Chemical Data Collections 30 (2020) 100562

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Chemical Data Collections

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A simple method of detection of 15 organochlorine pesticides

in human plasma using gas chromatography
Bouchra Birich a,b,∗, Souad El Hajjaji a,∗, Mohammed Ghandi a,b, Naima Ait
Daoud b, Narjis Badrane b, Rachida Bencheikh Soulaymani b
a
Mohammed V University in Rabat, Faculty of sciences, LS3MN2E-CERNE2D, Department of chemistry, 4 Avenue Ibn Battouta B.P. 1014
RP, Rabat, Morocco
b
Poison Control and Pharmacovigilance Centre of Morocco (CAPM), Laboratory of Toxicology and Pharmacology, Rue Lamfedel Cherkaoui,
Instituts Madinate Al Irfane, B.P. 66 71, Rabat, Morroco

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

Article history: The organochlorine (OCs) compounds are extremely toxic for human and are responsible
Received 6 March 2020 for a significant number of poisoning. Nowadays, the detection of OCs in biological sam-
Revised 5 September 2020
ples is highly recommended for agricultural countries. Many studies refer to this goal. Our
Accepted 5 October 2020
study reports a simple detection of 15 OCs pesticides (Alpha-Lindane, Beta-Lindane, Lin-
Available online 7 October 2020
dane, Aldrin, Dieldrin, Heptachlore, Alpha-Chlordane, Gamma-Chlordane, HCB, o,p’-DDE,
Keywords: p,p’-DDE, o,p’-DDT, p,p’-DDT, p,p’-DDD and o,p’-DDD) in human plasma by gas chromatog-
Organochlorine pesticides raphy coupled with mass spectrometry (GC–MS) using a liquid extraction. The purpose of
Plasma our study was to optimize the temperature program, the extraction method and the matrix
Liquid extraction effect. We used three programs and two extraction methods with or without deproteiniza-
Temperature program tion. We found that the first extraction method detects 11 of 15 OCs. According to our
GC–MS results, the method is optimized. It can be used for OCs’ determination in human plasma
for poisoning cases diagnosis or for biomonitoring of workers.
© 2020 Published by Elsevier B.V.

Specifications Table

Subject area Analytical Chemistry

Compounds Alpha-Lindane, Beta-Lindane, Lindane, Aldrin, Dieldrin,
Heptachlore, Alpha-Chlordane, Gamma-Chlordane, HCB,
o,p’-DDE, p,p’-DDE, o,p’-DDT, p,p’-DDT, p,p’-DDD and
o,p’-DDD
Data category Chromatographic and Spectrometric
Data acquisition format Chromatograms (GC–MS)
Data type Analyzed
Procedure For this optimization, we try to enhance the detection of
OCs, by adjusting all the parameters influencing the
detection. The temperature program, the extraction method
and the matrix effect was optimized. There is three
programs and two extraction methods with or without
deproteinization with GC–MS analysis.
Data accessibility Data is with this manuscript.

∗
Corresponding authors.
E-mail addresses: bouchra.birich1@gmail.com (B. Birich), souad.elhajjaji@um5.ac.ma (S. El Hajjaji).

https://doi.org/10.1016/j.cdc.2020.100562
2405-8300/© 2020 Published by Elsevier B.V.
B. Birich, S. El Hajjaji, M. Ghandi et al. Chemical Data Collections 30 (2020) 100562

