PTV_GC_MS_MS同時測定煙草中202種農(nóng)藥殘留_樓小華

1、PTV-GC-MS/MS 同時測定煙草中202種農(nóng)藥殘留樓小華1,高川川1,朱文靜1,張洪非2,唐綱嶺2,邊照陽2,巴金莎11.貴州省煙草質(zhì)量監(jiān)督檢測站,貴陽市金陽新區(qū)云潭北路5500252.國家煙草質(zhì)量監(jiān)督檢驗中心,鄭州高新技術(shù)產(chǎn)業(yè)開發(fā)區(qū)楓楊街2號450001摘要:研究了應(yīng)用程序升溫汽化進樣-氣相色譜-串聯(lián)質(zhì)譜(PTV-GC-MS/MS 技術(shù)檢測煙草中202種農(nóng)藥品種221個組分的高效方法。以QuEChERS 技術(shù)快速提取煙草中殘留農(nóng)藥并凈化,PTV 進樣后在TR-pesticide II 毛細(xì)管柱上分離,通過優(yōu)化串聯(lián)質(zhì)譜參數(shù),有效降低復(fù)雜基質(zhì)干擾及農(nóng)藥組分重疊峰的相互串?dāng)_,以保留時間窗口和

2、特征SRM (選擇性反應(yīng)監(jiān)測離子對定性、峰面積定量。結(jié)果表明:202種農(nóng)藥在0.012.50mg/L 范圍內(nèi)線性良好,相關(guān)系數(shù)為0.98000.9999,檢測限0.00020.0100mg/kg ,加標(biāo)回收率67.4%112.0%,RSD 0.30%20.30%。應(yīng)用該方法對44個進口煙葉樣品進行檢測驗證,效果良好。該方法對農(nóng)藥品種覆蓋面廣,前處理簡便、快捷,節(jié)省溶劑;一次進樣在46min 內(nèi)可分析221個組分,準(zhǔn)確、靈敏。關(guān)鍵詞:程序升溫汽化(PTV ;氣相色譜-串聯(lián)質(zhì)譜;煙草;農(nóng)藥殘留中圖分類號:TS411.2文獻標(biāo)識碼:B文章編號:1002-0861(201308-0045-13基金項目

3、:貴州省煙草專賣局資助項目“110種農(nóng)藥殘留物在卷煙燃吸微環(huán)境中的歸趨”(201031及“控制煙葉農(nóng)殘監(jiān)測體系研究”(200908。作者簡介:樓小華(1963,本科,高級工程師,主要從事氣相色譜、質(zhì)譜、三重四極桿串聯(lián)質(zhì)譜等分析煙草中農(nóng)藥殘留研究。E-mail :louxh6311 電話:0851-*收稿日期:2012-11-02責(zé)任編輯:茹呈杰E-mail :rucj69 電話:0371-*Simultaneous Determination of 202Pesticide Residues in Tobacco by PTV -Gas Chromatography -Tandem Mass

4、SpectrometryLOU Xiaohua 1,GAO Chuanchuan 1,ZHU Wenjing 1,ZHANG Hongfei 2,TANG Gangling 2,BIAN Zhaoyang 2,and BA Jinsha 11.Guizhou Tobacco Quality Supervision &Test Station,Guiyang 550025,China2.China National Tobacco Quality Supervision &Test Center,Zhengzhou 450001,ChinaAbstract:An effectiv

5、e method for detecting 202pesticide residues (221componentsin tobacco was developedbyPTV-GC-MS/MS(Programmedtemperaturevaporizationsamplingtechnology-gaschromatography-tandem mass spectrometry.The pesticide residues in tobacco sample were extracted rapidly and purified with QuEChERS technique,then s

6、eparated on TR-pesticideII capillary chromatographic column after PTV sampling.The interference of complex matrix and peak overlapping of various pesticide components were reduced by means of optimizing tandem mass spectrometry parameters.Qualitative and quantitative analyses were conducted by reten

