Food Chemistry 159 (2014) 367373

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Food Chemistry
journal homepage: www.elsevier.com/locate/foodchem

Analytical Methods

Determination of ten pyrethroids in various fruit juices:

Comparison of dispersive liquidliquid microextraction
sample preparation and QuEChERS method combined
with dispersive liquidliquid microextraction
Yaohai Zhang a, Xuelian Zhang a,b, Bining Jiao a,b,
a
b

Citrus Research Institute, Southwest University, Chongqing 400712, China

College of Food Science, Southwest University, Chongqing 400716, China

a r t i c l e

i n f o

Article history:
Received 2 October 2012
Received in revised form 6 November 2013
Accepted 7 March 2014
Available online 17 March 2014
Keywords:
Pyrethroids
Dispersive liquidliquid microextraction
(DLLME)
QuEChERS
Gas chromatographyelectron capture
detection (GCECD)
Fruit juices
Gas chromatographymass spectrometry
(GCMS)

a b s t r a c t
Dispersive liquidliquid microextraction (DLLME) sample preparation and the quick, easy, cheap, effective, rugged and safe (QuEChERS) method combined with DLLME were developed and compared for
the analysis of ten pyrethroids in various fruit juices using gas chromatography-electron capture detection (GCECD). QuEChERSDLLME method has found its widespread applications to all the fruit juices
including those samples with more complex matrices (orange, lemon, kiwi and mango) while DLLME
was conned to the fruit juices with simpler matrices (apple, pear, grape and peach). The two methods
provided acceptable recoveries and repeatability. In addition, the applicabilities of two methods were
demonstrated with the real samples and further conrmed by gas chromatographymass spectrometry
(GCMS).
2014 Published by Elsevier Ltd.

1. Introduction
Pyrethroids, a new-type of insecticide, have gained extensive
applications to prevent and treat insects in modern agriculture
due to their broad-spectrum insecticidal capacity and high effectiveness (Ye, Xie, Wu, & Lin, 2006). However, pyrethroid residues
are considered to be one of the most important sources of pollution
in agricultural production, and may be a potential threat to public
health (Kolaczinski & Curtis, 2004). Therefore, it is necessary to develop sensitive and selective methods for the analysis of pyrethroid
residues usually present in trace amounts. Potential analytical
methods include high performance liquid chromatography (HPLC)
(Boonchiangma, Ngeontae, & Srijaranai, 2012), capillary electrophoresis (CE) (Ye et al., 2006), gas chromatography (GC) (Du,
Yan, She, Liu, & Yang, 2010; Matsadiq et al., 2011), gas chromatographymass spectrometry (GCMS) (Cunha, Fernandes, & Oliveira,
Corresponding author at: Citrus Research Institute, Southwest University,
Chongqing 400712, China. Tel./fax: +86 23 68349046.
E-mail address: bljiao@tom.com (B. Jiao).
http://dx.doi.org/10.1016/j.foodchem.2014.03.028
0308-8146/ 2014 Published by Elsevier Ltd.

2009; Kok, Hiemstra, & Bodegraven, 2005), and gas chromatographytandem mass spectrometry (GCMS/MS) (Pay et al., 2007).
Quick and effective sample preparation coupled with a reliable
analytical method is imperative. Liquidliquid extraction (LLE) (Rezaee et al., 2006) and solid-phase extraction (SPE) (Sharif, Man, Hamid, & Keat, 2006) are the most common sample preparation
methods widely used for residue analysis. Recently, a growing
number of studies have focused on two kinds of micro-extractions
termed as liquid-phase microextraction (LPME) and solid-phase
microextraction (SPME), based on miniaturisation of conventional
LLE and SPE, respectively (Paillakis & Kalogerakis, 2003; Zambonin,
Cilenti, & Palmisano, 2002). In 2006, Rezaee et al. developed a novel liquidliquid microextraction method, dispersive liquidliquid
microextraction (DLLME) (Rezaee et al., 2006). The new method
has been widely recognised due to its simplicity, low cost and high
enrichment, which made it available to most analytical laboratories. Unfortunately, the lack of purication for samples with more
complex matrices, such as fruit and vegetable, has caused this
method to be limited to those with simpler matrices, specically
water and a few fruit juices.

