法是由Anastassiades等[11]于2003年首次提出,该技术分析速率快、使用溶剂量少、污染小、操作简单,已被广泛应用于农药残留分析。全自动QuEChERS前处理仪是自动程序控制的多功能样品制备工作站,它建立在六轴机械手平台上,集合样品管理、液体处理、开关盖、振荡提取、加盐模块、离心分离等六大模块,使QuEChERS方法样品制备过程无人化,减轻劳动力的同时减少了人员误差,极大地提高了样品的前处理效率。扈斌等[12]利用自动QuEChERS法检测香叶中212种农药残留,蒋康丽等[13]利用自动QuEChERS法检测花生中297种农药残留。以上研究结果表明:全自动QuEChERS前处理仪应用于农药残留检测,具有简便、快速、灵敏度高且自动化程度高等优势。然而运用全自动QuEChERS前处理仪检测橄榄油中农药多残留的分析鲜见报道。

农药残留分析常用技术有GC[14]、GC-MS[15]、GC-MS/MS[16]、LC、LC-MS、LC-MS/MS[17]等。色谱与质谱联用具有极大优势,可充分发挥高分离及高鉴别能力,提供高效、快速的微量组分分析和结构鉴定能力。气相色谱-四极杆-飞行时间质谱法(GC-QTOF-MS)具有高质量分辨率、高扫描速率等特点,在农药残留的非靶向筛查和定量检测方面具有极其广阔的应用前景,此外高分辨率精确质量测量使筛选结果更加可靠,其实验数据可进行重复分析,极大地提高了工作效率,适合农药残留的高通量检测。目前高分辨飞行时间质谱技术已应用于水果、蔬菜、谷物等样品中的农药残留分析[18,⇓-20],本文基于复杂基质背景下的高通量农药筛查以及自动化QuEChERS技术所带来的高度自动化等特点,针对数百种不同极性、不同化学性质的多农药残留分析展开研究,建立了一种准确、便捷且自动化程度高的橄榄油中多农药残留检测技术,以期为橄榄油中农药残留的监测以及复杂基质的自动化前处理发展提供参考。

1 实验部分

1.1 仪器、试剂与材料

GC-QTOF-MS 7890B-7200气相色谱-四极杆-飞行时间质谱仪(美国Agilent公司);全自动QuEChERS前处理仪,15 mL、50 mL QuEChERS离心管(睿科集团(厦门)股份有限公司); BSA822电子天平(赛多利斯科学仪器(北京)有限公司)。

222种农药标准品,均溶于乙酸乙酯,质量浓度为100 μg/mL(天津阿尔塔科技有限公司);正己烷(分析纯,国药集团化学试剂有限公司);乙腈、乙酸乙酯(分析纯,天津市富宇精细化工有限公司);甲酸、无水硫酸镁(分析纯,天津市百世化工有限公司);十八烷基硅烷键合硅胶(C18)粉末、N-丙基乙二胺(PSA)粉末(美国Agilent公司)。橄榄油样品均为市售特级初榨橄榄油(进口、国产)。

1.2 样品前处理

称取2.0 g橄榄油试样,置于50 mL离心管中,放入全自动QuEChERS前处理仪,通过参数设置加入10 mL 2%甲酸乙腈溶液提取,后经5 Hz频率垂直振荡2 min,并在4 ℃下以3500 r/min冷冻离心5 min。取7 mL上清液加入含有400 mg PSA、400 mg C18、1200 mg无水硫酸镁的离心管中净化离心,净化时设置垂直振荡频率5 Hz、时长2 min,离心温度4 ℃、转速4000 r/min、时长5 min。待净化、离心等步骤处理完成后,取4 mL净化液氮气吹干,用乙酸乙酯定容至0.8 mL后转移至进样瓶,进行GC-QTOF-MS测定分析。

1.3 标准溶液的配制

将222种农药标准品用乙酸乙酯配制得到质量浓度为10 μg/mL的农药混合标准储备溶液。混合标准储备溶液用经1.2节方法处理的空白橄榄油基质提取液逐级稀释,配制成系列质量浓度的基质混合标准溶液。

1.4 GC-QTOF-MS仪器条件

1.4.1 色谱条件

色谱柱:HP-5MS UI柱(30 m×250 μm×0. 25 μm);进样口温度:280 ℃;进样模式:不分流进样;载气:氦气,纯度≥99.999%;载气流速:1 mL/min;升温程序:初始温度50 ℃,保持2 min,以40 ℃/min升温至120 ℃,再以3 ℃/min升温至255 ℃,最后以10 ℃/min升温至300 ℃,保持6 min;进样量:1 μL。

1.4.2 质谱条件

离子化模式:电子轰击(EI)源;电子能量:70 eV;离子源温度:230 ℃;监测模式:全扫描模式;扫描范围:m/z 35~500;扫描速率:5 spectra/s;四极杆温度:150 ℃;碰撞气:高纯氮气(99.999%)。

1.5 数据处理

数据采集通过Agilent Mass Hunter Acquisition 7200软件完成,检测结果的数据处理通过Agilent Mass Hunter Qualitative Analysis B.07.00软件完成,数据分析通过Agilent Mass Hunter TOF定量分析软件分析。每种农药选择响应较好且无明显干扰的离子用于定量及定性,并参照GB 23200.8-2016 《食品安全国家标准 水果和蔬菜中500种农药及相关化学品残留量的测定 气相色谱-质谱法》[21]选定一个定量离子及两个定性离子(见表1)。

表 1.

