Application

Note: 52027
Fast GC-MS/MS for High Throughput
Pesticides Analysis
Igor Fochi, Elena Ciceri, Hans-Joachim Huebschmann, Thermo Fisher Scientific, Milan, Italy
Ciro D’Aniello, Laboratorio D’aniello – Via Nazionale, 81 S. Egidio M. Albino, Salerno, Italy

Introduction
Key Words A wide variety of phytosanitary products are commonly
• Fast GC applied in agricultural crops in order to increase production
yield and obtain high quality products. Consequently, the
• GC-MS/MS control of pesticide residue levels by the performance of
• Matrix Selectivity monitoring programs is currently an increasing concern
for producers, traders, and consumers.
• Multi-component The QuEChERS method is the most diffused analytical
analysis procedure for preparing samples of fruits and vegetables
• Pesticides while performing a multi-residues pesticides analysis in
combination with GC-MS and LC-MS systems.1-3 The
• Productivity analytical benefit of the QuEChERS method is the quick
• Quantitation procedure with only a short clean-up step to cover a wide
variety of polar and less polar pesticide compounds in a after evaporation of the acetonitrile extraction solvent.
• Timed-SRM multi-component approach. Due to the reduced clean-up 10 µL of a solution of Fenchlorphos (5 ppm in hexane) as
however, the produced sample extracts carry a high volumetric standard has been added before injection (1 µL).
concentration of vegetal matrix, that raise a particular A Thermo Scientific TSQ Quantum GC GC-MS/MS
challenge to the GC and MS systems. system with a Thermo Scientific TRACE GC Ultra gas
The application of structure selective MS/MS detection chromatograph and TriPlus AS liquid autosampler was
for the quantitation of pesticides residues using multiple used for analysis of the samples extracts, equipped and
reaction monitoring methods (MRM) in fruits and programmed for a Fast GC analysis method, using the
vegetables has been proven to overcome matrix effects.4-5 following analytical parameters.
The next challenge for commercial routine laboratories TRACE GC Ultra™ Conditions
is to increase sample throughput to keep pace with the
Carrier Gas: He, constant flow 1 mL/min
steady increase of the demand for food safety analysis.
Injector: PTV splitless mode with Siltek baffled liner 2 mm
In this work the Fast GC and tandem mass spectrometry ID (p/n 453T2120)
combination is presented as the analytical system to solve PTV Temp. Program: 70 °C, 0.02 min,
the requirement for matrix robustness with high sample 12 °C/s to 280 °C, 1.2 min,
throughput. The Fast GC-MS/MS analytical approach 14.5 °C/s to 320 °C, 6 min, clean flow 80 mL/min.
requires a robust, selective and sensitive instrumental Split: splitless injection, splitflow 50 mL/min at 1.3 min
system in order to quantify thousands samples/year with Column Type: Restek Rxi-5Sil MS, 20 m, 0.18 mm, 0.18 µm
short run times. The goal is to obtain a reliable pesticide (Restek p/n 43602)
compound detection and quantification at ppb levels while Transfer Line Temp.: 280 °C
avoiding breakdown phenomena for the more reactive GC Oven Program: 80 °C, 1.5 min
30 °C/min to 210 °C
compounds. The analytical setup and results for the screening
20 °C/min to 320 °C, 2 min
and quantitation of 233 pesticides in one Fast GC run is
described. For each pesticides compound 2 SRM transitions
TSQ Quantum GC™ Acquisition Parameter Setting
have been used to comply with EU regulations for compound
confirmation gaining 5 EU identification points.6 Source Temperature: 260 °C
Emission Current: 25 µA
Experimental Conditions Ionisation Mode: EI, 70 eV
Mass Resolution: Q1, Q3 at 0.7 Da (FWHM)
Sample Preparation Collision Gas: Ar, 1.5 mTorr
10 g of sample was processed in according with the Cycle Time: 0.30 s
QuEChERS procedures.1-3 In the clean-up step the Acquisition Mode: Timed-SRM
graphitized carbon black treatment was not utilized in
order to avoid the loss of planar compounds as there are Mass Table
the coplanar PCBs and pyrethroids. 1 mL of final volume 467 Timed-SRM transition/Fast GC run, see Table 1
of the extracts was reconstituted using acetone/hexane 1:1
Fast GC-MS/MS Data for Pesticide Standards (Table 1)
Precursor Product CE Rention Time Pesticide Precursor Product CE Rention Time Pesticide
212.02 182.02 10 8.09 Aclonifen 246.98 226.98 20 7.80 Chlorfenapyr
