Review

Electrochemical Detection of Gunshot Residue for Forensic

Analysis: A Review
Aoife M. OMahony, Joseph Wang*
Department of NanoEngineering, University of California, San Diego, La Jolla, CA 92093, USA
tel: + 1 (858) 246 0128; fax: + 1 (858) 534 9553
*e-mail: josephwang@ucsd.edu

Received: January 30, 2013

Accepted: March 4, 2013
Published online: && &&, 2013

Abstract
Current demands for detection of Gunshot Residue (GSR) require a reliable and rapid decentralized detection
system with high sensitivity and specificity. This article reviews the use of electrochemical devices for GSR detection
over the last 35 years and highlights recent advances associated with the demands of GSR field detection such as
portability, speed, cost and power. Anodic stripping voltammetry (ASV) has been widely implemented for the de-
tection of the metallic components of GSR at a variety of working electrodes. Efforts toward the detection of the
organic components of GSR have also been reported using cyclic- and square-wave voltammetry. The simultaneous
detection of both organic and inorganic GSR constituents has recently been examined to increase the overall infor-
mation content in a single voltammetric scan. As well as this, exploitation of screen-printing fabrication allows re-
placement of conventional electrochemical cells with easy-to-use sensor strips Sampling methods for electrochemi-
cal GSR analysis are also advancing from acid washes or swabs to simpler abrasive methods which integrate sam-
pling and analysis obviating the need for intermediate processing steps. The latest direction of electrochemical de-
tection of GSR involves chemometric treatment to evaluate data allowing for more objective conclusions and in-
creasing the automation of the system. These advances indicate great promise for investigating firearm-related
crimes, and bring significant changes to the detection of GSR making electroanalysis a powerful tool for decentral-
ized forensic analysis.

Keywords: Gunshot residue, Sensor strips, Integrated sampling, Chemometric

DOI: 10.1002/elan.201300054

1 Overview of Gunshot Residue Detection
The majority of homicides in the US are caused by fire-
arms [1]. The use of firearms in such acts of violence has
increased the role of forensics in criminal investigations
[2]. The data collection of gunshot residue (GSR) in
criminal investigations is used to estimate firing distances,
identify bullet holes, and most pertinently, to determine
whether or not a suspect has fired a gun [1–3]. The neces-
sity for this analysis has presented a wide variety of meth-
ods for detection of both organic and inorganic compo-
nents of GSR, and the majority of these methods are
competently outlined in a number of reviews [1–6]. These
publications outline different methods of collection and
analysis to decipher which are most effective, how can
false positive and negative results be minimized, and fi-
nally, whether it is possible to identify a person who has
discharged a firearm with certainty.
GSR detection methods are based on the analysis of
chemical residues produced by discharge of a firearm
whereby trace amounts of metallic and organic species
can be deposited on the hands, face, hair and clothing of
the shooter [2]. GSR is comprised of metallic and organic
components which are outlined in Table 1. Some of these
materials come from the primer which leaves residues of
lead styphnate, barium nitrate and antimony sulfide. Resi-
dues left by gunpowders include propellants such as nitro-
cellulose and nitroglycerin, as well as stabilizers such as
diphenylamine and ethyl centralite [2]. At discharge, the
majority of these residues are ejected downrange of the
barrel, but a small amount is deposited on the shooter,
the composition of which may be analyzed to make an
identification. On-the-spot field detection of residual
materials from firearm discharge is particularly important
for obtaining valuable forensic information and identify-
ing individuals firing a weapon. Such on-the-spot tests
would also simplify procedures such as sample storage
and custody, diminishing extra requirements of proce-
dures, facilities and personnel, which can be a burden in
forensic analysis. Here we review the use of electroanalyt-
ical techniques for detecting GSR, as well as the related
opportunities and challenges.

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2 Challenges of Gunshot Residue Identification
2.1 GSR Components in the Environment
The advantages and disadvantages of the more prominent
GSR analysis methods, such as scanning electron micros-
copy/energy-dispersive X-ray spectroscopy (SEM/EDX),
neutron activation analysis (NAA), high performance
liquid chromatography (HPLC) and gas chromatography
(GC) are discussed in depth in the reviews mentioned
above [1–6]. One major disadvantage to the majority of
these methods however is that they are capable of detect-
ing either the metallic or organic components of GSR,
not both. Inorganic GSR is generally analyzed using neu-
tron activation analysis (NAA), atomic absorption spec-
troscopy (AAS), inductively coupled plasma (ICP), scan-
ning electron microscopy in conjunction with energy dis-
persion X-ray (SEM/EDX), and organic GSR is regularly
Aoife OMahony is currently a post-
doctoral scholar at UCSD, Depart-
ment of Nanoengineering with 8
years experience in the field of elec-
trochemistry. She received her B.Sc.
degree in Chemistry at University
College Cork in 2005 and completed
her M.Sc. degree at Tyndall National
Institute in 2007. She received her
Ph.D. degree in electrochemistry
from Oxford University in 2010. She
has published 20 papers in interna-
tional journals in the field of electro-
chemical sensors and holds a patent for two of her studies. Her
current scientific interests include field-sensor and portable devi-
ces for forensic detection of gunshot residue and explosives,
along with related sensor microfabrication. Aoife OMahonys
interest is also in the fabrication of nanomaterials for fuel cell
applications and immunosensors for brain cell biomarkers.
Joseph Wang is a Distinguished Pro-
fessor in the Department of Nanoen-
gineering at the University of Califor-
nia, San Diego (UCSD). He received
the Ph.D. from the Technion (Haifa)
in 1978 and served as a research asso-
ciate at the University of Wisconsin
(Madison) from 1978 and 1980. He
joined New Mexico State University
(NMSU) in 1980 where he held a Re-
gents Professorship and Manasse
Chair positions. Between 2004 and
2008 Prof. Wang served as the Direc-
tor of Center for Bioelectronics and Biosensors of Arizona State
University (ASU). He has published more than 850 papers and
holds 15 patents. He became the most cited electrochemist in the
world and received 4th place in ISIs list of Most Cited Research-
ers in Chemistry from 1996–2006. Since 1980, over 25 Ph.D. can-
didates and 150 research associates have studied with him. He is
the Editor-in-Chief of Electroanalysis. His scientific interests are
concentrated in the areas of biosensors, bioelectronics, nanoma-
chines, bionanotechnology, and electroanalytical chemistry.
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A. M. OMahony, J. Wang
analyzed using gas chromatography (GC), high perfor-
mance liquid chromatography (HPLC) and capillary elec-
trophoresis (CE). The implications of this limited analysis
are a concern, considering the prevalence of many of
these species environmentally. In a detailed paper by
Wolton et al., the presence of the common components
of GSR was surveyed from the hands of people working
in certain industrial and commercial operations [7]. These
occupations included lead smelters, automobile brake me-
chanics, lead-acid battery assemblers, plumbers, laborato-
ry technicians and electricians, and were called critical
occupations. The presence of metallic GSR components
such as lead, antimony, barium and zinc were found on
a significant number of the samples examined, and in
some cases, the morphology of the particles was similar
to GSR. While none of the occupational samples was
falsely identified as gunshot residue by the experienced
analysts, it was conceded that less experienced personnel
would have encountered difficulties in obtaining correct
classification. This may unfortunately lead to the false
positive identification when examining a suspect in a fire-
arm-related crime. Therefore, the presence of metallic
species consistent with GSR should not be solely consid-
ered for forensic identifications. Other potential environ-
mental sources of GSR-relevant Ba, Sb and Pb contribu-
tions are outlined in Table 2 [1].
The organic species consistent with GSR should also be
examined. However, the presence of these components is
not indicative of discharge of a firearm, as they too, can
be present in diverse environmental sources and contact
can be made in a variety of industrial operations. The sta-
bilizer diphenylamine (DPA) is found on the surface of
apples, in rocket fuels, pesticides, dyes and pharmaceuti-
cals, while the analysis of ethyl centralite (EC) peaks
using HPLC is consistent with examination of different
fruits [5]. Nitrocellulose (NC) in propellants and explo-
sives is also present in lacquers, varnishes, celluloid films
and the printing and pharmaceutical industries [2]. Nitro-
glycerine (NG) occurs in both pharmaceutical prepara-
tions and explosives [2]. The detection of metallic or or-
ganic species alone can be inconclusive in criminal inves-
tigations since minimal amounts of these are not unique
to GSR. Simultaneous measurements of metallic and or-
ganic residues have recently been documented to provide
a new, information-rich, inorganic/organic fingerprint to
further enhance the reliability of forensic GSR investiga-
tions [8]. This will be further addressed below.
2.2 Persistence of GSR
Persistence of GSR on a shooters body is another chal-
lenge faced by the forensic community in criminal investi-
gations. GSR deposits on the hand of a shooter are con-
tinuously lost through a variety of common activities re-
sulting in a large variation of time periods over which
GSR may be sampled [2, 5]. A number of reports state
that there is a rapid decrease in GSR particles on the
hands of a shooter with respect to post-firing collection
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Electrochemical Detection of Gunshot Residue for Forensic Analysis