橄榄油中222种农药的保留时间、定量离子、定性离子、线性范围、检出限和定量限

Pesticide tR/min Quantitative ion
(m/z) 		Qualitative ions
(m/z) 		Linear range/
(μg/mL) 		LOD/
(mg/kg) 		LOQ/
(mg/kg)
Ethiolate (硫草敌) 7.664 100.0892 118.0609, 161.0781 0.02-2 0.002 0.007
Methamidophos (甲胺磷) 8.085 94.0009 95.0077, 140.9910 0.2-2 0.050 0.167
Dichlorvos (敌敌畏) 8.407 109.0083 184.9746, 219.9314 0.02-2 0.002 0.007
Dichlorobenzonitrile (敌草腈) 10.367 170.9696 172.9625, 135.9867 0.02-2 0.002 0.007
Biphenyl (联苯) 11.121 154.1009 153.0796, 152.0691 0.1-2 0.010 0.033
Mevinphos (速灭磷) 12.341 127.0167 192.0068, 164.0132 0.02-2 0.002 0.007
Acephate (乙酰甲胺磷) 12.401 136.0064 93.9982, 42.0310 0.2-2 0.050 0.167
Etridiazole (土菌灵) 12.975 210.9427 182.9124, 123.9262 0.02-2 0.002 0.007
Methacrifos (虫螨畏) 14.345 124.9783 207.9900, 240.0058 0.02-2 0.002 0.007
Chloroneb (氯苯甲醚) 14.495 190.9667 192.9600, 205.9843 0.02-2 0.002 0.007
Molinate (禾草敌) 15.165 126.0920 187.0895, 98.0902 0.02-2 0.002 0.007
Isoprocarb (异丙威) 15.341 121.0716 136.0862, 103.0472 0.1-2 0.020 0.067
Omethoate (氧乐果) 16.920 155.9903 110.0052, 78.9883 0.2-2 0.050 0.167
Tecnazene (四氯硝基苯) 17.232 260.8624 202.8758, 214.8703 0.02-2 0.002 0.007
Thionazin (虫线磷) 17.371 142.9932 191.9619, 219.9912 0.02-2 0.002 0.007
Fenobucarb (仲丁威) 17.437 121.0760 150.1006, 107.0426 0.2-2 0.050 0.167
Propoxur (残杀威) 17.564 110.0438 152.0756, 111.0321 0.1-2 0.020 0.067
Diphenylamine (二苯胺) 17.736 169.0927 167.0702, 168.0827 0.02-2 0.002 0.007
Cycloate (环草敌) 18.147 154.1340 186.0826, 215.1187 0.02-2 0.002 0.007
Ethoprophos (灭线磷) 18.197 157.9584 199.9963, 242.0395 0.02-2 0.002 0.007
Chlorpropham (氯苯胺灵) 18.758 213.0427 170.9985, 152.9868 0.02-2 0.005 0.017
Naled (二溴磷) 18.877 78.9884 108.9983, 112.9463 0.2-2 0.050 0.167
Atrazine-desethyl (脱乙基莠去津) 19.183 172.0505 187.0554, 145.0109 0.02-2 0.002 0.007
Ethalfluralin (乙丁烯氟灵) 19.196 276.0444 316.0723, 292.0355 0.02-2 0.002 0.007
Dicrotofos (百治磷) 19.461 127.0112 94.9817, 108.9966 0.02-2 0.005 0.017
Benfluralin (乙丁氟灵) 19.909 292.0515 264.0108, 276.0418 0.02-2 0.002 0.007
Monocrotophos (久效磷) 19.916 127.0099 97.0445, 108.9964 0.1-2 0.020 0.067
Sulfotep (治螟磷) 19.936 322.0146 201.9799, 237.9182 0.02-2 0.002 0.007
Phorate (甲拌磷) 20.052 259.9954 121.0357, 230.9612 0.02-2 0.002 0.007
α-Hexachlorocyclohexane (α-六六六) 20.112 218.9042 182.9330, 220.8959 0.02-2 0.002 0.007
Hexachlorobenzene (六氯苯) 20.566 283.8078 285.8024, 281.8039 0.02-2 0.002 0.007
Dicloran (氯硝胺) 20.914 175.9603 205.9528, 123.9870 0.02-2 0.005 0.017
Dimethoate (乐果) 21.097 87.0095 124.9745, 228.9845 0.02-2 0.005 0.017
Atratone (阿特拉通) 21.256 196.1111 211.1316, 197.1077 0.02-2 0.002 0.007
Carbofuran (克百威) 21.691 164.0770 131.0396, 149.0518 0.02-2 0.002 0.007
Simazine (西玛津) 21.877 201.0662 186.0428, 173.0353 0.02-2 0.002 0.007
Atrazine (莠去津) 21.880 200.0647 215.0820, 173.0357 0.02-2 0.002 0.007
Monolinuron (绿谷隆) 21.908 61.0492 126.0029, 214.0377 0.1-2 0.020 0.067
Clomazone (异噁草酮) 21.910 204.0997 138.0002, 205.0914 0.02-2 0.002 0.007
β-Hexachlorocyclohexane (β-六六六) 22.109 218.9013 216.9025, 180.9314 0.02-2 0.002 0.007
γ-Hexachlorocyclohexane (γ-六六六) 22.109 182.9336 218.9054, 253.8657 0.02-2 0.002 0.007
Propazine (扑灭津) 22.175 214.0791 229.0980, 172.0329 0.02-2 0.002 0.007
Pentachloronitrobenzene (五氯硝基苯) 22.457 294.8278 236.8424, 248.8362 0.02-2 0.002 0.007