264.03 194.02 15 8.09 Aclonifen 248.98 228.98 20 7.80 Chlorfenapyr
181.02 152.04 25 8.85 Acrinathrin 174.98 110.98 10 7.62 Chlorfenson
208.05 181.04 8 8.85 Acrinathrin 301.96 174.98 10 7.62 Chlorfenson
161.07 146.06 12 6.54 Alachlor 266.98 158.99 15 7.09 Chlorfenvinphos-E+Z
188.08 160.07 10 6.54 Alachlor 322.97 266.98 15 7.09 Chlorfenvinphos-E+Z
292.91 222.92 20 6.94 Aldrin 220.04 166.03 23 8.38 Chloridazon
292.91 257.91 20 6.94 Aldrin 220.04 158.03 25 8.38 Chloridazon
293.19 147.10 15 9.24 Amitraz 153.98 120.98 5 4.72 Chlormephos
293.19 162.10 10 9.24 Amitraz 233.97 120.98 14 4.72 Chlormephos
215.09 200.09 10 5.95 Atrazine 263.88 167.92 25 6.18 Chlorothalonil
215.09 173.08 10 5.95 Atrazine 265.88 169.92 25 6.18 Chlorothalonil
132.01 77.01 20 9.43 Azinphos-ethyl 213.06 127.03 15 5.61 Chlorpropham
160.02 104.01 10 9.43 Azinphos-ethyl 213.06 171.04 10 5.61 Chlorpropham
132.02 77.02 20 9.15 Azinphos-Methyl 313.93 257.95 15 6.85 Chlorpyrifos-ethyl
160.03 104.02 10 9.15 Azinphos-Methyl 315.93 259.95 12 6.85 Chlorpyrifos-ethyl
344.10 329.10 20 10.96 Azoxystrobin 285.91 92.97 20 6.49 Chlorpyrifos-methyl
388.11 345.10 15 10.96 Azoxystrobin 285.91 270.91 25 6.49 Chlorpyrifos-methyl
234.12 174.09 10 8.24 Benalaxyl 300.91 222.93 25 6.90 Chlorthal-dimethyl
266.14 148.08 10 8.24 Benalaxyl 331.90 300.91 15 6.90 Chlorthal-dimethyl
166.06 151.06 15 3.94 Bendiocarb 259.01 188.01 15 7.15 Chlozolinate
223.08 166.06 15 3.94 Bendiocarb 188.01 147.01 20 7.15 Chlozolinate
292.10 160.05 21 5.63 Benfluralin 349.05 266.04 15 8.33 Clodinafop-propargyl
292.10 264.09 10 5.63 Benfluralin 349.05 238.04 15 8.33 Clodinafop-propargyl
164.08 149.07 10 9.35 Benfuracarb 304.01 138.01 10 9.54 Clofentezine
190.09 144.07 10 9.35 Benfuracarb 304.01 132.01 10 9.54 Clofentezine
180.91 144.93 15 5.82 BHC, A+B+C+D 321.00 304.00 22 7.51 Clorfluazuron
218.89 182.91 15 5.82 BHC, A+B+C+D 323.00 306.00 20 7.51 Clorfluazuron
154.08 152.08 15 4.51 Bifenil 251.02 139.02 22 7.97 Clorpropilato
154.08 153.08 15 4.51 Bifenil 253.01 139.00 15 7.97 Clorpropilato
181.05 141.04 22 8.77 Bifenthrin 226.01 198.00 12 9.72 Coumaphos
181.05 153.05 6 8.77 Bifenthrin 226.01 163.01 20 9.72 Coumaphos
170.09 115.06 25 9.62 Bitertanol 225.08 198.07 10 6.86 Cyanazine
170.09 141.07 20 9.62 Bitertanol 225.08 189.07 10 6.86 Cyanazine
342.01 140.01 20 10.12 Boscalid (Nicobifen) 206.03 151.02 20 9.90 Cyfluthrin
344.01 140.01 20 10.12 Boscalid (Nicobifen) 226.03 206.03 17 9.90 Cyfluthrin
328.86 313.87 20 7.04 Bromophos-methyl 181.04 152.03 23 9.22 Cyhalothrin, lambda
330.86 315.87 20 7.04 Bromophos-methyl 197.04 141.03 15 9.22 Cyhalothrin, lambda
358.89 302.91 20 7.38 Bromophos-ethyl 163.03 127.02 12 10.07 Cypermethrin+alfametrina
358.89 330.90 10 7.38 Bromophos-ethyl 181.03 152.03 17 10.07 Cypermethrin+alfametrina
340.96 184.98 15 8.81 Bromopropylate 222.09 125.05 20 7.89 Cyproconazole
342.96 184.98 20 8.81 Bromopropylate 224.09 127.05 20 7.89 Cyproconazole
273.14 193.10 10 7.73 Bupirimate 224.13 208.12 20 7.14 Cyprodinil
316.16 208.10 10 7.73 Bupirimate 225.13 210.12 18 7.14 Cyprodinil
104.94 104.00 9 7.75 Buprofezin 234.98 164.98 20 7.75 DDD, o,p
249.13 193.10 10 7.75 Buprofezin 236.98 164.98 20 8.05 DDD, o,p
174.12 146.10 10 4.67 Butylate (Sutan) 234.97 198.97 18 8.05 DDD, p,p
217.15 156.11 5 4.67 Butylate (Sutan) 234.97 164.98 20 7.75 DDD, p,p
149.96 78.98 15 8.58 Captafol 245.96 175.97 25 7.42 DDE o,p
310.92 78.98 10 8.58 Captafol 317.94 245.95 20 7.42 DDE o,p
123.05 79.03 15 4.95 Captafol-captan Met. (THPI) 245.95 175.97 25 7.68 DDE p,p
151.06 122.05 10 4.95 Captafol-captan Met. (THPI) 247.95 175.97 20 7.68 DDE p,p
148.97 69.98 8 7.30 Captan 234.95 164.96 15 7.74 DDT o,p
148.97 104.98 8 7.30 Captan 236.94 164.96 20 7.74 DDT o,p
164.01 149.00 10 5.91 Carbofuran 234.94 198.95 15 8.04 DDT p,p
221.01 164.00 5 5.91 Carbofuran 234.94 164.96 20 8.04 DDT p,p
341.97 156.99 10 8.27 Carbophenothion 252.93 171.95 10 10.89 Deltamethrin+Tralometrina
341.97 295.98 5 8.27 Carbophenothion 252.93 173.95 10 10.89 Deltamethrin+Tralometrina
330.03 310.03 20 8.20 Carfentrazone-ethyl 199.06 93.03 15 6.09 Diazinon
340.03 312.03 20 8.20 Carfentrazone-ethyl 304.10 179.06 15 6.09 Diazinon
372.81 265.87 15 7.47 Chlordane 222.98 204.98 10 6.43 Dichlofenthion
374.81 267.87 15 7.47 Chlordane 278.97 222.98 15 6.43 Dichlofenthion

