高效液相色譜法測(cè)定果蔬中的5種農(nóng)藥殘留

1、PAGE 6食品安全質(zhì)量檢測(cè)學(xué)報(bào)第8卷第5期仲伶俐, 等: 高效液相色譜法測(cè)定果蔬中的5種農(nóng)藥殘留PAGE 5第8卷 第5期食品安全質(zhì)量檢測(cè)學(xué)報(bào)Vol. 8 No. 52017年5月Journal of Food Safety and QualityMay. , 2017 基金項(xiàng)目: 四川省財(cái)政基因工程專(zhuān)項(xiàng)資金項(xiàng)目(2016QNJJ-022)Fund: Supported by Sichuan Province Fiscal Genetic Engineering Special Fund Project (2016QNJJ-022)*通訊作者: 仲伶俐, 碩士, 助理研究員, 主要研究方向?yàn)?/p>

2、食品質(zhì)量安全. E-mail: HYPERLINK mailto:17916029 17916029*Corresponding author: ZHONG Ling-Li, Master, Research Assistant, Analysis and Testing Center of Sichuan Academy of Agricultural Sciences, Chengdu 610066, China. E-mail: 17916029高效液相色譜法測(cè)定果蔬中的5種農(nóng)藥殘留仲伶俐*, 李 曦, 李華仙, 付成平, 趙 珊, 雷欣宇(四川省農(nóng)業(yè)科學(xué)院分析測(cè)試中心, 成都 6100

3、66)摘 要: 目的 建立高效液相色譜法測(cè)定果蔬中啶蟲(chóng)脒、嘧霉胺、氟蟲(chóng)腈、辛硫磷和噠螨靈5種農(nóng)藥殘留。方法 樣品以乙腈為提取劑, NH2固相萃取小柱凈化和富集, 用二氯甲烷-甲醇(97:3, V:V)溶液進(jìn)行洗脫, 洗脫液濃縮、定容后, 以Dikma Spursil C18(250 mm4.6 mm, 5 m)色譜柱分離, 水和甲醇為流動(dòng)相梯度洗脫, 流速為1.0 mL/min, 于配有紫外可變波長(zhǎng)檢測(cè)器的高效液相色譜儀測(cè)定, 外標(biāo)法定量。結(jié)果 5種農(nóng)藥在0.12.0 g/mL的濃度范圍內(nèi)具有良好的線(xiàn)性關(guān)系, 相關(guān)系數(shù)為0.99950.9998。方法定量限為0.0060.02 mg/kg。當(dāng)添

4、加濃度在0.02、0.05、0.1 mg/kg時(shí), 5種農(nóng)藥在果蔬中的加標(biāo)回收率達(dá)到70.2%113.0%, 相對(duì)標(biāo)準(zhǔn)偏差為2.0%11.8%。結(jié)論 該方法操作簡(jiǎn)單、快速, 適用于果蔬中啶蟲(chóng)脒、嘧霉胺、氟蟲(chóng)腈、辛硫磷和噠螨靈殘留的測(cè)定。 關(guān)鍵詞: 高效液相色譜法; 果蔬; 農(nóng)藥殘留Determination of 5 kinds of pesticide residues in fruits and vegetables by high performance liquid chromatographyZHONG Ling-Li*, LI Xi, LI Hua-Xian, FU Cheng-P

5、ing, ZHAO Shan, LEI Xin-Yu(Analysis and Testing Center of Sichuan Academy of Agricultural Sciences, Chengdu 610066, China)ABSTRACT: Objective To establish a method for the determination of 5 kinds of pesticide residues (acetamiprid, pyrimethanil, fipronil, phoxim and pyridaben) in fruits and vegetab

6、les by high performance liquid chromatography (HPLC). Methods The samples were treated with acetonitrile as the extractant, then cleaned up and concentrated by NH2 solid phase extraction (SPE), and eluted with dichloromethane-methanol (97:3, V/V). The samples were separated by a Dikma Spursil C18 co

