Analytica Chimica Acta 1130 (2020) 126e136

Contents lists available at ScienceDirect

Analytica Chimica Acta

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

Simultaneous determination of lead and antimony in gunshot residue

using a 3D-printed platform working as sampler and sensor
Sílvia V.F. Castro a, Ana P. Lima a, Raquel G. Rocha a, Rafael M. Cardoso a,
Rodrigo H.O. Montes b, Ma
rio H.P. Santana c, Eduardo M. Richter a, Rodrigo A.A. Munoz a, *
a ^ndia, Institute of Chemistry, 38400-902, Uberla
Federal University of Uberla ^ndia, MG, Brazil
b
Superintend^encia da Polícia T

ecnico-Científica, 05507-060, Butanta~ , Sa
~o Paulo, Brazil
c
Unidade T
ecnico-Científica, Superintend^ ^ndia, Minas Gerais, Brazil
encia Regional Do Departamento de Polícia Federal Em MG, 38408-680, Uberla

h i g h l i g h t s g r a p h i c a l a b s t r a c t

3D-printed graphene/PLA for the

simultaneous determination of lead
and antimony.

The same 3D-printed platform as a
sampler and a voltammetric sensor of
gunshot residues.

No need of surface modification with
mercury/bismuth for highly sensitive
detection.

Gunshot residues were analyzed by
swabbing the 3D-printed electrode
for further detection.

Free from interference of Cd, Cu, Fe,
Hg and Zn and higher inter-electrode
precision (7%).

a r t i c l e i n f o a b s t r a c t

Article history: 3D-printing is an emerging technique that enables the fast prototyping of multiple-use devices. Herein
Received 12 May 2020 we report the fabrication of a 3D-printed graphene/polylactic acid (G-PLA) conductive electrode that
Received in revised form works as a sampler and a voltammetric sensor of metals in gunshot residue (GSR) using a commercially-
11 July 2020
available G/-PLA filament. The 3D-printed surface was used as swab to collect GSR and next submitted to
Accepted 14 July 2020
a square-wave voltammetric scan for the simultaneous detection of Pb2þ and Sb3þ. The proposed sensor
Available online 25 July 2020
presented excellent analytical performance, with limit of detection values of 0.5 and 1.8 mg L1 to Pb2þ
and Sb3þ, respectively, and linear ranges between 50 and 1500 mg L1. Sampling was performed through
Keywords:
3D printing
the direct contact of G-PLA electrode in hands and clothes of shooters, followed by immersion in the
Graphene electrochemical cell in the presence of supporting electrolyte for the SWASV scan. The proposed method
Gunshot residue showed a great performance in the recovery, identification and semi-quantification of Pb2þ and Sb3þ in
Stripping voltammetry the evaluated samples without the need for sample preparation. Moreover, the device can be reused as
Forensic sampler and sensor (until three times without loss of electrochemical performance) and the fabrication is
Printed sensor reproducible (RSD ¼ 7%, for three different devices). Hence, this 3D-printed material is an excellent
candidate for the analysis of GSR, an indispensable analysis in the forensic field.
© 2020 Elsevier B.V. All rights reserved.

* Corresponding author.
E-mail address: munoz@ufu.br (R.A.A. Munoz).

