Talanta 217 (2020) 120987

Contents lists available at ScienceDirect

Talanta
journal homepage: www.elsevier.com/locate/talanta

High-throughput screening of cocaine, adulterants, and diluents in seized T

samples using capillary electrophoresis with capacitively coupled
contactless conductivity detection
Diandra N. Barreto, Michelle M.A.C. Ribeiro, João T.C. Sudo, Eduardo M. Richter,
Rodrigo A.A. Muñoz, Sidnei G. Silva∗ Assinado de forma digital por
Federal University of Uberlândia, Institute of Chemistry, 38400–902, Uberlândia, MG, Brazil
PEDRO FERNANDO PEDRO FERNANDO VELOSO
VELOSO DOS DOS PASSOS:892297-1
Dados: 2022.06.08 10:59:09
ARTICLE INFO ABSTRACT
PASSOS:892297-1 -03'00'
Keywords: Cocaine is one of the most frequently used illicit drug in the world. Therefore, the development of simple and fast
Capillary electrophoresis methods for the detection of cocaine and common adulterants, diluents and impurities are extremely important
Contactless conductivity detection in forensic investigations. The present study describes, for the first time, a method based on capillary electro-
Ultrafast analysis phoresis with capacitively coupled contactless conductivity detection (CE-C4D) for the rapid (2.5 min) and si-
Adulterants
multaneous quantification of cocaine, levamisole, lidocaine, carbonate, borate, chloride, nitrate, nitrite and
Forensic chemistry
sulphate. In the experiment, anions were separated in co-electroosmotic mode and cations in counter-electro-
osmotic mode employing a buffer solution composed by 10.0 mmol L−1 TAPS, 12 mmol L−1 NaOH and
0.2 mmol L−1 CTAB as the background electrolyte (pH = 8.8). The developed CE method demonstrated some
interesting analytical characteristics such as: (i) a simple sample pretreatment step (only dilution in water and
filtering), (ii) high-throughput screening (24 injections h−1), (iii) proper recovery values (between 72 and
118%), and (iv) an inter-day precision of less than 7% for all analytes. The procedure was successfully applied in
the analysis of seized cocaine samples collected by the Integrated Forensics Post (PPI) of the Minas Gerais Civil
Police (Uberaba, Minas Gerais State, Brazil), during the year of 2018.

1. Introduction undesirable effects [10,12,13]. Phenacetin, levamisole, lidocaine and

The chemical composition of cocaine samples varies according to
the geographical region of the seizure, the production process (im-
purities), and the addition of adulterants and/or diluents [1,2]. The
characterization of seized cocaine street samples provides significant
information about its chemical profile and this allows the correlation
between traffic flow and the region where the cocaine supplies are
produced [3–5]. The concentration of cocaine in seized street samples
may vary from 16 to 91% (w/w), in either hydrochloride salt and/or in
the freebase form [4,6–8]. A variety of adulterants are added to the
drug during trafficking to increase profits in all the phases of drug
distribution [9]. The addition of diluents has been extensively reported
in the literature, and some of the common substances include carbo-
hydrates (mannitol, lactose or glucose), boric acid, starch and sodium
bicarbonate [10]. Nitrate, nitrite and sulphate anions were found in
seized cocaine samples and may have originated from nitrogen-based
fertilizers [11]. On the other hand, some adulterants are sometimes
added to the drug to enhance the psychotropic effects or to reduce
caffeine are the most frequently found adulterants in seizures [14].
Analytical techniques based on chromatography [9], such as high-
performance liquid chromatography (HPLC) [15–17] and gas chroma-
tography (GC) [18], have been used in the characterization of cocaine
samples, especially for the identification and quantification of organic
species. Alternatively, other papers have reported the determination of
inorganic species employing techniques, such as atomic spectrometry
[17], infrared [19] and Raman Spectroscopy [20,21]. However, few
analytical techniques have the ability to determine, in a single run, both
organic and inorganic species, without requiring instrumental changes.
Capillary electrophoresis (CE) is a well-established analytical tech-
nique that has been applied for the determination of trace components
in illicit drugs, including inorganic and organic compounds [11,22–27].
This technique offers several advantages, such as high sample
throughput, high efficiency and resolution, as well as minimal reagents
and sample consumption. Furthermore, due to the variety of separation
modes (e.g capillary zone electrophoresis, capillary isotachorphoresis
and capillary electrochromatography) and to the detection systems (e.g.

∗
Corresponding author.
E-mail addresses: sidgons@gmail.com, sidgon@ufu.br (S.G. Silva).

https://doi.org/10.1016/j.talanta.2020.120987
Received 30 December 2019; Received in revised form 27 March 2020; Accepted 28 March 2020
Available online 10 April 2020
0039-9140/ © 2020 Elsevier B.V. All rights reserved.
D.N. Barreto, et al. Talanta 217 (2020) 120987