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Y. Zhang et al. / Food Chemistry 159 (2014) 367373

At present, quick, easy, cheap, effective, rugged and safe (QuEChERS) sample preparation, is the most common technique for
multi-residue pesticides analysis in food, especially fruit and vegetable (Anastassiades, Lehotay, Stajnbaher, & Schenck, 2003). However, the major disadvantage of this technique is the poor
enrichment factor, which can lead to higher detection limits, i.e.
lower sensitivity, compared with other techniques. Researchers
proposed a new method comprised of DLLME pre-concentration
after QuEChERS extraction (Cunha & Fernandes, 2011; Zhao, Zhao,
Han, Jiang, & Zhou, 2007). Coupling these techniques takes advantages of the benets of both methods whilst reducing some of their
drawback. Moreover, QuEChERSDLLME sample preparation widens the use of DLLME to those samples with more complex matrices. To the best of our knowledge, there are a few reports on the
extraction and enrichment of pyrethroid residues in fruit juices
using QuEChERSDLLME method, although several studies on the
analysis of pyrethroids in fruit juices using only DLLME have been
reported (Boonchiangma et al., 2012; Cunha et al., 2009; Du et al.,
2010; Matsadiq et al., 2011).
In the paper, two sample preparation including DLLME and
QuEChERSDLLME followed by gas chromatography-electron capture detection (GCECD) were developed and compared for the
analysis of ten pyrethroids (tetramethrin, bifenthrin, lambdacyhalothrin, permethrin, cyuthrin, cypermethrin, ucythrinate,
fenvalerate, tau-uvalinate and deltamethrin) in various fruit
juices. Compared with the existing reports on the analysis of pyrethroid residues in fruit juices, more pyrethroids and fruit juicestypes were analysed in this study.

and 320 C, respectively. The column temperature program

was from 150 C (2 min) to 270 C at 6 C min1, then 270 C for
10 min.
2.4. Validation study
A test mixture with standard pyrethroids at a series of concentrations was prepared and analysed under optimised conditions to
determine linearity. Instrument precision and repeatability (intraand inter-day variation) were determined using three replicates of
the standard working solution (0.1 mg L1). The precision was expressed as relative standard deviation (RSD, %).
2.5. GCMS conrmation
Helium (P99.999%) was used as the carrier gas at a constant
pressure of 117.22 kPa. The injector temperature was 250 C. All
injections were pulse splitless and the volume was 1 lL. The column temperature program was from 70 C to 150 C at
25 C min1, from 150 C to 200 C at 3 C min1, from 200 C to
280 C at 8 C min1, then 280 C for 10 min. The temperatures of
the ion source and the MS transfer line were 230 C and 280 C,
respectively. Data were acquired in the electron impact (EI) mode
at a voltage of 70 eV using the selected ion monitoring (SIM) mode.
2.6. Calculations

2. Material and methods

Enrichment factor (EF), dened as the ratio of the analyte concentration after DLLME (Csed) to the initial analyte concentration
(C0), was calculated as:

2.1. Chemicals and standards

EF

Permethrin was purchased from SigmaAldrich Chemie GmbH

(Steinheim, Germany). The other nine pyrethroids were obtained
from Dr. Ehrenstorfer GmbH (Augsdburg, Germany).
HPLC-grade methanol and acetonitrile were from CNW Tech} sseldorf, Germany). Acetone, chloroform
nologies GmbH (Du
(CHCl3) and carbon tetrachloride (CCl4) were analytical reagents
from Kelong Chemcial Reagent Co. Ltd. (Chengdou, China). Chlorobenzene (C6H5Cl), tetrachloroethylene (C2Cl4), anhydrous MgSO4
and NaCl were analytical reagents from Sinopharm Chemcial Reagent Co. Ltd. (Shanghai, China). Primary secondary amine (PSA)
sorbent (4063 lm, 6 nm) was obtained from CNW Technologies
} sseldorf, Germany).
GmbH (Du
The stock solution of ten pyrethroids was prepared at
100 mg L1 in acetone and stored in glass volumetric ask at
50 C. Standard working solutions at a series of concentrations
were prepared by the dilution of aliquots of the stock solution into
CHCl3, CCl4, C6H5Cl and C2Cl4, respectively.