1. Rationale

For many years, the use of pesticides has produced high yields. This state pushed researchers to think out new synthetic
products for agriculture and public health. However, the misuse or the overuse of these compounds may be responsible of
many health and environmental harms.
According to the World Health Organization (WHO), there is one to five million cases of pesticide intoxication per year,
with many mortalities [1]. Nevertheless, the persistence, the wide dissemination and the ability to accumulate in organ-
isms; can enhance toxic effects of pesticides and causes negative impacts on health and well-being [2]. In 1960s, researchers
demonstrated that organochlorine pesticides) (OCs), caused physiological and environmental perturbations. Then the Stock-
holm Convention, an international pact started in 2004, aims to protect human health and the environment against Persis-
tent Organic Pollutants (POPs), including OCs, by prohibiting their use [3].
Besides, the OCs are still used in agricultural areas and continue to be a source of human poisoning. Many studies aim to
target those compounds in biological samples; in blood [4,5], serum [6-8], or even breast milk [9-11]. In several cases, those
pesticides are the cause of many acute [12] and chronic intoxications [13-14]. Various studies reports that an exposure to
this molecule may cause serious effects on human health (cancer, non-Hodgkin lymphoma [15], diabetes or thyroid diseases
[16] and effect on neurodevelopment of newborn [17]).
Gas chromatography (GC) is the most analytical technic used to determine pesticides in biological samples. Its efficiency
is related to sensitivity and the capacity to separate mixture of analytes [18]. Therefore, OCs analysis requires a GC technic
because of their thermolability.
In chromatography, there is various parameters interfering a separation: the pretreatment step, the extraction method,
the column, the flow, the temperature program, mobile phase, stationary phase…etc. An optimization step is always required
to build a selective method. The compound suppression or enhancement is reported for blood or plasma in toxicology
[19]. These two samples are complex, as they contain ions, proteins, lipids, glucose, vitamins, hormones and gasses [20].
Therefore, before analysis, it is recommended to remove proteins and other interfering substances to avoid injectors’ damage
[21]. This elimination is generally conducted by precipitation followed by filtration or centrifugation step. Different agents
are used with dissimilar modes of action to raise precipitation, specifically, organic solvents (acetonitrile (ACN) and methanol
(MeOH)) [22].
There are many extraction methods in toxicology and biomonitoring field used for the detection of pesticides other that
Liquid-Liquid Extraction (LLE) such as Liquid Phase Micro Extraction (LPME) [23-25], Solid Phase Extraction (SPE) [26] and
Solid Phase Micro Extraction (SPME) [27]. The LLE is the most used in toxicological analysis because of the low cost and the
time consuming of this extraction method.
In this context, the toxicological laboratory of Poison Control and Pharmacovigilance centre of Morocco (CAPM), a part
of the Moroccan study on POPs, focuses on improving the analytical method of OCs’s detection in human samples. The aim
of this work is to develop a simple method of detection of 15 OCs in human plasma by Gas Chromatography with a mass
spectrometer detector (GC–MS), in purpose to show the importance of toxicological analyzes support in the treatment of
pesticides’ intoxications.

2. Procedure

2.1. Instruments

2.1.1. GC–MS
Analysis are performed with the 680 PerkinElmer Clarus GC–MS and a column RESTEK RXI  R
5 ms (30 m × 0.25 mm,
250 mμ).The carrier gas is helium with 0.1 ml/min flow rate.
Mass spectrometry detector used an electron ionization mode with an ionization energy of 70 eV. The ion source tem-
perature was 250 °C.

2.1.2. Reagents
Mixture of 15 OCs (Alpha-Lindane, Beta-Lindane, Lindane, Aldrin, Dieldrin, Heptachlore, Alpha-Chlordane, Gamma-
Chlordane, HCB, o,p’-DDE, p,p’-DDE, o,p’-DDT, p,p’-DDT, p,p’-DDD and o,p’-DDD) prepared in acetone (10 ppm).
Human plasma was from the national transfusion center of Morocco in Rabat.
Solvents (MeOH, acetone, ACN, Hexane, Diethyl ether) were purchased from Sigma Aldrich.

2.1.3. Sample preparation

1 mL of plasma, 100 μL of the mixture of OCs (100 ppm), 50 μL of prazepam (internal standard) and 1 mL of depro-
teinization solvent, are mixed and centrifuged for 10 min at 20 °C. The organic supernatant was evaporated with nitrogen
gas at 40 °C. The solution is eluted with 100 μL of MeOH and injected in GC–MS.
The use of the prazepam as an internal standard is due to its availability in the laboratory. A deuterated standard is out
of reach because of its high cost. This compound is commonly used in the CAPM laboratory for optimized screening with
known retention time (Rt) and stability in GC–MS.

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Table 1
The temperature programs selected for the first optimization.