Table 1. Inorganic and Organic compounds that may contribute to gunshot residue. (Adapted from [5], Copyright 2010, with permis-
sion from Wiley.)
Inorganic compound Compound source Organic compound Compound source
Aluminum Primer/case 2,4,6-Trinitrotoluene (TNT) Propellant powder/primer mix
Aluminum sulfide Primer mix 2,4-Dinitrodiphenylamine (2,4-DPA) Propellant powder
Antimony Case/bullet 2,3-Dinitrotoluene (2,3-DNT) Propellant powder
Antimony sulfide Primer mix 2,4-Dinitrotoluene (2,4-DNT) Propellant powder
Antimony sulfite Primer mix 2,6-Dinitrotoluene (2,6-DNT) Propellant powder
Antimony trisulfide Primer mix 2-Nitrodiphenylamine (2-NDPA) Propellant powder
Arsenic Case 4-Nitrodiphenylamine (4-NDPA) Propellant powder
Barium nitrate Primer mix/propellant Akaridte II (AKII) Propellant powder
Barium peroxide Primer mix Butyl phthalate Propellant powder
Bismuth Case Butylcentralite (N,N-Dibutylcarbanilide) Propellant powder
Boron Primer mix Camphor Propellant powder
Brass Case Carbanilide Propellant powder
Bronze Bullet Carbazole Propellant powder
Calcium carbonate Propellant Charcoal (major carbon) Black powder
Calcium silicide Primer mix Cresol Propellant powder
Chromium Bullet Dextrin Primer mix
Copper Bullet jacket/primer cup/case Diazodinitrophenol Primer mix
Copper thiocyanate Primer mix Diazonitrophenol Primer mix
Cupro-nickel Bullet jacket Dibutyl phthalate Propellant powder
Gold Primer mix Diethyl phthalate Propellant powder
Ground glass Primer mix Dimethyl phthalate Propellant powder
Iron Rust, bullet Dimethylsebacate Propellant powder
Lead Bullet Dinitrocresol Propellant powder
Lead azide Primer mix Diphenylamine (DPA) Propellant powder
Lead dioxide Primer mix Ethyl centralite (N,N-Diethylcarbanilide) Propellant powder
Lead nitrate Primer mix Ethyl phthalate Propellant powder
Lead peroxide Primer mix Ethylene glycol dinitrate Propellant powder
Lead styphnate Primer mix Gum Arabic Primer mix
Lead thiocyanite Primer mix Gum tragacanth Primer mix
Magnesium Primer mix Karaya gum Primer mix
Mercury Primer mix Methyl cellulose Propellant powder
Mercury fulminate Primer mix Methyl centralite (N,N-Dimethylcarbanilide) Propellant powder
Nickel Case Methyl phthalate Propellant powder
Nitrate Black powder Nitrocellulose (NC) Propellant powder/ Primer mix
Phosphorus Case Nitroglycerine (NG) Propellant powder/Primer mix
Potassium chlorate Primer mix Nitroguanidine Propellant powder
Potassium nitrate Propellant powder/Primer mix Nitrotoluene Propellant powder
Prussian blue Primer mix N-Nitrosodiphenylamine (N-NDPA) Propellant powder
Red brass Bullet jacket Pentaerythritol tetranitrate (PETN) Propellant powder/Primer mix
Silicon Primer mix Picric acid Propellant powder
Sodium nitrate Primer mix RDX (Cyclonite) Propellant powder
Sodium sulfate Propellant powder Resorcinol Propellant powder
Steel Bullet core/case Rubber cement Primer mix
Strontium nitrate Primer mix Sodium Alginate Primer mix
Sulfur Primer mix/black powder Starch Propellant powder
Tim Primer mix Tetracene Propellant powder/Primer mix
Titanium Primer mix/lead free primer mix Tetryl Propellant powder/Primer mix
Tungsten Bullet Triacetin Propellant powder
Yellow brass Bullet jacket/case
Zinc Primer cup
Zinc peroxide Primer mix
Zirconium Primer mix

time, with the largest loss being within the first 2–4 h [4].
Reports outlined in a variety of reviews on the subject
state that the recovery time for inorganic GSR from the
hand of a shooter can range from 1–48 h, depending on
the activity of the shooter [2, 4, 5]. Such persistence stud-
ies examined include hand-washing and drying with
a paper towel, a light 3 s rinse under warm water, and
moving hands in and out of pockets several times. Few
particles were found on the hands after washing, and on
hands that were in and out of pockets. Some Sb and Ba
was recovered after 2 h from subjects who did not wash
their hands [2]. Persistence studies for organic GSR com-
ponents are quite similar, with reports on recovery times
for NG from the hands of a shooter ranging from 0.5 to

