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MALDI/TOF MS for Chemical Analysis of Fingerprint Residues using

Conventional Fingerprint Development Methods

Kimberly Kaplan*1,2, Mark L Miller2, and Marc A LeBeau3 1Oak Ridge Institute for Science and Education , Oak Ridge, Tennessee, 2Counterterrorism and Forensic Science Research Unit, 3Scientific Analysis Section,

Federal Bureau of Investigation, Quantico, Virginia USA, Laboratory Division, Federal Bureau of Investigation, Quantico, Virginia USA

OVERVIEW

Purpose: The critical capability was to evaluate “touch chemistry” for gaining intelligence/investigative information

from a fingerprint using conventional methods. Results: After developing fingerprints using conventional latent fingerprint methods, the ability to detect three targeted over-the-counter drugs and TNT in fingerprints was demonstrated using MALDI/TOF MS imaging. Conclusion: It is possible to measure chemical information after using conventional fingerprint methods .

INTRODUCTION Chemical information gained from analysis of latent fingerprints, “touch chemistry,” at a crime scene may provide

investigative or other forensically relevant information. Studies reported in the literature demonstrate the ability to gain intelligence information (smoker/non-smoker1, drug exposure2, and ingested drugs of abuse2) from chemicals recovered within fingerprint residue using matrix-assisted laser desorption ionization/time-of-flight mass spectrometry (MALDI/TOF MS). One of the main challenges with fingerprint imaging is the ability to integrate MALDI/TOF MS with current protocols used by latent fingerprint examiners. Four powders were investigated: black powder (BP), nano-powder (NP), magnetic powder (MP), and nano-magnetic powder (NMP). For this study, conventional methods used by latent fingerprint examiners will be evaluated as a way of visualizing a print and acting as the matrix for MALDI in order to ascertain chemical information that can be measured in fingerprint residue.

EXPERIMENTAL DESIGN

RESULTS

DISCUSSION & CONCLUSIONS

ACKNOWLEDGEMENTS This research is supported in part by the FBI’s Visiting Scientist Program, an educational opportunity administered by the Oak Ridge Institute for Science and Education. Names of commercial manufacturers are provided for identification purposes only, and inclusion does not imply endorsement of the manufacturer, or its products or services by the FBI. The views expressed are those of the authors’ and do not necessarily reflect the official policy or position of the FBI or the U.S. Government.

Figure 1: MALDI/TOF MS images of control and acetaminophen fingerprints developed with four different powders. Distribution of [M+K]+ is shown in the acetaminophen handled latent fingerprints but not in the controls. Corresponding spectra for the top slide is shown in Experimental Design 1.

POWDER COMPARISON CYANOACRYLATE FUMING AND POWDER COMPARISON LIFT COMPARISON

Control + BP Acetaminophen

+ BP

Control + NP Acetaminophen

+ NP

Control + MP Control + NMP Acetaminophen +

MP

Acetaminophen +

NMP

Control + BP TNT + BP Control + NP TNT + NP

Control + MP Control + NMP TNT + MP TNT + NMP

Control + BP Aspirin + BP Control + NP Aspirin + NP

Control + MP Control + NMP Aspirin + MP Aspirin + NMP

Control + BP Ibuprofen + BP Control + NP Ibuprofen + NP

Control + MP Control + NMP Ibuprofen + MP Ibuprofen + NMP


MP

Acetaminophen +

NMP








MP

Acetaminophen +

NMP







Acetaminophen

+ BP

Acetaminophen

+ NP

Control + BP Control + NP

Figure 2: MALDI/TOF MS images of control and TNT fingerprints developed with four different powders. Distribution of [M]- is shown in the TNT handled latent fingerprints but not in the controls.

Figure 3: MALDI/TOF MS images of control and aspirin fingerprints developed with four different powders. Distribution of [M-H]- is shown in the aspirin handled latent fingerprints but not in the controls.

Figure 4: MALDI/TOF MS images of control and ibuprofen fingerprints developed with four different powders. Images for [M-H]- shows chemical interference in the controls and ibuprofen handled latent fingerprints.

Figure 8: MALDI/TOF MS images of control and ibuprofen handled fingerprints developed using cyanoacrylate fuming followed by application of four different powders. Compared to Figure 4, chemical interference is reduced with cyanoacrylate fuming and powdering.

Figure 5: MALDI/TOF MS images of control and acetaminophen fingerprints developed using cyanoacrylate fuming followed by application of four different powders. Distribution of [M+K]+ is shown in acetaminophen handled latent fingerprints but not in the controls. Corresponding spectra for the top slide is shown in Experimental Design 2.

