Microchim Acta (2011) 173:477483
DOI 10.1007/s00604-011-0587-2
ORIGINAL PAPER
Ultratrace determination of carbamate pesticides in water
samples by temperature controlled ionic liquid dispersive
liquid phase microextraction combined with high
performance liquid phase chromatography
Qingxiang Zhou & Long Pang & Junping Xiao
Received: 22 December 2010 / Accepted: 4 March 2011 / Published online: 16 March 2011
# Springer-Verlag 2011
Abstract A simple and sensitive method was developed
for the determination of three carbamate pesticides in water
samples. It is based on temperature controlled ionic liquid
dispersive liquid phase microextraction combined with high-
performance liquid chromatography. The ionic liquid 1-hexyl-
3-methylimidazolium hexafluorophosphate was used as the
extractant, and the factors affecting the extraction were
investigated in detail. The detection limits obtained for
isoprocarb, diethofencarb and fenothiocarb are 0.91, 0.45,
and 1.40 gL-1, respectively, and the precisions are in the
range between 1.0 and 1.8% (n=6). The method was
validated with environmental water samples and the results
indicate that it represents a viable alternative to existing
methods.
Q. Zhou (*)
State Laboratory of Petroeum Resource and Prospecting,
College of Geosciences, China University of Petroleum,
Beijing Capmus(CUP),
Beijing 102249, China
e-mail: zhouqx@cup.edu.cn
e-mail: zhouqx@henannu.edu.cn
Q. Zhou : L. Pang
School of Chemistry and Environmental Sciences, Henan Key
Laboratory for Environmental pollution Control, Key Laboratory
for Yellow River and Huaihe River Water Environment and
Pollution Control, Ministry of Education, Henan Normal
University,
Xinxiang 453007, Peoples Republic of China
J. Xiao
Department of Chemistry,
University of Science and Technology Beijing,
Beijing 100083, China
Keywords 1-Hexyl-3-methylimidazolium
hexafluorophosphate . Carbamate pesticides . Temperature
controlled ionic liquid dispersive liquid phase
microextraction . High performance liquid chromatography
Introduction
Ionic liquids (ILs) consisted of the combination of organic
cations with delocalized charges and various anions [1].
Owing to their special properties, they have represented a
type of novel solvents at the beginning of the 21st century
[2]. Recently, ILs have become the focus of many academic
and industrial investigations, and mainly utilized as reaction
media for a number of organic synthesis reactions,
catalysis, separation processes and polymerization [311].
Compared to traditional organic solvents, they are nonvol-
atile, nonflammable, possess high thermal stability and are
excellent solvents for a wide range of inorganic and organic
materials. Due to these advantages, ILs have been widely
known as green solvents and good alternatives to
conventional organic solvents.
In general, environmental pollutants are present at
trace levels in environmental samples, which bring
difficulties in direct instrumental analysis. According to
this, sample pretreatment procedure prior to instrumental
analysis is necessary. Carbamate pesticides are mainly
used in agriculture, and most of them are prone to
distribute in the aqueous environments due to their high
solubility in water. Recently, increasing evidences
confirmed that carbamates are potential contaminants
of the ecosystem and human health [12]. Therefore, it is
of great importance to monitor their residual concentration
in environmental waters. There have been several sample
478
pretreatment methods for the analysis of carbamate
pesticides including solid-phase microextraction (SPME)
[13, 14], solid-phase extraction (SPE) [15, 16], matrix
solid-phase dispersion (MSPD) [17], liquid-liquid extrac-
tion (LLE) [18], etc. In general, high-performance liquid
chromatography coupled with mass spectrometry [15, 17]
or ultraviolet detector [16, 18] were the popularly used
techniques for the analysis of carbamate pesticides. Liquid
phase microextraction (LPME) developed in recent years
is a novel technique which has merit such as simplifica-
tion, sensitivity, high enrichment factor and inexpensiveness
and gradually attracted much more attention. Nowadays, typic
LPME methods are single drop microextraction (SDME)
[19], hollow fiber microextraction (HF-LPME) [20] and
dispersive liquid-liquid microextraction (DLLME) [21],
etc. SDME was developed by Jeannot and Cantwell [22]
for the determination of environmental pollutants firstly,
and the results confirmed that it was an ingenious sample
pretreatment method with advantage of simplicity, high
enrichment factors and less consumption of organic
solvents. DLLME was developed by Rezaee, Assadi and
coworkers, and has been regarded as a novel liquid phase
microextraction method [23]. Due to the merits, DLLME
has been widely used for the analysis of heterocyclic
insecticides [24], DDT and its main metabolites [25],
triazine herbicides [26], organophosporus pesticides [27],
Cadmium [28], palladium and cobalt [29] and so on.
