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Multiresidue Analysis of Pesticides in Fruits and Vegetables by Gas

Chromatography-mass Spectrometry

Article  in  Journal of Environmental Science and Health Part B · March 2007

DOI: 10.1080/03601230601123474 · Source: PubMed

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Journal of Environmental Science and Health Part B (2007) 42, 179–187
Copyright C Taylor & Francis Group, LLC

ISSN: 0360-1234 (Print); 1532-4109 (Online)

DOI: 10.1080/03601230601123474

Multiresidue analysis of pesticides in fruits and vegetables

by gas chromatography-mass spectrometry

M. ARAOUD2 , W. DOUKI3 , A. RHIM2 , M. F. NAJJAR3 and N. GAZZAH1

1
Ecole Supérieure des Sciences et Techniques de la Santé de Monastir, Tunisia
2
Laboratoire Régional de la Santé Publique de Monastir, Tunisia
3
Laboratoire de Biochimie-Toxicologie, EPS Fattouma Bourguiba de Monastir, Tunisia

A multiresidue method was assessed for the determination of several pesticides (organochlorine, organophosphorus, pyrethroids,
triazole, amidine) using gas chromatography/mass spectrometry. The extraction of pesticides was carried out by liquid-liquid extrac-
tion (LLE) and solid-phase extraction (SPE) using two types of columns (CN and C18). The extracts were cleaned by the addition
of florisil, the pesticides were separated by capillary column gas chromatography and detected by mass spectrometry in the electron
impact mode. The extraction using C18 column provided the best results for most of the analyzed pesticides. The majority of pesticides
recoveries from the four fruits and vegetables (apples, pears, tomatoes and pepper) were greater than 60%. Linearity and precision
were satisfactory. The estimated limits of detection and limits of quantification ranged from 0.01 to 0.1 mg/kg and from 0.02 to 0.3
mg/kg, respectively. The proposed procedure was found to be useful for the multiresidue analyses of pesticides in agricultural products
for routine monitoring programs.
Keywords: Pesticides; fruits; vegetables; gas chromatography/mass spectrometry.

Introduction pled to mass spectrometry (GC-MS or GC-MS-MS) to

Pesticides are applied worldwide to a broad variety of
crops to control pests and prevent diseases in order to in-
crease agricultural production. Moreover, owing to their
biocide activity and potential risk to consumers, concen-
tration of pesticides must always be minimal in fruits and
vegetables and have to be below the maximum residue lim-
its (MRL). The monitoring of pesticide residues in food
is nowadays a priority objective in pesticide research in
order to get extensive evaluation of food quality and to
avoid possible risks to human health. The development
of multiresidue methods is difficult, due to the fact that
compounds of different polarities, solubility and volatil-
ities have to be simultaneously extracted and analyzed.
Numerous analytical methods have been reported for the
determination of pesticide residues in various fruits and
vegetables.[1,2,3,4,5,6,7] Most of them used gas chromatog-
raphy (GC), either with electron-capture detection (ECD),
nitrogen-phosphorus detection (NPD) or flame photomet-
ric detection (FPD).[4,5,8,9,10] Other methods used GC cou-
have a highly selective detection.[2,7,11,12,13] High perfor-
mance liquid chromatography (HPLC) or simply liquid
chromatography with diode-array detection (DAD), MS or
fluorescence detection were also applied for the separation
of non-volatile and thermally labile compounds.[6,8,14] Mass
spectrometry is a very sensitive and selective technique for
both multiresidue determination and trace-level identifica-
tion of a wide range of pesticides. It can quantify and con-
firm the results by its full scan or selected ion monitoring
(SIM) spectra.[7,13] The aim of our work was the assessment
and the optimization of a multiresidue method for the deter-
mination of pesticides for the most widely used pesticides
(organochlorine, organophosphorus, pyrethroids, triazole
and amidine) in agriculture in the Sahel region of Tunisia.
The work also focused on SPE and clean-up procedures for
the multiresidue analysis method of various pesticides in
fruits and vegetables using GC/MSD.
Materials and methods

