1、Thermo FinniganTM 氣質(zhì)聯(lián)用在食品中農(nóng)藥殘留物氣質(zhì)聯(lián)用在食品中農(nóng)藥殘留物分析的解決方案分析的解決方案Thermo FinniganTM食品安全分析和色質(zhì)譜新技術(shù)講座食品安全分析和色質(zhì)譜新技術(shù)講座C&MS-SID, Thermo China2肯定列表制度（肯定列表制度（Positive List System）“肯定列表制度”(Positive list system) 是日本為加強(qiáng)食品中農(nóng)業(yè)化學(xué)品殘留管理而制定的一項(xiàng)新制度。 該制度要求： 食品中農(nóng)業(yè)化學(xué)品含量不得超過(guò)最大殘留限量標(biāo)準(zhǔn)；對(duì)于未制訂最大殘留限量標(biāo)準(zhǔn)的農(nóng)業(yè)化學(xué)品，其在食品中的含量不得超過(guò)“一律標(biāo)準(zhǔn)”，即0.0

2、1g/g。 該制度已經(jīng)于2006年5月29日起執(zhí)行。3“肯定列表制度肯定列表制度” 落實(shí)落實(shí) “肯定列表制度”提出了食品中農(nóng)業(yè)化學(xué)品殘留管理的總原則。厚生勞動(dòng)省根據(jù)該原則，采取了以下三項(xiàng)具體落實(shí)措施: (1) 確定“豁免物質(zhì)”，即在常規(guī)條件下其在食品中的殘留對(duì)人體健康無(wú)不良影響的農(nóng)業(yè)化學(xué)品。對(duì)于這部分物質(zhì)，無(wú)任何殘留限量要求； (2) 針對(duì)具體農(nóng)業(yè)化學(xué)品和具體食品制定的“最大殘留限量標(biāo)準(zhǔn)”。 (3) 對(duì)在豁免清單之外且無(wú)最大殘留限量標(biāo)準(zhǔn)的農(nóng)業(yè)化學(xué)品，制定“一律標(biāo)準(zhǔn)”。4肯定列表對(duì)我國(guó)產(chǎn)品影響肯定列表對(duì)我國(guó)產(chǎn)品影響 日本進(jìn)口新鮮蔬菜的總量比上年同期減少13%，約64,648噸，占蔬菜進(jìn)口六成的中

3、國(guó)蔬菜輸日量下降14%。 茶葉出口大省外銷(xiāo)受阻 ，福建省輸日茶葉頭7個(gè)月同比下降14，其中6月、7月降幅分別達(dá)49.7和37.3。 今年上半年，中國(guó)蜂王漿累計(jì)出口下降5.72%，6月份當(dāng)月出口就下降11.13%。我國(guó)最大的優(yōu)質(zhì)蜂王漿產(chǎn)地青海門(mén)源7月份蜂王漿收購(gòu)價(jià)由歷年的130元每公斤跌到了每公斤75元。5設(shè)置貿(mào)易壁壘設(shè)置貿(mào)易壁壘歐美相關(guān)法規(guī)歐美相關(guān)法規(guī) 歐盟提出對(duì)輸歐中國(guó)茶葉至少要檢驗(yàn)25種農(nóng)藥（包括異構(gòu)體）的殘留量。2000年6月22日歐盟發(fā)布了修訂的農(nóng)藥最高殘留限量規(guī)定，所訂的限量普遍越來(lái)越低，如氰戊菊酯最高殘留限量從原先規(guī)定10mg/kg，現(xiàn)改為其RR和SS異構(gòu)體/RS和SR異構(gòu)體0.0

4、5mg/kg+0.05mg/kg(0.1mg/kg)，標(biāo)準(zhǔn)嚴(yán)了100倍。 在美國(guó), 通過(guò)嚴(yán)格、嚴(yán)密的取樣網(wǎng)絡(luò)、測(cè)試、通報(bào)和對(duì)超標(biāo)樣品執(zhí)行強(qiáng)制措施等，監(jiān)控有可能進(jìn)入食品中的污染物，如實(shí)施動(dòng)物源食品中的獸藥殘留監(jiān)控工程。 印度可樂(lè)事件6 農(nóng)藥多殘留分析中使用的農(nóng)藥多殘留分析中使用的GC/MS 三重四極質(zhì)譜, GC/MS/MS 離子阱質(zhì)譜, GC/MS, GC/MS/MS, GC/MSn 單四極質(zhì)譜, GC/MS 三重四極質(zhì)譜離子阱質(zhì)譜單四極質(zhì)譜定性定性+定量定量+篩選分析篩選分析*(100 目標(biāo)化合物)+*7離子阱質(zhì)譜（離子阱質(zhì)譜（PolarisQ）用于食品中農(nóng)藥）用于食品中農(nóng)藥多殘留分析多殘留分

