Forensic Science International 119 (2001) 195±211

Identi®cation of gunshot residue: a critical review

Francesco Saverio Romoloa,*, Pierre Margotb
a
Head, Gunshot Residue Analysis Laboratory, Direzione Centrale Polizia Criminale, Servizio Polizia Scienti®ca,
Viale dell'Aeronautica 7, 00144 Rome, Italy
b
Director, Institut de Police Scienti®que et de Criminologie, University of Lausanne,
BCH-UNIL, 1015 Lausanne-Dorigny, Switzerland
Received 9 May 2000; received in revised form 7 November 2000; accepted 7 November 2000

Abstract

A review of the scienti®c papers published on inorganic gunshot residue (GSR) analysis permits to study how the particle
analysis has shown its capability in detection and identi®cation of gunshot residue. The scanning electron microscope can be
the most powerful tool for forensic scientists to determine the proximity to a discharging ®rearm and/or the contact with a
surface exposed to GSR. Particle analysis can identify individual gunshot residue particles through both morphological and
elemental characteristics. When particles are detected on the collected sample, the analytical results can be interpreted
following rules of a formal general interpretative system, to determine whether they come from the explosion of a primer or
from other possible sources. The particles on the sample are compared with an abstract idea of ``unique'' GSR particle
produced by the sole source of the explosion of a primer. ``Uniqueness'' is not the only problem related to GSR detection and
identi®cation for a forensic scientist. With ``not-unique'' particles interpretation of results is extremely important. The
evidential strength of ``not-unique'' particles can increase with a more fruitful interpretative framework based on Bayes rule.
For the assessment of the value of a GSR in linking a suspect and a crime, it is important to compare two hypothesis: the ®rst
can be that of the evidence if the suspect has been shooting in a speci®c situation, the second that of the evidence if the suspect
was not involved in this shooting. This case speci®c or case-by-case approach is closer to what the court is interested in. The
authors consider that a ``case-by-case'' approach should be followed whenever possible. Research of models and data such as
those developed in other trace evidence material (®bres, glass, etc.) using a Bayesian approach is suggested in the
interpretation of GSR. # 2001 Elsevier Science Ireland Ltd. All rights reserved.

Keywords: Gunshot residue; Firearms chemistry; Interpretation; Bayes rule

1. Introduction used, like cartridge discharge residue (CDR) [4] or ®rearm

In situations involving actual or suspected use of ®rearms,
detection and identi®cation of residual materials from ®re-
arms discharge may provide valuable investigative informa-
tion. These residues are principally composed of burnt and
unburnt particles from the propulsive charge, as well as
components from the primer, the bullet, the cartridge case
[1±3] and the ®rearm itself, and they are generally called
gunshot residue (GSR). Gunshot residue is not the only
de®nition used. There are articles where other de®nitions are
*
Corresponding author.
E-mail address: forensic.romolo@tiscalinet.it (F. Saverio Romolo).
discharge residue (FDR) [5].
Detection and identi®cation of GSR are commonly per-
formed with the aim of determining whether or not a suspect
®red a gun, to determine a bullet entrance hole or to estimate
a ®ring distance [6,7]. Little success has been achieved in
using GSR to provide investigative leads other than those
described [8].
The present methods of analysis make use of SEM/EDX
and are considered ``very speci®c''. Organic GSR identi®ca-
tion and characterisation methods were extensively
reviewed by Meng and Caddy but are used only in a limited
number of laboratories [8].
A review of the scienti®c papers published on inorganic
GSR analysis permits the study of several aspects of

