Anal Bioanal Chem (2017) 409:5803–5811
DOI 10.1007/s00216-017-0460-1
TRENDS
Trends in analysis of gunshot residue for forensic purposes
Zuzanna Brożek-Mucha 1
Received: 4 April 2017 / Revised: 25 May 2017 / Accepted: 8 June 2017 / Published online: 28 June 2017
# Springer-Verlag GmbH Germany 2017
Abstract Detection and identification of organic and inor-
ganic components of gunshot residue are well established
within forensic chemistry because of highly characteristic
and uncommon features of the products of ammunition dis-
charge at the time and place of a shooting incident in compar-
ison to other materials present in daily life of people. Both
types of residue play an important role in establishing various
circumstances of a shooting crime, though the most vital one
concerns the possibility of relating a suspect with the activity
of shooting. In this aspect, solid, inorganic particles, nowa-
days called characteristic, have been utilized. Their specific
features result from the primer mixture composition, including
compounds of heavy metals, lead, antimony, and barium, and
from the extraordinarily dynamic conditions of their forma-
tion, taking place at the moment of the primer detonation.
Scanning electron microscopy and X-ray microanalysis tech-
niques proved to be necessary and sufficient to reveal the
content and the spherical morphology of the particles for this
purpose. Recently, the recommendation that the potential for
lead exposure be minimized was followed in the production of
ammunition cal. 9 mm Luger, 0.40 S&W, 0.380 Auto, and
0.38 Special. These modern types of ammunition expel less
characteristic particles, the identification of which can be a
challenge for the examiners. At least two solutions to strength-
en the residue identity are taken into account: additional in-
sights into the internal structure of inorganic particles, e.g., by
means of electron backscattered diffraction and focused ion
* Zuzanna Brożek-Mucha
zbrozek@ies.krakow.pl
1
Department of Criminalistics, Institute of Forensic Research,
Westerplatte St. 9, 31-033 Krakow, Poland
beam, as well as complementary examinations of organic res-
idues with sensitive mass spectrometric techniques.
Keywords Forensic . Gunshot residue . SEM-EDX-EBSD .
Vibrational spectroscopy . GC-MS . LC-MS
Inorganic GSR – characteristic particles
Organic and inorganic components of gunshot residue (GSR)
are distributed in the place and time of a gunshot [1–3]. Thus,
collection of evidence materials from people and subjects re-
lated to a shooting incident and detection of GSR may con-
tribute to establishing some of its circumstances and possibly
to the reconstruction of its course. The investigations may
provide answers to questions related to the entrance and the
exit wound, the direction and distance of shooting, the type
and caliber of weapon and ammunition used, as well as time
elapsed after discharge of a gun or a cartridge. However, the
most frequent question directed by practitioners of the admin-
istration of justice to forensic experts is, whether a person was
related to a shooting incident.
The forensic expertise that may produce evidence of a per-
son being involved in a shooting incident has always been the
most demanding one and concerned the identification of par-
ticles as characteristic or consistent with gunshot residue, tak-
ing into account both their chemical content and spherical
morphology. This can be practically achieved by means of
scanning electron microscopy coupled with energy dispersive
X-ray spectrometry (SEM-EDX) that simultaneously provides
the information of the micro-objects’ appearance and their
elemental content. The specific features of particles result
from the composition of the primer mixture containing com-
pounds of heavy metals: lead azide or lead styphnate, antimo-
ny trisulfide, barium nitrate as well as from the extraordinarily
5804
dynamic conditions of their formation taking place at the mo-
ment of detonation of the primer, deflagration of the propellant
load, and finally fast transition of microscopic droplets of
molten metals dispersed in the air from the liquid to solid state
(Fig. 1). Particles simultaneously containing lead, antimony,
and barium (Pb-Sb-Ba), for many years called unique, are
nowadays classified as characteristic, and those containing
two component combinations or just one of these elements
(Pb-Sb, Pb-Ba, Sb-Ba, Pb, Sb, and Ba) as consistent with
gunshot residue. Establishing the presence of such particles
in the sample collected from hands or clothing of a person
allows the Court to relate the person with a high or very high
probability, either with shooting, or being in the nearest vicin-
ity of a firing gun, or else getting in contact with an object
highly contaminated with GSR.