Mass-Spectrometry, UV–visible, fluorescence and conductivity detec-

tion), CE is an attractive technique in forensic applications to determine
a wide variety of chemical substances including inorganic and organic
molecules.
Capillary electrophoresis with capacitively coupled contactless
conductivity detection (CE-C4D) allows the separation and detection of
ionic species with or without weak chromogenic or fluorogenic activity.
When this detector is used, all compounds with different conductivities
to the species used in background electrolyte can be detected (universal
detector) [28,29]. Recently, some interesting features of CE-C4D sys-
tems, such as low-cost, easy miniaturization, lower power consumption,
fast analysis, and minimal sample and reagent consumption, have been
explored for the development of portable instrumentation [30,31].
Therefore, thanks to its advantages, CE-C4D approaches has demon-
strated a considerable potential for use in decentralized places, which is
highly desirable in forensic analysis [30,32–35].
The purpose of the paper here described was to develop a simple
and fast screening method to evaluate the chemical profile of seized
cocaine samples. In a single run (2.5 min), nine potential constituents of
seized cocaine samples - cocaine, levamisole, lidocaine, carbonate, Fig. 1. Charge versus pH curves. ( ) H2CO3; ( ) H3BO3; ( ) levamisole; ( )
borate, chloride, nitrite, nitrate and sulphate - can be separated and lidocaine; ( ) cocaine. Data obtained from Ref. [31].
detected using the proposed method.

Table 1
2. Experimental
Electrophoretic parameters: studied ranges and selected values.

2.1. Chemicals and reagents Condition Range Selected Value

pH 7.7–9.0 8.8
All solutions were prepared with deionized water (R ≥ 18.8 MΩ cm, TAPS concentration (mmol L−1) 5–15 10
Direct-Q3, Bedford, USA). All used chemicals were reagent grade or CTAB concentration (mmol L−1) 0.1–0.3 0.2
better, and the solutions were prepared without further purification. Injection time (s) 0.5–1.5 1.0
3,4-Dimethoxycinnamic acid 99% (DMX), 2-amino-hydroxymethyl- Separation voltage (kV) +20 – +30 +25
Capillary effective length (cm) 10–40 40
propane-1,3-diol (TRIS) 98%, N-tris(Hydroxymethyl)methyl-3-amino-
propanesulfonic acid 99.5% (TAPS) and cetyltrimethylammonium
bromide (CTAB) were purchased from Sigma-Aldrich (98%, Germany).
Sodium hydroxide was acquired from PanReac (99.8%, Spain). The
optimized background electrolyte (BGE) consisted of 10.0 mmol L−1
TAPS, 12.0 mmol L−1 NaOH and 0.2 mmol L−1 CTAB (pH = 8.8). The
pH was measured using a digital pH meter (Bel Engineering® model
PHS3BW, Italy) calibrated with aqueous standard solutions prior to use.
Reference standard solutions were prepared in distilled-deionized
water from analytical grade reagents: sodium chloride (99%, Synth,
Brazil), sodium nitrite (97%, Synth, Brazil), sodium nitrate (99.5%,
Merck, Germany), sodium sulphate (99%, Carlo Erba, France), sodium
carbonate (99.5%, Carlo Erba, France), boric acid (99.8, PanReac,
Spain), lidocaine and levamisole hydrochloride (99%, Sigma-Aldrich,
Germany). Cocaine standard (99%) was provided by the National
Institute of Criminalistics (INC) of the Federal Police of Brazil (Brasília,
Federal District, Brazil).

2.2. Instrumentation

The capillary electrophoresis system was manufactured at the

Department of Fundamental Chemistry of the Institute of Chemistry of
the University of São Paulo (São Paulo/Brazil). The equipment has two
C4D detectors positioned along the capillary at 10 cm from each end.
Consequently, the CE system provides two electropherograms with a
single sample injection, one registered at the first detector (10 cm ef-
fective length) and the other at the second detector (40 cm effective
length; 50 cm total length). Both detectors operated at constant voltage
amplitude (4 Vpp) and frequency (1.1 MHz) wall covering [35]. The
fused silica capillary column used in the experiments was 50 cm length,
50 μm internal diameter, and 375 μm outside diameter (Agilent,
Folsom, CA, USA). Prior to analysis, the capillary was washed with
deionized water for 800 s, then with 1.0 mol L−1 HCl for 800s, again
with deionized water for 800 s, followed by injection of 0.2 mmol L−1
CTAB for 100 s, 500 s of water and finally the BGE solution for 1.000 s.
Fig. 2. Electropherograms for twelve successive injections of a standard solu-
tion containing COC (1.0 mmol L−1), LEV, LID, Cl−, NO3−, SO42−and CO32−
(0.5 mmol L−1), BO33− (5.0 mmol L−1) and NO2− (0.05 mmol L−1).
Experimental conditions: BGE: TAPS 10 mmol L−1 TAPS/CTAB 0.2 mmol L−1,
pH 8.8 (adjusted with NaOH). Separation voltage: +25 kV (inlet site); hydro-
dynamic injection: 25 kPa for 1.0 s; Capillary: total and effective length: 50 and
40 cm, respectively. The ordinal numbers correspond to the injection per-
formed. The superscript numbers indicate the analytes according to (1) Cl−; (2)
NO2−; (3) NO3−; (4) SO42−; (5) CO32−; (6) BO33−; (7) LEV.; (8) LID; and (9)
COC.

