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In-syringe low-density ionic liquid dispersive

liquid–liquid microextraction for the fast
Cite this: RSC Adv., 2016, 6, 69218
determination of pyrethroid insecticides in
environmental water samples by HPLC-DAD
Lu Hu, Xuan Wang, Heng Qian, Huazi Wang, Runhua Lu, Sanbing Zhang,
Published on 12 July 2016. Downloaded on 9/20/2019 12:49:04 AM.

Wenfeng Zhou and Haixiang Gao*

Received 14th April 2016
Accepted 12th July 2016
DOI: 10.1039/c6ra09668a
www.rsc.org/advances
A new microextraction technique named in-syringe low-density ionic liquid dispersive liquid–liquid
microextraction (LDIL-DLLME) followed by separation using high performance liquid chromatography
has been developed to determine the levels of four pyrethroid insecticides (i.e., deltamethrin,
fenvalerate, permethrin, and bifenthrin) in environmental water samples. In the developed method, an
ionic liquid (IL) was used for the first time instead of an organic solvent, which is most often used in
low-density solvent-based microextraction methods. The IL was placed in a long syringe needle using
a microsyringe. It was then dispersed by drawing the sample solution into the syringe. The extraction
was finished in the syringe, taking full advantage of the low-density property, and making this method
easier and quicker. Several parameters affecting the experimental efficiency of LDIL-DLLME, such as the
needle's inner diameter, salt addition, the volume of IL and sample, rotation speed and duration of
centrifugation and ultrasound were thoroughly studied. Under optimized conditions, in the range of 1
to 500 mg L
1, good linearity was obtained, with coefficients of determination greater than 0.9994.
Three spiked water samples were studied, and recovery ranged from 88.0 to 102.8%, with relative
standard deviations (RSDs) ranging from 0.3 to 6.7%. The limits of detection (LODs) for the four
pyrethroid insecticides were in the range of 0.88–1.71 mg L
1 and enrichment factors (EFs) were in the
range of 242 to 257. The proposed method provides an inexpensive, rapid, simple and eco-friendly
process for evaluating pyrethroid insecticides in environmental samples, making it a potential method
for the pretreatment of experimental samples.

maximum residue limits (MRLs) for pyrethroid residues has

1. Introduction
Pyrethroids were introduced in Japan in 1987 by Mitsui
Chemicals, Inc.1 They are widely used to control pests in agri-
culture, public health, forestry and veterinary medicine by
inhibiting the normal sodium channel function in the nerve
axons of insects. Pyrethroids also have relatively low toxicity to
mammals and can rapidly be degraded in the environment.2,3
However, wide application has resulted in the widespread
distribution of pyrethroid residues in the environment, which
are considered hazardous to human health. These residues may
remain on agricultural commodities, such as fruits and vege-
tables, and are classied as carcinogens and or toxins.4 Because
of their high solubility in water, they are typically distributed in
aqueous environments through leaching and run off from soil
into ground and surface water. To protect consumers, the
Department of Applied Chemistry, China Agricultural University, Yuanmingyuan West
Road 2#, Haidian District, Beijing 100194, China. E-mail: hxgao@cau.edu.cn; Tel:
+86-010-62730244
been established in various foods by several organizations. For
example, the European Union established MRLs of
0.01–0.2 mg kg
1 in vegetables.5 Therefore, a rapid and effective
pretreatment method for determining trace-level amounts of
pyrethroids in water samples is needed.
There is an increasing demand to develop sensitive and
selective methods to preconcentrate pyrethroid residues, which
are usually present in trace amounts. Many analytical methods
for evaluating pyrethroids have been reported, such as magnetic
solid phase extraction (MSPE) followed by high-performance
liquid chromatography with ultra violet detection (HPLC-UV),4
the QuEChERS method combined with gas chromatography
with electron capture detection (GC-ECD),6 dispersive liquid–
liquid microextraction (DLLME) combined with high-
performance liquid chromatography with diode array detec-
tion (HPLC-DAD),7 single-drop microextraction (SDME) fol-
lowed by gas chromatography coupled to mass spectrometry
(GC-MS),8 hollow bre-based liquid-phase microextraction (HF-
LPME) combined with gas chromatography-mass spectrometry