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Table 2. Sources of barium, antimony and lead in the general environment. (Adapted from [1], Copyright 1994, with permission from
Elsevier.)
Barium Antimony
Paint Paint
Grease Flame retardants
Rubber Lacquers
X-ray media Enamels
Paper Storage batteries
Printing fabric Pewter ware
Rat poison Tin alloys
Photocells Copper alloys
Sunscreen Lead alloys
Wood Printers type
Fireworks Matches
Lubricating oil Bearings
Printers ink Pyrotechnic mixture
Glass Eye makeup
7 h [5], and persistence of up to 48 h for cases of unwash-
ed hands or suicides [2]. Therefore, it is important to
obtain a sample from a suspect as soon as possible, and
also to correctly interpret the results of any given sample.
Obtaining a GSR sample from a suspect early, or even
collecting secondary contamination from a possible wit-
ness, can assist forensic investigators in confirming alibis,
questioning suspects, and making arrests.
3 Electroanalysis of Gunshot Residue
Current demands for detection of GSR require rapid and
reliable detection with high sensitivity and specificity at
a cost within the range of the average forensic laboratory.
It would also be advantageous to use nondestructive ana-
lytical methods. The ability to establish whether an indi-
vidual has discharged a firearm in the field would be of
great use to forensic investigations to arrest a suspect or
distinguish between suicide and homicide [9]. Atomic ab-
sorption spectroscopy (AAS) and scanning electron mi-
croscopy (SEM) are the current techniques of choice in
most forensic laboratories [10, 11]. However, these tech-
niques are time-consuming and require high levels of ex-
pertise. The expense of the instrumentation associated
with these techniques is usually beyond the reach of small
laboratories. Therefore, a low-cost alternative would be
hugely advantageous.
In past years, electrochemical devices have not received
the major share of the attention in forensic analysis. Tra-
ditionally, such measurements have been carried out in
a central laboratory, in connection with time-consuming
sampling, transportation and storage steps [12]. In situ
monitoring of trace metals is preferable for many practi-
cal situations. Due to its specificity, speed, portability, and
low cost, electroanalysis offers exciting opportunities for
numerous decentralized forensic applications, ranging
from alternative-site testing (e.g., at a crime scene) to
police-station screening [13]. Recent technological advan-
ces have successfully addressed previous obstacles for
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A. M. OMahony, J. Wang
Lead
Paint
Putty
Glass
Gasoline
Batteries
Pewter ware
Hair dye
Candle wicks
Printers ink
Glazed ceramics
Solder
Plumbing
Auto body filter
Wheel-balancing weights
such field operations. The consequence of these develop-
ments is that major considerations are now given to de-
centralized metal testing. Such devices produce a simple,
inexpensive and yet accurate and sensitive platform as
well as a wide range of electrode materials, analytes and
sampling methods which permit assays in a variety of en-
vironments [14]. Electrochemical sensors offer great pros-
pects for addressing the growing needs for field detection
in other forensic scenarios such as identification of explo-
sives [15]. Both the sensor and the controlled instrumen-
tation can be readily miniaturized utilizing microfabrica-
tion and microelectronics which has led to powerful, com-
pact and user-friendly analytical devices for on-site
(indoor and outdoor) testing [13].
To facilitate rapid sampling and processing, voltammet-
ric analysis is ideally poised as a field-deployable, rapid
and robust method for GSR detection. In particular,
anodic stripping voltammetry (ASV) is a simple, rapid,
sensitive and selective technique for the analysis of the
different components of GSR which can be implemented
by minimally trained operators, thus obviating the high-
cost requirements of more established GSR detection
methods [8–12]. Its remarkable sensitivity is attributed to
the preconcentration step in which the metal ions in the
sampled solution are reduced at a cathodic potential and
concentrated onto the working electrode surface. This
preconcentration makes stripping analysis much more
sensitive than other techniques because the concentration
of the metal at the electrode is 2–3 orders of magnitude
greater than the metal ion in solution [12]. The nondes-
tructive nature of this technique as well as portability of
instrumentation is also favorable. The onset of interest in
the use of voltammetry for the detection of GSR appears
to occur in the late seventies [16], and has received spora-
dic attention over the last 35–40 years.
3.1 Electrochemical Detection of Inorganic GSR
The most prevalent metallic particles observed in GSR
are outlined in Table 3. Wolten et al. produced this list of
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Electrochemical Detection of Gunshot Residue for Forensic Analysis
Table 3. Compositions of metallic gunshot residue particles.
(Adapted from [7], Copyright 1979, with permission from
Wiley.)
1. Unique
(a) Pb, Sb and Ba
(b) Ba, Ca, Si, trace S
(c) Ba, Ca, Si, trace Pb (if Cu and Zn absent)
(d) Sb and Ba
2. Characteristic, especially if spheriodal
(a) Pb and Sb
(b) Pb and Ba
(c) Pb (if Fe and P are absent)
(d) Ba (if S is absent or present in trace amounts)
(e) Sb (rare)
3. Any of the above may also contain only these elements
(a) Si, Ca, Al, Cu, Fe, S, P, Zn (only with Cu), Ni (only with
Cu and Zn)
(b) Sn (older ammunition)
(c) Presence of any other element usually indicates source
other than gunshot
particle types and categorized them as unique to (charac-
teristic of), and consistent with inorganic GSR particles
based on particle composition [7]. From this table we ob-
serve that the principle components of interest are pri-
marily Ba, Pb and Sb, and thus, these components have
been the focus of electrochemical detection of inorganic
GSR. Antimony is an under-explored element electroana-
lytically, particularly as compared to the attention re-
ceived by other heavy metals such as Pb, Cd or Cu [17].
Pioneering work on antimony at mercury electrodes was
conducted by Stromberg and the majority of voltammetry
reported has since been performed at mercury electrodes
[18]. Antimony has been well examined as a target for
GSR, but presents some difficulties in actual GSR sam-
ples as the copper stripping peak can overlap the antimo-
ny peak and often obscure it [11, 16, 19].
J. Heyrovsky showed that barium(II) can be deter-
mined by polarography in his pioneering work of 1948
[20]. However, barium is unsuited for mainstream elec-
trochemical detection (including field-deployable screen
printed electrodes) as it stripps at such negative poten-
tials, resulting in hydrolysis of aqueous solvent [21, 22].
This is a major limitation to this approach, because in the
interpretation of gunshot residues, the combination of Ba
and Sb is often more reliable as an indicator than Pb and
Sb alone. The simultaneous detection of Pb, Cu and Sb in
a single run has been achieved voltammetrically with sep-
arate detection of Ba using AAS [10]. The voltammetric
detection of Ba for GSR analysis has been reported
[8, 23], although it is difficult due to hydrogen evolution
and is most suitably examined at a mercury electrode.
Other inorganic constituents of GSR include Cu, Zn,
Sn, Ni, Bi and Hg [1–3, 5].These metals have been widely
measured by ASV for several decades [12, 24]. Pb and
Cu, along with 2–3 additional heavy metals, have been
commonly measured simultaneously in a single run for
over 5 decades using a wide range of working electrodes,
Electroanalysis 2013, 25, No. &, 1 – 18  2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
starting with the classical mercury drop electrodes
[12, 24]. Ammunition cartridge cases are typically brass,
with a basic composition of 70 % copper and 30 % zinc,
although aluminum and nickel-plated brass cases are also
reported [1]. The bullet can also contain a lead core that
is covered with a full metal jacket of copper alloyed with
5 to 10 % zinc [2]. Traces of nickel, lead, bismuth, and tin
have also been recorded for steel-jacketed ammunition
[1]. Zn and Sn feature in some lead-free ammunition, as
well as in common Czech and Russian ammunitions [3–
6].In particular, Cu and Zn have been electrochemically
measured simultaneously with other inorganic and organ-
ic GSR targets [8, 10, 25].
Initial attempts at the voltammetric detection of the
metallic components of GSR were carried out at mercury
electrodes. One of the first examples of this was outlined
in 1977 by the vanLoon group at Queens University, On-
tario, using ASV for the determination of Pb and Sb in
GSR at a graphite electrode coated with a preplated Hg
film [16]. Samples were taken from residue deposited by
a Smith & Wesson .357 magnum handgun. The collection
method employed was an acid wash of the hand of the
shooter in a polyethylene bag, whereupon samples were
transferred to nalgene bottles to prevent contamination
and kept for analysis. Voltammograms were run by a po-
larographic analyzer in electrolytes HNO3 and HCl,
which were de-aerated for 10 min with N2 prior to analy-
sis. Deposition times for detection of Pb and Sb ranged
from 180 to 280 s. The voltammetric outputs for Sb and
Pb are shown in Figures 1 A and 1 B, respectively, along
with a table outlining the detection levels of each metal.
The lead peak occurs at 0.50 V and the copper peak at
0.29 V in Figure 1 A, but the latter was not considered
in the present application. The antimony peak occurs at
0.24 V in Figure 1 B. The overall timeframe for the de-
termination of Pb and Sb from GSR was under 2 h, and
no separation or preconcentration techniques were re-
quired. This work constitutes the onset of many others
for the use of voltammetry for sensitive and selective de-
tection of GSR.
The use of preplated Hg-film electrodes continued to
enjoy popularity for the detection of the metallic compo-
nents of GSR during the 1980s. However, later works de-
posited the Hg-film in situ with the analyte metals.
In 1985, Briner et al. co-deposited a Hg-film onto
a glassy carbon electrode (GCE) for the detection of Sb
in GSR [10]. The targets for this work were taken from
GSR samples under controlled laboratory procedures as
well as actual evidence submitted by law enforcement
agencies from firearms including a 0.38 caliber Smith &
Wesson (2 in. and 1.5 in. barrel), and a 0.357 Magnum.
The collection method used was swabbing with a cotton
q-tip in 5 % HNO3. Voltammograms were run in HCl/hy-
drazine sulfate electrolyte which was de-oxygenated with
N2 for 180s prior to analysis. Co-deposition of the Hg-
film and analyte was implemented at the GCE for 540 s
with stirring and the limit of detection for Sb was ob-
served to be 10 ng of sample. The lead time for results
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Review A. M. OMahony, J. Wang

Fig. 1. (A) Anodic stripping voltammograms for lead on hands after firing a gun. Curve a, sample; Curves b–f, sample plus 100-ppm
incremental additions of lead. The small peak at 0.29 V is due to copper. (B) Anodic stripping voltammograms for antimony on
hands after firing a gun. Curve a, sample; Curves b–f, sample plus 10 ppm incremental additions of antimony. Table outlining detec-
tion levels of Pb and Sb. (Adapted from [16], Copyright 1977, with permission from Elsevier.)

was 26 min (not including sample preparation of swab-
bing and soakage of cotton tips in HCl for metal leach-
ing) and the detection levels were comparable with AAS.
The output of such voltammetry is shown in Figure 2. The
antimony signal is observed at 0.18 V and the presence
of small amounts of lead appears at 0.54 V along with
copper at 0.30 V in the control blank. The presence of
large amounts of copper and lead in the GSR voltammo-
gram provides the typical three-peak pattern giving im-
mediate indication that the sample may indeed be GSR.
Fig. 2. Voltammograms of a sample, blank and standard: (1)
gunshot residue showing Pb, Cu and Sb; (2) blank electrolyte;
(3) blank electrolyte spiked with 30 ng Sb. (Adapted from [10],
Copyright 1985, with permission from Elsevier.)
This presents the first example of simultaneous detection
of several components of GSR using ASV.
More recently, Dewald and colleagues (Ohio Universi-
ty) also utilized a Hg-film GCE (Hg deposited in situ) in
two different works for the simultaneous detection of Pb
and Sb in 1999, and the simultaneous detection of Ba and
Pb in 2001 [11, 23]. Samples were attained in controlled
scenarios using cotton q-tips for swabbing within 15 min
of discharge, which were then soaked in acid for 12–16 h
before analysis, similar to Briner et al. The handguns used
for the simultaneous detection of Pb and Sb were 0.22,
0.38 and 0.357 caliber pistols with different ammunition
[11]. Voltammograms were run in KNO3/hydrazine sul-
fate solution which was de-oxygenated for 180 s prior to
analysis. A deposition potential was then applied for
180 s with stirring to co-deposit the Hg-film along with
the metallic analytes. This lower deposition time de-
creased the time required for a single run by about 50 %
compared to previous work. A single scan detected both
metals in low concentration ranges (ng/ml) with no visible
interferences from Cu, shown in Figure 3 A. A lead peak
is observed at 0.45 V and an antimony peak at 0.15 V.
The absence of a Cu peak allows for a large, distinguisha-
ble Sb peak. The use of a KNO3/hydrazine sulfate matrix
allows for the production of this effect, which is not seen
for an HCl matrix. The GSR samples for simultaneous
detection of Ba and Pb were taken from a 0.357 caliber
pistol with two different types of ammunition [23]. Vol-
tammograms were recorded in a LiClO4 solution to which
Hg(NO3)2 was added and bubbled with N2 as before. A
deposition potential of 2.4 V was implemented to
ensure the preconcentration of Ba onto the electrode sur-
face. This resulted in a high level of hydrogen evolution
on the working electrode. The resulting voltammograms

