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Rapid Multiresidue Pesticides Analysis Using Fast-GC/MS and Chromatogram

Deconvolution Software

Richard Whitney1, Charles R. Lyle1, Haruhiko Miyagawa2, Keisuke Matsuda2, Katsuhiro Nakagawa2

1Shimadzu Scientific Instruments, Columbia, MD; 2Shimadzu Corporation, Kyoto, Japan

IntroductionGC/MS methods for pesticide residue analysis in food are commonly used for regulatory monitoring because fast pesticide determination is frequently required. Although fast-GC/MS is one of the methods of choice for increasing efficiency, the chromatographic separation using this technique is not as complete compared with conventional GC/MS.

Confirmation of target compounds in samples with complex matrices such as food is often very difficult because target compound peaks are often masked by co-eluting matrix background peaks of much higher intensity. In order to identify the target compound peaks in such complex matrices, deconvolution software was applied to data obtained using fast-GC/MS.

More than 100 pesticides were added to real samples and analyzed using fast-GC/MS. The data were processed by chromatogram deconvolution software to obtain mass chromatograms free from co-eluting compounds; the deconvolved mass chromatograms were then used for quantitative analysis. Fast-GC/MS coupled with chromatogram deconvolution software significantly shortened the analysis time and indicated accurate results for food samples with complex matrices.

Experimental

Shimadzu GCMS-QP2010 with GCMSsolution

Auto-injector: AOC-20i and AOC-20s, (Shimadzu) Column: DB-5MS 30m, 0.25mm ID, 0.25um, (J&W) Guard column: Deactivated tubing 2m, 0.25mm ID (J&W)Connector: Press-tight connector (Restek) Standards: Pesticides standard mixture #21,#22 (Kanto Chemical)Deconvolution Software: ‘IST for GC/MS’, Ion Signature Technology, Inc.

Analytical ConditionsGas Chromatograph GC-2010Injection Mode: SplitlessGlass Liner: Deactivated glass liner with glass wool (Restek)Inlet Temperature: 250ºCFlow Control Mode: Constant Linear Velocity (47.2 cm/sec)Temperature Program: 50ºC(1min)-(40ºC/min)-200ºC-(20ºC/min) - 300ºC

Mass Spectrometer GCMS QP-2010Ion Source Temperature: 200ºCInterface Temperature: 280ºCSolvent Cut Time: 2.5 minAcquisition Mode: ScanMass Range: m/z 50 - m/z 450Scan Interval: 0.3 sec (1425 amu/sec)Injection Volume: 2µL

STDs were added in food blank sampleConcentration: 0.1 µg/mL

Food blank sample Pesticides added sample

Sample Preparation

Sample

CH3CN Extraction

Dehydration

Salting Out

ENVI-Carb/LC-NH2

Acetone Solution

Sample Preparation

Acetone Solution

Carrot: 20g, Cabbage: 20g,Orange peel: 10g

20mL 20mL

100mL

40mL

Final matrix concentrationCarrot: 2g/mLCabbage: 2g/mLOrange peel: 1g/mL

Food Blank Sample

Target Compounds

ID Name R.T. Quantitation Ion1 Methamidophos 4.48 1412 DDVP(Dichlorvos) 4.54 1853 EPTC 4.98 1284 Butylate 5.24 1465 Acephate 5.26 1366 MIPC(Isoprocarb) 5.64 1367 BPMC(Fenobucarb) 5.90 1508 Ethoprophos 6.03 1589 IPC(Chlorpropham) 6.10 21310 Bendiocarb 6.14 15111 Cadusafos 6.23 15912 alpha-BHC 6.36 21913 Thiometon 6.38 8814 beta-BHC 6.54 21915 Dimethipin 6.52 5416 gamma-BHC 6.63 21717 Terbufos 6.60 23118 Diazinon 6.59 17919 Tefluthrin 6.67 17720 Etrimfos 6.74 29221 delta-BHC 6.83 21922 Pirimicarb 6.81 16623 Ethiofencarb 6.92 10724 Benfuresate 6.98 16325 Parathion-methyl 7.10 26326 Tolclophos-methyl 7.12 26527 NAC(Carbaryl) 7.16 14428 Pirimiphos-methyl 7.23 29029 MEP(Fenitrothion) 7.29 26030 Methiocarb 7.31 16831 Dichlofluanid 7.38 22632 Esprocarb 7.38 22233 Malathion 7.33 17334 Metolachlor 7.43 16235 Chlorpyrifos 7.42 31436 Thiobencarb 7.46 10037 Dimethylvinphos 7.44 29538 Diethofenccarb 7.37 26739 MPP(Fenthion) 7.46 278