2
D.N. Barreto, et al. Talanta 217 (2020) 120987

Table 2
Analytical characteristics of the proposed CE-C4D procedure.
Analyte Linear range Migration Peak LODb Resolutionc
(mmol L−1) timea (s) area (mmol L−1)
RSD
(%)a

Cl− 0.10–1.0 53.9 ± 0.5 5% 3.0×10−2 __

NO2− 0.05–2.0 55.4 ± 0.5 6% 1.5×10−2 0.9 ± 0.0
NO3− 0.05–1.2 59.1 ± 0.6 2% 1.5×10−2 1.9 ± 0.0
SO4−2 0.05–1.2 61.0 ± 0.6 3% 1.5×10−2 0.6 ± 0.0
CO3−2 0.05–1.0 69.4 ± 0.6 6% 1.5×10−2 3.4 ± 0.1
BO3−3 1.00–10.0 91.6 ± 0.0 4% 3.0×10−2 9.1 ± 0.8
Levamisole 0.10–0.80 121.5 ± 0.0 3% 3.0×10−2 1.8 ± 0.0
Lidocaine 0.10–0.80 123.4 ± 0.0 7% 3.0×10−2 1.1 ± 0.0
Cocaine 0.05–7.00 142.8 ± 0.0 3% 1.5×10−2 5.2 ± 0.2

a
n = 12.
b
(S/N = 3).
c
Calculated between the analyte and previous peak (confidence interval of
95%).

After 12 injections of sample solutions, the fused silica capillary was

rinsed with BGE solution for 5 min. The optimized injection time and
separation potential were 1.0 s and 25 kV, respectively. The injection Fig. 3. Electropherograms for standard solution and three samples (32, 61, and
62). The superscript numbers indicate the analytes according to (1) Cl−; (2)
pressure was constant (25 kPa).
NO2−; (3) NO3−; (4) SO42−; (5) CO32−; (6) BO33−; (7) LEV.; (8) LID; and (9)
COC. Experimental conditions: 10 mmol L−1 TAPS/CTAB 0.2 mmol L−1, pH
2.3. Sample preparation 8.8. Separation voltage: +25 kV (inlet site); hydrodynamic injection: 25 kPa for
1.0 s; Capillary: total and effective length: 50 and 40 cm, respectively.
Seized cocaine samples were provided by the Integrated Forensics
Post (PPI) of the Minas Gerais Civil Police (Uberaba, Minas Gerais State,
dimethoxycinnamic acid/NaOH solution (pH = 8.4) as the background
Brazil), during the year of 2018. The sample preparation consisted of
electrolyte (BGE) [27]. However, the use of the same BGE was dis-
the solubilization of 0.1 g of the seized sample (cocaine hydrochloride)
charged due to the fact that the BGE component, boric acid, was a di-
in 10 mL of deionized water. For all samples analysed, complete dis-
luent previously identified in the seized cocaine samples. According to
solution was observed. After proper dilution with deionized water and
our knowledge, the possibility of determination of borate, carbonate
filtration through a membrane filter (pore size of 0.45 μm), the samples
and cocaine in a single run has not been shown before.
were injected in the CE system.
In order to determine cocaine and the common species previously
related by CZE in a single run, information on the net charge versus pH
3. Results and discussion
curves of the target analytes was searched in the literature (Fig. 1) [37].
As can be seen in Fig. 1, all target compounds (carbonate, borate, co-
In some preliminary tests performed in collaboration with the Minas
caine, levamisole, and lidocaine) exhibit net positive or negative charge
Gerais State Police, Brazil, the presence of several substances was
(ionic form) in the pH region around 7.7 and 9.0. Therefore, a solution
identified by GC and/or colorimetric tests in cocaine samples seized in
with buffer capacity in this pH region (TAPS/TRIS) was tested, how-
this region. Many of the seized samples showed the presence of other
ever, the sensitivity for cocaine, levamisole and lidocaine was com-
substances, such as lidocaine, levamisole, carbonate and borate that are
promised due to similarity in mobility values between BGE and analytes
listed as common cocaine adulterants [36]. Based on these common
(conductometric detection). In the following test, a buffer solution with
species previously identified in these samples, the aim of this work was
higher conductivity (TAPS + NaOH) was selected as the BGE and
to develop a simple and fast procedure for the simultaneous determi-
higher analytical response was achieved for these compounds. In the pH
nation of cocaine and some common diluents (carbonate, borate) and
region (7.7–9.0) that needs to be used for the separation of the target
adulterants (levamisole and lidocaine).
compounds by CZE (Fig. 1), the EOF velocity using fused silica capillary
Recently, a method for simultaneous determination of cocaine and
is high and the simultaneous separation of anions and cations in a single
three common adulterants (levamisole, lidocaine and procaine) in
run can be performed in two ways: (i) using normal EOF, where cations
seized cocaine samples was proposed by CE-C4D using boric acid/

Table 3
Recovery for the analysis of spiked seized cocaine samples. Mean values are based on 3 analytical determinations. (concentration mg g−1).
Analyte Sample 1 Sample 2 Sample 3 Sample 4 Sample 5 Sample 6

Add Rec Add Rec Add Rec Add Rec Add Rec Add Rec

Cl- 14.0 114% 7.0 81% 7.0 113% 7.0 96% 3.5 85% – –
NO2− 18.0 118% 18.0 93% 23.0 88% – – 9.2 98% 23.0 107%
NO3− 24.8 112% 12.4 81% 37.2 91% 31.0 92% 12.4 72% – –
SO42- 38.4 84% 38.4 102% 57.6 86% 19.2 100% 9.6 114% – –
CO3− 24.0 83% 24.0 98% 36.0 150% 12.0 83% 6.0 112% – –
BO3−3 58.8 117% 2.0 130% 117.6 105% – – – – 58.1 101%
Levamisole 40.9 103% 81.7 116% 122.5 92% – – – – – –
Lidocaine 46.9 103% 93.7 114% – – – – – – – –
Cocaine 151.7 98% 303.4 100% 151.7 88% 151.7 106% 151.7 75% 151.7 106%

