fast multi-component pesticide analysis the world leader ... · 5 wctow, saskatoon, april 30, 2008...

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The world leader in serving science Fast Multi-Component Pesticide Analysis with GC-MS/MS Hans-Joachim Huebschmann GC/MS Technology Manager WCTOW, Saskatoon, April 30, 2008 WCTOW, Saskatoon, April 30, 2008 Multi-Residue GC-MS/MS Analysis - Overview TSQ Quantum GC • Analyzer Design • Hyperbolic Quadrupoles • Triple Quad Operation MS/MS Confirmation Applications Pesticides in Food Dioxins/Furans, dl-PCBs Conclusions • From Screening to Confirmation

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Page 1: Fast Multi-Component Pesticide Analysis The world leader ... · 5 WCTOW, Saskatoon, April 30, 2008 Quinoxyfen in Hops using SIM and MS/MS RT: 17.13 - 27.39 18 19 20 21 22 23 24 25

1

The world leader in serving science

Fast Multi-Component Pesticide Analysis

with GC-MS/MS

Hans-Joachim HuebschmannGC/MS Technology Manager

WCTOW, Saskatoon, April 30, 2008

WCTOW, Saskatoon, April 30, 2008

Multi-Residue GC-MS/MS Analysis - Overview

TSQ Quantum GC• Analyzer Design• Hyperbolic Quadrupoles• Triple Quad Operation• MS/MS Confirmation

Applications • Pesticides in Food• Dioxins/Furans, dl-PCBs

Conclusions• From Screening

to Confirmation

Page 2: Fast Multi-Component Pesticide Analysis The world leader ... · 5 WCTOW, Saskatoon, April 30, 2008 Quinoxyfen in Hops using SIM and MS/MS RT: 17.13 - 27.39 18 19 20 21 22 23 24 25

2

WCTOW, Saskatoon, April 30, 2008

Inside the TSQ Quantum GC

Q1

Q3

Collision Cell (Q2)

Conversion Dynode + MultiplierTurbo

DuraBriteTM

Ion Source

WCTOW, Saskatoon, April 30, 2008

* Patented HyperQuad™ Advantage available with TSQ Discovery

Technology Leadership with Hyperbolic Quadrupoles

TSQ 70001993 to 2000

r0 = 4 mmL = 250 mm

TSQ Quantum*2001 to …

r0 = 4/6 mmL = 250 mm

Why Hyperbolic Quadrupoles ?• Same basic design as predecessor TSQ 7000.• True hyperbolic pole face with high-precision• Improved Ion Transmission Sensitivity

• Large field radius - TSQ Quantum GC 4 mm• Unique length of 250 mm• Improved Resolution Selectivity

Page 3: Fast Multi-Component Pesticide Analysis The world leader ... · 5 WCTOW, Saskatoon, April 30, 2008 Quinoxyfen in Hops using SIM and MS/MS RT: 17.13 - 27.39 18 19 20 21 22 23 24 25

3

WCTOW, Saskatoon, April 30, 2008

TSQ Quantum GC – Standard Resolution at 0.7 Da FWHM

m/z 300/ 0.7 = R 428

m/z 500/ 0.7 = R 714

m/z 1000/ 0.7 = R 1428

0.7 u1.0 u

2.0 u

Only TSQ Quantum GC

Former technologies open upQ1 resolution to a multiple

of unit resolution to increaseion transmission

but severely sacrifice selectivity.

3.0 u

WCTOW, Saskatoon, April 30, 2008

m/z 300/ 0.4 = R 750

m/z 500/ 0.4 = R 1,250

m/z 1000/ 0.4 = R 2,500

m/z 3000/0.4 = R 7,500

0.4 u

H-SRM ModeOnly TSQ Quantum GC

TSQ Quantum GC – H-SRM Resolution at 0.4 Da FWHM

Page 4: Fast Multi-Component Pesticide Analysis The world leader ... · 5 WCTOW, Saskatoon, April 30, 2008 Quinoxyfen in Hops using SIM and MS/MS RT: 17.13 - 27.39 18 19 20 21 22 23 24 25