Extraction recovery (ER), used to estimate the preconcentration

efciency under the optimum conditions, was calculated as:

ER

C sed
C0

C sed  V sed
 100
C 0  V aq

where Vsed and Vaq are the volumes of the sedimented phase and the
sample, respectively.
2.7. Samples
Eight types of fruit juices were purchased from local supermarkets. Samples were ltered using Buchner funnel before extraction
to remove the sediments. All fruit pulps (2 kg each), excluding lemon, were prepared from peeled fruit. The whole fruit was used to
prepare lemon pulp. A representative portion of these samples
(200 g each) was chopped and homogenised in a food chopper.
2.8. DLLME procedure

2.2. Apparatus
An Agilent 7890A gas chromatograph (Palo Alto, USA) was used
to perform all GC analysis. Ten pyrethroid residues were separated
in a capillary column (DB-1, 30 m  0.25 mm id  0.25 lm lm).
An Agilent 5795C/7890A GC/MS (Palo Alto, USA) was used to perform the conrmation. A HP-5MS (30 m  0.25 mm id  0.25 lm
lm) capillary column was used.

A ltered sample of 5 g was placed in a sharp-bottom centrifuge

tube. The mixture of 1 mL of acetone and 60 lL of CCl4 was added
quickly into the tube and the mixture emulsied, forming cloudy
solution. The mixture was vortexed for 5 min and centrifuged at
4000 rpm for 5 min to sediment the CCl4. Finally, the sedimented
phase was transferred to a trace intubation in a sample vial.
2.9. QuEChERSDLLME procedure

2.3. GCECD analysis

All injections were splitless and the volume was 1 lL. The ow
rate of the carrier gas (N2, P99.999%) was 1 mL min1. The
temperatures of the injector and the l-ECD detector were 200 C

The QuEChERS procedure was used as the previously reported

with slight changes (Kok et al., 2005). 1 mL of the extract obtained
by QuEChERS was transferred into a centrifuge tube and 60 lL of
CCl4 was added and the mixture was vortexed for 1 min.

Y. Zhang et al. / Food Chemistry 159 (2014) 367373

The DLLME procedure described below was followed for enrichment. 5 g of deionized water was placed in a centrifuge tube. 1 mL
of the extract and 60 lL of CCl4 were rapidly injected into 5 g of
deionized water with a syringe to form cloudy solution. The samples were vortexed for 5 min and then centrifuged at 4000 rpm
for 5 min. Finally, the sedimented phase was transferred to a trace
intubation in a sample vial.
3. Results and discussion
3.1. Optimisation of DLLME
Factors likely to impact DLLME and QuEChERSDLLME such as
types and volumes of extraction solvents and dispersive solvents,
ultrasonic time, salt concentration, vortex and centrifugation time
were investigated in detailed.
3.1.1. Selection of extraction solvent and its volume
The correct solvents are vital for the success of DLLME. In our
study, four common halogenated solvents including CHCl3,
C6H5Cl, C2Cl4 and CCl4 were selected for extraction. Extraction efciency was evaluated by comparing the recoveries of the analytes.
Fig. 1A showed that carbon tetrachloride was most efcient and it
was therefore used in subsequent experiments.
To investigate the volume effect of CCl4, different quantities of
CCl4 (3070 lL) were used whilst the dispersant was maintained
at 1 mL. Observably, the extraction efciency was improved with

369

the increase of volume (Fig. 1B). When CCl4 was increased from
30 to 60 lL, the recovery of ten pyrethroids was increased from
4368% to 61103%. However, those peaks of some non-analytes
including interfering substances appeared more obviously with
volumes greater than 60 lL although the recovery of the pyrethroids continued to increase. Thus, 60 lL of CCl4 was selected as
the optimum volume.

3.1.2. Selection of dispersive solvent and its volume

Acetone, acetonitrile and methanol were chosen as the dispersive solvents. Fig. 1C showed that the highest recovery was
achieved with acetone and it was used for all subsequent
experiments.
To study the volume effect of acetone, it was varied from 0.4 to
1.2 mL in the interval of 0.2 mL while CCl4 was kept at 60 lL. With
the increase of acetone from 0.4 to 1.0 mL, the extraction efciency
increased gradually with recoveries from 2160% to 61103%,
while the extraction efciency dropped down slightly above 1 mL
(Fig. 1D). Therefore, 1 mL of acetone was selected as the optimum
volume.