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Electrochemical Detection of Gunshot Residue for Forensic Analysis

Fig. 3. (A) Voltammogram of a GSR sample from the back of the left hand. Pb peak at 450 mV, Sb peak at 150 mV. (B) GSR
sample from the palm of the left hand. Ba peak at 2.05 V, pb peak at 0.45 V. Weapon used (357 Ruger SP101), ammunition used
(38 Special, 158 grain from Ultramax). (Adapted from [11] & [23], Copyright 1999 & 2001, with permission from Elsevier.)

showed a stripping peak for Pb and a small, broad capaci-
tance peak for Ba outlined in Figure 3 B, proving that the
detection of trace Ba from actual GSR samples could be
achieved. Detection of Ba below 200 ng was accom-
plished from an actual GSR sample. However, it was not
observed for all of the GSR samples investigated.
The use of the hanging mercury drop electrode
(HMDE) has been examined in a number of studies for
the detection of the metallic species found in GSR. In
1980, Liu et al. described the use of a low-cost polaro-
graph for the simultaneous detection of multiple metals
at the HMDE in acetate buffer, as well as the detection

Table 4. Zinc, lead, copper and antimony (mg) deposited on the firing and non-firing hands. (Adapted from [25], Copyright 1980, with
permission from Elsevier.)
Experiment Hand Ammunition Species Deposits detected
1120 (experiment repeated  3 Firing hand Remington Zn 3.79 6.80 7.79
for each type ammunition) Pb 11.42 8.90 8.25
Cu 0.87 0.18 0.40
Sb 0.54 0.18 0.40
Federal Zn 3.29 3.09 6.59
Pb 14.91 14.20 18.43
Cu 2.07 1.77 8.69
Sb 0.09 0.51 0.94
Winchester Zn 2.09 8.24 6.18
Pb 12.85 16.83 14.82
Cu ND ND 1.28
Sb 0.26 0.26 0.43
1030 Firing hand Remington Zn 9.18
Pb 22.23
Cu 3.08
Sb 1.49
Non-firing hand Remington Zn 6.78
Pb 1.25
Cu ND
Sb ND
0906 Firing hand Remington Zn 1.60
Pb 6.12
Cu ND
Sb 0.75
Non-firing hand Remington Zn 13.90
Pb 1.18
Cu ND
Sb 0.24

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Table 5. Comparative results (mg) of different studies. (Adapted from [27], Copyright 1982, with permission from Elsevier.)
Reference (reference numbers Firearm Left hand Right hand
correspond to those in [27]) Pb Sb Pb Sb
Candela et al. [1] Beretta 0.17–1.36 0.03–0.14 3.10–3.37 2.28–2.98
S&W .375 0.31–1.53 0.04–12 9.26–10.12 9.01–10.54
Konanur et al. [2] S&W .375 5.5–16 0.016–0.043 63–115 0.25–1.31
Liu et al. [3] S&W .38 22 0.45 27.52 1.88
Zeichner et al. [4] F. N. Browning 0.23–0.45 < 0.005 0.40–0.72 0.33–0.63
S&W .375 0.39 < 0.005 0.42 < 0.005

of Sb, Pb, Cu and Zn in GSR samples [25, 26]. These sam- mercury drop electrodes. This is the first example of de-
ples were acquired from a Smith & Wesson 0.38 caliber tection of metallic components of GSR without the need
revolver. The sampling procedure involved an acid wash to de-oxygenate. A high sample throughput also allows
of the hand of the shooter in 70 mL HCl in a plastic bag, up to 20 samples per hour, which can be increased
whereby the test hand was rinsed ~ 60 times by motion of through modification of the voltammetric parameters.
the hand and plastic bag [26]. The acetate buffer electro- This represents a significant improvement in lead-time
lyte was bubbled with N2 for 10 min, and then a deposi- for sample analysis output. The limit of detection for Pb
tion potential was held (while solution was under a blan- in GSR samples was noted as 20 mg L 1. The authors men-
ket of N2) for 10 min with stirring. The average levels of tion that this method is not limited to detection of Pb,
Sb, Zn, Pb and Cu were 0.0, 1.26, 1.21 and 3.74 mg, re- however if detection of Sb and Ba were to be implement-
spectively. More detailed detection levels for different ed, this would slow the process significantly. A number of
types of ammunition from the firing hand and the non- sampling methods were also examined using this technol-
firing hand are shown in Table 4. In general, levels of resi- ogy: acid-wash procedure (as seen in Konanur et al.);
dues recovered from the firing hand are higher than acid-assisted swabbing method (similar to Briner et al.);
those recovered from the non-firing hand, as expected. adhesive tape-lift method. This work is also the first ex-
The authors examined the recovery efficiency of the GSR ample of the utilization of the tape-lift method in con-
over several washes, and reported that the levels of Pb junction with stripping voltammetry. While recovery for
and Sb detected were comparable to other analysis tech- Pb from GSR samples was noted to be 94 %, the use of
niques reported in literature, although data was not then chloroform to liberate metal from the adhesive material
available on detection levels of Zn and Cu. is not ideal.
Following on from this work, in 1982 Brihaye et al.
combined the detection of Pb and Sb in GSR at the
HMDE with the swabbing technique of sample acquisi-
tion [27]. These samples were obtained from a 7.65 cali-
ber pistol and a 0.357 magnum revolver using HNO3-
soaked q-tips (in accordance with Briner et al. [10]) and
overnight sample recovery in conc. HCl. Recovery of
GSR from the cotton swabs using dry ashing in activated
oxygen under reduced pressure, was also examined, but
this was noted to result in significant losses of Sb. The de-
tection range for Pb and Sb lay between 0.1 and 0.6 mg,
with similar limits of detection for both species
(0.008 mg). The authors compared their detection limits to
a number of other works, including Konanur et al. [16]
shown in Table 5, and attributed any significant discrep-
ancies in recovery levels to the method of sampling.
In 2005, examination of the Pb component of GSR has
been conducted at the HMDE using the new technique
of batch injection analysis formulated by the Brazil-based
group of Ivano Gutz in S¼o Paulo [9]. This is the first Fig. 4. Adaptation for BIA with a commercial HMDE stand
step towards an automated analysis technique for the and cell for ASV GSR analysis. (A) Detailed photograph of the
characterization of GSR. A schematic of the instrumenta- outlet section of the J-adaptor, fitted to the glass capillary. (B)
Schematic of the electrochemical cell showing; a) mercury reser-
tion developed is described in Figure 4. The proposed J- voir and valve; b) micropipettor; c) mercury electrode capillary;
adaptor was easy to construct, install and operate, d) hanging mercury drop; e) J-adaptor outlet; f) sealing pipettor
worked reliably without adjustments or maintenance, and tip; g) modified 100 uL pipette tip. (Adapted from [9], Copyright
opened a shortcut to automated flow electroanalysis on 2005, with permission from Wiley.)

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Electrochemical Detection of Gunshot Residue for Forensic Analysis

Fig. 5. Voltammograms and calibration graphs of SWCAdS for the determination of (A) lead, and (B) antimony in GSR by standard
addition method. (A): (a) BR buffer + 5  10 3 M catechol, (b) (a) + GSR and (b) + cPb : (c) 2.0, (d) 4.0, (e) 6.0, (f) 7.9, (g) 12.0, (h)
17.0, (i) 22.0, (j) 27.0, (k) 32.0 M (Inset in A), (B): (a) BR buffer + 5  10 3 M catechol, (b) (a) + GSR and (b) + cSb : (c) 3.4, (d) 6.8, (e)
10.0, (f) 14.0, (g) 20.0, (h) 23.0, (i) 26.0, (j) 29.0, (k) 32.0 M (Inset in B). (Adapted from [28], Copyright 2011, with permission from
Wiley.)