4

WCTOW, Saskatoon, April 30, 2008

Exit lensassembly

Entrance lensassembly,

controls collisionenergy

Collision cell housing, Argon, ca. 4 mTorr

Square quadrupolecollision cell

TSQ Quantum GC - The Innovative Collision Cell

Square Quad Collision CellHigh Speed + High Sensitivity:Improved SRM Efficiency

• 5 x higher than former octapole cells• 185 mm long ion path

No Neutral Noise• 90 Degree

Memory Eliminated• Active „cleaning“• No false positives at low LOQ

WCTOW, Saskatoon, April 30, 2008

Parathion – Structure Specific Selectivity

(mainlib) Parathion10 20 30 40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 210 220 230 240 250 260 270 280 290 300

0

50

100

15

29

39 45

65

75

81

97 109

125

139

150

155

172

186

201

218

235

246

263

275

291

N

O

OO

P

O

SO

Nominal mass axis

M+ m/z 291

MS/MSPrecursor

MS/MSProduct Ion

m/z 109C2H6OPS+

Page 5: Fast Multi-Component Pesticide Analysis The world leader ... · 5 WCTOW, Saskatoon, April 30, 2008 Quinoxyfen in Hops using SIM and MS/MS RT: 17.13 - 27.39 18 19 20 21 22 23 24 25

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WCTOW, Saskatoon, April 30, 2008

Quinoxyfen in Hops using SIM and MS/MSRT: 17.13 - 27.39

18 19 20 21 22 23 24 25 26 27Time (min)

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ndan

ceRT: 23.76

24.01

25.5223.55 24.11 24.55 25.3523.2822.9722.52 25.6522.17 25.87 26.45 26.7821.6721.3021.0920.4020.27

RT: 23.76

25.37

23.5327.3522.93

26.6220.19 23.43 24.55 25.4824.6721.25 26.2622.41 24.0220.57 22.1719.61

RT: 23.76

24.5923.13 24.17 25.18 25.3422.93 27.0926.31 26.4623.37

21.89 22.5221.6721.1520.5719.65 20.15

RT: 23.77

RT: 23.77

NL: 6.37E4m/z= 236.50-237.50 F: + c SIM ms [236.50-237.50, 271.50-272.50, 306.50-307.50] MS probe20f_sim

NL: 2.67E4m/z= 271.50-272.50 F: + c SIM ms [236.50-237.50, 271.50-272.50, 306.50-307.50] MS probe20f_sim

NL: 9.94E3m/z= 306.50-307.50 F: + c SIM ms [236.50-237.50, 271.50-272.50, 306.50-307.50] MS probe20f_sim

NL: 6.10E5m/z= 207.50-208.50 F: + c EI SRM ms2 237.000 [207.999-208.001] MS Genesis Probe20F

NL: 1.06E6m/z= 236.50-237.50 F: + c EI SRM ms2 272.000 [236.999-237.001] MS Genesis Probe20F

DSQII

Single Quad

SIM Mode

TSQ Quantum GC

Triple Quad

MS/MS (SRM Mode)

Superior Selectivity

Free from sample matrix

WCTOW, Saskatoon, April 30, 2008

TSQ Quantum GC: Selected Reaction Monitoring

Purpose of SRM: Quantitation on a single product ion, no spectrum

Park Q1 on precursor ione.g. Parathion m/z 291

Park Q3 on product ionSRM on m/z 109

“Monitor a Transition”from Precursor in Q1 to Product Ion in Q3

Page 6: Fast Multi-Component Pesticide Analysis The world leader ... · 5 WCTOW, Saskatoon, April 30, 2008 Quinoxyfen in Hops using SIM and MS/MS RT: 17.13 - 27.39 18 19 20 21 22 23 24 25

6

WCTOW, Saskatoon, April 30, 2008

QED MS/MS for Full Scan Substance Confirmation

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9.8 10.0 10.2 10.4 10.6

min

RT:10.0

m/z

Inte

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SRM data point

SRM chromatogram MS/MS spectrum

Set level closeto MRPL

concentration

WCTOW, Saskatoon, April 30, 2008

TSQ Quantum GC: QED - SRM Switched to MSMS

Purpose: Confirmation of a positive result

Library Search for Identification

Park Q1 on precursor ione.g. Parathion m/z 291

Scan Q3 for the fullproduct ion spectrum

Page 7: Fast Multi-Component Pesticide Analysis The world leader ... · 5 WCTOW, Saskatoon, April 30, 2008 Quinoxyfen in Hops using SIM and MS/MS RT: 17.13 - 27.39 18 19 20 21 22 23 24 25

