Forensic Analysis of Illicit Drugs and Trace Explosives using ......Plasma: APGD Analysis of...
Transcript of Forensic Analysis of Illicit Drugs and Trace Explosives using ......Plasma: APGD Analysis of...
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Forensic Analysis of Illicit Drugs and Trace
Explosives using Ambient Pressure
Ionization Mass Spectrometry
Tim M. Brewer, Christopher Szakal, Matthew Staymates, Ed Sisco, Lenny Demoranville, Thomas Forbes, Eric Windsor, Shin Muramato and Greg Gillen
Material Measurement Laboratory (MML)
Surface and Microanalysis Science Division
National Institute of Standards and Technology
The Science and Technology Directorate of the U.S. Department of Homeland Security sponsored
the production of portions of this work under Interagency Agreement HSHQDC-12-X-00024 and
HSHQDC-11-X-00420 with the National Institute of Standards and Technology
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Forensic and Trace Contraband Detection
Ambient Desorption
and Ionization
Specific Chemical
Analysis and Detection
Contraband Materials
-Organic
-Inorganic
-Nuclear
API-MS
Plasma Liquid
Photon Thermal
Goals:
1. Next generation technology
for DHS screening
2. Improved technologies for
high throughput forensic
analysis
3. Standard methods for
evaluation of API sources
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API-MS Surface Analysis Methodologies
Under Investigation at NIST • Liquid Based Sources
– Electrospray Ionization (ESI)
– Atmospheric Pressure Chemical Ionization (APCI)
– Desorption Electrospray Ionization (DESI) and (SESI)
– Desorption Electro-Flow Focusing Ionization (DEFFI)
– PaperSpray Ionization (PS)
• Plasma Based Sources
– Atmospheric Pressure Glow Discharge (APGD)
– Low Temperature Plasma (LTP)
• Thermal Based Sources
– Atmospheric Pressure Thermal Desorption Ionization (APTDI)
• Laser Based Sources
– Atmospheric Pressure Matrix-Assisted Laser Desorption Ionization (AP-MALDI)
– Laser Diode Thermal Desorption (LDTD)
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Why API-MS
• Fast analysis – high sample throughput
• Multiple sources – maximum flexibility
– High ionization efficiency
– Selectivity and flexibility of gas phase and solution phase chemistries
• Sample requirements minimized (direct analysis of wet/insulating/geometric
samples or swipes, + vacuum-incompatible surfaces, non planar, non
conductive)
– Can analyze solids, liquids and vapors both positive and negative polarities
• Performance of Mass Spectrometers and MS/MS (chemical speciation and
identification)
– No need for chromatographic separation
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Liquid: DESI Analysis of Explosives Residues
Szakal, C. and Brewer, T.M., Anal. Chem., 2009, 81, 5257-5266
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Liquid: DESI C-4 Spectra
C-4 samples from
Montgomery Country
bomb squad
Explosives-containing portions of C-4 samples obtained with liquid-liquid extraction in acetonitrile
(explosives, polars)
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Liquid: DESI Fingerprint analysis
Image of a fingerprint after DESI-MS
analysis
500 µm
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Sig
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m/z
Cholesterol
Oleic Acid
Squalene
Positive Ion Scan using DESI-MS
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Allows for analysis on metal surfaces
Typical enhancement of 10x but have seen up to 2000x enhancement
Liquid: Nebulizer Assisted DESI
Selected Ion Monitoring vs. Frequency
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1 11 21 31 41 51 61 71
TNT m/z 226 Cocaine m/z 304
time
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Liquid: Desorption Electro-Flow Focusing
Ionization
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Liquid: PaperSpray –Directly from Swipes
≤ 5 mm
300 ng RDX
3000 ng PETN
The Swipe is the Ion Source – Little to no Sample Preparation Required
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C4 IR Neg
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C4 IR Pos
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a.u
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C4 IL Pos
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C4 IL Neg
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m/z
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Plasma: APGD Analysis of C-4 Residues
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Negative
m/z
m/z
m/z
Positive
Positive
Negative
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RDX - 284, 268, 221, 129, 62, 46
DOS or DCA - 127
PIB – 95, 79, 65
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RDX – 222, 177,131
DOS – 427, 185
DCA – 371, 241, 113
PIB – 97,83,56
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Placed visible amount on explosive swipe. Plasma 75W and 1 L/min He and O 0.1 L/min. No liquid
needed for extraction.