3
D.N. Barreto, et al. Talanta 217 (2020) 120987

Table 4
Mean values (mg g−1) for the determination of nine analytes in seized cocaine samples.
Sample Cl− NO2− NO3− SO42- CO32- BO33- LEV LID COC

1 < LOD < LOD < LOD < LOD < LOD 838.9 29.8 < LOD 94.6
2 5.3 5.5 < LOD < LOD < LOD 453.8 < LOD < LOD 97.8
3 58.7 2.8 < LOD < LOD 23.1 95.2 441.0 57.2 205.7
4 < LOD < LOD < LOD < LOD < LOD 641.2 < LOD < LOD 123.4
5 7.3 23.6 3.3 8.2 < LOD 611.6 < LOD < LOD 84.7
6 < LOD < LOD < LOD < LOD < LOD 671.4 31.3 < LOD 86.8
7 10.5 37.0 2.2 7.8 11.4 < LOD 62.9 21.5 145.9
8 90.3 < LOD < LOD < LOD 16.0 < LOD 121.3 < LOD 362.5
9 28.5 < LOD < LOD < LOD 4.0 680.1 171.4 9.5 47.1
10 88.3 < LOD < LOD < LOD 36.72 < LOD 301.4 14.0 565.7
11 < LOD < LOD < LOD < LOD < LOD < LOD < LOD 6.7 98.8
12 5.3 11.6 < LOD 8.0 < LOD 631.4 50.6 < LOD 102.8
13 < LOD < LOD < LOD < LOD < LOD 624.1 < LOD < LOD 88.7
14 < LOD < LOD < LOD < LOD < LOD 739.0 < LOD < LOD 116.6
15 < LOD < LOD < LOD < LOD < LOD 104.6 32.0 9.3 107.3
16 < LOD < LOD < LOD < LOD 54.4 28.7 < LOD < LOD 26.2
17 93.7 4.5 5.5 < LOD 39.0 < LOD 551.8 155.77 273.2
18 < LOD < LOD < LOD < LOD < LOD 699.7 5.3 1.6 99.7
19 < LOD < LOD < LOD 10.6 < LOD 669.6 < LOD < LOD 90.4
20 23.4 < LOD < LOD < LOD 43.1 < LOD 213.7 124.94 239.7
21 < LOD < LOD < LOD < LOD < LOD 730.5 20.1 16.9 23.0
22 < LOD < LOD < LOD < LOD < LOD 773.2 < LOD < LOD 302.8
23 < LOD < LOD < LOD < LOD < LOD 598.3 < LOD < LOD 80.8
24 < LOD < LOD < LOD < LOD < LOD < LOD < LOD < LOD 86.8
25 51.9 < LOD < LOD < LOD 23.8 < LOD < LOD < LOD < LOD
26 < LOD < LOD < LOD < LOD < LOD < LOD < LOD < LOD 144.7
27 < LOD < LOD < LOD < LOD < LOD < LOD < LOD < LOD 121.4
28 < LOD < LOD < LOD < LOD 7.7 < LOD < LOD < LOD 94.7
29 < LOD < LOD < LOD < LOD < LOD < LOD < LOD < LOD 138.8
30 < LOD < LOD < LOD < LOD 84.9 < LOD < LOD < LOD 92.1
31 < LOD < LOD < LOD < LOD < LOD 684.8 < LOD < LOD 368.5
32 21.6 71.6 32.1 5.1 15.5 508.9 27.4 24.1 101.6
33 25.8 98.3 5.9 5.8 37.8 < LOD < LOD < LOD 0.5
34 2.9 5.96 < LOD < LOD < LOD 595.7 21.8 39.4 130.9
35 < LOD < LOD < LOD < LOD < LOD 640.0 32.9 < LOD 73.0
36 8.8 7.2 < LOD 4.3 2.4 798.3 < LOD < LOD 61.6
37 < LOD < LOD < LOD < LOD < LOD 699.3 < LOD 24.7 140.1
38 < LOD < LOD < LOD < LOD 151.2 < LOD < LOD < LOD < LOD
39 < LOD < LOD < LOD < LOD < LOD 770.2 < LOD < LOD 49.5
40 < LOD < LOD < LOD < LOD 619.8 < LOD < LOD < LOD 355.0
41 < LOD < LOD < LOD < LOD < LOD 388.2 < LOD < LOD 50.4
42 < LOD < LOD < LOD < LOD 42.9 < LOD < LOD < LOD 54.5
43 < LOD < LOD < LOD < LOD < LOD 915.5 < LOD < LOD 98.4
44 7.0 < LOD < LOD < LOD < LOD 788.3 < LOD < LOD 107.7
45 65.6 < LOD < LOD < LOD 20.5 74.3 181.8 86.8 281.5
46 38.67 < LOD < LOD < LOD 14.5 < LOD < LOD < LOD 454.1
47 10.1 17.6 < LOD 5.3 7.9 774.0 < LOD < LOD 134.3
48 15.2 73.7 4.9 9.0 20.7 < LOD < LOD 213.9 52.1
49 23.7 68.6 3.3 8.6 18.0 < LOD < LOD 210.9 70.6
50 < LOD < LOD < LOD < LOD < LOD 960.5 < LOD < LOD 45.3