https://doi.org/10.1016/j.aca.2020.07.033
0003-2670/© 2020 Elsevier B.V. All rights reserved.
 S.V.F. Castro et al. / Analytica Chimica Acta 1130 (2020) 126e136
1. Introduction
According to data presented by The Global Burden of Disease
2016 Injury Collaborators, the use of firearms has been one of the
major contributors to the number of deaths in the world [1]. In
countries like Brazil, for example, the large number of deaths
involving violence is attributed to several factors, such as the use of
alcohol and illicit drugs and the ease to find a firearm, becoming
one of the main public security problems [2]. For better under-
standing, data presented by Dare and collaborators showed that
about 855,000 people died from gunshot fire in the period between
1990 and 2015 in Brazil [3]. In the last decades, stricter policies
were adopted, such as the firearm control legislation since 2003
[1]; however, the results are still far from expected. In this scenario,
one possibility to try to combat these problems is in the strength-
ening of police strategies for the identification and capture of sus-
pects who have practiced such acts, being of fundamental
importance the availability of quick and accessible methods to
assist in the elucidation of criminal events.
In this context, analytical methods are great allies in the
investigative process, because they enable the analysis of residues
commonly generated in gunshot (GSR), either organics (OGSR) or
inorganics (IGSR). GSR easily adhere to surfaces close to shot, for
example, hands, clothes, hair [4,5] and nasal mucous [6,7] of the
shooter. Among the OGSR, the most common are some propellants,
such as diphenylamine, ethyl centralite and resorcinol, among
many others [8], whereas lead, barium and antimony are among the
most commonly IGSR generated, although residues of other metals,
such as copper, zinc and mercury, can also be found depending on
the type of ammunition used [9].
The IGSR analysis has been carried out using several analytical
techniques, such as high resolution inductively coupled plasma
mass spectrometry (HRICP-MS) [10e12], laser-induced breakdown
spectroscopy (LIBS) [13], electrothermal atomic absorption spec-
trometry (ETAAS) [14], scanning electron microscopy combined
with energy dispersive X-rays (SEM/EDX) [15], inductively coupled
plasma-optical emission spectroscopy (ICP OES) [16,17], graphite
furnace atomic absorption spectrometry (GFAAS) [7,18], capillary
electrophoresis (CE) [19], single particle inductively coupled
plasma mass spectrometry (spICP-MS) [20] and total reflection X-
ray fluorescence (TXRF) [21].
Although different methodologies are used due to the wide
variety of residues that can be found in the samples, the methods
described in the above-mentioned papers present similar forms of
sampling. In all of them, the residue is collected in cotton swabs or
GSR stubs, that is, the residue adheres to the device when moist-
ened and rubbed on the contaminated surface [6,9]. After the
collection, the extraction of residues from the collector is usually
carried out in the presence of organic solvents [15,22e24] or nitric
acid [17,25e28]. Some studies have reported that GSR stubs
perform better than cotton swabs [15,23,24,29], due to the amount
of residues recovered from the skin of shooters and the stability of
the residue on its surface in a storage period. However, the need to
extract residues from the collector can introduce additional errors
and increase in cost and time required to carry out the analysis.
For analysis of residues at crime scenes, electrochemical
methods have some advantages, such as the possibility of using
portable instrumentation for in-situ analysis [8,9]. For metallic
residues, stripping methods have been widely used in recent years,
associated with several types of working electrodes, for example a
mercury-film (MFE) modified glassy-carbon electrode [30e32],
tubular bismuth film electrode [33], hanging mercury drop work-
ing electrode (HMDE) [25], gold microelectrode [26,27], screen-
printed electrode on a fingertip [34], and several other screen-
printed electrodes (SPE), such as carbon SPE modified with Au
127
[35] and carbon SPE on a tape [36], bare carbon SPE and modified
with gold [37,38] and glassy-carbon electrode modified with a
composite of palladium particles and glassy-carbon microspheres
[39].
The “swipe and scan” protocol for sampling and detection of
GSR has been first reported by Wang’s group [35]. This method has
as its main characteristic the direct transfer of the analyte to the
electrode surface by direct contact, followed by the voltammetric
scan. In this report the authors proposed a screen-printed carbon
electrode modified with gold by electrodeposition, which is not so
robust as the abrasive sampling may remove the gold film from the
electrode; moreover, it was verified strong interference from cop-
per on the antimony signal [33]. Based on the “swipe and scan”
method and considering the successful association of electro-
chemistry with 3D-printed devices, for instance in the manufacture
of cells or electrodes with low cost and versatility using different
materials, shapes and designs with rapid prototyping [40], our
research group demonstrated the use of a 3D-printed electrode
using graphene-doped polylactic acid (G-PLA) for the sensing of
TNT in explosive samples [41]. Fused deposition modelling 3D
printing is the most inexpensive technique and has a special
advantage in the manufacture of an electrode as well as a sampler:
it generates porous 3D-printed surfaces [42]. Previous works have
reported the use of 3D-printed electrodes for metal determination,
such as copper [43], lead and cadmium [44e46], manganese [47]
and zinc [48]. A recent review has critically discussed 3D-printed
materials for electrochemical sensing applications, including
application for metal determination [49].
In this context, we introduce the use of a 3D-printed conductive
platform to work as a dual device, a sampler and a voltammetric
sensor, for the analysis of GSR at the forensic scenario. The fabri-
cation of this platform was enabled by commercially-available G-
PLA filaments and a desktop fused deposition modelling (FDM) 3D-
printer. The main objective of this work is the development of a
simple, fast, low-cost and portable analytical procedure for the
recovery, identification and estimation of Pb2þ and Sb3þ in GSR
samples. To our knowledge, the use of such 3D-printed G-PLA
electrodes has not been reported before for Sb3þ determination,
hence the simultaneous determination of both metals was first
investigated to reach the main objective of this work.
2. Experimental
2.1. Reagents and samples
Hydrochloric acid (37% w/v) was obtained from Synth (Diadema,
Brazil). Acetic acid (99.7% w/v) and nitric acid (65% w/v) were ob-
tained from Vetec (Rio de Janeiro, Brazil) and sodium hydroxide
(98% w/w) and dimethylformamide (98% w/w, DMF) were pur-
chased from Sigma-Aldrich (Steinheim, Germany). Aqueous stan-
dard solutions of antimony, lead, cooper, zinc, mercury, cadmium
and iron (1000 mg L1) were obtained from Quimlab (Jacareí,
Brazil).
The preparation of all supporting electrolytes and metal solu-
tions were performed with highly purity deionized water
(R  18 MΏ cm), obtained from a Milli-Q purification system
(Millipore Direct-Q3, Bedford, MA, USA).
2.2. Instrumentation and electrochemical measurements
Cyclic voltammetry and square-wave anodic stripping voltam-
metry (SWASV) measurements was performed in potentiostats/
galvanostats m-AUTOLAB type III (Metrohm Autolab B. V., Utrecht,
Netherlands), controlled by software NOVA 1.11. The conductive
filament made of PLA containing graphene was obtained from Black
128 S.V.F. Castro et al. / Analytica Chimica Acta 1130 (2020) 126e136
Magic 3D with volume resistivity of 0.6 U cm (New York, USA). The
fabricant does not present information on the amount of graphene
within PLA. All measurements were performed at room tempera-
ture and in the presence of dissolved oxygen.
2.3. Electrochemical cell and electrodes
The working electrode was built following the methodology
developed by our research group using commercially-available
conductive graphene-PLA filament from Black Magic® [42]. The
3D printer (FDM RepRap custom build Prusa clone) was equipped
with a hotend E3d v6 attached to a direct drive extruder and a
0.6 mm nozzle (wider walls to prevent leaking). Slicing parameters
were defined using Simplify 3D®: layer height of 0.1 mm, extrusion
width of 0.72 mm, nozzle temperature at 205  C with cooling
turned on before the first layer, and bed temperature at 65  C. The
sensor consisted in a hollow rectangular box (40  40  20 mm,
length x width x height) as shown in Scheme 1, printed with vase
mode on, with one perimeter, zero infill, zero top and bottom layer.
The side walls of the box served as the dual device (sampler/sensor)
after cutting each wall using a scissors (also shown in Scheme 1).
The 3D printing was thus vertically oriented. Each box resulted in
four devices (sampler/sensor). The printing speed was set at
20 mm/s.
Before use, each electrode was mechanically polishing for 30 s
followed by immersion in DMF for 10 min, which favours the
exposure of graphene and generation of more stable and repro-
ductive electrochemical responses [41,50]. Then the electrode was
assembled in a 3D-printed cell (shown in Scheme 2). Next, the
electrode was subjected to 10 cycles of cyclic voltammetry in a
potential range between 0.8 and þ 0.4 V until reaching the signal
stabilization. As a reference and auxiliary electrodes were used a
Ag|AgCl|KCl(sat.) [51] and a platinum wire, respectively. For SWASV
scans (for standard solutions), the initial parameters were selected:
amplitude of 90 mV; frequency of 30 Hz; step potential of 9 mV;
and conditioning potential of þ0.5 V, for 30 s. The other conditions,
such as deposition potential and time, and stirring rate, were
optimized, as well as the supporting electrolyte, and the selection
of these parameters is discussed below. The optimized conditions
for the SWASV determination of both metals were selected for the
GSR analysis. All experiments were performed in triplicate and the
Scheme 1. (A) A hollow rectangular box obtained by vertically-oriented 3D-printing;
(B) one side of the box used as the sampler/sensor device; (C) abrasive paper (1200
grit) used for mechanical polishing and (D) scissor used to cut the rectangular box.
results were expressed as average with corresponding standard
deviations.
2.4. Shooting tests and sampling and analysis of GSR
In the shooting tests, three pistols were used: Imbel, model
MD6, 0.40 caliber; Glock, model G19, 9 mm caliber; and Glock,
model G17, 9 mm caliber. The CBC Taurus brand ammunition was
used. For sampling, the sensor was swabbed on the hand (the
thumb and forefinger palm and thumb and forefinger back regions)
and on clothes of shooters. The samples collected in the hands were
made after 2 shots (identified as 2S); 3 shots (3S); 5 shots (5S); 8
shots (8S) and 10 shots (10S). The sample collected in the clothes
were made after 3 shots on shirt (3S e shirt) and on pants (3S e
pants) of the shooters. The GSR in all samples were collected
immediately after firing using the 3D-printed electrodes and after
each sampling, the electrodes were labelled and kept in separate
compartments of a box, which was sealed and stored in the labo-
ratory for further analysis. The blank (control experiments) was
carried out by contact of the electrode on the hands and clothes of
shooters prior to the shots. The data were collected according to the
number of shots, since the main objective was the identification of
metals in GSR, regardless of the ammunition or firearm used in the
shooting.
After swabbing, the sensors containing the microparticles of
GSR were connected to a 3D-printed electrochemical cell fabricated
using ABS designed as described in the literature [40]. The working
electrode containing GSR was assembled at the bottom of the cell
while counter and reference electrodes were placed through the
cover of the cell. The volume of 5 mL of supporting electrolyte was
added to the cell and SWASV scans were obtained.
3. Results and discussion
3.1. Optimization of experimental conditions for the determination
of Pb2þ and Sb3þ
3.1.1. Supporting electrolyte
A previous work has shown the promising SWASV determina-
tion of Pb2þ using 3D-printed G-PLA electrode using a HCl solution
as the supporting electrolyte [41]; however, the results were pre-
liminary, the optimization of the SWASV parameters was not per-
formed and the analytical characteristics were not obtained. On the
other hand, this is the first report showing the feasibility of this
graphene-based 3D-printed material for Sb3þ determination. Both
metals are of great interest in GSR analysis [9]. Hence, the simul-
taneous determination of both metals by SWASV was investigated.
The preliminary studies for the selection of the best supporting
electrolyte were carried out in the presence of 400 mg L1 of both
Pb2þ and Sb3þ and HCl solutions in three different concentrations:
0.5, 0.1 and 0.01 mol L1. Fig. 1A shows the peaks related to the
oxidation of Pb2þ (at around e 0.5 V) and Sb3þ (at around 0.0 V) in
the three different concentrations of HCl.
It is possible to observe that the electrochemical oxidation of
Pb2þ (at around 0.5 V) and Sb3þ (at around 0.0 V) is favoured by
the presence of higher concentration (0.5 mol L1) of HCl, especially
for Sb3þ. However, a significant fluctuation in the baseline between
the oxidation peaks of the two analytes was observed in 0.5 and
0.1 mol L1 HCl as well as the evolution of hydrogen became
evident in more acidic media. Although no clear explanation was
found for the baseline fluctuation, both hydrogen evolution and
background current variation may impair the determination of
Sb3þ at low concentrations. In this way, 0.01 mol L1 HCl was
chosen as the supporting electrolyte solution in all further mea-
surements. Nitric acid (0.01, 0.1 and 0.5 mol L1) and acetate buffer
 S.V.F. Castro et al. / Analytica Chimica Acta 1130 (2020) 126e136 129