The history of detection and identification of inorganic
GSR is not long as it started in the early1970s. Among the
pioneers in this area, G. M. Wolten, R. S. Nessbit, A. R.
Calloway, G. L. Loper, and P. F. Jones in USA as well as R.
Keeley and J. Andrasko in Europe should be named [1].
About 10 y later, automated programs for particle search
were introduced that saved excessive operator’s time
Fig. 1 A scheme of detection of
inorganic gunshot residue by
means of scanning electron
microscopy and X-ray spectrom-
etry: SEM stub with microtraces
collected, e.g.. from hands of a
suspect (a), the automatic search
for particles of defined properties
(b), X-ray spectrum and a
backscattered electron image of
an inorganic GSR particle (c)
Z. Brożek-Mucha
required for the search and identification of GSR. Later
developments brought in faster detection systems, such as
silicon drift detectors of large area, e.g., 80 or even
120 mm2 as well as more efficient programs for computer
controlling SEM-EDX systems. Only recently, the artificial
reference sample for particles containing lead, antimony,
and barium that fulfils the quality requirements for being
a proficiency test for GSR detection was worked out and
commercialized. These achievements enabled the GSR ex-
aminers to perform the necessary background research for
a robust interpretation of the analytical findings. The re-
search embraced not only differentiation of these particles
from similar ones, however of other source [4–6], but also
gathering information on the persistence, prevalence, pos-
sible secondary transfer of GSR, and the level of contam-
ination with these particles of a sample of a general popu-
lation of people as well as representatives of certain pro-
fessional activities, including firearm users [7–11]. Only
on the basis of this type of information setting up infer-
ences on people’s involvement in shooting incident could
have been practically approached by the administration of
justice [12, 13].
Trends in analysis of gunshot residue for forensic purposes
Nowadays, the identification of particles as GSR as well as
relating a suspect to a shooting incident has become even
more difficult with the advent of less toxic solutions in the
technology of production of ammunition that is inevitably
leading to a substitution of lead, antimony, and barium com-
pounds with more abundant substances [14–17]. It has always
been a variety of primer mixture compositions that were uti-
lized by ammunition manufacturers. The examples of fuels in
modern primer mixtures are pulverized titanium, aluminium,
calcium silicide, and amorphous boron; the oxidizers are typ-
ically zinc peroxide, potassium nitrate, and strontium nitrate.
Organic compounds such as diazo-dinitrophenol and tetrazene
play the role of the explosive and the sensitizer, respectively.
Moreover, powdered glass can be used as a fractionator. As
long as these heavy metal-free compounds were partially
substituting the traditional ones, there was no problem with
the identification of characteristic GSR, and these elements
that were detected in addition to lead, antimony, and barium
were usually related with a defined kind of ammunition or its
manufacturer, and called signature elements (private informa-
tion from R. Keeley, 1997). For some time, calcium and sili-
con were thought to be a signature of the ammunition factory
Sellier and Bellot, Vlašim, Czech Republic, and titanium and
zinc of sintox type ammunition by Dynamit Nobel, Troisdorf,
Germany. Ammunition cal. 9 mm of the latter make was sup-
plied to police forces, e.g., in Germany, The Netherlands, and
Belgium for health protection of the officers and also for dif-
ferentiation between GSR originating from the police firearms
and from those used in the crime. However, the current world-
wide production of this type of heavy metals-free (HMF) am-
munition cal. 9 mm Luger, 0.40 S&W, 0.380 Auto, and 0.38
Special [16] was followed by a further step to differentiate the
police ammunition from the other ones by marking it with
gallium or gadolinium, which are rarely seen otherwise and
make the GSR microspheres characteristic again [15].
Except for the special ammunition for police forces, mod-
ern types of ammunition produce particles that are less char-
acteristic in the aspect of the elemental contents; thus not only
examination of residue collected from the suspect’s hands but
also from the interior of a cartridge case revealed at the shoot-
ing scene ought to be performed [17]. Such comparative ma-
terial is not always available; thus to strengthen the residue
identity, additional examination of inorganic and organic com-
ponent of GSR are necessary [18–25].
Organic GSR for disclosing the circumstances
of a shooting
Examination of organic residue performed in parallel with the
inorganic ones may significantly contribute to understanding
particular problems of an investigated shooting incident.