7

WCTOW, Saskatoon, April 30, 2008

RER – Information Rich Product Ion Spectra

RERReverse Energy Ramp

17Oct04 #204-214 RT: 1.78-1.85 AV: 5 NL: 1.06E6F: + c ESI sid=7.00 Full ms2 [email protected] [30.000-190.000]

40 60 80 100 120 140 160 180m/z

0

20

40

60

80

100Re

lativ

e Abu

ndan

ce143.0

184.1166.2147.9

17Oct02 #104-111 RT: 1.75-1.87 AV: 8 NL: 8.07E4T: + c ESI sid=7.00 Full ms2 [email protected] [30.000-190.000]

40 60 80 100 120 140 160 180m/z

0

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100

Rela

tive

Abun

danc

e

143.0

124.995.1

94.1 184.1

148.3111.149.5 167.479.164.3 129.3

コリジョンエネルギー

(eV

)

30

40

20

10

17Oct04 #203-213 RT: 1.77-1.84 AV: 5 NL: 5.12E4F: + c ESI sid=7.00 Full ms2 [email protected] [30.000-190.000]

40 60 80 100 120 140 160 180m/z

0

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80

100

Rel

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ndan

ce

95.1

125.094.2

148.098.349.5

110.5 143.055.6 92.178.9 165.5

Colligion Energy

10 eV

Colligion Energy

30 eV

RER Spectrum – High to Low eV

The world leader in serving science

Multi-Component Analysis of Pesticides

using H-SRM

Kuniyo SugitateThermo Fisher, Yokohama, Japan

Inge de DobeleerInterscience, Breda, Netherlands

Page 8: Fast Multi-Component Pesticide Analysis The world leader ... · 5 WCTOW, Saskatoon, April 30, 2008 Quinoxyfen in Hops using SIM and MS/MS RT: 17.13 - 27.39 18 19 20 21 22 23 24 25

8

WCTOW, Saskatoon, April 30, 2008

Worldwide Impact of Japanese Positive List

WCTOW, Saskatoon, April 30, 2008

Multi-Residue Analysis: Method for > 200 Pesticides Pesticide Compound seg RT Precursor Product 1 Product 2 Coll EDiflubenzuron (degradation: iso-cyanaat) 1 8.00 153.00 90.00 124.95 20Diflubenzuron (degradation: aniline) 1 8.56 126.90 65.03 99.93 30Methamidofos 1 8.77 141.00 95.01 79.98 10Dichloorvos 1 8.92 184.98 93.01 12Trichloorfon 1 8.92 109.00 79.00 20Teflubenzuron (degradation: iso-cyanaat) 1 9.03 223.10 159.88 194.88 20Dichlobenil 1 9.75 170.96 99.98 135.96 20Teflubenzuron (degradation: aniline) 1 9.95 197.00 134.88 25Lufenuron (degradation: iso-cyanaat) 1 10.20 353.00 202.85 173.86 25Mevinfos 1 10.25 192.02 127.02 10Etridiazole 1 10.54 210.95 139.87 182.88 15Fthalimide (=degradation folpet) 1 10.59 147.03 103.00 76.00 10Tetrahydroftalimide (=degr.captan/c.fol) 1 10.76 151.06 79.00 122.00 10Lufenuron (degradation: aniline) 1 10.97 176.00 147.93 120.84 20Fenylfenol-2 (= orthofenylfenol) 1 11.09 170.00 169.00 141.00 20Tecnazeen 2 11.96 260.90 203.00 15Difenylamine 2 12.06 169.06 168.08 20Ethoprofos . 2 12.12 200.00 114.00 158.00 10Chloorprofam 2 12.27 213.06 171.00 127.00 5Trifluralin 2 12.45 306.07 264.02 160.00 15Pentachlooranisole 3 13.29 277.86 234.85 20Ethoxyquin 3 13.23 202.10 159.00 145.00 20Dichloran 3 13.27 205.97 175.93 10Profluralin 3 13.70 318.20 198.20 15Terbutylazin 3 13.73 214.09 132.00 10Lindane (gamma-HCH) 3 13.78 216.91 180.94 15Propyzamide 3 13.81 254.10 225.98 15Quintozeen 3 13.89 292.84 234.85 262.88 15Diazinon 3 13.96 179.12 137.05 15Tefluthrin 3 14.15 197.03 141.01 161.00 10Anthraceen (IS) 3 14.17 178.20 150.00 40.00Paraoxon-methyl 3 14.19 230.02 200.00 136.00 10Etrimfos 4 14.34 292.06 181.00 153.00 10Chloorthalonil 4 14.46 265.88 169.88 132.88 20Dichlofenthion 4 15.01 279.00 222.94 15Formothion 4 14.73 171.98 92.98 5Metribuzin 4 15.11 198.06 82.07 110.02 20Vinchlozoline 4 15.26 285.00 212.00 178.00 10Chloorpyrifos-methyl 4 15.32 285.93 93.00 270.90 20Parathion-methyl 4 15.31 263.00 246.00 108.99 10Tolclofos-methyl 4 15.45 264.99 249.96 93.00 15Paraoxon ethyl 4 15.60 275.06 149.00 247.00 5Pirimifos-methyl 4 16.03 305.09 290.07 276.05 10Methiocarb 4 16.04 168.06 153.04 109.03 15Fenithrothion 4 16.05 277.02 260.01 108.99 8Diethofencarb 4 16.36 225.00 125.00 15Chloorpyrifos-ethyl 4 16.64 313.96 257.85 12Parathion-ethyl 4 16.67 291.03 108.99 15Triadimefon 4 16.73 208.03 181.02 10Dichloorbenzofenon(4,4-) (=degr.dicofol) 4 16.77 139.00 111.00 15Chloorthaldimethyl 4 16.82 300.86 272.89 222.91 20