3.2. Optimisation of QuEChERSDLLME

Since the ultimate solution obtained after QuEChERS was used
for dispersive solvent, the types and volumes of extraction solvents
were the only parameters to be optimised. 60 lL of CCl4 was the

Fig. 1. Effects (A) of extraction solvents, (B) of the volumes of extraction solvents, (C) of dispersive solvents, and (D) of the volumes of dispersive solvents on the recoveries of
analytes in DLLME. 5.00 g of spiked apple juices at 0.01 mg kg1.

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Y. Zhang et al. / Food Chemistry 159 (2014) 367373

pyrethroids was slightly enhanced when ultrasonic treatment

was increased from 0 to 1 min. However, the recoveries remained
inconstant above 1 min and even decreased. Moreover, the repeatability of the recoveries was not satisfactory. So, ultrasound was
not used for DLLME.
To evaluate salting out effect (commonly sodium chloride), different concentrations of NaCl in a range of 05% (w/v) at a 1-%
interval were investigated. The results revealed that the recoveries
of analytes decreased gradually with the increasing of salt concentration. Thus, NaCl was not applied for DLLME.
Centrifugation time has no obvious inuence on the extraction
efciency in DLLME (Boonchiangma et al., 2012). Thus, a vortex
time of 5 min and centrifugation time of 5 min were used to help
the cloudy solution form and precipitate at the bottom of the tube.
3.4. Analytical performance

Fig. 2. Chromatogram of a standard mixture at 0.1 mg L1: 1, tetramethrin; 2,

bifenthrin; 3, lambda-cyhalothrin; 4, permethrin; 5, cyuthrin; 6, cypermethrin; 7,
ucythrinate; 8, fenvalerate; 9, tau-uvalinate; 10, deltamethrin.

optimum extraction solvent in QuEChERSDLLME (data not

shown), which was the same as the results obtained in DLLME.
3.3. Other conditions of DLLME and QuEChERSDLLME
To evaluate ultrasonic effect, ultrasound-assisted extraction
was tested (05 min). The result showed that recovery of ten

A typical gas chromatogram under the conditions described in

Section 2.3 is shown in Fig. 2. Ten pyrethroids were separated in
29 min. Although peaks of pyrethroid enantiomers partially overlapped, they were together integrated without difculty because
quantication depends on peak area sum for pyrethroid
enantiomers.
Fig. 3A displays the chromatogram of ten pyrethroids at
0.01 mg L1 without DLLME, while Fig. 3B shows the chromatogram from an apple juice spiked at 0.01 mg kg1 of each of the
pyrethroids after DLLME. There was no interference peak in the
typical chromatogram of a blank apple juice after DLLME.
Obviously, the signal intensities of all the pyrethroids, namely
the method sensitivity, improved many-fold with application of

Fig. 3. Chromatograms (A) of a standard mixture at 0.01 mg L1, (B) of a spiked apple juice at 0.01 mg kg1 after DLLME, (C) of a spiked orange juice at 0.01 mg kg1 after
QuEChERSDLLME, and (D) a spiked orange juice at 0.01 mg kg1 after DLLME while the spiked sample is diluted to ve times: 1, tetramethrin; 2, bifenthrin; 3, lambdacyhalothrin; 4, permethrin; 5, cyuthrin; 6, cypermethrin; 7, ucythrinate; 8, fenvalerate; 9, tau-uvalinate; 10, deltamethrin.

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Y. Zhang et al. / Food Chemistry 159 (2014) 367373

Table 1
Analytical performance optimised for the determination of ten pyrethroids.
Linear
range
(lg L1)

Linear equation

Tetramethrin
Bifenthrin
Lambda-

210,000
0.510,000

Permethrin
Cyuthrin
Cypermethrin
Flucythrinate
Fenvalerate
Tauuvalinate
Deltamethrin

Pyrethroids

Correlation
coefcient (r2)

LOD
(lg L1)

LOQ
(lg L1)

Enrichment
factor of DLLME

Enrichment factor of
QuEChERSDDLME

Precision (% RSD)
Intraday
(n = 3)

Inter-day
(n = 3  3)