ID Name R.T. Quantitation Ion40 Parathion 7.49 29141 Isofenphos P=O 7.48 22942 dicofol deg. 7.60 25043 Fosthiazate-1 7.66 19544 Fosthiazate-2 7.68 19545 Pendimethalin 7.71 25246 CVP(Chlorfenvinphos)-E 7.68 26747 Pyrifenox-Z 7.81 26248 Isofenphos 7.77 21349 CVP(Chlorfenvinphos)-Z 7.79 26750 PAP(Phenthoate) 7.85 27451 Quinalphos 7.87 14652 Captan 7.94 7953 Triadimenol-1 7.90 16854 Triadimenol-2 7.96 11255 Chinomethionat 8.11 23456 Pyrifenox-E 8.03 26257 Pacrobutrazol 8.09 23658 Flutolanil 8.17 17359 Prothiophos 8.25 30960 Tricyclazole 8.40 18961 Pretilachlor 8.24 23862 p,p'-DDE 8.34 24663 Myclobutanil 8.35 17964 Flusilazole 8.36 23365 Cyproconazole 8.56 22266 Chlorobenzilate 8.62 25167 Fensulfothion 8.64 29368 p,p'-DDD 8.72 23569 Mepronil 8.80 26970 Propiconazole-1 8.97 25971 EDDP(Edifenphos) 9.01 31072 Propiconazole-2 9.03 25973 Lenacil 9.03 15374 Thenylchlor 9.15 28875 Tebuconazole 9.19 25078 Acetamiprid 9.44 152

ID Name R.T. Quantitation Ion79 EPN 9.50 15780 Tebufenpyrad 9.58 33381 Phosalon 9.82 18282 Cyhalothrin-1 9.81 18183 Pyriproxyfen 9.87 13684 Mefenacet 9.95 19285 Cyhalothrin-2 9.90 18186 Acrinathrin 9.94 18187 Fenapanil 10.13 13988 Pyraclofos 10.22 36089 Bitertanol-1 10.39 17090 Permethrin-1 10.40 18391 Bitertanol-2 10.46 17092 Permethrin-2 10.47 18393 Pyridaben 10.55 14794 Cyfluthrin-1 10.72 20695 Cyfluthrin-2 10.78 20696 Cyfluthrin-3,4 10.83 20697 Cypermethrin-1 10.97 16398 Halfenprox 11.04 26399 Cypermethrin-2 11.03 163

100 Cypermethrin-3,4 11.11 163101 Flucythrinate-1 11.08 199102 Flucythrinate-2 11.22 199103 Silafluofen 11.33 179104 Pyrimidifen 11.54 184105 Fenvalerate-1 11.72 167106 Fluvalinate-1 11.78 250107 Fluvalinate-2 11.83 250108 Fenvalerate-2 11.91 167109 Difenoconazole-1 12.17 323110 Difenoconazole-2 12.24 323111 Deltamethrin 12.45 181112 Imibenconazole 13.60 125

The target compounds are all regulated pesticides in Japan. These compounds are commonly analyzed by the GC/MS multiresidue method.

Chromatogram

Fast-GC/MS Total Ion Chromatogram (0.1µg/mL)

Using conventional conditions, the pesticides eluted in 4.48min (Methamidophos) to 13.60min (Imibenconazole). Total analysis time was 30min., including column bake time. All pesticides of 0.1 µg/mL concentration were readily detected in the full-scan mode.

5.0 7.5 10.0 12.5 15.0 17.5 20.0 22.5 25.0 27.5 30.0

1.0

2.0

3.0

4.0

5.0

(x100,000)TIC

5.0 7.5 10.0 12.5

1.0

2.0

3.0

4.0

5.0

6.0

7.0

8.0

9.0(x100,000)

TIC

Conventional Analysis(Total Ion Chromatogram)

0.1µg/mL

Compound Identification

6.75 7.00 7.25 7.50 7.75 8.00 8.25

2.5

5.0

7.5

10.0

(x100,000)TIC

7.3 7.4 7.5 7.60.0

0.5

1.0

1.5

(x100,000)

238.00211.00162.00

7.3 7.4 7.5 7.60.0

1.0

2.0

(x10,000)

316.00286.00314.00

7.3 7.4 7.5 7.60.0

2.5

5.0

7.5

(x10,000)

297.00204.00295.00

7.3 7.4 7.5 7.60.0

0.5

1.0

(x100,000)

279.00169.00278.00

7.3 7.4 7.5 7.60.0

0.5

1.0

1.5

(x10,000)

201.00120.00229.00

Six pesticides eluted between 7.4 and7.5 min, and the TIC shows overlapping chromatograms. By selecting the appropriate target ion and reference ions, these pesticide peaks were readily resolved. The mass chromatograms were used for quantitative analysis and accurate identifications were made possible using ion ratios.