0379-0738/01/$ ± see front matter # 2001 Elsevier Science Ireland Ltd. All rights reserved.
PII: S 0 3 7 9 - 0 7 3 8 ( 0 0 ) 0 0 4 2 8 - X
196 F.S. Romolo, P. Margot / Forensic Science International 119 (2001) 195±211
detection and identi®cation of gunshot residue. The differ-
ences in fundamental de®nitions used in the interpretation of
results reveal that the meaning of ``very speci®c'' is rather
vague and follows more from the personal skill of the experts
than from standardised procedures. Particles with the same
composition were de®ned ``characteristic'' or ``consistent''
by Wolten et al. [9] and ``unique'' or ``indicative'' by
Wallace and McQuillan [4]. The ASTM standard guide
for GSR analysis is not a strictly standardised procedure
and the de®nition and the classi®cation do not give an in
depth view of the problem [10].
The lack of precise interpretative framework gives the
meaning of such conclusive statements as ``very speci®c'',
``unique'', ``characteristic'' an undeserved impression of
precision which is often subject to discussion in disputed
cases. It is our aim to analyse the meaning of such conclusive
statements in GSR detection and identi®cation. We will
consider a formal general interpretative view and a case
speci®c or case-by-case approach.
A critical review of methods is necessary to get a deep
understanding of conclusive statements.
2. A survey of methods for inorganic GSR analysis
2.1. Colour tests and bulk analysis
In 1933, Teodoro Gonzalez of the Mexico City Police
Laboratory introduced the dermal nitrate or paraf®n test.
This involved the taking of a cast of the back of the suspect's
hand using hot paraf®n wax. When cooled and set, the wax
was peeled off along with embedded GSR particles. The cast
was then sprayed with a 0.25% solution of N,N0 -diphenyl-
benzidine in concentrated sulphuric acid. The reagent, like
diphenylamine used later, gave a deep blue coloration with
nitro-compounds from the partially burnt and unburnt pro-
pellant particles [11,12].
Whilst the test gave good information regarding the
distribution of these particles, the test itself was only indi-
cative for nitrates. Oxidisers causing a positive reaction are
found in fertilisers, pharmaceuticals, ®ngernail polish, urine
and on hands of people after striking a match [13±15]. The
Griess reagent was found later to be a little more selective
[16].
In 1959, Harrison and Gillroy developed a test for the
identi®cation of lead, barium and antimony from lead
styphnate, barium nitrate and antimony sulphide used in
the manufacture of primers. Swabs moistened with dilute
hydrochloric acid were used to collect GSR on hands [17].
The swabs were dried and treated with triphenylmethylar-
sonium iodide, then, after drying again, a solution of sodium
rhodizonate was added. The ®rst reagent produced orange
spots if antimony was present. The second one gave a red
coloration with lead or barium and after addition of dilute
hydrochloric acid, the spots turned purple due to the pre-
sence of lead.
The great advantage of this test over the dermal nitrate
test was the low incidence of false positives. In the following
years forensic scientists interested in GSR analysis looked
for more sensitive techniques in detecting these three
elements.
In 1962, Ruch et al. presented the use of neutron activa-
tion analysis (NAA) for the identi®cation of antimony and
barium in GSR at the meeting of the California Association
of Criminalists. This research was published in 1964 [18].
NAA was used for the ®rst time in court in Canada in 1958 as
supporting evidence [19]. At that time it was the most
sensitive means of analysing for a majority of the elements
in the periodic system. One of the most interesting cases of
analysis using NAA was the determination of arsenic in
Napoleon's hair [20].
Ruch et al. used a 1% HNO3-®lter paper removal tech-
nique and analysed 130 samples to determine the control
levels of Ba and Sb on hands [18]. They found only 0.05±
0.10 mg of Ba and 0.01±0.03 mg of Sb in most cases of
controls (blank levels). Sampling hands for GSR after dis-
charging a handgun resulted in values as high as 4 mg of Ba
and 1 mg of Sb, respectively. This technique was not applic-
able to lead and analysis had to be conducted by trained
personnel using a nuclear reactor as the neutron source.
Despite these limitations, NAA has been extensively used to
detect gunshot residues [21±26] and to solve different
problems in forensic science like shooting distance deter-
mination [27,28] or bullet identi®cation [29,30].
In 1971, a method was reported for the analysis of GSR
using atomic absorption spectroscopy (AAS) [31]. Conven-
tional ¯ame AAS had suf®cient sensitivity for detection of
the levels of lead encountered in hand samples (1.3±7.6 mg
non-®ring hand, 5.2±30.0 mg ®ring hand) but it was inade-
quate for barium and antimony [32]. Development of elec-
trothermal atomisers (carbon rod, tantalum strip and
graphite tube furnaces type) has made ¯ameless AAS more
attractive for forensic laboratories [33]. GSR could be
collected using swabs moistened with diluted acid, washing
the hands with diluted acid or lifting the particles with an
adhesive surface [34,35]. The last sampling procedure is
called ``tape lifting''.
Jones and Nesbitt in 1975 [36] and 2 years later, Nesbitt
et al. [37] introduced a photoluminescence technique for
GSR analysis. The sample put in liquid nitrogen was excited
with a quartz-xenon arc lamp to detect the emission of Pb
(385 nm) and Sb (660 nm). In the ®rst article, a wash
procedure for the collection of GSR was presented but in
the second paper a tape-lift method, used in 168 test ®rings,
was found to be superior. Handblank samples were taken
from 45 different people including auto mechanics, painters
and workers in other ®elds, while at work. Considerably
more residues were found indoors than outdoors. Sb was
detected in samples obtained from ®rings of antimony-free
ammunition (which do not contain Sb in the primer). A study
was made of the persistence of GSR on hands, showing a
drop of about an order of magnitude after 1 h. It was shown
 F.S. Romolo, P. Margot / Forensic Science International 119 (2001) 195±211
that GSR could be transferred from hand to hand and from
hand to clothing, especially into trouser pockets. Similar
results were obtained in 1975 by Kilty determining anti-
mony and barium concentrations by NAA [24].
In 1977, Krishnan reported the results of the development
effort of nearly 8 years and of more than 1500 test shots, in
which 57 weapons were used [38]. The analytical procedure
involved washing the hands with 50 ml, 5% nitric acid and
freeze-drying. A part of the solution was analysed by NAA
and the other by AAS. In actual cases Pb, Sb and Ba levels
were above the amounts found in tests and well above
handblanks. The persistence was up to 24 h in actual cases
and 2 h in tests. The ratio of ®ring to non-®ring and back to
palm was studied and found to be unpredictable. Positive
results could be caused by handling a weapon, a spent
cartridge case or a target containing the bullet hole.
Numerous other different techniques have been studied
for GSR analysis. Anodic stripping voltammetry (ASV)
could be conducted with relatively inexpensive equipment
but could not determine barium [39±41]. Differential pulse
anodic stripping voltammetry (DPASV) allowed faster and
more sensitive simultaneous detection of lead and antimony
[42]. Proton-induced X-ray emission (PIXE) offered good
sensitivity but suffered from a number of limitations for
routine applications [43]. Inductively coupled plasma
atomic emission spectroscopy (ICP/AES) was found more
sensitive than AAS only for Ba [44]. X-ray micro¯uores-
cence permitted the analysis of GSR on human tissues and
clothing, con®rming the possibility of an entry hole and
giving information on ®ring distance [45]. The use of
inductively coupled plasma-mass spectrometry in analysis
of gunshot primer residue was reported in 1998 [46]. A
simple histochemical technique for identi®cation of GSR
using alizarin red S (ARS) was studied as well [47].
In 1996, Singer et al. presented a survey sent to 80
forensic laboratories in 44 States of the USA and two
Canadian Provinces concerning methodology in analysing
GSR and interpreting the results [48]. The results were
compared to a previous survey reported in 1990 by De
Gaetano and Siegel [49]. The majority (44%) utilised only
AAS, a slight decrease ( 4%) over the value reported in
1990. Only 2% used NAA and no laboratories used ICP. In
1990, the NAA users were 1.6% and ICP users were 4%.
2.2. Particle analysis of GSR
The methods based on bulk analysis techniques lack the
speci®city required for GSR detection in forensic science.
The results only show that the three elements (Pb, Sb and
Ba) are present on a surface, but they could be picked up
separately from the environment. Particles containing lead
and bromine are found in the emissions from the combustion
of leaded petrol. Lead is found in plumbing materials, in
battery plates, in type metal, in solder, in glass and in paint.
Antimony is found in several alloys, often with lead, and its
oxide is used as a ®re retarding in cotton and polyester blend
197
®bres. Barium is found in paint, in automobile grease and
barium sulphate from paper is probably the dominant source
of environmental barium on hands [50,51]. Havekost et al.
studied barium and antimony distribution on the hands of
269 non-shooters and found that activities such as working
as an auto mechanic, electrician or construction worker had
a tendency to result in higher levels of Ba and Sb on the
hands [52]. Brandone et al. tested the introduction of
samarium oxide to label gunpowder, resulting in a speci®c
way of detecting gunshot residues by NAA [53].
A scanning electron microscope (SEM) equipped with a
X-ray detector is capable of analysing X-ray spectra in
sample volumes of a few cubic microns. A X-ray spectro-
meter can separate X-ray emission, according to the wave-
length, by diffraction from a crystal (wavelength dispersion
or WDX) or by use of energy-dispersion characteristic of a
solid-state detector (EDX). In a lithium-drifted silicon solid-
state detector, the output signal is proportional to X-ray
photon energy [54].
Probably the earliest researches into the use of the SEM/
EDX for GSR analysis were carried out in the Metropolitan
Police Forensic Laboratory, New Scotland Yard, England
around 1968 [15].
Basically, the SEM is a microscope which uses a beam of
electrons rather than visible light to visualise the object.
SEM has a depth of ®eld over 200 times greater than an
optical microscope, an extremely high resolution and a
magni®cation capability in excess of 100 000. In addition,
on striking the sample, the electrons give up some of their
energy to the elements present and this energy can be re-
emitted as X-rays, the wavelength of which is particular to
the elements. A SEM, equipped with a X-ray analyser is a
powerful tool, providing morphological and analytical infor-
mation for single particles in a non-destructive way and
allowing the ``maximum speci®city'' in GSR detection. No
bulk analysis technique can reach such a high selectivity.
In 1971, Boehm presented micrographs of GSR particles
during the workshop on forensic applications of the scanning
electron microscope following the 4th Annual Scanning
Electron Microscopy Symposium [55]. He studied gunshot
wounds and found particles of ``gun smoke deposits'' around
bullet entrance holes. The elements present in such deposits
were mainly lead, antimony and barium. Both morphology
(see Fig. 1) and analysis (see Fig. 2) of these particles were
important for their identi®cation.
Because of these encouraging results and the interest
generated, a symposium on particulate GSR was held at
The Aerospace Corporation in 1975. Attending were 19
individuals associated with crime laboratories who had an
interest in the subject. One of them, Matricardi, came from
the FBI Laboratory in Washington, where the method used
to determine if a person had been exposed to the discharge of
a ®rearm consisted in swabbing each hand and determining
the amount of Sb and Ba using NAA [24]. The decision had
already been made that an in-house evaluation and a corre-
lation between the analytical results obtained by SEM and
198 F.S. Romolo, P. Margot / Forensic Science International 119 (2001) 195±211