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(GC-MS), and more. Although these methods have some
advantages, they also have some disadvantages; for example,
the MSPE method requires a tedious preparation procedure
before extraction, QuEChERS uses a high level of organic
solvent as the extraction solvent, DLLME consumes high level of
dispersive solvent, and SDME and HF-LPME require long
extraction times.
Among these methods, DLLME is the most commonly used
method to evaluate pesticide residue concentrations because it is
simple, efficient, and inexpensive. Additionally, it has higher pre-
concentration factors and uses less toxic extraction agents. It was
introduced by Rezaee et al. in 2006.9 This method has been used in
many analytical applications and as a successful aqueous sample
pretreatment method. Based on these advantages, several DLLME
methods have been successfully introduced, such as DLLME based
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on the solidication of oating organic drops (DLLME-SFO),10
ultrasound-assisted dispersive liquid–liquid microextraction (UA-
DLLME),11 elevated-temperature dispersive liquid–liquid micro-
extraction (ET-DLLME),12 in situ ionic liquid dispersive liquid–
liquid microextraction (in situ IL-DLLME),13 low-density solvent
dispersive liquid–liquid microextraction (LDS-DLLME),14 and
supramolecular-based DLLME (SM-DLLME).15
In traditional DLLME, a high-density extraction solvent, such
as tetrachloroethane, carbon tetrachloride, chloroform,
dichloromethane, or chlorobenzene, is generally required, and
these solvents are environmentally unfriendly, highly toxic and
may limit the applicability of the method. Another disadvantage
is that the GC peaks of halogenated hydrocarbons partially
overlap with those of some analytes. In addition, because they
are volatile, they must evaporate to dryness. Additionally, ana-
lytes must be reconstituted in a suitable solvent prior to LC,
which is a laborious approach.16–18 Therefore, a low-density
solvent dispersive liquid–liquid microextraction (LDS-DLLME)
technique was developed. The range of organic solvents that
have a lower density than water is broader than that of high-
density solvents.19 Several types of extraction solvents that are
less dense than water can be selected, including alkanes, alco-
hols, ethers, ketones and acetates.20 However, the most
commonly used extraction solvents in LDS-DLLME are toluene,
n-hexane and 1-octanol which are considered hazardous to the
health of analysts or are dangerous liquids because they are
inammable or explosive.
Other alternative extractants for DLLME are ionic liquids,
which have negligible vapor pressures, variable viscosities and
high thermal stabilities. IL has been successfully used in
numerous DLLME studies, such as in situ IL-DLLME,13 magnetic
stirrer IL-DLLME,21 ultrasound-assisted IL-DLLME,22
temperature-assisted IL-DLLME and gas-assisted IL-DLLME,24
23
for the detection of pesticides, pharmaceuticals, organic
pollutants and metal ions in water, food, urine and serum.25–33
However, most ILs are imidazolium salts, and their densities
are higher than that of water. In this work, the IL [P14,6,6,6]Cl,
with a density of 0.89 g cm
1,3,34,35 was used for the rst time as
an extraction solvent in DLLME. ILs are consist of organic
cations and organic or inorganic anions. As both the anion and
cation can be altered, these solvents can be designed for
a particular set of properties, leading to ionic liquids known as
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“Designer Solvents”.36 Some quaternary phosphonium salt and
quaternary ammonium salt ionic liquids have a lower density
than water, and they can be used in the low-density ionic liquid
DLLME.37–40 The proposed method broadens the range of
extractants that can be used in DLLME, but it also increases the
number of applications of the low-density methods.
To overcome the collection problem aer phase separation,
signicant efforts have been made to improve extraction devices