Pesticide Compound seg RT Precursor Product 1 Product 2 Coll EBromofos-methyl 5 17.21 330.88 315.82 15Fluazinam (degradation 2) 5 17.65 417.80 317.90 20.00Pirimifos-ethyl 5 17.22 333.13 168.00 188.00 20Chloorfenvinfos (alfa-) 5 17.49 323.00 267.00 10Pendimethalin 5 17.62 252.10 191.00 162.00 15Penconazool 5 17.66 248.10 192.00 157.00 15Chlozolinaat 5 17.20 188.00 147.00 20Pyrifenox I 5 17.75 262.20 200.00 192.00 20Thiabendazool 5 17.85 201.04 174.00 15Fipronil 5 17.86 366.90 212.95 254.90 25Chloorfenvinfos (beta-) 5 17.86 323.00 267.00 10Mecarbam 5 17.88 329.05 131.00 160.00 10Chloorbromuron 5 17.71 294.01 61.05 10Captan 5 17.97 148.88 105.00 70.00 8Triadimenol I 5 17.98 168.00 70.00 5Fenthoaat 5 17.98 273.99 124.98 120.98 7Procymidon 6 18.18 283.02 254.99 96.06 15Triadimenol II 6 18.19 168.00 70.00 5Folpet 6 18.17 259.93 125.00 232.90 10Triflumizool 6 18.20 278.06 73.10 188.00 15Chlordane I 6 18.46 372.83 266.00 15DDE (o,p) 6 18.57 317.94 245.95 20Pyrifenox II 6 18.56 262.20 200.00 192.00 20Endosulfan (alfa-) 6 18.85 195.00 159.00 15Chlordane II 6 18.93 372.83 266.00 15Ditalimfos 6 18.95 271.01 243.01 10Triforine 6 ? 288.00Hexaconazool 6 19.20 214.03 171.95 20Prothiofos 6 19.31 266.95 238.89 10Imazalil 6 19.32 173.00 145.00 20Fludioxonil 7 19.48 248.04 182.01 15DDE (p,p) 7 19.54 317.94 245.95 20Dieldrin 7 19.68 276.90 206.90 20Myclobutanil 7 19.76 179.06 125.10 152.12 15DDT (o,p) 7 21.03 235.01 165.07 15Flusilazool 7 19.85 233.06 165.04 152.05 20Kresoxim-methyl 7 19.96 206.05 131.05 116.03 15Fluazinam (degradation 1) 7 20.10 418.00 372.00 20Chloorfenapyr 8 20.35 246.90 226.96 20Endrin 8 20.39 262.86 190.90 25Chloorbenzilaat 8 20.56 251.00 139.00 15Endosulfan (beta-) 8 20.68 195.00 159.00 15DDT (p,p) 8 22.14 235.01 165.07 15DDD (o,p) 8 19.84 235.01 165.07 15Oxadixyl 8 21.07 163.10 132.09 10Mepronil 8 21.28 269.14 210.10 199.10 10