7、lumn (250 mm4.6 mm, 5 m) at the flow rate of 1.0 mL/min using water and methanol as mobile phase for the gradient elution. The target compounds were determined by HPLC equipped with an ultraviolet variable wavelength detector, and then quantitatively analyzed by external standard method. Results Fiv

8、e kinds of pesticides had good linear relationships between peak areas and concentrations in the concentration range of 0.12.0 g/mL, and the correlation coefficients were 0.99950.9998. The limits of quantification (LOQs) were 0.0060.02 mg/kg. The recoveries of 5 pesticides in fruits and vegetables r

9、eached 70.2%113.0% when spiked at 0.02, 0.05 and 0.1 mg/kg, with relative standard deviations of 2.0%11.8%. Conclusion This method is rapid and simple, and can be applied for the determination of acetamiprid, pyrimethanil, fipronil, phoxim and pyridaben residues in fruits and vegetables.KEY WORDS: h

10、igh performance liquid chromatography; fruits and vegetables; pesticide residues1 引 言近年來(lái), 農(nóng)藥殘留檢測(cè)技術(shù)逐漸由單殘留檢測(cè)向多殘留檢測(cè)發(fā)展1。農(nóng)藥多殘留的測(cè)定方法主要有氣相色譜法(gas chromatography, GC)2、氣質(zhì)聯(lián)用法(gas chromatography-mass spectrometry, GC-MS) 3,4、高效液相色譜法(high performance liquid chromatography, HPLC)5-8和液相色譜-串聯(lián)質(zhì)譜法(liquid chromatogr

11、aphy-tandem mass spectrometry, LC-MS/MS)9-14等。質(zhì)譜以及色譜質(zhì)譜聯(lián)用技術(shù)的應(yīng)用實(shí)現(xiàn)了對(duì)多組分農(nóng)藥的高通量、高靈敏度定性及定量分析, 已成為農(nóng)藥多殘留分析的主導(dǎo)技術(shù)和未來(lái)發(fā)展的趨勢(shì)1, 但其操作復(fù)雜, 價(jià)格昂貴, 目前尚不能普及。而現(xiàn)有的GC或HPLC測(cè)定農(nóng)藥殘留的標(biāo)準(zhǔn)或方法基本集中在單一農(nóng)藥殘留測(cè)定或同一種類(lèi)農(nóng)藥的多殘留測(cè)定15,16, 這往往導(dǎo)致在同一樣品上要進(jìn)行許多單一殘留物測(cè)定方法, 耗時(shí)且昂貴14。因此, 研究低成本、簡(jiǎn)單、快速且通用的農(nóng)藥多殘留分析方法仍然很有必要。啶蟲(chóng)脒、辛硫磷、氟蟲(chóng)腈是廣譜類(lèi)殺蟲(chóng)劑, 嘧霉胺屬苯氨基嘧啶類(lèi)殺菌劑, 噠螨靈

12、為廣譜、觸殺性殺螨劑, 它們?cè)诠叩绒r(nóng)作物種植中應(yīng)用廣泛。目前我國(guó)標(biāo)準(zhǔn)中涉及果蔬中這5種農(nóng)藥測(cè)定方法的只有LC-MS/MS法和GC-MS法, 尚未有HPLC法的檢測(cè)標(biāo)準(zhǔn), 本研究以NH2固相萃取小柱凈化樣品, 旨在建立一種簡(jiǎn)單、快速、通用的HPLC同時(shí)測(cè)定果蔬中啶蟲(chóng)脒、嘧霉胺、氟蟲(chóng)腈、辛硫磷和噠螨靈5種農(nóng)藥。2 材料與方法2.1 儀器與設(shè)備LC-20A高效液相色譜儀(配有紫外-可見(jiàn)光檢測(cè)器, LCsolution色譜工作站, 日本島津公司); 培英THZ-C恒溫振蕩器(大倉(cāng)市實(shí)驗(yàn)設(shè)備廠); LD5-2A高速離心機(jī)(北京京立離心機(jī)有限公司); R-210旋轉(zhuǎn)蒸發(fā)儀(德國(guó)BUCHI公司); DT-