MPP(Fenthion)Metolachlor Chlorpyrifos Dimethylvinphos

Isofenphos P=O

Carrot (ENVI-Carb/LC-NH2 SPE cleanup)

5.0 7.5 10.0 12.5 15.0 17.5

0.25

0.50

0.75

1.00

(x100,000,000)TIC

5.0 7.5 10.0 12.5 15.0 17.5

2.5

5.0

(x1,000,000)

Total ion chromatogram of carrot extract sample

Overlaid total ion chromatogram with analytical standard (0.1µg/mL)

Quantitative Evaluation 1

ID Compound GCMSsolution IST for GC/MS1 Methamidophos 113 1102 DDVP(Dichlorvos) 111 1073 EPTC 106 1054 Butylate 104 1135 Acephate 125 1076 MIPC(Isoprocarb) 251 1527 BPMC(Fenobucarb) 113 1038 Ethoprophos 108 1099 IPC(Chlorpropham) 111 10510 Bendiocarb 138 13411 Cadusafos 108 10812 alpha-BHC 97 10813 Thiometon 101 10714 beta-BHC 107 10915 Dimethipin 97 10716 gamma-BHC 104 11117 Terbufos 104 11018 Diazinon 101 10219 Tefluthrin 106 10620 Etrimfos 102 8521 delta-BHC 143 11022 Pirimicarb 98 8823 Ethiofencarb 198 12324 Benfuresate 97 10425 Parathion-methyl 108 12226 Tolclophos-methyl 110 10427 NAC(Carbaryl) 112 10428 Pirimiphos-methyl 104 10829 MEP(Fenitrothion) 106 11430 Methiocarb 123 13831 Dichlofluanid 115 12432 Esprocarb 94 8933 Malathion 115 10034 Metolachlor 103 11035 Chlorpyrifos 101 9336 Thiobencarb 98 9137 Dimethylvinphos 111 9638 Diethofenccarb 109 10739 MPP(Fenthion) 100 118

ID Compound GCMSsolution IST for GC/ MS40 Parathion 110 10841 Isofenphos P=O 176 14142 dicofol deg. 102 11843 Fosthiazate-1 212 12844 Fosthiazate-2 151 12845 Pendimethalin 139 12446 CVP(Chlorfenvinphos)-E 114 15647 Pyrifenox-Z 87 11848 Isofenphos 123 10949 CVP(Chlorfenvinphos)-Z 114 10350 PAP(Phenthoate) 119 10851 Quinalphos 100 12452 Captan 114 14353 Triadimenol-1 109 11454 Triadimenol-2 100 11755 Chinomethionat 115 11556 Pyrifenox-E 92 12157 Pacrobutrazol 122 12358 Flutolanil 105 11359 Prothiophos 105 11160 Tricyclazole 92 10361 Pretilachlor 114 10862 p,p'-DDE 113 10563 Myclobutanil 95 12664 Flusilazole 87 12865 Cyproconazole 133 12666 Chlorobenzilate 107 10867 Fensulfothion 152 15968 p,p'-DDD 125 11369 Mepronil 99 9770 Propiconazole-1 136 12471 EDDP(Edifenphos) 135 13872 Propiconazole-2 126 10873 Lenacil 97 9574 Thenylchlor 113 10275 Tebuconazole 91 10578 Acetamiprid 118 13679 EPN 139 129