Figure 6: MALDI/TOF MS images of control and TNT fingerprints developed using cyanoacrylate fuming followed by application of four different powders. Distribution of [M]- is shown in the TNT handled latent fingerprints but not in the controls.

Figure 7: MALDI/TOF MS images of control and aspirin handled fingerprints developed using cyanoacrylate fuming followed by application of four different powders. Distribution of [M-H]- is shown in the aspirin handled latent fingerprints but not in the controls.

Figure 9: MALDI/TOF MS images of control and acetaminophen fingerprints developed with four different powders and lifted using hinge lifting tape. Distribution of [M+K]+ is shown in acetaminophen handled latent fingerprints but not in the controls. Corresponding spectra for the bottom slide is shown in Experimental Design 3.

Figure 10: MALDI/TOF MS images of control and TNT fingerprints developed using four different powders and lifted using hinge lifting tape. Distribution of [M]- is shown in the TNT handled latent fingerprints but not in the controls.

Figure 11: MALDI/TOF MS images of control and aspirin handled fingerprints developed using four different powders and lifted using hinge lifting tape. Distribution of [M-H]- is shown in aspirin handled latent fingerprints but not in the controls.

Figure 12: MALDI/TOF MS images of control and ibuprofen handled fingerprints developed using four different powders and lifted using hinge lifting tape. Compared to Figure 4, chemical interference is reduced after lifting.

Nano-powders provided higher visual contrast than conventional powders.

All powders demonstrated the ability to act as a MALDI matrix depending on the chemical of interest.

Chemical information was still observed after cyanoacrylate fuming followed by powdering.

For the fingerprint lift analysis, the laser intensity was significantly increased to gain signal and provided

broad peaks in the mass spectra.

Chemical information was observed in both the form of mass spectral data and imaging mass spectra.

Future work will look at investigating alternative fingerprint processing methods.

Acetaminophen

+ BP

Acetaminophen

+ NP

Control + BP Control + NP 8

1

8

1

49

3

49

3

54

3

38

0

13

0

13

0

23

4

23

4

9

0

23

0

8

0

8

0

13

0

17

0

37

0

37

0

44

2

44

2

23

2

23

2

22

0

22

0

1 Benton M, et al. (2009) Surf. Interface Anal.;42:378-385 2 Rowell F, et al. (2009) Analyst;4:701-707.

Barr

ier

Control Prints After Handling Drugs or Explosive Prints

Barr

ier

Barr

ier

Slide #1

Slide #2

Black

Powder

Magnetic

Powder

Nano-

magnetic

Powder

Nano-

Powder

Black

Powder


Nano-

Powder

Magnetic

Powder

Nano-

magnetic

Powder


Barr

ier


Barr

ier

Barr

ier

Slide #1

Slide #2

Black

Powder

Magnetic

Powder

Nano-

magnetic

Powder

Nano-

Powder

Black

Powder


Nano-

Powder

Magnetic

Powder

Nano-

magnetic

Powder


Barr

ier


Barr

ier

Barr

ier

Slide #1

Slide #2

Black

Powder

Magnetic

Powder

Nano-

magnetic

Powder

Nano-

Powder

Black

Powder


Nano-

Powder

Magnetic

Powder

Nano-

magnetic

Powder


Black

Powder

Nano-

Powder

Black

Powder


Nano-

Powder


Lif

t Tap

eL

ift Tap

e

Slide #1

Slide #1

Attach lifting tape sticky side up

1.) Prepare fingerprints by rubbing fingers across face or neck.

Deposit fingerprints before and after handling four compounds:

1) Tylenol (acetaminophen/paracetamol ) ground tablets

2) Advil (ibuprofen) ground tablets

3) Aspirin (acetylsalicylic acid) ground tablets

4) TNT (2,4,6-trinitrotoluene) ground powder

Allow the prints to age for ~30 minutes

2.) Powder the fingerprints 3.) Analyze using MALDI/TOF MS 4.) Generate

spectral and image

data

1.) Deposit fingerprints as described above and

allow to age for ~30 minutes

2.) Fume the fingerprints using cyanoacrylate 4.) Analyze using

MALDI/TOF MS

5.) Generate

spectral and image

data 3.) Powder the fingerprints after

cyanoacrylate fuming

Analyze cyanoacrylate fumed prints directly

1.) Deposit fingerprints as described above and allow

to age for ~30 minutes

2.) Powder the fingerprints 4.) Analyze using MALDI/TOF MS 5.) Generate

spectral and image

data

3.) Lift fingerprints

60th ASMS

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