The most recent use of the HMDE for GSR analysis
was in 2011 in the KiliÅ group, where Erden et al. utilized
cathodic adsorptive stripping voltammetry (CAdSV) for
the simultaneous determination of Sb and Pb [28]. Ad-
sorptive accumulation of Sb and Pb in the presence of
catechol was carried out on the surface the HMDE in
Britton-Robinson solutions at varying pH values, with
prior de-oxygenation using argon. The resulting voltam-
metry for Pb and Sb is shown in Figures 5 A and 5 B, re-
spectively. In this work, the voltammetry of the GSR
sample was implemented and followed by standard addi-
tions of Pb or Sb to attain the concentration of each spe-
cies in the sample. The linear range for Sb detection was
2  10 9 to 7  10 7 M with a limit of detection (LOD) of
7  10 10 M. The linear range for Pb detection was 2  10 9
to 3  10 7 M with LOD of 6  10 10 M. The preferred
waveform examined was square-wave. The quantification
of these cations was shown to be feasible by these meth-
ods at the respective detection limits mentioned above.
The results were in good agreement with AAS data.
Up to 2009, the electrode material utilized for detec-
tion of metallic components of GSR was mercury. How-
ever, due to its toxicity, the use of mercury has declined
in recent years. In 2009, Rodriguez et al. presented work
on the determination of Pb from GSR at a tubular Bi-
film electrode as an attractive alternative to mercury, uti-
lizing differential pulse anodic stripping voltammetry
(DPASV) [29]. In this work, Bi was co-deposited onto
a carbon paste electrode with the analytes of the GSR
sample. N2 purging was not implemented in the electro-
lyte solution as the Bi-film electrode is less susceptible to
background interference from O2, and a deposition time
of 60 s meant that the lead-time for analysis was signifi-
cantly shortened. This electrode was installed into a flow-
through small-volume electrochemical cell; it allowed re-
generation of the Bi-film which was newly-plated for
each analytical cycle. A detailed schematic of this flow
system is outlined in Figure 6. The linear range for Pb in
GSR was noted to be 0.8–40 mg L 1, with a limit of detec-
tion of 0.2 mg L 1. However, the presence of other species
aside from Pb in the GSR sample caused deviation in the
stripping signal. The sampling method utilized for this
work was q-tip swabbing with sonication in buffer which
allowed GSR sampling within 10 min. This work indeed
was a significant advance in the detection of the metallic
components of GSR.
More recently, other electrode materials have been ex-
amined for the detection of metallic species in GSR. In
2012, Salles et al. examined the feasibility of utilizing
a bare Au microelectrode for the detection of Pb in GSR
[30]. The use of a microelectrode presents several advan-
tages for voltammetric detection including increased effi-
ciency of mass transport. The determination of Pb was ex-
amined at the bare Au electrode in acidic solution in the
presence of chloride ions yielding a LOD of 1.7 nM. GSR
was examined using this system from samples collected
from 4 firearms (1 pistol and 3 rifles) using the swabbing
method of sample collection. Swabs were soaked in
EDTA, and then placed in vials of HNO3 whereupon
they were subject to ultrasound for 2 h at 60 8C. The
levels of Pb were determined from each sample, and
when compared with AAS analysis, no significant varia-
tions were observed. These results are outlined in
Table 6.
In order to address the needs of field sensing of GSR,
it is necessary to move away from traditional bulky elec-
trodes and cells (commonly used in research laborato-
ries). The exploitation of advanced microfabrication tech-
niques allows for the replacement of conventional
(beaker-type) electrochemical cells and electrodes with

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Fig. 6. Multicommuted flow system for Pb(II) determination in GSR: S, sample; SS, standard solution of Pb(II); CS, carrier solution
(10 mg L 1 of Bi(III) in 0.1 mol L 1; acetate buffer solution, pH 4.5); D, detector; Sy, 10.0 mL syringe; W, waste; V1, V2, V3, three-
way solenoid valves; R1, R2, reaction coils (60 cm). (Adapted from [29], Copyright 2009, with permission from Wiley.)

Table 6. Results obtained from two different methods (stripping and AAS) for analysis of GSR samples. (Adapted from [30], Copy-
right 2012, with permission from Elsevier.)
Gun Ammunition #shots ASV/mg Pb2 + AAS/mg Pb2 +
0.38 revolver CleanRange 18 0.014  0.001 0.0147  0.0001
CleanRange 18 0.015  0.002 0.0144  0.0001
CleanRange 18 0.017  0.002 0.0154  0.0001
Normal 1 0.019  0.008 0.025  0.001
Semi-jacketed 1 0.019  0.008 0.0260  0.0004
12-caliber pump-action shotgun 3T 1 0.021  0.008 0.019  0.002
3T 1 0.021  0.008 0.0217  0.0004
0.38 repeating rifle Semi-jacketed 1 0.022  0.008 0.022  0.002
Semi-jacketed 1 0.03  0.01 0.0313  0.0005
Semi automatic 0.22 caliber rifle Eley 1 0.039  0.006 0.045  0.001
0.38 repeating rifle Semi-jacketed 1 0.04  0.01 0.0445  0.0004
Semi-jacketed 1 0.04  0.02 0.0519  0.0005
Semi automatic 0.72 caliber rifle CBC 1 0.06  0.01 0.0670  0.0008
Eley 1 0.07  0.02 0.078  0.002
12-caliber pump-action shotgun Especial 24g 1 0.12  0.02 0.1441  0.0004

easy-to-use sensor strips. These sensor strips have been
utilized for over 2 decades by Wangs group at UC San
Diego and elsewhere [31], and permit the use of simple,
rapid and portable electroanalytical detection with low
volume electrolytes, and due to the disposable nature of
the strips, each electrochemical measurement can be
made on a clean surface. The use of these sensor strips in
connection with GSR electroanalysis has first been exam-
ined by O Mahony et al. at Au-modified carbon screen
printed electrodes in acetate buffer [19]. A novel swipe
and scan sampling method, which obviates the need for
intermediate sample processing, has been used, as dis-
cussed in the next section. These sensor strips were suc-
cessfully utilized for the detection of Pb and Cu from the
hands of shooters in a variety of scenarios, including no
contact with GSR, secondary contact and subsequent to
firearm discharge. The resulting voltammetry showed
good discrimination between the various control scenar-
ios for 4 subjects examined. The results are outlined in
Figure 7. The application of ASV for the detection of
GSR samples at a screen-printed sensor strip shows
promise for addressing the limitations associated with the
effective collection of residues and simplifying the overall
electroanalytical protocol.
While the principle metallic components of GSR have
been analyzed, including important targets such as Sb and
Pb, the detection of Ba is still outside the capabilities of
electroanalysis due to its highly negative stripping poten-
tial. Because of this, additional criteria are required to
minimize the false positive identification of a person sus-
pected of discharging a firearm. In addition to analysis of
metallic species in GSR, some work on the detection of
the organic components of GSR has also been conducted.
As seen from the overview above, the presence of metal-
lic components alone seems insufficient to deduce with
certainty (either with or without the inclusion of Ba),
whether a subject has discharged a firearm or not, due to
the abundant presence of these components in a variety
of occupations and environments. Therefore, the detec-
tion of the organic species as well as inorganic ones in-
creases the certainty with which GSR is identified.

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Electrochemical Detection of Gunshot Residue for Forensic Analysis

Fig. 7. AbrSV of GSR samples from 4 subjects for 3 different conditions: in the laboratory, prior to any contact with GSR, named
C1: 1st Control; at the shooting lanes where others were discharging firearms, but without handling or discharging a firearm, named
C2: 2nd Control; after discharging several rounds from the weapon (10 rounds for a Glock 40 and 8 rounds for a Sig Sauer 45) – F:
Firing. (Adapted from [19], Copyright 2013, with permission from Elsevier.)

3.2 Electrochemical Detection of Organic GSR

The electrochemical analysis of GSR has predominantly
been directed towards determination of trace metal spe-
cies. The drawback of this however, as we have previously
observed, is that there are potential contaminants in a va-
riety of occupations and environments. Therefore, there is
a need for additional criteria for analysis of GSR. Table 1
outlines the organic components that can be found in
GSR, which are as numerous as the metallic components.
Despite the predominance of electroactive compounds in

Fig. 8. Summary of cyclic voltammetric data for selected explosive compounds. Supporting electrolyte was 0.06 M monochloroacetic
acid, 0.44 M sodium acetate, 0.001 M EDTA, in 15 % (v/v) l-propanol, pH 3.5. Scan rate, 300 mV s 1. Concentrations of explosives
were between 100 and 200 mg mL 1. (Adapted from [35], Copyright 1981, with permission from Elsevier.)