ID Compound GCMSsolution IST for GC/ MS80 Tebufenpyrad 95 8781 Phosalon 107 10982 Cyhalothrin-1 88 9683 Pyriproxyfen 96 10584 Mefenacet 88 9785 Cyhalothrin-2 101 6886 Acrinathrin 111 12987 Fenapanil 99 9088 Pyraclofos 141 11989 Bitertanol-1 171 15990 Permethrin-1 98 9091 Bitertanol-2 56 22392 Permethrin-2 88 9293 Pyridaben 95 9294 Cyfluthrin-1 125 13795 Cyfluthrin-2 119 10096 Cyfluthrin-3,4 327 10897 Cypermethrin-1 136 10598 Halfenprox 101 10099 Cypermethrin-2 99 113100 Cypermethrin-3,4 123 113101 Flucythrinate-1 116 133102 Flucythrinate-2 129 112103 Silafluofen 80 80104 Pyrimidifen 118 132105 Fenvalerate-1 92 94106 Fluvalinate-1 119 124107 Fluvalinate-2 159 138108 Fenvalerate-2 149 113109 Difenoconazole-1 254 129110 Difenoconazole-2 143 129111 Deltamethrin 98 104112 Imibenconazole 152 212

Abundance of pesticide in real sample Abundance of pesticide in STD

x 100

To evaluate the quantitative results for the fast-GC/MS’s multiresidue simultaneous analysis, the peak abundance obtained by the analysis of pesticides, which were added in the real sample, was compared with the peak abundance obtained by the analysis of the same concentration standard sample. The data were processed using GCMSsolution software with ‘IST for GC/MS’ deconvolution software.


0 50 100 150 200 250 300

M ethamidophos

DDVP(Dichlorvos)

EPTC

Butylate

Acephate

M IPC(Isoprocarb)

BPM C(Fenobucarb)

Ethoprophos

IPC(Chlorpropham)

Bendiocarb

Cadusafos

alpha-BHC

Thiometon

beta-BHC

Dimethipin

gamma-BHC

Terbufos

Diazinon

Tefluthrin

Etrimfos

delta-BHC

Pirimicarb

Ethio fencarb

Benfuresate

Parathion-methyl

To lclophos-methyl

NAC(Carbaryl)

P irimiphos-methyl

M EP(Fenitro thion)

M ethiocarb

Dichlofluanid

Esprocarb

M alathion

M eto lachlor

Chlorpyrifos

Thiobencarb

Dimethylvinphos

Diethofenccarb

M PP(Fenthion)

GCMSsolutionIST for GC/ MS

0 50 100 150 200 250 300

Parathion

Isofenphos P=O

dicofo l deg.

Fosthiazate-1

Fosthiazate-2

PendimethalinCVP(Chlorfenvinp

hos)-EPyrifenox-Z

IsofenphosCVP(Chlorfenvinp

hos)-ZPAP(Phenthoate)

Quinalphos

Captan

Triadimenol-1

Triadimeno l-2

Chinomethionat

Pyrifenox-E

Pacrobutrazo l

Fluto lanil

Prothiophos

Tricyclazole

Pretilachlor

p,p'-DDE

M yclobutanil

Flusilazole

Cyproconazo le

Chlorobenzilate

Fensulfothion

p,p'-DDD

M epronil

Propiconazole-1

EDDP(Edifenphos)

Propiconazo le-2

Lenacil

Thenylchlor

Tebuconazo le

Acetamiprid

EPN


0 50 100 150 200 250 300 350

Tebufenpyrad

PhosalonCyhalo thrin-1

Pyriproxyfen

M efenacet

Cyhalothrin-2Acrinathrin

Fenapanil

Pyraclofos

Bitertano l-1Permethrin-1

Bitertanol-2

Permethrin-2

PyridabenCyfluthrin-1

Cyfluthrin-2

Cyfluthrin-3,4

Cypermethrin-1

Halfenprox

Cypermethrin-2

Cypermethrin-3,4

Flucythrinate-1

Flucythrinate-2

Silafluofen

Pyrimidifen

Fenvalerate-1

Fluvalinate-1

Fluvalinate-2

Fenvalerate-2

Difenoconazole-1

Difenoconazole-2

Deltamethrin

Imibenconazo le


The ratio of 100% is the theoretical value, but most ratios were greater than 100% . This was attributed to a matrix effect. The pesticides indicated by red arrows showed a ratio of over 200% using only GCMSsolution (without deconvolution) processing; this anomaly was due to co-eluting compounds overlapping. Using deconvolutionprocessing, the overlapping was eliminated and the pesticides were selectively detected accurately.