7、tion time window and SRM (selective reaction monitoringwith peak area respectively.The results showed that:1The 202pesticides kept good linear relationships in the range of 0.01-2.50mg/L with the correlative coefficients between 0.9800and 0.9999.The limits of detection (LODwere from 0.0002to 0.0100m

8、g/kg,and the recoveries of added standards ranged from 67.4%to 112.0%with the relative standard deviations (RSDof 0.30%-20.30%.2This method was verified with 44samples of imported tobacco leaves,and results were satisfied.3This method covered a wide range of pesticides,featured煙草科技/Tobacco Science &

9、amp;Technology 2013年第8期(總第313期煙草化學(xué)/Tobacco Chemistry目前,煙草中的農(nóng)藥殘留日益受到關(guān)注,國際上有28個國家及地區(qū)對卷煙和煙葉中殘留最高限量做出規(guī)定的農(nóng)藥多達660余種。CORESTA農(nóng)用化學(xué)品咨詢委員會(ACAC2003年發(fā)布了農(nóng)用化學(xué)品指導(dǎo)性殘留限量的基本原則與實施意見,對99種農(nóng)藥殘留提出了指導(dǎo)性限量(GRLs,2008年增加到了118種,今后將會繼續(xù)增加。我國目前尚無系統(tǒng)的限量列表,主要參照ACAC限量作為進出口煙草貿(mào)易評價依據(jù),殘留農(nóng)藥的分析方法主要圍繞此名單開發(fā)建立。為提高農(nóng)藥殘留分析效率,傳統(tǒng)的一種方法一種殘留(特殊農(nóng)藥除外的檢測

10、技術(shù)逐步被多種、多類農(nóng)殘的高通量殘留分析技術(shù)所取代,儀器分析也從單純的氣相色譜(GC、液相色譜(LC,發(fā)展到氣相(液相色譜-質(zhì)譜聯(lián)用(GC/ MS,LC/MS及液相色譜-串聯(lián)質(zhì)譜聯(lián)用(LC-MS/MS,甚至全二維氣相色譜-飛行時間質(zhì)譜(GC×GC-TOF-MS1-4。美國和歐洲煙草中農(nóng)藥殘留量的測定方法比較完備,方法分為單殘留測定和同時多殘留測定5-11;我國對煙草中多種農(nóng)藥殘留分析方法作了大量研究12-13,并頒布了一系列農(nóng)殘檢測方法標(biāo)準(zhǔn)14-17。以上研究動向總體表現(xiàn)在前處理逐漸簡化、一次性分析農(nóng)藥殘留品種逐步增加,大大提高了分析效率;但迄今尚無統(tǒng)一的方法發(fā)布。GC-MS/MS具

11、有高選擇性、高靈敏度等優(yōu)點18,對大多數(shù)熱穩(wěn)定性、揮發(fā)及半揮發(fā)性農(nóng)藥殘留分析有著無可比擬的優(yōu)勢,然而此類技術(shù)應(yīng)用在煙草中農(nóng)藥殘留分析卻少見報道。為此,建立了以QuEChERS技術(shù)一次性前處理、GC-MS/MS一針進樣分析202種有機磷、有機氯、有機氮及雜環(huán)類、擬除蟲菊酯類殺蟲劑和殺菌劑,以及植物生長調(diào)節(jié)劑殘留量的方法。1材料與方法1.1儀器和試劑Thermo Scientific Trace GC Ultra-TSQ Quantum XLS 氣相色譜-三重四極桿串聯(lián)質(zhì)譜聯(lián)用儀(美國ThermoFisher Scientific公司;Labnet VX200漩渦振蕩器(美國Labnet公司;Ce