5、析 用于食品安全分析農(nóng)藥殘留分析的性能價(jià)格必最高的儀器。l 定性準(zhǔn)確l 定量精確l 超高的性能價(jià)格比l 優(yōu)秀的售后服務(wù)81. 進(jìn)進(jìn)入入2.隔離隔離3. 碎裂碎裂4. 檢測(cè)檢測(cè)高靈敏和高選擇性的二級(jí)質(zhì)譜檢測(cè)高靈敏和高選擇性的二級(jí)質(zhì)譜檢測(cè)母離子母離子9二級(jí)質(zhì)譜和多級(jí)質(zhì)譜的優(yōu)點(diǎn)二級(jí)質(zhì)譜和多級(jí)質(zhì)譜的優(yōu)點(diǎn)GC/MS 全全掃掃描描m/z 373337301266GC/MS/MS 質(zhì)譜圖質(zhì)譜圖373337301266來(lái)自于來(lái)自于樣樣品基品基質(zhì)質(zhì)的干的干擾擾離子離子337301266m/z 373373337301266373373GC/MS 選擇選擇離子離子檢測(cè)檢測(cè) 增加對(duì)樣品基質(zhì)中目標(biāo)化合物定性的可靠性及

6、定量的準(zhǔn)確性10適用于氣相分析的農(nóng)藥殘留檢測(cè)過(guò)程適用于氣相分析的農(nóng)藥殘留檢測(cè)過(guò)程樣樣品品 SPE 凈凈化化乙乙腈腈提取提取 從水中從水中鹽鹽析析 最最終終溶液溶液 1- 5 g/mlTrace PolarisQ 離離子阱子阱 GC/MSnFocus PolarisQ 離子阱離子阱 GC/MSn11樣品前處理之一樣品前處理之一樣品切碎后,攪拌機(jī)打均 取10g樣品, 10ml乙腈, (可添加內(nèi)標(biāo)) 加4g 無(wú)水MgSO4, 1g無(wú)水NaAc搖動(dòng),振蕩,離心 取1ml 萃取液加到SPE微離心管搖動(dòng),振蕩,離心 1ul 進(jìn)樣到 GC/MS, GC/MS/MS 12 PolarisQ的全掃描檢測(cè)的全掃描

7、檢測(cè) POLARIS Q方便的儀器方法設(shè)置方便的儀器方法設(shè)置目標(biāo)化合物不限目標(biāo)化合物不限 高靈敏度高靈敏度13 儀器方法儀器方法 POLARIS Q儀器儀器質(zhì)譜氣相柱氣相條件氣相條件 程序升溫 進(jìn)樣口溫度 載氣流速 進(jìn)樣模式 脈沖壓力 質(zhì)譜條件質(zhì)譜條件 離子源模式 分析模式 掃描范圍 微掃描次數(shù) 傳輸線溫度 離子源溫度 :Polaris Q:Trace GC:TR-5MS 30m, 0.25mmID, 0.25mDf: 50(1min)-25/min-125(0min) -10/min-300(7.5min): 240: 1.0mL/min : Splitless with Surge: 20

8、0 kPa,1min: EI: Full Scan Mode: m/z 50-550: 3 : 280: 220 14高靈敏全掃描檢測(cè)高靈敏全掃描檢測(cè)-大豆中大豆中10 ppb的農(nóng)藥的農(nóng)藥C:XcaliburdataPQ_EI_Soybeansstd_5_012005/11/29 17:30:29std_5_10ppbTR-5MS 30m*0.25mm I.D. df=0.25umRT: 5.33 - 7.46SM: 5G5.56.06.57.0Time (min) DDVP020406080100Relative Abundance6.40RT: 11.82 - 13.51SM: 5G12.