Fig. 1. SE/SEM image of a particle found in a sample from the barrel of a pistol Pietro Beretta cal. 7.65 mm, after shooting a Giulio Fiocchi
Lecco cartridge 7.65 Browning with jacketed bullet.

the quantitative results obtained by NAA should be under-
taken in the FBI Laboratory. After the meeting of The
Aerospace Corporation, where the status of the research
and the prevalent experimental methods had been presented,
this work started.
In 1976, Nesbitt et al. Presented a ®rst paper about
detection of GSR using scanning electron microscope
[56]. They conducted test ®rings in The Aerospace Corpora-
tion with seven different guns. GSR were collected with a
SEM specimen stub covered with a layer of adhesive (tape
lifting). In 1977, Matricardi and Kilty produced an extensive
paper with the ®rst results of the research in FBI Laboratory
[57]. GSR were collected in a way similar to the one
described in 1976 by Nesbitt et al. [56]. They showed that
using back-scattered electron (BSE) image approach, the
particles were easier to be detected than with normal sec-
ondary imaging (see Figs. 3 and 4). In some cases GSR
identi®cation with energy dispersive detectors (EDX) could
be dif®cult. Calcium peaks overlapped antimony peaks and
similar overlaps occurred for titanium and barium. For Sb,
the problem was more serious because of its poor detection
limit in lead, due to high X-ray absorption of lead. A
wavelength dispersive analyser (WDX) showed a higher
resolution but it was slower than EDX and its use was limited
to eliminate ambiguity in single particle identi®cation after
EDX analysis of the sample. A lack of reproducibility of

Fig. 2. EDX spectrum of a particle found in a sample from the barrel of a pistol Pietro Beretta cal. 7.65 mm, after shooting a Giulio Fiocchi
Lecco cartridge 7.65 Browning with jacketed bullet.
 F.S. Romolo, P. Margot / Forensic Science International 119 (2001) 195±211 199

Fig. 3. SE/SEM image of a group of particles found in a sample from the barrel of a pistol Pietro Beretta cal. 7.65 mm, after shooting a Giulio
Fiocchi Lecco cartridge 7.65 Browning with jacketed bullet.

particle counts was found from shot to shot. The deposition
varied as much as 10 times when analysing samples from
subsequent ®rings of the same weapon. One very large
particle of Pb, Sb and Ba was fractured with a scalpel.
The distribution of lead was mainly on the external surface
of the particle while barium and calcium/antimony were
distributed in the bulk. In a very important test described, a
weapon was ®red in a clean room. After 1 min, a piece of
tape was moved around in the room for 1 min, 15 spherical
lead particles per square millimetre were found. The

Fig. 4. BSE/SEM image of the same group of particles of Fig. 3.

200 F.S. Romolo, P. Margot / Forensic Science International 119 (2001) 195±211
conclusion was that the presence of GSR on an individual's
hand does not necessarily prove that the person discharged
or handled a ®rearm.
During the same year, Andrasko and Maehly published
the results of the work of the National Laboratory of
Forensic Science of Sweden [50]. They tested more than
10 different tapes, choosing SellotapeTM for the weakly
interfering background. Using SEM/EDX, particles consist-
ing of lead, barium and antimony present on tapes lifted
from hands were identi®ed as GSR. Different ammunition
was tested but the type of ammunition could not be deter-
mined by this method, since the relative amounts of lead,
antimony and barium in different particles were different.
Different regions of the same GSR particle were found to
vary in their elemental composition, too. Most of the GSR
observed had a diameter of 1±5 mm and were almost sphe-
rical and a few large particles with diameters of up to 30 mm
were occasionally found. Persistence was also studied,
particles larger than approximately 10 mm disappeared from
the hands after the ®rst hour after ®ring. Only small GSR
particles of less than 3 mm were observed after 2 h or more
and could still be detected 3 h after a single pistol shot had
been discharged. This time limit depended on the activity
after shooting. Rinsing the hands with low pressure water
and wiping them with a towel decreased the number of GSR.
Washing hands with water and soap removed GSR com-
pletely.
In 1979, Wolten et al. published the most extensive work
on the subject of SEM/EDX used for GSR analyses to date.
The ®rst paper presented the characterisation of GSR from a
broad range of handgun cartridges in several hundred sam-
ples analysed [9]. GSR particles were classi®ed following
compositional criteria, morphology and size. Four composi-
tions were observed in GSR only and were, therefore,
considered ``characteristic'':
1. Pb±Sb±Ba,
2. Ba±Ca±Si with traces of S,
3. Ba±Ca±Si with traces of Pb if Cu and Zn are absent,
4. Sb±Ba.
The following compositions were considered ``consistent
with GSR'' but not-unique:
1. Pb±Sb,
2. Pb±Ba,
3. Pb,
4. Ba if S is absent or present only as a trace,
5. Sb (rare).
In both ``characteristic'' and ``consistent'' with GSR
particles, one or several of the following and only the
following elements could also be present: Si, Ca, Al, Cu,
Fe, S, P (rare), Zn (only if Cu is also present), Ni (rare and
only with Cu and Zn), K and Cl.
Elements from bullets or brass cases were detected. The
occurrence of a few copper-bearing particles in residues
from ammunition with bare lead bullets was attributed to
retention in the gun of residues from previous ®rings with
coated or jacketed bullets. In the majority of cases, 70±100%
of the particles in a sample of GSR were spheroidal, with a
surface smooth or fuzzy, scaly or covered with smaller
spheres. A relationship showing a decrease in the total
number of spheroidal particles with the muzzle velocity
of the bullet was presented.
In a second paper, approximately 80 samples of particu-
late matter were collected from the hands of a variety of
industrial and commercial workers, including those consid-
ered most critical (from people working with lead smelting
and explosive rivets) [58]. It was found that spheroidal
particles containing elements heavier than sodium are not
abundant in the natural environment. In most cases, there
was no resemblance with GSR and ``characteristic'' particles
of type 1 and 4 were never detected. Some particles
were similar but none of the occupational samples were
falsely identi®ed by experienced personnel following the
criterion that particles similar to GSR individually should
not be found with particles that are produced by other
sources.
A third paper described the ®rst extensive application of
the SEM/EDX method to casework. In all, 86 cases in which
samples from hands were submitted for analysis by law-
enforcement agencies were evaluated statistically [59]. One
case went to appeal and the appeals court upheld the
conviction and speci®cally af®rmed the scienti®c validity
of the method. The conclusion of the authors was that
particle analysis ``has been fashioned into the most de®nitive
method of identifying and the most successful method of
detecting gunshot residue to date. It identi®es gunshot
residue with greater certainty than any previous method
because discrimination from a majority of occupational
deposits of lead, barium and antimony is possible. It is
effective for a much longer time after a ®ring than previous
methods because particle analysis does not have a threshold
problem''.
A serious disadvantage to the use of the SEM for the
detection of ®rearms residue particles was the excessively
long time required to search for and locate the particles. The
lengthy searching was due to:
1. the large sample area,
2. the time spent examining, analysing and rejecting a
large number of non-®rearms particles,
3. extraneous material such as ®bres and skin debris which
could make the particles dif®cult to ®nd or even conceal
them from view.
These problems could be solved by increasing the sample
concentration, increasing the sampling ef®ciency, decreas-
ing the area to be scanned and using sample clean-up
procedures. Wallace and Keeley introduced a two stage
®ltration apparatus to recover particles in the size range
2±50 mm, reducing searching times by a factor of ®ve [60]. A
method was described by Ward for the collection and
concentration of GSR in a density gradient, using disposable
 F.S. Romolo, P. Margot / Forensic Science International 119 (2001) 195±211 201