Page 2 of 8
Precursor Product CE Rention Time Pesticide Precursor Product CE Rention Time Pesticide
223.97 122.99 15 6.79 Dichlofluanid 145.08 117.07 15 8.97 Fenazaquin
225.97 122.99 15 6.79 Dichlofluanid 160.09 117.07 20 8.97 Fenazaquin
205.97 175.97 10 5.92 Dichloran 129.04 102.03 15 9.91 Fenbuconazole
207.96 177.97 10 5.92 Dichloran 198.07 129.04 10 9.91 Fenbuconazole
184.95 92.98 17 3.82 Dichlorphos 284.82 269.97 12 6.61 Fenchlorphos (VS)
219.95 184.95 10 3.82 Dichlorphos 286.72 272.08 12 6.61 Fenchlorphos (VS)
270.07 159.04 15 7.80 Diclobutrazol 177.04 113.02 15 8.39 Fenhexamid
272.08 161.04 15 7.80 Diclobutrazol 301.06 97.02 15 8.39 Fenhexamid
138.97 110.97 20 6.98 Dicofol (1st, 2nd degr.) 277.02 109.01 8 6.72 Fenitrothion
250.94 138.97 15 6.98 Dicofol (1st, 2nd degr.) 277.02 260.02 10 6.72 Fenitrothion
276.92 206.93 20 7.83 Dieldrin 265.13 89.04 10 8.86 Fenpropathrin
276.92 240.92 10 7.83 Dieldrin 265.13 210.10 15 8.86 Fenpropathrin
267.15 225.12 8 6.83 Diethofencarb 145.13 117.11 10 6.72 Fenpropidin
267.15 168.09 10 6.83 Diethofencarb 274.25 98.09 10 6.72 Fenpropidin
323.05 265.04 15 10.75 Difenoconazole 1+2 128.11 70.06 15 6.89 Fenpropimorph
325.05 267.04 20 10.75 Difenoconazole 1+2 128.11 110.09 15 6.89 Fenpropimorph
266.05 246.05 10 8.48 Diflufenican 267.98 77.00 20 7.03 Fenson
394.07 266.05 10 8.48 Diflufenican 267.98 141.00 10 7.03 Fenson
125.00 79.00 15 5.92 Dimethoate 293.03 125.01 10 7.97 Fensulfothion
229.01 87.01 5 5.92 Dimethoate 293.03 97.01 16 7.97 Fensulfothion
301.10 165.05 10 11.04 Dimethomorph 1+2 278.02 109.01 18 6.88 Fenthion
387.12 301.10 12 11.04 Dimethomorph 1+2 278.02 169.01 20 6.88 Fenthion
268.06 232.05 15 8.02 Diniconazole 167.05 125.04 10 10.52 Fenvalerate 1+2
270.06 234.05 15 8.02 Diniconazole 419.13 225.07 10 10.52 Fenvalerate 1+2
305.08 244.07 15 6.17 Dinitramine 419.94 350.95 15 7.03 Fipronil
307.08 216.06 15 6.17 Dinitramine 421.94 352.95 15 7.03 Fipronil
167.09 165.09 20 7.04 Diphenamid 383.13 254.09 20 7.85 Fluazifop-P-butyl
239.13 167.09 10 7.04 Diphenamid 383.13 282.10 15 7.85 Fluazifop-P-butyl
167.10 166.09 25 5.51 Diphenylamine 388.90 352.20 12 7.72 Fluazinam
169.10 168.09 20 5.51 Diphenylamine 388.90 354.20 12 7.72 Fluazinam
142.01 109.01 10 6.20 Disulfoton 167.00 77.00 15 7.52 Flubenzimine
186.02 153.02 5 6.20 Disulfoton 186.00 77.00 25 7.52 Flubenzimine
271.03 243.03 5 7.51 Ditalimfos 199.07 107.04 22 10.14 Flucitrinate 1+2
299.04 243.03 10 7.51 Ditalimfos 199.07 157.06 10 10.14 Flucitrinate 1+2
273.88 238.89 15 7.54 Endosulfan A+B 248.04 154.02 20 7.60 Fludioxonil
271.88 236.89 15 7.54 Endosulfan A+B 248.04 182.03 15 7.60 Fludioxonil
280.91 244.92 5 8.07 Endrin 211.04 183.03 10 6.89 Flufenacet
344.88 280.90 8 8.07 Endrin 211.04 123.02 10 6.89 Flufenacet
192.04 138.03 10 8.26 Epoxiconazole 346.95 171.93 26 8.36 Fluopicolide
192.04 111.02 10 8.26 Epoxiconazole 346.95 176.02 26 8.36 Fluopicolide
128.08 86.05 5 4.35 EPTC 313.01 174.01 15 6.96 Fluorocloridone I+II
189.12 128.08 5 4.35 EPTC 313.01 187.01 15 6.96 Fluorocloridone I+II
245.04 173.03 15 8.00 Etaconazole 1+2 340.01 286.01 25 9.73 Fluquinconazole
245.04 191.03 10 8.00 Etaconazole 1+2 340.01 298.01 22 9.73 Fluquinconazole
230.99 129.01 20 8.03 Ethion 233.07 152.05 20 7.72 Flusilazole
230.99 174.99 15 8.03 Ethion 233.07 165.05 20 7.72 Flusilazole
202.14 145.10 20 5.91 Ethoxyquin 123.04 75.03 15 7.55 Flutriafol
202.14 174.12 15 5.91 Ethoxyquin 219.07 123.04 15 7.55 Flutriafol
163.09 135.07 10 10.21 Etofenprox 250.06 200.05 20 10.57 Fluvalinate tau
163.09 107.06 16 10.21 Etofenprox 252.06 200.05 20 10.57 Fluvalinate tau
158.04 130.03 10 5.53 Etoprofos 261.60 129.80 15 7.35 Folpet
200.05 158.04 10 5.53 Etoprofos 261.60 234.40 5 7.35 Folpet
210.93 182.94 15 4.78 Etridiazole (Terrazole) 146.98 103.24 15 4.86 Folpet met.
210.93 139.95 15 4.78 Etridiazole (Terrazole) 146.98 104.39 15 4.86 Folpet met.
292.06 153.03 10 6.21 Etrimfos 137.02 109.01 10 6.11 Fonofos
292.09 181.04 10 6.21 Etrimfos 246.03 137.02 10 6.11 Fonofos
238.08 209.07 20 8.88 Fenamidone 224.01 125.01 15 6.34 Formothion
238.08 237.08 20 8.88 Fenamidone 224.01 196.01 10 6.34 Formothion
288.10 260.09 10 7.54 Fenamiphos 242.11 95.04 15 7.26 Furalaxyl
303.11 260.09 15 7.54 Fenamiphos 301.13 225.10 10 7.26 Furalaxyl
139.01 111.01 15 9.38 Fenarimol 375.05 316.04 10 7.33 Haloxyfop-methyl
251.03 139.01 15 9.38 Fenarimol 375.05 288.04 20 7.33 Haloxyfop-methyl