Scheme 2. 3D printed cell and electrodes. (A) All components of the electrochemical cell in detail (CE: counter electrode; RE: reference electrode; WE: working electrode); (B)
assembled cell ready-to-use and (C) transversal cut of the cell to show internally the cell (supporting electrolyte in contact with the electrodes is represented).

Fig. 1. Effects of (A) HCl concentration as the supporting electrolyte: 0.5 (blue line), 0.1 (black line) and 0.01 mol L1 (red line); (B) deposition potential; (C) deposition time; and (D)
stirring rate in the voltammetric responses of Pb2þ (black square) and Sb3þ (red circle). Experimental conditions: 90 mV (amplitude); 30 Hz (frequency); 9 mV (step
potential); þ0.5 V (conditioning potential) for 30 s, and, for (A) 0.9 V (deposition potential), 90 s (deposition time) and 1000 rpm (stirring rate), for (B) 90 s (deposition time) and
1000 rpm (stirring rate), for (C) e 1.0 V (deposition potential) and 1000 rpm (stirring rate), for (D) e 1.0 V (deposition potential) and 180 s (deposition time). (B), (C) and (D)
measurements were carried out in 0.01 mol L1 HCl solution (n ¼ 3). [Pb2þ] ¼ [Sb3þ] ¼ 400 mg L1. (For interpretation of the references to colour in this figure legend, the reader is
referred to the Web version of this article.)

(0.1 mol L1) solutions (pH 4.5) were also evaluated. However, the
results (not shown here) demonstrated lower sensitivity for mea-
surements in nitric acid medium. In acetate buffer solution, it was
observed that the oxidation signal of Sb3þ is completely overlapped
by the fluctuation presented in the background signal. These results
showed that the HCl solution (0.01 mol L1) performed better as
the supporting electrolyte.
3.1.2. Parameters of the SWASV technique
All parameters of the electrochemical technique were optimized
using a concentration of 400 mg L1 of both analytes. Fig. 1B shows
the influence of the potential for the deposition of the species
(interval: 0.7 to 1.1 V) and the results exhibited that more
negative potentials favour the determination of Sb3þ (red circle),
but for Pb2þ (black square), the influence was lower and the analyte
response presents an almost constant behaviour in the range of
potentials studied. Thus, the e 1.0 V potential was chosen, due to
better relationship between signal and measurement accuracy in-
tensity (higher standard deviation was found for Sb3þ when
applying 1.1 V probably due to hydrogen evolution) and consid-
ering the higher response of Pb2þ than that obtained at 1.1 V.
The deposition time was also evaluated (interval: 90e300 s) and
the results (Fig. 1C) evidenced a linear behaviour of the oxidation
signal of both analytes with increasing time. Thus, we opted for the
130 S.V.F. Castro et al. / Analytica Chimica Acta 1130 (2020) 126e136

180 s to obtain analytical data with a good relationship between Table 1

measurement time and sensitivity. Compaarison of limit of detection (LOD) values obtained for Pb2þ and Sb3þ using the
proposed SWASV-based method with other analytical methods reported in the
The last evaluated parameter was the stirring rate of the solu- literature (techniques are listed to simplify information in the table).
tion (interval: 250e2500 rpm), which directly influences the mass
transport from the solution to the surface of the G-PLA electrode. In Analytical Techniques Analyte LOD (mg L1) Ref.

this study (Fig. 1D), it was observed that the stirring rate of the HRICP-MS Antimony 0.045 [10]
solution has a greater influence on the determination of Pb2þ, with Barium 0.507
Lead 0.117
an almost linear signal increase in relation to the increasing rate. On
HRICP-MS Antimony 45 [11]
the other hand, the intensity of the oxidation signal of Sb3þ Barium 507
remained almost constant between the range of 500e2000 rpm. A ETAAS Antimony 0.4 [14]
possible explanation is the saturation of Sb on the electrode surface GFAAS Antimony 3.30 [18]
Barium 11.94
as a result of a film formation (as reported in the literature [52])
Lead 56.22
while this condition favors the deposition of Pb and consequently ICP OES Antimony 4.79 [16]
increases its analytical response. Therefore, the rate of 1750 rpm Barium 0.15
was chosen due the intense oxidation signal for both analytes and Lead 4.97
proper precision between measurements. DPASV Lead 200 [33]
DPCAdsSV Antimony 0.16 [25]
Lead 0.6
3.2. Analytical properties of the method SWCAdsSV Antimony 0.09 [25]
Lead 0.12
By successive additions of increasing concentrations of Pb2þ and SWASV Lead 0.37 [26]
SWASV Antimony 1.8 This work
Sb3þ in the electrochemical cell, an analytical curve was con-
Lead 0.5
structed. The voltammograms obtained are displayed in Fig. 2A,
a
DPASV: differential-pulse anodic stripping voltammetry; DPCAdsSV:
while the calibrations curves are displayed in Fig. 2B.
differential-pulse cathodic adsorptive stripping voltammetry; SWCAdsSV: square-
The results showed a satisfactory performance for the proposed wave cathodic adsorptive stripping voltammetry.
sensor. Wide linear ranges (R > 0.99) were obtained between 50
and 1500 mg L1, with slope values of 0.07 and 0.02 mA/mg L1 for
Pb2þ and Sb3þ, respectively. The limit of detection (LOD) for each
analyte was calculated (3  standard deviation of baseline noise  precision of the sensor in the determination of the analytes, with
slope-1) and the values were 0.5 for Pb2þ and 1.8 mg L1 for Sb3þ RSD values of 3% for Pb2þ and 2% for Sb3þ. In addition, the results
according to IUPAC guideline, which demonstrate a similar also demonstrated that the presence of Sb3þ in high concentrations
detectability compared to other methods reported in the literature contributes to improve the intensity and precision of the Pb2þ
that used the same approach for LOD obtaining, as presented in signal, which may be related to the formation of a Sb film on the
Table 1. However, more realistic LOD values were determined surface of G-PLA during the application of the deposition potential,
experimentally by measuring lower concentrations of both ele- increasing the analytical response for the Pb2þ determination
ments until reaching the lowest measurable concentrations. These [52,53]. In the third condition (Fig. 3C and C’), the concentration of
experimentally determined LOD values were 10 for Pb2þ and Sb3þ was kept at 150 mg L1 while the concentration of Pb2þ was
40 mg L1 for Sb3þ, which are comparable with the values obtained increased to 800 mg L1. Again, proper precision was achieved with
by GFAAS. RSD values of 12% for Sb3þ and 7% for Pb2þ. These results obtained
Next, the repeatability of the sensor for the determination of in different concentrations of the analytes demonstrate that the
both metals was evaluated under three different conditions. In the sensor can be used reliably for samples that present different
first, successive SWASV scans (n ¼ 10) were performed in the proportions of Pb2þ and Sb3þ.
presence of 150 mg L1 of both analytes. The results in Fig. 3A and A0 The effect of one analyte on the current response of the other
demonstrate good precision for both analytes, with relative stan- was evaluated by determining Pb2þ and Sb3þ under different con-
dard deviation (RSD) values of 7% for Pb2þ and 10% for Sb3þ. In the ditions. First, the Sb3þ concentration was fixed at 200 mg L1 and
second condition (Fig. 3B and B0 ), the concentration of Pb2þ was increasing concentrations of Pb2þ (from 200 to 1000 mg L1) were
maintained at 150 mg L1 while the concentration of Sb3þ was added to the electrochemical cell and the results are shown in
increased to 800 mg L1. The results also demonstrated an excellent