Address correspondence to Noureddine Gazzah, Ecole Reagents

Supérieure des Sciences et Techniques de la Santé de Monastir,
Avenue IBN SINA, 5000 Monastir, Tunisia. E-mail: noureddine. The solution and chemical reagents used (acetone,
gazzah@laposte.net dichloromethane, methanol, hexane, ethyl acetate and tri-
Received June 22, 2006. ethylamine) were of analytical grade and were obtained
180
from ProlaboTM , LabscanTM , and Carlo ErbaTM . The pes-
ticides studied were: Methomyl, Dichlorvos, Heptenophos,
Gamma-HCH, Heptachlor, Chlorpyriphos, Penconazole,
Bifenthrin, Tetradifon, Amitraze, Coumaphos, Cyfluthrin,
Cypermethrin, and Deltamethrin. The reference standards
of these pesticides were purchased from Dr. EhrenstorferTM
(Ausberg, Germany) which were of >80% certified purity.
Heptachlor was used as an internal standard. Individual
stock standard solution was prepared at 2 g/L in toluene
and stored in darkness. The working solutions were pre-
pared at 20 mg/L.
Materials for solid-phase extraction (SPE)
Two columns were separately evaluated for solid phase
extraction: octadecylsilane (C18) and cyanopropyl (CN)
containing each 500 mg of sorbent (500 mg/6 mL).
These columns were obtained from BAKERBONDTM and
CHROMABONDTM .
Samples
The studied fruits and vegetables (apples, pears, tomatoes
and peppers) were collected from local markets. Each ma-
trix was used as blank and to prepare fortified samples for
recovery assays.
Gas chromatography/mass spectrometry
Agilent Technologies 6890 gas chromatography with an
Agilent 5973 mass selective detector was employed. The
gas chromatograph was equipped with an Agilent 7683
autosampler and split/splitless capillary injection port.
Chromatographic separation was performed on a 30 m ×
0.25 mm I.D. HP-5, 5% dimethyl polysiloxane capillary col-
umn from (Agilent Technologies) with a 0.25 μm thickness
film. The oven temperature programme was 70◦ C (2 min),
25◦ C/min to 150◦ C (0 min), 3◦ C/min to 200◦ C (0 min) and
finally 8◦ C/min to 280◦ C (15 min). The carrier gas (helium)
flow rate was in constant flow mode at 1.0 mL/min. Splitless
injection of 1 μL volume was carried out at 250◦ C. The mass
spectrometer was operated in electron ionization mode with
transfer line temperature of 280◦ C and scan mode. Data
analyses were assured by software Chemstation (Agilent
TechnologiesTM ).
Preparation of samples and liquid-liquid extraction (LLE)
Each sample of fruits or vegetables (100g) was chopped,
blended at high speed for 2-3 min using a blender to achieve
the best sample homogeneity and was submitted to extrac-
tion. A 50 g portion of the homogenized crop sample was
weighed in a 100 mL beaker and spiked with 100 μL of stan-
dard working solution (20 mg/L). This portion was mixed
and homogenized successively with 30 mL acetone, 30 mL
Araoud et al.
of petroleum ether, and finally 30 mL of dichloromethane
(DCM) for 1 min using stirring bar. Afterward, the ho-
mogenate was centrifuged at 4000 rpm for 10 min. The
total organic phase was cleaned-up and then evaporated to
low volume at 35◦ C under a gentle steam of nitrogen. The
residue was redissolved in 1 mL of hexane-acetone (90:10,
v/v). Then 1 μL of this solution was injected into GC/MS
system.
Solid-phase extraction (SPE)
A 10g aliquot of previously homogenized sample of fruits
or vegetables was weighed in a 100 mL beaker, spiked with
100 μL of working solutions (20 mg/L) and mixed with
20 mL of acetone by vortexing for 2 min and centrifuged
at 3000 rpm for 5 min. The total recuperated supernatant
was passed through the column which had previously been
conditioned with 6 mL of ethyl acetate and then with 6 mL
of methanol followed by 8 mL of distilled water. The car-
tridge was washed with 2 mL of distilled water and then
was dried under stream of nitrogen for two minutes. The
pesticides were eluted with 2 mL of ethyl acetate with 1%
triethylamine and three times with 2 mL of ethyl acetate-
acetone (90:10, v/v). The eluate obtained was submitted to
clean-up and then evaporated to less than 1 mL under nitro-
gen at 35◦ C. The solvent exchange to hexane was performed
by adding two times 2 mL of hexane and evaporated to low
volume after each addition. The final residue was redis-
solved in 0.5 mL of hexane. Twenty microliters of internal
standard solution were added and 1 μL was injected into
GC/MS.
Clean-up procedure
One gramme of florisil was added directly to the super-
natant obtained by LLE or to the eluat recuperated after
SPE (CN and C18) procedure, then mixed for one minute
and centrifuged for 5 min at 3000 rpm to separate solid
from solution.
Validation
All validation procedures were performed using pesticide-
free fruits and vegetables. The detection limit (LOD) was
determined as the lowest concentration giving a response
of three times the average of baseline. The limit of quan-
tification (LOQ) was determined as the lowest amount of a
given pesticide giving a response of ten times the average of
baseline. The LOD and LOQ were determined in full scan
mode from sample of tomato fortified at 0.5 mg/kg.
The linearity in the response was studied with standard
solutions prepared in both blank matrix extract and pure
solvent. The concentration range studied was from 0.02 to
2 mg/kg.
Recovery studies were determined in triplicate at three
concentration levels (0.5, 1 and 2 mg/kg) for each type of
the studied matrix. The repeatability was assessed at three
Multiresidue analysis of pesticides in produce 181
Table 1. Mass spectral fragments and retention time of 14 pesticides studied