13、1002A電子天平(常熟市金羊砝碼儀器有限公司); 0.22 m微孔濾膜(天津津騰實(shí)驗(yàn)設(shè)備有限公司); HYPERLINK /bill_cpc?v=1&p=WJh2U0LwC9lUBsbLbsNhW6$Z6VFbrVeeH8mBJJ2GBGVje9cSx3TLBAzFTbxu7iN6E1tbEl7aGS39R7buMGyFPj1QxQiyXmemp$em6w99t43vvatFh4n65KWdE1Ks7OGdYEf$OhdNMT1dbnbgednVqbaD1dsKHL4txXMMdT37EdJesb6eKL5fogsEhKWpCWNEc1LZMnTgMnVUNTVZDb7AfTSEmEXXzL

14、go1bbTiskVovNzaPlrMqAlUbwqCYTx9tGMkwsZ1Pwylz33bIknTLYhVVDvjIc16jxOHIRSA2prZ3p8pgHLceVsRKPTPVWuj$JMwUl3OKgQ6QqyzBjKu8x3zGlb7Fk1w6D6k7zDLcfpQYGKJ9paMw7dujQeL8wWcpg9hkXYm95PJPL2YHPMAnBbvSFIxI6bzRaNnpNOEz9L7rUq8UBoFVDI6Qiyg3Iq6t4TBWcBPeI2wD17j3Xj0wlsXiYK4v7mz0w7pC91oVEY2k$VRi2rHghPnD8Lo96S9BcOVWxxfi8Gp7

15、NXyw0VKRW0qSyy$hq6zEG3f3rFmo1Nw$MtzVG3QVzxXXumkAszXVwWalWWQHnJjS9eujQKx5tBPK6hw298L7ShB3uF$kx$BiFvU6Dddrh19ZIYqvHweexxu3pCl8vsO5hnWocAOErtdzgCTURzqKOSOMULyDeOifOLUAuXAqPvJMpDT2$GU6fvl3oFha3CzzU7nGdOVpVZ95w7Oj$EAy8MlVwGfM9=&q=WJe0lllllylx&query=%B0%AC%BF%C6%C6%D6%B3%AC%B4%BF%CB%AE%BB%FA t _blank超純水系統(tǒng)

16、(成都優(yōu)普公司)。2.2 材料與試劑水果和蔬菜樣品(購(gòu)買(mǎi)于當(dāng)?shù)厥袌?chǎng)), 粉碎備用。啶蟲(chóng)脒、嘧霉胺、氟蟲(chóng)腈、辛硫磷和噠螨靈標(biāo)準(zhǔn)物質(zhì)(濃度1000 g/mL, 農(nóng)業(yè)部環(huán)境質(zhì)量監(jiān)督檢驗(yàn)測(cè)試中心); 甲醇、乙腈(色譜純, 美國(guó)Thermo Fisher公司); 二氯甲烷(色譜純, 美國(guó)Honeywell Burdick&Jackson公司); 氯化鈉(分析純, 汕頭市西隴化工廠有限公司); NH2小柱(500 mg/6 mL, 美國(guó)Thermo公司); 實(shí)驗(yàn)用水均為超純水。2.3 試驗(yàn)方法2.3.1 標(biāo)準(zhǔn)溶液的配制100 g/mL農(nóng)藥標(biāo)準(zhǔn)儲(chǔ)備溶液: 吸取1000 g/mL各農(nóng)藥標(biāo)準(zhǔn)溶液1 mL于10