are carried toward the detector in co-EOF-mode (EOF + electro-
phoretic velocity) and anions with low mobility in counter-EOF-mode
(EOF velocity ≫ analyte electrophoretic velocity); (ii) using reverse
EOF, where anions are carried toward the detector in co-EOF-mode
(EOF + electrophoretic velocity) and cations with low mobility in
counter-EOF-mode (EOF velocity ≫ analyte electrophoretic velocity).
In both ways (i and ii), anions and cations with high electrophoretic
velocity, respectively, usually do not reach the detector. According to
previous knowledge, inorganic ions with high electrophoretic velocity
(Cl– NO2−, NO3−, SO42−) are commonly present in seized cocaine
samples (impurities). Therefore, in this work, the inverted EOF mode
(ii) was selected for subsequent studies. As EOF modifier, CTAB was
selected [38,39].
To find the optimal pH value for the simultaneous separation of all
target analytes (according Fig. 1), studies were performed in the pH
range between 7.7 and 9.0. Efficient separation of the target analytes
was obtained at pH 8.8. In these conditions, cocaine and some common
diluents (carbonate, borate), adulterants (levamisole and lidocaine),
and inorganic ions (Cl– NO2−, NO3−, SO42−) could be separated and
detected in a single run (~2.5 min).
The effect of parameters, such as the concentration of CTAB (Fig.
S1) and TAPS (Fig. S2), injection time (Fig. S3) and separation potential
(Fig. S4), were evaluated. Table 1 shows the studied ranges and the
selected values for subsequent studies. The optimized values were se-
lected according to the best performance in buffering capacity, sensi-
tivity and peak shape (TAPS concentration), robustness and stability of
the reversed EOF (CTAB concentration), adequate resolution for all
target analytes (capillary length), sensitivity and resolution (injection
time), and shorter analysis time with baseline stability (separation po-
tential).
The precision of the method was evaluated by 12 successive injec-
tions (Fig. 2) of a solution containing all target analytes using the op-
timized operating conditions (Table 1), performed by the same analyst,
and in the same day (intra-day precision) and in five separate days
(inter-day precision). The relative standard deviation values were lower
than 7% and 14% in intra-day and inter-day studies, respectively.
The LODs were obtained experimentally and ranged from
0.015 mmol L−1 to 0.3 mmol L−1 for a 1.0 s injection time. The linear