Terbufos (特丁硫磷) 22.686 230.9712 153.0030, 288.0232 0.02-2 0.002 0.007
Terbuthylazine (特丁津) 22.756 214.0771 229.0932, 173.0370 0.02-2 0.002 0.007
Fonofos (地虫硫磷) 22.759 246.0186 137.0167, 173.9606 0.02-2 0.002 0.007
Propetamphos (胺丙畏) 22.961 138.0151 193.9762, 236.0145 0.02-2 0.002 0.007
Pronamide (炔苯酰草胺) 22.965 172.9631 255.0082, 239.9837 0.02-2 0.002 0.007
Profluralin (环丙氟灵) 23.167 318.0563 302.0540, 347.0856 0.02-2 0.002 0.007
Pyrimethanil (嘧霉胺) 23.197 198.1227 199.1151, 200.1024 0.02-2 0.002 0.007
Diazinon (二嗪磷) 23.685 304.0832 179.1140, 137.0686 0.02-2 0.002 0.007
δ-Hexachlorocyclohexane (δ-六六六) 23.711 218.8959 216.8989, 180.9252 0.02-2 0.002 0.007
Paraoxon-methyl (甲基对氧磷) 23.778 230.0102 247.0119, 200.0130 0.1-2 0.020 0.067
Triallate (野麦畏) 24.242 268.0215 270.0159, 142.9132 0.02-2 0.002 0.007
Isazofos (氯唑磷) 24.381 161.0293 256.9648, 284.9919 0.02-2 0.002 0.007
Etrimfos (乙嘧硫磷) 24.561 292.0529 181.0911, 277.0242 0.02-2 0.002 0.007
Iprobenfos (异稻瘟净) 24.750 203.9990 246.0325, 288.0748 0.02-2 0.002 0.007
Tebupirimfos (丁基嘧啶磷) 24.863 318.1006 261.0352, 234.0133 0.02-2 0.002 0.007
Pentachloroaniline (五氯苯胺) 24.919 264.8560 262.8546, 229.8748 0.02-2 0.002 0.007
Formothion (安硫磷) 24.995 169.9500 223.9988, 256.9761 0.1-2 0.010 0.033
Pirimicarb (抗蚜威) 25.218 166.1011 238.1300, 138.0683 0.02-2 0.002 0.007
Desmetryn (敌草净) 25.569 213.0994 198.0735, 171.0488 0.02-2 0.005 0.017
Dichlofenthion (除线磷) 25.768 278.9934 222.9357, 250.9569 0.02-2 0.002 0.007
Propanil (敌稗) 25.818 160.9772 216.9907, 162.9712 0.02-2 0.002 0.007
Metribuzin (嗪草酮) 25.878 198.0642 199.0560, 144.0356 0.1-2 0.010 0.033
Phosphamidon (磷胺) 25.904 264.0847 138.0818, 226.9717 0.1-2 0.010 0.033
Acetochlor (乙草胺) 26.239 146.0888 162.0820, 223.0629 0.02-2 0.005 0.017
Parathion-methyl (甲基对硫磷) 26.279 262.9886 233.0082, 245.9810 0.02-2 0.002 0.007
Chlorpyrifos-methyl (甲基毒死蜱) 26.283 285.9319 287.9240, 196.9072 0.02-2 0.005 0.017
Vinclozolin (乙烯菌核利) 26.346 284.9771 211.9911, 197.9749 0.02-2 0.002 0.007
Tolclofos-methyl (甲基立枯磷) 26.515 265.0004 266.9819, 249.9527 0.02-2 0.002 0.007
Malaoxon (马拉氧磷) 26.704 127.0199 267.9982, 194.9738 0.1-2 0.010 0.033
Alachlor (甲草胺) 26.813 188.1010 237.0754, 269.0989 0.02-2 0.002 0.007
Ronnel (皮蝇磷) 27.172 284.9383 286.9299, 124.9791 0.02-2 0.002 0.007
Metalaxyl (甲霜灵) 27.208 206.1056 249.1186, 234.0966 0.02-2 0.002 0.007
Ametryn (莠灭净) 27.221 227.1147 212.0883, 185.0617 0.02-2 0.002 0.007
Prometryn (扑草净) 27.221 241.1373 184.0705, 226.1089 0.02-2 0.002 0.007
Paraoxon (对氧磷) 27.228 275.0425 219.9897, 247.0123 0.1-2 0.020 0.067
Terbutryn (特丁净) 27.951 226.1065 241.1234, 185.0702 0.02-2 0.002 0.007
Fenitrothion (杀螟硫磷) 28.057 277.0019 260.0004, 247.0253 0.02-2 0.002 0.007
Pirimiphos-methyl (甲基嘧啶磷) 28.339 290.0641 276.0468, 305.0817 0.02-2 0.002 0.007
Ethofumesate (乙氧呋草黄) 28.343 207.1015 161.0605, 286.0749 0.02-2 0.005 0.017
Bromacil (除草定) 28.353 204.9531 206.9509, 230.9601 0.02-2 0.002 0.007
Aldrin (艾氏剂) 28.509 262.8441 264.8383, 292.9078 0.02-2 0.002 0.007
Phorate sulfoxide (甲拌磷亚砜) 28.522 276.8945 142.9300, 198.9867 0.1-2 0.020 0.067
Thiobencarb (禾草丹) 28.655 100.0792 125.0116, 257.0521 0.02-2 0.002 0.007
Dipropetryn (异丙净) 28.827 255.1433 240.1147, 222.1578 0.02-2 0.002 0.007
Malathion (马拉硫磷) 28.907 173.0771 157.9537, 142.9852 0.02-2 0.005 0.017