17、mL刻度試管中, 用甲醇稀釋至刻度, 搖勻。1.0 g/mL農(nóng)藥標(biāo)準(zhǔn)工作液: 移取0.1 mL該標(biāo)準(zhǔn)儲(chǔ)備液于10 mL刻度試管中, 用甲醇稀釋至刻度, 搖勻。上機(jī)標(biāo)準(zhǔn)使用液: 根據(jù)需要用甲醇-水(1:1, V:V)稀釋成適當(dāng)濃度。2.3.2 樣品前處理(1) 樣品的提取稱(chēng)取10 g粉碎好的試樣于100 mL離心管中, 加入20 mL乙腈, 于振蕩器上振蕩30 min, 加入10 g氯化鈉, 蓋上蓋子, 震搖1 min, 4000 r/min離心5 min, 取10 mL上清液于50 mL梨形瓶中, 40 水浴旋轉(zhuǎn)蒸干, 加入4 mL二氯甲烷-甲醇(97:3, V:V)淋洗液溶解殘?jiān)? 待凈化。

18、(2) 樣品的凈化用5 mL淋洗液活化NH2小柱, 棄去淋洗液, 當(dāng)液面快到NH2小柱吸附層表面時(shí), 立即將樣品溶液轉(zhuǎn)移至NH2小柱中, 收集流出液于50 mL雞心瓶中, 再用淋洗液洗滌梨形瓶2次, 每次3 mL, 同樣轉(zhuǎn)移至NH2小柱, 合并淋洗液于雞心瓶, 在30 水浴下旋轉(zhuǎn)蒸發(fā)至近干, 洗耳球吹干, 用1.00 mL甲醇-水(1:1, V:V)定容, 渦旋混勻, 用0.22 m濾膜過(guò)濾后經(jīng)HPLC測(cè)定。2.3.3 液相色譜條件色譜柱: Dikma Spursil C18(250 mm4.6 mm, 5 m); 流速: 1.0 mL/min; 柱溫: 35 ; 進(jìn)樣量: 20 L; 流動(dòng)相

19、A: 水, 流動(dòng)相B: 甲醇。梯度洗脫程序、紫外檢測(cè)波長(zhǎng)及波長(zhǎng)切換時(shí)間程序見(jiàn)表1和表2。表1 流動(dòng)相梯度程序Table 1 Mobile phase gradient program時(shí)間t/minA/%B/%0.0055458.00208016.00209018.0059521.0059523.00554528.005545表2 檢測(cè)波長(zhǎng)和波長(zhǎng)切換時(shí)間程序Table 2 Detection wavelength and wavelength switching time時(shí)間t/min波長(zhǎng)切換時(shí)間t/min波長(zhǎng)/nm0.000.002458.0010.0028016.0014.5023018.0

20、015.6528021.0017.5029523.00-28.00-3 結(jié)果與討論3.1 提取、凈化方法的選擇乙腈對(duì)所測(cè)農(nóng)藥具有較好的溶解性, 對(duì)樣品具有較強(qiáng)的滲透性, 且可以通過(guò)鹽析法將蔬菜水果中的糖類(lèi)等強(qiáng)極性雜質(zhì)去除, 因此本研究采用乙腈作為提取溶劑。NH2固相萃取小柱的主要作用力是極性陰離子交換, 對(duì)提取液中的碳水化合物、色素等極性化合物以及有機(jī)酸、酚類(lèi)等干擾組分有較好的凈化效果, 因此本研究采用NH2固相萃取小柱凈化, 二氯甲烷和-甲醇為洗脫液。通過(guò)比較二氯甲烷-甲醇洗脫液在不同體積比和洗脫體積下的回收率(結(jié)果見(jiàn)圖1), 隨著洗脫液中甲醇含量的增加, 5種農(nóng)藥尤其是極性較大的農(nóng)藥啶蟲(chóng)脒