12、nturion K-241高速離心機(英國Centurion公司。44個進口煙葉(中部葉樣品(貴州省煙葉進出口有限公司提供。乙腈、甲苯、正己烷、丙酮(色譜純,德國Merck公司;超純水(電阻率18.2M,自制;QuEChERS試劑盒(美國Agilent公司;24種有機氯殺蟲劑、78種有機磷殺蟲劑、11種氨基甲酸酯類殺蟲劑、5種雜環(huán)類殺蟲劑、14種擬除蟲菊酯類殺蟲劑、12種殺螨劑、39種殺菌劑、6種抑芽劑和13種除草劑標(biāo)準(zhǔn)品(純度9599%,德國Augshurg公司,分別用正己烷或丙酮溶解并配制成單獨的50mg/L的標(biāo)準(zhǔn)溶液,再以甲苯稀釋配制成0.01 2.50mg/L的混合標(biāo)準(zhǔn)溶液;內(nèi)標(biāo)物“氯

13、唑磷”、“滅蟻靈”(純度99%,德國Augshurg公司,分別配成0.2mg/L的甲苯溶液,儲存于4冰箱備用。1.2樣品處理1.2.1煙葉樣品制備煙葉樣品在40下烘干,粉碎,過20目篩,避光低溫保存。1.2.2樣品前處理(1提取:稱取2g煙末樣品于50mL具蓋離心試管中,加10mL水充分浸潤,靜置10min。移取10mL乙腈和一定量的“氯唑磷”、“滅蟻靈”內(nèi)標(biāo)工作液到離心管中,漩渦振蕩2min,加入QuEChERS試劑盒1(4g無水硫酸鎂,1g氯化鈉,1g檸檬酸鈉和0.5g檸檬酸氫二鈉和5mL甲苯,立即手持振蕩,防止無水硫酸鎂結(jié)塊,以4000r/min的轉(zhuǎn)速離心10min。(2凈化:移取5mL

14、樣品提取液上清液于10mL離心管中,加入QuEChERS試劑盒2(500mg無水硫酸鎂+ 150mg N-丙基乙二胺鍵合固相吸附劑,PSA,渦旋振蕩2min,以6000r/min的轉(zhuǎn)速離心10min。吸取上清液,經(jīng)0.22µm有機相濾膜過濾后進行GC-MS/MS分析。分析條件為:氣相色譜(GC:進樣模式:帶PTV功能的不分流進樣; Surge壓力:150kPa(2min;進樣口初始溫度:70,進樣后以4/s快速升至280;毛細(xì)管柱:TR-Pesticide II(50%苯基甲基聚硅氧烷,30m×0.25mm×0.25µm+5m×0.25

15、1;m Guard (預(yù)柱;載氣:He;載氣流速:1.2mL/min;程序升溫:90(5min25/min180(15min5/min280(4.5min;后運行溫度:320(5min。GC/MS傳輸線溫度:270。串聯(lián)質(zhì)譜(MS/MS:離子源溫度:250;發(fā)射電流:50A;離子化模式:EI;離子源:封閉式EI源;分析模式:timed-SRM (定時選擇性反應(yīng)監(jiān)測;掃描寬度:0.002m/z;掃描周期0.4s;峰寬:Q10.7Da,Q30.7Da;碰撞氣壓力:1.5mTorr(Ar;色譜過濾峰寬:10s。液體自動進樣器:進樣體積:1L;進樣模式:PTV進樣;the advantages of

16、simple and rapid in pre-treatment,solvent saving and capable of analyzing221components accurately and sensitively within46minutes by a single sample injection.Keywords:Programmed temperature vaporization(PTV;Gas chromatography-tandem mass spectrometry(GC-MS/MS; Tobacco;Pesticide residue進樣前后駐留模式:3和2s

17、 。2結(jié)果與討論2.1樣品前處理條件的選擇2.1.1樣品的提取鑒于煙草中的復(fù)雜基質(zhì),在乙腈、丙酮和乙酸乙酯3種常用提取溶劑中,乙腈對煙草樣品中的蠟質(zhì)、色素、糖類溶解最少或雜質(zhì)可隨水相分離,因此,作為提取溶劑的首選。在檸檬酸鈉和檸檬酸氫二鈉緩沖溶液條件下,在提取液中加入氯化鈉可增加極性農(nóng)藥的回收率,減少共提取極性物糖類分解產(chǎn)物,減少提取物中水含量,降低基質(zhì)增強效應(yīng)。使用硫酸鎂可顯著增加上層乙腈的體積,通過減少水相的體積,更方便地促使極性農(nóng)藥進入有機相,提高回收率;并且硫酸鎂吸水時放熱,有利于提高提取效率;通過離心可以避免液-液分配時可能遇到的乳化現(xiàn)象。2.1.2樣品的凈化本法采用少量吸附試劑與提