9、012.513.013.5Time (min) Etrimfos020406080100Relative Abundance12.6312.0412.25RT: 15.79 - 17.49SM: 5G16.016.517.0Time (min) Isoxathion020406080100Relative Abundance17.4016.6515.8515.9916.0517.02RT: 10.50 - 11.93SM: 5G10.511.011.5Time (min) Salithion020406080100Relative Abundance11.22RT: 13.52 - 14.99

10、SM: 5G14.014.5Time (min) Chlorpyriphos020406080100Relative Abundance14.24RT: 17.75 - 19.78SM: 5G18.018.519.019.5Time (min) Piperophos020406080100Relative Abundance18.7419.30RT: 11.27 - 13.04SM: 5G11.512.012.513.0Time (min) Phorate020406080100Relative Abundance12.19RT: 14.17 - 15.90SM: 5G14.515.015.5

11、Time (min) Isofenphos020406080100Relative Abundance15.0414.2414.71RT: 17.66 - 19.99SM: 5G1819Time (min) Azinphos-methyl020406080100Relative Abundance18.8115質(zhì)量提取色譜圖質(zhì)量提取色譜圖 1 C:Xcalibur.040406_AS2000scan_10ppb2004/04/18 12:57:3310ppbDB-5MS 30m*0.25mmID df=0.25umRT: 4.60 - 10.00SM: 5G5678910Time (min)2

12、04060801002040608010020406080100Relative Abundance20406080100204060801005.249.005.666.039.648.869.149.004.745.675.085.849.148.869.64RT: 9.00 - 11.00SM: 5G9.09.510.010.511.0Time (min)20406080100Relative Abundance20406080100Relative Abundance20406080100Relative Abundance20406080100Relative Abundance20

13、406080100Relative Abundance9.649.149.669.9910.6010.9610.2310.5810.2710.26RT: 10.00 - 12.00SM: 5G10.010.511.011.512.0Time (min)20406080100Relative Abundance20406080100Relative Abundance20406080100Relative Abundance20406080100Relative Abundance20406080100Relative Abundance10.5911.6510.6811.9010.6511.7

14、810.8911.5610.8111.3410.96Diflubenzuronm/z=153DDVPm/z=185MIPCm/z=121Molinatem/z=126XMCm/z=122BPMCm/z=121PHCm/z=110Ethoprophosm/z=158+200IPCm/z=213Trifluralinm/z=264+306Cadusafosm/z=159Phoratem/z=231Pencycuronm/z=180BHCm/z=181 +183Thiometonm/z=8816質(zhì)量提取色譜圖質(zhì)量提取色譜圖2 C:Xcalibur.040406_AS2000scan_10ppb200

15、4/04/18 12:57:3310ppbDB-5MS 30m*0.25mmID df=0.25umRT: 10.80 - 11.50SM: 5G10.811.011.211.4Time (min)020406080100020406080100020406080100Relative Abundance02040608010002040608010011.0710.8111.3411.0711.2211.2211.3411.0210.9811.3810.9211.1011.4910.8310.8111.34RT: 11.00 - 12.00SM: 5G11.011.211.411.611.8

16、12.0Time (min)020406080100020406080100020406080100Relative Abundance02040608010002040608010011.3511.7811.6511.0611.5611.4311.5611.3411.6511.65RT: 11.50 - 12.50SM: 5G11.611.812.012.212.4Time (min)020406080100020406080100020406080100Relative Abundance02040608010002040608010011.7811.8911.9011.9612.1012

17、.03Dimethoatem/z=87Dicloranm/z=206CATm/z=201Dimethipinm/z=54-BHCm/z=181+183Triflumizole-metam/z=167PCNBm/z=237-BHCm/z=181+183Cyanophosm/z=243Terbufosm/z=231Diazinonm/z=179Pyrimethanilm/z=198TPNm/z=264+266Flufenoxronm/z=331Terbacilm/z=16117質(zhì)量提取色譜圖質(zhì)量提取色譜圖3 C:Xcalibur.040406_AS2000scan_10ppb2004/04/18

18、12:57:3310ppbDB-5MS 30m*0.25mmID df=0.25umRT: 11.80 - 12.80SM: 5G11.812.012.212.412.612.8Time (min)020406080100020406080100020406080100Relative Abundance02040608010002040608010012.1012.1712.1912.3412.5212.72RT: 12.20 - 13.20SM: 5G12.212.412.612.813.013.2Time (min)020406080100020406080100020406080100