4
D.N. Barreto, et al.
ranges (concentration as a function of conductivity variation) for the
determination of the nine species of interest were evaluated simulta-
neously, and the following results were obtained: 0.05–7.0 mmol L−1
for COC, 0.1–0.8 mmol L−1 for LEV and LID, 0.1–1.0 mmol L−1 for Cl−,
0.05–2.0 mmol L −1 for NO2−, 0.05–1.2 mmol L−1 for NO3− and
SO42−, 0.05–1.0 mmol L for CO32− and 1.0–17.0 mmol L for BO33−.
Correlation coefficients were all better than or equal to 0.998. A sum-
mary of the analytical characteristics of the proposed CE-C4D method is
displayed in Table 2.
Spiked and recovery tests were performed by adding different
amount of standard solutions into the six samples for all species studied
(Table 3). Recoveries values were obtained in the range of 72–118% for
all samples, which are considered as acceptable values [40], except for
borate (sample 2) and carbonate (sample 3).
The developed method was applied to the determination of cocaine,
levamisole, lidocaine, CO32−, BO33−, Cl−, NO2−, NO3− and SO42− in
cocaine seizure. An example of a typical full scan electropherogram is
displayed in Fig. 3. Table 4 shows the results for the samples analysed
by the proposed method. All the samples were seized in the Minas
Gerais state. The cocaine concentrations ranged from 0.5 to
565.6 mg g−1. Levamisole was detected in 34% of the samples and the
concentrations ranged from 5.3 to 551.8 mg g−1. Lidocaine was de-
tected in 32% of the samples and ranged from 1.6 to 213.9 mg g−1.
Carbonate concentration was present in the samples in the range from
2.4 to 619.8 mg g−1 and borate in the range from 28.7 to 960.5 mg g−1,
and were found in 44% and 60% of the samples, respectively. The
presence of chloride, nitrite, nitrate and sulphate was confirmed in
42%, 26%, 14% and 2%, respectively. The quantification of all species
was possible only in the sample 32.
Other adulterants found in seized cocaine [41], such as caffeine and
benzocaine, could be detected by CE-C4D considering previous reports
that used CE for the determination of both species [42,43]. However,
the BGE needs to be adjusted to a different pH value or mixed with
complex agents to enable the detection of such adulterants in seized
cocaine. Future investigations are required for this aim.
4. Conclusions
The procedure based on CE-C4D developed in this work presented
satisfactory linearity, selectivity, accuracy, precision and robustness for
the analysis of cocaine and some adulterants. Cocaine, levamisole and
lidocaine simultaneous determinations by CE-C4D were previously re-
ported in the literature. Importantly, two other diluents (borate and
carbonate) and four species (Cl−, NO2−, NO3−, SO42−) could be de-
termined simultaneously in seized cocaine samples. It is important to
highlight that this is the first procedure for borate determination re-
ported in the literature. Several desirable characteristics were obtained
in this work, such as a short analysis time and small amount of solvent
consumption, inherent to CE analysis. Alternatively, the cationic and
anionic profile performed on CE-C4D can be used as a screening tool to
aid the Police investigations to obtain preliminary information of the
constituents in seized cocaine which may be give a correlation between
trafficking flow, as well as the local cocaine supplies.
CRediT authorship contribution statement
Diandra N. Barreto: Conceptualization, Methodology, Validation,
Formal analysis, Writing - original draft. Michelle M.A.C. Ribeiro:
Methodology, Validation, Formal analysis, Writing - original draft.
João T.C. Sudo: Conceptualization, Formal analysis, Investigation,
Resources. Eduardo M. Richter: Conceptualization, Methodology,
Resources, Writing - review & editing, Supervision, Funding acquisi-
tion. Rodrigo A.A. Muñoz: Conceptualization, Resources, Writing -
review & editing, Funding acquisition. Sidnei G. Silva:
Conceptualization, Investigation, Resources, Writing - original draft,
Writing - review & editing, Supervision, Project administration,
5
Talanta 217 (2020) 120987
Funding acquisition.
Declaration of competing interests
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influ-
ence the work reported in this paper.
Acknowledgements
The authors would like to thank the financial support from National
Council for Scientific and Technological Development (CNPq, process
number: 425494/2018–7, 307271/2017–0 and 465389/2014-7-
INCTBio) and Coordination for the Improvement of Higher Education
Personnel (CAPES, financial code 001). Support from the Minas Gerais
State Agency for Research and Development (FAPEMIG, RED-00042-1)
and Integrated Forensics Post (PPI) of the Minas Gerais Civil Police
(Uberaba, Minas Gerais State, Brazil) is greatly appreciated.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.talanta.2020.120987.
References
[1] N. Violante, M.G. Quaglia, A. Lopez, S. Caroli, Characterization of cocaine and
heroin samples as a function of their trace element content: an analytical pilot
study, Microchem. J. 45 (1992) 79–89, https://doi.org/10.1016/0026-265X(92)
90075-E.
[2] A.F. da Silva, T.S. Grobério, J.J. Zacca, A.O. Maldaner, J.W.B. Braga, Cocaine and
adulterants analysis in seized drug samples by infrared spectroscopy and MCR-ALS,
Forensic Sci. Int. 290 (2018) 169–177, https://doi.org/10.1016/j.forsciint.2018.07.
006.
[3] E.J. Magalhães, C.C. Nascentes, L.S.A. Pereira, M.L.O. Guedes, R.A. Lordeiro,