or collection strategies. Several interesting types of special
extraction devices have been designed and applied in the LDS-
DLLME procedure.14,41–46 Most of them are designed to have
a narrow neck, which is followed by squeezing the device or
adding some water to allow for the movement of the light
organic extract into the narrow stem, making them collectable.
When the liquid moves, it is easy for some of the liquid to
remain on the wall of the vessel, especially for high viscosity
liquids. Therefore, we propose a special method for use with
high viscosity extraction collection solvents, such as ILs, that
takes advantage of their high viscosity. The extraction is
nished in a syringe and, aer centrifugation, when the IL is
stuck to the syringe wall, the aqueous phase is discarded from
the top of the syringe. The extractant is then collected by pulling
the plunger to the top of syringe. This method is simple and
inexpensive.
In conventional DLLME, a dispersion solvent is needed to
dissipate the extraction solvents in the aqueous solution. Most
of these solvents are volatile organic compounds that can
damage the health of analysts and pollute the environment. In
addition, they can easily dissolve the analytes, resulting in
decreased recovery. To avoid these problems, a new dispersion
method, named impulsion dispersion, was adopted. The IL was
added in a long syringe needle using a microsyringe; then, it
was dispersed by drawing the sample solution into the syringe,
which is easy and quick.
In this study, a novel and efficient method, named in-syringe
LDIL-DLLME combined with HPLC-DAD, was developed for the
rst time to determine the levels of four pyrethroid insecticides
in environmental water samples. The IL was used as an
extraction solvent in the low-density solvent based method. The
IL was dispersed by drawing the sample solution into the
syringe, and the extraction was nished in the syringe with
a special procedure. The effects of some experimental parame-
ters, such as the needle's inner diameter, salt addition, the
volume of IL and sample, the rotation speed and time of
centrifugation and ultrasound were thoroughly studied. Finally,
the optimized conditions were used for determination of pyre-
throid insecticides in real environmental water samples.
2. Materials and methods
2.1. Reagents
Four pyrethroid insecticides (deltamethrin, fenvalerate,
permethrin and bifenthrin) were supplied by the Agricultural
Environmental Protection Institution (Tianjin, China) and the
purities are in the range of 97% to 98%. Trihexyl(tetradecyl)
phosphonium tetrauoroborate ([P14,6,6,6]Cl) was obtained from
J & K Chemical Technology Co., Ltd (Beijing, China). Milli-QSP
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Reagent Water System (Millipore, Bedford, MA, USA) was used
to purify deionized water. HPLC-grade acetonitrile was supplied
by Dikma Limited (Beijing, China). Sodium chloride (analytical
grade) was supplied by Beijing Chemical Reagent Company.
Mixed standard solution of 100 mg L
1 of four pyrethroid
insecticides were prepared in acetonitrile and the solutions
were stored at 4  C. The working standard aqueous solutions
were prepared daily by diluting an appropriate amount of the
mixed standard solution in different concentrations using
acetonitrile.
Three river water samples from Qujiang (Quzhou, Zhejiang
Province), Tongli (Sushou, Jiangsu Province) and Changyuan He
(Jinzhong, Shanxi Province) and one reservoir water sample
from Yinjiaju (Chuxiong, Yunnan Province) were used for
method validation. The environmental water samples were
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ltered through a 0.22 mm mixed cellulose membrane and
stored in the dark at 4  C prior to use.
2.2. Instruments
An Agilent 1200 HPLC system (California, USA), which was
equipped with an automated sample injector and a diode array
detector (DAD) system, was used to perform the chromato-
graphic analysis of the four pyrethroid pesticides. An Agilent
Eclipse Plus C18 analytical column (5 mm, 4.6 mm  250 mm)