Page 3 of 8
Fast GC-MS/MS Data for Pesticide Standards (Table 1 continued)
Precursor Product CE Rention Time Pesticide Precursor Product CE Rention Time Pesticide
273.87 238.88 15 6.63 Heptachlor 127.03 95.03 20 7.72 Monocrotophos
271.87 236.89 15 6.63 Heptachlor 192.05 127.03 10 7.72 Monocrotophos
182.91 154.93 15 7.26 Heptachlor epoxide B 179.07 125.05 15 3.82 Myclobutanil
134.93 98.95 15 7.26 Heptachlor epoxide B 179.07 90.00 30 7.58 Myclobutanil
352.83 262.87 15 7.23 Heptachlor epoxide A 109.00 79.00 12 7.58 Naled
352.83 281.86 16 7.23 Heptachlor epoxide A 128.07 72.04 10 7.91 Napropamide
124.01 89.01 10 5.26 Heptenophos 271.16 128.07 5 7.91 Napropamide
250.02 89.01 25 7.62 Heptenophos 201.99 138.99 21 8.48 Nitrofen
283.81 213.86 20 7.62 Hexachlorobenzene (HCB) 282.98 252.98 15 8.48 Nitrofen
283.81 248.84 20 7.47 Hexachlorobenzene (HCB) 235.05 139.03 15 5.09 Nuarimol
214.05 172.04 20 7.47 Hexaconazole 314.06 139.03 15 5.09 Nuarimol
214.05 187.04 15 5.26 Hexaconazole 170.07 115.05 20 7.68 Ortho-phenylphenol
184.05 149.04 10 7.62 Hexythiazox 170.07 141.06 20 7.68 Ortho-phenylphenol
227.07 149.04 10 7.62 Hexythiazox 258.05 175.04 10 8.02 Oxadiazon
173.00 145.00 20 10.79 Imazalil 304.06 260.05 10 8.02 Oxadiazon
175.00 147.00 16 10.79 Imazalil 163.07 117.05 40 7.71 Oxadixyl
203.03 106.01 20 8.72 Indoxacarb 163.07 132.06 10 7.71 Oxadixyl
203.03 134.02 20 8.72 Indoxacarb 300.03 223.02 10 7.46 Oxyfluorfen
314.03 245.03 15 8.00 Iprodione 361.03 300.03 12 7.46 Oxyfluorfen
316.03 247.03 15 8.00 Iprodione 236.10 125.06 15 7.01 Paclobutrazol
243.88 187.00 16 6.08 Iprodione degr. 236.10 167.07 15 7.01 Paclobutrazol
243.88 188.00 16 6.08 Iprodione degr. 149.03 119.02 10 6.19 Paraoxon-ethyl
213.07 121.04 17 7.05 Isofenphos 220.05 174.04 10 6.19 Paraoxon-ethyl
213.07 185.06 10 7.05 Isofenphos 230.02 136.01 10 6.92 Paraoxon-methyl
280.15 180.10 15 7.72 Isopropalin 230.02 200.02 10 6.92 Paraoxon-methyl
280.15 238.13 10 7.72 Isopropalin 291.03 109.01 15 6.53 Parathion-ethyl
131.06 116.05 20 8.34 Kresoxim-methyl 291.03 137.02 10 6.53 Parathion-ethyl
206.09 131.06 15 8.34 Kresoxim-methyl 262.99 109.00 15 7.18 Parathion-methyl
153.09 82.05 15 5.00 Lenacil 262.99 246.00 15 7.18 Parathion-methyl