Revealing solid particles of unburned or partially burned
5805
propellant grains in patterns of gunshot wounds of people’s
tissue and clothing contribute to estimation of a short-range
shooting distance, i.e., the distance between the gun muzzle
and the target being enclosed between contact and ca 50 cm
[19]. The propellant grains revealed in the surroundings or
inside the channel of the gunshot wound as well as collected
from the interior of cartridge cases are traditionally identified
by means of infrared spectroscopy that discloses the main
component of smokeless powder, i.e., nitrocellulose as pre-
sented in Fig. 2. However, a complementary application of
Raman spectroscopy enables one to identify other compo-
nents being added to the propellant in much smaller quantities,
such as plasticizers and stabilizers, e.g., diphenylamine and
ethylcentralite. In practice, gaining this type of information
may be useful in differentiation of residue originating from
various types and calibers of ammunition [18, 20, 21, 23, 24].
Vibrational spectroscopy techniques apply to macroscopic
particles mainly originating from the propellant and, so, of
limited use in contemporary shooting incident expertise; how-
ever, they give great opportunity to study both organic and
inorganic components usually mixed together, which can be
observed by means of SEM-EDX (Fig. 2c). As demonstrated
by Bueno et al. (see e.g., [22, 25]), such information can be
related strictly to a certain type and caliber of ammunition and
may also put more light on the complex mechanism of chem-
ical reactions of the gun discharge that might be utilized for
practical purposes in future.
Moreover, analysis of traces of volatile organic compounds
of smokeless powder and products of its deflagration can be
carried out shortly after the shooting incident, using gas and
liquid chromatographs usually coupled to mass spectrometers,
taking the advantage of their low limits of detection [18]. The
interest of detection of gaseous and volatile organic residue
concerned their usefulness in the estimation of time after dis-
charge of a firearm or a cartridge was initially demonstrated by
Andrasko et al. in 1999 [26, 27]. The authors utilized gas
chromatography hyphenated with thermal energy absorption
(GC-TEA) and flame ionization detection (GC-FID) to ana-
lyze samples taken from the barrels by means of solid phase
microextraction (SPME). The study yielded the assessment of
the time after discharge of a long barrel firearm in three cate-
gories: (1) 1–3 d, (2) 1–3 wk, and (3) period longer than 3 wk.
In certain cases such evaluation might be decisive, though the
crucial point is to obtain the gun of interest right after the
incident and choke up the muzzle of its barrel to preserve
the volatile products of smokeless powder discharge from
evaporation. This, however, is difficult to realize in practice,
as the crime scene investigation is rarely performed immedi-
ately after the shooting incident but usually after some time
has elapsed.
Recently, Gallidabino et al. [28–30] returned to the re-
search of volatile GSR to be of potential use in every-day
casework and demonstrated the efficiency of collecting
5806
Fig. 2 Examinations of gun powder residue: with the naked eye in a
gunshot pattern on clothing (a), under an optical microscope magnified
about 100× (b); backscattered electron image together with inorganic
samples from inside small caliber cartridge cases by head-
space sportive extraction (HSSE) for thermal desorption-gas
chromatography-mass spectrometry (TD-GC-MS) technique.
Results obtained by these authors allowed estimating time
since discharge up to 48 h and to differentiate recently fired
cartridges from the older ones, i.e., to distinguish between the
period less than 5 h from those of 1 to 2 d.
Outlook
With respect to the problem of relating a suspected person to a
shooting incident, the analytical methods to be applied for the
identification of GSR should be highly specific and selective
Z. Brożek-Mucha
GSR visible as bright spheres, magnification about 200× (c); an IR
spectrum of a thinned fragment of an unburned propellant grain
revealing the main component – nitrocellulose (d)
as well as nondestructive for preservation of the possibility of
repeated analysis and a confirmation of the analytical findings.