Phorate sulfone (甲拌磷砜) 29.000 198.9963 170.9637, 214.9855 0.02-2 0.002 0.007
Metolachlor (异丙甲草胺) 29.030 238.0921 162.1263, 240.0823 0.02-2 0.002 0.007
Fenthion (倍硫磷) 29.252 278.0226 169.0053, 153.0263 0.02-2 0.002 0.007
Chlorpyrifos (毒死蜱) 29.388 313.9399 257.8800, 285.9072 0.02-2 0.002 0.007
Parathion (对硫磷) 29.431 291.0141 185.9818, 234.9534 0.02-2 0.002 0.007
Triadimefon (三唑酮) 29.600 208.0170 210.0096, 181.0042 0.02-2 0.002 0.007
Trichloronat (毒壤磷) 30.061 296.9569 268.9284, 195.9114 0.02-2 0.002 0.007
Tetraconazole (四氟醚唑) 30.124 336.0521 338.0360, 170.9659 0.02-2 0.002 0.007
Isocarbophos (水胺硫磷) 30.131 135.9955 229.9885, 289.0336 0.1-2 0.010 0.033
Isofenphos-oxon (氧异柳磷) 30.214 229.0271 200.9983, 314.0973 0.02-2 0.002 0.007
Bromophos (溴硫磷) 30.314 330.8732 328.8720, 212.8542 0.02-2 0.002 0.007
Fosthiazate (噻唑磷) 30.493 194.9978 226.9682, 283.0267 0.1-2 0.020 0.067
Cyprodinil (嘧菌环胺) 30.864 224.1262 225.1251, 210.0900 0.02-2 0.002 0.007
Pirimiphos-ethyl (嘧啶磷) 30.980 333.1124 318.0908, 304.0730 0.02-2 0.002 0.007
Terbufos sulfone (特丁硫磷砜) 31.030 230.9698 288.0501, 185.9850 0.02-2 0.002 0.007
Isofenphos-methyl (甲基异柳磷) 31.037 199.0125 230.9753, 241.0477 0.02-2 0.002 0.007
Pendimethalin (二甲戊灵) 31.339 252.0933 220.0907, 162.0677 0.02-2 0.002 0.007
Penconazole (戊菌唑) 31.392 248.0891 250.0777, 160.9680 0.02-2 0.002 0.007
Mephosfolan (地胺磷) 31.807 196.0078 226.9698, 167.9790 0.02-2 0.005 0.017
Phosfolan (硫环磷) 31.807 196.0056 139.9479, 167.9762 0.02-2 0.005 0.017
Chlorfenvinphos (毒虫畏) 31.976 322.9819 266.9282, 268.9218 0.02-2 0.002 0.007
Isofenphos (异柳磷) 32.031 213.0393 255.0684, 185.0048 0.02-2 0.002 0.007
Quinalphos (喹硫磷) 32.049 146.0470 298.0389, 157.0727 0.02-2 0.002 0.007
Triadimenol (三唑醇) 32.105 112.0441 168.1019, 129.9898 0.02-2 0.005 0.017
Allethrin (烯丙菊酯) 32.231 123.1238 105.0626, 134.0626 0.02-2 0.002 0.007
Fipronil (氟虫腈) 32.268 366.9288 368.9224, 350.9279 0.02-2 0.002 0.007
Beflubutamid (氟丁酰草胺) 32.298 176.1074 193.0209, 221.0503 0.02-2 0.002 0.007
Procymidone (腐霉利) 32.384 283.0095 285.0025, 255.0050 0.02-2 0.002 0.007
trans-Chlordane (反式-氯丹) 32.483 372.8155 374.8121, 376.8029 0.02-2 0.002 0.007
Methoprene (烯虫酯) 32.762 73.0648 191.1665, 153.0803 0.02-2 0.002 0.007
Methidathion (杀扑磷) 32.765 145.0061 156.9427, 301.9400 0.02-2 0.002 0.007
o,p'-DDE (o,p'-滴滴伊) 33.001 246.0098 317.9305, 176.0581 0.02-2 0.002 0.007
Bromophos-ethyl (乙基溴硫磷) 33.041 358.8926 302.8351, 356.8924 0.02-2 0.002 0.007
Paclobutrazol (多效唑) 33.087 236.0509 238.0410, 167.0151 0.02-2 0.002 0.007
α-Endosulfan (α-硫丹) 33.147 240.8893 264.8366, 338.8507 0.02-2 0.002 0.007
Fenothiocarb (苯硫威) 33.273 72.0496 160.0766, 253.1013 0.02-2 0.002 0.007
Tetrachlorvinphose (杀虫畏) 33.562 328.9254 330.9222, 332.9077 0.02-2 0.002 0.007
Mepanipyrim (嘧菌胺) 33.711 222.1103 223.1070, 221.0833 0.02-2 0.002 0.007
Ditalimfos (灭菌磷) 33.820 130.0330 148.0389, 299.0278 0.02-2 0.002 0.007
Butachior (丁草胺) 33.877 176.1016 160.1064, 188.0981 0.02-2 0.002 0.007
Chlorfenson (杀螨酯) 34.009 301.9401 174.9608, 176.9507 0.1-2 0.010 0.033
Napropamide (敌草胺) 34.185 271.1420 128.1027, 171.0691 0.02-2 0.002 0.007
Hexaconazole (己唑醇) 34.285 213.9848 231.0183, 255.9863 0.02-2 0.002 0.007
Butamifos (抑草磷) 34.308 286.0915 200.0019, 231.9714 0.02-2 0.005 0.017
Fluorodifen (三氟硝草醚) 34.570 190.0035 328.0072, 162.0046 0.1-2 0.010 0.033