153.09 136.08 15 5.00 Lenacil 248.06 157.04 25 5.75 Penconazole
175.99 120.99 20 4.60 Lufenuron 1 248.06 192.04 15 5.75 Penconazole
175.99 147.99 20 4.60 Lufenuron 1 125.05 89.04 12 7.12 Pencycuron
352.99 173.99 25 6.77 Lufenuron 2 180.07 125.05 12 7.12 Pencycuron
352.99 202.99 25 6.77 Lufenuron 2 252.13 162.08 12 9.64 Pendimethalin
173.02 99.01 10 8.60 Malathion 252.13 191.09 12 9.64 Pendimethalin
173.02 127.01 10 8.60 Malathion 183.04 153.03 15 7.24 Permethrin 1+2
253.04 190.03 20 7.49 Mefenpyr-diethyl 183.04 165.03 15 7.24 Permethrin 1+2
253.04 189.03 20 7.49 Mefenpyr-diethyl 274.03 246.02 10 5.75 Phenthoate
222.11 207.10 15 6.58 Mepanipyrim 274.03 121.01 7 5.75 Phenthoate
223.11 208.10 15 6.58 Mepanipyrim 231.01 203.01 10 9.11 Phorate
234.11 174.11 10 7.81 Metalaxyl 260.01 75.01 5 9.11 Phorate
249.13 190.10 10 7.81 Metalaxyl 181.99 111.00 15 8.79 Phosalone
202.09 174.07 5 7.11 Metamitron 366.99 181.99 10 8.79 Phosalone
202.09 186.08 10 7.11 Metamitron 160.01 77.01 20 6.40 Phosmet
133.05 117.04 20 5.71 Metazachlor 160.01 133.01 15 6.40 Phosmet
209.07 132.05 12 5.71 Metazachlor 227.05 127.03 15 6.29 Phosphamidon I+II
164.05 136.04 20 7.38 Methabenzthiazuron 264.06 127.03 15 6.29 Phosphamidon I+II
164.05 135.04 20 7.38 Methabenzthiazuron 166.10 137.08 10 7.00 Pirimicarb
144.98 57.99 15 8.48 Methidathion 238.14 166.10 15 7.00 Pirimicarb
144.98 84.99 10 8.48 Methidathion 304.12 168.06 15 6.68 Pirimiphos-ethyl
227.01 169.01 20 6.85 Methoxychlor I 333.13 318.12 15 6.68 Pirimiphos-ethyl
227.01 212.01 15 6.85 Methoxychlor I 290.09 233.07 10 9.76 Pirimiphos-methyl
162.08 133.06 15 6.48 Metolachlor 305.10 290.09 15 9.76 Pirimiphos-methyl
238.11 162.08 15 6.48 Metolachlor 180.01 138.01 15 7.29 Prochloraz
198.08 82.03 20 4.64 Metribuzin 308.03 70.01 10 7.29 Prochloraz
198.08 110.05 20 4.64 Metribuzin 283.02 255.02 10 7.66 Procymidone
127.04 109.02 10 9.37 Mevinphos 285.02 257.02 10 7.66 Procymidone
192.04 127.03 12 9.37 Mevinphos 336.94 266.95 20 6.01 Profenofos
269.81 234.84 15 5.18 Mirex 338.94 268.95 20 6.01 Profenofos
271.81 236.84 15 5.18 Mirex 318.10 198.05 15 5.91 Profluralin
126.07 55.03 10 5.67 Molinate (Ordram) 330.10 302.10 5 5.91 Profluralin
187.10 126.07 10 5.67 Molinate (Ordram) 225.16 183.13 10 6.60 Prometon

