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
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
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
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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+
5
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)
0
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100
Rel
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100
Rel
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100
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60
80
100
Rel
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20
40
60
80
100R
elat
ive
Abu
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
6
WCTOW, Saskatoon, April 30, 2008
QED MS/MS for Full Scan Substance Confirmation
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Rel
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9.8 10.0 10.2 10.4 10.6
min
RT:10.0
m/z
Inte
nsi
ty
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
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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
20
40
60
80
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
20
40
60
80
100
Rel
ativ
e Abu
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
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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
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
1000
50
1000
50
1000
50
1000
50
1000
50
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)
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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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50
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1000
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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
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 !
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)
0
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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
12
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
13
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
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Rel
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e A
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ance 0
50
1000
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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
14
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
15
WCTOW, Saskatoon, April 30, 2008
ThankThank youyou veryvery muchmuch forfor youryour attentionattention !!
WCTOW, Saskatoon, April 30, 2008
DuraBriteTM Ion Source – No Tools Access !