1st program 2nd program 3rd program

Initial temperature 80 °C for 2.5 min 90 °C for 1 min 40 °C for 1 min

Ramp 1 50 °C / min 140 °C for 0 min 12 °C / min 150 °C for 1 min 20 °C / min 150 °C for 0 min
Ramp 2 5 °C / min 260 °C for 3 min 2 °C / min 230 °C for 3 min 5 °C / min 300 °C for 5 min
Ramp 3 10 °C / min 275 °C for 25 min
Injection temperature 200 °C 240 °C 230 °C
Total analysis time 32 min 80 min 42 min

Table 2
The extraction methods selected for optimization.

Extraction Solvents Deproteinization solvents

Extraction N°1 [12] Hexane ACN

Extraction N°2 [21] N hexane/ diethyl ether MeOH

Table 3
The retention times and the percentage matching of molecules detected by
the selected temperature programs.

1st program 2nd program 3rd program

Molecules Rt % Rt % Rt %

Aldrin 17.95 97 17.87 94.6 24.15 98.3

Alpha-Lindane 13.34 40.8 13.26 43.1 14.9 33.2
Beta-Lindane 14.21 27.4 14.14 27 16.63 33.6
Chlordane 20.7 53.6 20.61 50.8 30.44 49.1
Dieldrin —- —- —- —- 32.18 84
Gamma-Chlordane 20.17 46.2 20.07 45.4 —- —-
HCB 13.6 39.1 13.54 40.9 15.34 59.8
Heptachlore 16.77 98.1 16.67 96.5 21.68 98.2
Lindane 15.18 26.8 —- —- —- —-
O,p’-DDD 21.77 32.1 21.67 31.9 —- —-
O,p’-DDE —- —- —- —- 32.57 57.7
O,p’-DDT 23.04 48.7 22.94 12.47 36.11 41.3
P,p’-DDE 21.48 54.3 21.4 52.7 — —
P,p’-DDD —- —- 22.86 49.2 36 38.1
P,p’-DDT 22.94 48.1 —- —- —- —-

2.1.4. Optimization
There are several steps in a toxicological analysis: sampling, sample preparation, extraction, detection and data analysis.
Obviously, the sample preparation is a critical step [22]. For a successful detection, all the steps must be perfectly operated.
In this study, we optimized the temperature program, the extraction method and the matrix effect using two different
solvents.

2.1.4.1. The effect of temperature program. The temperature program is the first parameter optimized. We choose three pro-
grams with different analysis times and injection temperatures (Table 1).

2.1.4.2. The matrix effect. To overcome matrix effect, we use ACN and MeOH for protein precipitation.

2.1.4.3. The effect of the extraction method. We choose an easy operational LLE method with simple equipment. It is about
changing both, the extraction solvent and the deprotenization one, for the tow extraction methods (Table 2).

3. Data, value and validation

The main objective of this study is to optimize the detection of OCs in plasma by LLE using GC–MS. This is the first
study in Morocco interested in the detection of OCs in human samples. It is an optimization of the detection influencing
parameters of these insecticides in human plasma, namely the temperature program, the extraction method and the matrix
effect.

3.1. Temperature program

The injection of the spiked samples for the three programs shows different retention times (Rt). An interesting percentage
matching with GC–MS NIST Library (Table 3) and selective chromatograms are found (Fig. 1).

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Fig. 1. The chromatograms detected successively with the three programs.

We observe that the modification of the Rts is due to the changed temperature program. Each compound will act differ-
ently according to the temperature used for heat. The percentages are almost equal for the same compound, for example;
Aldrine has 97%, 94.6% and 98.3% respectively for the three programs.
Only in 32 min, we detected 13 OCs using the first program. The second program detects, in 42 min, just 12 compounds
but with a well-separated peaks. The third program also detects 12 OCs with better separation, but in 80 min for a single
analysis, a very long time for emergency testing.
Our data show that the three temperature programs can be applied for the detection of the studied OCs, with a detection
of 87% of the starting molecules. However, the first program shows a detection of a significant number of molecules, good
peak’s resolution and reasonable time of analysis. This program is used for the next extraction step. The table 4 summarizes
the results of the three temperature programs.

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Fig. 1. Continued

Table 4
Summary of organochlorines detected for the three temperature programs.

Temperature program Analysis time (min) OCs detected Quality of separation

N°1 (chromatogram A) 32 13 Accepted

N°2 (chromatogram B) 80 12 Accepted
N°3 (chromatogram C) 42 12 Not accepted

Table 5
Comparison of Retention time found with those found by the
author M. Frias et al.