Page 4 of 8
Precursor Product CE Rention Time Pesticide Precursor Product CE Rention Time Pesticide
225.16 210.15 10 6.60 Prometon 145.00 117.00 10 8.91 tebufenozide
226.13 184.10 12 5.43 Prometryn 160.00 145.00 15 8.91 tebufenozide
241.15 184.10 15 5.43 Prometryn 276.13 171.08 15 5.35 Tebufenpyrad
176.06 120.04 10 6.44 Propachlor 318.15 145.07 15 5.35 Tebufenpyrad
196.07 120.04 10 6.44 Propachlor 260.88 202.90 15 6.19 Tecnazene
217.01 161.00 10 8.49 Propanil 258.88 200.90 15 6.19 Tecnazene
219.01 163.00 10 8.49 Propanil 177.02 127.02 20 6.07 Tefluthrin
135.06 107.05 15 6.03 Propargite 197.03 141.02 15 6.07 Tefluthrin
173.08 105.05 12 6.03 Propargite 231.04 175.03 15 6.02 Terbufos
236.07 166.05 15 4.79 Propetamphos 231.04 203.03 10 6.02 Terbufos
236.07 194.06 5 4.79 Propetamphos 214.10 104.05 10 6.70 Terbuthylazine
137.07 93.05 8 8.30 Propham 214.10 132.06 10 6.70 Terbuthylazine
179.09 93.05 15 8.30 Propham 241.14 185.10 10 7.42 Terbutryn
259.02 173.02 20 5.41 Propiconazole 1+2 241.14 170.10 15 7.42 Terbutryn
261.02 175.02 20 5.41 Propiconazole 1+2 328.91 108.97 22 6.89 Tetrachlorvinphos
110.00 64.00 10 6.10 Propoxur 330.91 108.97 22 6.89 Tetrachlorvinphos
152.00 110.00 10 6.10 Propoxur 336.02 218.01 20 9.06 Tetraconazole
145.01 109.01 15 7.63 Propyzamide 336.02 204.01 20 9.06 Tetraconazole
173.01 109.01 18 7.63 Propyzamide 226.93 198.94 18 8.72 Tetradifon
266.97 238.97 10 10.56 Prothiofos 355.88 228.93 10 8.72 Tetradifon
308.97 238.97 5 10.56 Prothiofos 164.09 107.06 17 6.55 Tetramethrin
132.03 77.02 15 9.33 Pyraclostrobin 164.09 135.07 10 6.55 Tetramethrin
325.08 132.03 20 9.33 Pyraclostrobin 264.96 92.99 20 7.20 Tolclofos-methyl
221.05 193.04 10 9.74 Pyrazophos 264.96 249.96 15 7.20 Tolclofos-methyl
232.05 204.05 10 9.74 Pyrazophos 238.09 137.05 15 6.93 Tolylfluanid
147.06 117.04 20 8.69 Pyridaben 240.09 137.05 15 6.93 Tolylfluanid
309.12 147.06 15 8.69 Pyridaben 208.07 111.04 25 7.28 Triadimefon
340.06 109.02 10 7.20 Pyridaphenthion 208.07 181.06 10 7.28 Triadimefon
340.06 199.04 10 7.20 Pyridaphenthion 128.05 100.04 10 8.15 Triadimenol
262.03 192.02 20 6.16 Pyrifenox 1+2 168.06 70.03 10 8.15 Triadimenol
262.03 200.02 20 6.16 Pyrifenox 1+2 161.03 105.02 13 3.82 Triazophos
198.11 118.07 35 7.25 Pyrimethanil 257.05 162.03 10 3.82 Triazophos
198.11 183.10 15 7.25 Pyrimethanil 161.94 160.93 8 7.69 Triciclazole
146.03 91.02 15 8.34 Quinalphos 188.98 160.93 20 7.69 Triciclazole
146.03 118.02 15 8.34 Quinalphos 116.04 89.03 15 8.24 Trifloxystrobin
237.05 208.00 20 6.03 Quinoxyfen 131.04 130.04 10 8.24 Trifloxystrobin
272.01 237.00 20 6.03 Quinoxyfen 306.10 160.05 15 5.61 Trifluralin
292.84 234.87 15 6.68 Quintozene (PCNB) 306.10 264.09 15 5.61 Trifluralin
294.84 236.87 20 6.68 Quintozene (PCNB) 145.02 87.01 10 7.43 Vamidothion
129.93 94.95 22 8.53 S421 145.02 112.02 10 7.43 Vamidothion
131.93 96.95 22 8.53 S421 284.97 212.00 15 6.51 Vinclozolin
178.01 81.00 24 5.65 Sethoxydim 286.97 214.00 15 6.51 Vinclozolin
178.01 107.95 21 5.65 Sethoxydim 187.01 159.01 15 7.67 Zoxamide
202.01 146.01 15 7.31 Sulfotep 258.02 187.01 15 7.67 Zoxamide
322.02 202.01 15 7.31 Sulfotep 187.02 159.01 15 7.30 Zoxamide-metab.
255.78 159.87 12 8.50 Sulphur 242.01 214.01 15 7.30 Zoxamide-metab.
255.78 95.83 24 8.50 Sulphur Table 1: 467 Timed-SRM transitions used in one run for pesticide compound
250.12 125.06 20 8.97 Tebuconazole detection and quantitation
252.12 127.06 20 8.97 Tebuconazole

