11 © 2009 PerkinElmer

Andrew Tipler, Frank De Lorenzo,

Ruben Garnica, Yury Kaplan, Dawn

May

PerkinElmer Inc., Shelton Ct

A novel high sensitivity mass spectrometric detector for gas chromatography

22

Goals

Present a GC/MS with novel ion source and detector design.

Provide experimental results from both environmental and food applications.

33

Introduction

• Overview of general analytical system

• Ion source

• Detector

• Analytical results

• Performance standard - OFN

• SVOA by 8270D (environmental application)

• Pesticides by AOAC 2007.1 (food application)

• VOC by 8260C (environmental application)

• Conclusions

44

The GC/MS System

Clarus 680 GCSQ 8 MS

55

The GC/MS System

SQ 8 MS

Clarus 680 GCDual channel GC

Low thermal mass oven

PPC gas control

Programmable split/splitless injectors

66

The GC/MS System

SQ 8 MSHeated transfer line

Removable ion source

Quadrupole with pre-quad filters

Noise cancelling detector optics

Electron multiplier based detection

Clarus 680 GCDual channel GC

Low thermal mass oven

PPC gas control

Programmable split/splitless injectors

77

SMARTsource – Quick Change Capabilities

Novel grooved cam-locked design for

quick removal and insertion improves

usability and

88

Removal and Insertion of the Source With No Tools

99

Ion source yoke with quick connect electronics

Quick Connect plug

Guide pins

Yoke receptacle

1010

Quick change ion source – flame retardant analysis

…analysis by Positive CI…

From a single sample…

…without the need to reprep the sample.

…followed by EI…

1111

Quick change ion source

1212

Electron Multiplier based ion detector

Noise reducing detector design

• Novel ion optics

• Advanced material

• Discrete EM for max gain

Benefits

• Enhanced sensitivity

• Operational flexibility

1313

EM Detector – Design

Conversion Dynode

Grounded entrance plate

Advanced Ion

Optics

270º ion path

Discrete electron multiplier

1414

EM Detector – Function

Neutrals filtered

Unwanted charged ions filtered

1515

Clarifi Detector – Ion Simulation

1616

Setting EM Voltage – Wide Functional Range

0.0E+00

1.0E+07

2.0E+07

3.0E+07

4.0E+07

5.0E+07

6.0E+07

1160 1260 1360 1460 1560 1660 1760 1860

Inte

nsi

ty o

f N

aph

thal

ene

(m/z

= 1

28)

Multiplier (V)

1717

Analytical Results

Test Standard

(Octafluoronaphthalene)

1818

Maximum Sensitivity – OFN Standard

, 09-May-2011 + 14:11:36

4.75 5.75 6.75 7.75 8.75Time0

100

%

0

100

%

0

100

%

648N1042202_1pg ofn 17 1: Scan EI+ 272

2.03e6S/N:RMS=1176.27

648N1042202_1pg ofn 16 1: Scan EI+ 272

2.03e6S/N:RMS=1148.58

648N1042202_1pg ofn 15 1: Scan EI+ 272

2.03e6S/N:RMS=1526.68

Sensitivity Measurements

• 1 pg/ L OFN

• 1 L pressure pulse injection

• Scanning m/z = 50 – 300

> 800:1 s/n (RMS)

1919

Analytical Results

SVOA by GC/MS

EPA 8270D

2020

SVOA by GC/MS

Standard US EPA Method 8270D

• Extraction of solid waste samples (among others)

• Analysis by liquid injection GC/MS

• Tens to hundreds of target compounds

Experiment Focus

• Optimize EM setting for maximum dynamic range

Method

• Standard EPA 8270D methodology followed

• Mega Mix with internal standards

2121

SVOA by GC/MS – example chromatogram (40 g/mL)

3.00 5.00 7.00 9.00 11.00 13.00 15.00 17.00 19.00Time0

100

%

Scan EI+ TIC63

43

3623

20

2

1

12

8

18

27

24

29

5754

46

52

47

4856

62

60

59

71

67

65

69

72

53

66

68

58

55

51

50

30

31

25

32

38

4115

16

17

13

10

28

2222

Average %RSD ~ 11%

(all 78 compounds)

SVOC by GC/MS – Calibration Results (1-150 g/mL)

# CompoundRT

(min)Average RRF RRF %RSD

1 Pyridine 3.09 0.2 8.98

2 Aniline 4.44 1.2 13.16

4 N-Nitrosodimethylamine 4.45 0.1 10.3

26 Naphthalene 6.24 1.1 9.63

27 Hexachlorobutadiene 6.39 0.2 10.38

42 2,4- Dinitrophenol 8.60 0.1 8.17

49 Fluorene 9.15 1.3 11.93

57 Pentachlorophenol 10.18 0.1 8.01

64 Pyrene 12.26 1.2 9.62

67 Benzo[a]anthracene 13.89 1.0 11.8

70 Bis (2-ethylhexyl) phthalate 13.98 0.6 17.47

74 Benzo[a]pyrene 16.29 1.0 9.46

2323

Analytical Results

Pesticides by GC/MS

AOAC 2007.1

2424

AOAC 2007.1

• Association of Analytical Chemists

• Pesticides in grapes, lettuces, tomatoes, oranges

• QuEChERS extraction (not performed)