Bromfenvinfos (溴苯烯磷) 34.583 266.9329 322.9840, 294.9512 0.02-2 0.002 0.007
Prothiofos (丙硫磷) 34.583 308.9848 266.9392, 161.9586 0.02-2 0.002 0.007
Imazalil (抑霉唑) 34.600 214.9888 172.9450, 296.0288 0.02-2 0.002 0.007
Flutolanil (氟酰胺) 34.646 173.0370 281.0648, 323.1041 0.02-2 0.002 0.007
Isoprothiolane (稻瘟灵) 34.723 290.0518 231.0042, 204.0208 0.02-2 0.002 0.007
Dieldrin (狄氏剂) 34.726 262.8407 276.8541, 379.8423 0.02-2 0.002 0.007
Profenofos (丙溴磷) 34.786 338.9458 373.9085, 296.8982 0.02-2 0.002 0.007
p,p'-DDE (p,p'-滴滴伊) 34.942 317.9264 315.9269, 245.9984 0.02-2 0.002 0.007
Fludioxonil (咯菌腈) 35.078 248.0389 127.0367, 154.0442 0.02-2 0.002 0.007
Tribufos (脱叶磷) 35.084 201.9631 226.0507, 258.0214 0.02-2 0.002 0.007
Pretilachlor (丙草胺) 35.084 238.0887 202.1120, 262.1641 0.02-2 0.002 0.007
o,p'-DDD (o,p'-滴滴滴) 35.416 235.0092 237.0020, 165.0656 0.02-2 0.002 0.007
Oxadiazon (噁草酮) 35.492 174.9555 258.0203, 302.0050 0.02-2 0.002 0.007
Myclobutanil (腈菌唑) 35.539 179.0302 288.0941, 150.0029 0.1-2 0.010 0.033
Oxyfluorfen (乙氧氟草醚) 35.924 252.0335 361.0175, 299.9916 0.02-2 0.002 0.007
Endrin (异狄氏剂) 35.970 262.8402 316.9855, 344.8754 0.02-2 0.002 0.007
Bupirimate (乙嘧酚磺酸酯) 36.047 273.0912 316.1370, 208.1364 0.02-2 0.002 0.007
Nitrofen (除草醚) 36.156 282.9688 252.9662, 202.0076 0.02-2 0.002 0.007
Kresoxim-methyl (醚菌酯) 36.176 116.0527 206.0747, 131.0703 0.02-2 0.002 0.007
Cyproconazole (环丙唑醇) 36.216 222.0360 224.0290, 223.0340 0.02-2 0.002 0.007
Isoxathion (噁唑啉) 36.285 313.0337 105.0291, 177.0167 0.1-2 0.020 0.067
β-Endosulfan (β-硫丹) 36.594 240.8945 264.8716, 338.8511 0.02-2 0.002 0.007
Fluazifop-butyl (吡氟禾草灵) 36.863 282.0727 383.1197, 254.0441 0.02-2 0.002 0.007
Cyflufenamid (环氟菌胺) 36.866 91.0556 412.1057, 294.0675 0.02-2 0.002 0.007
Chlorobenzilate (乙酯杀螨醇) 36.959 251.0241 253.0118, 152.0522 0.02-2 0.002 0.007
Fenthion sulfoxide (倍硫磷亚砜) 37.211 278.0210 279.0198, 294.0194 0.02-2 0.002 0.007
Fensulfothion (丰索磷) 37.214 292.0167 308.0106, 292.9980 0.02-2 0.002 0.007
Diniconazole (烯效唑) 37.228 267.9920 269.9865, 232.0118 0.02-2 0.002 0.007
Aclonifen (苯草醚) 37.420 264.0316 212.0507, 266.0158 0.02-2 0.002 0.007
o,p'-DDT (o,p'-滴滴涕) 37.553 235.0120 237.0045, 165.0672 0.02-2 0.002 0.007
Oxadixyl (噁霜灵) 37.722 163.0906 233.0769, 278.1072 0.1-2 0.010 0.033
p,p'-DDD (p,p'-滴滴滴) 37.729 235.0081 237.0011, 199.0195 0.02-2 0.002 0.007
Ethion (乙硫磷) 37.924 230.9695 383.9613, 198.9868 0.02-2 0.002 0.007
Chlorthiophos (虫螨磷) 38.104 324.9752 359.9349, 296.9411 0.02-2 0.002 0.007
Triazophos (三唑磷) 38.701 161.0492 172.0750, 256.9840 0.02-2 0.002 0.007
Carbophenothion (三硫磷) 38.993 156.9838 341.9531, 198.9884 0.02-2 0.002 0.007
Benalaxyl (苯霜灵) 39.152 148.1155 206.1085, 325.1462 0.02-2 0.002 0.007
Edifenphos (敌瘟磷) 39.165 310.0146 172.9787, 201.0044 0.02-2 0.002 0.007
Famphur (伐灭磷) 39.165 218.0307 124.9781, 216.9966 0.02-2 0.002 0.007
Quinoxyfen (喹氧灵) 39.238 237.0510 272.0121, 306.9770 0.02-2 0.002 0.007
Propiconazole (丙环唑) 39.507 259.0143 172.9486, 261.0098 0.02-2 0.002 0.007
p,p'-DDT (p,p'-滴滴涕) 39.606 235.0079 237.0011, 245.9832 0.02-2 0.002 0.007
Trifloxystrobin (肟菌酯) 40.230 116.0482 131.0682, 222.0624 0.02-2 0.002 0.007
Hexazinone (环嗪酮) 40.290 171.0916 252.1403, 128.0729 0.02-2 0.005 0.017
Tebuconazole (戊唑醇) 40.429 250.0604 163.0190, 252.0540 0.1-2 0.010 0.033
