Forensic Applications of Pyrolysis Gas Chromatography
Anwendung der Pyrolyse-Gas-Chromatographie in der gerichtschemischen Analytik
Application en expertise I~gale de la CG des produits de pyrolyse
B. B. Wheals/W. Noble
Metropolitan Police Forensic Science Laboratory, London, W. C.1., England
Summary:The role of pyrolysis gas chromatography in
forensic chemistry is discussed. Application of the tech-
nique to the characterisation of paints, adhesives, plastics,
synthetic fibres and soil extracts are descried.
Zusammenfassung: Es wird die Rolle der Pyrolyse-Gas-
Chromatographic in der gerichtlichen Chemic diskutiert.
Die Anwendung der Technik zur Charakterisierung von
Anstrichstoffen, Klebstoffen, Kunststoffen und Chemie-
fasern sowie Bodenprobenextrakten wird beschrieben.
R6sum6: On 6tudie le r61e de la chromatographic en phase
gazeuse des produits de pyrolyse en chimie d'expertise
16gale. Les applications du proc6d6 ~ la caract~risation des
peintures, des adh6sifs, des mati6res plastiques, des fibres
synth6tiques et des extraits de sol sont d6crites.
In discussing the application of any analytical procedure
to forensic science it is first necessary to consider the
problems associated with this type of work. If one ex-
cludes the drug and blood alcohol areas, two general types
of problem are encountered. The first, and by far the
most common, involves the comparison of samples found
at the scene of a crime with those associated with, or
found on, a suspect. Items overlooked by the criminal
frequently constitute the samples examined, they are as
a result often small in size and cover a wide range of manu-
factured and natural products - glass, paint, plastics,
metals, hair, fibres, adhesives, waxes, wood, blood etc. It
is essential that the comparative analytical technique used
to examine such samples be both sensitive and capable of
displaying high discriminatory power, because the ultimate
aim o f the analysis is to show that the samples are of
identical origin - not just similar. The second type of
problem is one in which it is required to obtain qualita-
tive information about a single sample, a typical example
being the need to derive from a paint flake information
about the type of resin used in its manufacture.
In the last decade pyrolysis gas chromatography (PGC) has
evolved as a very powerful technique in the analysis of
organic polymeric materials, and since many of the ma-
terials, listed above fall in this class, it follows that PGC
is potentially capable of making a major contribution in
forensic science. In both sensitivity and discriminatory
power PGC is readily applicable to solving the first type
of problem mentioned above and applications to the
forensic characterisation of paints [ 1,2], plastics [3],
synthetic fibres [4, 5], drugs [6, 7, 8] and hair [9] have
been reported. In providing qualitative information about
a sample, however, PGC still has far to go, although the
coupling of mass spectrometers to PGC systems is making
a start in the unraveling of the complexities of pyrolytic
breakdown.
In the Metropolitan Police Laboratory PGC has been in
use for some years and has proved of value in numerous
cases. Initially a furnace type pyrolyzer was used but this
has now been superseded by a Curie-point system, which
has been found to give highly reproducible pyrograms.
The following sections describe some of the applications
of PGC explored in this laboratory.
Paint
Paint flakes constitute a very important source of evidence
in forensic work and arise in such cases as hit and run
vehicle incidents, or during breaking and entry into prem-
ises. The traditional methods of characterisation involve
observation of colour, microscopic examination of paint
layer structures and spectrographic analysis.
Although PGC has been shown to be capable of differentiat-
ing the acrylic type vehicle paints [2], in this laboratory it
used relatively infrequently for this purpose. This is be-
cause the diversity of colours used on motor vehicles,
and the comprehensive collections of topcoat/undercoat
sequences such as those held by the Cardiff Forensic La-
boratory, enable characterisation to be made by the tra-
ditional techniques.
In our work emphasis has been concentrated on the pyro-
lysis of flakes of alkyd - based paints which derive from
finishes used on industrial and domestic buildings. Many
of these commonly used paints are formulated from
similar alkyd resins and the pyrolyzates of such paints
are, therefore, also similar.
If pyrolysis gas chromatography is to be fully exploited
in resolving the problems posed in the differentiation of
Chromatographia $, 1972 Official Papers 553
Table 1. Stationary Phases Screened in the Development of a Table 2. Discrimination of Paint Pyrolyzates on Various Column
Method Suitable for the Differentiation of Alkyd-Based Paints Packings
Silicones Number of Differences
SE 30 Column
MS 200/50, 20/12500
DC 200/350, 200/12, 500, 200/2, 5000, 000 la b c d e fl
Silicone Oil (Embaphase) Paints
Silicone Oil (May & Baker) AB 4 8 1 3 6 2
OV 17, 101,210 AC 2 6 1 8 7 7
AD 4 4 1 4 3 3
Other Stationary Phases BC 2 2 1 9 4 5
Neopentyl glycol, sebacate BD 1 7 1 4 3 0
1,4 Butanediol Succinate CD 0 3 1 3 1 4
Apiezon L
total 13 30 6 31 24 21
Ucon Fluid 550X
Carbowax 20M Key to Column Packings
Igepal CO-630
Versamid a Porapak Q, 80-100 mesh in a 1.5 m 2.2 mm i.d. stainless steel
FFAP column
b MS 200/50 -]
All the above stationary phases were assesed by being coated onto
Chromosorb P at the 15 % level. c Apiez0nL L15 % Chromosorb P (80-100) mesh
d Carbowax 20M l i n 4 m 2.2 mm i.d. stainless steel column
e Uconfluid
f
F
Neopentyl glycol sebacateA