0.9998
0.9998
0.210,000
0.9996
0.9996
0.9995
0.9995
0.9990
0.9993
0.9992

2
0.5

5
2

110
65

25
18

2.9
2.2

4.1
4.9

210,000
110,000
210,000
110,000
0.510,000
0.510,000

y = 251.85x + 9849.36
y = 358.74x + 29175.27
cyhalothrin
y = 1570.54x + 74876.51
y = 205.10x + 8595.29
y = 2201.21x + 67955.49
y = 1460.15x + 83946.31
y = 201.19x + 29722.88
y = 564.36x + 33944.35
y = 1381.12x + 57236.53

0.2
2
1
2
1
0.5
0.5

1
5
4
5
4
2
2

64
104
78
86
104
107
93

19
24
18
20
24
16
26

3.9
2.1
2.8
2.5
2.3
2.4
2.8

6.3
4.0
6.4
4.5
5.3
5.8
6.2

0.510,000

y = 383.27x + 56526.79

0.9990

0.5

92

17

3.1

6.0

DLLME. The enrichment factors were in a range of 64110 (Table 1).

Thus, DLLME is a very simple and effective method for preconcentrating pyrethroid residues in apple juices. In addition, recoveries
from the other spiked fruit juices including pear, grape, peach, orange, lemon, kiwi and mango juices at 0.01 mg kg1 were examined. Unfortunately, recoveries from orange, lemon, kiwi and
mango juices were less than 50% while recoveries from pear, grape
and peach juices were in the range from 64.0% to 108.4%, which
was caused by different matrices.
Fig. 3C shows the chromatogram from a spiked orange juice at
0.01 mg kg1 after QuEChERSDLLME. There is no obvious interference peak in the typical chromatogram of a blank orange juice after
QuEChERSDLLME. Fig. 3D shows the chromatogram from a spiked
orange juice at 0.01 mg kg1 after DLLME while the spiked sample
is diluted ve times in order to compare DLLME with QuEChERS
DLLME. Clearly, better recoveries were obtained by QuEChERS
DLLME than only DLLME alone even if the orange juice has to be
diluted. And so it was in lemon, kiwi and mango juices. Thus, QuEChERSDLLME was more suitable for the preconcentration of pyrethroids in orange, lemon, kiwi and mango juices than DLLME
although the latter had a higher enrichment factor than the former
(Table 1). Interestingly, using both DLLME and QuEChERSDLLME,
achieved acceptable recoveries from fruit juices such as apple,
pear, grape and peach in the range 60% to 120%. Considering the
purication capacity of QuEChERS, these results can be explained
in terms of simper matrices in the apple, pear, grape and peach
juices than the orange, lemon, kiwi and mango juices. As a result,
QuEChERSDLLME has found been used widely for extracting and
enriching pyrethroid residues in not only rich pulps but also more
complex matrices than DLLME.
Table 1 provides the linear regression equation and the other
corresponding results. The results reveal a satisfactory linearity
for all analytes with excellent correlation coefcients (r2) higher

than 0.999 in linear regression equation. The relative standard

deviations (RSDs) of peak areas were below 4% for intra-day precision and less than 7% for inter-day precision. The limits of detection (LODs, S/N = 3) and the limits of quantication (LOQs, S/
N = 10) of ten pyrethroids ranged from 0.2 to 2 lg L1 and 1 to
5 lg L1, respectively. Considering the high enrichment factors of
DLLME and QuEChERSDLLME, LODs and LOQs of the two methods
are below the MRLs established in China (Chinese pesticide MRLs,
Regulation (GB) No. 19648-2006).
Recoveries achieved from the spiked fruit juices (apple, pear,
grape and peach) at two concentrations (0.01 and 0.1 mg kg1)
using DLLME ranged from 61.5% to 108.4% (RSDs, 1.35.6%) and
64.3% to 98.9% (RSDs, 2.06.3%), respectively. The recovery of some
pyrethroids was less than 70% (bifenthrin, lambda-cyhalothrin,
cyuthrin, cypermethrin, ucythrinate, tau-uvalinate and deltamethrin). On the other hand, the recovery achieved from the
spiked samples (orange, lemon, kiwi and mango) at the same concentrations using QuEChERSDLLME ranged from 65.5% to 137.5%
(RSDs, 2.88.6%) and 62.6% to 126.7% (RSDs, 2.47.2%), respectively. The recoveries of bifenthrin in spiked mango juices were
less than 70%, and those of some pyrethroids were higher than
130% (tetramethrin, permethrin and tau-uvalinate). Hence we
can conclude that DLLME and QuEChERSDLLME provide acceptable accuracy and precision.
Table 2 summarises the details of the proposed method and the
other methods which have been applied for pyrethroids determination. Clearly, the proposed method has higher sensitivity than
most of the recently published methods.
3.5. Matrix effects
Matrix components have an observable effect on the detection
of target analytes by either enhancing or weakening their signal

