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Cylindrical Ion Trap Mass Spectrometer for Chemical Warfare Agent Detection and

Identification

Cylindrical Ion Trap Mass Spectrometer for Chemical Warfare Agent Detection and

IdentificationM. Todd Griffin, Jack E. Fulton, Jr., Robert F. McAtee,

Norm Popkie, Michael A. Eagan, Mike Jahn

Night Vision/Electro Optics and Chemical/Biological/Explosives Detection Group Naval Surface Warfare Center, Crane Division

Crane, IN 47522

Rong Gao, Lefteri H. Tsoukalas, R. Graham CooksPurdue University

W. Lafayette, IN 47907-1290Distribution Statement A - Approved for public release; distribution unlimited.

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4. TITLE AND SUBTITLE Cylindrical Ion Trap Mass Spectrometer for Chemical Warfare AgentDetection and Identification

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Standard Form 298 (Rev. 8-98) Prescribed by ANSI Std Z39-18

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Selective, Rapid Detection of Chemical Warfare Agents

in Air by Ion Trap Mass Spectrometry! Requirements, field portable plus

" Speed of analysis: < 10 seconds" Sensitivity: LOD < 1 part per trillion by volume" Selectivity: samples are complex mixtures of organics

! The Solution" Miniature mass spectrometer" Ion trap with simple cylindrical electrodes " Rapid, selective membrane introduction of samples

! Basis for Effort" Detailed simulations of ion motion in ion traps" Decade-long study of ion trap performance" Collaboration between Purdue, Crane, and Griffin, a start-up

company who will manufacture instruments

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Methodology

•Selective Adsorption/Desorption•Selective Ionization•Selective Mass Analysis•Selective Dissociation and MS/MS Analysis

Air Sample

Membrane Selective Desorption

Mass Analysis

MS/MSAnalysis

Detection

DataAnalysis

Preconcentration of analytes

Thermal Release Laser or CI

Multiple Stages of Selectivity

Ion trap (CIT)Selective Binding

SelectiveIonization

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BEEQ –Research grade laboratoryInstrumentSize: BigWeight : 4 tonsPower : 15,000 W

Mini-CIT Ver. 5.0Size: 45 x 60 x 71 cmWeight: 140 lbsPower: 200 - 300 W

Mini-CIT Ver. 7.0•Size 18cm x 28cm x 65cm•Weight: 60 lbs•Power 120W

Miniaturization of the Mass Spectrometer

Modified ITSModified ITS--40 40 Rugged Rugged TransportableTransportableSize: 200x 200x 100 cmWeight: 800 lbsPower: 4500 W

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Current Commercial System

Griffin Analytical Technologies

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0

0 .0 5

0 .1

0 .1 5

0 .2

0 .2 5

0 .3

0 .3 5

0 .4

50 70 90 110 130 150 170 190

156

123

55,57

69,71

78-87

95

109

m/z Thomson

Rel

ativ

e In

tens

ity

Halls cough drops (12 mg menthol per drop) in airmini 5.0 with internal unheated membrane

OH

Menthol

C10H20O

MW 156.27

Mini Mass Spec Monitoring of Menthol from Cough Drops in Air

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0.9 V peak heightRise :30 sec.Fall: 30 sec.

0.45 V peak heightRise :26 sec.Fall: 26 sec.

Altoid in Air: Mini Mass Spec Trap and Release MIMS

30s heatBlank

15s Altoid

60s heat

30s heat

3 .00E +00

4 .00E +00

5 .00E +00

6 .00E +00

7 .00E +00

8 .00E +00

9 .00E +00

1 .00E +01

1 .1 0E +01

1 .2 0E +01

1 .3 0E +01

0 1 6 3 2 4 8 6 4 8 0 9 6

1 2 3 4 5 6

3 .0 0 E + 0 0

4 .0 0 E + 0 0

5 .0 0 E + 0 0

6 .0 0 E + 0 0

7 .0 0 E + 0 0

8 .0 0 E + 0 0

9 .0 0 E + 0 0

1 .0 0 E + 0 1

1 .1 0 E + 0 1

1 .2 0 E + 0 1

1 .3 0 E + 0 1

0 1 6 3 2 4 8 6 4 8 0 9 6

1 2 3 4 5 6

30s heat

30s Altoid

60s heat

30s heat

Blank

Blank

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Membrane Introduction Test Set