hardware, in 15 min [61]. The process minimised the area to Matricardi and Kilty were the ®rst to study elemental
be searched and avoided the presence of extraneous debris distribution inside GSR by fracturing one large particle with
with minimal losses. Another method of concentrating GSR a scalpel [57].
was presented by Sugarman [62]. A different concentration Tassa and Zeldes in 1979 studied the distribution of
technique was reported by Zeichner et al. in 1989, who chemical elements over the morphological features of the
concluded that direct observation of a tape-lift surface was particle's surface [75]. They found that in nodule-bearing
preferable to concentration [63]. GSR, the chemical composition of nodules differed from the
In 1992, DeGaetano et al. compared three methods for composition of the ``body'' of the particle and suggested that
sampling GSR from hands and analysing by SEM/EDX when a not-unique particle was found, these nodules
[64]: tape-lift, concentration technique and glue-lift, intro- strongly indicated a GSR origin. When analysing such
duced by Basu and Ferries in 1980 [65]. The concentration nodules attention must be paid because X-ray emission from
technique gave highly variable results. Glue-lift, designed to an irregular surface can be misleading. The varying absorp-
be less sticky than the tape-lift surface, thus, collecting less tion of X-rays into the specimen with take-off angle and
epidermal cells and other debris, did not pick up much GSR matrix inter-element effect in¯uence the results.
either. Tape-lift collection devices proved to be the most Wolten and Nesbitt presented the results of their study
ef®cient particle-lifting device examined. In the same supporting the hypothesis that gunshot residue was formed
experimental conditions, it was possible to detect a mean by the condensation of vaporised bullet and primer materials
of six particles per hour using tape lifting as the collecting [76]. They called ``bullet'' particles of the residue the ones
technique and only a mean of 2.5 particles per hour using originating from the bullet material. They also found so
glue lifting. The ideal collecting device was described as a called ``primer'' particles produced by both primer-derived
surface that does not require carbon coating, polished and bullet-derived materials. Tassa et al. studied gunshot
smooth and ¯at, with no contaminating elements of high residues by X-ray diffraction and concluded that ``the
atomic number. residues are formed from a mixture of partially molten
A method for the removal of organic material from the and vaporised materials, which are derived mainly from
adhesive tape employed for collecting particles on the hands the bullet and the primer'' [77].
utilised oxygen plasma ashing [66,67]. The sample was Basu in 1982 established that GSR particles were con-
attacked by oxygen, excited by RF energy, and oxidisable densates not only in their surface morphology, as presented
materials were converted to gases which were continuously by Wolten and Nesbitt in 1980, but also deep in the particles
removed from the chamber by a vacuum pump. Oxidation in terms of distribution of lead, antimony and barium [78].
occurred usually at 1508C. The application of this technique He studied the distribution of Pb, Sb and Ba in 227 cross-
to SEM samples was improved in 1990 employing the action sections of GSR, and found three main categories of parti-
of the electron beam of the SEM before plasma ashing [68]. cles. He presented a hypothesis of formation process based
The cells of the epidermis were destroyed and only thin on the thermodynamical data in Table 1 [79]. Most GSR
®laments were left, while particles that were previously smaller than 10 mm are formed as droplets at equilibrium
concealed became evident. The treatment did not alter the during primer explosion. Regular spheroids are the most
morphology or composition of GSR or of inorganic envir- stable among these con®gurations of a condensate droplet.
onmental particles. While the temperature increases, larger spheres grow by
The problem of scanning a large sample area combined
with the time spent examining, analysing and rejecting a
large number of non-®rearms particles became less impor- Table 1
tant with automated SEM/EDX systems for the detection of Melting and boiling point of some elements present in GSR [79]a
GSR, either using custom-written software or commercial Name Atomic Atomic Tm (8C) Tb (8C)
software [69±72]. number mass
Statistical considerations are commonly used to justify a
Aluminum 13 26.98 660 2519
reduction in the total specimen area to be searched, but a
Antimony 51 121.75 631 1587
great deal of caution should be exercised because it was
Barium 56 137.34 727 1897
shown how the probability of a false negative report Calcium 20 40.08 842 1484
increases rapidly as the number of gunshot residue particles Copper 29 63.54 1085 2562
assumed to be present decreases [73,74]. Iron 26 55.85 1538 2861
Lead 82 207.19 328 1749
2.3. Formation and deposition of lead, antimony and Magnesium 12 24.31 650 1090
barium GSR Mercury 80 200.59 39 357
Tin 50 118.69 232 2602
The problem of understanding the origin and formation of Zinc 30 65.37 420 907
GSR is essential in order to distinguish them from the a
This table gives the melting point (Tm) and the boiling point
environmental particles. (Tb) at a pressure of 101.325 kPa (1 atm). Values are given in 8C.
202 F.S. Romolo, P. Margot / Forensic Science International 119 (2001) 195±211
coalescence of the smaller droplets. These particles pass
through various metastable forms and then solidify. During
the decreasing temperature phase of the explosion, a few
semisolid spheroids of Ba and Sb may capture Pb vapours
and form particles showing a ``peeled oranges'' morphology.
Lead, antimony and barium are not the only elements
coming from the primer. For example, phosphorus can
originate from lead hypophosphite, which is a constituent
of certain primers [4]. Calcium silicide is found in several
primers lacking antimony sulphide. Both, 6.35 mm Hirten-
berg and 0.38 Kynoch ammunitions were found to produce
Pb±Ba±Ca±Si particles [77]. A qualitative analysis of the
particles from 7:62 mm  25 mm Chinese ammunitions
showed a composition containing Pb, Sb, Sn, Cl and S
[80]. Tassa et al. reported the composition of two ``corro-
sive'' primers, where potassium chlorate replaces barium
nitrate. The 7:62 mm  39 mm manufactured in former
Eastern Germany were found to produce S±Cl±K±Sb par-
ticles [77]. Ammunition having mercury fulminate-based
primers are commonly manufactured by former Eastern
Bloc countries and used extensively in the Middle East.
Russian and Egyptian have 7.62 primer mixtures, which
consist mainly of mercury fulminate, potassium chlorate and
antimony sulphide. Their GSR consist of Sn, Sb, Hg, S, Cl
and Cu accompanied by small amounts of Al, Si, Fe and Zn
[81]. Wallace investigated the presence of mercury in dis-
charge residue particles from mercury-containing ammuni-
tion [82]. He found that mercury did not make a signi®cant
contribution to the elemental composition of the GSR
because a high percentage was released into the atmosphere
and was not detectable by SEM.
The particles detected by SEM are composed of elements
not only from the primer and the projectile. The cartridge
case and the ®rearm itself contribute as well. Firearms that
are in rusted condition can produce discharge particles with
iron [4].
In 1998, the analysis by SEM/EDX of the smokeless
powder in 22 kinds of ammunitions were reported [83]. Cu,
S, K, Si, Al, Ca, Fe, Cl and Ba were detected. Cu was found
in all samples and one sample contained a high amount of
Ba. Hence, smokeless powder could be the source of some of
the elements detected in GSR.
The results of a study concerning the identi®cation of
GSR by Raman microscopy were published in 1998 [84].
Raman spectra permitted identi®cation of compounds in
GSR. It was found that most of the particles consisted of
carbon. Anions of lead and barium were identi®ed as well.
Particles consisting of BaCO3 or PbO were detected. Other
particles consisted of a mixture of compounds such as
BaCO3, PbSO4 and PbO. One interesting feature of Raman
spectra was the capability of showing evidence of a parti-
cular crystal structure and stoichiometry (e.g. orthorombic
PbO).
The GSR particles can escape from the ®ring chamber
through the muzzle or the breeches and are blown at once
onto the immediate surfaces of the ®rearm, including any
hand in contact with or in close proximity to the ®rearm. The
deposits on the hands of the shooter are mainly the trigger-
blast residues coming out from the breeches and if the gun is
pre-cleaned, using the same ammunition and the same hand
grasp, a reasonably constant amount of residues is deposited
per ®ring on the back of the ®ring hand. If the ®rearm is not
pre-cleaned, the residues of previous ®rings lodged as foul-
ing in the interior of the gun are blown-off rather irregularly
through the breeches and the muzzle in the subsequent
®rings [85].
2.4. The casework experience of GSR particle analysis
There are hardly any reports in the literature on the
success rate of GSR detection in casework. The results of
Wolten et al. [59] reported quite a high success rate (about
80%) in samples collected from hands using the tape-lift
technique and performing a manual search.
A work reporting the SEM/EDX experience of 5 years
(195 sets of swabs from hands, head hair and face, 301 items
of clothing and 372 spent cartridges) in the Northern Ireland
Forensic Science Laboratory has been published in 1984 [4].
The authors changed the classi®cation made by Wolten et al.
[9], considering two ``unique'' particles coming speci®cally
from a primer discharge:
1. Pb±Sb±Ba,
2. Sb±Ba.
Their new discharge residue particle classi®cation is
presented in Table 2.
The classi®cation system was based on available experi-
ence and was intended as a general guide only. If the gun and
the ammunition used in the crime were available, test ®rings
should be conducted for comparative purpose. Particles
containing elements other than the permitted accompanying
elements were classi®ed as inconsistent with ®rearms dis-
charge unless the relevant element was present in the dis-
charge residue from the gun and/or ammunition used in the
crime.
Zeichner et al. found that the composition encountered in
casework could differ appreciably from the classic criteria
for identi®cation of GSR [86]. They presented two examples
of some exceptional composition of GSR particles, formed
using different types of ammunition in the same ®rearm.
Khanmy and Gallusser demonstrated that the type of clean-
ing procedure (normal or ``professional cleaning'') does not
in¯uence the presence of primer residues from shots ®red
before cleaning [87]. Sinoxid primer residues were detected
in all samples, collected after shooting Sintox ammunition.
Harris found that lead, barium and antimony had been
deposited inside the chamber of an old revolver analysing
the metal shavings from inside the chamber [88].
Zeichner et al. found that the concentration of antimony
on the surface of lead alloy bullets is higher than in the bulk
and made some tests using ammunition with antimony-free
primer [89]. Even when the surface of the bullet was highly
 F.S. Romolo, P. Margot / Forensic Science International 119 (2001) 195±211
Table 2
Discharge residue particle classi®cationa[4]
Unique Indicative
Pb, Sb and Ba Ba, Ca and Sib
Sb and Ba Pb and Sb
Pb and Ba
Sb (with S)
Sb (without S)
Bab
Pb
Pb, Sb and Ba absentc,d
a