Pesticide TR (min) MM Main characteristic (m/z)

Methomyl 4.58 162 105, 88, 45, 71

Dichlorvos 5.98 220 109, 79, 185, 145, 220
Heptenophos 9.90 250 124, 89, 109, 77, 141, 215, 250
Gamma-HCH 13.66 288 183, 111, 219, 51, 77, 147, 85, 121, 156, 61, 96, 290
Heptachlor 17.04 370 100, 272, 65, 273, 135, 194, 337
Chlorpyriphos 19.55 349 197, 97, 314, 258, 210, 125, 169, 65, 109
Penconazole 21.33 283 248, 159, 213, 186, 250
Bifenthrin 29.05 422 181, 165, 141, 152
Tetradifon 29.58 354 159, 229, 356, 111, 75, 127, 175, 99, 220
Amitraze 30.34 293 121, 132, 147, 162, 293, 106, 77, 91, 42
Coumaphos 31.85 362 109, 226, 97, 364, 210, 125, 65, 89, 137, 182, 334
Cyfluthrin 32.46
32.76 433 163, 206, 226, 91, 77, 51, 127, 65, 151
32.81
Cypermethrin 32.96
33.12 415 163, 181, 91, 77, 127, 51, 152, 115, 209
33.24
33.30
Deltamethrin 36.18 503 181, 253, 77, 93, 51, 209, 152, 115, 65, 281, 297
TR: retention time, MM: molecular mass.

concentration levels (0.5, 1 and 2 mg/kg) by extraction and
analysis on the same day and in each level of fortified fruits
and vegetables samples. Three assays were performed for ev-
ery sample. For the reproducibility, spiked samples at three
concentration levels were analyzed each day for three days.
Results and discussion
The SPE columns had increased the purity of extracts
obtained and thus they decrease matrices effects that influ-
ence the analysis and the detection of studied compounds.
Recoveries were determined in triplicate for each pesti-
cide from a peach sample spiked with 1 mg/kg of pes-
ticides mixture. The recoveries (Table 2) were above 70%
for seven pesticides using SPE-C18, for six pesticides using