Fig. 2. (A) SWASV responses for the study of linear range (from 50 to 1500 mg L1 for both analytes) and, (B) respective calibrations curves (Pb2þ: black squares; Sb3þ: red circle, for
n ¼ 3). Experimental conditions: 0.01 mol L1 HCl solution (supporting electrolyte); 90 mV (amplitude); 30 Hz (frequency); 9 mV (step potential); - 1.0 V (deposition potential);
180 s (deposition time) and 1750 rpm (stirring rate). (For interpretation of the references to colour in this figure legend, the reader is referred to the Web version of this article.)
 S.V.F. Castro et al. / Analytica Chimica Acta 1130 (2020) 126e136 131

Fig. 3. SWASV responses for the study of the electrode precision for measurements (n ¼ 10) of the electrochemical oxidation of (A) 150 mg L1 of Pb2þ and Sb3þ, (B) 150 mg L1 of
Pb2þ and 800 mg L1 of Sb3þ and (C) 800 of Pb2þ and 150 of Sb3þ. (A0 ), (B0 ) and (C0 ) corresponds to current variations as a function of the number of readings (Pb2þ: black square;
Sb3þ: red circle). Experimental conditions: see Fig. 2. Every reading corresponds to a single replicate measurement (total ¼ 10 measurements). (For interpretation of the references
to colour in this figure legend, the reader is referred to the Web version of this article.)

Fig. 4A. improvement or analytical sensitivity for the determination of Pb2þ

These results demonstrated a low influence on the Sb3þ oxida-
tion signal, with an RSD value of 9%. It also possible to observe that
the presence of Sb3þ does not interfere in a selective and inde-
pendent determination of Pb2þ, as a linear behaviour was observed
(R > 0.99) with a slope of 0.08 mA/mg L1 (Fig. 4A’), which indicates a
slightly higher sensitivity for Pb2þ determination in the presence of
low concentrations of Sb3þ compared to the curve for simultaneous
determination (Fig. 2). This slight increase in sensitivity may be a
consequence of the lower concentration of Sb3þ present in the cell,
which decreased the competition for active sites on the electrode
surface and favours the deposition of greater amounts of Pb2þ.
A similar study (Fig. 4B and B’) was performed with a higher
concentration of Sb3þ (1000 mg L1) in the cell and increasing the
amounts of Pb2þ (200e1000 mg L1). The results pointed to a low
deviation of the Sb3þ signal (RSD ¼ 5%) and the Pb2þ increments
resulted in the same slope value obtained in the study of simulta-
neous determination (0.07 mA/mg L1), indicating that the high
concentration of Sb3þ in the solution also does not affect the pre-
cision of independent determination of Pb2þ. The signal
was not verified as shown in Fig. 3B; however, Sb3þ concentration
was much higher than Pb2þ concentration which can explain this
different. This statement requires further investigation which was
not the main purpose of this work, for this reason no deeper
investigation is presented herein.
The opposite study was also carried out keeping the Pb2þ con-
centration at 200 mg L1 (Fig. 5A and A’) and 1000 mg L1 (Fig. 5B
and B’) and increments from 200 to 1000 mg L1 of Sb3þ in the
cell. Unlike what was observed in the previous study, it is observed
that the increase in the concentration of Sb3þ has a great influence
on the Pb2þ oxidation. Fig. 5A displays that the Pb2þ signal tends to
decrease with each increase in Sb3þ concentration, in addition to
the appearance of a second oxidation peak (- 0.4 V), which is an
indication that the electrochemical reduction of Pb2þ and re-
oxidation (stripping away from the electrode) may be occurring
under two conditions: the first, directly on the conductive G-PLA
surface, and the second, through the formation of an intermetallic
alloy between Pb0 and Sb0 during the deposition time, as reported
in previous work [54]. However, the presence of Pb2þ does not
132 S.V.F. Castro et al. / Analytica Chimica Acta 1130 (2020) 126e136

Fig. 4. SWASV responses for Sb3þ concentrations fixed in (A) 200 and (B) 1000 mg L1 and increments of Pb2þ concentration (200e1000 mg L1). (A0 ) and (B0 ) corresponds to the
respective calibration curves for Pb2þ oxidation (n ¼ 3). Experimental conditions: see Fig. 2.

Fig. 5. SWASV responses for Pb2þ concentrations fixed in (A) 200 and (B) 1000 mg L1 and increments of Sb3þ concentration (200e1000 mg L1). (A0 ) and (B0 ) corresponds to the
respective calibration curves for Sb3þ oxidation (n ¼ 3). Experimental conditions: see Fig. 2.