The indicative particle types are listed in approximate order of
decreasing signi®cance.
b They have been found only as residues of primers, in ®re-
S absent or acceptable as trace only when Ba present at major
level.
c
Any of the above may also include some or all of the
following: Al, Ca, S, Si at major, minor or trace level; Cl, Cu, Fe,
K, Zn (only if Cu also present and Zn:Cu < 1) at minor or trace
level; Mg, Na, P at trace level only, P only if Pb present and
substantially greater than P level. Major: any element whose main
peak height is greater than one-third of the peak height of the
strongest peak in the spectrum. Minor: any element whose main
peak height is between one-tenth and one-third of the peak height
of the strongest peak in the spectrum. Trace: any element whose
main peak height is less then one-tenth of the peak height of the
strongest peak in the spectrum. The primary elements (Pb, Sb or
Ba) can occur at major, minor or trace levels, though for particles
involving more than one of the primary elements at least one of
them is typically present at major level. For particles involving
only one primary element, the element is typically present at a
major level, occasionally minor and never trace.
d
Particles containing no Pb, Sb or Ba may be considered
indicative if they are composed entirely of the elements in three
above and are accompanied by other types of indicative particles.
enriched with antimony, he found a small probability of
®nding GSR with a high level of antimony.
Wallace and MacQuillan considered of very limited
practical value, except in suicide cases, the distribution
on skin surfaces, because it is very easily altered. Statistics
gathered from casework showed that 98% of all suspects
with discharge residues on their hands were apprehended
within 2 h of the shooting incident. They studied the pos-
sibility of discriminating between discharge residues from
cartridge-operated industrial tools and from ®rearms using
SEM as well [4]. They tested all the different types of tools,
cartridges and nails sold in Northern Ireland and found one
primer containing lead, antimony and barium (Obo SG75). It
was suggested that ``when interpreting the results, the
particles must be considered as a group''. The most striking
difference between the two sources of discharge particles
was the scarcity of lead-only particles from the cartridge
tools. The second important difference is that 99% of the
cartridge tool discharge particles detected contained iron.
Wallace published later another work about blank car-
tridges, where the residue produced by discharging a total of
203
79 different cartridges were analysed [90]. He found that
``individually the particles (produced by blank cartridges)
could not be distinguished from ®rearms discharge residue''.
Considering the group of particles, the ratio of indicative to
unique for ®rearms was 35:1, whereas for blank cartridges
discharge, the overall ratio was around 1:9, blank cartridges
were found to produce very few lead-only particles and a
limited range of discharge particle types. Vinci et al. demon-
strated the impossibility of ®nding signi®cant qualitative
differences between residue from Fiocchi blank cartridges
and GSR from regular ball-cartridges [91].
In the survey by Singer, the particles containing Pb, Sb
and Ba were ``still considered to be the most speci®c'' [48].
arms cartridges and in hand grenades as well [92]. Singer
reported that ®ve laboratories out of nine considered the
particles containing only the two components Sb and Ba
``less speci®c'' [48].
In an interesting work by Liu et al. 172 230 polydisperse
particles originating from ®reworks have been analysed
using aerosol time-of-¯ight mass spectrometry (ATOFMS).
Particles containing magnesium, potassium, barium and lead
have been detected but no ``unique'' particle was reported
[93].
Mosher et al. found on the hands of professional ®reworks
technicians ``GSR-similar particles'' [94]. The use of pri-
mers and other compounds of Pb, Ba and Sb in ®reworks
manufacturing was reported by the authors. The pictures of
four particles with ``a morphology consistent with rapid
cooling from a liquid-state'' containing Ba, Sb and S were
shown. Pictures and EDX spectra of particles from con-
sumer-grade devices were reported as well. In one case, two
Ba and Sb particles were found in uncombusted ®reworks. In
another case, eight particles containing Pb, Sb and Ba were
detected. Most of them lacked the morphology considered
typical of GSR and all of them contained Mg and/or Cu at
major level.
In 1997, Zeichner and Levin proposed to include in the
group of ``unique'' GSR, the composition Pb±Ba±Ca±Si±
Sn, formed in ®ring of 9 and 7.65 mm Sellier Bellot of
Prague (SBP) [95]. They examined 1211 samples from 482
cases, starting in the year 1989. In 12 of these cases, SBP
cartridges were recovered from the crime scene. In three of
these cases, particles characteristic of the SBP ammunition
were identi®ed. In every case where Pb±Ba±Ca±Si±Sn
particles were identi®ed, the recovered cartridge cases were
SBP. Such particles were detected and classi®ed, among
others, during auto-search run and manually examined.
Thus, in the period of 7 years, several hundred thousand
particles were analysed and characteristic particles of SPB
were identi®ed only in three cases (out of 12) in which SBP
ammunition cartridges were found at the scene of crime. The
authors concluded that the experimental data base was
extensive enough to consider that ``the uniqueness of
SBP, GSR composition is not less than that of the composi-
tion Pb±Sb±Ba or Sb±Ba''. It was pointed out by Stoney that
204 F.S. Romolo, P. Margot / Forensic Science International 119 (2001) 195±211
is not possible to reach uniqueness through statistics [96]. In
a meaningful identi®cation of GSR particles, the comparison
of the particles found on a speci®c surface with those of the
ammunition used is as important as the ``formal'' idea of
uniqueness. It is always desirable to examine the spent
cartridge case and/or gun (if available) in order to determine
the primer type [4]. Whenever no cartridge cases are found,
it is possible to ®nd GSR particles on the ``bottom of
discharged bullets'', including those severely deformed on
impact [97], or near the bullet hole [89,98].
King reported the results of the work of the Home Of®ce
Forensic Science Laboratory of Birmingham using a swab-
bing kit to recover explosives and gunshot residue from skin
surfaces and hair, and examining clothing by vacuum ®ltra-
tion [99,100]. Of 91 shooting cases (April 1992±April 1993),
propellant was detected in 33% of them, while the success
rate in GSR detection by SEM/EDX was 10% before the
introduction of propellant analysis.
Casework experience in Israel, in the detection of GSR
particles on samples from hands, hair and clothing was
reported for a period of 6 years (1989±1994) [101]. The
overall success rate on the examined samples was about 10%
(the success rate increased by approximately 50% after the
introduction of the automated GSR search system). Only
68% of the submitted cases were examined. In most case-
work samples (83%) only a few (up to ®ve) GSR particles
were found and in a high percentage of these samples only
one particle was found (39%).
Since the beginning of 1991, one stub was used for both
hands (25 dabbing each hand) and the other one for sampling
the hair (200 dabbing) while the clothes were sampled using
the tape-lift method.
In laboratory experiments, it was possible to ®nd GSR
even 24 h after shooting if the hair had not been washed.
Non-signi®cant difference in collection ef®ciency was
found between tape-lift technique and the more complicated
method of swabbing. In some cases, GSR were found in
samples from hair but not in samples from hands [102].
2.5. Sampling procedures
Tape lifting is the most common procedure for inorganic
GSR sampling from skin surfaces, and is used for clothing
as well [103]. Wrobel et al. tested a number of adhesives
for their suitability in the areas of elemental composition,
adhesive properties and adhesive stability under vacuum
and an electron beam. They found that the best overall
was SellotapeTM 404 [104]. The adhesive surface, if non-
conductive, has to be coated with a thin ®lm of carbon
before SEM/EDX analysis. Vacuum lifting is widely used
for collecting GSR from clothes onto a ®lter disk [105,
106]. Swabbing is the most common technique for the
collection of organic compounds from skin surfaces, and
is used for inorganic particles as well [107]. A method was
reported to recover GSR in human nasal mucus from 48 h
post-®ring sample collection times [108]. Polyvinyl alcohol
(Polyviol1) was tested to collect gunshot residue from the
hands of shooters. The application of this polymer in
sampling procedures was found promising only on dead
people, because it takes 45 min to produce the ®lm to be
analysed [109,110].
2.6. GSR produced by lead-free ammunition
In 1980, Dynamit Nobel AG commercialised a new
ammunition, called Sintox, developed to minimise airborne
lead levels and possibly other metallic residues such as
barium and antimony.
In 1987, Hellmiss et al. used a SEM equipped with Auger
electron spectroscopy instead of EDX and an ion gun in a
research project about the analysis of gunshot residue [111].
Auger spectroscopy permitted the analysis of elements with
low atomic number and elements whose peaks overlap in
EDX analysis. The instrumental combination allowed a
spatial resolution of 0.3±3 nm (with EDX the characteristic
X-rays used for the analysis come from an area that has a
width and a depth in the order of 1 mm). Using simultaneous
Auger electron spectroscopy and ion sputtering etching, a
pro®le of the in-depth composition variations of GSR was
studied. Two different kinds of particles formed by Sintox
9 mm para ammunition were found, both with a porous
surface. The ®rst had a fairly irregular morphology and
consisted of titanium dioxide (TiO2) with only a thin layer of
nearly 5 nm covering it containing zinc (Zn), sulphur (S),
potassium (K), calcium (Ca), carbon (C), oxygen (O) and
silicon (Si). The second kind of particle contained consider-
able amounts of copper (Cu). The authors believed that the
primer contained titanium and zinc compounds, whereas the
copper came from the jacket of the bullet.
Gunaratnam and Himberg used SEM/EDX to identify
discharge residues produced by Sintox cartridges (cal. 357
Magnum) manufactured by Geco [112]. They found spher-
oidal particles mainly composed of titanium (Ti) and zinc
(Zn).
Titanium and zinc are commonly used in paints as pig-
ments. Paint particles are irregular in shape and these two
elements are never present as major elements, but the
problem of similar particles coming from other sources
(e.g. particles formed in burning Ti±Zn pigment paints)
has to be investigated.
Harris made SEM/EDX analysis of primer residue from
CCI Blazer Lead Free TMJ ammunition and of gunshot
residue generated by test ®ring a series of ®rearms using the
same ammunition [88]. The primer residue analysis
obtained, striking the primer cup directly over a SEM stub,
determined that the only signi®cant element present was
strontium (Sr). Some particles contained trace amounts of
barium (Ba) probably because natural deposits of strontium
are often associated with barium. Most particles were in 0.5±
10 mm range with a spherical morphology. Tricomponents
unique particles (Pb±Sb±Ba) were found in all ®ring tests,
even after the extensive and repeated cleaning of ®rearm, in
 F.S. Romolo, P. Margot / Forensic Science International 119 (2001) 195±211
Table 3