19、Relative Abundance02040608010002040608010012.5412.8812.7113.1812.7412.8812.8812.9713.13RT: 12.50 - 13.50SM: 5G12.612.813.013.213.4Time (min)020406080100020406080100020406080100Relative Abundance02040608010002040608010012.9713.3313.0613.0513.1312.9713.17Tefluthrinm/z=177Ethorimfosm/z=292-BHCm/z=217+2

20、19Primicarbm/z=166Formothionm/z=93Ethiofencarbm/z=168Benfuresatem/z=163Dichlofenthionm/z=279Chlorpyrifos-methylm/z=286Metribuzinm/z=198Vinclozolinm/z=285Tolclofos-methylm/z=265Alachlorm/z=188Simetrynm/z=213NACm/z=14418PolarisQ 全掃描檢測(cè)快速篩選方法全掃描檢測(cè)快速篩選方法19 PolarisQ的二級(jí)質(zhì)譜檢測(cè)的二級(jí)質(zhì)譜檢測(cè) POLARIS Q高選擇性和高靈敏度 準(zhǔn)確對(duì)不同基

21、質(zhì)中農(nóng)藥進(jìn)行定性-排除假陽(yáng)性和假陰性結(jié)果實(shí)際樣品的精確定量20 儀器方法儀器方法 POLARIS Q:Polaris Q:Trace GC:TR-5MS 30m, 0.25mmID, 0.25mDf: 50(1min)-25/min-125(0min) -10/min-300(7.5min): 240: 1.0mL/min : Splitless with Surge: 200 kPa,1min: EI: MS/MS: 280: 220 儀器儀器質(zhì)譜氣相柱氣相條件氣相條件 程序升溫 進(jìn)樣口溫度 載氣流速 進(jìn)樣模式 脈沖壓力 質(zhì)譜條件質(zhì)譜條件 離子源模式 分析模式 傳輸線溫度 離子源溫度 21用

22、于二用于二級(jí)質(zhì)譜檢級(jí)質(zhì)譜檢索的索的Thermo譜庫(kù)譜庫(kù) GC/MS/MS部分包含大約500個(gè)農(nóng)藥, LC/MS/MS部分包含大約700個(gè)農(nóng)藥)TerbucarbPrecursor ion; m/z=205 CID；0.8VQ value；0.30022MS/MS 檢測(cè) - 165 農(nóng)藥 (1)1 Diflubenzuron22 Dimethipin43 Alachlor64 Dicofol2 DDVP23 Triflumizole-metabolite44 Simetryn65 Fthalide3 MIPC24 PCNB45 NAC66 Fosthiazate4 Molinate25 Cyan

23、ophos46 Metalaxyl67 Pendimethalin5 XMC26 Terbufos47 Ametryn68 CVP-E6 BPMC27 Diazinon48 Cinmethylin69 CVP-Z7 PHC28 Pyrimethanil49 Pirimiphos-methyl70 Fipronil8 Ethoprophos29 TPN50 MEP71 Penconazole9 IPC30 Flufenoxron51 Methiocarb72 Isophenphos10 Trifluralin31 Terbacil52 Dimethylvinphos-E73 Pyrifenox-

24、E11 Cadusafos32 Tefluthrin53 Dimethylvinphos-Z74 PAP12 Phorate33 Ethorimfos54 Esprocarb75 Quinalphos13 Pencycuron34 Primicarb55 Malathion76 Procymidone14 -BHC35 Formothion56 Metolachlor77 Triflumizole15 -BHC36 Ethiofencarb57 Chlorpyrifos78 Dimepiperate16 -BHC37 Benfuresate58 Benthiocarb79 Folpet17 -

25、BHC38 Dichlofenthion59 Diethofencarb80 Methoprene18 Thiometon39 Chlorpyrifos-methyl60 Cyanazine81 Triazimenol19 Dimethoate40 Metribuzin61 MPP82 DMTP20 Dichloran41 Vinclozorin62 Tetraconazole83 Propaphos21 CAT42 Tolchlofos-methyl63 Triadimefon84 Chinomethionate23MS/MS 檢測(cè)檢測(cè) - 165 農(nóng)藥農(nóng)藥 (2)85 Pyrifenox-

26、Z106 Carpropamide126 Pyridafenthion146 Pyraclofos86 CVMP107 Pyriminobac-methyl-Z127 Iprodion147 fenoxaprop-ethyl87 Paclobutrazol108 Chlobenzilate128 Sethoxydim148 Bitertanol88 Butachlor109 Fensulfothion129 Bifenthrin149 Permethrin89 -Endosulfan110 -Endosulfan130 EPN150 Pyridaben90 Mepanipilim111 Eth