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Review
Fig. 9. Cyclic voltammograms of (A) diphenylamine and (B) Centralite I, in acetonitrile. Sweep rate 100 mV/s, concentration
0.2 mM. (Adapted from [40], Copyright 1985, with permission from Elsevier.)
this list, few attempts at electrochemical detection in con-
nection with GSR are found. This is somewhat surprising
as the voltammetric detection of the nitro-explosive com-
pounds that constitute several of the organic GSR species
is well documented in literature at a variety of electrode
surfaces in a variety of media, including sea water [5, 32–
34]. These species are commonly examined using voltam-
metric detection for security screening and forensics
[15, 35–39].These are popular analytes due to the pres-
ence of easily-reducible nitro groups, the voltammetry of
which is well understood [35]. There are few reports of
the voltammetric examination of these targets in GSR
studies, instead they are commonly analyzed using chro-
matographic or electrophoretic separation techniques.
However, some work on the voltammetric characteriza-
tion of these species has been performed for forensic ex-
amination of GSR, and is outlined herein.
In 1981, Kissinger presented a comprehensive bench
top study of a variety of common organic GSR constitu-
ents using cyclic voltammetry at a Hg-film Au electrode
as well as at a GCE [35]. Among the samples character-
ized were trinitrotoluene (TNT), dinitrotoluene (DNT),
diphenylamine (DPA), nitroglycerin (NG), cyclotrimethy-
lenetrinitramine (RDX) and cyclotetramethylene-tetra-
nitramine (HMX). DPA, NG and DNT are listed as 3 of
the 5 major volatile components commonly found in
smokeless gunpowders (the other two being diphenylben-
zene (DPB) and ethyl centralite (EC) and thus their ubiq-
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A. M. OMahony, J. Wang
uitous nature in GSR makes them ideal candidates for
voltammetric analysis. DPA is a particularly important
target analyte as it is the most frequently used stabilizer
in smokeless gunpowder. NG is also an attractive analyte
of GSR, and due to this compounds uniqueness, concerns
over occupational and environmental contamination are
significantly diminished [35]. While no real GSR sample
analysis for organic components was carried out (real
samples were examined using liquid chromatography),
the voltammetric signatures of the organic species were
finally recognized in relation to GSR. The signal outputs
for such voltammetry are summarized in Figure 8.
Further study was carried out in 1985 by Bergens et al.
on the voltammetric characterization of the stabilizers
acardite II, centralite I and DPA (to prevent degradation
of NG and NC) in relation to shelf-life of powder in am-
munition [40]. Again, no actual samples were used;
merely bench top studies were carried out to examine the
redox behavior of these species. This was achieved at
a GCE in acetonitrile/methanol matrix utilizing cyclic and
differential pulse voltammetry. Cyclic Voltammetry (CV)
scans of DPA and EC are presented in Figures 9 A and
9 B, respectively. This work further contributed to the li-
brary of redox properties of species commonly found in
GSR with potential to be included in future investiga-
tions.
It is surprising that, despite the knowledge of presence
of organic and metallic components in GSR, no attempt
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Electrochemical Detection of Gunshot Residue for Forensic Analysis
Fig. 10. Cyclic square-wave voltammogram for a mixture of
trace metals and explosives constituents of GSR: 2 ppm Zn,
2 ppm Pb, 20 ppm Sb, and 200 ppm DPA. Square wave parame-
ters: Estep = 4 mV; amplitude = 25 mV; frequency = 25 Hz; and
taccum = 120 s; (reduction) Estart,accum = 1.2 V and Estop = 1.3 V; (oxi-
dation) Estart,accum = 1.3 V; Estop = 1.2 V; and taccum = 120 s. Elec-
trolyte, acetate buffer (pH 4.5). (Adapted from [8], Copyright
2012, with permission from the Royal Society of Chemistry.)
at the simultaneous voltammetric detection of these spe-
cies had been made until recently. Early work by Dahl
et al. examined the detection of both organic and inor-
ganic components utilizing two separate analytical meth-
ods [41]. Analysis of the gunpowder stabilizers including
DPA and EC was performed by HPLC with oxidative
electrochemical detection followed by graphite furnace
atomic absorption spectrophotometry for the determina-
tion of trace metals Sb, Ba and Pb. The coupling of detec-
tion of both organic and inorganic components yielded
substantial evidence as to the presence of a gunshot resi-
due.
In 2012, the Wang group at UC San Diego published
the first work outlining the simultaneous electrochemical
detection of the organic and metallic species found in
GSR [8]. The higher information content of such single-
run inorganic/organic electrochemical fingerprint aims at
enhancing the reliability of forensic GSR investigations.
In this work, cyclic voltammetry and square-wave voltam-
metry (in cyclic form) were utilized to detect, in a single
run, common organic propellants and heavy metals in
GSR. Mixtures of Pb, Sb, DNT, NG and mixtures of Zn,
Pb, Sb and DPA (shown in Figure 10) were examined in
buffer solution at a bare GCE, and a mixture of Ba and
DNT were examined at a Hg-film GCE electrode (Hg de-
posited in situ) in LiClO4 solution. Combining analysis of
both groups enhances the reliability of GSR forensic in-
vestigations. A clear voltammetric signature for the differ-
ent mixtures was attained utilizing this cyclic-square
wave voltammetric waveform. This was accomplished by
reversing the potential to the anodic direction after com-
pleting the reductive detection of nitro-containing propel-
Electroanalysis 2013, 25, No. &, 1 – 18  2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
lants and a brief metal preconcentration time, to allow
metal stripping for GSR analysis. The lead-time for analy-
sis output was ~ 3 min, including deposition of the metal-
lic species. This simultaneous detection of organic and
metallic GSR components had still not been implemented
with real GSR samples in this work, but it is the first ex-
ample of single-instrument analysis for key components
of GSR. While it was still not feasible to electrochemical-
ly incorporate Ba, the combination of propellants, stabil-
izers and metals certainly improved the specificity of the
method in forensic analysis towards minimization of false
positives from occupational and environmental contami-
nations.
Further work has since incorporated this method for
the detection of real GSR samples and will be discussed
later on, but first, we shall briefly look at the sampling
techniques most commonly used for electroanalysis of
GSR.
4 Sampling Methods for Gunshot Residue
It is worth noting the variety of sampling techniques for
GSR detection used in the electrochemical analysis out-
lined above, as not only do they differ between individual
studies, but recent advances may prove to simplify the
procedure substantially. There are a variety of sampling
techniques reported for the collection of GSR, including
acid wash, swabbing, tape lifts, glue lifts, nasal collection
and hair collection [5]. The most popular sampling meth-
ods encountered for the voltammetric detection of GSR
are acid-wash, swabbing and tape lifts.
Earlier work on electroanalysis of GSR used the acid-
wash sampling method. Konanur et al. [16] and Liu et al.
[25] utilized this method in 1977 and 1980, respectively,
for the detection of metallic components of GSR. It in-
volved a volume (about 50 mL) of 1 M HCl in a polyethy-
lene bag. The suspects hand is inserted into the bag and
shaken in the acid for several washes, or 30 s. The acid
containing the GSR is then transferred for storage and
ready to be sampled. This is not an ideal method for
GSR sampling for 2 reasons: (a) the acid solution is
likely to irritate skin; (b) this method is quite cumber-
some and confined to a laboratory.
More recently, the method of tape lifts have been eval-
uated for GSR extraction from the hand of a shooter
[9, 28]. This involves the placing of adhesive tape over the
area of the hand to be examined to lift the GSR sample.
The tape is them glued onto polyethylene pieces, soaked
with chloroform and HCl, shaken, and aliquots are re-
moved from the aqueous phase for analysis [9]. This
method removes the use of acid over the skin and elimi-
nates any irritation from the hand of the suspect. This
method has not been examined with respect to detection
of organic GSR components for electroanalytical detec-
tion.
By far the most popular method of metallic GSR col-
lection for analysis with voltammetry is cotton swabbing
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Review
Fig. 11. “Swipe-and-Scan” sequence for GSR based on abrasive stripping voltammetry (AbrSV): Shoot, swipe, scan, signatures (for
firearm discharge and no discharge) and study (from stock solutions). (Adapted from [19].)
[10, 11, 23, 27, 29, 30].This involves soaking a cotton q-tip
with HNO3 (usually 5 % v/v) and running the swab over
the hand of the shooter. The cotton swabs are then cut
from the handle and placed into a plastic vial, to which is
added strong acid (usually 4 M HCl) which will leach out
the metals from the swab. The swab is left in the vial for
times ranging from 1 h [10] to overnight with stirring
[27]. Other metal extraction procedures from cotton
swabs include sonication [29] and ultrasound [30]. This
method was utilized as far back as 1982 by Brihaye et al.
[27] for detection of Pb and Sb, and as recently as 2012
by Salles et al. [30] for Pb determination. This sampling
method represents a significant improvement on the acid-
wash method as it causes less irritation to a suspect being
tested, and uses smaller volumes. However, follow-up ex-
traction methods from the swab including stirring and
sonication, increase the time over which the sample can
be analyzed, and confine this method largely to the bench
top.
The swabbing method has also been implemented for
the isolation of organic GSR from the hand of a shooter,
where cotton swabs are soaked in an organic solution to
extract the propellants and stabilizers from GSR. Howev-
er, the samples isolated were not analyzed with voltam-
metry.
In 2012, a novel “swipe and scan” protocol integrating
the GSR sampling with voltammetric detection at
a screen printed electrochemical sensor was reported by
O Mahony et al. [19] Integrated sampling and analysis
was implemented using a protocol known as abrasive
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A. M. OMahony, J. Wang
stripping voltammetry (AbrSV) based on an initial me-
chanical transfer of trace amounts of the GSR from the
hand of the suspect directly to the surface of the working-
electrode sensor strip without intermediate processing
steps. Samples were isolated by abrasively rubbing the 3-
electrode strip surface over the back of the firing hand
5 times from wrist to knuckle, and over the surface of the
thumb 5 times from knuckle to tip. Figure 11 displays the
sequence of events for the facile integrated sampling and
analysis. This sampling method addresses the key chal-
lenge of field-deployable recovery of GSR from a subject
who has discharged a firearm, as well as the preservation
of the sample integrity (i.e., minimizing errors associated
with the transport and storage of samples). This sampling
protocol was implemented for the metallic components of
GSR only in this work, but was also implemented in fur-
ther work for the simultaneous detection of the organic
and inorganic constituents of GSR.
5 The Next Step in Gunshot Residue Analysis:
Chemometric Data Treatment
The use of chemometric treatment for data analysis of
GSR has become popular in the last 5 years [42–46]. This
allows an objective approach to classification of GSR
levels or components in a variety of scenarios, obviating
the need of subjective judgment of a highly trained opera-
tor. This characterization can also increase the automa-
tion and field-deployable nature of a GSR detection
Electroanalysis 2013, 25, No. &, 1 – 18
Electrochemical Detection of Gunshot Residue for Forensic Analysis
Fig. 12. Binary plots of the most significant elements pairs for
differentiation of ammunition branches. (a) Ca and Pb; (b) Zn
and Pb. (Adapted from [44], Copyright 2012, with permission
from Elsevier.)
system to analyze and classify residue within minutes of
sampling.
Chemometric treatment of GSR analysis has been uti-
lized in connection with a variety of techniques, such as
SEM/EDX [42], Raman spectroscopy [43] and AAS/ICP-
OES [44]. In each case, the application of chemometric
analysis, including regularized discriminant analysis
(RDA) and partial least squares (PLS) resulted in more
evident differentiation between two controls than could
be achieved with a subjective operator, decreasing the
risk of misclassification significantly. YÇez et al. ana-
lyzed inorganic elements in gunshot residue using AAS
and ICP-OES in order to differentiate the two most used
ammunition brands in Chile (FAMAE – Fabrica y Maes-
tranza del Ejercito and CBC – Companhia Brasileira de
Cartuchos respectively), employing simple analytical
methods, conventional statistical, and more advanced che-
Electroanalysis 2013, 25, No. &, 1 – 18  2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
mometric techniques such as RDA [44]. Figure 12 dis-
plays a binary graph in which each one of the gunshot
residue samples is represented in function of the Pb and
Ca concentrations (Figure 12 a) and the Pb and Zn con-
centrations (Figure 12 b). In the samples, the brands can
be differentiated by colors and a bidimensional classifica-
tion is observed in both cases. In general, the elements
Pb, Ca and Zn are found to have higher concentrations in
the CBC brand.
Chemometric treatment of cyclic voltammograms for
evaluation of different explosive species commonly found
in GSR has also been reported [47]. This was done em-
ploying electronic tongue principles that allow resolution
of signal overlapping and extraction of the characteristic
fingerprints, although this has not yet been implemented
for real GSR samples. Such advanced analysis and infor-
mation content could provide higher information content
as to the identification of different GSR components, and
may enhance the identification process in forensic analy-
sis.
There are only two examples so far of the combination
of voltammetry and chemometric treatment for the analy-
sis of GSR. Paix¼o at S¼o Paulo examined the cyclic vol-
tammetry of GSR samples at a gold microelectrode taken
from the hands of a shooter to discriminate between dif-
ferent firearms and different ammunitions [45]. Within
the potential window was the inclusion of organic and in-
organic components of GSR to provide a more sensitive
detection method. They successfully implemented this
analysis to distinguish GSR from handguns and long-bar-
relled guns with several kinds of ammunition. Using the
cyclic voltammetric data and a non-supervised pattern
recognition method, the analysis was carried out in two
independent groups: the residues from the handguns and
the residues from the long-barrelled guns. The principal
component analysis (PCA) score plot for the handguns is
shown in Figure 13, which summarizes up to 73.78 % of
the variance in the original voltammetric data with only
the first two PCs; clear separation is observed for the
four types of ammunition, obtaining a distinct group for
each class. This is the first example of the integration of
voltammetry and nonsupervised pattern-recognition
methods for forensic GSR identification purposes.
More recently, the Wang group in San Diego demon-
strated a powerful chemometric-electroanalytical system
for the detection and discrimination of varying levels of
exposure to gunshot residue from subjects in various con-
trol scenarios [46]. Multiple samples were taken from
subjects in controlled tests such as secondary contact with
GSR, loading a firearm and post-discharge of a firearm.
These controls were examined at bare carbon screen-
printed electrodes using the swipe method [19] with in-
tegrated sampling and electroanalysis. Consistent canoni-
cal variate analysis (CVA) discrimination - with well-es-
tablished minimally-dispersed clusters – was illustrated
for several different control signals taken before and after
the discharge of the firearm for each subject examined by
Cto et al., illustrated in Figure 14. Such distinction holds
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Review A. M. OMahony, J. Wang