Ammunition Primer composition Elemental primer Case [113] Bullet [113] Primer residue Gunshot residue
composition [114]

CCI Blazer Lead Tetracene, diazodinitrophenol, Sr Al TMJ±CU Sr, Al, with Cu trace [113], Pb/Sb/BA, Pb/Ba, Pb/Sb Pb, Sr,
Free (Blount Inc.) smokeless powder, strontium spherical morphology Sr, Sr/Pb/Sb/Ba [88]
nitrate [88] with Ba traces [88]
Fabrique FeÂdeÂrale de Zn, Ti
Munitions
Federal Cartridge Solid±Cu Irregular morphology and
Company porous surface Ca, Si [113]
Fiocchi Sb, Cu, Zn, Sr
Geco Sintox Typical Sintox: tetracene, Zn, Ti Ti, Zn [115] Irregular form and porous surface:
diazodinitrophenol, zinc (A.1) TiO2 core with Zn, S, K,
peroxide, titanium metal Ca, C, O, Si on surface; (A.2)
powder [112] considerable amount of Cu [111];
(B) spheroidal shape Ti, Zn [112]
Hirtenberger-Patronen Sr Sr [115]
Speer Lawman Clean Sr Cu, Zn (brass) TMJ±Cu Irregular morphology and
Fire (Blount Inc.) porous surface Sr, Cu, Zn [113]
Winchester Super K, Sr Cu, Zn (brass) FMJ base plugged Irregular form and porous
Unleaded with a brass disk surface K, Cu, Zn [113]