Programming Conditions
alkyd paint flakes it is essential that the column adopted a) 100-200 ~ at 8 ~
for routine use should display high discriminatory power. b-f) 60-160 ~ at 2 ~
Although capillary columns would no doubt show these
qualities, our work has concentrated on packed columns.
We have carried out extensive screening experiments by collection only rarely do two different brands of paint
pyrolyzing a standard paint sample under standard condi- give identical pyrograms. Paints of the same brand also
tions and separating the pyrolyzate on a variety of columns differ from time to time, when price variations of raw
containing different stationary phases. The stationary materials dictate compositional changes.
phases examined are shown in Table 1, and of these the
Deriving qualitative data from complex pyrograms is a
six most promising were further investigated. This was
somewhat more difficult problem. At the present time
done by pyrolyzing four different brands of white alkyd
we rely upon work carried out by the Home Office Central
- based paint in the form of thin flakes and separating
Research Establishment [10] in which a coupled PGC/
the pyrolyzates under standard conditions on the six dif-
Mass spectrometer system was used to identify a nqmber
ferent columns. The number of observable differences be-
of the compounds present in paint pyrolyzates. Using the
tween paint pairs was noted and are tabulated in Table 2
information obtained in that study we are currently able
as a function of column type. The results show that the
to characterise a number of the compounds formed by
ability to discriminate between these paint pyrolyzates is
using retention time data. Despite the advances made by
markedly linked to the type of stationary phaseused. A
this approach many of the peaks encountered still remain
column containing Carbowax 20M was finally selected for
uncharacterised.
routine use and the operating conditions are as follows:

Column: 4 m stainless steel column of 2.2 mm Adhesives

i. d. containing 15 % Carbowax 20M
Another group of materials which we have studied in some
on Chromosorb P (80-100) mesh
depth are adhesives. Particles or smears of these materials
Carrier Gas: Nitrogen at 30 ml/min do not occur very frequently as samples but we have on
Detector: Flame Ionisation Detector occasion been posed the problem of characterising the
Temperature: 7 0 - 1 9 0 ~ at 10 ~ then isother. adhesives used in the manufacture of 'homemade' bombs
mat for 15 mins. and also on articles of disputed ownership.
Pyrolysis Curie Point Pyrolyzer 0aye) 10 sec burn The adhesives available through retail outlets constitute
conditions: at 610 ~ a whole range of materials: animal glues, collulosic ma-
Sample size: 10-50/~g terials, rubber based products, polyvinyl acetate and the
copolymers, epoxy resins and phenol formaldehyde re-
Typical pyrograms of three alkyd paints pyrolyzed and sins. All these materials give characteristic pyrograms and
chromatographed using the above conditions are shown there are often sufficient differences between different
in Fig. 1. From a comparative standpoint the multiplicity brands of adhesives to enabIe a particular product to be
9 f peaks encountered is of considerable practical value identified. Typical pyrograms are shown in Fig. 2 (pyro-
and in the analysis of the many paints in our reference lysis and chromatographic conditions as described above).

554 Chxomatographia5, 1972 Official Papers

 / CarsonsGlossWhite

t
Epoxy Resin

Dulux GlossWhite

L
Styrene 8utadleneCopolymer

Humbrol

70 100 130 ;60 1 9 0 - - isoth. . . . I )Temp "C 70 100 130 160 190- isothermal Temp"C
~ ~ ~ i2 ;5 Time m~, o ; ; ; ;2 ;5 Time min

Fig. 1 Fig. 2
9 Pyrograms of alkyd-based paints 9 Pyrograms of adhesives

9 Pyrogramme yon Alkydharzlaeken 9 Pyrogramme yon Klebstoffen

9 Chrornatogrammesdes produits de pytolyse de peintures ~ base 9 Chromatogrammes des produits de pyrolyse d'adh6sifs
de r6sine alkyde

Filled adhesives, used extensively for tiling cements, ceil- Case 3. Particles of polyurethane foam found in a girl's
ing tile adhesives etc. can be readily characterised by underwear gave very similar pyrograms to foam
P. G. C. whereas the presence of filler poses problems when present in the cab of a lorry where an alleged
I.R. spectroscopy is used. rape had occurred.

Hasties
The characterisation of plastics by PGC is too well docu-
mented to require extensive coverage in this discussion,
but the following case applications indicate the potential
of the technique in forensic work.
Case 1. Particles of a green substance on bolt-cutters
found in a suspects possession gave similar pyro-
grams to the PVC coating of a cable cut at the
scene of a crime.
Case 2. A false number plate had been attached to a
vehicle used in a robbery by having bolt holes
drilled through the underlying plastic number
plate. Fragments of a black substance found on
a drill in a suspects possession gave identical
pyrograms to that of the plastic number plate.
Textile Fibres
Textile Fibres rival paint flakes in their frequency of oc-
curence'as forensic samples. This is because they are so
readily transferred from the clothing of the criminal, to
the victim, or to the environment and vice versa. Fibres
are traditionally analyzed by biologists in this laboratory
although the increasingly synthetic nature of these ma-
terials necessitates a knowledge of their chemistry and
the application of chemical techniques. The analytical
techniques normally used in the characterisation of these
materials involve a combination of microscopy and infra-
red spectroscopy of the fibre, with fluorimetry and thin-
layer chromatography of the optical brighteners and dyes
they contain. PGC is currently being studied to ascertain
its value in this area.

Chromatogtaphia 5, 1972 Official Papers 555

 Nylon 66,H -NI-KCH2)6NHCO(CH2)4CC]n-OH to pyrolyze a soil sample directly, a soil extract will pro-
bably give a result less subject to random variation arising
from the incorporation of fragments of plant material.
Fig. 5 shows pyrograms of the organic residues obtained
from three different topsoils by Soxhlet extraction with
acetone. The variation is sufficiently encouraging to
warrant further work in this area.
The species identification of wood, currently achieved by
microscopic examination, may also be amenable to treat-
Ny,onS..[-NH~CH2)sCO]~
ment by PGC. Although the major pyrolysis products ap-
pear to derive from the cellulose and lignin components
common to all woods some minor variations in pyrograms
do appear which may be species specific.
One area we have not so far studied is the use of PGC in
the characterisation of drugs. The literature indicates this
as being quite a useful field to explore and provided the
gas chromatographic conditions could be established to
Ny,on810. H[-NH~CN)6NHCOCCH2~CO]n-O. allow a rapid through-put of samples the technique may
well have a place in the characterisation of tablets and
powders.