Optimization of chromatographic analysis

Table 2. Average recoveries of pesticides from a peach sample
Several tests were performed in order to obtain the best spiked with 1 mg/kg of pesticides mixture (n = 3) by LLE, SPE-
compromise separation-resolution of different groups of C18 and SPE-CN (% ± RSD)
the studied pesticides, in the shortest time. The chro-
Type of extraction
matogram of the studied standard pesticides is presented
in Figure 1. The retention time (RT) and main characteris- SPE
tic m/z for the 14 pesticides are presented in Table 1. The
prominent fragments were arranged in order of decreasing Pesticide LLE CN C18
magnitude. Methomyl ND ND ND
Dichlorvos 42 ± 26 ND 7±0
Comparison of extraction techniques Heptenophos 70 ± 14 14 ± 1 20 ± 0
Gamma-HCH 79 ± 11 29 ± 2 75 ± 4
The choice of the best method of extraction was based on Chlorpyriphos 86 ± 21 50 ± 3 90 ± 1
three parameters: the recovery, the purity of extracts, and Penconazole 64 ± 5 24 ± 2 60 ± 2
the number of pesticides extracted. The extraction was per- Bifenthrin 58 ± 20 80 ± 6 87 ± 8
formed three times for each method. Figure 2 shows chro- Tetradifon 72 ± 2 54 ± 6 77 ± 1
matograms of a spiked peach sample (1 ppm) obtained af- Amitraze ND 1±4 22 ± 1
ter extraction by LLE, SPE-C18 and SPE-CN and clean-up Coumaphos ND 78 ± 19 55 ± 3
Cyfluthrin 77 ± 35 85 ± 8 72 ± 12
with florisil. The extract obtained by LLE was less pure than
Cypermethrin 55 ± 33 82 ± 9 98 ± 7
those obtained by SPE methods. This extract contains a Deltamethrin 159 ± 7 126 ± 12 84 ± 3
co-extractive matrix (consisting of pigments, saturated and
unsaturated fatty acids) that interferes with the detection SPE: Solid-phase extraction; LLE: Liquid-liquid extraction; ND: Not
of pesticides at trace levels. detected, RSD: relative standard deviation.
182
Fig. 1. Gas chromatography/mass spectrometry (GC/MS) chromatograms (full-scan mode) of pesticides standard mixture
(20 μg/mL). Peaks: 1: Methomyl, 2: Dichlorvos, 3: Heptenophos, 4: Gamma-HCH, 5: Heptachlor, 6: Chlorpyriphos, 7: Penconazole,
8: Bifenthrin, 9: Tetradifon, 10: Amitraze, 11: Coumaphos, 12: Cyfluthrin, 13: Cypermethrin, 14: Deltamethrin.
LLE and only five pesticides by SPE-CN. Thus, the SPE-
C18 method was for the most of the studied pesticides the
best method of extraction except for some pesticides such as
dichlorvos and coumaphos. The recovery of dichlorvos, po-
lar organophosphorus (water solubility: 18000 mg/L), was
very low (6.98%) by SPE-C18. The coumaphos, unextracted
by LLE, was better extracted by SPE-CN (78.19%) than
SPE-C18 (25.26%). The SPE-C18 method seems to be the
best method of extraction for most studied pesticides and it
was selected to be validated. Methomyl, the only carbamate
studied, was undetectable by all methods tested. Although,
Kim et al.[16] had extracted this compound as well as other
carbamates (including carbofuran, carbaryl, isoprocarb,
bediocarb and aldicarb) by GC-ECD after derivatization by
trifluoromethyl benzylamine (TFBA). The average recover-
ies ranged from 67 to 94%. However, the best analysis of
carbamate pesticides was HPLC because of thermolability
and/or low volatility of these compounds.[14] Acetone was
selected as a solvent for extraction because of its effective-
ness for polar and non-polar pesticides from diverse ranges
of matrices.[13] Some studies had used methanol, ethyl ac-
etate and petroleum ether to extract residues of pesticides
from honey, water, fruits and vegetables.[5,9,13,17,18] Other
studies had applied a mixture of solvent. Lacassie et al.[11]
had used a mixture of acetone-DCM-hexane for extrac-
tion of nine pesticides from apples and pears. The method
applied by Harry et al.[9] was based on LLE with separa-
tory funnel using a mixture of propanol-petroleum ether
with the aim of extraction of non-polar organochlorines
Araoud et al.
and organophosphorus pesticides from fresh fruits and
vegetables.
Clean-up of sample extract
Whatever technique used for extraction, various compo-
nents with a higher molecular size such as lipids and
pigments are always present and need to be eliminated
to permit a more definitive identification of lower limit
residues and to minimize adverse effects on the detection
instruments.[19] Many clean-up procedures employ frac-
tionation of extracts based on polarity, as in liquid-liquid
partitioning and column chromatography, or adsorption
chromatography using either florisil, neutral alumina or
silica gel column.[19] The study of Schenck et al.[20] was
designed to determine the relative degree of sample clean-
up obtained by using various types of SPE columns, oc-
tadecylsilyl (C18), graphitized carbon black (GCB), amino-
propyl ( NH2 ) and primary-secondary amine (PSA),
strong anion exchange (SAX) or tandem (GCB + SAX,
and C18 + GCB + SAX). This study showed that the NH2
and PSA columns were found to provide the most effective
clean-up, removing the greatest number of sample matrix
interferences.[19]
Nakamura et al.[15] had used a florisil column for clean-up
step after LLE of 12 pyrethroids from fruits and vegetables.
Doong and Lee[10] had compared results of studies of four
different SPE procedures using octadecyl, tandem C18 and
florisil, alumina-N and florisil cartridges for the clean-up of
Multiresidue analysis of pesticides in produce 183

