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 technique to the characterisation of paints, adhesives, plastics, synthetic fibres and soil extracts are descried. Zusammenfassung: Es wird die Rolle der Pyrolyse-GasChromatographic in der gerichtlichen Chemic diskutiert. Die Anwendung der Technik zur Charakterisierung von Anstrichstoffen, Klebstoffen, Kunststoffen und Chemiefasern 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.

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 Initially a furnace type pyrolyzer was used but this has now been superseded by a Curie-point system, which has been found to give highly reproducible pyrograms.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.

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 excludes 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 manufactured 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 qualitative 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-

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 premises. 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 differentiating the acrylic type vehicle paints [2], in this laboratory it used relatively infrequently for this purpose. This is because the diversity of colours used on motor vehicles, and the comprehensive collections of topcoat/undercoat sequences such as those held by the Cardiff Forensic Laboratory, enable characterisation to be made by the traditional techniques. In our work emphasis has been concentrated on the pyrolysis 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 Method Suitable for the Differentiation of Alkyd-Based Paints
Silicones

Table 2. Discrimination of Paint Pyrolyzates on Various Column Packings Number of Differences Column la Paints AB AC AD BC BD CD total 4 2 4 2 1 0 13
b c d e fl

SE 30 MS 200/50, 20/12500 DC 200/350, 200/12, 500, 200/2, 5000, 000 Silicone Oil (Embaphase) Silicone Oil (May & Baker) OV 17, 101,210 Other Stationary Phases Neopentyl glycol, sebacate 1,4 Butanediol Succinate Apiezon L Ucon Fluid 550X Carbowax 20M Igepal CO-630 Versamid FFAP All the above stationary phases were assesed by being coated onto Chromosorb P at the 15 % level.

8 6 4 2 7 3 30

1 1 1 1 1 1 6

3 8 4 9 4 3 31

6 7 3 4 3 1 24

2 7 3 5 0 4 21

Key to Column Packings

a

b c d e f

Porapak Q, 80-100 mesh in a 1.5 m 2.2 mm i.d. stainless steel column MS 200/50 -] Apiez0nL L15 % Chromosorb P (80-100) mesh Carbowax 20M l i n 4 m 2.2 mm i.d. stainless steel column Uconfluid F Neopentyl glycol sebacate A

Programming Conditions alkyd paint flakes it is essential that the column adopted for routine use should display high discriminatory power. Although capillary columns would no doubt show these qualities, our work has concentrated on packed columns. We have carried out extensive screening experiments by pyrolyzing a standard paint sample under standard conditions and separating the pyrolyzate on a variety of columns containing different stationary phases. The stationary phases examined are shown in Table 1, and of these the six most promising were further investigated. This was done by pyrolyzing four different brands of white alkyd - based paint in the form of thin flakes and separating the pyrolyzates under standard conditions on the six different columns. The number of observable differences between paint pairs was noted and are tabulated in Table 2 as a function of column type. The results show that the ability to discriminate between these paint pyrolyzates is markedly linked to the type of stationary phaseused. A column containing Carbowax 20M was finally selected for routine use and the operating conditions are as follows: Column: 4 m stainless steel column of 2.2 mm i. d. containing 15 % Carbowax 20M on Chromosorb P (80-100) mesh Nitrogen at 30 ml/min Flame Ionisation Detector 7 0 - 1 9 0 ~ at 10 ~ mat for 15 mins. then isother. a) 100-200 ~ at 8 ~ b-f) 60-160 ~ at 2 ~

collection only rarely do two different brands of paint give identical pyrograms. Paints of the same brand also differ from time to time, when price variations of raw materials dictate compositional changes. Deriving qualitative data from complex pyrograms is a somewhat more difficult problem. At the present time we rely upon work carried out by the Home Office Central Research Establishment [10] in which a coupled PGC/ Mass spectrometer system was used to identify a nqmber of the compounds present in paint pyrolyzates. Using the information obtained in that study we are currently able to characterise a number of the compounds formed by using retention time data. Despite the advances made by this approach many of the peaks encountered still remain uncharacterised.

Adhesives Another group of materials which we have studied in some depth are adhesives. Particles or smears of these materials do not occur very frequently as samples but we have on occasion been posed the problem of characterising the adhesives used in the manufacture of 'homemade' bombs and also on articles of disputed ownership. The adhesives available through retail outlets constitute a whole range of materials: animal glues, collulosic materials, rubber based products, polyvinyl acetate and the copolymers, epoxy resins and phenol formaldehyde resins. All these materials give characteristic pyrograms and there are often sufficient differences between different brands of adhesives to enabIe a particular product to be identified. Typical pyrograms are shown in Fig. 2 (pyrolysis and chromatographic conditions as described above).