Pesticide Compound segEpoxiconazool I 9Benalaxyl 9Quinoxyfen 9Endosulfan-sulfaat 9Methoxychloor I 9DDD (p,p) 9Dicofol (1st degradation) 9Propargiet I 9Propargiet II 9Triphenylphosphate (IS) 9Piperonyl-butoxide 9Captafol 9Epoxiconazole II 9Methoxychloor II 9Iprodion 9Pyridafenthion 9Broompropylaat 9Bifenthrin 9Fenpropathrin 10Methoxychloor III 10Tetradifon 10Fosalone 10Pyriproxyfen 10Cyhalothrin (lambda-) I 10Cyhalothrin (lambda-) II 10Dicofol 10Fenarimol 10Pyrazofos 10Permethrin (cis-) 11Permethrin (trans-) 11Pyridaben 11Fluquinconazool 11Cyfluthrin I 11Fenbuconazool 11Cyfluthrin II 11Cyfluthrin III 11Cyfluthrin IV 11Cypermethrin I 11Cypermethrin II 11Cypermethrin III 11Cypermethrin IV 11Flucythrinaat I 11Flucythrinate II 11Fenvaleraat 12Fluvalinaat I 12Fluvalinaat II 12Difenoconazool I 12Difenoconazool II 12Indoxacarb 12Deltamethrin 12Famoxadone 12

Page 9: Fast Multi-Component Pesticide Analysis The world leader ... · 5 WCTOW, Saskatoon, April 30, 2008 Quinoxyfen in Hops using SIM and MS/MS RT: 17.13 - 27.39 18 19 20 21 22 23 24 25

9

WCTOW, Saskatoon, April 30, 2008

Speed - Segments with > 100 Transitions/Segment

Adjusted byusing a standardchromatogram

EXTREMELY FAST !!

min. Cycle Time 2 ms

up to 500 Transitions/s

WCTOW, Saskatoon, April 30, 2008

Sensitivity - 1 ppb in Green Pepper (1.2 pg on column)green-paprika_spiked_1ppb 2007/03/29 15:57:47 green-paprika_spiked_1ppbRti-5MS scan time 0.010 SETTIME=0.001

RT: 15.32 - 18.40 SM: 5G

16 17 18Time (min)

0

50

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50

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50

1000

50

1000

50

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10015.82

15.84

16.25

16.43

16.7618.19

16.86

NL: 2.71E4TIC F: + c CI SRM ms2 [email protected] [207.999-208.001] MS green-paprika_spiked_1ppb

NL: 9.50E4TIC F: + c CI SRM ms2 [email protected] [428.999-429.001] MS green-paprika_spiked_1ppb

NL: 3.54E4TIC F: + c CI SRM ms2 [email protected] [154.999-155.001] MS green-paprika_spiked_1ppb

NL: 2.09E5TIC F: + c CI SRM ms2 [email protected] [138.999-139.001] MS green-paprika_spiked_1ppb

NL: 2.12E5TIC F: + c CI SRM ms2 [email protected] [255.799-255.801] MS green-paprika_spiked_1ppb

NL: 6.54E4TIC F: + c CI SRM ms2 [email protected] [131.999-132.001] MS green-paprika_spiked_1ppb

RT: 16.60 - 18.66 SM: 5G

17.0 17.5 18.0 18.5Time (min)

0

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1000

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1000

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1000

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17.38

17.72

17.74

17.78

18.01

NL: 3.32E4TIC F: + c CI SRM ms2 [email protected] [161.999-162.001] MS green-paprika_spiked_1ppb

NL: 4.61E4TIC F: + c CI SRM ms2 [email protected] [128.899-128.901] MS green-paprika_spiked_1ppb

NL: 4.48E4TIC F: + c CI SRM ms2 [email protected] [172.999-173.001] MS green-paprika_spiked_1ppb

NL: 1.59E5TIC F: + c CI SRM ms2 [email protected] [236.999-237.001] MS green-paprika_spiked_1ppb