affect the linearity for the variation of Sb3þ concentrations, with
R > 0.99 and slope 0.02 mA/mg L1, which is the same slope value
found for the simultaneous determination (Fig. 2).
The results in Fig. 5B show an increase in the Pb2þ signal along
with the increase in the concentration of Sb3þ added in the cell,
presenting a 16% deviation. As previously discussed, the increasing
concentration of Sb3þ improved the detectability of Pb2þ. The
linearity of Sb3þ was observed with R > 0.99 and slope 0.02 mA/mg
L1, similar to that observed in previous studies (Fig. 2). Similarly,
high concentrations of Pb2þ do not significantly affect the
 S.V.F. Castro et al. / Analytica Chimica Acta 1130 (2020) 126e136
independent determination of Sb3þ.
3.3. Interference study
The selectivity of the proposed method was evaluated in the
presence of Cd2þ, Cu2þ, Fe3þ, Hg2þ and Zn2þ, considering the pos-
sibility of these metals being present in GSR samples acting as
interferents [9]. For this, 200 mg L1 of both Pb2þ and Sb3þ were
added to the electrochemical cell containing the supporting elec-
trolyte. Then, the same concentration of each one of the selected
interfering metals was added and the variation of the Pb2þ and Sb3þ
signal, expressed as a percentage, was monitored. SWASV re-
sponses are presented in Fig. S1 (Supporting information) and the
percentage values are presented in Table 2. Next, the concentration
of the interferent was doubled to 400 mg L1 and the signal varia-
tion of both analytes is also shown in Table 2.
This interferent test showed that Cu2þ was the only metal tested
that presented an oxidation signal in the studied potential range
(0.8 to 0.2 V). The signal of Cu2þ appeared as a shoulder of the
Pb2þ peak (0.35 V). Thus, the presence of Cu2þ in greater amounts
leads to a small decrease in the signal of Pb2þ and Sb3þ, which may
be related to the competition for active sites during the application
of the deposition potential. However, as Pb2þ is the metal presented
in greater amount in GSR, unlike Cu2þ, these results do not repre-
sent a major problem. Cd2þ, Fe3þ and Zn2þ did not represent a great
influence on the oxidation of analytes (below 10%), unlike Hg2þ,
which resulted in a great increase in the signal of both analytes,
mainly when the concentration of Hg2þ was increased to
400 mg L1. The explanation may be related to the formation of
mercury films on G-PLA surface during the application of the
deposition potential and the consequent formation of amalgams
with the analytes, improving the analytical sensitivity of Pb2þ and
Sb3þ [25,30]. As a summary, the results demonstrated the possi-
bility of the selective determination of both analytes in the pres-
ence of other metals, especially due to the absence of peaks in the
studied potential range. It is also important to emphasize that if the
standard addition method is used, precise quantification of both
metals is possible because the concentrations of interfering metals
will remain constant during the analysis.
3.4. Inter-electrode performance and reuse of the sensor
The reproducibility of the fabrication of G-PLA electrodes was
evaluated by an inter-electrode study. For this, four different elec-
trodes were used for the analysis of a solution containing
200 mg L1 of both Pb2þ and Sb3þ by SWASV (Fig. 6A). The RSD value
was estimated at 7% for both analytes, which indicates an excellent
reproducibility in the manufacture and treatment of the 3D-printed
electrodes. Fig. 6A also shows small shifts in peak potential for both
analytes, which may be related to small variations during the
Table 2
Variation of the current intensity of the electrochemical oxidation of Pb2þ and Sb3þ
in the presence of interfering metals at concentrations of 200 and 400 mg L1
(Positive values indicates an increase in the signal; negative values indicates a
decrease in the signal).
Interferents Pb2þ Sb3þ
200 (mg L ¡1
) 400 (mg L ¡1
) 200 (mg L¡1) 400 (mg L¡1)
- 14.91 1.24
Cd2þ 14.61 (e 2%) 15.06 (þ1%) 1.29 (þ4%) 1.36
Cu2þ 15.06 (þ1%) 13.12 (e 12%) 1.26 (þ2%) 1.12
Fe3þ 16.25 (þ9%) 15.80 (þ6%) 1.31 (þ6%) 1.34
Hg2þ 17.89 (þ20%) 32.80 (þ120%) 2.10 (þ69%) 2.69
Zn2þ 15.51 (þ4%) 16.10 (þ8%) 1.34 (þ8%) 1.30
133
electrode printing or mechanical polishing. However, these low
deviations are acceptable and did not affect the analytical perfor-
mance of the 3D-printed G-PLA electrode in the determination of
the metals.
Although the developed sensor has a low production cost, the
possibility of reuse in more analysis was also studied. As presented
in the methodology, prior the use, the electrode was mechanically
polished for 30 s and then immersed in a DMF solution for 10 min,
followed by voltammetric cycles for signal stabilization. In this
study, the electrode was subjected to three scans in the presence of
200 mg L1 of Pb2þ and Sb3þ in solution of supporting electrolyte.
Then, it was removed from the solution, polished again for another
30 s (no immersion in DMF was performed again between mea-
surements), stabilized by cyclic voltammetry in blank solution, and
placed to repeat the measurements under the same conditions. This
test was performed five times and Fig. 6B displays the obtained
results.
A good reproducibility between the first three measurements,
with RSD of 8% and 15% for Pb2þ and Sb3þ, respectively, was ob-
tained, indicating that the electrode surface was cleaned and
renewed during the polishing. In the fourth and fifth measure-
ments, although the Pb2þ signal showed a small variation, it is
observed that the Sb3þ signal tended to fall after each new pol-
ishing, which may be an indication of wear on the electrode surface
due to the excessive polishing performed. Hence, the electrodes
continued to respond to both analytes with clear, stable and well-
defined peaks when the electrode was polished up to three times,
without considerable loss in the electrochemical performance.
Importantly, qualitative determinations were still possible even
when reusing the electrode in more than five analysis.
3.5. Analysis of GSR samples
After the use as a sample collector, the G-PLA electrode was
immersed in the electrochemical cell containing 5 mL of
0.01 mol L1 HCl solution and the SWASV scan was performed. The
swabbing process resulted in the adsorption of metallic micropar-
ticles on the G-PLA surface. The electrochemical reduction of the
metals is necessary as the metals after shooting are probably found
as oxides in GSR. Hence, the SWASV scan involved the electro-
chemical reduction of the respective oxides to Pb0 and Sb0 without
stirring as the microparticles are immobilized at the electrode
surface. Next, the stripping process (re-oxidation of both metals)
occurs in the voltammetric scan resulting in the two peaks. The
results obtained for the samples collected from the hands of
shooters after 2, 5, 8 and 10 shots are displayed in Fig. 7, together
with the blanks (sampling before shooting).
It is important to observe the absence of oxidation signals in the
blank, indicating that there was no previous contamination of the
analytes (or other metals) in the hands of shooters. After contact
with the samples, the characteristic profile of the electrochemical
oxidation of Pb2þ and Sb3þ in the samples was observed, with the
peaks appearing in potential ranges characteristic of previous
studies (Fig. 2). There are also some deformations of the peaks
(Fig. 7A and D) and small variations in peak potential, which may be
related to the natural fat of the skin that can impregnate on the
electrode surface and cause changes in its performance. However, it
was still possible to observe the oxidation peaks of both analytes in
the evaluated samples and to confirm the presence of lead and
antimony in GSR.
(þ10%) It is possible to calculate the amount of metals based on the
(e 10%) voltammetric peaks obtained by SWASV using the Faraday’s Law of
(þ8%) electrolysis (m ¼ MM * Q/96485.3329 * n, where m corresponds to
(þ117%) the mass of the analyte; MM to the molar mass; Q the charge
(þ5%)
generated in the oxidation of the analyte; and n the number of
134 S.V.F. Castro et al. / Analytica Chimica Acta 1130 (2020) 126e136

Fig. 6. (A) SWASV responses for different electrodes (n ¼ 5) in the presence of 200 mg L1 of Pb2þ and Sb3þ. (B) Currents responses (n ¼ 3) in the electrochemical oxidation of Pb2þ
(squares) and Sb3þ (circles), where each colour represents the triplicate measurements after one mechanical polishing (n ¼ 5). Experimental conditions: see Fig. 2. As each symbol
represents one measurement, no error bars are presented. (For interpretation of the references to colour in this figure legend, the reader is referred to the Web version of this
article.)

Fig. 7. SWASV responses for the blank obtained by contact of G-PLA electrode with the hands of shooters prior to shooting (red line) and for the GSR samples collected after (A) 2,
(B) 5, (C) 8 and (D) 10 shots. SWASV conditions similar to Fig. 2, except to absence of stirring. (For interpretation of the references to colour in this figure legend, the reader is
referred to the Web version of this article.)