18、取溶劑混合,然后采用離心機將固體吸附劑與凈化的溶液分離。PSA 是弱離子交換的固相吸附劑,不保留農(nóng)藥,但能有效去除樣品中極性干擾物質(zhì)。用無水硫酸鎂作吸水干燥劑,具有比無水硫酸鈉吸水更快更徹底的優(yōu)點,能有效避免水分直接進入GC ,避免影響色譜柱壽命。2.1.3內(nèi)標(biāo)物的選擇“滅蟻靈”、“氯唑磷”是兩種較為穩(wěn)定的有機氯和有機磷殺蟲劑,在煙草上不使用,本研究分別用來作為有機氯、擬除蟲菊酯類農(nóng)藥和有機磷、有機氮及雜環(huán)類農(nóng)藥的內(nèi)標(biāo)物。以上提取、凈化方法,其基本原理為近年來較常用作多農(nóng)殘分析的QuEChERS 法19-20,其試劑盒已商品化。2.2PTV 進樣參數(shù)的優(yōu)化程序升溫汽化進樣技術(shù)(PTV ,Pro

19、grammed Temperature Vaporization 由V ogt 等20首次公布,主要是通過增大進樣體積、低溫進樣口吹掃多余溶劑、富集溶質(zhì)、快速升溫進入色譜柱,從而達到提高檢測靈敏度的目的,適合于基質(zhì)復(fù)雜樣品中的農(nóng)殘分析18,21-23。由于煙草基質(zhì)較為復(fù)雜,為保護色譜柱和離子源,本研究不采取大體積進樣,而是利用PTV 進樣口的程序升溫技術(shù),從較低溫度開始,將極性較強、容易熱分解的“敵百蟲”、“甲胺磷”、“乙酰甲胺磷”、“氧化樂果”和“久效磷”等5種農(nóng)藥組分在低溫下導(dǎo)入色譜柱,再以快速升溫程序升至280,使全部農(nóng)藥組分進入色譜柱。以上述5種農(nóng)藥組分和24種有機磷農(nóng)藥組分作為代表物

20、選擇PTV 條件(見圖1:進樣口初始溫度50,最后溫度280,吹掃時間2min 。由于溶劑為甲苯,初始溫度過低,溶質(zhì)在溶劑之前蒸發(fā),峰高較低。進樣口初始圖1PTV 進樣口不同初始溫度對29種有機磷農(nóng)藥組分(全掃描峰高的影響Fig.1Influence of different initial temperatures of PTV injector on height of peak of 29organophosphorus pesticide components(full scan a.初始溫度/initial temperature 50b.初始溫度/initial temperatu

21、re 70c.初始溫度/initial temperature 100圖2“甲胺磷”(a 、“敵百蟲”(b 、“乙酰甲胺磷”(c 、“氧化樂果”(d 和“久效磷”(e SRM 掃描色譜圖(PTV 進樣Fig.2SRM chromatogram of methamidophos(a,trichlorphon(b,acephate(c,omethoate(dand monocrotophos(e(with PTV injection溫度70,最后溫度280,吹掃時間2min 。溶質(zhì)峰高較前一個條件提高410倍。進樣口初始溫度100,最后溫度280,吹掃時間2min 。溶質(zhì)峰高減低,且峰型拖尾。因此