Mass Chromatogram Integration

7.65 7.70 7.750.00

0.25

0.50

0.75

1.00

1.25

1.50 (x10,000)

283.00199.00195.00

10.7 10.8 10.90.0

1.0

2.0

3.0

4.0

5.0

6.0

7.0(x1,000)

226.00165.00206.00

6.85 6.90 6.95 7.00

2.5

5.0

7.5

10.0

(x10,000)

168.00108.00107.00

10.75 10.80 10.85 10.90 10.950.0

1.0

2.0

3.0

4.0

5.0

6.0

7.0

8.0

(x1,000)

226.00165.00206.00

7.60 7.65 7.70 7.750.00

0.25

0.50

0.75

1.00

1.25

(x10,000)

283.00199.00195.00

6.85 6.90 6.95 7.000.00

0.25

0.50

0.75

1.00

1.25

1.50

(x100,000)

168.00108.00107.00

Ethiofencarb Fosthiazate-1 Cyfuluthrin-3,4



Standard Chromatogram

Target Compound Chromatograms in Carrot Matrix

Deconvolved Mass Chromatograms in Carrot Matrix Using IST for GC/MS Software

Interference by the Matrix

Orange Peel (ENVI-Carb/LC-NH2 SPE cleanup)

5.0 7.5 10.0 12.5 15.0 17.5

1.0

2.0

3.0

4.0

(x1,000,000)

5.0 7.5 10.0 12.5 15.0 17.5

0.5

1.0

1.5

2.0

2.5

3.0

3.5

4.0(x10,000,000)

TIC

Total ion chromatogram of orange peel extract sample


ID Compound GCMSsolution IST for GC/ MS1 Methamidophos 120 1232 DDVP(Dichlorvos) 115 983 EPTC 111 1364 Butylate 115 1185 Acephate 121 1316 MIPC(Isoprocarb) 114 1107 BPMC(Fenobucarb) 112 978 Ethoprophos 115 1179 IPC(Chlorpropham) 108 12910 Bendiocarb 88 10411 Cadusafos 135 11412 alpha-BHC 119 10313 Thiometon 118 10814 beta-BHC 127 10615 Dimethipin 108 13216 gamma-BHC 118 10117 Terbufos 120 14218 Diazinon 114 10919 Tefluthrin 108 9820 Etrimfos 111 11421 delta-BHC 358 9622 Pirimicarb 108 12123 Ethiofencarb 103 11724 Benfuresate 109 10525 Parathion-methyl 151 14926 Tolclophos-methyl 113 11727 NAC(Carbaryl) 74 7528 Pirimiphos-methyl 114 10729 MEP(Fenitrothion) 142 14530 Methiocarb 95 9531 Dichlofluanid 78 7832 Esprocarb 110 10933 Malathion 113 11634 Metolachlor 111 10835 Chlorpyrifos 194 19436 Thiobencarb 105 11437 Dimethylvinphos 112 12038 Diethofenccarb 106 11039 MPP(Fenthion) 105 108

ID Compound GCMSsolution IST for GC/MS40 Parathion 131 12041 Isofenphos P=O 201 19442 dicofol deg. 124 12543 Fosthiazate-1 156 11644 Fosthiazate-2 100 10745 Pendimethalin 150 15346 CVP(Chlorfenvinphos)-E 126 13547 Pyrifenox-Z 107 11048 Isofenphos 121 12649 CVP(Chlorfenvinphos)-Z 117 11150 PAP(Phenthoate) 113 10651 Quinalphos 101 11952 Captan 119 13153 Triadimenol-1 129 16654 Triadimenol-2 154 15555 Chinomethionat 109 10256 Pyrifenox-E 110 10857 Pacrobutrazol 136 16158 Flutolanil 111 10859 Prothiophos 111 10960 Tricyclazole 113 16361 Pretilachlor 116 12662 p,p'-DDE 112 10863 Myclobutanil 132 17564 Flusilazole 167 19365 Cyproconazole 155 15366 Chlorobenzilate 109 11267 Fensulfothion 159 10868 p,p'-DDD 110 11069 Mepronil 119 12270 Propiconazole-1 179 16571 EDDP(Edifenphos) 121 12672 Propiconazole-2 138 13673 Lenacil 115 13974 Thenylchlor 122 14075 Tebuconazole 113 14178 Acetamiprid 162 18679 EPN 121 127

ID Compound GCMSsolution IST for GC/ MS80 Tebufenpyrad 111 10981 Phosalon 128 12882 Cyhalothrin-1 109 10483 Pyriproxyfen 112 12784 Mefenacet 114 12485 Cyhalothrin-2 149 13086 Acrinathrin 80 8687 Fenapanil 115 13388 Pyraclofos 167 14389 Bitertanol-1 292 27690 Permethrin-1 115 12791 Bitertanol-2 332 28392 Permethrin-2 115 11593 Pyridaben 122 13894 Cyfluthrin-1 163 12795 Cyfluthrin-2 125 14496 Cyfluthrin-3,4 225 13297 Cypermethrin-1 83 12598 Halfenprox 133 11599 Cypermethrin-2 88 115