electrons transferred). This equation shows that charge is propor- values of Pb2þ and Sb3þ calculated using the data from SWASV
tional to the mass of the respective metal. Table 3 shows the mass scans (first scan) obtained for three different electrodes used for
GSR sampling.
The mass values found on G-PLA surfaces show that the number
Table 3
of shots has a direct influence in the amount of residue produced in
Mass values found on the electrode surface (three different electrodes) calculated the shots, since there was an increase in the amounts recovered
using the Faraday’s Law for the peaks obtained in the first SWASV scan on the G-PLA from the two analytes in samples 2S, 3S, 5S, 8S and 10S. As the
electrode after collection. residues can spread during the shooting and deposit on other
Samples Pb2þ (ng) Sb3þ (ng) surfaces, such as clothes of shooters, the ability of the sensor to
collect, identify and quantify residues deposited on the shirt (3S e
2S 1.7 ± 1.0 0.04 ± 0.02
3S 2.00 ± 0.02 0.2 ± 0.1 shirt) and pants (3S e pants) was also evaluated. The results were
5S 6±2 0.3 ± 0.2 satisfactory, as showed in Table 3, and it was possible to find and
8S 16 ± 6 1.1 ± 0.2 estimate the concentration of Pb2þ and Sb3þ in these samples. In
10S 29 ± 7 4±1
the cases of sampling on hand after 1 shot and on shirt/pant after 2
3S - shirt 0.9 ± 0.3 6±3
3S - pants 2.50 ± 0.04 0.5 ± 0.3
shots, no stripping peaks for Pb2þ and Sb3þ were observed which
 S.V.F. Castro et al. / Analytica Chimica Acta 1130 (2020) 126e136
indicates a situation where the concentration of both metals are
below the LOD values of the proposed procedure. Based on these
results, the LODs using this approach can be estimated as 0.04 and
0.02 ng for Pb2þ and Sb3þ.
Previous works have reported that stubs are better collector
devices than alcohol swabs [15,23,24,29]. Regarding the amount
recovered on surfaces, the comparison of this work with other re-
ported works that used stubs for the collection of IGSR is very
difficult, since the methodology for collection and data analysis are
very different. Moreover, stubs associated with SEM/EDS are the
standard methodology adopted during forensic investigations
involving GSR [55] and the results are evaluated according to the
identity of the metal or the number of particles collected, and not
mass values [15]. In the proposed 3D-printed sensor combined with
SWASV, the same qualitative information can be obtained.
Considering the stability of GSR in storage over time, Taudte and co-
authors reported substantial degradation of OGSR in the first 4 days
of storage [24]. For IGSR, to our knowledge, no studies on the
evaluation of the degradation of inorganic residues on stub surfaces
have been reported. However, considering the experiments per-
formed in this work, we verified that the metallic residues still
remain stable on the 3D-printed G-PLA surface for analysis even
after 8 months of the shooting tests.
The ability of the sensor to collect GSR from the hands of
shooters 1 h after firing was also evaluated. The results (Fig. S2 in
Supporting Information) were satisfactory and allowed the iden-
tification of both analytes. Using Faraday’s Law to calculate the
mass values of Pb2þ and Sb3þ on G-PLA surface corresponding to
the SWASV responses presented in Fig. S2 were 0.44 ng and 0.28 ng,
respectively. It is important to emphasize that the police or those
responsible for the investigation need to identify the metals typi-
cally found in GSR after swabbing different surfaces to confirm the
presence of GSR in the analyzed material. The qualitative infor-
mation can confirm if a suspect is the shooter at the crime scene to
enable fast elucidation of the crime. The quantification of the
metals in GSR is secondary in such cases. Therefore, the combina-
tion of 3D-printed G-PLA electrodes for sampling and voltammetric
detection of Pb2þ and Sb3þ is practicable at crime scenes, requiring
low volumes of supporting electrolyte (5 mL of 0.01 mol L1 HCl per
measurement), a compact cell (that can also be 3D-printed) and a
portable (or handheld) mini-potentiostats which are commercially-
available [56].
4. Conclusion
This work demonstrated the excellent analytical performance of
3D-printed G-PLA electrodes for simultaneous determination of
Pb2þ and Sb3þ. The proposed sensor showed stable and repetitive
responses in different proportions of the analytes, good selectivity,
high sensitivity (LOD ¼ 0.5 and 1.8 mg L1 to Pb2þ and Sb3þ,
respectively), in addition to good inter-electrode reproducibility
(RSD ¼ 7%) and capacity of reuse of the sensor due to surface
renewal through simple mechanical polishing. The performance
was also evaluated in analysis of real samples from the collection
made through simple contact of the sensor with hand and clothes
of shooters, which allowed the qualitative determination of both
analytes through the electrochemical profile of the simultaneous
analysis, and the estimation of the amount of metals adhered to the
surface of the material through the Faraday’s Law using the vol-
tammetric data. These results demonstrate the high potential of a
3D-printed material that associates low cost with good perfor-
mance for analysis of forensic interest, further highlighting the role
of 3D printing today. Moreover, this work shows that the sampling
and detection approach using the 3D-printed G-PLA platform
combined to a 3D-printed cell and handheld potentiostat is feasible
135
to serve police experts in forensic scenarios.
CRediT authorship contribution statement
Sílvia V.F. Castro: Methodology, Validation, Data curation,
Formal analysis, Investigation, Writing - original draft, Validation,
Visualization. Ana P. Lima: Methodology, Data curation. Raquel G.
Rocha: Methodology, Data curation. Rafael M. Cardoso: Method-
ology, Investigation. Rodrigo H.O. Montes: Methodology, Writing -
review & editing. Ma
rio H.P. Santana: Methodology, Writing - re-
view & editing. Eduardo M. Richter: Writing - review & editing,
Supervision, Resources. Rodrigo A.A. Munoz: Writing - review &
editing, Conceptualization, Supervision, Resources, Project admin-
istration, Funding acquisition.
Declaration of competing interest
The authors declare that they have no known competing
financial interests or personal relationships that could have
appeared to influence the work reported in this paper.
Acknowledgements
The authors are grateful to FAPEMIG (APQ-03141-18, PPM-
00614-18 and RED-00042-16), CNPq (307172-2017-0 and 308504/
2018-6), CAPES and INCTBio (CNPq grant no. 465389/2014-7) for
the financial support.
Appendix A. Supplementary data
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.aca.2020.07.033.
References
[1] Global burden of Disease 2016 Injury collaborators, global mortality from
firearms, 1990-2016, J. Am. Med. Assoc. 764 (2018) 792e814, https://doi.org/
10.1001/jama.2018.10060.
[2] M.E. Reichenheim, E.R. De Souza, C.L. Moraes, M.H.P. de M. Jorge, C.M.F.P. da
Silva, M.C. de S. Minayo, Viole ^ncia e leso
~es no Brasil : efeitos, avanços alcan-
çados e desafios futuros, Lancet (2011) 75e89, https://doi.org/10.1016/S0140-
6736(11)60053-6.