Sample Measurements
More than 3,500 samples were analysed in 6 months. meets the optimum acquisition conditions for each
A weekly calibration curve for each of the pesticide compound by only monitoring the pesticides compound
components in the assay and volumetric standard in a small window around the compound retention time.
quantification has been performed. With a short retention time window of 18 seconds for
Figure 1 shows the highly overlapped elution of the every compound, even in the highest density elution zone,
compounds in a single run. The SRM distribution in there are up to 80 SRM scans with a scan time lower than
Figure 2 shows the typical low homogeneity of the retention 4 ms. For the other areas of the chromatogram, scan times
time distribution of a Fast GC run. The unique acquisition of up to 30 ms are resulting.
mode “Timed-SRM” of the TSQ Quantum series instruments

Page 5 of 8
 RT: 1.99 - 11.34
4.52
100 4.53

90

80

70
5.93
60
4.54 9.62
50 5.92
9.62
9.72
10.14
40 5.11 8.79
5.54
6.45 6.56 8.33 8.79
30
7.05 7.62

20
10.51
10
3.81
3.72
0
2 3 4 5 6 7 8 9 10 11
Time (min)
Figure 1: Highly overlapped elution of the compounds in a single run

450

400

350
Precursor (m/z)

300

250

200

150

100
3 4 5 6 7 8 9 10 11 12
RT (min)
Figure 2: Timed-SRM distribution during the Fast GC chromatography

Page 6 of 8
Figure 3: Calibration curve and integrated peak area of the lowest level (5 ppb) in apple matrix (Dichlorvos, Mevinphos, Propargite, Quinoxifen)

Results With the Timed-SRM acquisition setting the two mass

Figure 3 shows the operative calibration curves and separating quadrupoles Q1 and Q3 increase the efficiency
integrated peak area of the lowest calibration level (5 ppb) of sampling with only short acquisition windows around
in apple matrix. The correlation factor of the linear the expected compound retention time of every eluted
calibration was always higher than 0.9950. A great compound. This acquisition mode is ideally suited for
sensitivity could be shown at the 5 ppb level with a S/N Fast GC separations.
better than 15 for the compounds investigated.
RT: 7.60 - 7.90
The analysis was run at the increased mass resolution MA: 32850
100
set to 0.7 Da peak width (FWHM) in Q1 and Q3. The
hyperbolic rods of the mass separating quadrupoles produce 90

a high precision quadrupolar electrical field that allow a

80
high ion transmission coupled with increased selectivity
against the unspecific matrix of the extracts. The curved 70

square rods of the collision cell provide increased efficiency

60
of the fragmentation especially with high ion transmission
for high sensitivity. The often observed high background of 50

neutral compounds is efficiently removed by the 90° bended

40
collision cell and the off axis multiplier for low noise
detection with high S/N values at low pesticides 30

concentrations in these matrix samples.