100 Cypermethrin-3,4 134 141101 Flucythrinate-1 121 129102 Flucythrinate-2 150 145103 Silafluofen 113 117104 Pyrimidifen 148 158105 Fenvalerate-1 83 120106 Fluvalinate-1 147 138107 Fluvalinate-2 153 148108 Fenvalerate-2 150 165109 Difenoconazole-1 269 156110 Difenoconazole-2 301 197111 Deltamethrin 116 118112 Imibenconazole 125 198


Abundance of pesticide in real sample Abundance of pesticide in STD x 100

0 50 100 150 200 250 300 350 400

M ethamidophos

DDVP(Dichlorvos)

EPTC

Butylate

Acephate

M IPC(Isoprocarb)

BPM C(Fenobucarb)

Ethoprophos

IPC(Chlorpropham)

Bendiocarb

Cadusafos

alpha-BHC

Thiometon

beta-BHC

Dimethipin

gamma-BHC

Terbufos

Diazinon

Tefluthrin

Etrimfos

delta-BHC

Pirimicarb

Ethio fencarb

Benfuresate

Parathion-methyl

Tolclophos-methyl

NAC(Carbaryl)

P irimiphos-methylM EP(Fenitro thion)

M ethiocarb

Dichlofluanid

Esprocarb

M alathion

M eto lachlorChlorpyrifos

Thiobencarb

Dimethylvinphos

Diethofenccarb

M PP(Fenthion)


0 50 100 150 200 250 300

Parathion

Isofenphos P=O

dicofo l deg.

Fosthiazate-1

Fosthiazate-2

PendimethalinCVP(Chlorfenvinp

hos)-EPyrifenox-Z



Quinalphos

Captan

Triadimenol-1

Triadimenol-2

Chinomethionat

Pyrifenox-E

Pacrobutrazo l

Fluto lanil

Pro thiophos

Tricyclazo le

Pretilachlor

p,p'-DDE

M yclobutanil

Flusilazo le

Cyproconazo le

Chlorobenzilate

Fensulfo thion

p,p'-DDD

M epronil

Propiconazole-1

EDDP(Edifenphos)

Propiconazo le-2

Lenacil

Thenylchlor

Tebuconazole

Acetamiprid

EPN


0 50 100 150 200 250 300 350

Tebufenpyrad

Phosalon

Cyhalothrin-1

Pyriproxyfen

M efenacet

Cyhalothrin-2

Acrinathrin

Fenapanil

Pyraclo fos

Bitertanol-1

Permethrin-1

Bitertanol-2

Permethrin-2

Pyridaben

Cyfluthrin-1

Cyfluthrin-2

Cyfluthrin-3,4

Cypermethrin-1

Halfenprox

Cypermethrin-2

Cypermethrin-3,4

Flucythrinate-1

Flucythrinate-2

Silafluofen

Pyrimidifen

Fenvalerate-1

Fluvalinate-1

Fluvalinate-2

Fenvalerate-2

Difenoconazole-1

Difenoconazole-2

Deltamethrin

Imibenconazo le



6.7 6.8 6.9 7.00.0

2.5

5.0

7.5

(x10,000)

254.00217.00219.00

8.5 8.6 8.70.0

1.0

2.0

3.0

4.0

(x10,000)

308.00156.00293.00

10.7 10.8 10.90.0

2.5

5.0

7.5

10.0(x1,000)

226.00165.00206.00

6.75 6.80 6.85 6.900.0

0.5

1.0

1.5

2.0

2.5

3.0 (x10,000)

254.00217.00219.00

8.55 8.60 8.65 8.700.0

1.0

2.0

3.0

4.0

(x10,000)

308.00156.00293.00

10.70 10.75 10.80 10.85 10.900.0

1.0

2.0

3.0

4.0

5.0

6.0

7.0

(x1,000)

226.00165.00206.00



Target Compound Mass Chromatograms in Orange Peel Matrix

Deconvolved Mass Chromatograms in Orange Peel Matrixusing IST for GC/MS Software


delta-BHC Fensulfothion Cyfluthrin-3,4



Cabbage (extraction only)

5.0 7.5 10.0 12.5 15.0 17.5

0.25

0.50

0.75

1.00

1.25

1.50

1.75

2.00(x10,000,000)

TIC

5.0 7.5 10.0 12.5 15.0 17.5

0.5

1.0

1.5

2.0

(x1,000,000)


Total ion chromatogram of cabbage extract sample

Cabbage sample was left untreated by the sample pretreatment process in order to examine the maximum matrix interferences.