L.M.L.A. Auler, R. Augusti, M.E.L.R. de Queiroz, Evaluation of the composition of
street cocaine seized in two regions of Brazil, Sci. Justice 53 (2013) 425–432,
https://doi.org/10.1016/j.scijus.2013.05.003.
[4] A.O. Maldaner, É.D. Botelho, J.J. Zacca, M.A. Camargo, J.W. Braga, T.S. Grobério,
Brazilian federal district cocaine chemical profiling - mass balance approach and
new adulterant routinely quantified (Aminopyrine), J. Braz. Chem. Soc. 26 (2015)
1227–1231, https://doi.org/10.5935/0103-5053.20150088.
[5] J. Broséus, S. Huhtala, P. Esseiva, First systematic chemical profiling of cocaine
police seizures in Finland in the framework of an intelligence-led approach,
Forensic Sci. Int. 251 (2015) 87–94, https://doi.org/10.1016/j.forsciint.2015.03.
026.
[6] L.E.C. Benedito, A.O. Maldaner, A.L. Oliveira, An external reference 1H qNMR
method (PULCON) for characterization of high purity cocaine seizures, Anal.
Methods 10 (2018) 489–495, https://doi.org/10.1039/c7ay02343j.
[7] M.C.A. Marcelo, T.R. Fiorentin, K.C. Mariotti, R.S. Ortiz, R.P. Limberger,
M.F. Ferrão, Determination of cocaine and its main adulterants in seized drugs from
Rio Grande do Sul, Brazil, by a Doehlert optimized LC-DAD method, Anal, Methods
8 (2016) 5212–5217, https://doi.org/10.1039/c6ay01157h.
[8] S.F. Lapachinske, G.G. Okai, A. dos Santos, A.V. de Bairros, M. Yonamine, Analysis
of cocaine and its adulterants in drugs for international trafficking seized by the
Brazilian Federal Police, Forensic Sci. Int. 247 (2015) 48–53, https://doi.org/10.
1016/j.forsciint.2014.11.028.
[9] L. Harper, J. Powell, E.M. Pijl, An overview of forensic drug testing methods and
their suitability for harm reduction point-of-care services, Harm Reduct. J. 14
(2017) 1–13, https://doi.org/10.1186/s12954-017-0179-5.
[10] J. Broséus, N. Gentile, P. Esseiva, The cutting of cocaine and heroin: a critical re-
view, Forensic Sci. Int. 262 (2016) 73–83, https://doi.org/10.1016/j.forsciint.
2016.02.033.
[11] E. Evans, C. Costrino, C.L. do Lago, C.D. Garcia, C. Roux, L. Blanes, Determination
of inorganic ion profiles of illicit drugs by capillary electrophoresis, J. Forensic Sci.
61 (2016) 1610–1614, https://doi.org/10.1111/1556-4029.13175.
[12] T.M. Brunt, J. van den Berg, E. Pennings, B. Venhuis, Adverse effects of levamisole
in cocaine users: a review and risk assessment, Arch. Toxicol. 91 (2017) 2303–2313,
https://doi.org/10.1007/s00204-017-1947-4.
[13] R. Solimini, M.C. Rotolo, M. Pellegrini, A. Minutillo, R. Pacifici, F.P. Busardò,
S. Zaami, Adulteration practices of psychoactive illicit drugs: an updated review,
Curr. Pharmaceut. Biotechnol. 18 (2017) 524–530, https://doi.org/10.2174/
1389201018666170710184531.
[14] S. Martello, M. Pieri, C. Ialongo, S. Pignalosa, G. Noce, F. Vernich, C. Russo,
F. Mineo, S. Bernardini, L.T. Marsella, Levamisole in illicit trafficking cocaine
seized: a one-year study, J. Psychoact. Drugs 49 (2017) 408–412, https://doi.org/
10.1080/02791072.2017.1361558.
D.N. Barreto, et al.
[15] T.R. Fiorentin, M. Fogarty, R.P. Limberger, B.K. Logan, Determination of cutting
agents in seized cocaine samples using GC–MS, GC–TMS and LC–MS/MS, Forensic
Sci. Int. 295 (2019) 199–206, https://doi.org/10.1016/j.forsciint.2018.12.016.
[16] F. Tagliaro, C. Antonioli, S. Moretto, S. Archetti, S. Ghielmi, M. Marigo, High-
sensitivity low-cost methods for determination of cocaine in hair: high-performance
liquid chromatography and capillary electrophoresis, Forensic Sci. Int. 63 (1993)
227–238, https://doi.org/10.1016/0379-0738(93)90276-G.
[17] E.J. Magalhães, C.C. Nascentes, L.S.A. Pereira, M.L.O. Guedes, R.A. Lordeiro,
L.M.L.A. Auler, R. Augusti, M.E.L.R. de Queiroz, Evaluation of the composition of
street cocaine seized in two regions of Brazil, Sci. Justice 53 (2013) 425–432,
https://doi.org/10.1016/j.scijus.2013.05.003.
[18] T.R. Fiorentin, M. Fogarty, R.P. Limberger, B.K. Logan, Determination of cutting
agents in seized cocaine samples using GC–MS, GC–TMS and LC–MS/MS, Forensic
Sci. Int. 295 (2019) 199–206, https://doi.org/10.1016/j.forsciint.2018.12.016.
[19] T.S. Grobério, J.J. Zacca, É.D. Botelho, M. Talhavini, J.W.B. Braga, Discrimination
and quantification of cocaine and adulterants in seized drug samples by infrared
spectroscopy and PLSR, Forensic Sci. Int. 257 (2015) 297–306, https://doi.org/10.
1016/j.forsciint.2015.09.012.
[20] W.W.F. Rocha, J.D.A. Leite, R.M. Correia, F. Tosato, N.C.L. Madeira, P.R. Filgueiras,
V. Lacerda, J.C.C. Freitas, W. Romão, Á.C. Neto, Quantification of cocaine and its
adulterants by nuclear magnetic resonance spectroscopy without deuterated sol-
vents (No-D qNMR), Anal. Methods 10 (2018) 1685–1694, https://doi.org/10.
1039/c7ay03000b.
[21] A.F. da Silva, T.S. Grobério, J.J. Zacca, A.O. Maldaner, J.W.B. Braga, Cocaine and
adulterants analysis in seized drug samples by infrared spectroscopy and MCR-ALS,
Forensic Sci. Int. 290 (2018) 169–177, https://doi.org/10.1016/j.forsciint.2018.07.
006.
[22] X. Cui, C. Ni, C. Liang, F. Gong, R. Wang, G. Chen, Y. Zhang, Screening and
quantitation of forty-six drugs of abuse and toxic compounds in human whole blood
by capillary electrophoresis: application to forensic cases, Microchem. J. 144
(2019) 403–410, https://doi.org/10.1016/j.microc.2018.09.031.
[23] M.C. Breadmore, W. Grochocki, U. Kalsoom, M.N. Alves, S.C. Phung, M.T. Rokh,
J.M. Cabot, A. Ghiasvand, F. Li, A.I. Shallan, A.S.A. Keyon, A.A. Alhusban, H.H. See,