20
For the large number of pesticide compounds in a
Fast GC separation Figure 4 shows the sampling rate with 10

the chromatographic profile of Flusilazole at the lowest

0
calibration point of 5 ppb in apple matrix. The high statistics 7.65 7.70 7.75 7.80 7.85
Time (min)
of sampling is the instrumental characteristics that allow
the high repeatability and precision of peak integration. Figure 4: Flusilazole at 5 ppb in apple matrix

Page 7 of 8
 Figure 5 shows the superimposed chromatographic As one of the compounds with most critical In addition to these
profiles of 5 repeated injections of Flucythrinate at 5 ppb chromatographic behavior, Figure 6 shows the elution offices, Thermo Fisher
in apricot matrix. The coefficients of variation (CV%) of profile of Iprodione at the 15 ppb level in an onion sample. Scientific maintains
the area integration was in the range and below of 10%. A very symmetrical peak shape is associated with a very a network of represen-
These results demonstrate the compatibility of the Fast good sensitivity demonstrating the inertness and integrity tative organizations
GC solution with the TSQ Quantum GC for a true fast of the chromatographic system from injector to transfer throughout the world.
and reliable quantification. line and ion source. The high speed of the analysis
additionally decreases the residence.
RT: 10.18 - 10.51
100 Conclusion
90
With the described method, a very good linearity, Africa-Other
sensitivity and robustness have been obtained at the +27 11 570 1840
sensitivity levels required for being fully compatible with Australia
80 +61 3 9757 4300
the reliable quantification of pesticides in vegetal matrix, Austria
70 with very limited breakdown phenomena and without any +43 1 333 50 34 0
tailing chromatographic peaks. Belgium
60
+32 53 73 42 41
The Fast GC-MS approach using the TSQ Quantum Canada
GC-MS/MS system is not only a faster method to obtain +1 800 530 8447
50
high throughput of analysis, but also the productive China
+86 10 8419 3588
40
solution to improve the general quality of the analytical
Denmark
results. The Thermo Fisher TSQ Quantum GC-MS/MS +45 70 23 62 60
30 system has proven to provide fast data acquisition for Europe-Other
+43 1 333 50 34 0
reliable integration of short Fast GC peaks with high
Finland / Norway /
20 selectivity and sensitivity. Sweden
+46 8 556 468 00
10 References France
+33 1 60 92 48 00
1. Efficient sample preparation and clean-up using the QuEChERS Method, Germany
0 Thermo Scientific Product Information, BRO-GSC-QUECHERS-1108, 2008. +49 6103 408 1014
10.2 10.3 10.4 10.5
2. QuEChERS, European Standard, EN 15662 India
Time (min)
+91 22 6742 9434
3. M. Anastassiades, S. J. Lehotay, D. Stajnbaher, F. J. Schenck: Fast and
Figure 5: 5 injections of Flucythrinate at 5 ppb in apricot matrix Easy Multiresidue Method Employing Acetonitile Extraction/Partitioning Italy
and “Dispersive Solid-Phase Extraction” for the Determination of Pesticide +39 02 950 591
Residues in Produce, J. AOAC Int., 86 (2003) 412-431 Japan
RT: 8.30 - 9.10 SM: 7G
RT: 8.69
+81 45 453 9100
MA: 10499 5 4. M. Hetmanski, High sensitivity multi-residue pesticide analyses in foods
100
T Latin America
S
using the TSQ Quantum GC-MS/MS, presented at RAFA conference,
95 3
[
+1 561 688 8700
90 2 Prague, Nov 2009.
85
0
Middle East
5. B. Chen, A. Huang, et al., Timed SRMs method on a GC triple quad +43 1 333 50 34 0
80

75
mass spectrometer for pesticides, presented at the CRC Conference, Sydney, Netherlands
70
Oct 2009. +31 76 579 55 55
65
6. Commission Directive of 12 August 2002, implementing Council Directive New Zealand
60
96/23/EC concerning the performance of analytical methods and the +64 9 980 6700
55
interpretation of results, Official Journal of the European Communities L Russia/CIS
50

45
221/9, 17.8.2002. +43 1 333 50 34 0
40 South Africa
35 +27 11 570 1840
30
Spain
25 +34 914 845 965
20
Switzerland
15
+41 61 716 77 00
10

5 UK
0
+44 1442 233555
8.4 8.5 8.6 8.7 8.8 8.9 9.0 9.1
Time (min) USA
+1 800 532 4752
Figure 6: Iprodione at 15 ppb in onion sample

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