NL: 7.33E4TIC F: + c CI SRM ms2 [email protected] [135.999-136.001] MS green-paprika_spiked_1ppb

NL: 2.06E4TIC F: + c CI SRM ms2 [email protected] [161.899-161.901] MS green-paprika_spiked_1ppb

RT: 17.64 - 20.09 SM: 5G

18 19 20Time (min)

0

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1000

50

1000

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1000

50

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18.39

18.51

19.15

19.24

19.46

NL: 1.93E5TIC F: + c CI SRM ms2 [email protected] [255.799-255.801] MS green-paprika_spiked_1ppb

NL: 5.74E4TIC F: + c CI SRM ms2 [email protected] [124.999-125.001] MS green-paprika_spiked_1ppb

NL: 7.13E4TIC F: + c CI SRM ms2 [email protected] [161.999-162.001] MS green-paprika_spiked_1ppb

NL: 1.06E5TIC F: + c CI SRM ms2 [email protected] [188.999-189.001] MS green-paprika_spiked_1ppb

NL: 2.04E5TIC F: + c CI SRM ms2 [email protected] [107.999-108.001] MS green-paprika_spiked_1ppb

NL: 5.00E4TIC F: + c CI SRM ms2 [email protected] [198.999-199.001] MS green-paprika_spiked_1ppb

Bupirimate

Thifluzamide

Fenoxanil

Chlorbenzilate

Pyriminobac-methyl

-Z -E

Oxadixyl

Triazophos

Fluacrypyrim

Edifenphos

Quinoxyfen

Lenacil

Trifloxystrobin

Pyriminobac-methyl-E

Tebuconazole

Diclofop-methyl

Mefenpyr-diethyl

Pyributicarb

Pyridafenthion

Page 10: Fast Multi-Component Pesticide Analysis The world leader ... · 5 WCTOW, Saskatoon, April 30, 2008 Quinoxyfen in Hops using SIM and MS/MS RT: 17.13 - 27.39 18 19 20 21 22 23 24 25

10

WCTOW, Saskatoon, April 30, 2008

Speed - How many compounds in one run?

20 datapoints

1803-21 - m/z= 212.00-212.00 SM: 5 RT: 14.90 - 15.65 NL: 2.23E5F: + c EI SRM ms2 285.000 [ 177.995-178.005, 211.995-212.005]

14.9 15.0 15.1 15.2 15.3 15.4 15.5Time (min)

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RT: 15.27MA: 521598SN: NA

15.35 15.45 15.56

Vinchlozolin

Segment 4 with:

35 transitions

Cycle time 5 msec

WCTOW, Saskatoon, April 30, 2008

Speed with FAST FAST GC: 170 Pesticides in 20 min

Cond‘s: 11 windows with up to 25 transitions, total scan time: 25 ms !

ApplicationNote by

Weiguo Zhang and Lin Lu !

Page 11: Fast Multi-Component Pesticide Analysis The world leader ... · 5 WCTOW, Saskatoon, April 30, 2008 Quinoxyfen in Hops using SIM and MS/MS RT: 17.13 - 27.39 18 19 20 21 22 23 24 25

11

WCTOW, Saskatoon, April 30, 2008

H-SRM Selectivity: Pyrethroids in Cabbage 5ppb

RT: 28.32 - 30.28

28.4 28.6 28.8 29.0 29.2 29.4 29.6 29.8 30.0 30.2Time (min)

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RT: 29.23AA: 350016SN: 53RMS

RT: 28.83AA: 247550SN: 39RMS

RT: 29.62AA: 252929SN: 36RMS

RT: 29.01AA: 148416SN: 28RMS

RT: 29.26AA: 1197987SN: 182RMS

RT: 28.85AA: 842637SN: 134RMS RT: 29.04

AA: 574343SN: 93RMS RT: 29.66

AA: 467638SN: 65RMSRT: 29.39

AA: 171523SN: 26RMS

RT: 29.83AA: 72207SN: 9RMS

NL:1.63E5TIC F: + c EI SRM ms2 181.060 [152.055-152.065] MS ICIS 1703-18

NL:4.49E5TIC F: + c EI SRM ms2 181.060 [152.055-152.065] MS ICIS 1803-21

Q1@ 0.7 Da

2µl injection

Q1@ 0.4 Da

10µl injectionH-SRM

5x more matrix

Lower noise

WCTOW, Saskatoon, April 30, 2008

Linearity – Oxadixyl Quantitative CalibrationOxadixyl

Y = -5261+170609*X R̂ 2 = 0.9998 W: Equal

0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75 80 85 90 95 100 105 1100