Fig. 2. Gas chromatography/mass spectrometry (GC/MS) chromatograms (full scan mode) of pesticides studied: (a) extracts of peach
sample spiked at 1 ppm obtained by SPE-C18, (b) LLE, (c) and SPE-CN, (d) florisil was used for clean-up. 1: Methomyl, 2: Dichlorvos,
3: Heptenophos, 4: Gamma-HCH, 5: Heptachlor, 6: Chlorpyriphos, 7: Penconazole, 8: Bifenthrin, 9: Tetradifon, 10: Amitraze, 11:
Coumaphos, 12: Cyfluthrin, 13: Cypermethrin, 14: Deltamethrin.
184 Araoud et al.

Fig. 3. Gas chromatography/mass spectrometry (GC/MS) chromatograms (full scan mode) of an extract of blank tomato samples
fortified at 2 mg/kg by pesticides studied (a) without and (b) with clean-up step.

OC pesticide residues in nine kinds of fatty and two kinds selective detection. Nevertheless, LOD of all compounds
of non-fatty samples extracted by soxhlet (SOX). Better were lower than the MRL admitted for these commodities.
recoveries were achieved using a tandem C18 and florisil The linearity in the response was studied with standard
column.[10] solution prepared in both blank matrix extract and pure
In our study, we performed a clean-up step by direct ad-
Table 3. Linear relationships for the pesticides in blank matrix
dition of florisil to the final extracts for reduction of both
extract, pure solvent, limit of detection (LOD) and limit of quan-
cost and analysis time. Figure 3 illustrates a comparison tification (LOQ)
of chromatograms of an extract of blank tomato samples
fortified at 2 mg/kg by pesticides studied with and without Linearity (r)
clean-up step. Some interferents that were not eliminated LOD LOQ
Pesticide (mg/kg) (mg/kg) Pure solvent Spiked matrix
by the clean-up procedure can be overcome owing to the
performances of the GC/MS Software like subtract and Dichlorvos 0.1 0.3 0.98 0.98
Extract Ion Chromatogram functions. Heptenophos 0.05 0.1 1.00 0.99
G-HCH 0.01 0.02 0.97 0.98
Heptachlor 0.01 0.02 1.00 0.99
Validation of method Chlorpyriphos 0.01 0.02 0.99 0.99
Penconazole 0.01 0.02 0.98 0.99
LOD and LOQ of studied compounds are summarized Bifenthrin 0.01 0.02 0.98 0.97
in Table 3. LOD varied from 0.01 mg/kg (lindane, hep- Tetradifon 0.01 0.02 0.99 0.99
tachlor, chlorpyriphos, penconazol, tetradifon, amitraze) to Amitraze 0.05 0.1 0.98 0.97
0.1 mg/kg for dichlorvos. These LOD were similar to those Coumaphos 0.05 0.1 0.98 0.99
of the study of Lacassie et al.[11] as well as for the LOQ that Cyfluthrin 0.05 0.1 0.99 0.98
Cypermethrin 0.05 0.1 0.99 0.98
were varied from 0.02 to 0.1 mg/kg except for dichlorvos
Deltamethrin 0.05 0.1 0.96 0.98
(0.3 mg/kg). According to Stajnbaher et al.,[13] LOQ of this
compound was 0.01 ppm by gas chromatography and mass r: coefficients of correlation.
 Table 4. Repeatability and reproducibility of the studied pesticides at three levels of concentration in fruits and vegetables