27、ion131 Cumyluron151 Cafenstrole91 Flutolanil112 Mepronil132 Fenpropathrin152 Cyfluthrin92 Fludioxonil113 Trizophos133 Indanofan153 Cypermethrin93 Hexaconazole114 Cyanofenphos134 Tebfenpyrad154 Halfenprox94 Prothiofos115 EDDP135 Bifenox155 Flucythrinate95 Pretilachlor116 Propiconazole136 Furametpyr15

28、6 Etofenprox96 Profenofos117 Pyriminobac-methyl-E137 Phosalone157 Silafluofen97 Uniconazole-P118 Lenacil138 Cyhalothrin158 Pyrimidifen98 Thifluzamide119 Endosulfan-sulfate139 Pyriproxyfen159 Fenvalerate99 Myclobutanil120 Pyraflufen-ethyl140 Cyhalofop-buthyl160 Fluvalinate100 Flusilazole121 Tenylchlo

29、r141 Mefenacet161 Difenoconazole101 Buprofezin122 Tebuconazole142 Amitraz162 Pyrazoxyfen102 Kresozim-methyl123 Diflufenican143 Cyhalothrin163 Deltamethrin103 Chlofenapyr124 Bioresmethrin144 Fenarimol164 Tralomethrin104 Isoxathion125 Pyributicarb145 Acrinathrin165 Azoxystrabin105 Cyproconazole24質(zhì)量提取色

30、譜圖質(zhì)量提取色譜圖 1 A-groupc:xcalibur.ms2_5ppb_022004/04/19 3:10:275ppbDB-5MS 30m*0.25mmID df=0.25umRT: 4.60 - 10.00SM: 5G5678910Time (min)020406080100020406080100020406080100Relative Abundance0204060801000204060801005.246.028.869.009.14NL: 1.17E3m/z= 124.50-125.50 F: + c SRM ms2 153.001.00 60.00-160.00 MS

31、ms2_5ppb_02NL: 1.88E2m/z= 92.50-93.50 F: + c SRM ms2 185.001.00 80.00-190.00 MS ms2_5ppb_02NL: 4.62E2m/z= 92.50-93.50 F: + c SRM ms2 121.001.00 80.00-125.00 MS ms2_5ppb_02NL: 1.76E2m/z= 97.50-98.50 F: + c SRM ms2 126.001.00 60.00-130.00 MS ms2_5ppb_02NL: 1.00E3m/z= 106.50-107.50 F: + c SRM ms2 122.0

32、01.00 100.00-125.00 MS ms2_5ppb_02RT: 9.00 - 11.00SM: 5G9.09.510.010.511.0Time (min)020406080100020406080100020406080100Relative Abundance0204060801000204060801009.639.659.9910.0010.25NL: 1.26E3m/z= 90.50-91.50+92.50-93.50 F: + c SRM ms2 121.001.00 70.00-130.00 MS ms2_5ppb_02NL: 2.93E2m/z= 109.50-11

33、0.50 F: + c SRM ms2 152.001.00 100.00-120.00 MS ms2_5ppb_02NL: 1.83E2m/z= 113.50-114.50 F: + c SRM ms2 158.001.00 80.00-160.00 MS ms2_5ppb_02NL: 5.62E1m/z= 157.50-158.50 F: + c SRM ms2 200.000.80 140.00-200.00 MS ms2_5ppb_01NL: 7.59E1m/z= 99.50-100.50 F: + c SRM ms2 127.001.40 60.00-130.00 MS ms2_5p

34、pb_02RT: 9.50 - 12.00SM: 5G101112Time (min)020406080100020406080100020406080100020406080100Relative Abundance02040608010002040608010010.2710.2710.5910.6810.6411.22NL: 1.93E3m/z= 263.50-264.50 F: + c SRM ms2 306.000.80 250.00-310.00 MS ms2_5ppb_01NL: 5.68E2m/z= 205.50-206.50 F: + c SRM ms2 264.001.00