6 Future Prospects for Electroanalytical Detection

of Gunshot Residue

Electrochemical devices offer attractive opportunities for

Fig. 13. PCA score plots of current signals obtained with a gold
microelectrode in a solution containing the gunshot residues ex-
tracted from a 0.380 pistol with full jacketed (A) and normal am-
munition (B), and from a 0.38 revolver with normal (C) and sem-
ijacketed ammunition (D). (Adapted from [45], Copyright 2012,
with permission from Elsevier.)
considerable importance demonstrating involvement, or
mere presence in the vicinity of a firearm-related crime,
to minimize the occurrence of a false positive identifica-
tion of a suspect. This is the first example of the effective
discrimination of different control experiments in the de-
termination of levels of contact with GSR using the com-
bination of electrochemical signals with advanced chemo-
metric data treatment. This method serves to examine
and maximize variations in the signals generated by mul-
tiple organic and inorganic GSR constituents. This system
has the potential to be incorporated into a hand-held
device to provide a simple response outlining a subjects
complicity in a crime involving the discharge of a firearm
to provide a portable, field-deployable system which can
be conducted by minimally-trained operators.
addressing GSR detection needs. We are no longer bound
by the traditional use of bulky electrodes and cumber-
some operation, but rather rely on faster, smaller and
better easy-to-use sensor strips, hand-held analyzers or
micromachined systems. The examples described in this
review illustrate the power and versatility of modern elec-
trochemical devices for detecting GSR towards the inves-
tigation of firearm-related crimes. Table 7 summarizes the
experimental aspects of the studies reviewed in this arti-
cle. These advances would allow field testing for GSR to
be performed more rapidly, sensitively, inexpensively, and
reliably and should therefore greatly facilitate the realiza-
tion of in-situ detection protocols. This article has re-
viewed recent improvements in electrochemical detection
systems with chemometric analysis for the fully objective
discrimination of GSR from different firearms and am-
munitions, as well as different levels of GSR from sub-
jects in a variety of scenarios. The specificity, rapidity and
portability of electroanalytical/chemometric systems at
low-cost, disposable screen-printed electrodes indicate
considerable promise for a field-deployable, hand-held
device for the forensic investigation of firearm-related
crimes and address the key challenge of decreasing the
occurrence of false positive identifications for discharge
of a firearm. Furthermore, the implementation of the
Electronic Tongue approach involving coupling of the re-
sponses obtained from an array of sensors with marked
mix-response and applying the same chemometric data
treatment can result in the extraction of more informa-
tion of the sample. While electroanalytical devices for for-
ensics are still in their infancy, they are expected to rise
rapidly in popularity due to the rapidly changing interface
of technology such as microfabrication of tools (smart-
phones), new flexible electrode materials and improved
communication of field results. These developments bring
significant changes to the detection of GSR and make

Fig. 14. (A) Example of the different cyclic square-wave stripping voltammetric signals obtained with “swiping” samples at a bare
SPCE electrode. Score plot of the functions obtained after CVA analysis of the GSR samples according to (B) exposure level or (C)
3-class response mode. Samples in (B) correspond to: N – no contact, S – Secondary exposure, P – presence at discharge, L – load, F
– fire and W – wash. Samples in (C) correspond to Free (N), Witness (S & P) and Involved (L, F & W). See Section 2.3 for the elec-
trochemical conditions. (Adapted from [46], Copyright 2012, with permission from the American Chemical Society.)