Target

• Meet <10 ng/g method specification using SIFI

SIFI = simultaneous selected ion full scan

Success

• Good Chromatography

• +24 compounds meeting specs

Pesticides in Food – AOAC 2007.1

2525

Pesticides in Food – AOAC 2007.1

3.50 4.50 5.50 6.50 7.50 8.50 9.50 10.50 11.50 12.50 13.50 14.50 15.50 16.50 17.50 18.50 19.50Time0

100

%

110411_Pest_010

14.80

3.49

3.40

6.12

5.59

4.77

11.35

9.517.36

6.388.13

7.39

8.92

9.30

9.65

10.85

10.26

9.72

14.5712.27

11.43

15.71

14.98

15.59

17.61

16.2316.48

16.66

16.71

18.80

17.91

AnalyteRetention

TimeMethamidophos 3.40Dichlorovos (DDVP) 3.49Omethoate 6.12Demeton-s-methyl 6.38Dimethoate 7.36Dichloran 7.39Tefluthrin 8.13Tolclofos-methyl 8.92Pirimiphos-methyl 9.30Chlorpyrifos(Dursban) 9.65Pendimethalin 10.26Methidathion 10.85Tetrachlorvinphos 10.95Tokuthion 11.35Profenofos 11.43Ethion 12.27Azinphos methyl (guthion) 14.57L-Cyhalothrin 14.80Pyrazophos 14.98cis-Permethrin 15.59trans-Permethrin 15.71Cyfluthrin-1 16.12Cyfluthrin-2 16.23Cyfluthrin-3 16.28Cyfluthrin-4 16.33Cypermethrin-1 16.48Cypermethrin-2 16.59Cypermethrin-3 16.66Cypermethrin-4 16.71Fenvalerate-1 17.61Fenvalerate-2 17.91Deltamethrin 18.80

Organophosphorous Pesticides

Synthetic Pyrethroids

32 components – SIFI analysis in < 20min

2626

Pesticides in Food – AOAC 2007.1

On column Reporting Levels ng Methamidophos 0.02

Omethoate 0.04

Dimethoate 0.008

Dichloran 0.004

Tefluthrin 0.004

Azinphos methyl (guthion) 0.008

L-Cyhalothrin 0.016

Cis-Permethrin 0.04

Trans-Permethrin 0.02

Cyfluthrin-1 - 4 0.04

Cypermethrin-1 - 4 0.04

Fenvalerate 1-2 0.04

Deltamethrin 0.02

2727

Analytical Results

VOC by P&T GC/MS

EPA 8260C

2828

VOC by purge & trap GC/MS

Standard US EPA Method 8260C

• Extraction of solid waste samples (among others)

• Analysis by purge & trap GC/MS

• Tens to hundreds of target compounds

Experiment Focus

• Optimize EM setting for maximum dynamic range

Method

• Standard EPA 8260C methodology followed

• Mega Mix with internal standards

2929

VOC by purge & trap GC/MS – example chromatogram (40 g/mL)

1.00 3.00 5.00 7.00 9.00 11.00 13.00Time0

100

%

Scan EI+ TIC3.13e8

21

3

45

6

79 10

11

14

15

16

18

1719

22

26

23

29

31

32

34 3537

36

39

40

41

4243

44

45

47

48

4950

51

52

53

55

56 57

59

64

6871

76

73 74

78

79

80

83

84

81

3030

SVOC by GC/MS – Calibration Results (0.5-200 mg/L)

# COMPOUND

Avg

RRF %RSD

MDL

(mg/L)

Precision

%Rec

Accuracy

%RSD

3 Vinyl Chloride 0.79 8.2 0.21 95 1.8

14 trans-1,2 Dichloroethene 0.46 9.3 0.34 105 1.3

31 Benzene 1.33 6.9 0.22 90 1.6

35 Trichloroethene 0.32 8.9 0.28 103 2.5

36 1,2-Dichloropropane 0.47 6 0.15 96 1.8

43 Toluene 0.67 6.5 0.22 100 1.5

48 1,3-Dichloropropane 0.65 4.4 0.06 94 3.1

50 Ethylene Dibromide 0.40 3.6 0.07 111 2.8

52 Chlorobenzene 1.08 4.7 0.23 102 1.0

54 1,1,1,2-Tetrachloroethane 0.27 7.8 0.19 105 1.9

63 1,1,2,2-Tetrachloroethane 1.17 5.9 0.16 93 9.9

74 1,3-Dichlorobenzene 1.64 9 0.22 98 0.7

83 Naphthalene 3.60 7.3 0.06 102 2.4

84 1,2,3-Trichlorobenzene 1.13 7.2 0.09 94 1.6

Average %RSD ~ 8%

(all 80 compounds)

3131

VOC by Purge & Trap – EIC reproducibility at MDL

Extracted Ion of Naphthalene

@ m/z = 128

12.35 12.37 12.39 12.41 12.43 12.45 12.47 12.49 12.51 12.53 12.55Time0

100

%

Scan EI+ 128

1.12e6

0.5 g/L

%RSD = 3.8

3232

Conclusions

• PerkinElmer Clarus SQ 8 GC/MS

• SMARTsource for quick ion source change

• EM Detector for enhanced sensitivity and flexibility

• Analytical results

• Test Standards

• US EPA Method 8270D

• AOAC 2007.1 Pesticide analysis

• US EPA Method 8260C

3333

Thank you and acknowledgement to the SQ 8 team