with Spursil C18 guard cartridges (5 mm, 2.1 mm  10 mm,
Dikma Limited) was used for the separations. The Agilent
Chem-Station soware was used to operate the HPLC-UV
system and perform data analysis. Both a high-speed centri-
fuge was purchased from USTC Zonkia Scientic Instruments
Co., Ltd. (Anhui, China) and an ultrasonic cleaner (KQ3200DE,
Kunshan, China) were used for sample treatment. The mobile
phase was a methanol/water mixture (82 : 18, v/v), delivered at
a ow rate of 1 mL min
1, and the column temperature was
maintained at 25  C. The detection wavelength was 230 nm and
the sample injection volume was 10 mL. A Mettler-Toledo AL104
electronic balance (Shanghai, China) was used to weight the
materials. A 10 mL syringe was purchased from Cheng Dou Xin
Jin Shi Feng Medical Apparatus & instruments Co., Ltd. A long
syringe needle was obtained from Wen Zhou Needle Factory
(Zhejiang, China). Sodium chloride (analytical grade) was
supplied by Beijing Chemical Reagent Company.
2.3. LDIL-DLLME procedure
An aliquot of [P14,6,6,6]Cl (40 mL) was injected into a 10 cm
needle using a microsyringe, and the needle was connected to
a 10 mL syringe. Then, 10 mL of deionized water that was
spiked with four pyrethroid insecticides was drawn into the
syringe, forming a cloudy solution. A gel cap was used to seal
the top of the syringe. The syringe was then placed in an
ultrasound bath for 90 s to make the extraction more complete,
and 0.1 g sodium chloride was added to demulsify the emul-
sion to promote separation. Then, the plunger was pulled out
and the syringe was centrifuged at 6000 rpm for 10 min; the IL
remained on the wall of the syringe. The gel cap was removed,
and the aqueous phase completely owed out of the syringe.
Finally, the IL was collected at the top of the syringe plunger by
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Fig. 1 Schematic procedure for in-syringe LDIL-DLLME.
withdrawing the plunger to the top of the syringe. A 30 mL
aliquot of acetonitrile was added through the injector nipple to
dilute the IL phase; 10 mL of the mixture was directly injected
into the HPLC system for analysis. The procedure is schemat-
ically shown in Fig. 1.
2.4. Calculation of EF and R%
Enrichment factors (EFs) and extraction recoveries (ER%) were
determined to evaluate the extraction efficiency of different
experimental conditions by a step-by-step optimization proce-
dure, and they were calculated using the following equations:
CIL
EF ¼
Cwater
CIL  VIL
ER ð%Þ ¼  100%
Cwater  Vwater
where CIL, Cwater, VIL and Vwater are the concentration of the
analytes in the sediment phase, initial concentration of the
analytes in the water sample, volume of the sediment phase and
volume of the water sample, respectively.
3. Results and discussion
3.1. Optimization of the in-syringe LDIL-DLLME method
3.1.1. Optimization of the needle's inner diameter. The
needle's inner diameter has a signicant effect on the strength
of the produced impulsion and has a direct inuence on the
dispersion result. Four different inner diameters (0.7, 0.9, 1.1
and 1.3 mm) were evaluated. As shown in Fig. 2, a needle with
an inner diameter of 0.7 mm obtained the highest recovery,
while the other needle inner diameters yielded similar results
but with a marginally lower recovery. Due to the small inner
diameter, a high impulsion can be obtained when withdrawing
the samples. When the inner diameter is large, the impulsion is
small. Additionally, in this situation, some IL remained on the
wall of the needle and could not be washed into the syringe,
decreasing the extraction efficiency. Furthermore, lower
impulsion cannot effectively disperse IL. Therefore, a needle
with an inner diameter of 0.7 mm was selected for subsequent
experiments.
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Fig. 2 Effect of the needle's inner diameter on the recoveries of the
pyrethroid insecticides (extraction conditions: salt addition, 1%;
volume of IL, 40 mL; volume of sample, 10 mL; rotation speed, 7000
rpm; centrifugation time, 10 min; and ultrasound time, 60 s).