Repeatability (%) Reproducibility (%)

Matrix Pear Apple Tomato Pepper Pear Apple Tomato Pepper

concentration
(ppm) 0.5 1 2 0.5 1 2 0.2 1 2 0.5 1 2 0.5 1 2 0.5 1 2 0.5 1 2 0.5 1 2

Dichlorvos — 12.4 14.5 13.5 21.1 12.9 — 10.8 8.7 — — 8.7 — 16.9 30.7 25.6 21.8 13.7 — 25.5 11.2 — — 10.9
Heptenophos 19.1 13.9 18.5 7.0 22.7 25.8 24.7 8.5 5.8 18.7 15.6 15.1 28.7 22.5 19.8 4.9 20.2 27.1 24.6 9.6 13.5 9.3 22.7 12.4
Gamma-HCH 5.4 13.6 10.7 18.2 23.2 27.0 11.7 11.9 15.8 28.3 5.5 3.6 9.2 10.3 12.8 24.6 23.7 26.1 12.6 18.0 33.6 17.7 13.5 16.9
Chlorpyriphos 22.2 7.9 12.1 8.5 11.4 26.1 11.4 18.8 4.4 5.2 15.8 8.4 22.9 10.7 10.9 23.7 15.3 26.1 11.6 10.6 13.5 16.5 14.0 11.6
Penconazole 13.3 12.1 5.8 5.3 5.0 10.6 8.7 2.9 3.5 17.9 15.2 5.5 26.4 12.0 9.1 24.2 16.4 17.0 15.4 4.9 11.6 21.5 17.2 9.5
Bifenthrin 5.5 11.4 1.6 8.4 3.3 5.2 8.9 7.0 17.2 5.1 4.7 2.7 8.7 12.8 8.2 29.2 11.0 6.2 11.2 10.5 11.9 16.4 14.0 10.7
Tetradifon 7.5 7.6 6.6 12.8 4.5 3.4 6.8 9.0 6.0 6.9 13.3 9.2 20.2 22.2 13.2 14.9 23.8 6.9 13.7 18.2 12.6 19.1 16.9 12.7
Amitraze 13.0 27.6 3.4 14.8 16.0 9.4 14.0 25.9 14.5 — 4.3 18.1 11.4 31.2 6.8 23.4 15.0 16.1 16.9 34.8 8.8 — 17.2 24.6
Coumaphos 14.5 18.7 15.7 28.9 19.2 18.2 20.1 8.5 14.5 — 15.6 25.3 24.6 19.8 16.7 22.0 27.8 12.9 35.2 9.6 31.2 22.2 26.4 18.7
Cyfluthrin 16.1 13.1 5.1 12.1 12.9 19.6 8.0 8.6 13.9 13.7 17.7 9.2 17.4 16.9 14.2 20.9 24.6 17.1 12.6 15.3 14.2 16.1 18.8 10.0
Cypermethrin 18.1 8.4 17.3 15.7 13.5 13.4 7.2 8.1 5.2 7.6 12.9 15.3 10.6 22.9 13.2 26.2 25.5 19.0 15.1 13.9 16.2 17.0 12.7 16.8
Deltamethrin 8.0 9.3 2.5 13.5 21.1 12.9 13.9 4.3 2.8 3.4 18.1 4.1 21.4 16.9 13.1 8.1 21.2 18.7 25.3 21.1 11.6 6.3 17.7 11.0

185
186 Araoud et al.
Table 5. Recoveries (mean ± RSD, %) of the studied pesticides in fruits and vegetables (n = 3), using SPE-C18 and florisil