Table 2
Comparison of the proposed methods and some other methods for the determination of pyrethroids residues in fruit juices.
Extraction method

Instrument
detector

Analyte

Sample

LOD

Recovery (%)

EF

Ref.

DLLME

HPLCUV

6 Pyrethroids

25 lg L1

8494

6284

Boonchiangma, Ngeontae,
and Srijaranai (2012)

UA-DLLME

GCFID

2 Pyrethroids

Apple, red grape, orange,

kiwi, passion fruit,
pomegranate and
guava juices
Pear juice

23 lg kg1

92107

344351

DLLME
DLLME

GCECD
GCMS

4 Pyrethroids
24 Pesticides including 2
pyrethroids
10 Pyrethroids

Peach juice, pulp and peel 318 ng L1

Apple juice
0.42 lg L1

73106
60105

4091089
4258

62108 and
63138

64110 and
1626

Du, Yan, She, Liu, and Yang

(2010)
Matsadiq et al. (2011)
Cunha, Fernandes, and
Oliveira (2009)
Proposed method

DDLME and
GCECD
QuEChERSDDLME

Apple, pear, grape, peach,

orange, lemon, kiwi and
mango juices

0.22 lg L1

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Y. Zhang et al. / Food Chemistry 159 (2014) 367373

Fig. 4. Chromatograms (A) of apple juice by GCECD after DLLME, (B) by of apple juice GCMS after DLLME, (C) of orange pulp by GCECD after QuEChERSDLLME, and (D) of
orange pulp by GCMS after QuEChERSDLLME: (1) lambda-cyhalothrin standard at 0.2 mg L1; (2) sample contaminated with lambda-cyhalothrin; (3) tau-uvalinate
standard at 0.2 mg L1; (4) sample contaminated with tau-uvalinate.

intensities, so different matrix-matched calibrations were put into

use (Boonchiangma et al., 2012). The matrix effects in organic solvent and in blank samples were estimated by comparing the slopes
of the calibration curves. The test revealed that there was no significant difference between the organic solvent and the real samples
(data not shown).
3.6. Analysis of real samples
The proposed analytical methods were used for the determination of ten pyrethroid residues in marketed fruit juices. In addition,
pyrethroid residues in fruit pulps and peels were tested using QuEChERSDLLME. One of ten pyrethroids, namely lambda-cyhalothrin, was found in fresh apple juice at about 2 lg kg1. Tauuvalinate was found in the orange pulp at about 3 lg kg1
(Fig. 4A and C). To conrm these results, the same samples were
analysed using GCMS (Gianni et al., 2008), a technique recommended for pesticides. About 2 lg kg1 of lambda-cyhalothrin
was found in the apple juice and about 3 lg kg1 of tau-uvalinate
was found in the orange pulp, which were in accordance with the
results by GC analysis (Fig. 4B and D).

4. Conclusions
In this paper, two rapid and simple sample preparation methods DLLME and QuEChERSDLLME followed by GCECD were
developed and compared for ten pyrethroid residues in various
fruit juices. These methods offered acceptable recoveries and limited variation from day-to-day. DLLME was suitable for those fruit
juices with simper matrices and QuEChERSDLLME for all the fruit
juices. The proposed methods demonstrated pyrethroid residues in
some fruit juices in the Chinese market.

Acknowledgements
This work was supported by the National Key Technology R&D
Program (Nos. 2007BAD47B07 and 2009BADB7B04), China
Agriculture Research System (No. CARS-27), Natural Science
Foundation of Chongqing (Nos. cstc2013jcyjA0435 and
cstc2013jjB80009) and Fundamental Research Fund for the Central
Universities (No. XDJK2012C059).