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Plasma: OTC Pharmaceutical - Aleve
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m/z
*Naproxen – 230, 185, 170, 154, 116
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* M+
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NIST EI Database Aleve
Molecular ion Signal at m/z 230
EI “like” fragmentation - NIST EI Database Searchable (>200,000 compounds)
Active Ingredient – Naproxen
MW = 230
APGD-MS spectra of Aleve Pill. Plasma 75W and 1 L/min He and O 0.1 L/min
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Plasma: APGD Analysis of Forensic Compounds
APGD-MS spectra of Musinex DM and Sudafed Pills. Plasma 75W and 1 L/min He and O 0.1 L/min
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m/z
*Pseudoephedrine – 330, 165, 118, 77
* M+
* M+M
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*Methamphetamine – 150, 134, 58
* MH+
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Forensic Compounds Characterized by APGD
OTC pharmaceuticals
Mucinex DM
Aleve
Sudafed
Alka-Selzter Plus Nightime
Ibuprofen
Tylenol
Asprin
Explosives
C-4
RDX
PETN
TNT
NG
HMX
Semtex H
Semtex A
Narcotics
THC
Cocaine
Heroin
MDMA
Methamphetamine
Hydrocodone
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Plasma: APGD-MS Analysis of Ecstasy and
Cocaine Mixture
APGD-MS spectra of Ecstasy and Cocaine. Plasma 75W and 1 L/min He fragmentation pattern with O to
extensive.
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m/z
* [M+H]+- Cocaine
* [M+H]+- Ecstasy
MW = 303 MW = 193
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Plasma: Low Temperature Plasma –
Explosive Particles
SEMTEX H SEMTEX A
PETN - 378
RDX - 284
PETN - 378
Discha
rge
Gas Plas
ma MS
Inlet
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Plasma: LTP Depth Profiling - PMMA
1 2
3
4 5
500µm 1500µm Crater cross section
PMMA
SiO2/Si
ToF-SIMS analysis spots
5 4 3 2 1
ToF-SIMS analysis spots
SIMS depth profiling can reveal changes in chemistry along the depth of the film
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Sputter Time (s)
Spot 4
Spot 3
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4 3 2 1
m/z 69
C2H3O2+
Results suggest damage is localized at the
surface, and the extent of damage seems
proportional to plasma exposure. In the
sub-surface region, the intensity is seen to
quickly return to steady state values
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Laser: AP Laser Diode Thermal Desorption Mass
Spectrometry (LDTD-MS)
Q1 RDX #21-26 RT: 0.18-0.23 AV: 6 SB: 18 0.01-0.17 NL: 3.62E7T: - p APCI Q1MS [15.070-400.000]
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255.15
268.16
283.07
227.08
157.30 336.13
46.08
199.29
291.19
143.2388.91319.19
115.16341.3845.03 87.16
41.88
Rela
tiv
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bu
nd
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TNT
[M-H]-
[NO2]- m/z 226
[M]-
m/z 227
m/z 46
Q1 amm_nitrate #76-80 RT: 0.28-0.30 AV: 5 SB: 31 0.16-0.27 NL: 1.02E8T: - p APCI Q1MS [15.070-150.000]
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m/z
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tive
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89.1
143.187.0 98.163.945.9 121.3 130.9114.959.0 71.142.031.815.8
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[NO3]-
[NO2]-
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m/z 46
Ammonium Nitrate
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Laser: Narcotics on Currency with AP-MALDI
Matrix Matrix Heroin
0.5 μL CHCA matrix on US Currency with doped heroin
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RDX TNT
Thermal: AP Thermal Desorption Ionization -
Mass Spectrometry (APTDI-MS)
Pseudoephedrine Methamphetamine Thermal wire rapidly heated
without subsequent
ionization technique of both
liquids and solids
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How do we evaluate APIMS Systems? - Standard
Test Materials • Flexible – many different compounds
• Rapid
• Large dynamic range in mass
• Quantifiable
• Precise high
• Accuracy approximately 5% depending on
material and the ability to measure starting
material purity
Stability of drop size during ~2 hours of jetting
0.2 %0.1260.5Volume, pL
0.2 %0.1048.7Mass, ng
0.2 %0.1260.5Volume, pL
0.2 %0.1048.7Mass, ng
mean SD RSDmean SD RSD
500 m image field SIMS of single inkjet droplet
of cocaine on silicon
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Preliminary Quantification with Inkjet Printing
Plasma: APGD of Cocaine
Liquid: DESI of Cocaine and RDX
y = 4496.7x + 29807 R² = 0.9994
0.00E+00
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1.00E+06
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2.00E+06
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3.50E+06
4.00E+06
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Co
un
ts (a.u
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Mass (ng)
y = 78806x + 129902 R² = 0.9992
0.00E+00
2.00E+07
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1.00E+08
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Co
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Mass (ng)
Cocaine
y = 7899.6x - 743.47 R² = 0.9993
0.00E+00
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4.00E+06
6.00E+06
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Mass (ng)
RDX
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Useful Yields for APIMS Analysis
SIMS community have used for years, there is also growing interest in APIMS.
