Forensic Science International 206 (2011) e5e7

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Forensic Science International

journal homepage: www.elsevier.com/locate/forsciint

Case report

Bullets fragments identication by comparison of their chemical composition

obtained using instrumental neutron activation analysis
Antioco Franco Sedda *, Gabriele Rossi
MAT-STG, ENEA (Italian National Agency for New Technologies, Energy and Economically Sustainable Development), Rome, Italy

A R T I C L E I N F O A B S T R A C T

Article history: Bullets found in crime scenes are usually compared by examination of the riing impressions produced
Received 9 November 2009 in the barrel of the questioned rearm. When, however, a bullet is fragmented or highly deformed, the
Received in revised form 29 May 2010 comparison of riing micro striations cannot be performed, and the only way two compare two or more
Accepted 3 June 2010
bullets is by a match of their chemical analysis. In spite of the limits of the chemical analysis methods,
Available online 1 July 2010
due to the frequent compositional lead variability of ammunition boxes, the technique still keeps its full
value, both as trial element, and as an aid in the investigations. A case is reported in the present paper, in
Keywords:
which some crushed and deformed bullets, recovered from a murder victim body, have been analyzed by
Bullet analysis
INAA
Instrumental Neutron Activation Analysis. The analysis allowed the assignation of the bullets to one of
Lead analysis the ammunitions lots owned by one of the murder suspect.
0.22 Ammunition 2010 Elsevier Ireland Ltd. All rights reserved.

1. Introduction elemental composition, originated from the choice of the starting

The commonly used method to compare bullets found in crime
scenes with the ones coming from a questioned rearm and
ammunition lot, is the examination of the projectile under optical
microscopy, to compare its riing impressions, usually markings
and striations produced by the grooves of the weapon barrel, with
the traces obtained on a bullet of the same brand and type of the
one under investigation. When a bullet goes through a barrel, it is
engraved by the riing, and each set of riing grooves has unique
machining marks, which in turn leave a theoretically unique and
identiable imprint on the bullet itself. An optical microscope
known as comparison microscope allows a comparison of the
striations, that can be used for exclusion or identication purposes,
like an human ngerprint. In some cases, unfortunately, this
examination produces ambiguous results; in other cases, the bullet
under investigation is strongly deformed, or only non-signicant
fragments can be recovered in a crime scene. In all such cases, a
chemical analysis of bullets can be attempted; if a direct
compositional comparison with the ammunitions under investi-
gation can be performed, highly satisfactory results can often be
obtained. It is a well known fact that the chemical composition of
bullets of different caliber, type and brand, can present a wide
compositional variance, both in trace elements and in raw
* Corresponding author. Tel.: +39 06 30483806; fax: +39 06 30483844.
E-mail addresses: antioco.sedda@enea.it, antioco.sedda@casaccia.enea.it
(A.F. Sedda).
metallic lead alloy, and from the lead alloy smelting and rening
process. Due to these differences, even different lots of a same
ammunition brand can often been efciently distinguished.
Theoretically, there are potentially millions of possible element
combinations for a bullet, due to the heterogeneity of starting raw
metallic materials. A variety of analytical methods, including
neutron activation analysis [1], atomic absorption spectroscopy
[2], spark source mass spectrometry [3], inductively coupled
plasma-mass spectrometry [4], have been successfully used for the
chemical analysis and comparison of lead bullet analysis.
2. Case summary
A 37-year-old white male was found dead into a country gutter.
The autopsy revealed two fatal wounds in the head; three strongly
deformed bullet fragments were recovered from the brain of the
victim. After some investigations, in the house of one of the
suspects, a rie Winchester 9422.22, with some old 0.22
ammunitions of different brands an types were found. The seized
ammunitions were: RSW long rie hollow point, RSW High
velocity long rie (lot 1, and lot 2), Winchester H, Winchester super
X; for each ammunition brand the number of bullets ranged from 9
to 25. The recovered bullets were so strongly fragmented and
deformed, that any affordable comparison of dimensions, weight,
or striations by using optical microscopy, was considered
unfeasible. Due to this fact, the investigating magistrate decided
to order an analysis of the chemical composition of the murder
bullets, and of the seized bullets, aimed to the determination of the

0379-0738/$ see front matter 2010 Elsevier Ireland Ltd. All rights reserved.
doi:10.1016/j.forsciint.2010.06.003
e6 [(Fig._1)TD$IG]
A.F. Sedda, G. Rossi / Forensic Science International 206 (2011) e5e7

type and brand of the used ammunition, and also to check a

possible compatibility of the recovered fragments with all the
ammunitions under investigation, owned by the suspect.

