MALDI-MS for the forensic analysis of

ANDREW SMITH
fingermarks
DIRECTOR OF STUDIES: DR. SIMONA FRANCESE

Contents
What are fingermarks?
Traditional fingermark analysis
MALDI-MSI workflow for the forensic analysis of
latent fingermarks
MALDI-MSI applications
Fingermark ageing
Applying a novel MALDI-MSI methodology to an age
old forensic conundrum
Wrap-up

What are fingermarks?

Often referred to as a latent, or invisible,
fingermarks
Friction ridge skin
A number of secreting glands; eccrine,
apocrine and sebaceous
Form as a result of a transfer of material
present on a fingertip onto a surface
following contact
Have been employed for criminal
investigation purposes since the early 19th
century and are still considered to be one
of the best forms of biometric
HAZARIKA. P and RUSSELL.
D.A. (2012). Advances in Fingerprint Analysis. Analytical Chemistry, 51, 3524-3531
identification

Traditional fingermark analysis

The fingermark of an person is
rendered unique by a number of
characteristics within the distinct ridge
patterns

These are known as minutiae

Allow us to differentiate between any

two individuals

Matching of a number of minutiae to a

known fingerprint (currently no universal
number)
GUTIERREZ. E, GALERA. V, MARTINEZ. J and ALONSO. C (2007). Biological variability of the minutiae in the fingerprints of a sample of the Spanish population. Forensic
Science International, 72, 98-105.

The problem?
It is not uncommon for fingermarks left at
a crime scene to be smudged or distorted

This renders
impossible

biometric

identification

Advances in analytical
instrumentation

Supplementary chemical information

Gender, lifestyle, recent activities
FERGUSON. L, BRADSHAW. R, WOLSTENHOME. R, CLENCH. M.R. and FRANCESE. S (2011). Two-step Matrix Application for the Enhancement and Imaging of Latent Fingermarks.
Analytical Chemistry, 83, 5585-5591.

MALDI-MS analysis of latent

fingermarks
Groomed or
ungroomed
fingermarks

Fingermarks tape
lifted from SOC

FERGUSON. L, CREASEY. S, WOLSTENHOME. R, CLENCH. M.R. and FRANCESE. S (2013).. Efficacy of the dry-wet method for the MALDI-MSI analysis of latent fingermarks. Journal of
Mass Spectrometry, 48, 677-684.

Fingermark visualisation
Dusting the fingermark with a MALDI
matrix leads to image enhancement and
clearer ridge details
Applicable on a wide variety of surfaces

Can separate overlapping fingermarks

Can be separated based upon both
endogenous or exogenous substances

FERGUSON. L, BRADSHAW. R, WOLSTENHOME. R, CLENCH. M.R. and FRANCESE. S (2011). Two-step Matrix Application for the Enhancement and Imaging of Latent Fingermarks.
Analytical Chemistry, 83, 5585-5591.

Drugs and other exogenous

substances
Attain information about lifestyle and/or
drug handling and ingestion
Can visualise caffeine and its metabolites

in fingermarks following consumption

Can detect and visualise drugs of abuse,
such as cocaine
Distinguish between drug dealers (parent
drug and drug users (metabolites)

FRANCESE. S, BRADSHAW. R, FERGUSON. L.S., WOLSTENHOME. R, CLENCH. M.R. and BLEAY. S (2013). Beyond the ridge pattern: multi-informative analysis of latent fingermarks by
MALDI mass spectrometry. Analyst, 138, 4215-4228.

Sexual assault cases

An increase in the use of condoms in
sexual assault cases has been observed
The analysis of different condom lubricants

with the aim of proving corpus delicti

Identification based upon polymeric
constituents of condom lubricant (eg. PEG
and nonoxynol-9)
Determine more than just circumstantial
evidence. Correlate findings with residues
from vaginal swabs taken from victim?

BRADSHAW. R, WOLSTENHOME. R, BLACKLEDGE. R.D., CLENCH. M.R., FERGUSON. L.S., and FRANCESE. S (2010) A novel matrix-assisted laser desorption/ionisation mass
spectrometry imaging based methodology for the identification of sexual assault suspects . RAPID Communications in Mass Spectrometry, 25, 415-422.

But ..
When was the
fingermak left?
?