A. Wuethrich, M. Dawod, J.P. Quirino, Recent advances in enhancing the sensitivity
of electrophoresis and electrochromatography in capillaries and microchips
(2016–2018), Electrophoresis 40 (2019) 17–39, https://doi.org/10.1002/elps.
201800384.
[24] A.S. Krawczeniuk, V.A. Bravenec, Quantitative determination of cocaine in illicit
powders by free zone capillary electrophoresis, J. Forensic Sci. 43 (1998) 14299J,
https://doi.org/10.1520/jfs14299j.
[25] C.L. Flurer, K.A. Wolnik, Chemical profiling of pharmaceuticals by capillary elec-
trophoresis in the determination of drug origin, J. Chromatogr. A 674 (1994)
153–163, https://doi.org/10.1016/0021-9673(94)85223-5.
[26] F. Tagliaro, C. Poiesi, R. Aiello, R. Dorizzi, S. Ghielmi, M. Marigo, Capillary elec-
trophoresis for the investigation of illicit drugs in hair: determination of cocaine
and morphine, J. Chromatogr. A 638 (1993) 303–309, https://doi.org/10.1016/
0021-9673(93)83442-U.
[27] M.C. Marra, B.M. De Castro Costa, R.A.A. Munoz, M.H.P. Santana, A.O. Maldaner,
É.D. Botelho, W.K.T. Coltro, E.M. Richter, Fast determination of cocaine and some
common adulterants in seized cocaine samples by capillary electrophoresis with
capacitively coupled contactless conductivity detection, Anal. Methods 10 (2018)
2875–2880, https://doi.org/10.1039/c8ay00795k.
[28] J.G. Alves Brito-Neto, J.A. Fracassi Da Silva, L. Blanes, C.L. Do Lago, Understanding
capacitively coupled contactless conductivity detection in capillary and microchip
electrophoresis. Part 1. fundamentals, Electroanalysis 17 (2005) 1198–1206,
https://doi.org/10.1002/elan.200503237.
Talanta 217 (2020) 120987
[29] P. Kubáň, P.C. Hauser, 20Th Anniversary of axial capacitively coupled contactless
conductivity detection in capillary electrophoresis, TrAC Trends Anal. Chem. 102
(2018) 311–321, https://doi.org/10.1016/j.trac.2018.03.007.
[30] P. Kubáň, H.T.A. Nguyen, M. Macka, P.R. Haddad, P.C. Hauser, New fully portable
instrument for the versatile determination of cations and anions by capillary elec-
trophoresis with contactless conductivity detection, Electroanalysis 19 (2007)
2059–2065, https://doi.org/10.1002/elan.200703908.
[31] M. Greguš, F. Foret, P. Kubáň, Portable capillary electrophoresis instrument with
contactless conductivity detection for on-site analysis of small volumes of biological
fluids, J. Chromatogr. A 1427 (2016) 177–185, https://doi.org/10.1016/j.chroma.
2015.11.088.
[32] T. Baciu, F. Borrull, C. Aguilar, M. Calull, Sensitivity enhancement in capillary
electrophoresis using magnetic particles as solid-phase extraction sorbents for the
determination of drugs of abuse in urine, Methods Mol. Biol. 1810 (2018) 89–96,
https://doi.org/10.1007/978-1-4939-8579-1_8.
[33] Y. Xu, W. Wang, S.F.Y. Li, Simultaneous determination of low-molecular-weight
organic acids and chlorinated acid herbicides in environmental water by a portable
CE system with contactless conductivity detection, Electrophoresis 28 (2007)
1530–1539, https://doi.org/10.1002/elps.200600654.
[34] A.A. Elbashir, H.Y. Aboul-Enein, Recent applications and developments of capaci-
tively coupled contactless conductivity detection (CE-C4D) in capillary electro-
phoresis, Biomed. Chromatogr. 28 (2014) 1502–1506, https://doi.org/10.1002/
bmc.3230.
[35] K.J.M. Francisco, C.L. Do Lago, A compact and high-resolution version of a capa-
citively coupled contactless conductivity detector, Electrophoresis 30 (2009)
3458–3464, https://doi.org/10.1002/elps.200900080.
[36] UNODC, Recommended Methods for the Identification and Analysis of Cannabis
and Cannabis Products, UNODC, Vienna, https://doi.org/10.18356/1e8e4f16-en.
2013.
[37] M. Swain, chemicalize.org, J. Chem. Inf. Model. 52 (2012) 613–615, https://doi.
org/10.1021/ci300046g.
[38] X.W. Yao, D. Wu, F.E. Regnier, Manipulation of electroosmotic flow in capillary
electophoresis, J. Chromatogr. A 636 (1993) 21–29, https://doi.org/10.1016/0021-
9673(93)80052-A.
[39] A.G. Diress, C.A. Lucy, Electroosmotic flow reversal for the determination of in-
organic anions by capillary electrophoresis with methanol-water buffers, J.
Chromatogr. A 1027 (2004) 185–191, https://doi.org/10.1016/j.chroma.2003.10.
081.
[40] UNODC, Guidance for the Validation of Analytical Methodology and Calibration of
Equipment Used for Testing of Illicit Drugs in Seized Materials and Biological
Specimens, UNODC, Vienna, 2009.
[41] J.M. Freitas, D.L.O. Ramos, R.M.F. Sousa, T.R.L.C. Paixão, M.H.P. Santana,
R.A.A. Muñoz, E.M. Richter, A portable electrochemical method for cocaine
quantification and rapid screening of common adulterants in seized samples,
Sensor. Actuator. B Chem. 243 (2017) 557–565, https://doi.org/10.1016/j.snb.
2016.12.024.
[42] R.R. Cunha, S.C. Chaves, M.M.A.C. Ribeiro, L.M.F.C. Torres, R.A.A. Muñoz,
W.T.P.D. Santos, E.M. Richter, Simultaneous determination of caffeine, para-
cetamol, and ibuprofen in pharmaceutical formulations by high-performance liquid
chromatography with UV detection and by capillary electrophoresis with con-
ductivity detection, J. Separ. Sci. 38 (2015) 1657–1662, https://doi.org/10.1002/
jssc.201401387.
[43] A.S. Junger, F.F.S. Jesus, J.A. Fracassi da Silva, D. Daniel, D.P. Jesus, A simple and
fast method for determination of benzocaine and lidocaine in pharmaceutical for-
mulations by capillary electrophoresis with spectrophotometric detection, Sep. Sci.
Plus 2 (2019) 422–427, https://doi.org/10.1002/sscp.201900054.