But, how sensitive are these method of analysis? How does sensitivity
vary between compounds, ion source type and instrument configurations?
One method for evaluation is to measure the useful yield.
Useful yield = number of molecules detected/molecules in analytical volume.
The useful yield takes into account beam induced damage, ionization probability,
instrument transmission and detector efficiency. It is the best measure of the
analytical sensitivity for a given molecule under a given set of experimental
conditions.
SF5
C60
Useful yields of organic molecules under dynamic SIMS cluster
bombardment, Greg Gillen, Christopher Szakal, Tim M. Brewer,
Surf. Interface Anal. 43, 376. 2011
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Useful Yield Calculations
Compound Ion m/z DESI APGD LDTD DEFFI LTP APTDI
Cocaine (M+H)+ 304 7.5x10-8
1.8x10-8 2.5x10-11
TNT (M-H)- 226 6.5x10-8 3.9x10-10
7.7x10-7 3.1x10-12
RDX (M+NO3)-
(M+35Cl)- 284
235
2.5x10-8
3.9x10-7 2.5x10-8 3.2x10-8
3.5x10-7 5.2x10-12
PETN (M+NO3)-
(M+35Cl)- 378
351
6.8x10-8
1.5x10-8 5.9x10-8 2.5x10-9
6.5x10-8
AN (NO3)- 62 1.5x10-10 7.0x10-7
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Conclusions
• Develop next generation technologies
– Multi-source approach
– Mixture analysis without chromatographic separation
• Improved technologies for high throughput forensic analysis
– Multi-source approach for API-MS of trace and forensic contraband materials allows for
fast, chemical surface analysis of a wide range of materials on multiple substrates
– Characteristic mass spectra for all molecules studied from multiple sampling media
• Objectively evaluate the API sources by leveraging inkjet printing
– A procedure and test materials have been developed to quantify the difference sources
– A procedure and test materials have been developed measure useful yields of a range of organic compounds
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Analysis and mechanisms of cyclotrimethylenetrinitramine ion formation in desorption electrospray ionization.
Szakal C, Brewer TM., Anal Chem. 2009 Jul 1;81(13):5257-66
Flow Visualization Techniques for the Evaluation of Non-Contact Trace Contraband Detectors,
M Staymates, G Gillen and W Smith, ASME, 2010, 203-209,
DESI Source Research -
Schlieren imaging
High speed videography,
3000 frames per second
20° incidence angle 65° incidence angle
Recirculation zone formed from jet entrainment
Work with Prosolia
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0.0E+00
2.0E+05
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6.0E+05
8.0E+05
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1.2E+06
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Inte
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y (a.u
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m/z
*Hydrocodone – 301, 270, 242
* *
* MH+
0.0E+00
8.0E+04
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3.2E+05
4.0E+05
4.8E+05
5.6E+05
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m/z
*Methamphetamine – 150, 134, 58
* MH+
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Plasma: APGD-MS Analysis of Illicit
Drugs
MW = 301
MW = 149
APGD-MS spectra of Hydrocodone and Methamphetamine. Plasma 75W and 1 L/min He and O 0.1 L/min
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He Low Temperature Plasma
• 20 KV peak-peak , 20-70 KHZ high frequency power supply
• Automated x, y sample stage – lab view
• Multiple gas flow controller
• Heated gas jet
• Sample rotation stage for 2000 RPM depth profiling
• Integrated optical spectroscopy for beam characterization
Atmospheric identification of active ingredients in over-the-counter pharmaceuticals and drugs of abuse by atmospheric
pressure glow discharge mass spectrometry (APGD-MS)† Tim M. Brewer*, Jennifer R. Verkouteren, 2011.
Dischar
ge
Gas Plasm
a MS
Inlet
http://onlinelibrary.wiley.com/doi/10.1002/rcm.5136/abstract
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APDTI-MS - Repeatability
Cocaine Cocaine repeat analysis
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APTDI-MS
Pseudoephedrine Methamphetamine
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APTDI-MS – solid mixture
APTDI mass spectrum of Tylenol Allergy. a) is m/z 151,
M+H+ for acetaminophen, b) is m/z 167, M+ for
phenylephrine, and c) is m/z 256, M+H+ for
diphenhydramine
APTDI mass spectrum of m/z 151, M+H+ for
acetaminophen