35、 130.00-270.00 MS ms2_5ppb_02NL: 5.01E2m/z= 130.50-131.50 F: + c SRM ms2 159.001.00 100.00-160.00 MS ms2_5ppb_02NL: 4.47E2m/z= 174.50-175.50+202.50-203.50 F: + c SRM ms2 231.001.00 80.00-240.00 MS ms2_5ppb_02NL: 7.80E2m/z= 124.50-125.50 F: + c SRM ms2 180.000.80 110.00-185.00 MS ms2_5ppb_01NL: 3.72E

36、2m/z= 172.50-173.50 F: + c SRM ms2 201.001.00 130.00-210.00 MS ms2_5ppb_02Diflubenzuronm/z=153125DDVPm/z=18593MIPCm/z=12193Molinatem/z=12698XMCm/z=122107BPMCm/z=121 91+93PHCm/z=152110Ethoprophosm/z=158 114IPCm/z=127 100Trifluralinm/z=306 264Cadusafosm/z=159131Phoratem/z=231175+203Pencycuronm/z=180 1

37、25Trifluralinm/z=264 206CATm/z=201 173Ethoprophosm/z=200 15825質(zhì)量提取色譜圖質(zhì)量提取色譜圖 2 c:xcalibur.ms2_5ppb_022004/04/19 3:10:275ppbDB-5MS 30m*0.25mmID df=0.25umRT: 10.58 - 13.38SM: 5G111213Time (min)020406080100020406080100020406080100020406080100Relative Abundance02040608010002040608010011.4411.5111.7811.7

38、911.9612.3512.34NL: 5.62E1m/z= 142.50-143.50 F: + c SRM ms2 237.001.40 120.00-240.00 MS ms2_5ppb_02NL: 4.00E2m/z= 136.50-137.50+164.50-165.50 F: + c SRM ms2 179.001.00 80.00-190.00 MS ms2_5ppb_02NL: 2.91E2m/z= 178.50-179.50 F: + c SRM ms2 304.001.20 110.00-310.00 MS ms2_5ppb_03NL: 6.59E2m/z= 267.50-

39、268.50 F: + c SRM ms2 331.001.00 110.00-340.00 MS ms2_5ppb_02NL: 4.98E2m/z= 165.50-166.50 F: + c SRM ms2 238.001.00 150.00-200.00 MS ms2_5ppb_02NL: 1.44E2m/z= 95.50-96.50 F: + c SRM ms2 166.001.40 90.00-170.00 MS ms2_5ppb_02RT: 12.78 - 14.83SM: 5G1314Time (min)020406080100020406080100020406080100020

40、406080100Relative Abundance02040608010002040608010013.0513.5513.5514.0314.0314.6014.5414.44NL: 3.22E3m/z= 249.50-250.50 F: + c SRM ms2 265.001.00 190.00-270.00 MS ms2_5ppb_02NL: 5.23E2m/z= 232.50-233.50+261.50-262.50 F: + c SRM ms2 290.001.00 100.00-300.00 MS ms2_5ppb_02NL: 2.46E2m/z= 179.50-180.50

41、F: + c SRM ms2 305.001.00 150.00-310.00 MS ms2_5ppb_02NL: 6.58E2m/z= 71.50-72.50 F: + c SRM ms2 100.000.80 46.00-110.00 MS ms2_5ppb_01NL: 8.43E2m/z= 195.50-196.50+196.50-197.50 F: + c SRM ms2 225.001.00 120.00-230.00 MS ms2_5ppb_02NL: 2.35E2m/z= 103.50-104.50+138.50-139.50+166.50-167.50 F: + c SRM m

42、s2 195.000.80 90.00-200.00 MS ms2_20ppb_01RT: 14.41 - 16.47SM: 5G1516Time (min)020406080100020406080100020406080100020406080100Relative Abundance02040608010002040608010014.7515.2115.2715.4515.5915.6115.7116.05NL: 9.24E2m/z= 161.50-162.50+190.50-191.50+207.50-208.50 F: + c SRM ms2 252.001.00 150.00-2

43、60.00 MS ms2_5ppb_02NL: 1.58E2m/z= 254.50-255.50 F: + c SRM ms2 283.001.00 94.00-290.00 MS ms2_5ppb_02NL: 1.71E2m/z= 178.50-179.50+185.50-186.50 F: + c SRM ms2 206.001.40 80.00-210.00 MS ms2_5ppb_04NL: 9.75E2m/z= 191.50-192.50+199.50-200.50+226.50-227.50 F: + c SRM ms2 262.001.40 180.00-270.00 MS ms