21、的回收率逐漸增高, 減少洗脫體積導(dǎo)致回收率不能滿(mǎn)足要求, 洗脫體積太大又會(huì)使更多的雜質(zhì)共流出, 最終確定洗脫液為二氯甲烷-甲醇(97:3, V:V), 洗脫體積為10 mL, 此條件下既能保證5種農(nóng)藥的回收率均符合多農(nóng)殘檢測(cè)要求, 又能最大程度地分離雜質(zhì)。圖1 不同體積比和洗脫體積下的回收率Fig.1 Recoveries under different volume ratios and elution volumesa. 二氯甲烷-甲醇(99:1, V:V), 10 mL; b. 二氯甲烷-甲醇(98:2, V:V), 10 mL; c. 二氯甲烷-甲醇(97:3, V:V), 7 mL;

22、 d. 二氯甲烷-甲醇(97:3, V:V), 10 mL.a. dichloromethane-methanol (99:1, V:V), 10 mL; b. dichloromethane- methanol (98:2, V:V), 10 mL; c. dichloromethane-methanol (97:3, V:V), 7 mL; d. dichloromethane-methanol (97:3, V:V), 10 mL.3.2 儀器條件的優(yōu)化通過(guò)光譜掃描, 發(fā)現(xiàn)5種化合物的最大吸收波長(zhǎng)各不相同, 為了達(dá)到分析所需靈敏度, 采用各化合物最佳紫外吸收波長(zhǎng)進(jìn)行變波長(zhǎng)測(cè)定, 波長(zhǎng)切換

23、條件見(jiàn)表1。本研究采用普通的Dikma Spursil C18色譜柱進(jìn)行分析, 5種化合物均有較好的保留, 以水和甲醇為流動(dòng)相時(shí), 即可獲得良好的色譜峰形。但由于5種農(nóng)藥極性范圍較寬, 尤其是啶蟲(chóng)脒和噠螨靈極性相差較大, 當(dāng)采用等度洗脫時(shí), 分析時(shí)間長(zhǎng), 溶劑消耗大, 而采用梯度洗脫后, 縮短了分析時(shí)間, 節(jié)約了溶劑的消耗, 同時(shí)還提高了分析靈敏度, 因此本研究采用水和甲醇進(jìn)行梯度洗脫, 梯度洗脫程序見(jiàn)表1。標(biāo)樣色譜圖(圖2)顯示, 此條件下5種化合物能夠在較短的時(shí)間內(nèi)獲得較好的分離效果, 經(jīng)過(guò)SPE小柱凈化處理的樣品去除了大部分干擾成分, 對(duì)目標(biāo)化合物基本無(wú)干擾(如圖3所示), 可準(zhǔn)確用于定

24、性定量分析。圖2 5種農(nóng)藥色譜圖Fig. 2 Chromatogram of 5 kinds of pesticides1.啶蟲(chóng)脒(acetamiprid); 2.嘧霉胺(pyrimethanil); 3.氟蟲(chóng)腈(fipronil); 4.辛硫磷(phoxim); 5.噠螨靈(pyridaben)圖3 蘋(píng)果加標(biāo)樣品色譜圖(0.05 mg/kg)Fig.3 Chromatogram of apple spiked at 0.05 mg/kg1.啶蟲(chóng)脒(acetamiprid); 2.嘧霉胺(pyrimethanil); 3.氟蟲(chóng)腈(fipronil); 4.辛硫磷(phoxim); 5.噠螨靈(