3. Materials and method

From each seized ammunition group (brand and type), ve bullets have been
chosen. This number was chosen as a reasonable compromise between the need of
obtaining a reasonable statistical signicance in analytical procedure, and the need
to keep intact some of the bullet samples for ballistic expert witness tests. Most of
the seized bullets were unpacked and loose, and the samples for the analytical
determinations have been randomly chosen.
From each of the recovered samples, and from each bullet of seized
ammunitions, a lead fragment was cut. The fragments were sampled by cutting
them with a new scalpel blade from the inner of the lead shot, by operating under a
laminar ux fume hood. Each of the fragment, weighting from 12 to 18 mg, was put Fig. 1. Plot of Principal Component 1 vs. Principal Components 2 for the
into an high purity plastic sealed vial, and irradiated for about 15 min into the fast ammunitions under investigation, and for the bullet fragments extracted from
pneumatic transfer line (rabbit) of the 1 MW TRIGA reactor of ENEA-Casaccia the body of the victim.
Center, under a thermal neutron ux of 1.25  1013 neutrons/cm2/s. Primary and
secondary analytical standards (lead BCR CRM 288) were simultaneously irradiated,
Table 2
and used for gamma energy spectra calibration. After irradiation, the vials have
Coefcients of linear combination of each element in the rst three Principal
been opened, and the samples transferred to the counting system, for gamma
Components.
spectra recording. Data collection for measurements of the net area of gamma peaks
was performed using an ORTEC high-purity germanium detector, coupled with a PRIN 1 PRIN 2 PRIN 3
CANBERRA pulse height/multichannel analyzer system. The obtained spectra have
been normalized and the isotopes identied by the software CANBERRA Genie-2K. Ag 0.32 0.94 0.13
The statistical analysis of the data has been performed by the software package SAS- As 0.57 0.17 0.40
Statistics 6.12. Sb 0.58 0.10 0.38
Cd 0.49 0.28 0.82

4. Results

The activation analysis allowed the determination of the
elements Ag, Sb, Cd, Cu, As, Na, Nb, and Pb (see Table 1) in all
the bullet samples. In order to identify the chemical elements with
the maximum informative power for the discrimination of the
samples, a general screening was preliminary performed, by using
the Principal Component Analysis statistical method. Briey,
Principal Components Analysis is a mathematical procedure that
can transform a number of possible variables into a smaller
number of uncorrelated variables, called Principal Components.
The rst Principal Component accounts for as much as variability
as possible, each successive Principal Component accounts as
much of the remaining variability as possible, and so on
successively [5].
The elements that in the present case accounted for the most of
the variability were Ag, As, Sb and Cd. A Principal Components
Analysis has been performed by using only these four elements.
Table 2 reports the coefcients of the linear combination of these
elements in the three Principal Components; the greater the
absolute value in the table, the higher the weight and importance
of the element in the discrimination analysis. It must be outlined
that in the present case the rst two Principal Components
accounted for more than 90% of the variability, and the rst three
Principal Components for 99%. In such a way the entire data set of
analytical data can be reduced and summarized into a simple plot
of Principal Component 1 vs. Principal Component 2, still keeping
the 90% of explained variance, i.e. of informative discrimination
power. More than this, an high accuracy in the analytical
measurements of the elements concentrations is not necessary,
due to the fact that the variance of the group possess most of the
informative discrimination power, rather than the absolute value
of the elements; only an high precision analytical technique is
therefore required, without the need of an high accuracy. In Fig. 1
the plot of Principal Component 1 vs. Principal Component 2 is
showed, which describes the distribution of the entire group of
ammunition seized in the house of the suspect, and the fragments
extracted from the body of the victim. It should be noted in the
gure that different brands, and also different lots, have generally
slight different composition and different variance (Table 1).
In order to quantitatively evaluate the group attribution, a
Canonical Discriminant Analysis was performed on the analytical
data, by dening six groups (one containing the murder recovered
fragments, and the others corresponding to the ve bullets
brands). If some groups of observations are dened, each with
several quantitative variables, the Canonical Discriminant Analysis
can transform the variables into a linear combination of the same
variables that has the highest possible multiple correlation with
the groups. This maximal multiple correlation is called the rst
canonical discriminant. The second canonical correlation is the
linear combination, uncorrelated with the rst canonical variable,
that has the highest possible correlation with the groups, and so on.
Basically, the canonical variable summarizes the between-class
variation, while Principal Components Analysis summarize total
variation. The probability of a point belonging to a certain non-
spherical group can be expressed in terms of its Mahalanobis
distance, i.e. the distance of a point from a group center of mass,
divided by the width of the ellipsoid in the direction of that point.

Table 1
Mean element concentration in the bullets under investigation.
Sb(%) 0.46  0.02 0.48  0.02 0.44  0.62  0.03 0.29  0.02 0.47  0.02
Ag 284  25 253  28 210  19 72  15 77  22 257  31
Na 480  12 507  24 412  18 498  24 278  26 515  33
As 32  0.7 35  0.9 29  0.9 4  0.3 19  0.8 33  1.2
Nb 0.7  0.01 0.6  0.01 0.4  0.01 <0.02 0.7  0.01 0.6  0.01
Cd 3.8  0.5 3.7  0.6 4  0.6 3  0.4 0.6  0.1 3.9  0.5
Cu 226  32 167  28 573  67 21  4 950  75 97  34