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Electrochemical Detection of Gunshot Residue for Forensic Analysis

Table 7. Summary of experimental conditions and target GSR analytes of literature reviewed.
Name Working electrode Technique Sampling Analyte(s) Time
Konanur et al. [16] Hg-film graphite ASV Acid wash Pb, Sb > 10 min
Briner et al. [10] Hg-film GCE ASV Swab Sb > 10 min
Woolever et al. [11, 23] Hg-film GCE ASV Swab Ba, Pb, Sb 6 min
Liu et al. [26] HDME ASV Acid wash Sb, Pb, Cu, Zn > 10 min
Briahye et al. [27] HDME ASV Swab Pb, Sb 8 min
deDonato et al. [9] HDME BIA Acid/Swab/Tape Pb 3 min
Erden et al. [28] HDME AdSV Tape Sb, Pb 6 min
Rodriguez et al. [29] Bi-film CPE ASV Swab Pb 2 min
Salles et al. [30] Au melectrode ASV Swab Pb 10 min
OMahony et al. [19] Au-modified SPCE ASV Swipe Pb, Cu 2 min
Salles et al. [45] Au melectrode CV/PCA Swab Org/Inorg 1 min
Cet et al. [46] Bare SPCE ASV/LDA Swipe Org/Inorg 2 min

electroanalysis a powerful tool for decentralized forensic [18] K. E. Toghill, M. Lu, R. G. Compton, Int. J. Electrochem.
analysis. Sci. 2011, 6, 3057.
[19] A. M. O Mahony, J. R. Windmiller, I. A. Samek, A. J. Ban-
dodkar, J. Wang, Electrochem. Commun. 2012, 23, 52.
[20] J. Heyrovsky, Polarographishes Praktikum, Berlin, Springer
Acknowledgements
1948; translated under the title Tekhnika, polyarografiche-
skogo issledovaniya, Inostrannaya Literatura, Moscow 1951.
This work is supported by the Department of Defense [21] S. V. Kovaleva, V. P. Gladyshev, N. V. Chikineva, J. Anal.
Biometrics and Forensics Office under Contract No. Chem. 2001, 56, 449.
HQ0034-11-C-0034. Any opinions, findings and conclu- [22] K. M. McIntire, H. D. Dewald, Microchem. J. 2001, 69, 21.
sions or recommendations expressed in this material are [23] C. A. Woolever, H. D. Dewald, Forensic Sci. Int. 2001, 117,
those of the author(s) and do not necessarily reflect the 185.
[24] J. Wang, Stripping Analysis, VCH, Deerfield Beach 1985.
views of the Washington Headquarters Services-Acquisi-
[25] J. H. Liu, W-F. Lin, L. Taylor, Forensic Sci. Int. 1980, 16, 43.
tion Directorate [Assistant Secretary of Defense for Re- [26] J. H. Liu, W.-F. Lin, J. D. Nicol, Forensic Sci. Int. 1980, 16,
search and Engineering (Defense Biometrics and Forensics 53.
Office)]. [27] C. Brihaye, R. Machiroux, G. Gillian, Forensic Sci. Int.
1982, 20, 269.
[28] S. Erden, Z. Durmus, E. KiliÅ, Electroanalysis 2011, 23,
References 1967.
[29] J. A. Rodriguez, I. S. Ibarra, C. A. Galan-Vidal, M. Vega, E.
[1] J. I. Thornton, Anal. Chim. Acta 1994, 288, 71. Barrado, Electroanalysis 2009, 21, 452.
[2] H-H. Meng, B. Caddy, J. Forensic Sci. 1997, 42, 553. [30] M. O. Salles, J. Naozuka, M. Bertotti, Microchem. J. 2012,
[3] F. S. Romolo, P. Margot, Forensic Sci. Int. 2001, 119, 195. 101, 49.
[4] A. Zeichner, Anal. Bioanal. Chem. 2003, 376, 1178. [31] J. Wang, B. Tian, Anal. Chem. 1992, 64, 1706.
[5] O. Dalby, D. Butler, J. W. Birkett, J. Forensic Sci. 2010, 55, [32] M. Galik, A. M. OMahony, J. Wang, Electroanalysis 2011,
924. 23, 1193.
[6] K. H. Chang, P. T. Jayaprakash, C. H. Yew, A. F. L. Abdul- [33] C. K. Chua, M. Pumera, Electroanalysis 2011, 23, 2350.
lah, Aust. J. Forensic Sci. 2012, 1. [34] K. Malzahn, J. R. Windmiller, G. Valdes-Ramirez, M. J.
[7] G. M. Wolten, R. S. Nesbitt, A. R. Calloway, G. L. Loper, J. Schçning, J. Wang, Analyst 2011, 136, 2912.
Forensic Sci. 1979, 24, 423. [35] K. Bratin, P. T. Kissinger, R. C. Briner, C. S. Bruntlett, Anal.
[8] M. Vuki, K-K. Shiu, M. Galik, A. M. O Mahony, J. Wang, Chim. Acta 1981, 130, 295.
Analyst 2012, 137, 3265. [36] J. Wang, F. Lu, D. MacDonald, J. Lu, M. E. S. Ozsoz, K. R.
[9] A. De Donato, I. G. R. Gutz, Electroanalysis 2005, 17, 105. Rogers, Talanta 1998, 46, 1405.
[10] R. C. Briner, S. Chouchoiy, R. W. Webster, R. E. Popham, [37] J. Wang, S. Thongngamdee, Anal. Chim. Acta 2003, 485,
Anal. Chim. Acta 1985, 172, 31. 139.
[11] C. A. Woolever, D. E. Starkey, H. D. Dewald, Forensic Sci. [38] X. Fu, R. F. Benson, J. Wang, D. Fries, Sens. Actuators B
Int. 1999, 102, 45. 2005, 106, 296.
[12] J. Wang, B. Tian, J. Wang, J. Lu, C. Olsen, C. Yarnitzky, K. [39] K. Cizek, C. Prior, C. Thammakhet, M. Galik, K. Linker, R.
Olsen, D. Hammerstrom, W. Bennett, Anal. Chim. Acta Tsui, A. Cagan, J. Wake, J. La Belle, J. Wang, Anal. Chim.
1999, 385, 429. Acta 2010, 661, 117.
[13] J. Wang, TrAC 2002, 21, 226. [40] A. Bergens, K. Lundstrçm, J. Asplund, Talanta 1985, 32,
[14] J. Wang, in Analytical Electrochemistry, 3rd ed. (Ed: J. 893.
Wang), Wiley-VCH, Hoboken, NJ 2006, pp. 86 – 89. [41] D. B. Dahl, P. F. Lott, Microchim. J. 1987, 35, 347.
[15] J. Wang, Electroanalysis 2007, 19, 415. [42] B. Knauthe, S. Steffen, M. Barth, L. Niewoehner, M. Otto,
[16] N. K. Konanur, G. W. vanLoon, Talanta 1977, 24, 184. J. Chemometrics 2008, 22, 252.
[17] M. Lu, K. E. Toghill, M. A. Phillips, R. G. Compton, Int. J. [43] J. Bueno, V. Sikirzhytski, I. K. Lednev, Anal. Chem. 2012,
Environ. Anal. Chem. 2013, 93, 213. 84, 4334.

Electroanalysis 2013, 25, No. &, 1 – 18  2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim www.electroanalysis.wiley-vch.de &17&
These are not the final page numbers! ÞÞ
Review A. M. OMahony, J. Wang

[44] J. YÇez, M. P. Far as, V. ZfflÇiga, C. Soto, D. Contreras, E.
Periera, J. D. Mansilla, R. Saavedra, R. Castillo, P. Sez, Mi-
crochem. J. 2012, 101, 43.
[45] M. A. Salles, M. Bertotti, T. R. L. C. Paix¼o, Sens. Actuators
B 2012, 166, 848.
[46] X. Cet, A. M. OMahony, I. A. Samek, J. R. Windmiller, J.
Wang, Anal. Chem. 2012, 84, 10306 – 10314.
[47] X. Cet, A. M. OMahony, J. Wang, M. del Valle, Talanta
2013, 107, 270.

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