Diclofop-methyl (禾草灵) 40.824 252.9747 280.9980, 342.0070 0.02-2 0.002 0.007
Fenthion sulfone (倍硫磷砜) 41.249 309.9884 136.0236, 231.0079 0.2-2 0.050 0.167
Piperonyl butoxide (增效醚) 41.342 176.0851 149.0510, 177.0810 0.02-2 0.002 0.007
Epoxiconazole (氟环唑) 41.507 192.0245 183.0484, 138.0017 0.02-2 0.005 0.017
Iprodione (异菌脲) 42.304 186.9480 244.9718, 245.9635 0.02-2 0.005 0.017
Phosmet (亚胺硫磷) 42.393 160.0480 161.0339, 316.9728 0.02-2 0.002 0.007
Pyridaphenthion (哒嗪硫磷) 42.466 340.0495 199.0774, 188.0462 0.02-2 0.002 0.007
Tetramethrin (胺菊酯) 42.669 164.0711 165.0613, 135.0338 0.02-2 0.002 0.007
Bromopropylate (溴螨酯) 42.795 340.8932 182.9389, 338.8881 0.02-2 0.002 0.007
Phosphonothioic acid (苯硫磷) 42.873 156.9916 169.0369, 323.0179 0.02-2 0.005 0.017
Piperophos (哌草磷) 43.093 320.1320 140.1009, 122.0916 0.02-2 0.002 0.007
Dicofol (三氯杀螨醇) 43.103 138.9872 140.9822, 249.9779 0.02-2 0.020 0.067
Mothoxychlor (甲氧滴滴涕) 43.130 227.1176 228.1008, 212.0698 0.02-2 0.002 0.007
Bifenthrin (联苯菊酯) 43.213 181.1216 166.0839, 165.0741 0.02-2 0.002 0.007
Fenpropathrin (甲氰菊酯) 43.462 265.0586 181.0619, 349.1436 0.02-2 0.002 0.007
Fenamidone (咪唑菌酮) 43.558 268.0885 238.1106, 206.0665 0.02-2 0.005 0.017
Etoxazole (乙螨唑) 43.604 300.1014 330.1098, 359.1463 0.02-2 0.002 0.007
Tebufenpyrad (吡螨胺) 43.644 318.1257 333.1460, 276.0770 0.02-2 0.002 0.007
Bifenox (甲羧除草醚) 43.797 340.9716 309.9480, 342.9655 0.1-2 0.020 0.067
Anilofos (莎稗磷) 43.896 226.0439 183.9984, 334.0212 0.02-2 0.002 0.007
Tetradifon (三氯杀螨砜) 44.128 226.8787 355.8862, 158.9619 0.02-2 0.002 0.007
Phosalone (伏杀硫磷) 44.775 181.9980 366.9629, 154.0091 0.02-2 0.002 0.007
Leptophos (溴苯磷) 44.845 376.8865 374.8858, 378.8734 0.02-2 0.002 0.007
Pyriproxyfen (吡丙醚) 45.210 136.0821 226.0844, 185.0466 0.2-2 0.050 0.167
Mefenacet (苯噻酰草胺) 45.354 192.0106 120.0732, 136.0140 0.02-2 0.002 0.007
Fenarimol (氯苯嘧啶醇) 46.242 138.9904 219.0196, 330.0112 0.02-2 0.002 0.007
Iambda-cyhalothrin (高效氯氟氰菊酯) 46.451 181.0636 197.0287, 141.0438 0.02-2 0.002 0.007
Azinphos (益棉磷) 46.776 160.0417 132.0434, 77.0350 0.02-2 0.005 0.017
Pyrazophos (吡菌磷) 47.005 221.0761 232.0964, 373.0626 0.02-2 0.002 0.007
Acrinathrin (氟丙菊酯) 47.294 181.0606 289.0513, 247.0059 0.02-2 0.002 0.007
Permethrin (氯菊酯) 48.528 183.0765 184.0712, 255.0391 0.02-2 0.002 0.007
Pyridaben (哒螨灵) 48.747 147.1213 117.0628, 364.1121 0.02-2 0.002 0.007
Fluquinconazole (氟喹唑) 49.009 340.0395 342.0248, 341.0252 0.02-2 0.002 0.007
Coumaphos (蝇毒磷) 49.075 361.9983 225.9739, 363.9892 0.02-2 0.002 0.007
Dioxathion (敌噁磷) 49.467 269.9964 197.0255, 168.9962 0.1-2 0.020 0.067
Fenbuconazole (腈苯唑) 50.044 129.0564 198.0787, 125.0073 0.02-2 0.002 0.007
Cyfluthrin (氟氯氰菊酯) 50.711 206.0457 199.0421, 226.0504 0.02-2 0.005 0.017
Boscalid (啶酰菌胺) 50.900 139.9894 342.0169, 344.0113 0.02-2 0.002 0.007
Cypermethrin (氯氰菊酯) 51.378 181.0535 152.0515, 180.0686 0.02-2 0.005 0.017
Flucythrinate (氟氰戊菊酯) 51.500 199.0846 157.0405, 451.1299 0.02-2 0.002 0.007
Fenvalerate (氰戊菊酯) 52.745 167.0533 225.0676, 419.1027 0.02-2 0.002 0.007
Fluvalinate (氟胺氰菊酯) 53.259 250.0609 252.0467, 181.0552 0.02-2 0.002 0.007
Difenoconazole (苯醚甲环唑) 53.511 323.0021 324.9986, 264.9639 0.1-2 0.020 0.067
Deltamethrin (溴氰菊酯) 54.082 181.0551 171.9773, 173.9753 0.02-2 0.002 0.007
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2 结果与讨论