As mentioned before, in the case of traditional ammunition,
the SEM-EDX method was necessary and sufficient to state
that the group of particles containing lead, antimony, and bar-
ium revealing the morphology of fast cooled droplets of mol-
ten matter are characteristic or consistent with gunshot resi-
due. However, the recommendation that the potential for lead
exposure should be minimized was followed not only by re-
moval of lead from fuel, brake pads, and other automotive
components, but also by changing technologies in other
branches of industry, e.g., in the production of ammunition
cal. 9 mm Luger, 0.40 S&W, 0.380 Auto, and 0.38 Special
into leadless solutions. With the advent of these modern HMF
Trends in analysis of gunshot residue for forensic purposes
types of ammunition, the expelled particles contained abun-
dant chemical elements and became less characteristic. Thus,
the identification of GSR of such types of ammunition may
cause difficulties for the forensic experts as SEM-EDX alone
may not be selective enough.
Two general trends of scientific attempts to enhance the
forensic credibility to gunshot residue analysis can be ob-
served in the literature these days. Whereas some scientists
rely on the established inorganic residue examinations meth-
od, i.e., SEM-EDX, adding some extra information based on
reference material, e.g., residue taken from the interior of a
cartridge case, others turn to analysis of organic component of
gunshot residue.
The first interesting trend observed in the literature holds
on to solid inorganic particle examinations and relates to the
fundamentals of their origin, i.e., the extreme conditions of
their formation that determine their structure and morphology
(as shown in Fig. 3), even though their elemental contents may
not be as uncommon and characteristic as the well-known set
of lead, antimony, and barium.
So far, the morphology as well as distribution of particles of
certain shapes, e.g., in the function of the distance from the
explosion center, were not studied, with the exceptions of
works by Brożek-Mucha [7, 17, 31] and Abdul-Karim et al.
[32]. These authors demonstrated significant morphologic
consequences of the extraordinary conditions of the origina-
tion and spread of the particles, even though they were not
derived from Bclassic^ detonating mixtures of lead, antimony,
and barium compounds.
Christopher et al. utilized an integrated ion beam analysis
(IBA) technique in addition to SEM-EDX [33] to prove the
Fig. 3 Typical backscattered
electron images of Bair-borne^
characteristic primer particles
obtained at various
magnifications 500–5000×
5807
ability of detection of trace amounts of the classic elements:
lead, antimony, or barium besides the main components of
particles originating from HMF primers, such as boron or
silicon and calcium. The trend to use more sensitive tech-
niques, however, necessitates checking the possible sources
the traces of lead, antimony, and barium. One of the most
probable sources is the interior of the barrel of the weapon,
usually revealing the effect of memory of previous shots, e.g.,
with traditional ammunition that left the characteristic Pb-Sb-
Ba particles [34].
A deeper insight into the internal structure of inorganic
GSR particles, e.g., with the use of integrated ion beam anal-
ysis (IBA) technique, has been presented already in 1999 by
Niewöhner and Wenz [35]. Though, the rapid cooling of drop-
lets of molten metals or their compounds predetermine their
being amorphous, locally ordered structural domains can be
observed. These authors revealed the presence of spherical
cavities inside the particles, sometimes filled with crystallites.
Locally crystalline phases can be occasionally observed in
SEM-EDX images of large airborne GSR particles
(Fig. 4a, b) and those remaining in the interior of a cartridge
case (Fig. 4c, d). The crystallinity of GSR has been confirmed
by Tassa et al. already in 1982 for relatively voluminous res-
idue taken from inside of several cartridge cases [36].
However, recent application of transmission electron micro-
scope (TEM), with its high magnification capability and the
ability to explore chemical composition and the internal struc-
ture of particles, has confirmed that GSR are partially com-
posed of crystalline lead oxide domains that are agglomerated
into larger particles [37]. Contemporary analytical equipment
such as electron backscattered diffraction detectors (EBSD)
5808
Fig. 4 Backscattered electron
images of primer residues: Bair-
borne^ (a, b) and solidified inside
the cartridge cases (c, d) obtained
at various magnifications 500–
5000×
attached to the SEM-EDX system also may contribute to
gaining more information on the specific structural features
of GSR [38–41]. This technique is capable of revealing
nano-crystalline domains present in the particles that occur
as a result of extreme temperature and pressure conditions
and then rapid cooling. Confirming the presence of a high-
pressure phase of spinel type in a particle consisting of titani-
um, zinc, and oxygen that originates from a sintox type of
ammunition may increase its value as a GSR [40, 41].