25、pyridaben)3.3 方法的線(xiàn)性范圍、檢出限和定量限配制質(zhì)量濃度為0.1、0.25、0.5、1.0、2.0 g/mL的混合標(biāo)準(zhǔn)溶液, 經(jīng)儀器測(cè)定, 5種農(nóng)藥在0.12.0 g/mL濃度范圍內(nèi)與色譜峰面積呈現(xiàn)良好的線(xiàn)性關(guān)系, 相關(guān)系數(shù)(r2)為0.99950.9998。根據(jù)儀器靈敏度和添加回收實(shí)驗(yàn), 以信噪比(S/N)10計(jì)算方法的定量限(limit of quantitation, LOQ)為0.0060.02 mg/kg, 能夠滿(mǎn)足國(guó)家限量標(biāo)準(zhǔn)要求。5種農(nóng)藥的回歸方程、相關(guān)系數(shù)和LOQ見(jiàn)表3。表3 5種農(nóng)藥回歸方程、相關(guān)系數(shù)和LOQsTable 3 Regression equatio

26、ns, correlation coefficients and LOQs of 5 kinds of pesticides化合物回歸方程相關(guān)系數(shù)LOQ/(mg/kg)啶蟲(chóng)脒Y=144457.1X-827.680.99970.01嘧霉胺Y =160095.3X -695.010.99980.006氟蟲(chóng)腈Y =48920.03X -547.850.99980.02辛硫磷Y=47534.13X-80.420.99950.02噠螨靈Y=42192.7X949.250.99950.023.4 方法回收率與精密度對(duì)水果和蔬菜樣品進(jìn)行添加回收實(shí)驗(yàn), 加標(biāo)濃度為0.02、0.05和0.1 mg/kg, 5種

27、農(nóng)藥的加標(biāo)回收率為70.2%113.0%, RSD為2.0%11.8%(見(jiàn)表4), 結(jié)果表明, 經(jīng)NH2固相萃取小柱凈化, HPLC紫外變波長(zhǎng)測(cè)定果蔬中5種農(nóng)藥殘留的方法準(zhǔn)確度和精密度較好, 能滿(mǎn)足農(nóng)藥多殘留檢測(cè)要求。3.5 實(shí)際樣品測(cè)定采用本方法對(duì)10個(gè)水果樣品(包括蘋(píng)果、葡萄、桃子、梨和柑橘)和10個(gè)蔬菜樣品(包括白菜、菜心、番茄、辣椒和四季豆)中5種農(nóng)藥的殘留量進(jìn)行了測(cè)定, 檢出樣品的結(jié)果見(jiàn)表5。結(jié)果表明, 氟蟲(chóng)腈和辛硫磷在所測(cè)樣品中均未檢出, 啶蟲(chóng)脒的檢出率最高, 在蔬菜和水果中都有檢出, 但含量均小于0.1 mg/kg, 葡萄中檢出嘧霉胺0.098 mg/kg, 白菜和菜心中分別檢出

28、噠螨靈0.15 mg/kg和0.22 mg/kg, 檢出含量均低于相應(yīng)農(nóng)藥最新殘留限量值。4 結(jié) 論 本研究建立了果蔬中啶蟲(chóng)脒、嘧霉胺、氟蟲(chóng)腈、辛硫磷和噠螨靈5種農(nóng)藥殘留的高效液相色譜測(cè)定方法, 樣品經(jīng)乙腈提取, NH2固相萃取小柱富集、凈化, 將樣品中的目標(biāo)化合物與干擾共提物分離的同時(shí)將被分析物濃縮, 方法定量限達(dá)0.0060.02 mg/kg。方法具有通用性和簡(jiǎn)便性, 且能夠滿(mǎn)足多農(nóng)殘檢測(cè)要求和國(guó)內(nèi)外限量標(biāo)準(zhǔn)要求, 適用于大多數(shù)果蔬中啶蟲(chóng)脒、嘧霉胺、氟蟲(chóng)腈、辛硫磷和噠螨靈表4 果蔬中5種農(nóng)藥的加標(biāo)回收率和相對(duì)標(biāo)準(zhǔn)偏差(n=6)Table 4 Spiked recoveries and RS