205
206 F.S. Romolo, P. Margot / Forensic Science International 119 (2001) 195±211
addition to strontium or Sr±Pb±Sb±Ba particles. The ana-
lysis of the metal shavings from inside the chamber of an
older revolver, used with SINOXID ammunition, revealed
that lead, antimony and barium had been deposited inside
the chamber.
Particles of strontium with spherical shape could result
from exposure to ignited ¯ares and ®reworks. The possibility
that gunshot residue containing strontium particles and Pb±
Sb±Ba particles may also be deposited from tracer ammuni-
tions was stated.
Haag reported the results of his tests on American lead-
free ammunitions 9 mm para (CCI Blazer Lead Free and
Speer Lawman Clean Fire by Blount Incorporated of Lewis-
ton, Idaho; Super Unleaded by Olin/Winchester of East
Alton, Illinois; 9 mm Luger Federal Premium by Federal
Cartridge Company of Anoka, Minnesota) [113]. He ana-
lysed primer residues on the inside walls of ®red cartridges
(®red with and without the bullet and propellant charge)
using SEM/EDX. He found particles with Sr and with
aluminium (Al) from the cartridge case and a small Cu
peak from the bullet in CCI Blazer Lead Free primer residue.
Strontium was detected with Cu and Zn from the brass case
in Speer Lawman Clean Fire primer residue. Potassium was
found with Cu and Zn from the brass case in Winchester
Super Unleaded primer residue. Calcium and silicon was
detected in primer residue of Luger Federal Premium. The
picture of the particles showed a fairly irregular shape with a
porous surface.
Herdener et al. determined the elemental composition of
the primers in six different types of lead-free ammunitions
with a XRF analysis [114]. The authors found the following
elemental composition (only the elements corresponding to
main peaks are reported):
CCI Blazer Lead Free Sr
Fabrique Federale de Munitions Zn Ti
Fiocchi Sb Cu Zn Sr
Geco Sintox Zn Ti
Hirtenberger-Patronen Sr
Speer Lawman Clean Fire Sr
Winchester Super Unleaded K Sr
Recently NiewoÈhner and Wenz studied the interior mor-
phology of particles using a focused ion beam (FIB) system.
They analysed particles from Geco SinoxidTM, Geco Sin-
toxTM, Hirtenberger Lead FreeTM and a lead-free ammuni-
tion which is currently not on the market [115]. The major
components of the examined types of ammunition were Pb,
Sb and Ba in Geco SinoxidTM, Ti and Zn in Geco SintoxTM,
Sr in Hirtenberger Lead FreeTM and Mn and K in the
ammunition not in the market. The four kinds of ammunition
produced some particles with individual and unique interior
morphologies. Further investigations are necessary because
only four ammunition types were examined and the analyses
on the interior of the particles were carried out with partial
success.
As shown, there is little work on lead-free ammunition in
the literature. Not all the products commercially available
have been analysed and no extensive studies have been done
with particles similar to the ones formed by ®ring lead-free
ammunitions produced by different sources. Without big
research efforts in this ®eld, SEM/EDX analysis of samples
from real cases could give information of poor evidential
value.
All the data related to the GSR produced by lead-free
ammunition in this paragraph are presented in Table 3.
3. Discussion
Particle analysis can identify individual gunshot residue
particles through both morphological and elemental char-
acteristics. In the literature three elemental compositions of
so called ``unique'' GSR particles are mentioned:
Pb±Sb±Ba [4],
Sb±Ba [4],
Pb±Ba±Ca±Si±Sn [95].
These particles are produced under ``speci®c'' conditions.
Temperature and pressure after the explosion of the primer
rise from ambient to 1500±20008C and 104 kPa in a tenth of
a millisecond. The gunpowder de¯agration begins 0.5 ms
after the crushing of the primer. In 0.5±0.75 ms temperature
and pressure reach peak values of about 36008C and
3  105 kPa [51]. Melting and boiling points of Pb, Sb,
Ba and other elements are reported in Table 1 [79].
If proper attention is paid to avoid secondary gunshot
residue transfer from of®cers onto subjects to be tested for
GSR [116±118] and to avoid contamination in the labora-
tories [119], particle analysis can be the most powerful tool
for forensic scientists to determine the proximity to a
discharging ®rearm and/or the contact with a surface
exposed to GSR (®rearm, spent cartridge case, target hole).
Recently Garofano et al. [120] studied particles of envir-
onmental and occupational origin and proposed a slight
change in the classi®cation. They detected some Sb and
Ba particles in samples from people handling ®reworks. The
particles were ``partially molten and generally consisting of
not completely aggregated structures essentially composed
of only Sb or only Ba''. Different Sb and Ba particles with
irregular shape, always containing Fe, were found on the
hands of people having automobile-related jobs (i.e.
mechanics, automobile electricians, tyre repairmen). Auto-
mobile disk brakes hubs were proposed as the source of this
kind of particles. It is reported that these particles ``have a
metallic composition (differentiated only by the absence of
Pb and traces amount of Fe), and a morphologic aspect that
could be indistinguishable from some irregular particles
originating from ascertained GSR cases''. Garofano et al.
suggested that Sb, Ba and Fe particles are to be considered as
``indicative''. It was also proposed that when particles with
Sb and Ba but without Fe are found, the distribution of
 F.S. Romolo, P. Margot / Forensic Science International 119 (2001) 195±211
elements in the particle determined by means of X-ray dot
mapping or de¯ection modulation imaging [121] should be
investigated.
When a particle with one of the ``unique'' composition is
detected, it is necessary to check the presence of elements
not admitted in ``unique'' GSR. Then it is important to
investigate the spheroidal shape and/or the condensate mor-
phology exhibiting molten features and, if necessary, the
distribution of the elements, to exclude an origin different
from the cooling of molten material. The only source of GSR
``unique'' particles is the explosion of a primer mixture.
These rules are a formal general interpretative system.
The particles on the sample are compared with an abstract
idea of ``unique'' GSR particle. The ASTM standard guide
for GSR analysis is a formal approach procedure [10]. The
authors hope that in the following issues the Pb±Ba±Ca±Si±
Sn particle will be included and that the whole procedure
will be more precisely described. The effect on ``unique-
ness'' of elemental distribution, morphology, other per-
mitted elements and population of particles detected
should be clari®ed. It was reported by Zeichner and Levin
that ``with the advent of auto-search systems for GSR
analysis in crime labs, a better statistical basis for the extent
of uniqueness of various types of GSR particles may be
achieved'' [95].
Is ``uniqueness'' the only problem related to GSR detec-
tion and identi®cation for a forensic scientist? The role of
evidence is to help assess whether or not a particular
individual is associated with a particular crime. The identi-
®cation of a ``unique'' GSR particle using the formal
approach is not enough. The particle(s) found on a speci®c
surface should be compared with those of the crime under
investigation whenever possible. This case speci®c or case-
by-case approach is closer to what the court is interested in.
The drawbacks of the ``speci®c approach'' are that the
``shape and appearance of particles in a spent cartridge case
are not typical of the particles detected in casework'' [4] and
that GSR particles of exceptional composition are formed
using different types of ammunition in the same ®rearm [86].
Despite these problems, the speci®c approach permits, in
some cases, the use of analytical results undervalued by the
formal approach. In fact, in the ``formal approach'' not-
unique particles are considered not speci®c and the eviden-