RWS/hp = RSW long rie hollow point; RWS/pf1 = RSW high velocity long rie, lot 1: RWS/pf2 = RSW high velocity long rie, lot 2; W/H = Winchester H; W/sX = Winchester
super X.
 A.F. Sedda, G. Rossi / Forensic Science International 206 (2011) e5e7
The greater this distance, the lower is the associated probability of
belonging to the same group. The associated probabilities were
found all <0.0001, except for the one corresponding to the distance
RWS/fp1-RWS/fp2, with a value of <0.006, and RW/fp2-Victim
Fragments, with a value of 0.32.
The evidence of a statistically highly signicant similarity
between the fragments extracted from the body of the victim and
the composition of the ammunition RWS full point (lot 2) found in
the house of the suspect, was evident. These results led the
investigators to look for further probation elements in the places
frequented by the suspect. A thorough search revealed the
presence of traces of the blood of the victim in an agricultural
greenhouse owned by the father of the suspect; clear evidence of
bullet ricochets were also found on the walls of the site, and a third,
deformed bullet was found on the site, whose analysis revealed the
same composition of the fragments extracted from the body of the
victim. After this sum of evidence, the suspect confessed that he
had shot the victim using the seized rie, during a quarrel
regarding an illicit drug supply, and had tried to dispose the body of
the victim, by throwing it far from the homicide site.
5. Discussion
The principle of compositional bullet lead comparison is based
on the assumption that each batch of molten lead has its own
characteristic elemental composition. Lead used in the bullet-
manufacturing process is generally obtained from secondary lead
smelters, where the raw material is made primarily of recycled
automobile batteries, and from other sources, and is melted in
kettles with capacities of 75100 tons [6]. Each bullet lot is
obtained from ingots, each from 30 kg to 1 ton, depending from
brand and production process and plant. In this phase, antimony
may be added to harden the alloy; hardened lead is generally used
in non-jacketed bullets, whereas soft lead, where antimony has a
low concentration, is generally used in jacketed bullets, or in some
bullets, like 0.22 ammunitions. Other elements are present in trace
amounts and can greatly vary in concentration; generally, the
bullets produced from a single ingot or billet are analytically
indistinguishable.
The chemical composition of bullet lead has been widely used
in the past, in the attempt to match a brand or a production lot with
the bullet of a crime scene, by starting from the assumption that
bullets with the same chemical composition were considered to
come from the same molten batch. Of course, the same concept has
been used to exclude suspects from further investigations, or as a
court discharge proof.
Unfortunately, during the processes of cutting, swaging,
nishing, and jacketing bullets, assembling cartridges and
packaging boxes, the bullets from various melts are sometimes
intermingled, so that more than one compositional group can be
present in the same box, and the assumption of an in-the-box
bullets homogeneity of composition cannot be always considered
valid [7].
Due to this fact, in 2002 the FBI asked the National Research
Council of the National Academy of Sciences to have an
independent evaluation of the scientic bases of comparative
bullet lead analysis. While the NRC found that the analytical
instrumentation and the elements selected for the analysis were
appropriated, some doubts have been raised on the general validity
e7
of interpretation of the results of bullet lead examinations. The
main argument was that neither scientist nor bullet manufacturers
were able to denitely attest the signicance of an association
between bullets during a bullet examination, given the above
mentioned lack of bullets homogeneity in a single ammunition
box.
For these reasons, while the FBI Laboratory still rmly supports
the scientic foundation of bullet lead analysis, given the costs of
maintaining the equipment and the resources necessary to do the
examination, and its relative probative value, this institution has
decided that it will no longer conduct this exam. Notwithstanding
this decision, FBI afrmed that chemical lead bullet analysis will
still be useful in linking individuals to a crime as well as to exclude
others. These conclusions have raised a large debate among
expert witnesses, about the real affordability and potential risks of
comparative bullet lead analysis [811].
In spite of the criticism raised on this technique, we afrm that
in strictly selected cases in which an heuristic approach can be
applied, the analysis of lead bullet can still furnish fundamental
information in criminal investigations, both as a trial and as an
investigation support.
In the present paper, an example of a crime case is reported, in
which the compositional lead bullet comparison technique
practically demonstrated its full validity in the orientation and
information power during the investigations; the fact that precise
analytical determinations and a direct comparison with bullets
under investigation were possible, has also been considered as a
valid probation element in court.
Instrumental Neutron Activation Analysis is a powerful, rapid,
multielemental analytical technique, particularly useful in many
forensic applications. In the determination of bullet chemical
composition, this technique is particularly appreciable, due to the
lack of interference from the lead matrix, to its high sensitivity, and
to the possibility of carrying out non-destructive assays. Unfortu-
nately the availability of a nuclear reactor strongly limits its
widespread application. In these cases also the most commonly
available analytical techniques (atomic absorption, mass spec-
trometry, polarography or UVvis spectrophotometry), can furnish
useful data for discrimination, by using a judicious choice of the
most discriminating chemical elements, and should be considered
a complement to traditional ballistic studies. The use of advanced
statistical analysis in data treatment is also highly recommended,
due to its power in extracting and summarizing the discrimination
informative power in an easy and affordable way [12,13].
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