Field-Portable GC/MS Characterization and Testinghems-workshop.org/5thWS/Talks/Wednesday/Patterson.pdf · Field-Portable GC/MS Characterization and Testing Garth E. Patterson, John

1 of 385th HEMS Workshop 2005

Field-Portable GC/MS Characterization and Testing

Garth E. Patterson, John W. Grossenbacher, J. Mitchell Wells, Anthony J. Cochran, Caryn O’Hearn, Brent D. Rardin, Brent A. Knecht, Jason L.

Springston, Mark A. Gregory, Dennis J. Barket, Jr.

Griffin Analytical Technologies, Inc.3000 Kent Avenue

West Lafayette, IN 47906


Field Portable Mass Spectrometry


Field Portable Mass Spectrometry“To improve upon the trace detection systems currently employed in airports across the US, mass spectrometry (MS) is an obvious candidate to consider. It has become the gold standard for resolving high-consequence analyses …”

But

“Mass spectrometers have historically been large, complex systems. …commercially-available chemical analysis systems…are not designed for an environment as harsh as an airport or other transportation arena.”

-or a battlefield, a depot perimeter, an office building HVAC system…

Committee on Assessment of Security Technologies for Transportation, National Research Council of the National Academies. The National Academies Press: Washington,D.C., 2004.


Griffin’s Portable GC/MSCylindrical Ion Trap Mass Analyzer• Easily miniaturized trap geometry• MS/MS capability• Lower voltage, higher pressure operation• Internal electron ionization (EI)

~1 cm3

Low Thermal Mass-GC• Ramp rate ≥200˚ C/min• Maximum Temp 350˚C • Cooling time ~2 min• Variety of phases• 1 m – 30 m standard

~10 cm


Griffin’s Portable GC/MSMinotaur 300 Instrument Specifications:

•MS/MS capable•Picogram sensitivity

(application dependent)•Low thermal mass GC, SPME, MIMS, and direct SPME sample introduction available

•Multi-level software control•Helium or ambient air bath gas •Ruggedized and shock-

mounted for outside-the-lab operation (Minotaur 400)

•Network communication compatible

Minotaur 400


Shock Mount platform

Wire-rope isolators are used to provide shock and vibration isolation of the most fragile components


Layered Software ArchitectureLayered Software Architecture

Level 1 simplified user interface

scientific user interface

Level 2

fundamental development

tool and expert user interface

Level 3


Analysis of CW agent simulantsSeparation of 9 organophosphorus pesticides30 m x 0.25 mm Rtx-5MS column

2 4 6 8 10 12 14retention time (min)

1

2

3

4

5

6

78

9

1) O,O,O-Triethyl Thiophosphate

2) Thionazin

3) Sulfotep

7) Methyl Parathion

4) Phorate

5) Dimethoate

6) Disulfoton

8) Parathion

9) Famphur


Analysis of CW agent simulants

(Text File) Griffin50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 210 220 230 240 250 260 270 280

0

50

100

51

63

76

79

93

109

127

137

155 234

247

263

268

MS of Peak #7

NIST MS ofMethyl Parathion

Match Probability 88.5%

(replib) Methyl pa ra thion50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 210 220 230 240 250 260 270 280

0

50

100

50 6375

79

93

96

109

125

139 155 201233

246

263

O

NO

O

P

O

O

S


Analysis of CW agent simulants

(Text File) Griffin50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 210 220 230 240 250 260 270 280 290 300 310

0

50

100

51

57

63

73 8191

97

109

125

139

155

165186

199207 236 255

291

MS of Peak #8

NIST MS ofParathion


(ma inlib) Pa ra thion50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 210 220 230 240 250 260 270 280 290 300 310

0

50

100

50

65

75

81

97 109

125

139

150

155

172

186

201

218

235

246

263

275

291

N

O

OO

P

O

SO


Analysis of CW agent simulantsPesticide Quantitation

y = 317554.5020x + 18347.1768R2 = 0.9992

0

50000

100000

150000

200000

0 0.1 0.2 0.3 0.4 0.5 0.6

ng/µL

Pea

k A

rea

Methyl Parathiony = 269482.7262x + 15513.2492

R2 = 0.9990

0

50000

100000

150000

200000

0 0.1 0.2 0.3 0.4 0.5 0.6

ng/µL

Pea

k A

rea

Parathion

Compound Limit of Detection (pg/µL)O,O,O-triethylthiophosphate 9thionazin 21sulfotep 45phorate 10dimethoate 44disulfoton 34methyl parathion 26parathion 41famphur ~1000 pg (not detected in 500 pg/uL sample)


Analysis of CW agent simulantsDimethyl methylphosphonate (DMMP)

CEESDMMP

IPA

124

123109

94

79DMMP

Chloroethyl ethyl sulfide (CEES)

y = 793.54x + 73898r2 = 0.988

0.0E+00

2.0E+05

4.0E+05

6.0E+05

8.0E+05

1.0E+06

1.2E+06

1.4E+06

1.6E+06

1.8E+06

2.0E+06

0 500 1000 1500 2000 2500

[DMMP], pg/uL

peak

are

a, a

rb. u

nits

y = 174.58x + 11765r2 = 0.9962

0.0E+00

5.0E+04

1.0E+05

1.5E+05

2.0E+05

2.5E+05

3.0E+05

3.5E+05

4.0E+05

4.5E+05

0 500 1000 1500 2000 2500

[CEES], pg/uL

peak

are

a, a

rb. u

nits

LOD ~ 1.5 pg

LOD ~ 1.0 pg


Analysis of ExplosivesSeparation of 14 nitrated organics15 m x 0.25 mm Rtx-TNT1 column