Determining the age of a

fingermark
Changes in the endogenous composition of fingermark
residue is considered to be the most promising method
(Wertheim 2003)
Initial studies involved the use of GC-MS and
demonstrated that changes in endogenous lipid
composition were correlated with fingermark age
(Archer 2005)

Built upon further (Weyermann 2011) with the changes

in the levels of cholesterol and squalene monitored

Large degree of intra- and inter- donor variability. This

highlights the need for reproducible fingermark
deposition

ARCHER. N.E., CHARLES. Y, ELLIOTT. J.A. and JICKELLS. S (2005). Changes in the lipid composition of latent fingerprint residue with time after deposition on a surface. Forensic
Science International 2005, 154, 224-239. WEYERMANN. C, ROUX. C and CHAMPOD. C (2011). Initial Results on the Composition of Fingerprints and its Evolution as a Function of

A MALDI-MSI approach
Methodology first pioneered by Wolstenhome et
al., (2009)
- Age of fingermark is linked to the levels of oleic acid
(OA), dehydated
...oleic acid (deOA) and
double dehydrated oleic acid (di-deOA)
- Could serve as an empirical method of determining
fingermark age

WOLSTENHOME. R, BRADSHAW. R, CLENCH. MR and FRANCESE. S (2009). Study of latent fingermarks by matrix-assisted laser desorption/ionisation mass
spectrometry imaging of endogenous lipids. Rapid Communications in Mass Spectrometry. 23: 3031-3039

Reproducible fingermarks
Address the issue related to intra- and inter- donor variability by developing a
method of depositing reproducible fingermarks

Consistent time of deposition

Consistent angle of deposition
Consistent pressure

Fingermark sampler produced by Sarah Fieldhouse for

the deposition of reproducible fingermarks
FIELDHOUSE. S (2011). Consistency and reproducibility in fingermark deposition. Forensic Science International, 207, 96-100.

Reproducible fingermarks
UV-Vis
(254nm)
images of
fingermarks
deposited
with pressrig

Press-rig Replicate
A
B
C
D
E
F
G
H
I
J
Mean
Standard Deviation

Pixel Intensity Score

107.96
107.70
113.64
111.26
110.87
108.37
108.50
109.53
111.42
105.50
109.48
2.35

Control Replicate
1
2
3
4
5
6
7
8
9
10
Mean
Standard Deviation

Pixel Intensity Score

100.78
101.51
111.34
104.09
112.17
114.03
109.25
113.90
121.07
119.30
110.74
6.94

MALDI-MSI workflow

?
Press-rig
system

SunCollect
autosprayer for
solvent deposition

?
.

Dry matrix
application

Materials and methods

Fingermark Preparation

MALDI-MSI analyses

Silicone stamp cleaned using ethanol and lint free

tissue
Fingermark deposited using press-rig system by
lowering silicone stamp into reference lipid pad for
~3s and then depositing onto aluminium slide
Fingermarks aged for designated time in incubator
at 37oC w/5% CO2

All mass spectrometric analyses were

performed using an Applied Biosystems
Q-Star Pulsar i Hybrid QToF instrument
at a resolution of 150m

Matrix Application (Dry-wet method)

MALDI-MS images were produced using

Biomap 3.7.5 software
Empirical analysis performed using
FingermarkViewer software
PCA performed using MarkerView
software v1.2.1

Powdered -CHCA (~0.07g) deposited onto

fingermark
Solvent solution (70:30 ACN:H 2O w/0.5% TFA)
deposited onto fingermark using the SunCollect
autosprayer

Data Analysis

Empirical analysis
OA (m/z
283.2)

deOA (m/z
265.2)

di-deOA (m/z
247.2)

Fingermar

OA

deOA

di-deOA

Ratio

Fres
h

k Age
Fresh

88.67

79.49

85.45

1.00:0.90:0

1
Day

1 Day

45.67

111.33

139.22

.96
1.00:2.43:3

4 Day

86.88

96.00

128.20

.04
1.00:1.10:1

8 Day

76.35

139.44

134.38

.48
1.00:1.83:1

Blind Time

78.07

79.23

126.62

.76
1.00:1.01:1

4
Day

8
Day

Point
Blin
d

MALDI-MS images displaying the

distribution of OA (m/z 283.2),
deOA (m/z 265.2) and di-deOA (m/z
247.2) at fresh, 1 day, 4 day, 8 day
and blind time points

.62

Levels of OA, deOA and di-deOA in ageing

fingermarks with ratio of each species relative to
OA. Using the ratios provided, the blind time
point fingermarks (red) were most similar to 4
day aged fingermarks(red), the correctly
assigned age

Multivariate analysis
OA (m/z
283.2)

deOA (m/z
265.2)

di-deOA (m/z
247.2)

Fres
h

1
Day

4
Day

8
Day

Blin
d

MALDI-MS images displaying the

distribution of OA (m/z 283.2),
deOA (m/z 265.2) and di-deOA (m/z
247.2) at fresh, 1 day, 4 day, 8 day
and blind time points

PCA score chart of total lipid composition

of all fingermark ages, including blind time
point

Conclusions

Successfully developed instrumentation capable of

producing reproducible fingermarks, imperative when
performing fingermark ageing studies
Oleic acid degradation is associated with the age of the
fingermark
Total lipid composition of fingermark residue alters
significantly during the first 24 hours following deposition

Future prospective
Analyse the compositional changes during the first 24 hours
following deposition
Greater sample number and statistical analysis. Determine other,
possibly more significant, lipids capable of providing an indication of
fingermark age
Real world context Use real fingermarks
Application Inclusion in scene of crime workflow

Thank you. Any questions?