2.1 色谱条件的优化

农药残留分析中最普遍使用的两种色谱柱是弱极性HP-5毛细管柱和中等极性的HP-1701毛细管柱,其中HP-1701毛细管柱不适用于部分高沸点菊酯类及唑类农药的分析,弱极性HP-5毛细管柱在分析极性较强化合物时易出现峰拖尾现象[22],因此本实验选择超高惰性的HP-5MS UI毛细管柱;同时实验考虑到少数目标物灵敏度较低,选择不分流进样;当载气流量过小时,少数目标色谱峰出现峰拖尾、峰展宽等现象,无法满足定量要求,当载气流量过大时,会影响分离度,甚至导致色谱峰重叠,不能实现目标物的有效分离[23],综合考虑选择1 mL/min载气流量;升温程序在借鉴GB 23200.113-2018 《食品安全国家标准 植物源性食品中208种农药及其代谢物残留量的测定 气相色谱-质谱联用法》[24]色谱分析条件的基础上,延长了升温程序的时间,更有利于目标物的有效分离。加标样品中222种农药(0.5 μg/mL)的总离子流色谱图见图1。

图 1. 加标样品中222种农药(0.5 μg/mL)的总离子流色谱图.

Fig. 1

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2.2 前处理条件的优化

2.2.1 乙腈酸化浓度的优化

橄榄油的主要成分为油脂,油脂会给后续分析带来强烈干扰。乙腈中可溶入的油脂量极少,对绝大多数农药溶解度则较大,故采用乙腈来作为橄榄油中农药残留的提取溶剂,同时考虑到部分农药可能对酸碱度较为敏感,因此考察了含0、0.1%、0.5%、1%、2%、5%甲酸的乙腈溶液对222种农药的提取效果,结果如图2所示。222种农药的回收率在70%~120%范围的农药数量随甲酸体积分数的增大先增多后减少,说明乙腈酸化程度对农药回收率有着较大影响。在采用含2%甲酸的乙腈溶液提取时,回收率在70%~120%范围的农药数量最多,占全部被测农药的80.18%,因此选择使用含2%甲酸的乙腈溶液进行提取。

图 2. 采用含不同体积分数甲酸的乙腈溶液提取时 222种农药的回收率分布.

Fig. 2

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2.2.2 正己烷体积的优化

橄榄油基质成分复杂,油脂干扰较大,实验预设先使用正己烷对橄榄油进行溶解,用含2%甲酸的乙腈溶液进行反提取,其中油脂溶于正己烷相,农药组分转移至乙腈相中。考察了不同正己烷体积(0、1、2、3、4 mL)对222种农药的提取效果,结果见图3。未加正己烷时,222种农药中有80.18%的农药回收率在70%~120%范围内,而加入1、2、3、4 mL正己烷时,222种农药中分别有74.77%、74.32%、74.77%和74.77%的农药回收率在70%~120%范围内。结果表明,不加正己烷时农药的回收率更高,可能是有些农药极易溶于正己烷相中,导致其回收率降低,因此选择不加正己烷,只使用含2%甲酸的乙腈溶液进行提取。

图 3. 采用不同体积的正己烷提取时222种农药的回收率分布.

Fig. 3

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2.2.3 振荡时间的优化

全自动QuEChERS前处理仪的应用使样品处理过程无人化,减轻劳动力的同时减少了人员误差,极大地提高了样品的前处理效率和平行性。该设备具有垂直振荡和涡旋振荡两种模式,经实验室前期测试发现垂直振荡的效率更高,且在振荡频率为5 Hz时能够使基质分散均匀,可高效地进行农药残留的提取。实验对振荡频率在5 Hz时的振荡时间(1、2、3、4、5 min)进行优化,不同振荡时间下222种农药的回收率结果见图4。结果表明:振荡时间为1 min时,222种农药中有73.87%的农药回收率在70%~120%范围内;而振荡时间为2 min和3 min时,该占比分别提高至80.18%和79.28%; 3 min以后农药回收率在70%~120%范围内的数量略有下降,但基本保持不变。振荡时间为1 min时提取效率较低,可能与振荡不充分有关,导致农药未被完全提取,而振荡时间为2 min和3 min时结果基本一致,考虑到工作效率,实验选择垂直振荡2 min。

图 4. 不同振荡时间提取时222种农药的回收率分布.