• Flow-Bench with mass flow meters• RTDs/Humidity sensors• Variable membrane heater• Vacuum chamber with variable pump• Dual chamber vapor generator• Automated testing

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Mini-Mass Spectrometer

Ion Lenses

Cylindrical Ion Trap

r0 = 2.5 mm

Sample Inlet

Current DesignNew DesignFilament

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1 pg of methyl salicylate in 1 µL methanol

0

0.05

0.1

0.15

70 90 110 130 150 170 190

Methyl Salicylatem/z 152

m/z (Thomson)

0

0.05

0.1

0.15

70 90 110 130 150 170 190

nitrotoluenem/z 137

nitrotoluenem/z 107

nitrotoluenem/z 91

m/z 77, 79

m/z 156

152Resolution ~100

Toluene with membrane inlet91

92

90 95m/z (Thomson)

Performance Characteristics: Sensitivity and Resolution

background subtracted

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MSn of Methyl Salicylate

0.00

0.50

1.00

1.50

5.0 6.0 7.0 8.0 9.0 10.0 11.0 12.0 13.0 14.0 15.0

152CID: 0 Vm/z 152

0.00

0.50

1.00

1.50

5.0 6.0 7.0 8.0 9.0 10.0 11.0 12.0 13.0 14.0 15.0time (ms)

152

120CID: 0.02 V

CID: 0 Vm/z 120

0.00

0.50

1.00

1.50

5.0 6.0 7.0 8.0 9.0 10.0 11.0 12.0 13.0 14.0 15.0time (ms)

152CID: 0.02 V

m/z 120

m/z 92m/z 152

0.00

0.50

1.00

1.50

5.0 6.0 7.0 8.0 9.0 10.0 11.0 12.0 13.0 14.0 15.0

m/z 92m/z 120

m/z 152

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• Wavelet transform

– Definition

– Admissible condition

– Inverse transform

( ) ( )∫

−= dt

a

ttx

aaWTx

τψτ *1,

( )∞<

Ψ= ∫

∞

0

2

ωωω

ψ dc

( ) ( )∫ ∫∞ ∞+

∞−

−=

0 2

1,

1 ττψτψ

da

t

aaWT

a

da

ctx x

Wavelets

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0 5 0 0 1 0 0 0 1 5 0 0 2 0 0 0 2 5 0 0- 0 . 8

- 0 . 6

- 0 . 4

- 0 . 2

0

0 . 2

0 . 4

0 . 60 5 0 0 1 0 0 0 1 5 0 0 2 0 0 0 2 5 0 0

- 0 . 8

- 0 . 6

- 0 . 4

- 0 . 2

0

0 . 2

0 . 4

0 . 6

Single scan of methyl salicylate

Original and processed data

Signal Processing of DataWavelet Filtering

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0 500 1000 1500 2000 2500-0.2

-0.15

-0.1

-0.05

0

0.05

0.1

0.15

0.2

0.25

Results after trend removal

Signal Processing of DataWavelet Filtering

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CIT Automated Test Set

• Fully automated PXI based control system • Control software written in LabVIEW• Leak valve and membrane introduction system• Couple with flow bench and vapor generator

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Future Work

IMS Einzel Lens

Square Quad

CITSkimmer

Tube Lens

IMS-MS

CITCIT

Einzel Lens

Einzel Lens

Source Array

Source Array

Filament Array

Filament Array

Multiplexed CIT

• System integration• Performance optimization• IMS-MS• Multiplexed CIT• Biological Capabilities• Algorithm Development

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Funding:Integrated Detection of Hazardous Materials (IDHM) Program, a Department of Defense project managed jointly by Center for Sensing Science and Technology, Purdue University, and Naval Surface Warfare Center, Crane, Indiana

Robert Santini, Andy Guymon, Chris Doerge, Mark Carlsen, MikeEverly, Jim Zimmerman, Alan Ronemus, Robert Fagan, RandyRapogle, and Greg Hawkins.

Dr. Cooks acknowledges the technical support of the Amy Instrumentationand Dr Robert Santini provided via the Indiana Instrumentation Institute (III).

Acknowledgements