22、,采用進樣口初始溫度70、升溫速率4/s 、最后溫度280和吹掃時間2min ,并在色譜柱前加預(yù)柱保護作為優(yōu)選條件,“敵百蟲”、“甲胺磷”、“乙酰甲胺磷”、“氧化樂果”和“久效磷”5個組分的峰型良好(圖2。以上初始溫度對其余沸點較高組分影響不大。2.3色譜柱的選擇本研究曾使用非極性毛細(xì)管柱HP -101,中等極性柱HP -5MS ,DB -17和DB -1701,極性柱PEG -20M 和FFAP 等,長度分別為15和30m 。在質(zhì)譜全掃描條件下,主要考察所有農(nóng)藥在上述色譜柱上的分離度。結(jié)果表明,上述色譜柱對一針進樣的所有農(nóng)藥均存在分離度不佳、保留時間疏密不均等現(xiàn)象,特別是非極性柱和極性柱在某

23、一個保留時間存在35個組分的峰群重疊現(xiàn)象,不利于準(zhǔn)確定性定量。最后選擇由Thermo Scientific 公司提供的TR-Pesticide II 30m×0.25mm×0.25m+5m×0.25m 預(yù)柱(弱極性,具有良好的分離性能,其極限溫度可達360,有利于高沸點農(nóng)藥組分如溴氰菊酯、烯酰嗎啉的快速出峰,且在后運行階段可將柱溫升至300以上,以避免煙草中高沸點基質(zhì)污染。雖仍存在一些重疊峰,但峰群較為勻稱,分析周期縮短到了46min (圖3。2.4SRM 質(zhì)譜參數(shù)的優(yōu)化先以全掃描方式確定每一種農(nóng)藥單標(biāo)的保留時間,或以一定品種數(shù)量的混標(biāo)以質(zhì)譜農(nóng)殘專用譜庫(Pest

24、icide Libraries 定性并確定保留時間,再通過更換不同的碰撞能量(CID 選擇豐度相對較高、體現(xiàn)特征的母離子子離子對,同時得到離子對的豐度比。將每一種組分至少2個離子對及碰撞能量在Excel 表中進行編輯,或?qū)⒉殚單墨I得到的優(yōu)化參數(shù)通過EZmethod 功能直接導(dǎo)入到儀器方法中。為避免煙草基質(zhì)的串?dāng)_而出現(xiàn)假陽性,采取“保留時間+定性定量離子對+豐度比”三重定性方式,使定性定量結(jié)果更加可靠。加上三重四極桿串聯(lián)質(zhì)譜具有高通量離子傳輸性能和碰撞室零串?dāng)_技術(shù)特點,有效解決了重疊農(nóng)藥組分和基質(zhì)的干擾問題。202種農(nóng)藥的SRM 監(jiān)測參數(shù)見表1。2.5煙草中常用農(nóng)藥的定性定量中國煙葉公司每年均發(fā)

25、布煙草上推薦使用的農(nóng)藥品種列表,限定能在煙草上使用的高效、低毒、低殘留化學(xué)農(nóng)藥或生物農(nóng)藥品種。各產(chǎn)煙省均據(jù)此統(tǒng)一采購農(nóng)藥并下發(fā)給煙農(nóng);但不排除煙農(nóng)市場上自行采購農(nóng)藥并在煙草上使用的可能。同時,世界各產(chǎn)煙國在煙草上所使用的農(nóng)藥品種不盡相同,ACAC 的GRLs 也很難兼顧到所有正在或?qū)⒁褂玫霓r(nóng)藥。各國與之配套1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26“3-羥基克百威”“乙酰甲胺磷”“啶蟲脒”“甲草胺”“艾氏劑”“雙甲脒”“益棉磷”“谷硫磷”“嘧菌酯”“苯霜靈”“氟草胺”“丙硫克百威”“排草丹”“聯(lián)苯菊

26、酯”“溴硫磷”“溴螨酯”“噻嗪酮”“仲丁靈”“硫線磷”“克菌丹”“甲萘威”“卡草胺”“克百威”“三硫磷”“滅螨猛”“-氯丹”3-HydroxycarbofuranAcephateAcetamiprideAlachlorAldrinAmitrazAzinphos-ethylAzinphos-methylAzoxystrobinBenalaxylBenfluralinBenfuracarbBentazonBifenthrinBromophos-ethylBromopropylateBuprofezinButralinCadusafosCaptanCarbarylCarbetamidCarbofur