44、2_5ppb_04NL: 1.63E2m/z= 313.50-314.50 F: + c SRM ms2 329.001.40 180.00-340.00 MS ms2_5ppb_02NL: 2.61E3m/z= 144.50-145.50 F: + c SRM ms2 173.001.00 130.00-180.00 MS ms2_5ppb_02Diazinonm/z=179137+165Diazinonm/z=304 179Flufenoxronm/z=331 268Primicarbm/z=238 166Tolclofos-methylm/z=265 250Pirimiphos -met

45、hylm/z=290233+262Benthiocarbm/z=100 72Diethofencarbm/z=225196+197Pendimethalinm/z=252162+191+208Procymidonem/z=283 255Pyrifenox-Zm/z=262192+200+227Triazimenolm/z=206 179+186CVMPm/z=329 314Flutolanilm/z=173 145Pirimiphos -methylm/z=305 180Primicarbm/z=166 96PCNBm/z=237 143Fosthiazatem/z=195104+139+16

46、7A-group20ppb26質(zhì)量提取色譜圖質(zhì)量提取色譜圖 3 A-groupc:xcalibur.ms2_5ppb_022004/04/19 3:10:275ppbDB-5MS 30m*0.25mmID df=0.25umRT: 15.65 - 18.37SM: 5G161718Time (min)020406080100020406080100020406080100020406080100Relative Abundance02040608010002040608010016.1016.5216.5217.6317.6717.67NL: 1.38E3m/z= 126.50-127.50+

47、153.50-154.50+181.50-182.50 F: + c SRM ms2 248.001.00 120.00-250.00 MS ms2_5ppb_02NL: 3.62E2m/z= 131.50-132.50 F: + c SRM ms2 175.001.00 110.00-180.00 MS ms2_5ppb_02NL: 2.71E2m/z= 192.50-193.50 F: + c SRM ms2 249.001.20 180.00-250.00 MS ms2_5ppb_03NL: 5.57E2m/z= 209.50-210.50 F: + c SRM ms2 269.001.

48、00 110.00-280.00 MS ms2_5ppb_02NL: 3.39E2m/z= 161.50-162.50 F: + c SRM ms2 257.001.00 100.00-260.00 MS ms2_5ppb_02NL: 1.83E2m/z= 118.50-119.50 F: + c SRM ms2 162.001.00 60.00-170.00 MS ms2_5ppb_02RT: 17.55 - 20.97SM: 5G181920Time (min)020406080100020406080100020406080100020406080100Relative Abundanc

49、e02040608010002040608010018.1518.1418.7719.3019.6820.0720.48NL: 9.08E2m/z= 306.50-307.50 F: + c SRM ms2 349.001.40 120.00-360.00 MS ms2_5ppb_03NL: 1.34E3m/z= 348.50-349.50 F: + c SRM ms2 412.001.60 140.00-420.00 MS ms2_5ppb_04NL: 6.34E2m/z= 127.50-128.50 F: + c SRM ms2 143.001.00 50.00-150.00 MS ms2

50、_5ppb_02NL: 4.52E3m/z= 250.50-251.50 F: + c SRM ms2 267.001.20 90.00-280.00 MS ms2_10ppb_03NL: 7.90E2m/z= 110.50-111.50 F: + c SRM ms2 182.001.00 90.00-190.00 MS ms2_5ppb_02NL: 5.38E2m/z= 131.50-132.50 F: + c SRM ms2 162.001.40 80.00-170.00 MS ms2_5ppb_04RT: 20.44 - 25.44SM: 5G2224Time (min)02040608

51、0100020406080100020406080100Relative Abundance02040608010002040608010021.0921.0821.1822.0321.9422.6622.8824.59NL: 3.04E2m/z= 131.50-132.50+137.50-138.50 F: + c SRM ms2 194.001.00 110.00-200.00 MS ms2_5ppb_02NL: 2.35E2m/z= 193.50-194.50+209.50-210.50+289.50-290.50+317.50-318.50 F: + c SRM ms2 360.001

52、.00 180.00-370.00 MS ms2_5ppb_02NL: 4.98E1m/z= 118.50-119.50 F: + c SRM ms2 188.001.00 70.00-190.00 MS ms2_5ppb_02NL: 4.43E2m/z= 234.50-235.50 F: + c SRM ms2 263.001.00 100.00-270.00 MS ms2_5ppb_02NL: 1.78E2m/z= 171.50-172.50+173.50-174.50 F: + c SRM ms2 253.001.00 90.00-260.00 MS ms2_5ppb_02Buprofe