1000000

2000000

3000000

4000000

5000000

6000000

7000000

8000000

9000000

10000000

11000000

12000000

13000000

14000000

15000000

16000000

17000000

18000000

Are

a

3.6 % RSD at 5 PPB

RT: 15.6143 - 19.0842 SM: 3B

16.0 16.5 17.0 17.5 18.0 18.5 19.0Time (min)

0

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RT: 16.8519 NL:1.06E5TIC F: + c CI SRM ms2 [email protected] [131.999-132.001] MS std_04

1 ppb

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The world leader in serving science

Dioxins/Furans and dl-PCBsby EI SRM

on TSQ Quantum GC

Dirk KrumwiedeThermo Fisher Scientific, Bremen, Germany

WCTOW, Saskatoon, April 30, 2008

Question: HRMS or Triple Quad for PCBs, Dioxins?

EU Commission Directive 96/23/EC• concerning the performance of analytical methods and the interpretation of

results, 12 August 2002• Grants identification points to analytical methods

Today valid, but in discussion: • HRMS still required for confirmation (DFS High Res GC-MS)• QQQ for screening (TSQ Quantum GC)

Technique Number of Ions Identification Points GC-MS (EI or CI) n n GC-MS (EI and CI) 2 (EI) + 2 (CI) 4 GC-MS/MS 1 precursor and 2 daughters 4 GC-MS-MS 2 precursor ions, each with 1 daughter 5 HRMS n 2n Table 2. Examples of the number of identification points earned for analytical GC/MS techniques,(n = integer)3

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WCTOW, Saskatoon, April 30, 2008

TSQ Quantum GC – PCDD/Fs EPA1613 CS1, 1/10 dilutedC:\XCalibur\Data\dk_test\dio122 9/20/2007 4:31:46 PM 2 ul DF CS1 (1/10), 5 win, SRMSRM (pw 0.7), coll en 22, gas pressure 2.0, 40eV, 100 uA, closed EI vol., 30 m DB5MS (0.1), 120(2)-10-220(2)-3-260, scan width 0.002, ists 250, xline 290

RT: 12.56 - 27.47

14 16 18 20 22 24 26Time (min)

0

50

1000

50

1000

50

1000

50

100

Rel

ativ

e A

bund

ance 0

50

1000

50

1000

50

10013.65

13.76 14.7213.99

14.15 14.6613.8716.4615.77

16.6115.6616.70

16.8315.6118.8518.74 19.43 20.14

20.2718.4917.5719.73

19.9519.63

20.5719.2017.6313.66 13.99

15.76 16.4618.73 19.72 26.4420.13 21.75 23.05

20.3014.10 23.6517.09 21.98 26.23

NL: 1.28E4TIC F: + c EI SRM ms2 305.900 [242.899-242.901] MS dio122

NL: 1.33E4TIC F: + c EI SRM ms2 321.900 [258.899-258.901] MS dio122

NL: 5.30E4TIC F: + c EI SRM ms2 339.900 [276.800-277.000] MS dio122

NL: 4.53E4TIC F: + c EI SRM ms2 355.900 [292.800-293.000] MS dio122

NL: 3.75E4TIC F: + c EI SRM ms2 373.800 [310.700-310.900] MS dio122

NL: 3.74E4TIC F: + c EI SRM ms2 389.800 [326.700-326.900] MS dio122

NL: 1.77E6TIC MS dio122

(concentrations of natives: tcdd/tcdf: 50 fg/ul; penta to hepta dioxins/furans: 250 fg/ul; octas: 500 fg/ul)

tcdf

tcdd

pcdf

pcdd

hcdf

hcdf

TIC

WCTOW, Saskatoon, April 30, 2008

TSQ Quantum GC – PCB‘s in Fish ExtractFish extract blank

RT: 11.81 - 34.84

12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34Time (min)