tial value of particle analysis results in these cases is poor. In
other cases, the speci®c approach allows to avoid the over-
valuing of results. If Ni, Cr, Fe or any other element not
permitted in ``unique'' GSR are found in particles sampled
around a bullet hole, can we consider ``unique'' similar
particles found on the hands of the suspect? On the other
hand how can we consider one Pb±Ba±Ca±Si±Sn ``unique''
GSR found on clothes of a suspect in a crime where an
ammunition producing different GSR has been used? And
what about tin, which is not included in the lists of permitted
elements for modern ammunition? These simple questions
suggest how interpretation of results using a ``case-by-case''
approach can be critical.
207
The main problem of the ``formal'' approach is that some
ammunition does not produce ``unique'' GSR [77,80,81,
122±124] and the diffusion of lead-free ammunitions is
expected to increase in the coming years.
With ``not-unique'' particles interpretation of results is
extremely important. It is surprising the number of articles
concerning interpretation of glass or ®bre evidence. It is
more surprising that it is not possible to ®nd a single article
about interpretation of ``not-unique'' GSR particles. Glass
fragments and ®bres are two ``transfer evidence'' types.
They support an inference of contact between speci®c
source and receiving objects. The strength of this kind of
evidence has increased with a more fruitful interpretative
framework based on Bayes rule [125±127].
At the beginning, transfer evidence was interpreted fol-
lowing a two-stage approach. In the ®rst stage some material
from unknown source was compared to determine whether
they come from the same source or not. The probability that
they are found to match with respect to some characteristic is
known as the probability of non-discrimination or the prob-
ability of a match (PM). The complementary probability, the
probability they are found not to match with respect to this
characteristic is known as the probability of discrimination
or discriminating power (DP). If a method distinguishes
more or less easily between two samples of material from
different sources it is considered more or less selective. A
speci®c method can always discriminate between two dif-
ferent samples (DP ˆ 1). If the comparison results in a
match, the second stage of interpretation estimates the
probability of a coincidental match. This coincidence
approach can overvalue a match and undervalue a non-
match and there are cases where it does not work at all.
The Bayesian approach provides a conceptually simple
and coherent one-stage solution to the problem of interpret-
ing transfer evidence. To assess the strength of scienti®c
evidence, it considers at least two explanations for its
occurrence. The evidence is evaluated by assessing its
probability under competing explanations (Bayes' rule).
The strength of the evidence is measured by the probability
of the evidence given an explanation divided by the prob-
ability of the evidence given an alternative exclusive expla-
nation. The probability of the evidence supposing the ®rst
hypothesis divided by the probability of the evidence sup-
posing the second hypothesis is called likelihood ratio (LR).
In this way evidential value is measured by a continuous
function with no arbitrary cut-off.
For the assessment of the value of a GSR ®nding in
linking a suspect and a crime it is important to compare two
hypotheses, the ®rst being, for example, that of the evidence
if the suspect shot in a speci®c situation, the second being
that of the evidence if the suspect was not involved in this
shooting.
The ®nding of GSR on a surface can follow proximity to a
discharging ®rearm or a contact with a surface contaminated
with GSR (shooting hand, ®rearm, spent cartridge case,
target hole, etc.).
208 F.S. Romolo, P. Margot / Forensic Science International 119 (2001) 195±211
The likelihood ratio for evaluating evidence under con-
¯icting hypotheses permits the forensic scientist to consider
not only the information relative to the possible source of
one or more particles, but whatever is related to the speci®c
activity of the suspect.
Generally, the pair of hypotheses or propositions con-
sidered to express an opinion about the evidential weight
associated with the presence or absence of transferred
material could represent, respectively, and roughly speaking,
the prosecution and the defence positions. It is helpful to
regard these pairs of propositions as falling into three
different classes or levels, which can be called ``source'',
``activity'' and ``offence'' [128]. At the ®rst level, the pro-
positions relate to the source of evidentiary material and the
recovered sample is compared with a control sample. At the
``activity'' level, in addition to comparison, it is necessary to
consider other aspects like the probability of evidential
transfer and the persistence. It could be dif®cult to distin-
guish the ``offence'' level and the ``activity'' level. Some
activities are necessarily crimes. More often at this level
there are considerations which are completely outside the
domain of the scientist. If the expert has information which
leads to a framework of circumstances, the presence or the
absence of materials can be interpreted at least at the
``activity'' level, giving a greater assistance to the court.
The simple methods developed following the Bayes' rule
cannot effectively incorporate the range of issues that arise
in actual casework as transfer evidence is discovered. Never-
theless, they helped in many cases to present scienti®c
evidence to a court in the best way. To help the introduction
of a Bayesian approach in interpreting GSR particles a lot of
work has to be done. The rates of deposition, transfer and
persistence of GSR are not well understood and are critical
for any proper interpretation [129,130]. Without this effort a
``not-unique'' particle could be left aside as having little
value in court, whereas a glass fragment with less informa-
tive content could be regarded as valuable evidence because
research has demonstrated how valuable it can be.
4. Conclusion
A review of the scienti®c papers published on inorganic
GSR analysis permits to study how the scanning electron
microscope has shown its capability in detection and iden-
ti®cation of gunshot residue. The scienti®c effort of devel-
oping the methods used in forensic laboratories to analyse
GSR particles follows more the aim to study their ``unique-
ness'' than the statistical interpretation of observations.
When particles possibly from the explosion of a primer
are detected on a sample, the analytical results can be
interpreted using different approaches. In a ``formal''
approach the particles on the sample are interpreted follow-
ing rules of a formal general interpretative system, to
determine whether they come from a speci®c source or
not. GSR are ``unique'' if the explosion of a primer is the
only possible source. In the ``speci®c'' or ``case-by-case''
approach, the particles found on a speci®c surface are
compared to those of the ammunition used. The speci®c
approach is of much higher help to the court. It permits the
use of analytical results underestimated by the formal
approach in some cases and avoids overestimation of results
in other cases.
We consider that a ``case-by-case'' approach should be
followed whenever possible and we hope in a more sensible
approach to GSR interpretation. We feel that a correct use of
statistical concepts like speci®city or selectivity could help
to avoid discussion in disputed cases. Statistical considera-
tions and databases could help, not only to express the
``extent of uniqueness'' [95] of various particles, but to
evaluate the strength of a particular evidence, too. We
suggest research of models and data such as have been
developed in other trace evidence material (®bres, glass,
etc.) in the interpretation of gunshot residue in a Bayesian
approach.
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