Feedback de Xevo TQ-S con interfase APGC para cuantificación de plaguicidas

Madrid, 21 Març 2012

Dr. Juan Vicente Sancho

Laboratory of Pesticide Residue Analysis Research Institute for Pesticides and Water

Universitat Jaume I, Castelló, Spain

MS Technology Days H10 Marina Barcelona

MS Technology Days Sesión Alimentación y Medioambiente

There is a clear trend towards LC-MS methods in pesticide analysis as new pesticides are more polar, less volatile and thermostable, thus less GC amenable

However, highly used pesticides (in Europe or in developing countries) are still volatile and thermostable, therefore GC-MS methods cannot be abandonded yet

Electron ionization (EI) is the queen of the GC ionization techniques: robust source, standardized mass spectra, commercially available libraries but its extensive fragmentation is still its Achilles’ heel

MS Technology Days EI extensive fragmentation

Mix D 1 ppm

m/z60 80 100 120 140 160 180 200 220 240 260 280 300 320 340 360 380

%

0

100API034 603 (11.041) Cm (599:607-627:652) TOF MS EI+

1.84e5198.0995

137.0685

93.0441

66.034896.9508

179.1166152.0933

153.0983

199.1024

304.1025276.0707227.0947

289.0791

N

N

CH3

CH CH3

CH3

OPCH3CH2O

OCH2CH3

S

Diazinon

C12H21N2O3SP M+· 304.1011

EI extensive fragmentation

Organophosphorous insecticides

Malathion

C10H19N2O6S2P M+· 330.0361

CHSP(OCH3)2

SCH3CH2OC

CH3CH2OCCH2

O

O

Organophosphorous insecticides

MS Technology Days EI extensive fragmentation

Mix D 1 ppm

m/z60 80 100 120 140 160 180 200 220 240 260 280 300 320 340

%

0

100API034 815 (13.868) Cm (812:818-791:806) TOF MS EI+

8.71e4127.0387

99.0122

55.0181

86.9907

124.9805

100.0078

173.0818

157.9625

142.9965

256.0001174.0849210.9664 283.9969

Piretroid insecticides

Deltamethrin

C22H19Br2NO3 M+· 502.9732

C CH C

O

O

CH3CH3

Br

BrCH

CN

O

MS Technology Days EI extensive fragmentation

Mix D 1 ppm

m/z50 100 150 200 250 300 350 400 450 500

%

0

100API034 2062 (30.496) Cm (2058:2068-2015:2052) TOF MS EI+

4.29e4181.0668

171.9901

169.0749

168.0673114.0254141.1344

252.9057

209.0904

250.9083

210.0718

254.9055

296.9008 344.0701

Novel soft-ionization techniques in GC would overcome this issue, if extensive fragmentation could be considered a problem

The lack of molecular ion in the EI mass spectra is a handicap during developing tandem mass spectrometry methods, i.e. available precursor ions only at low masses

The specificity of the SRM transitions selected might be questioned when low mass fragment ions are used

The availability of molecular ion or high mass fragment can be used to improve both selectivity and sensitivity

Finally, this source (APGC) allows us to couple GC to a novel triple quadrupole mass spectrometer, TQ-S

MS Technology Days Soft ionization in GC-MS

MS Technology Days GC-APGC-TQS

UPLC TQ-S GC

APGC

MS Technology Days APGC source

APGC

Ion chamber

APCI needle

APGC

MS Technology Days APGC source

MS Technology Days APGC source

“APCI-like” soft ionization for GC eluate

N2 320 mL/min

Transfer line 300 ºC

Corona current 0.8-2.2 µA

Cone gas 150-200 L/hr

Cone 30-50 V

GC eluate

Modifiers

MS Technology Days APGC source – Ionization modes

Modifiers (H2O, MeOH)

MS Technology Days APGC source – Ionization modes

N2+· + M M+· + N2

m/z60 80 100 120 140 160 180 200 220 240 260 280

%

0

100DAVFLET070 708 (12.182) 1: TOF MS AP+

1.01e5249.8491

247.8515

191.8324145.0647

79.9393

63.9412127.888296.9424

112.9199 159.8627 172.9556

206.1665

224.9465

251.8460

252.8532

253.8432

254.8506

255.8394

Pentachlorobenzene

C6HCl5 M+· 247.8521

MS Technology Days APGC source – Ionization modes

H3O+ + M MH+ + H2O+

m/z60 80 100 120 140 160 180 200 220 240 260 280 300 320 340 360

%

0

100DAVFLET111 1165 (18.450) 1: TOF MS AP+

6.71e5305.1087

289.1312153.1016127.0162 273.1382171.0245

209.0611 250.0778

306.1119

307.1070

308.1074 337.1011

N

N

CH3

CH CH3

CH3

OPCH3CH2O

OCH2CH3

S

Diazinon

C12H21N2O3SP MH+ 305.1089

APGC in-source fragmentation?