Fig. 4

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2.2.4 离心温度及净化剂的选择

根据侯靖等[22]在实验室前期积累的数据可知,乙腈提取液在冷冻条件下离心可以在一定程度上除去油脂类干扰物,因此在使用全自动QuEChERS前处理仪中的离心分离模块时,选择其可以设置的最低温度4 ℃作为离心温度。对于离心后的样品,考虑到依然存在少量油脂、脂肪及色素,实验参照GB 23200.113-2018[24]中的前处理方法,选择适用于谷物、油料和坚果净化的净化剂400 mg C18、400 mg PSA、1200 mg无水硫酸镁。

2.3 基质效应

基质效应是指样品基质中除分析物以外的其他成分所引起的检测信号增强或减弱[25]。实验对222种农药的基质效应(ME=农药在基质标准溶液中的响应/农药在溶剂标准溶液中的响应)进行了考察,ME<0.8为基质抑制效应,ME在0.8~1.2范围内为弱基质效应,ME>1.2为基质增强效应。222种农药中有6种农药表现为基质抑制效应,206种农药表现为弱基质效应,10种农药表现为基质增强效应(见附表1,详见 https://www.chrom-China.com)。为了使农药项目定量定性更加准确、可靠,实验采用空白基质配制标准溶液的方式进行定量。

2.4 方法学考察

2.4.1 线性范围、检出限和定量限

对1.3节配制的基质混合标准溶液进行分析,以目标化合物的质量浓度为横坐标(x, μg/mL),峰面积为纵坐标(y)绘制标准曲线。如表1所示,86.04%农药的线性范围为0.02~2.00 μg/mL, 10.81%农药的线性范围为0.1~2.0 μg/mL, 3.15%农药的线性范围为0.2~2.0 μg/mL,相关系数(R2)均大于0.99,222种农药在各自线性范围内线性关系良好,满足检测要求。以3倍和10倍信噪比(S/N)为检出限和定量限,结果表明,222种农药的检出限为0.002~0.050 mg/kg,定量限为0.007~0.167 mg/kg,其中有170种农药定量限可以达到0.007 mg/kg, 21种农药定量限可以达到0.017 mg/kg,占总数量的86.04%; 11种农药的定量限为0.033 mg/kg, 13种农药的定量限为0.067 mg/kg, 7种农药的定量限大于0.1 mg/kg。

2.4.2 正确度及精密度

在空白橄榄油试样中,分别选择0.2、0.5和0.8 mg/kg 3个水平进行加标回收试验,每个水平做6个平行,考察222种农药的正确度与精密度。结果表明:在3个添加水平下,回收率为70%~120%的农药占全部被测农药的79.58%以上,回收率为80%~110%的农药占全部被测农药的65.92%,相对标准偏差(RSD)小于10%的农药占总数的93.54%以上,RSD小于20%的农药占总数的98.35%以上(见附表1)。表明该方法准确度与精密度良好,可满足多农药残留分析的要求。

2.5 实际样品检测

实验对14份市售橄榄油试样进行检测,共检出7种农药,含量为0.0044~0.0490 mg/kg, 7种农药对应的提取离子色谱图见图5。

图 5. 实际样品中7种农药的提取离子色谱图.

Fig. 5

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其中10份橄榄油试样中均检出腈苯唑,含量为0.0148~0.0319 mg/kg;1份橄榄油试样中检出禾草敌、绿谷隆、毒死蜱、烯虫酯和腈苯唑5种农药,详细检出情况见表2。与我国现行GB 2763-2021《食品安全国家标准 食品中农药最大残留限量》[26]相比较,腈苯唑、毒死蜱、烯虫酯的残留量未超过其最大残留限量值,禾草敌、绿谷隆、苯霜灵、禾草丹暂未制定对应的最大残留限量值。

表 2.

市售橄榄油样品中农药残留的检测结果

Sample No. Detected pesticides Contents/(mg/kg)
1 methoprene, benalaxyl 0.0259, 0.0065
2 fenbuconazole 0.0252
3 thiobencarb 0.0044
4 fenbuconazole 0.0244
5 fenbuconazole 0.0288
6 fenbuconazole 0.0263
7 fenbuconazole 0.0293
8 fenbuconazole 0.0252
9 benalaxyl 0.0180
10 fenbuconazole, thiobencarb 0.0148, 0.0126
11 fenbuconazole 0.0240
12 fenbuconazole 0.0260
13 benalaxyl 0.0172
14 molinate, monolinuron, 0.0145, 0.0490,
chlorpyrifos, methoprene, 0.0102, 0.0140,
fenbuconazole 0.0319
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3 结论

本研究将全自动QuEChERS前处理仪与气相色谱-四极杆-飞行时间质谱法相结合,建立了一种准确、便捷且自动化程度高的橄榄油多农药残留的检测方法。该方法利用飞行时间质谱的高质量分辨率特点,可以在保证灵敏度的基础上提高检测通量,此外高分辨率精确质量测量使筛选结果更加可靠,适合农药残留的高通量检测,其中前处理步骤运用全自动QuEChERS前处理仪减少了人员误差以及实验人员精力的投入,尤其是需要进行大批量样品处理时优势更加显著。该方法操作简单、快速,灵敏度高,自动化程度较强,正确度及精密度良好,满足了橄榄油中农药残留高通量检测的要求,并为其他油类农药残留检测以及复杂基质的自动化前处理发展提供了参考。

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