27、anCarbophenothionChinomethionatChlordane-cis18013615218829329316016034426629216419818135934317226615914914411916434220637513794116160258147771323291482641491191653031855719097701159114915714826815151510251520520101010121520201015201220151010151514.9612.1035.7016.9519.8538.4338.9037.4546.0432.9311.83

28、39.0417.8236.2926.2536.0529.6221.9312.1724.5210.1517.2912.9933.1425.7927.030.0010.00020.0050.0020.00050.0010.0050.0050.0080.0050.0030.0010.0050.0010.00050.00080.0010.0050.0080.0080.0080.0050.00020.00050.0080.00050.99420.98810.99560.99610.99320.98890.99660.98120.98630.99560.98970.99220.99630.99610.98

29、750.99560.99440.99790.98680.98720.99430.98770.99470.99450.99520.998682.980.184.686.792.3102.287.995.279.986.395.092.592.497.6106.2104.3100.296.6104.478.980.2103.685.887.790.595.98.810.36.53.23.612.32.210.112.59.56.75.56.45.13.96.62.35.910.914.39.53.68.23.36.66.5序號名稱英文通用名母離子/(m/z子離子/(m/z碰撞能/eV保留時間/mi

30、nLOD/(mg/L相關(guān)系數(shù)r2回收率/%變異系數(shù)CV/%圖3221個農(nóng)藥組分選擇性離子監(jiān)測總離子流圖(煙草基質(zhì)中Fig.3SRM TIC of221pesticide components(tobacco matrix表1202種農(nóng)藥(221個組分的SRM質(zhì)譜參數(shù)及檢測限、回收率Tab.1SRM Mass parameters,LOD and recoveries of202pesticides(221components 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 5

31、5 56 57 58 59 60 61 62 63 64 65 66 67 68 69 70 71“-氯丹”“殺螨酯”“毒蟲畏”“氯甲磷”“乙酯殺螨醇”“丙酯殺螨醇”“百菌清”“毒死蜱”“甲基毒死蜱”“敵草索”“蠅毒磷”“苯腈膦”“氟氯氰菊酯-1”“氟氯氰菊酯-2”“氟氯氰菊酯-3”“氟氯氰菊酯-4”“氯氰菊酯-1”“氯氰菊酯-2”“氯氰菊酯-3”“氯氰菊酯-4”“環(huán)唑醇-1”“環(huán)唑醇-2”“二溴氯丙烷”“溴氰菊酯”“內(nèi)吸磷”“異吸硫磷”“異吸硫磷砜”“二嗪農(nóng)”“芐氯三唑醇”“除線磷”“敵敵畏”“禾草靈”“氯硝胺”“三氯殺螨醇”“百治磷”“狄氏劑”“惡醚唑-1”“惡醚唑-2”“甲氟磷”“樂果”

32、“烯酰嗎啉-1”“烯酰嗎啉-2”“烯唑醇”“敵螨普”“雙苯酰草胺”Chlordane-transChlorfensonChlorfenvinphosChlormephosChlorobenzilateChloropropylateChlorothalonilChlorpyrifosChlorpyrifos-methylChlorthal-dimethylCoumaphosCyanofenphosCyfruthrin-1Cyfruthrin-2Cyfruthrin-3Cyfruthrin-4Cypermethrin-1Cypermethrin-2Cypermethrin-3Cypermethri

33、n-4Cyproconazol-1Cyproconazol-2DBCPDeltamethrinDemeton-SDemeton-s-methylDemeton-S-methyl sulfoneDiazinonDiclobutrazolDichlofenthionDichlorovosDiclofop methylDicloranDicofolDicrotophosDieldrinDifenoconazol-1Difenoconazol-2DimefoxDimethoateDimethomorph-1Dimethomorph-2DiniconazolDinocapDiphenamid373175