MS Technology Days APGC-TQS vs EI-Quattro Micro GC

Piretroid insecticides Deltamethrin Permethrin Lambda-cyhalothrin Fluvalinate

Bifenthrin Cypermethrin Cyfluthrin Fenvalerate

MS Technology Days EI vs APGC ionization

LAMBDA-CYHALOTHRIN BIFENTHRIN

C23H19ClF3NO3 M+· 449.1006

C23H22ClF3O2 M+· 422.1260

EI

APGC

MS Technology Days APGC ionization (N2 vs H2O)

LAMBDA-CYHALOTHRIN

BIFENTHRIN

C23H19ClF3NO3 M+· 449.1006

C23H22ClF3O2 M+· 422.1260

C23H20ClF3NO3 MH+ 450.1084

MH+ N2

H2O

MS Technology Days Product ion spectra (20 eV) EI

DELTAMETHRIN

BIFENTHRIN

C23H22ClF3O2 M+· 422.1260

APGC

C23H19Br2NO3 M+· 502.9732

Plenty of product ions

Plenty of product ions

MS Technology Days Specific SRM transitions

EI APGC

CYPERMETHRIN

CYFLUTHRIN

C22H19Cl2FNO3 MH+ 434.0726

C22H20Cl2NO3 MH+ 416.0820

CYPERMETHRIN? CYFLUTHRIN?

163 > 91

416 > 191

434 > 191

MS Technology Days Linearity, precision and LODs

DELTAMETHRIN

0.025 pg/µL

Linearity

0.025-250 pg/µL (4 orders)

MS Technology Days Linearity, precision and LODs

Precision

Q q Q qBifenthrin 5% 7% 6% * 9% *Permethrin 8% 10% 8% 10%Cypermethrin 6% 11% 6% 11%Cyfluthrin 7% 6% 9% 9%lambda-cyhalothrin 7% 7% 5% 8%Fluvalinate 7% 8% 4% 4%Deltamethrin 7% 10% 4% 11%Fenvalerate 7% 10% 7% 9%

* Experiments for bifenthrin at 1 ppb also with N2

Q, quantification transition

q, confirmation transtition

N225 ppb (n=10) 1 ppb (n=20)

H2O

<15%

MS Technology Days Linearity, precision and LODs

LODs

Time13.00 14.00 15.00 16.00

%

0

100

13.00 14.00 15.00 16.00

%

0

100APGC430 6: MRM of 4 Channels AP+

450 > 225.1 (lambda-cyhalothrin)5.23e4

S/N:PtP=9.08

APGC433 2: MRM of 9 Channels AP+ 391 > 355 (Permethrin)

9.37e3S/N:PtP=3.26

50 fg/μL

500 fg/μL

Time15.00 16.00 17.00 18.00 19.00 20.00

%

0

100

15.00 16.00 17.00 18.00 19.00 20.00

%

0

100APGC429 7: MRM of 6 Channels AP+

503.1 > 181.1 (Fluvalinate)6.80e4

S/N:PtP=39.53

APGC429 8: MRM of 6 Channels AP+ 503.9 > 278.8 (Deltamethrin)

6.46e4S/N:PtP=118.69

25 fg/μL

25 fg/μL

1 fg/µL

MS Technology Days Dwell time vs sensitivity

0,0

2000,0

4000,0

6000,0

8000,0

10000,0

12000,0

14000,0

0 5 10 15 20 25 30

Dwell time

Peak

are

a

27 3 7 12 17

4-7%

10-12% 9-13% 4-8% 12-16% 1 ppb (n=5)

MS Technology Days Application to samples. Confirmation

Q/q (1)=82

Q/q (2)=227

Q/q (1)=76 7%

LAMBDA-CYHALOTHRIN

Nectarine previously blank by

EI-Micro GC

1 µg/kg

Q/q (2)=143 37%

APGC-TQS

MS Technology Days GC-APGC-TQS

APGC is a valuable ionization source for coupling GC to novel tandem mass spectrometers (Xevo TQ-S, Xevo G2 Q-Tof, Synapt G2-S HDMS or Xevo TQD)

APGC allows a “universal” soft-ionization for GC-amenable compounds

APGC allows selecting molecular ion/protonated molecule as precursor ion rendering more selective and sensitive SRM transitions than EI

GC-APGC-TQS presents good analytical characteristics regarding linearity, precision and limits of detection for determination of pesticide residues in food and environment

GC-APGC-QTof allows screening and confirmation of GC-amenable pesticides and contaminants based on expected M+·/MH+ and MSE acquisitions, like UPLC-ESI-QTof using Posi±ive

Conclusions

T Portolés

www.iupa.uji.es www.iupa.uji.es

Moltes gracies per la seva atenció

I Cervera L Cherta

M Barreda

Feedback de Xevo TQ-S con interfase APGC para cuantificación de plaguicidas

Barcelona, 21 Març 2012

Dr. Juan Vicente Sancho

Laboratory of Pesticide Residue Analysis Research Institute for Pesticides and Water

Universitat Jaume I, Castelló, Spain

MS Technology Days H10 Marina Barcelona