Recently, DLLME was also developed for the enrichment
and determination of three organophosphorus pesticides
[30]. However, toxic and volatile organic solvents such as
benzene, chlorobenzene, and chloroform were often
employed as the extraction solvent in DLLME, which
would generate secondary pollution and put a severe threat
on the environment human health. Therefore, the special
characteristics of ILs were utilized and a new method
named temperature controlled ionic liquid dispersive
liquid phase microextraction was described. 1-hexyl-3-
methylimidazolium hexafluorophosphate ([C6MIM] [PF6])
was utilized as the extractant and the temperature was used
as the driving force in the dispersing procedure. The factors
that would influence the extraction were investigated in
detail.
Experimental
Reagents
1-Hexyl-3-methylimidazolium hexafluorophosphate ([C6MIM]
[PF6]) was prepared in lab [31]. Isoprocarb, diethofencarb
and fenothiocarb were purchased from Institute of Envi-
ronmental Prevention and Monitoring of Agriculture
Q. Zhou et al.
Ministry (Beijing, China). Methanol and acetonitrile of
HPLC grade were obtained from Jiangsu Guoda Chemical
Reagent Co., Ltd (Huaian, China). Ultrapure water was
prepared by a Milli-Q purification system (Millipore,
Bedford, MA, USA).
Apparatus
A high-performance liquid chromatography system, which
consisted of two Waters 1,525 pumps and a Waters 2998
diode-array detector (Waters, Milford, USA), was utilized
for the separation and analysis. A reversed-phase Waters
SunFireTM C18 column (4.6150 mm, 5 m) was used for
separation at 25 C. The mobile phase, the flow rate and the
injection volume were methanol/water (60/40, v/v),
0.6 mLmin-1, and 20 L. Detection wavelengths for
isoprocarb, diethofencarb and fenothiocarb were set at
200, 243.3 and 225 nm, respectively.
Temperature controlled ionic liquid dispersive liquid phase
microextraction
In the experimental procedure, 40 L 1-hexy-3- meth-
ylimidazolium hexafluorophosphate ([C6MIM] [PF6]) was
added into a 10 mL glass conical tube, and 10 mL ultra-pure
water was added. This solution was spiked with different
concentration of 200, 125 and 150 gL-1 for isoprocarb,
diethofencarb and fenothiocarb, respectively. Then the
conical tubes were heated with the temperature controlled
at 70 C. Then IL was dispersed into the aqueous solution
completely, and a homogenous solution formed. The
analytes would migrate into the IL in a short time because
of the higher solubility of analytes in IL. The tube was
thereafter cooled with ice water and kept for 20 min and a
cloudy solution formed. Then the cloudy solution was
centrifuged for 15 min at 3,000 rpm. The upper aqueous
phase was removed with a syringe and the residue was
dissolved in 200 L methanol and 20 L was injected into
the HPLC system for analysis.
Real water samples
Four real water samples were collected and utilized for
validating the method. Melted snow water was collected from
Henan Normal University, Xinxiang city, Henan Province.
Tap water was collected from our laboratory. Wastewater
sample was taken from the exit of Xiaoshangzhuang
wastewater treatment factory in Xinxiang city, Henan
Province. Lake water sample was collected from Shouxihu
park, Yangzhou city, Jiangsu Province. All the real water
samples were filtered through 0.45 m micro-pore mem-
branes and stored for use.
Ultratrace determination of carbamate pesticides in water samples
Results and discussion
Effect of the volume of ionic liquid
IL volume is an essential factor in the procedure, which can
influence the formation of the cloudy solution and also
affect the enrichment performance. The effect of IL volume
on the extraction procedure was investigated over the range
of 2545 L. The results were exhibited in Fig. 1. The
results indicated that the peak areas of target analytes also
increased in the range of 2540 L and slightly decreased
in the range of 4045 L with the increase of of IL volume.
The reason was that some IL would adsorb onto the tube
wall when the IL volume exceeded a certain value.
According to these facts, 40 L [C6MIM][PF6] was
selected in the subsequent experiments.
Effect of sample pH
Sample pH is another important factor in LLE procedure,
which determined the present form of target analytes in
aqueous solution. A series of experiments were carried out to
achieve the optimal pH. The pH was investigated over the
range of pH 28 and the experimental results were shown in
Fig. 2. From the Fig. 2, it was found that the peak areas of
these three compounds changed very slightly when the
sample was in acidic or neutral conditions, and decreased in
alkalescent conditions. Moreover, isoprocarb was disap-
peared in alkalescent environment. This accounted for the
fact that these compounds were stable in acidic and neutral
environment, and instable in alkalescent environment.