Although crystal structure solution for such small domains
with the combined technique of SEM-EDX-EBSD still re-
mains a challenge, it seems to be potentially the most specific
method for recognition of post-blast and gunshot residue for
its ability to simultaneously answer the question on the chem-
ical content, morphology, and the internal structure, all of
which are characteristic physical and chemical properties of
this type of particles.
HMF primer residue will not be easily recognized; howev-
er the challenge at present will be solved in the near future
along with an increasing interest of forensic scientists towards
inner structure of the particles and the mechanism of their
formation that has never been explored extensively.
Parallel to the efforts to analyze the inorganic component of
gunshot residue in detail, several forensic research groups
have been independently performing examinations of the or-
ganic component of GSR for demonstration of the potential
usefulness of liquid chromatography coupled with mass spec-
trometry (LC-MS) techniques for separation and detection of
organic gunshot residue (see e.g., [42–49]). The only draw-
back of LC-MS is that the evidence sample is consumed dur-
ing the analysis.
Z. Brożek-Mucha
Benito et al. applied liquid chromatography-quadrupole time-
of-flight mass spectrometry (LC-QToF-MS) to detect and iden-
tify 18 gunpowder additives in GSR using MS/MS mode.
Instead of swabbing, which is the commonly used sampling
technique for organic GSR collection, the authors applied tape
lift stubs partially covered with a polytetrafluoroethylene (PTFE)
layer that provided better extraction recoveries and enabled par-
allel analyses of inorganic and organic GSR. The developed
method was applied to the analysis of GSR originating from four
different lead-free ammunition brands. DPA and its nitrated deg-
radation products and centralites were identified in all samples
that were taken from the shooter’s hands immediately after shoot-
ing [42].
Taudte et al. [43, 44] described the development and opti-
mization of an ultra-high performance liquid chromatographic
method (UHPLC) for rapid separation of 32 compounds po-
tentially present in organic GSR. The final analysis time for
the target analytes was 27 min, with limits of detection ranging
from 0.03 to 0.21 ng at 214 nm. Taking into account 15 chosen
compounds, the authors worked out two protocols of analysis
of both organic and inorganic GSR. They demonstrated that
the collection efficiency of SEM stubs was significantly supe-
rior to swabs for both types of GSR on the skin sampled after
single or triple experimental shots. They recommended the
protocol of sampling using SEM stubs, SEM-EDX analysis,
and then liquid extraction with acetone for 5 min at room
temperature and preconcentration by drying and reconstituting
in small amount of solvent prior to UHPLC analysis.
A similar study was performed by Gassner et al. [45, 46],
who also developed a LC-MS method, using QTrap-type MS
instrument with a C18 column, to compare the efficiency of
Trends in analysis of gunshot residue for forensic purposes
various sampling materials for the collection and subsequent
analysis of organic GSR. Seven sampling materials, two
swab-like and five stub-like, were tested. Taking into account
the analysis of blank extracts of the materials to check for
potential interferences and determining matrix effects as well
as the collection efficiency during shooting experiments using
a set of 9 mm Luger ammunition, the authors found that the
tape from 3 M was capable of recovering the highest amounts
of organic GSR at the sensitivity level of pg/mL in few hours
after discharge.
The challenge of making the analytical potential of chro-
matographic methods usable for police forces in their routine
work with the aim of associating a person with the fact of
using a firearm was undertaken by Schumacher and a group
of representatives of European forensic science institutes with-
in a project financially supported by the European
Commission (see e.g., [47, 48]). The protocols of collection
of organic GSR and methodology of their analysis was
worked out to detect at least some of the following com-
pounds: trinitroglycerine, nitroguanidine, 2,4-dinitrotoluene,
stabilizers: diphenylamine, n-nitrosodiphenylamine, 2-
nitrodiphenylamine, 4-nitrodiphenylamine; stabilizers/plasti-
cizers: ethylcentralite, methylcentralite, akardite I, akardite
II, plasticizers: dibutyl phthalate, dimethyl phthalate,
triethylcitrate, and tributylcitrate. The thorough study was per-
formed for unburned smokeless powder grains, the residue
taken from inside the cartridge cases, from the surface of shot
targets, as well as from shooters’ hands few minutes after
shooting. An LC-MS protocol was developed that provides
detection limits in the low picogram and in the sub-picogram
range for the majority of the target compounds.