pez, L.K. Watson, P. Kolpak,
[3] A.J. Dare, H. Irving, C.M. Guerrero-lo
L.M.R. Shigematsu, M. Sanches, D. Gomez, H. Gelband, P. Jha, Geospatial, racial,
and educational variation in firearm mortality in the USA, Mexico, Brazil, and
Colombia, 1990 e 2015: a comparative analysis of vital statistics data, Lancet
Public Heal (2019) e281ee290, https://doi.org/10.1016/S2468-2667(19)
30018-0, 2019.
[4] A. Gassner, C. Ribeiro, J. Kobylinska, A. Zeichner, C. Weyermann, Organic
gunshot residues : observations about sampling and transfer mechanisms,
Forensic Sci. Int. 266 (2016) 369e378, https://doi.org/10.1016/
j.forsciint.2016.06.029.
[5] I. Kara, The influence of different skin types on GSR sampling by tape lifting for
SEM analysis, Microsc. Resarch Tech (2017) 1310e1314, https://doi.org/
10.1002/jemt.22942.
[6] E. Goudsmits, G.P. Sharples, J.W. Birkett, Recent trends in organic gunshot
residue analysis, Trends Anal. Chem. 74 (2015) 46e57, https://doi.org/
10.1016/j.trac.2015.05.010.
[7] M. Aliste, L.G. Cha
vez, Analysis of gunshot residues as trace in nasal mucus by
GFAAS, Forensic Sci. Int. 261 (2016) 14e18, https://doi.org/10.1016/
j.forsciint.2016.01.034.
[8] L.P. de Oliveira, D.P. Rocha, W.R. de Araujo, R.A.A. Mun ~ oz, T.R.L.C. Paix~
ao,
M.O. Salles, Forensics in hand: new trends in forensic devices (2013e2017),
Anal. Methods 10 (2018) 5135e5163, https://doi.org/10.1039/c8ay01389f.
[9] A.M.O. Mahony, J. Wang, Electrochemical detection of gunshot residue for
forensic Analysis : a review, Electroanalysis 25 (2013) 1341e1358, https://
doi.org/10.1002/elan.201300054.
[10] E.L.T. Reis, J.E.S. Sarkis, O.N. Neto, C. Rodrigues, M.H. Kakazu, S. Viebig, A new
method for collection and identification of gunshot residues from the hands of
shooters, J. Forensic Sci. 48 (2003) 1e6, https://doi.org/10.1520/JFS2002441.
[11] E.L.T. Reis, J.E.S. Sarkis, C. Rodrigues, Identification of gunshot residues by high
resolution inductively coupled plasma mass spectrometry, Quim. Nova 27
(2004) 409e413, https://doi.org/10.1590/S0100-40422004000300009.
[12] J.E.S. Sarkis, O.N. Neto, S. Viebig, S.F. Durrant, Measurements of gunshot
136 S.V.F. Castro et al. / Analytica Chimica Acta 1130 (2020) 126e136
residues by sector field inductively coupled plasma mass spectrometry d
further studies with pistols, Forensic Sci. Int. 172 (2007) 63e66, https://
doi.org/10.1016/j.forsciint.2006.12.007.
[13] C.R. Dockery, S.R. Goode, Laser-induced breakdown spectroscopy for the
detection of gunshot residues on the hands of a shooter, Appl. Optic. 42 (2003)
6153e6158, https://doi.org/10.1364/AO.42.006153.
[14] N.S. Fidan, B. Izgi, Determination of antimony in gunshot residues (GSR) by
electrothermal atomic absorption spectrometry, Bulg. Chem. Commun. 41
(2009) 404e408.
[15] L. Reid, K. Chana, J.W. Bond, M.J. Almond, S. Black, Stubs versus Swabs ? A
comparison of gunshot residue collection techniques, J. Forensic Sci. 55 (2010)
753e756, https://doi.org/10.1111/j.1556-4029.2010.01332.x.
[16] G. Vanini, R.M. Souza, C.A. Destefani, B.B. Merlo, T.M. Piorotti, E.V.R. De Castro,
M.T.W.D. Carneiro, W. Roma ~o, Analysis of gunshot residues produced by . 38
caliber handguns using inductively coupled plasma-optical emission spec-
troscopy ( ICP OES ), Microchem. J. 115 (2014) 106e112, https://doi.org/
10.1016/j.microc.2014.03.003.
[17] A. Amadasi, D. Merli, A. Brandone, P. Poppa, D. Gibelli, C. Cattaneo, The sur-
vival of gunshot residues in cremated Bone : an inductively coupled plasma
optical emission spectrometry study, J. Forensic Sci. 58 (2013) 964e966,
https://doi.org/10.1111/1556-4029.12149.
[18] B. Yüksel, A. Ozler-yigiter, T. Bora, N. Sen, Z. Kayaalti, GFAAS determination of
antimony, barium, and lead levels in gunshot residue swabs: an application in
forensic chemistry, At. Spectrosc. 37 (2016) 164e169.
[19] O.O. Erol, B.Y. Erdogan, A.N. Onar, Nitrate and nitrite determination in gunshot
residue samples by capillary electrophoresis in acidic run buffer, J. Forensic
Sci. 62 (2017) 423e427, https://doi.org/10.1111/1556-4029.13275.
[20] R. d Heringer, J.F. Ranville, Gunshot residue ( GSR ) analysis by single particle
inductively coupled plasma mass spectrometry (spICP-MS), Forensic Sci. Int.
288 (2018) e20ee25, https://doi.org/10.1016/j.forsciint.2018.05.010.
[21] L.P. Ferreira, C.C. Nascentes, F.N. Vallada~o, R.A. Lordeiro, Feasibility of a new
method for identification and discrimination of gunshot residues by total
reflection X-ray fluorescence and principal component analysis, J. Braz. Chem.
Soc. 30 (2019) 2582e2589, doi: 10.21577/0103-5053.20190173.
[22] S. Benito, Z. Abrego, A. Sa
nchez, N. Unceta, M.A. Goicolea, R.J. Barrio, Char-
acterization of organic gunshot residues in lead-free ammunition using a new
sample collection device for liquid chromatography e quadrupole time-of-
flight mass spectrometry, Forensic Sci. Int. 246 (2015) 79e85, https://
doi.org/10.1016/j.forsciint.2014.11.002.
[23] A. Gassner, C. Weyermann, LC e MS method development and comparison of
sampling materials for the analysis of organic gunshot residues, Forensic Sci.
Int. 264 (2016) 47e55, https://doi.org/10.1016/j.forsciint.2016.03.022.
[24] R.V. Taudte, C. Roux, A. Beavis, Stability of smokeless powder compounds on
collection devices, Forensic Sci. Int. 270 (2017) 55e60, https://doi.org/
10.1016/j.forsciint.2016.11.027.
[25] S. Erden, Z. Durmus, E. Kiliç, Simultaneous determination of antimony and
lead in gunshot residue by cathodic adsorptive stripping voltammetric
methods, Electroanalysis 23 (2011) 1967e1974, https://doi.org/10.1002/
elan.201000612.
[26] M.O. Salles, J. Naozuka, M. Bertotti, A forensic study : lead determination in
gunshot residues, Microchem. J. 101 (2012) 49e53, https://doi.org/10.1016/
j.microc.2011.10.004.
[27] M.O. Salles, M. Bertotti, T.R.L.C. Paixa ~o, Use of a gold microelectrode for
discrimination of gunshot residues, Sensor. Actuator. B Chem. 166e167
(2012) 848e852, https://doi.org/10.1016/j.snb.2012.02.097.
[28] M.H. Seltenhammer, C. Fitzl, I. Wieser, R. Binder, P. Paula, D.U. Risser, Does the
prior application of the field kit bullet hole testing kit 3 on a suspected bullet
hole bias the analysis of atomic absorption spectrophotometry ? J. Forensic
Sci. 59 (2014) 1364e1367, https://doi.org/10.1111/1556-4029.12530.
[29] R.V. Taudte, C. Roux, L. Blanes, M. Horder, K.P. Kirkbride, A. Beavis, The
development and comparison of collection techniques for inorganic and
organic gunshot residues, Anal. Bioanal. Chem. 408 (2016) 2567e2576,
https://doi.org/10.1007/s00216-016-9357-7.
[30] C.A. Woolever, D.E. Starkey, H.D. Dewald, Differential pulse anodic stripping
voltammetry of lead and antimony in gunshot residues, Forensic Sci. Int. 102
(1999) 45e50.