ID Compound GCMSsolution IST for GC/MS1 Methamidophos 34 512 DDVP(Dichlorvos) 99 1043 EPTC 95 1064 Butylate 112 965 Acephate 10 106 MIPC(Isoprocarb) 101 967 BPMC(Fenobucarb) 101 1058 Ethoprophos 105 1069 IPC(Chlorpropham) 93 9210 Bendiocarb 140 13011 Cadusafos 95 9912 alpha-BHC 102 8713 Thiometon 96 11714 beta-BHC 97 9815 Dimethipin 123 12616 gamma-BHC 99 10717 Terbufos 93 10418 Diazinon 106 9019 Tefluthrin 94 8720 Etrimfos 79 8221 delta-BHC 134 12822 Pirimicarb 89 8223 Ethiofencarb 176 15324 Benfuresate 85 8925 Parathion-methyl 83 8526 Tolclophos-methyl 88 9527 NAC(Carbaryl) 244 21228 Pirimiphos-methyl 83 8429 MEP(Fenitrothion) 76 10430 Methiocarb 166 16631 Dichlofluanid 53 032 Esprocarb 90 8233 Malathion 76 8734 Metolachlor 87 8135 Chlorpyrifos 92 9936 Thiobencarb 88 9437 Dimethylvinphos 54 5138 Diethofenccarb 95 9239 MPP(Fenthion) 79 73

ID Compound GCMSsolution IST for GC/MS40 Parathion 114 10741 Isofenphos P=O 103 10142 dicofol deg. 98 10443 Fosthiazate-1 774 8544 Fosthiazate-2 788 10445 Pendimethalin 119 13846 CVP(Chlorfenvinphos)-E 108 9247 Pyrifenox-Z 90 9348 Isofenphos 93 9849 CVP(Chlorfenvinphos)-Z 90 10050 PAP(Phenthoate) 74 7751 Quinalphos 82 9352 Captan 189 21353 Triadimenol-1 103 9254 Triadimenol-2 95 10655 Chinomethionat 98 9656 Pyrifenox-E 101 8857 Pacrobutrazol 101 10458 Flutolanil 94 10259 Prothiophos 89 9460 Tricyclazole 99 11361 Pretilachlor 75 7862 p,p'-DDE 90 8863 Myclobutanil 82 9264 Flusilazole 90 8965 Cyproconazole 94 11066 Chlorobenzilate 92 9667 Fensulfothion 110 5568 p,p'-DDD 99 9569 Mepronil 95 9170 Propiconazole-1 110 11271 EDDP(Edifenphos) 73 7072 Propiconazole-2 105 11173 Lenacil 95 8974 Thenylchlor 60 6575 Tebuconazole 95 9678 Acetamiprid 153 26079 EPN 143 136

ID Compound GCMSsolution IST for GC/ MS80 Tebufenpyrad 90 9281 Phosalon 75 6882 Cyhalothrin-1 110 9783 Pyriproxyfen 87 9284 Mefenacet 87 8985 Cyhalothrin-2 110 7886 Acrinathrin 123 12687 Fenapanil 94 9388 Pyraclofos 59 5789 Bitertanol-1 137 15090 Permethrin-1 101 9391 Bitertanol-2 135 16592 Permethrin-2 93 9793 Pyridaben 107 9394 Cyfluthrin-1 98 9695 Cyfluthrin-2 119 11296 Cyfluthrin-3,4 122 11297 Cypermethrin-1 113 14198 Halfenprox 112 10999 Cypermethrin-2 91 117100 Cypermethrin-3,4 394 141101 Flucythrinate-1 119 123102 Flucythrinate-2 123 123103 Silafluofen 96 97104 Pyrimidifen 127 130105 Fenvalerate-1 146 119106 Fluvalinate-1 166 126107 Fluvalinate-2 186 167108 Fenvalerate-2 99 63109 Difenoconazole-1 211 177110 Difenoconazole-2 192 166111 Deltamethrin 143 169112 Imibenconazole 163 181