53、zinm/z=175 132Buprofezinm/z=249 193Mepronilm/z=269 210Triazophosm/z=257 162Pyraflufen-ethylm/z=349 307Pyraflufen-ethylm/z=412 349Bioresmethrinm/z=143128Cumylronm/z=26725110ppbPhosalonem/z=182 111Amitrazm/z=162132Pyraclofosm/z=194132+138Cafenstrolem/z=188 119Halfenproxm/z=263 235Deltamethrinm/z=25317

54、2+174Pyraclofosm/z=360194+210+290+318Triazophosm/z=162 119Fludioxonilm/z=248127+154+18227實(shí)際樣品檢測(cè)實(shí)際樣品檢測(cè)C:LinLu.Pesticides_OCStd6pg0106/02/2006 15:27:01OC standard, 6-50pg/ulRT: 3.63 - 23.5146810121416182022Time (min)20406080100Relative Abundance20406080100Relative Abundance18.2417.5218.9616.4820.4221.

55、295.7115.6313.7212.744.1011.4916.3118.0821.9610.4118.308.3514.7920.576.7513.3215.508.6517.0314.5220.135.074.6012.557.8012.175.598.7822.36NL:1.00E8TIC F: MS Std6pg01NL:1.00E8TIC F: MS bro6pg03西藍(lán)花的總離子流圖西藍(lán)花的總離子流圖空白溶劑總離子流圖空白溶劑總離子流圖28添加水平為添加水平為10 ppb 的西藍(lán)花樣品的西藍(lán)花樣品 西藍(lán)花西藍(lán)花c:linlu.pesticides_ocbro6pg0306/02/

56、2006 17:02:43OC standard, 6-50pg/ul spiked into broccoliRT: 7.27 - 9.10SM: 3B7.58.08.59.0Time (min)20406080100Relative Abundance20406080100Relative AbundanceRT: 8.27AA: 55942SN: 40RMSRT: 8.34AA: 20899SN: 17RMSRT: 7.88AA: 20020SN: 13RMSRT: 8.28AA: 53491SN: 21RMSRT: 7.89MA: 35984SN: 11RMS8.358.937.517

57、.838.377.617.927.428.798.66NL:3.98E4m/z= 180.50-181.50+182.50-183.50 F: MS ICIS Std6pg01NL:5.59E4m/z= 180.50-181.50+182.50-183.50 F: MS bro6pg03RT: 6.71 - 8.37SM: 3B7.07.58.0Time (min)20406080100Relative Abundance20406080100Relative AbundanceRT: 7.66AA: 12717SN: 136RMSRT: 7.30AA: 7028SN: 62RMSRT: 7.

58、71AA: 3311SN: 35RMSRT: 7.68AA: 13415SN: 60RMSRT: 7.30MA: 5354SN: 227.738.287.25NL:8.38E3m/z= 180.50-181.50+182.50-183.50 F: MS ICIS ocsta02NL:1.58E4m/z= 180.50-181.50+182.50-183.50 F: MS ocbro01a-a-BHCb-b-BHCg-g-BHCg- ?g- ?c:linlu.pesticides_ocbro6pgsim0108/02/2006 12:33:45OC standard, 6-50pg/ul spi

59、ked into broccoli, SIM 10msRT: 7.16 - 9.02 SM: 3B7.58.08.59.0Time (min)30405060708090100Relative Abundance20406080100Relative AbundanceRT: 8.28AA: 53491SN: 22RMSRT: 7.89MA: 32349SN: 118.358.937.518.128.377.617.428.798.66RT: 8.29AA: 40140SN: 23RMS8.718.357.447.848.948.637.537.388.387.57NL: 5.59E4m/z=

60、 180.50-181.50+182.50-183.50 F: MS bro6pg03NL: 8.52E4m/z= 180.50-181.50+182.50-183.50 F: + c SIM ms 180.50-181.50, 182.50-183.50, 218.50-219.50 MS ICIS bro6pgsim01RT: 6.92 - 8.47 SM: 3B7.07.58.0Time (min)020406080100Relative Abundance020406080100Relative AbundanceRT: 7.68MA: 16141SN: 897RMSRT: 7.31AA: 4