[31] C.A. Woolever, H.D. Dewald, Differential pulse anodic stripping voltammetry
of barium and lead in gunshot residues, Forensic Sci. Int. 117 (2001) 1e6,
https://doi.org/10.1016/S0379-0738(00)00402-3.
[32] M. Vuki, K. Shiu, M. Galik, A.M.O. Mahony, J. Wang, Simultaneous electro-
chemical measurement of metal and organic propellant constituents of gun-
shot residues, Analyst 137 (2012) 3265e3270, https://doi.org/10.1039/
c2an35379b.
[33] J.A. Rodriguez, I.S. Ibarra, C.A. Galan-vidal, M. Vega, H. Barrado, Multi-
commutated anodic stripping voltammetry at tubular bismuth film electrode
for lead determination in gunshot residues, Electroanalysis 21 (2009)
452e458, https://doi.org/10.1002/elan.200804420.
[34] A.J. Bandodkar, A.M.O. Mahony, J. Ramírez, I.A. Samek, S.M. Anderson,
J.R. Windmiller, J. Wang, Solid-state Forensic Finger sensor for integrated
sampling and detection of gunshot residue and explosives: towards “Lab-on-
a-finger, Analyst 138 (2013) 5288e5295, https://doi.org/10.1039/
c3an01179h.
[35] A.M.O. Mahony, J.R. Windmiller, I.A. Samek, A.J. Bandodkar, J. Wang, “Swipe
and Scan ”: integration of sampling and analysis of gunshot metal residues at
screen-printed electrodes, Electrochem. Commun. 23 (2012) 52e55, https://
doi.org/10.1016/j.elecom.2012.07.004.
[36] A.M.O. Mahony, I.A. Samek, S. Sattayasamitsathit, J. Wang, Orthogonal iden-
tification of gunshot residue with complementary detection principles of
voltammetry, scanning electron microscopy, and energy-Dispersive X-ray
spectroscopy: sample, screen, and Confirm, Anal. Bioanal. Chem. 86 (2014)
8031e8036, https://doi.org/10.1021/ac5016112.
[37] N.H.M. Hashim, Z.M. Zain, M.Z. Jaafar, Copper determination in gunshot res-
idue by cyclic voltammetric and inductive coupled plasma-optical emission
spectroscopy, MATEC Web Conf 59 (2016) 1e5, https://doi.org/10.1051/
matecconf/20165904005.
[38] T. Trejos, C. V Pyl, K. Menking-hoggatt, A.L. Alvarado, L.E. Arroyo, Fast iden-
tification of inorganic and organic gunshot residues by LIBS and electro-
chemical methods, Forensic Chem 8 (2018) 146e156, https://doi.org/10.1016/
j.forc.2018.02.006.
[39] K. Promsuwan, P. Kanatharana, P. Thavarungkul, W. Limbut, Nitrite ampero-
metric sensor for gunshot residue screening, Electrochim. Acta (2019) 135309,
https://doi.org/10.1016/j.electacta.2019.135309.
[40] A. Ambrosi, M. Pumera, 3D-printing technologies for electrochemical appli-
cations, Chem. Soc. Rev. 45 (2016) 2740e2755, https://doi.org/10.1039/
c5cs00714c.
[41] R.M. Cardoso, S.V.F. Castro, M.N.T. Silva, A.P. Lima, M.H.P. Santana, E. Nossol,
R.A.B. Silva, E.M. Richter, T.R.L.C. Paixa ~o, R.A.A. Mun ~ oz, 3D-printed flexible
device combining sampling and detection of explosives, Sensor. Actuator. B
Chem. 292 (2019) 308e313, https://doi.org/10.1016/j.snb.2019.04.126.
[42] R.M. Cardoso, D.M.H. Mendonça, W.P. Silva, M.N.T. Silva, E. Nossol, R.A.B. da
Silva, E.M. Richter, R.A.A. Mun ~ oz, 3D printing for electroanalysis: from
multiuse electrochemical cells to sensors, Anal. Chim. Acta 1033 (2018)
49e57, doi: 10.1016/j.aca.2018.06.021.
[43] A.F. Jo~ao, A.L. Squissato, E.M. Richter, R.A.A. Mun ~ oz, Additive-manufactured
sensors for biofuel analysis : copper determination in bioethanol using a 3D-
printed carbon black/polylactic electrode, Anal. Bioanal. Chem. 412 (2020)
2755e2762, https://doi.org/10.1007/s00216-020-02513-y.
[44] D.P. Rocha, A.L. Squissato, S.M. Silva, E.M. Richter, R.A.A. Munoz, Improved
electrochemical detection of metals in biological samples using 3D-printed
electrode: chemical/electrochemical treatment exposes carbono-black
conductive sites, Electrochim. Acta 335 (2020) 135688, https://doi.org/
10.1016/j.electacta.2020.135688.
[45] C.W. Foster, H.M. Elbardisy, M.P. Down, E.M. Keefe, G.C. Smith, C.E. Banks,
Additively manufactured graphitic electrochemical sensing platforms, Chem.
Eng. J. 381 (2020) 122343, https://doi.org/10.1016/j.cej.2019.122343.
[46] J.G. Walters, S. Ahmed, I.M. Terrero Rodríguez, G.D. O’Neil, Trace analysis of
heavy metals ( Cd , Pb , Hg ) using native and modified 3D printed graphene/
poly ( lactic acid ) composite electrodes, Electroanalysis (2020) 1e9, https://
doi.org/10.1002/elan.201900658.
[47] D.P. Rocha, C.W. Foster, R.A.A. Munoz, G.A. Buller, E.M. Keefe, C.E. Banks, Trace
manganese detection via differential pulse cathodic stripping voltammetry
using disposable electrodes: additively manufactured nanographite electro-
chemical sensing platforms, Analyst 145 (2020) 3424e3430, https://doi.org/
10.1039/d0an00018c.
[48] K.C. Honeychurch, Z. Rymansaib, P. Iravani, Anodic stripping voltammetric
determination of zinc at a 3-D printed carbon nano-
fiberegraphiteepolystyrene electrode using a carbon pseudo-reference elec-
trode, Sensor. Actuator. B Chem. 267 (2018) 476e482, https://doi.org/
10.1016/j.snb.2018.04.054.
[49] R.M. Cardoso, C. Kalinke, R.G. Rocha, P.L. dos Santos, D.P. Rocha, P.R. Oliveira,
B.C. Janegitz, J.A. Bonacin, E.M. Richter, R.A.A. Munoz, Additive-manufactured
(3D-printed) electrochemical sensors: a critical review, Anal. Chim. Acta 1118
(2020) 73e91, https://doi.org/10.1016/j.aca.2020.03.028.
[50] C.L.M. Palenzuela, F. Novotny, P. Krupicka, Z. Sofer, M. Pumera, 3D-printed
graphene/polylactic acid electrodes promise high sensitivity in electroanal-
ysis, Anal. Chem. 90 (2018) 5753e5757, https://doi.org/10.1021/
acs.analchem.8b00083.
[51] J.J. Pedrotti, L. Angnes, I.G.R. Gutz, Miniaturized reference electrodes with
microporous polymer junctions, Electroanalysis 8 (1996) 673e675, https://
doi.org/10.1002/elan.1140080713.
[52] 
S.B. Hocevar, I. Svancara, B. Ogorevc, K. Vytras, Antimony film electrode for
electrochemical stripping analysis, Anal. Chem. 79 (2007) 8639e8643, https://
doi.org/10.1021/ac070478m.
[53] R. Liu, H. Cao, Z. Nie, S. Si, X. Zhao, X. Zeng, A disposable expanded graphite
paper electrode with self-doped sulfonated polyaniline/antimony for strip-
ping voltammetric determination of trace Cd and Pb, Anal. Methods 8 (2016)
1618e1625, https://doi.org/10.1039/c5ay03094c.
[54] K.E. Toghill, L. Xiao, G.G. Wildgoose, R.G. Compton, Electroanalytical deter-
mination of cadmium ( II ) and lead ( II ) using an antimony nanoparticle
modified boron-doped diamond electrode, Electroanalysis 21 (2009)
1113e1118, https://doi.org/10.1002/elan.200904547.
[55] S. Charles, N. Geusens, E. Vergalito, B. Nys, Interpol review of gunshot residue
2016-2019, Forensic Sci. Int. (2020), https://doi.org/10.1016/j.fsi-
syn.2020.01.011 in press.
[56] W.R. de Araujo, T.M.G. Cardoso, R.G. Rocha, M.H.P. Santana, R.A.A. Munoz,
E.M. Richter, T.R.L.C. Paixa ~o, W.K.T. Coltro, Portable analytical platforms for
forensic chemistry: a review, Anal. Chim. Acta 1034 (2018) 1e21, https://
doi.org/10.1016/j.aca.2018.06.014.