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3.1.2. Optimization of salt addition. In this paper, the
extraction solvent, [P14,6,6,6]Cl, has a hydrophobic long-chain
alkane and hydrophilic chloride ion making it an emulsifying
agent. Then, salt is needed for the demulsication process;
otherwise, the IL cannot be completely separated. Therefore, the
effect of salt addition on recoveries was studied using NaCl
concentrations in the range of 0% to 5% (w/v). The results are
shown in Fig. 3. When no salt was added to the sample, an
extremely low recovery was obtained because less IL could be
separated from the aqueous samples, but when the salt concen-
tration increased to 1%, the recovery of all analytes increased
noticeably, indicating that a small amount of salt has a positive
effect on demulsication. However, the extraction efficiency
decreased as the salt concentration increased to more than 1%.
This phenomenon can be explained by the fact that a high salt
concentration can cause an increase in the viscosity, which
conceivably inhibited the extraction by slowing the mass transfer
of the analytes and thus decreases the extraction efficiency. For
these reasons, 1% NaCl in the aqueous phase was selected.
3.1.3. Optimization of the volume of IL. In this study, the
volume of IL had a direct inuence on the extraction efficiency;
a sufficient amount of extraction solvent can completely extract
Fig. 3 Effect of salt addition on the recoveries of the pyrethroid
insecticides (extraction conditions: needle's inner diameter, 0.7 mm;
volume of IL, 40 mL; volume of sample, 10 mL; rotation speed, 7000
rpm; centrifugation time, 10 min; and ultrasound time, 60 s).
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Fig. 4 Effect of the volume of IL on the recoveries of the pyrethroid
insecticides (extraction conditions: needle's inner diameter, 0.7 mm;
salt addition, 1%; volume of sample, 10 mL; rotation speed, 7000 rpm;
centrifugation time, 10 min; and ultrasound time, 60 s).
the analytes and ensure a good recovery. The maximum level of IL
the needle (0.7 mm inner diameter) can hold is 40 mL; therefore,
the inuence of the IL volume on the extraction performance was
determined by evaluating volumes of [P14,6,6,6]Cl between 30 and
40 mL. As shown in Fig. 4, the recovery increased when the volume
increased from 30 to 40 mL and reached the maximum at 40 mL.
To more thoroughly determine the inuence the volume of IL,
volumes of 45 and 50 mL were used in the needle with an inner
diameter of 0.9 mm. There was a slight increase when larger
volumes of IL were used, but higher RSDs were obtained due to
the larger inner diameter. Furthermore, a larger extraction
solvent volume may decrease the enrichment factor, which can
reduce the sensitivity of this method. As a result, 40 mL of [P14,6,6,6]
Cl was adopted in the following LDIL-DLLME experiments.
3.1.4. Optimization of the volume of sample. The volume
of sample has three different effects on the extraction efficiency.
First, higher volume water samples can dissolve more extraction
solvent, leading to a decrease in the recovery. Second, increasing
the volume of the water samples can wash the extraction solvent
from the needle more completely, leading to an increase in the
Fig. 5 Effect of the volume of sample on the recoveries of the pyre-
throid insecticides (extraction conditions: needle's inner diameter, 0.7
mm; salt addition, 1%; volume of IL, 40 mL; rotation speed, 7000 rpm;
centrifugation time, 10 min; and ultrasound time, 60 s).
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extraction efficiency. Finally, a higher water sample volume
increases the pyrethroid insecticides levels that need to be
extracted. This can decrease the extraction efficiency if the
extractant is insufficient to extract all of the analytes. Water
samples of 5–15 mL were used to evaluate the extraction effi-
ciency. Other factors were at previously determined optimum
levels. Fig. 5 shows the results for the four pyrethroid insecti-
cides. Similar recovery was obtained for the 5 and 8 mL samples,