References
Anastassiades, M., Lehotay, S. J., Stajnbaher, D., & Schenck, F. J. (2003). Fast and easy
multiresidue method employing acetonitrile extraction/partitioning and
dispersive solid-phase extraction for the determination of pesticide residues
in produce. Journal of AOAC International, 86, 421431.
Boonchiangma, S., Ngeontae, W., & Srijaranai, S. (2012). Determination of six
pyrethroid insecticides in fruit juice samples using dispersive liquidliquid
microextraction combined with high performance liquid chromatography.
Talanta, 88, 209215.
Cunha, S. C., & Fernandes, J. O. (2011). Multipesticide residue analysis in maize
combining acetonitrile-based extraction with dispersive liquidliquid
microextraction followed by gas chromatographymass spectrometry. Journal
of Chromatography A, 1218, 77487757.
Cunha, S. C., Fernandes, J. O., & Oliveira, M. B. P. P. (2009). Fast analysis of multiple
pesticide residues in apple juice using dispersive liquidliquid microextraction
and multidimensional gas chromatographymass spectrometry. Journal of
Chromatography A, 1216, 88358844.
Du, J. J., Yan, H. Y., She, D. D., Liu, B. M., & Yang, G. L. (2010). Simultaneous
determination of cypermethrin and permethrin in pear juice by ultrasoundassisted dispersive liquidliquid microextraction combined with gas
chromatography. Talanta, 82, 698703.
Gianni, S., Giovanni, C., Gloria, C., Dario, G., Massimo, R., Rosaria, V., et al. (2008).
Determination of ink photoinitiators in packaged beverages by gas
chromatographymass spectrometry and liquid chromatographymass
spectrometry. Journal of Chromatography A, 1194, 213220.
Kok, A. D., Hiemstra, M., & Bodegraven, P. V. (2005). Validation of a fast and easy
method for the determination of residues from 229 pesticides in fruits and
vegetables using gas and liquid chromatography and mass spectrometric
detection. Journal of AOAC International, 88, 595614.

Y. Zhang et al. / Food Chemistry 159 (2014) 367373

Kolaczinski, J. H., & Curtis, C. F. (2004). Chronic illness as a result of low-level
exposure to synthetic pyrethroid insecticides. Food Chemistry Toxicology, 42,
697706.
Matsadiq, G., Hu, H. L., Ren, H. B., Zhou, Y. W., Liu, L., & Cheng, J. (2011).
Quantication of multi-residue levels in peach juices, pulps and peels using
dispersive liquidliquid microextraction based on oating organic droplet
coupled with gas chromatography-electron capture detection. Journal of
Chromatography B, 879, 21132118.
Paillakis, E., & Kalogerakis, N. (2003). Developments in liquid-phase
microextraction. Trends in Analytical Chemistry, 22, 565574.
Pay, P., Anastassiades, M., Mack, D., Sigalova, I., Tasdelen, B., Oliva, J., & Barba, A.
(2007). Analysis of pesticide residues using the Quick Easy Cheap
Effective Rugged and Safe (QuEChERS) pesticide multiresidue method
in combination with gas and liquid chromatography and tandem
mass spectrometric detection. Analytical and Bioanalytical Chemistry, 389,
16971714.

373

Rezaee, M., Assadi, Y., Hosseini, M. R. M., Aghaee, E., Ahmadi, F., & Berijani, S. (2006).
Determination of organic compounds in water using dispersive liquidliquid
microextraction. Journal of Chromatography A, 1116, 19.
Sharif, Z., Man, Y. B. C., Hamid, N. S. A., & Keat, C. C. (2006). Determination of
organochlorine and pyrethroid pesticides in fruit and vegetables using solid
phase extraction clean-up cartridges. Journal of Chromatography A, 1127,
254261.
Ye, F., Xie, Z., Wu, X., & Lin, X. (2006). Determination of pyrethroid pesticide residues
in vegetables by pressurized capillary electrochromatography. Talanta, 69,
97102.
Zambonin, C. G., Cilenti, A., & Palmisano, F. (2002). Solid-phase microextraction and
gas chromatographymass spectrometry for the rapid screening of triazole
residues in wine and strawberries. Journal of Chromatography A, 967, 255260.
Zhao, E., Zhao, W., Han, L., Jiang, S., & Zhou, Z. (2007). Application of dispersive
liquidliquid microextraction for the analysis of organophosphorus pesticides
in watermelon and cucumber. Journal of Chromatography A, 1175, 137140.