34、325154139253266314286301226169226226226226163163163163222222157251109142169304270223185253206251193277325325154125301301268253239266111269121111141133258271223163141206206206206127127127127125125751728179109179159205931621761391272412672671114727327323223616718101051515201525251510151515151010101020

35、2058151015151510121510151010202010151010151025.9228.0523.486.4431.1531.1414.3419.9616.4820.3340.3322.9641.4441.6641.7741.8841.9042.3042.4042.9020.9821.986.5945.7012.7811.2617.8614.0820.2616.117.9924.1412.8821.259.7828.8644.8044.965.4012.8346.3347.2231.2814.0022.070.00050.0010.0010.0010.0020.0020.008

36、0.0020.0020.0080.0020.0040.0010.0010.0010.0020.0010.0080.0080.0150.00080.0040.0050.00050.0050.00050.0050.0010.00050.0080.0010.00080.010.0050.0050.010.99960.98470.98520.99550.99000.99310.98440.99650.99410.98920.99630.99930.99680.99350.98810.98520.99620.98840.99290.98000.99990.98630.99650.99660.98210.

37、99670.98850.99270.99960.98550.99750.98990.98440.99280.98740.9898101.197.3110.283.384.687.775.3102.393.679.885.293.2100.4103.578.269.596.776.586.267.498.982.2112.0101.279.688.575.079.296.9103.296.5102.5107.585.778.668.71.70.69.53.16.610.69.95.512.512.53.910.00.73.69.915.92.96.39.818.71.65.03.83.214.4

38、5.714.411.65.06.63.11.65.110.313.219.6序號名稱英文通用名母離子/(m/z子離子/(m/z碰撞能/eV保留時間/minLOD/(mg/L相關(guān)系數(shù)r2回收率/%變異系數(shù)CV/% (續(xù)表172 73 74 75 76 77 78 79 80 81 82 83 84 85 86 87 88 89 90 91 92 93 94 95 96 97 98 99 100 101 102 103 104 105 106 107 108 109 110 111 112 113 114 115 116“乙拌磷”“乙拌磷砜”“滅菌磷”“嗎菌靈-1”“嗎菌靈-2”“克瘟散”“-硫丹

39、”“-硫丹”“硫丹硫酸酯”“異狄氏劑”“苯硫磷”“乙硫磷”“滅線磷”“醚菊酯”“乙螨唑”“乙嘧硫磷”“氨磺磷”“苯線磷”“苯線磷砜”“苯線磷亞砜”“皮蠅硫磷”“殺螟硫磷”“甲氰菊酯”“除螨酯”“倍硫磷”“倍硫磷亞砜”“氰戊菊酯-1”“氰戊菊酯-2”“氟氰戊菊酯-1”“氟氰戊菊酯-2”“氟節(jié)胺”“粉唑醇”“氟胺氰菊酯-1”“氟胺氰菊酯-2”“滅菌丹”“安果”“地蟲硫磷”“-六六六”“-六六六”“-六六六”“-六六六(林丹”“七氯”“順-環(huán)氧七氯”“反-環(huán)氧七氯”“庚蟲磷”DisulfotonDisulfoton sulfonDitalimfosDodemorph-1Dodemorph-2Edif

40、enphosEndosulfan-alphaEndosulfan-betaEndosulfan sulfateEndrinEPNEthionEthoprophosEtofenproxEtoxazolEtrimfosFamphurFenamiphosFenamiphos-sulfonFenamiphos-sulfoxidFenchlorphosFenitrothionFenpropathrinFensonFenthionFenthion sulfoxideFenvalerate-1Fenvalerate-2Flucythrinate-1Flucythrinate-2FlumetralinFlut

41、riafolFluvalinate-1Fluvalinate-2FolpetFormothionFonofosHCH-alphaHCH-betaHCH-deltaHCH-gamma(LindanHeptachlorHeptachlorepoxid-cisHeptachlorepoxid-transHeptenophos14221329915415417327227227228116938420016330029221830329230428527726526827829441941919919914314325225226017224621721721721733728928912410912