but the recovery slightly increased when the sample volume
increased up to 10 mL. The results can be explained by the fact
that IL has a low solubility in water, and the volume of IL that
was used is sufficient to extract all analytes from 10 mL samples.
Furthermore, because IL was drawn into a needle, its high
viscosity makes it stick to the needle wall. A high water volume
(larger than 10 mL) can wash IL completely out of the syringe
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when drawing the water sample into the syringe, increasing the
recovery. Considering all of these observations, a 10 mL water
sample volume was selected for the following experiments.
3.1.5. Optimization of the rotation speed and centrifuga-
tion time. In the proposed method, centrifugation was needed
to separate the IL and aqueous phases from the cloudy solution.
This procedure has a direct effect on the amount of collected IL,
and can signicantly inuence the recovery. The effects of
rotation speed, in the range of 2000–10 000 rpm, and centrifu-
gation duration, in the range of 6–14 min, on the extraction
efficiency were studied to obtain the optimal conditions. Fig. 6
shows the effect of the centrifugation rotation speed on the
recoveries of the four compounds. As the rotation speed
increased from 2000 to 6000 rpm, the recoveries for all analytes
increased accordingly. When the rotation speed increased to
more than 6000 rpm, the percentage of recovery decreased
noticeably. When the rotation speed is too high, the syringe
cannot withstand the force of rotation and can be distorted or
even broken. Therefore, 6000 rpm was adopted as the centri-
fugation rotation speed. Fig. 7 illustrates the recovery obtained
from different centrifugation durations. Recovery for all analy-
tes increased with increasing duration from 6 to 10 min and
then an equilibrium state was reached. As a result, centrifuga-
tion for 10 min at 6000 rpm was used for further investigation.
Fig. 6 Optimization of the rotation speed on the recoveries of the
pyrethroid insecticides (extraction conditions: needle inner diameter,
0.7 mm; salt addition, 1%; volume of IL, 40 mL; volume of sample, 10
mL; centrifugation time, 10 min; and ultrasound time, 60 s).
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Fig. 7 Effect of centrifugation time on the recoveries of the pyrethroid
insecticides (extraction conditions: needle inner diameter, 0.7 mm; salt
addition, 1%; volume of IL, 40 mL; volume of sample, 10 mL; rotation
speed, 6000 rpm; and ultrasound time, 60 s).
3.1.6. Optimization of ultrasound time. Ultrasound treat-
ment, which making the extraction more complete, is a key
factor in this method. To study the effect of ultrasound on the
extraction efficiency, a series of experiments was performed
with ultrasound times in the range of 0–90 s. As shown in Fig. 8,
a sufficient ultrasound time accelerates the formation of a ne
dispersive mixture and results in higher recovery levels. Nearly
one hundred percent recovery was obtained when the 90 s
ultrasound duration was adopted. Therefore, the ultrasound
duration was set at 90 s.
3.2. Method validation
The optimal conditions selected for LDIL-DLLME were as
follows: the needle's inner diameter was 0.7 mm, containing
40 mL [P14,6,6,6]Cl. The sample solution volume was 10 mL, and
1% salt solution was added. An ultrasonic treatment time of 90 s
was used, and the samples were centrifuged for 10 min at
6000 rpm. Using the above mentioned optimum conditions,
parameters such as the linearity, repeatability, limits of detec-
tion (LODs) and EFs were determined. Three replicate
Fig. 8 Effect of ultrasound time on the recoveries of the pyrethroid
insecticides (extraction conditions: needle inner diameter, 0.7 mm; salt
addition, 1%; volume of IL, 40 mL; volume of sample, 10 mL; rotation
speed, 6000 rpm; and centrifugation time, 10 min).
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Table 1 The performance characteristics of the LDIL-DLLME method combined with HPLC-UV analysis