From the study, of nearly 30 various sampling materials,
adhesives, and swabs, three different sampling materials are
recommended: (1) tape-lifting using ‘Tesa Tack^ on an alu-
minium pin stub for skin, (2) swabbing with Texwipe Alpha
TX761 swab for smooth surfaces to be moistened with aceto-
nitrile (or isopropanol) prior to swabbing, and (3) vacuuming
using an Zefluor 0.5 μm PTFE filter for clothing. These sam-
pling materials are compatible with the same extraction meth-
od developed to keep the process as simple and quick as pos-
sible. It was demonstrated that organic GSR can be recovered
and analyzed from the shooter’s hand after a single shot of
9 mm Luger ammunition. The pattern of additives was qual-
itatively comparable to results from the appropriate unburnt
propellant and the spent cartridge case. A quantification of the
recovered organic GSR traces is possible from the analytical
point of view, but from the forensic point of view, organic
GSR deposition seems to be rather random in the shooting
process itself and the specimen collection concerns only a
fraction of the emerging and depositing residue; therefore,,
the method should be used as a qualitative method to prove
the presence of certain propellant additives. A simple protocol
for a combined collection of inorganic and organic GSR was
5809
proposed to sample the hand first with standard carbon tape
SEM stubs and then with a stub covered with ‘Tesa Tack’
adhesive. The collected material was found to be sufficient
to perform a qualitative analysis of organic GSR.
Although the analytical problem of organic GSR detection
seems to be solved, the forensic understanding of the results
still needs more research. The fields of prevalence, persis-
tence, transfer, and aging were only investigated superficially
and need more in-depth research in the future. One of the first
publications undertaking the subject of persistence of organic
GSR was that of Moran and Bell [49], who pointed out the
complex mechanism of organic residue adherence to the sur-
face of human skin, including its chemical and biochemical
permeation in addition to physical interaction that solely take
place in the case of inorganic particles [7]. The loss of every
target compound differs in time due to different evaporation
and absorption properties. The longest persistence on the arti-
ficial skin, i.e., 12–24 h, revealed 2-nitrodiphenylamine,
ethylcentralite, and 4-nitrodiphenylamine. Also Gassner
et al. [46] performed studies for various exposed skin surfaces
and hair as well as clothing to estimate what surfaces might be
best for organic GSR sampling by comparing results just after
discharge and 2 h after discharging a pistol. The autors indi-
cated that organic GSR were more rapidly lost from hands
than from clothing and that the face and hair of a suspect might
be contaminated through secondary transfer. They found that
organic GSR might remain longer on hair, clothing, and other
skin surfaces than on the hands of a suspect; thus they recom-
mended that sampling should also include clothing, hair, and
face. In real samples collected from people’s hands persisted
not more than 2–4 hours, which remains in agreement with
findings of the analysis of inorganic GSR [7].
In summary, both analytical trends, i.e., towards the inner
structure of inorganic GSR as well as detection of organic
residue at trace levels in the environment of a used firearm
are necessary to sustain the scientific grounds for illuminating
various aspects of a criminal investigation in cases of shooting
incidents, among which a special attention is being paid to the
identification of GSR for the purpose of facilitating the Court
to associate a suspected person with the act of shooting.
Acknowledgments The author is grateful to Dr. Rüdiger Schumacher,
Bundeskriminalamt (BKA - Federal Criminal Police Office), Wiesbaden,
Germany, the leader of the project no. HOME/2011/ISEC/AG/
4000002504 financially supported by the Prevention of and Fight against
Crime Programme European Commission – Directorate-General Home
Affairs for his invitation to participate in the project that provided unique
premises for exchange of experiences and better understanding of various
aspects of gunshot residue analysis for forensic purposes.
The author is grateful to Dr. Robert A. Jackson, School of Chemical
and Physical Sciences, Keele University, Staffordshire, UK for his proof-
reading and valuable remarks.
The views presented here were partially gained within the project
number VIII/K, 2013–2016 financially supported by the Institute of
Forensic Research, Krakow.
5810
Compliance with ethical standards
Conflict of interests The author reports no conflict of interests. The
author alone is responsible for the content and writing of the paper.
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