0

50

1000

50

1000

50

100

0

50

100

Rel

ativ

e A

bund

ance

0

50

1000

50

10015.38

20.60

23.4122.1620.77

19.52 21.7813.32 14.08 24.5520.3216.08 23.19

19.52

17.6616.8319.60

19.30 24.2918.22 20.31 25.51 27.8123.1422.40

23.4120.59

22.16

20.7719.52

21.78 24.5620.32 29.6923.19 28.45

24.30

27.8125.51

23.1425.4224.0122.60 26.70

29.68

28.4426.07

27.37

33.83

27.58 28.4511.96 18.54 25.42

NL: 1.75E4TIC F: + c EI SRM ms2 255.950 [185.650-186.350] MS gva07

NL: 3.65E4TIC F: + c EI SRM ms2 291.900 [221.650-222.350] MS gva07

NL: 1.05E5TIC F: + c EI SRM ms2 325.900 [255.550-256.250] MS gva07

NL: 2.73E5TIC F: + c EI SRM ms2 359.850 [289.550-290.250] MS gva07

NL: 2.21E4TIC F: + c EI SRM ms2 393.810 [358.450-359.150] MS gva07

NL: 1.52E3TIC F: + c EI SRM ms2 463.750 [428.350-429.050] MS gva07

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WCTOW, Saskatoon, April 30, 2008

TSQ Quantum GC – Dioxins from a Fish ExtractC:\XCalibur\...\dio220 9/21/2007 4:22:52 PM 1 ul dioxins fish extract 1SRM (pw 0.7), coll en 22, gas pressure 2.0, 40eV, 100 uA, closed EI vol., 30 m DB5MS (0.1), 120(2)-10-220(2)-3-260 sample 4278: Blue Swimmer Crab

RT: 12.78 - 14.48

12.8 13.0 13.2 13.4 13.6 13.8 14.0 14.2 14.4Time (min)

0

20

40

60

80

100

0

20

40

60

80

100

0

20

40

60

80

100

Rel

ativ

e A

bund

ance

0

20

40

60

80

100

RT: 13.99AA: 147134

RT: 13.46AA: 118203

RT: 12.96AA: 77093 RT: 14.09

AA: 75177RT: 13.04AA: 42016 RT: 13.53

AA: 24861RT: 14.22AA: 21444RT: 13.71

AA: 4143RT: 13.09AA: 1119

RT: 13.38AA: 1325

RT: 13.46AA: 107459 RT: 13.99

AA: 129040RT: 12.96AA: 81402 RT: 14.09

AA: 75512RT: 13.04AA: 40518

RT: 13.50AA: 27461

RT: 14.22AA: 18253RT: 13.72

AA: 4918RT: 13.38AA: 1490

RT: 13.82AA: 10033891

RT: 14.09AA: 5193487

RT: 14.22AA: 43397

RT: 13.94AA: 20934RT: 13.36

AA: 1116RT: 13.83AA: 9604228

RT: 14.09AA: 4897430

RT: 14.23AA: 36225

RT: 13.98AA: 11505

NL: 4.95E4TIC F: + c EI SRM ms2 319.900 [256.899-256.901] MS ICIS dio220

NL: 4.64E4TIC F: + c EI SRM ms2 321.900 [258.899-258.901] MS ICIS dio220

NL: 3.83E6TIC F: + c EI SRM ms2 331.900 [267.899-267.901] MS ICIS dio220

NL: 3.65E6TIC F: + c EI SRM ms2 333.900 [269.899-269.901] MS ICIS dio220

Native tcddQuanmass

Native tcddRatiomass

13C12 TCDDQuanmass

13C12 TCDDRatiomass

WCTOW, Saskatoon, April 30, 2008

TSQ Quantum GC – Conclusion

Unique Target Compound Selectivity• Hyperbolic quads and H-SRM

Superior Results with Complex Matrix Samples• Shorten sample clean-up• Reliable quantitation – peak integration

Superior Sensitivity• Trace levels at your syringe tip

Unique High Speed Data Acquisition• Especially multi-component trace analysis• For Fast GC applications

High Productivity• Increased throughput – get results faster • Most cost efficient analysis

Confirmation of Positive Compounds• In only one run – full MS/MS spectra

Ease-of-Use • QuanLab and ToxLab Workflow SW

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WCTOW, Saskatoon, April 30, 2008

ThankThank youyou veryvery muchmuch forfor youryour attentionattention !!

WCTOW, Saskatoon, April 30, 2008

DuraBriteTM Ion Source – No Tools Access !