Linearity Linearity Enrichment LOD LOQ Recovery

Analytes equation (mg L
1) R2 RSD (%) factor (mg L
1) (mg L
1) (%)

Deltamethrin Y ¼ 6.08X
6.98 1–500 0.9994 0.7 257 0.83 2.77 102.6
Fenvalerate Y ¼ 5.48X + 1.10 2–500 0.9999 2.9 256 1.40 4.65 102.3
Permethrin Y ¼ 6.61X
12.43 2–500 0.9994 1.9 242 1.71 5.71 96.7
Bifenthrin Y ¼ 6.10X
9.84 2–500 0.9994 1.5 244 1.20 4.00 96.6

extractions were performed at each concentration level. Because
fenvalerate has a chiral structure47 and the two peaks were
connected, they were considered as a single peak in qualitative
and quantitative analyse. Permethrin has two structure types,
cis- and trans-,48 and both of them were used in quantitative
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from Yijiaju (Chuxiong, Yunnan Province) were used for pyre-
throid determinations to evaluate the applicability of the in-
syringe LDIL-DLLME method. No signicant matrix effects
were present in this method. No target analytes were detected in
the blank samples or in the residues were below the detectable

analyse. The two peaks are independent, and the lower peak was
used in qualitative analyse. Water samples with deltamethrin in
the range of 1–500 mg L
1 and three other analytes in the range
of 2–500 mg L
1 were studied. The characteristic calibration data
are summarized in Table 1. Good linearity and repeatability
were obtained for all four pyrethroids, with R2 values ranging
from 0.9994 to 0.9999 and relative standard deviations (RSDs)
ranging from 0.7 to 2.9%. The limits of detection for the four
pyrethroid insecticides, calculated at S/N ¼ 3, were in the range
of 0.83–1.71 mg L
1 and the limit of quantication were in the
range of 2.77–5.71 mg L
1. High EF and recovery of the four
analytes were obtained, ranging from 242 to 257 and 96.6 to
102.6%, respectively. In conclusion, the proposed LDIL-DLLME
method proved to be an efficient and facile method for the
preconcentration and detection of pyrethroids in spiked water
samples.
3.3. Analysis of spiked real water samples
Three river water samples from Qujiang (Quzhou, Zhejiang
Province), Tongli (Sushou, Jiangsu Province), and Changyuan
He (Jinzhong, Shanxi Province) and one reservoir water sample
level (as shown in Fig. 9a). The environmental samples were
spiked at three concentrations (10, 50 and 100 mg L
1) and were
used to evaluate the matrix effects. The resulting typical chro-
matograms are shown in Fig. 9. The analytical results are
summarized in Table 2. As can be seen, the average recoveries
for the four pyrethroids were in the range of 88.0% to 102.8%,
and the RSDs ranged from 0.3 to 6.7% (n ¼ 3). These results
indicated that the LDIL-DLLME method was reliable and
appears to be a promising method for evaluating of pyrethroids
in water samples.
3.4. Comparison of in-syringe LDIL-DLLME with other
analytical methodologies
The proposed in-syringe LDIL-DLLME method was compared
with other analytical methodologies for preconcentrating and
evaluating pyrethroid insecticides. As shown in Table 3, several
analytical methods, including DLME/D-m-SPE,5 DLLME,49 UA-
DLLME-SFO11 and SSIL-DLLME,50 were compared in terms of
the extraction solvent, extraction time, solvent usage, recovery
and enrichment factors. The organic solvent level required for
this technique is lower than that required for DLME/D-m-SPE

Fig. 9 The HPLC chromatograms of pyrethroids in the spiked and blank environmental water samples: (1) deltamethrin; (2) fenvalerate; (3)
permethrin; (4) bifenthrin. In chromatograms a, b, c and d, the spiked levels were 0, 10, 50 and 100 mg L
1, respectively.

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Table 2 Spiked recoveries (%) of the lake water and river watera

Qujiang Tongli Changyuan He Yijiaju

Analytes Spiked level (mg L
1) ER RSD ER RSD ER RSD ER RSD

Deltamethrin 10 88.1 0.7 94.7 3.8 99.3 6.7 95.4 1.8

50 102.7 2.7 91.5 3.5 100.0 2.0 92.7 4.7
100 98.7 2.7 96.6 2.9 98.2 5.4 98.0 2.5
Fenvalerate 10 102.8 3.2 100.2 1.5 94.3 4.4 94.5 5.4
50 100.3 4.0 91.5 4.6 97.2 5.3 94.3 2.3
100 98.2 2.7 91.1 3.8 96.2 4.8 94.0 5.6
Permethrin 10 90.5 2.4 96.7 4.9 93.5 5.6 91.0 0.8
50 102.5 1.3 97.2 5.3 94.0 5.3 97.3 4.0
100 97.8 2.4 94.7 3.7 100.2 4.7 99.9 2.2
Bifenthrin 10 96.4 6.4 89.5 6.3 90.5 4.8 88.0 5.0
50 102.6 0.3 95.8 4.6 101.8 3.4 95.2 5.9
100 96.6 3.1 96.1 4.9 97.5 5.9 99.4 2.9
Published on 12 July 2016. Downloaded on 9/20/2019 12:49:04 AM.