Matrix Pear Apple Tomato Pepper

concentration
(ppm) 0.5 1 2 0.5 1 2 0.4 1 2 0.5 1 2

Dichlorvos — 10 ± 1 8±0 1±0 18 ± 10 8±7 — 2±2 24 ± 14 — — 7±3

Heptenophos 9±2 8±1 7±1 9±1 10 ± 0 9±2 22 ± 7 4±5 8±0 4±4 2±1 18 ± 8
Gamma-HCH 14 ± 3 28 ± 3 17 ± 2 12 ± 12 19 ± 10 32 ± 9 36 ± 24 31 ± 20 26 ± 4 16 ± 4 13 ± 1 16 ± 4
Chlorpyriphos 73 ± 1.6 96 ± 6 59 ± 7 30 ± 13 54 ± 6 59 ± 14 64 ± 24 56 ± 15 27 ± 1 87 ± 5 34 ± 3 64 ± 18
Penconazole 14 ± 7 21 ± 3 14 ± 1 13 ± 9 33 ± 2 29 ± 13 54 ± 16 10 ± 8 33 ± 2 17 ± 6 8±1 18 ± 8
Bifenthrin 53 ± 3 58 ± 8 68 ± 1 51 ± 15 53 ± 2 85 ± 9 72 ± 17 64 ± 3 56 ± 8 83 ± 3 74 ± 13 106 ± 6
Tetradifon 31 ± 8 47 ± 2 33 ± 2 25 ± 1 51 ± 1 60 ± 17 53 ± 20 63 ± 10 50 ± 1 87 ± 10 38 ± 5 62 ± 18
Amitraze 15 ± 5 25 ± 1 18 ± 6 10 ± 2 30 ± 19 50 ± 20 58 ± 8 15 ± 15 7±1 — 35 ± 13 11 ± 12
Coumaphos 36 ± 19 96 ± 5 54 ± 14 48 ± 20 48 ± 9 63 ± 24 96 ± 12 49 ± 30 22 ± 3 14 ± 24 31 ± 8 50 ± 19
Cyfluthrin 44 ± 7 91 ± 12 77 ± 4 43 ± 20 93 ± 8 96 ± 18 10 ± 30 83 ± 9 67 ± 12 74 ± 7 118 ± 23 86 ± 10
Cypermethrin 49 ± 9 101 ± 7 95 ± 16 28 ± 14 69 ± 5 94 ± 13 109 ± 23 78 ± 7 100 ± 7 117 ± 7 142 ± 18 83 ± 7
Deltamethrin 56 ± 12 105 ± 8 89 ± 2 62 ± 21 74 ± 10 124 ± 18 112 ± 28 110 ± 18 81 ± 3 78 ± 2 116 ± 26 74 ± 4
RSD: relative standard deviation, SPE: Solid-phase extraction.

solvent. Integrated peak area data were used to construct
the curves. The linear relationships for the pesticides in
blank matrix extract and pure solvent are shown in Table 3.
In both cases, a linear correlation was observed for all com-
pounds in the studied range with a correlation coefficient
(r) between 0.96 and 1. The precision of the method was
demonstrated by repetitive analysis (Table 4). The method
provided satisfactory repeatability and reproducibility for
most compounds in the four studied matrix.
The recoveries of extraction procedure were studied by
spiking each type of the four matrix studied (n = 3). The
average recoveries were determined for each pesticides ma-
trix combinations at three concentration levels (Table 5).
Recoveries were high for moderately polar to non-polar
pesticides, but less than desired for the most polar one such
as dichlorvos and heptenophos. It had low average recov-
eries in some concentration levels. Nevertheless, even in the
case of the lowest recoveries, the overall repeatability and
sensitivity of the method were good enough to ensure a reli-
able determination at levels lower than the respective MRL.
The best recoveries were obtained for pyrethroid pesticides
(bifenthrin, cyfluthrin, cypermethrin and deltamethrin).
Conclusion
A proposed method using SPE-C18 extraction, florisil
for clean-up procedure and specific gas chromatography-
mass spectrometry detection permits the selective deter-
mination of 13 pesticides, from several compound classes
(organochlorine, organophosphorus, pyrethroids, triazole
and amidine), in four fruits and vegetables samples. Recov-
eries were better for apolar pesticides such as pyrethroids.
The LOD were lower than the MRL admitted for these
compounds in studied commodities. This method is suitable
for routine monitoring of residual amounts of non-polar
pesticides in agricultural products.
Acknowledgments
This study was supported by DHMPE (Direction
Hygiénique du Milieu et Protection Environnemental) and
ANCSEP (Agence Nationale de Contrôle Sanitaire et En-
vironnemental des Produits). We would like to express our
thanks for their financial support.
References
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