29、Ds of 5 kinds of pesticides in fruits and vegetables (n=6)樣品添加水平( mg/kg )啶蟲(chóng)脒嘧霉胺氟蟲(chóng)腈辛硫磷噠螨靈回收率(%)RSD(%)回收率(%)RSD(%)回收率(%)RSD(%)回收率(%)RSD(%)回收率(%)RSD(%)蘋(píng)果0.02108.06.5113.06.998.011.4106.08.884.07.40.0594.47.2100.45.5104.46.33.890.87.391.27.290.26.788.24.3白菜0.0283.75.380.45.3101.42.1

30、92.59.583.65.00.0595.26.9105.14.286.28.994.37.877.82.088.26.491.54.7105.47.876.15.7葡萄0.0281.56.680.87.081.47.890.211.8585.14.782.06.382.58.480.12.893.011.283.18.381.73.491.24.983.58.1四季豆0.0288.08.7103.07.884.09.487.05.885.07.70.0593.25.479.25.978.46.682.47.473.610.30.18

31、3.590.64.878.04.475.44.8柑橘0.0270.210.581.62.779.13.585.44.783.05.60.0583.55.283.77.981.66.273.46.490.06.977.05.877.68.288.58.997.15.1番茄0.0282.75.977.59.485.55.080.57.1592.97.292.03.576.54.782.74.790.44.390.34.292.13.293.78.277.76.5表5 5種農(nóng)藥在果蔬中的檢出結(jié)果(mg/kg)Table

32、 5 Contents of 5 kinds of pesticides in fruits and vegetables (mg/kg)啶蟲(chóng)脒嘧霉胺氟蟲(chóng)腈辛硫磷噠螨靈葡萄0.0420.098NDNDND桃子0.066NDNDNDND柑橘0.046NDNDNDND白菜NDNDNDND0.15菜心0.031NDNDND0.22注: ND表示未檢出5種農(nóng)藥殘留的測(cè)定。但仍存在液相色譜法在多農(nóng)殘測(cè)定中的不足, 即由于果蔬樣品種類(lèi)多, 基質(zhì)差異大, 對(duì)基質(zhì)更加復(fù)雜和干擾嚴(yán)重的果蔬樣品可能存在基質(zhì)干擾, 需要應(yīng)用質(zhì)譜法進(jìn)一步定性確證。參考文獻(xiàn)朱盼, 苗虹, 杜娟, 等. 食品中農(nóng)藥多殘留檢測(cè)新技術(shù)研究進(jìn)

33、展J. 食品安全質(zhì)量檢測(cè)學(xué)報(bào), 2013, 4(1): 410.Zhu P, Miao H, Du J, et al. Progress on multi-residue determination of pesticides in food J. J Food Saf Qual, 2013, 4(1): 410.王會(huì)鋒, 馮書(shū)惠, 賈斌. 香菇中40種農(nóng)藥殘留量的氣相色譜法測(cè)定J. 食品科學(xué), 2010, 20(31): 335341.Wang HF, Feng SH, Jia B. GC Method for the determination of forty pesticide res

34、idues in shiitake mushroom J. HYPERLINK /link?url=http%3A%2F%2F%2Fqk%2F95574X%2F&q=%E9%A3%9F%E5%93%81%E7%A7%91%E5%AD%A6&ts=1490680594&t=5d45d7fb054bec58e3baf566d303e6d&src=haosou t _blank Food Sci, 2010, 20(31): 335341.Yang X, Zhang H, Liu Y. Multiresidue method for determination of 88 pesticides in

35、 berry fruits using solid-phase extraction and gas chromatography-mass spectrometry: Determination of 88 pesticides in berries using SPE and GC-MS J. Food Chem, 2011, 127: 855865. 謝建軍, 陳捷, 李菊, 等. 改良QuEChERS法結(jié)合氣相色譜串聯(lián)質(zhì)譜測(cè)定果蔬中20種殺菌劑J. 食品安全質(zhì)量檢測(cè)學(xué)報(bào), 2013, 4(1): 8288.Xie JJ, Chen J, Li J, et al. Determinati