Molecules Rt found (min) Rt of M. Frias et al. (min)

HCB 13.60 12.71

Aldrin 17.95 16.49
P,p’-DDE 21.48 20.30
O,p’-DDT 23.04 22.34

3.2. Extraction methods and matrix effect

The first extraction shows a chromatogram with many interference’s peaks. We hardly see peaks related to our com-
pounds (Fig. 2). For both methods of extraction, the presence of deproteinizing solvent decrease the number of chromato-
graphic peaks, but enhance the recovery rate (Table 6). Therefore, an extraction with a deproteinization solvent is needed.
The first extraction method detected 11 OCs with or without ACN. For the second one, the presence of MeOH helps to detect
just 10 OCs and eight without it.
The evaluation of extraction methods requires calculation of the recovery rate. As shown in Table 6, many OCs reached
good rates for the two method (Lindane and DDT). The calculation shows considerable recovery for both extraction methods,
but the first one can detect a large number of OCs.
We note that the results for the extraction methods are comparable to those obtained by K.Subramaniam and J. Solomon
[12] and M. Frias et al. [20] (Table 5), because we could detect, Lindane, Alderine, p,p’-DDE, o,p’-DDT and p,p’-DDT for the
first extraction and HCB and DDE for the second one. Among the 15 OCs spiked, 11 were detected for the first method and
10 for the second one. There is a significant effect of MeOH, this solvent could add two molecules to the list (Table 6). This
method is simple and can detect OCs in human plasma with a GC–MS.

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Fig. 2. The chromatograms of OCs detected by the two extraction methods.

The detection of OCs is done with other extraction methods and technics. J.R. Barr et al. [28] detected 11 OCs in human
serum using SPE method and GC–High Resolution Mass Spectrometry (HRMS) analysis. For instance, HCB is detected at
6.40 min and o,p’-DDT at 15.58. This Rts are related to the technic and extraction method. R.Lopez et al. [29] proposed a
simple procedure for the determination of OCs in human serum by developing a headspace solid-phase microextraction (HS-
SPME). They consumed 50 min for the extraction step using an SPE C18 and clean-up with sulfuric acid/silica gel column.
In this method, the author used hexane-dichloromethane elution under nitrogen. However, for this proposition, the sample
is reconstituted in cyclohexane before GC analysis. HCB, p,p’- DDE and p,p’- DDT was respectively detected at; 12.88, 28.60
and 36.94 min.

Conclusion

The aim of this work was to develop and optimize an OCs’ detection method in human plasma by GC–MS, to contribute
to the diagnostic of OCs intoxication and biomonitoring. We carried out the study of three different temperature programs
and two LLE methods with or without deproteinization.

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Fig. 2. Continued

According to the results, the program with 200 °C as an injection temperature, gave well-separated peaks and detected
13 OCs just in 32 min. Using ACN in the extraction method, as deproteinization solvent, enhanced the detection of OCs. This
method is simple for the detection of 11 OCs pesticides in human plasma using GC–MS. This is a perfect method to validate
for biomonitoring and intoxication studies.

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.

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Table 6
The recovery rate related to the extraction methods.

Extraction N°1 Extraction N°2

Molecules With ACN Without ACN Without MeOH With MeOH

Aldrin ——— ——— 144.25 56.96

Alpha-Chlordane 81.1 34.61 15.14 22.49
Alpha-Lindane 135.2 109.25 ———— 90.02
Beta-Chlordane ——— ——— 16.62 34.58
Beta-Lindane 142.01 110.56 ———– 46.21
Gamma-Chlordane 13.25 17.13 ——— ———
Heptachlore 13.64 32.42 124.83 16.58
HCB 44.9 14.99 24.12 10.29
O,p’-DDD 127.58 134.69 27.18 ———
O,p’-DDT 129.28 145.64 87.01 111.36
P,p’-DDE 12.24 33.65 47.8 77.95
P,p’-DDD 50.83 46.2 ——– 8.13
P,p’-DDT 11.42 13.14 ——— ———

Acknowledgments

The authors wish to acknowledge the Poison Control and Pharmacovigilance Center of Morocco (CAPM) and the National
Center of Scientific and Technical Research (CNRST) for the financial support for this study.

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