Abundance of pesticide in real sample Abundance of pesticide in STD x 100

0 100 200 300 400

ParathionIsofenphos P=O

dicofo l deg.Fosthiazate-1

Fosthiazate-2Pendimethalin

CVP(Chlorfenvinphos)-EPyrifenox-Z



Quinalphos

Captan

Triadimenol-1

Triadimenol-2

Chinomethionat

Pyrifenox-E

Pacrobutrazol

Fluto lanilPro thiophos

Tricyclazo lePretilachlor

p,p'-DDEM yclobutanil

Flusilazo leCyproconazo le

ChlorobenzilateFensulfothion

p,p'-DDD

M epronil

Propiconazole-1

EDDP(Edifenphos)

Propiconazo le-2

Lenacil

Thenylchlor

Tebuconazo le

AcetamipridEPN


0 50 100 150 200 250 300

M ethamidophos

DDVP(Dichlorvos)

EPTCButylate

Acephate

M IPC(Isoprocarb)BPM C(Fenobucarb)

Ethoprophos

IPC(Chlorpropham)Bendiocarb

Cadusafos

alpha-BHCThiometon

beta-BHC

Dimethipingamma-BHC

Terbufos

DiazinonTefluthrin

Etrimfos

delta-BHCPirimicarb

Ethio fencarb

BenfuresateParathion-methyl

Tolclophos-methyl

NAC(Carbaryl)P irimiphos-methyl

M EP(Fenitro thion)

M ethiocarbDichlo fluanid

Esprocarb

M alathionM eto lachlor

Chlorpyrifos

ThiobencarbDimethylvinphos

Diethofenccarb

M PP(Fenthion)


0 100 200 300 400

TebufenpyradPhosalon

Cyhalothrin-1Pyriproxyfen

MefenacetCyhalothrin-2

AcrinathrinFenapanil

PyraclofosBitertanol-1

Permethrin-1Bitertanol-2

Permethrin-2Pyridaben

Cyfluthrin-1Cyfluthrin-2

Cyfluthrin-3,4Cypermethrin-1

HalfenproxCypermethrin-2Cypermethrin-

3,4Flucythrinate-1Flucythrinate-2

Silaf luofenPyrimidifen

Fenvalerate-1Fluvalinate-1Fluvalinate-2

Fenvalerate-2Difenoconazol

e-1Difenoconazole-2

DeltamethrinImibenconazole



7.60 7.65 7.70 7.750.0

0.5

1.0

1.5

2.0

2.5

3.0

(x10,000)

283.00199.00195.00

10.45 10.50 10.55 10.600.0

1.0

2.0

3.0

4.0

5.0

6.0

7.0

(x10,000)

309.00148.00147.00

11.0 11.1 11.20.0

2.5

5.0

7.5

10.0(x1,000)

181.00165.00163.00

7.5 7.6 7.7 7.80.00

0.25

0.50

0.75

1.00

(x10,000)

283.00199.00195.00

10.45 10.50 10.55 10.60 10.650.0

1.0

2.0

3.0

4.0

5.0

6.0

7.0

8.0(x10,000)

309.00148.00147.00

10.9 11.0 11.10.0

1.0

2.0

3.0

4.0

5.0

6.0

(x1,000)

181.00165.00163.00



Target Compound Mass Chromatograms in Cabbage Matrix

Deconvolved Mass Chromatograms in Cabbage Matrixusing IST for GC//MS Software


Fosthiazate-1 Pyridaben Cypermethrin-3,4



Screening of PesticidesUsing IST software for GC/MS, chromatograms were reconstructed for the target pesticides’identification. The reconstructed ion chromatograms showed clear positive detection in samples with very complex matrices. The six pesticides whose retention times were very close were easily and clearly identified.

Cabbage Sample

reconstructed chromatogram

Conclusions• Analytical productivity is significantly increased by fast-GC/MS. More

than 100 pesticides are detected with a 15-minute GC/MS run.• By selecting appropriate ions, overlapping pesticide peaks can be easily

resolved. Each pesticide was identified clearly and accurately using ion ratios.

• The GCMS-QP2010 could detect low-level pesticides in the full-scan mode. Accurate qualitative analysis was possible using the GCMSsolution workstation for samples employing the SPE cleanup sample (carrot, orange peel) and the untreated sample extracts (cabbage).

• For some pesticides, the chromatographic peaks were overlapped by the co-eluting peaks from the sample matrix, which affected the quantitative results. IST deconvolution software was effective in decreasing the interferences and producing accurate results.

rapid multiresidue pesticides analysis using fast-gc/ms ... · rapid multiresidue pesticides...

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