36、on of 20 kinds of fungicide residues in vegetables and fruits by gas chromatography-mass spectrometry combined modified QuEChERS method J. J Food Saf Qual, 2013, 4(1): 8288.劉景坤, 武春媛, 鄧曉, 等. 液相色譜法同時(shí)測(cè)定豇豆中吡蟲(chóng)啉和啶蟲(chóng)脒殘留J. 浙江農(nóng)業(yè)學(xué)報(bào), 2014, 26(1): 131134.Liu JK, Wu CY, Deng X, et al. Simultaneous detection for r

37、esidue of imidacloprid and nitenpyram in cowpea using HPLC method J. Acta Agric Zhejiangensis, 2014, 26(1): 131134.陽(yáng)辛鳳, 劉春華, 樂(lè)淵. UPLC法快速測(cè)定果蔬中8種農(nóng)藥多殘留J. 熱帶作物學(xué)報(bào), 2012, 32(8): 15051509.Yang XF, Liu CH, Le Y. Multi-residue Analysis of Eight Pesticides Residue in Vegetables and Fruits by Ultra-high-perfor

38、mance Liquid Chromatography (UPLC) J. Chin J Trop Crops, 2012, 32(8): 15051509.許燕平, 朱金蘭. 超高效液相色譜法測(cè)試分析蔬菜的多種農(nóng)藥殘留J. 南方農(nóng)業(yè), 2016, 10(3): 159160.Xu YP, Zhu JL. Analysis of various pesticide residues in vegetables by ultra performance liquid chromatography J. South China Agric, 2016, 10(3): 159160.張曉強(qiáng), 包素萍

39、, 武中平, 等. 2種HPLC法聯(lián)用技術(shù)同時(shí)檢測(cè)13種農(nóng)業(yè)殺蟲(chóng)劑J. 江蘇農(nóng)業(yè)科學(xué), 2014, 42(7): 296298.Zhang XQ, Bao SP, Wu ZP, et al. Simultaneous detection of 13 agricultural insecticides by two HPLC methods J. Jiangsu Agric Sci, 2014, 42(7): 296298.張璇, 姜敏, 何錦惠, 等. 高效液相色譜-質(zhì)譜聯(lián)用儀測(cè)定韭菜中多菌靈、吡蟲(chóng)淋等種農(nóng)藥殘留量J. 農(nóng)藥科學(xué)與管理, 2016, 37(4): 4247. Zhang X,

40、Jiang M, He JH, et al. Determination the Residue of Seven Pesticides in Leek by HPLC-MS J. Pest Sci Admin, 2016, 37(4): 4247. 劉春華, 尹桂豪, 樂(lè)淵, 等. 超高效液相色譜-串聯(lián)質(zhì)譜法快速測(cè)定豇豆中氟蟲(chóng)腈等8種農(nóng)藥殘留J. 廣東農(nóng)業(yè)科學(xué), 2013, 34(11): 7376.Liu CH, Yin GH, Le Y, et al. Determination of eight pesticides in cowpea by ultra performance liq

41、uid chromatography-tandem mass spectrometric J. HYPERLINK /link?url=http%3A%2F%2F%2FQK%2F93806X%2F&q=%E5%B9%BF%E4%B8%9C%E5%86%9C%E4%B8%9A%E7%A7%91%E5%AD%A6&ts=1490682719&t=9f94f4342354721f97cff52eccb72e8&src=haosou t _blank Guangdong Agric Sci, 2013, 34(11): 7376.李芳, 張靜, 楊中, 等. QuEChERS/液質(zhì)聯(lián)用法測(cè)定蔬菜中17種農(nóng)藥殘留J. 吉林農(nóng)業(yè)科學(xué), 2013, 38(3): 9396.Li F, Zhang J, Yang Z. et al. Determination of 17 pesticide residues in vegetables using QuEChERS extraction and high