Carrier Gas: Detector: Temperature: Pyrolysis conditions: Sample size:

Curie Point Pyrolyzer 0aye) 10 sec burn at 610 ~ 10-50/~g

Typical pyrograms of three alkyd paints pyrolyzed and chromatographed using the above conditions are shown in Fig. 1. From a comparative standpoint the multiplicity 9 f peaks encountered is of considerable practical value and in the analysis of the many paints in our reference 554 Chxomatographia 5, 1972 Official Papers

Carsons GlossWhite

t
L

Epoxy Resin

Dulux GlossWhite

Styrene 8utadlene Copolymer

Humbrol

70

100

130

;60

1 9 0 - - isoth. . . . I

)Temp "C

70

100

130

160

190- isothermal

Temp"C Time
min

~
Fig. 1

i2

;5

Time

m~,

o
Fig. 2

;2

;5

9 Pyrograms of alkyd-based paints 9 Pyrogramme yon Alkydharzlaeken 9 Chrornatogrammesdes produits de pytolyse de peintures ~ base de r6sine alkyde

9 Pyrograms of adhesives 9 Pyrogramme yon Klebstoffen 9 Chromatogrammes des produits de pyrolyse d'adh6sifs

Filled adhesives, used extensively for tiling cements, ceiling tile adhesives etc. can be readily characterised by P. G. C. whereas the presence of filler poses problems when I.R. spectroscopy is used. Hasties The characterisation of plastics by PGC is too well documented 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 pyrograms 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.

Case 3. Particles of polyurethane foam found in a girl's underwear gave very similar pyrograms to foam present in the cab of a lorry where an alleged rape had occurred.

Textile Fibres Textile Fibres rival paint flakes in their frequency of occurence'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 materials 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 infrared spectroscopy of the fibre, with fluorimetry and thinlayer 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 probably 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 treatment by PGC. Although the major pyrolysis products appear 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 allow a rapid through-put of samples the technique may well have a place in the characterisation of tablets and powders.
Nylon 66

Ny,onS..[-NH~CH2)sCO]~

Ny,on810. H[-NH~CN)6NHCOCCH2~CO]n-O.

~0

;00

i30

iS0

;90

isoth. . . . I--'=~l'em p C

F~. 3

9 Pyrograms of synthetic fibres (nylons) 9 Pyrogcammeyon Chcmiefasern(Nylon) 9 Chromatogrammesdes produits de pyrolyse de fibres synth6tiques (nylons)

Nylon 6

The various types of fibres - eeUulosics, polyesters, polyamides, and acrylics can be readily differentiated from each other by PGC. In many cases fibres falling within the 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 pyrograms, 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

Nyton 610

~ooo ~ooo Although the areas mentioned above are the only ones where we have carried out extensive investigations other applications of PGC have been superficially examined and in some cases found to appear promising. The characterisation of soils, for example, is a subject of forensic interest and we have carried out an initial survey to explore the potential of PGC in this area. Although it may be possible 556 Cl~omatographia 5, 1972 Official Papers

~ooo isoo i6oo i40o i~oo 1000 800

Wavenumber (cm-1)

F~g.4
9 Infrared spectra of nylons 9 Infrarot-Spektren yon Nylonproben 9 Spectres infrarouges de nylons

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] [21 ,lain,N. C., Fontan, C. R., Kirk, P. L., J. For. Sci. Soc. 5, 102 (1965). Thomson, D. B., Cerar, F. B., Clair, E. G., The Centre of Forensic Sciences, Toronto, Ontario, Canada (Unpublished Work). Nelson, D. F., Yee, J. L., Kirk, P. L., Microchem J. 6, 225 (1962). Janiak R. A., Damerau, K. A., J. Crim. Law. Crimino159, 434 (1968). Bortniak, J.P.,Brown, S.E.,Sild, E.H.,J. FoLSci. 16, 380 (1971). Nelson, D. F., Kirk, P. L., Anal. Chem. 34, 899 (1962). Fontan, C. R., Jain, N. C., Kirk, P. L., Mikrochim Acta 326 (1964). Nelson, D. F., Kirk, P. L., Anal. Chem. 36, 875 (1964). Kirk, P. L., J. Gas Chromat0g. 5, 11 (1967). May, R. W., Pearson, E. F., Seothern, M.D., Home Office Central Research Establishment, Aldermaston, England, Report No. 54, June 1971.

[31 [4] [51 [6] [7] [8] [9] 110]

"/0 0

iO0 3

i30
6

i60
9

190--isothermal 12 15

'Temp ~ C Time min

Fig.5 t Pyrograms of acetone extracts from three different topsoils I Pyrogtamme yon Aceton-Extrakten dreier verschiedener Oberfl~ichenbodenproben e Chromatogtammes des produits de pyrolyse des extraits ae6toniques de trois 6chantillons diff6rents de eouehe superfieieile de sol

Chromatographia 5, 1972

Official Papers

557