Nylon 66

~0 ;00 i30 iS0 ;90 isoth. . . . I--'=~l'em p C

F~. 3

9 Pyrograms of synthetic fibres (nylons) Nylon 6

9 Pyrogcammeyon Chcmiefasern(Nylon)

9 Chromatogrammesdes produits de pyrolyse de fibres synth6tiques

(nylons)

The various types of fibres - eeUulosics, polyesters, poly-

amides, and acrylics can be readily differentiated from
each other by PGC. In many cases fibres falling within the Nyton 610

same broad class can also be differentiated to some extent.

In the case of the polyamides (nylons) it is interesting to
see the extent of the differences appearing in the pyro-
grams, see Fig. 3 (conditions as before). The nylons are
chemically very similar and other techniques such as I.R.
spectroscopy reveal far fewer differences between these
materials, see Fig. 4.

Miscellaneous
~ooo ~ooo ~ooo isoo i6oo i40o i~oo 1000 800
Although the areas mentioned above are the only ones Wavenumber (cm-1)

where we have carried out extensive investigations other F~g.4

applications of PGC have been superficially examined and
in some cases found to appear promising. The characterisa- 9 Infrared spectra of nylons
tion of soils, for example, is a subject of forensic interest
9 Infrarot-Spektren yon Nylonproben
and we have carried out an initial survey to explore the
potential of PGC in this area. Although it may be possible 9 Spectres infrarouges de nylons

556 Cl~omatographia5, 1972 Official Papers

 In conclusion it can be said that PGC has a very promising
future in the forensic field. By using a variety o f ancillary
techniques such as precolumn reactions, selective detectors
or coupling with a mass spectrometer, PGC can be made
to reveal far more qualitative information than is the case
at present. The use o f columns with greater resolving
power than the packed columns currently in use can also
be expected to improve the comparative aspects o f the
technique.

References
|1] ,lain,N. C., Fontan, C. R., Kirk, P. L., J. For. Sci. Soc. 5,
102 (1965).
[21 Thomson, D. B., Cerar, F. B., Clair, E. G., The Centre of
Forensic Sciences, Toronto, Ontario, Canada (Unpublished
Work).
[31 Nelson, D. F., Yee, J. L., Kirk, P. L., Microchem J. 6, 225
(1962).
[4] Janiak R. A., Damerau, K. A., J. Crim. Law. Crimino159,
434 (1968).
[51 Bortniak, J.P.,Brown, S.E.,Sild, E.H.,J. FoLSci. 16,
380 (1971).
[6] Nelson, D. F., Kirk, P. L., Anal. Chem. 34, 899 (1962).
[7] Fontan, C. R., Jain, N. C., Kirk, P. L., Mikrochim Acta 326
(1964).
[8] Nelson, D. F., Kirk, P. L., Anal. Chem. 36, 875 (1964).
"/0 iO0 i30 i60 190--isothermal 'Temp ~ C [9] Kirk, P. L., J. Gas Chromat0g. 5, 11 (1967).
0 3 6 9 12 15 Time min 110] May, R. W., Pearson, E. F., Seothern, M.D., Home Office
Central Research Establishment, Aldermaston, England,
Fig.5 Report No. 54, June 1971.

t Pyrograms of acetone extracts from three different topsoils

I Pyrogtamme yon Aceton-Extrakten dreier verschiedener Ober-

fl~ichenbodenproben

e Chromatogtammes des produits de pyrolyse des extraits ae6toni-

ques de trois 6chantillons diff6rents de eouehe superfieieile de sol

Chromatographia 5, 1972 Official Papers 557