1

234

5

6

7

8

9

10

11

12

13

1) Nitrobenzene2) 2-Nitrotoluene3) 3-Nitrotoluene4) 4-Nitrotoluene5) 1,3-Dinitrobenzene6) 2,6-Dinitrotoluene7) 2,4-Dinitrotoluene8) 1,3,5-Trinitrobenzene9) 1,3,5-Trinitrotoluene10) RDX11) 4-Amino-2,6-dinitrotoluene12) 2-Amino-4,6-dinitrotoluene13) Tetryl[14) HMX not observed]


Analysis of Explosives

(Text File) Griffin50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 210 220 230

0

50

100

51

53

63

6674

76

7987

89

92 104 120

134149

152

164180 194

210

MS of Peak #9

NIST MS ofTNT


(replib) Benzene, 2-methyl-1,3,5-trinitro-50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 210 220 230

0

50

100

51

63

6974

76

89

9296

104 120

134149

152

164180 193

197

210

O

NO

N

N

O

O

OO


Analysis of Explosives

(Text File) Griffin50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 210

0

50

100

56

71

75

81

98

120

128

159 205

MS of Peak #10

NIST MS ofRDX


(ma inlib) 1,3,5-Tria zine, hexa hydro-1,3,5-trinitro-50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 210

0

15

30

56

69

71

75

83

85

97

102

112

120

128

133

148

205

N

N

NN

N

N

O

O O

O

OO


Analysis of ExplosivesExplosive separation at faster ramp rates

5oC/min

20oC/min


80oC/min


Analysis of ExplosivesExplosive separation at faster ramp rates

5oC/min

5 10 15 20 25 30 35

1

23 4

5

67

8

9

10

1112

13

2 104 6 8

20oC/min1

2

3 4

5

67

8

9

10

1112

13

80oC/min1

23

45

6

78

9

10

11

12

13

1 2 3 4


Analysis of ExplosivesExplosive separation on a 5 m Rtx-5MS column

1 2 3

Nitrobenzene

TNT

DNB

RDX

DNT

TNB 2-amino-DNT

retention time (min)

50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 210 2200

50

10051

56

62

68

75

77

87

89

105120

134 149 164

180193

197

210MS at 2:01 min, matches NIST TNT spectrum with 93% probability

(Text File) Griffin

m/z


Sample loop

He source

MFC

Vent

Pump and needle valve

needle valve

Solenoid

Linier actuator

Valve 2cold

Minotaur400

Sample loop

He source

MFC

Vent


needle valve

Solenoid

coldhot

Vent

Ambient air in

Manifold

Nafion dryer

“Dry air” cylinder

Valve 1

PROPHET On-line GC-CITMS Atmospheric VOC Monitoring System (Gavin Edwards, Paul Shepson)


Sample loop

He source

MFC

Vent


needle valve

Solenoid

Linier actuator

V2

V1

coldMinotaur

Sample loop

He source

MFC

Vent


Solenoid

Linier actuator

coldhotMinotaur

Vent

Ambient air in

Manifold

Nafion dryer

“Breathing air” cylinder

Analysis Mode


Sample loop

He source

MFC

Vent


needle valve

Solenoid

Linier actuator

V2

V1

coldhotMinotaur

Sample loop

He source

MFC

Vent


needle valve

Solenoid

Linier actuator

V2

V1

coldhotMinotaur

Vent

Ambient air in

Manifold

Nafion dryer

“Breathing air” cylinder

Sampling Mode











Verified new inlet and MS system in an atmospheric chemistry field study

9 calibrations, humidity blanks evaluated

>2000 measurements (7/11/2005-8/16/2005, off and on)

14 days with 24 hr coverage, 7 days with partial coverage

Isoprene concentrations between <70 ppt (LOD) and >8 ppb

Potential for intercomparison with other techniques such as FIS, DEA and PTRMS

Field Study Summary


Direct SPMEDirect Inject SPMESPME fiber is directly inserted intothe vacuum chamber for rapid desorption

Max temp 300˚CReplaceable septum with novacuum vent


Direct SPMEDirect SPME analysis of DMMP, headspace sampling of neat compound

124109

94

79

63

77

~30 second desorption, ambient temperature


Direct SPME

166138139122

111

109

93

658182

~1.5 minute desorption,ambient temp.

Direct SPME analysis of DEEP, headspace sampling of neat compound


Direct SPME

~1 minute desorption, ambient temp.

155

182

127

125109

111

99

8182

97

Direct SPME analysis of TEP, headspace sampling of neat compound


Direct SPMEDirect SPME analysis of TNT, headspace sampling 100 ng/uL solution

210

180149

134

~10 second desorption, 200oC


Conclusions• New GC/MS instruments based on LTM-GC and

CIT mass analyzer provide:Small footprint, ruggedized package for field use

Rapid separation of complex mixtures

MS analysis with good database matching (NIST and user-defined) for compound ID, MS/MS for ID confirmation

Quantitation to low pg (ppt-ppb) levels without preconcentration

Complementary sample inlets are also available


Acknowledgments• Acknowledgements

– Brad Rowland, US Army DPG– Prof. Graham Cooks, Purdue University– Prof. Paul Shepson, Purdue University

• The Griffin Team

Field-Portable GC/MS Characterization and Testinghems-workshop.org/5thWS/Talks/Wednesday/Patterson.pdf · Field-Portable GC/MS Characterization and Testing Garth E. Patterson, John

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