42、52439797109237237235245772311581352701531091951961962701098977109279225225107107107107200200130931371811811811813022532538910101010101515151581610810221022151310132020201881010222220202020155888881215151014.5426.9329.8218.3018.6033.0326.9030.8233.0330.1335.9431.7611.4442.7326.0114.8122.7028.1635.593

43、5.3817.5418.5836.6117.4120.2331.4944.0044.5042.1443.0127.4218.9043.8643.9625.0814.1013.9812.4913.2614.7613.6517.3023.5923.9010.650.0080.010.0080.0080.010.00050.00050.00050.00050.0050.0080.0080.0020.010.0080.010.0080.010.010.0050.0010.0020.0080.0020.010.00080.00080.0020.0010.0010.0040.0050.0050.00020

44、.00020.00020.00020.00050.00050.00050.0020.98530.98700.98750.99500.98660.99960.99650.99490.99900.98670.98580.99500.99910.98530.99740.99820.98990.98440.98660.99560.99920.99400.98630.99520.98540.99930.99800.99130.99650.98880.98110.99660.99410.99980.99290.99770.99400.99970.99360.99430.984779.875.670.080

45、.372.695.6100.692.594.084.882.480.095.589.199.076.577.869.272.388.6100.2106.582.388.970.296.392.695.585.690.887.283.369.999.296.6104.893.596.393.495.490.714.017.213.36.011.72.24.65.43.35.56.610.53.35.42.217.36.013.315.67.93.48.99.01.018.66.65.13.34.48.710.70.611.05.53.05.56.82.34.55.97.3序號名稱英文通用名母離子

46、/(m/z子離子/(m/z碰撞能/eV保留時間/minLOD/(mg/L相關(guān)系數(shù)r2回收率/%變異系數(shù)CV/% (續(xù)表1117 118 119 120 121 122 123 124 125 126 127 128 129 130 131 132 133 134 135 136 137 138 139 140 141 142 143 144 145 146 147 148 149 150 151 152 153 154 155 156 157 158 159 160 161“六氯苯”“環(huán)嗪酮”“抑霉唑”“異稻瘟凈”“異菌脲”“氯唑磷”(內(nèi)標(biāo)“水胺硫磷”“異柳磷”“甲基異柳磷”“異丙樂靈”“稻瘟

47、靈”“異-唑磷”“稻瘟凈”“高效氯氟氰菊酯”“馬拉氧磷”“馬拉硫磷”“嘧菌胺”“地胺磷”“甲霜靈”“吡唑草胺”“蟲螨畏”“甲胺磷”“殺撲磷”“滅蟲威”“滅蟲威砜”“滅多威”“烯蟲酯”“甲氧氯”“異丙甲草胺”“速滅磷(E”“速滅磷(Z”“滅蟻靈”(內(nèi)標(biāo)“久效磷”“二溴磷”“除草醚”“酞菌酯”“o,p'-DDD”“o,p'-DDE”“o,p'-DDT”“氧化樂果”“殺線威”“p,p'-DDD”“p,p'-DDE”“p,p'-DDT”“多效唑”HexachlorobenzeneHexazinonImazalilIprobenfosIprodioneIs

48、azophos(ISIsocarbophosIsofenphosIsofenphos-methylIsopropalinIsoprothiolaneIsoxathionKitazinLambda-cyhalothrinMalaoxonMalathionMepanipyrimMephosfolanMetalaxylMetazachlorMethacrifosMethamidophosMethidathionMethiocarbMethiocarb sulftoneMethomylMethopreneMethoxychlorMetolachlorMevinphos(EMevinphos(ZMire

49、x(ISMonocrotophosNaledNitrofenNitrothal-isopropylo,p'-DDDo,p'-DDEo,p'-DDTOmethoateOxamylp,p'-DDDp,p'-DDEp,p'-DDTPaclobutrazole28417121520431425728921324128029031316920812717322319623413324014114515320010523522716219219227219214528323623731823715616223524623523624971145912451191361851992382041771411819999208140174117180805810912188147169133127127237127109253148165246165791451651761651252010201515151010810151515101010151510205101561081020