a
ER: extraction recovery (%); RSD: relative standard deviation (%).

and traditional DLLME, making it more environmentally
friendly and better for health of analysts. Furthermore, when
compared with UA-DLLME-SFO and SSIL-DLLME, it does not
need a solidication procedure, making the method simpler
and quicker. The recovery and EFs in the proposed method are
superior to those of most other methods. In conclusion, less
organic solvent and a lower extraction time were required, and
high recovery and EFs were obtained with the proposed
method, demonstrating that it is a simple, fast, effective and
environmentally friendly technique.
3.5. Comparison of IL with the solvent as extraction solvent
in LDS-DLLME
In this method, [P14,6,6,6]Cl was used as the low density extrac-
tion solvent, for the rst time, in LDS-DLLME. Using ILs as
extraction solvent is superior to the use of other solvents in the
following ways. (i) ILs are not ammable and have negligible
vapor pressures, making them healthier and safer for the
analyst than some volatile, ammable and combustible
solvents. (ii) ILs can be designed to have special properties. This
means that more potential ILs can be found with the property of
low density, which can broaden the application of the LDS-
DLLME method. (iii) Due to the high viscosity of IL, it can
stick to the wall of the extraction vessel and quickly separate
from the aqueous phase. The proposed device for LDIL-DLLME
is simpler than in other methods. However, the higher viscosity
property also limits the devices that can be adopted for the
LDIL-DLLME method. Because most of the devices proposed for
LDS-DLLME cannot be used in LDIL-DLLME, the development
of other devices is necessary. In conclusion, the adoption of IL
in LDS-DLLME greatly broadens the application of the low
density method and makes these methods sampler and more
efficient.
4. Conclusions
In this study, a novel liquid-phase microextraction technique,
in-syringe LDIL-DLLME combined with HPLC-DAD, was
successfully applied to determine the levels of four pyrethroid
insecticides in environmental water samples. An IL was used
as the extraction solvent in LDS-DLLME, for the rst time,
which widely broadened the application of the low density
method. With the high viscosity of IL, the proposed method
was nished in a syringe, enabling rapid collection of the
extraction phase. To avoid the use of a dispersion solvent in
traditional DLLME, the process of drawing the sample solu-
tion into a long needle was used to disperse the IL, making
this method more environmentally friendly. Several signi-
cant experimental parameters were studied. Under the opti-
mized conditions, satisfactory results were obtained and no
signicant matrix effects were observed for evaluating of four

Table 3 Comparison of the proposed LDIL-DLLME method with other methods for the determination of pyrethroid insecticidesa

Extraction Solvent usage Extraction Linearity Recovery

Method solvent Sample (mL) time (min) (mg L
1) EFs (%) Ref.

DLME/D-m-SPE-HPLC 1-Octanol Water 180 4 5–400 51–108 91.7–104.5 5

DLLME-HPLC Chloroform Fruit juices 1650 1 2.00–1000 62–84 85.8–94.0 49
UA-DLLME-SFO-GC-FID 1-Dodecanol Water 300 4 0.5–200 143–813 65.7–73.2 11
SSIL-DLLME-HPLC [P12,4,4,4][PF6] Water 30 1 1–500 145–157 90.1–97.4 50
LDIL-DLLME-HPLC [P14,6,6,6]Cl Water 30 2 1–500 242–257 97.0–102.6 This work
a
DLME, dispersive liquid microextraction; D-m-SPE, dispersive m-solid phase extraction; SSIL, solidication of sedimentary ionic liquids.

69224 | RSC Adv., 2016, 6, 69218–69225 This journal is © The Royal Society of Chemistry 2016

Paper
pyrethroid insecticides in real samples. This method provides
good repeatability, great enrichment factors and high recovery
levels. In addition, this approach required less time and
organic solvent, resulting in an environmentally friendly,
efficient and simple method for determining trace levels of
pyrethroid insecticides in water samples.
Acknowledgements
This work was supported by the fund National Natural Science
Foundation of China (Project no. 21507159, 21277172 and
21377163) and Chinese Universities Scientic Fund (Project no.
2016QC082).
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