Hence, pH 6 was used in the following experiments.
Fig. 1 The effect of ionic liquid volume. Extraction condition:
spiked level, 200 gL-1 (isoprocarb), 125 gL-1 (diethofencarb),
150 gL-1(fenothiocarb); sample volume, 10 mL; pH 6; extraction
temperature, 70 C; extraction time, 20 min; centrifuging time, 20 min;
salt addition, 0% (w/v). isoprocarb fenothiocarb fenothiocarb
479
Fig. 2 The effect of sample pH. Extraction condition: sample volume,
10 mL; [C6MIM][PF6] volume, 40 L; extraction temperature, 70 C;
extraction time, 20 min; centrifuging time, 20 min; salt addition, 0% (w/v)
Effect of dissolving temperature
In this special enrichment procedure, temperature was the
key factor, which can accelerate the transformation of target
analytes from aqueous solution to IL phase. In general, the
recoveries of the analytes would be enhanced with the
increase of temperature. However, high temperature will
also lead to the loss of some target analytes by
volatilization in some cases. Hence a suitable tempera-
ture is very important for developing a reliable method.
Here the optimization of temperature was conducted
between 60100 C and the results were exhibited in
Fig. 3. It is easy to see that the optimal temperature was
70 C.
Fig. 3 The effect of extraction temperature. Extraction condition:
sample volume, 10 mL; [C6MIM][PF6] volume, 40 L; pH 6;
extraction time, 20 min; centrifuging time, 20 min; salt addition,
0% (w/v)
480 Q. Zhou et al.

Table 1 Linear ranges,

precisions, detection limits Compound Linear range (g L-1) R2 RSDs (n=6) (%) LOD (g L-1)
of the established method
Isoprocarb 5.01,000 0.9993 1.0 0.91
Diethofencarb 3.1625 0.9989 1.8 0.45
Fenothiocarb 3.8750 0.9991 1.6 1.40

Effect of extraction time
In this experiment, extraction procedure is a time consum-
ing process, which means the time from the solution to be
cooled to centrifuging. The effect of extraction time was
examined in the range of 1050 min and the results showed
that the best results were achieved at 20 min. The peak
areas slightly decreased during 2050 min largely because
part of [C6MIM][PF6] was dissolved in aqueous solution
gradually. According to these results, 20 min was selected
as the optimal extraction time.
sodium chloride in the range of 015%, and obviously
declined when further addition. Addition of a proper
amount of sodium chloride would promote the transforma-
tion of analytes from sample solution to the ILs drops, but
some of sodium chloride would salt out at low temperature
when the amount of sodium chloride was over 15%, which
would adsorb part of analytes and lead to the decrease of
recoveries finally. Hence, 15% addition of sodium chloride
was used in this experiment.
Analytical parameters of the developed method

Effect of centrifuging time
Phase separation is a popular procedure in liquid phase
extraction methods, and centrifugation is an often used and
convenient means. Herein ILs phase can be easily obtained
by centrifugation after a certain extraction time. Centrifu-
gation time is also of great importance to the enrichment
performance. A series experiments were designed in order
to achieve the optimal centrifuging time. The experiments
demonstrated that it could reach the optimal extraction
performance at 15 min. With a longer time, the peak area
decreased. Maybe parts of [C6MIM] [PF6] drops were
redissolved in the solution due to the heat generation
resulted from longer centrifugation time. In order to obtain
the best extraction performance, 15 min was adopted.
Effect of salting-out effect
Salting-out effect is a popular parameter in the sample
pretreatment procedures, which has significant influence on
the extraction efficiency. So it was studied in detail in the
range of 020% (w/v) with addition of sodium chloride
with the temperature was controlled at 70 C at dispersing
step. The results exhibited that the peak areas of target
analytes increased with the increase of the concentration of
Under the optimal conditions, some important parameters
such as linear range, precisions and detection limits, which
significant influence the extraction performance, were
investigated. It can be seen from the Table 1, the
experimental results exhibited that there were good linearity
over the concentration range of 5.01,000, 3.1625, and
3.8750 gL-1 for isoprocarb, diethofencarb and fenothio-
carb, respectively and the correlation coefficients (R2) were
in the range of 99.8999.93%. The detection limits (LODs)
were in the range of 0.451.40 g L-1, and good precisions
were achieved in the range of 1.01.8% by performing six
extractions at the same concentration under optimal
extraction condition. The comparison of this method with
existing method for different matrices was demonstrated in
Tables 2 and 3. From Table 3, it was found that this
developed method utilized conventional and low cost
instrument LC-UV and developed a new method with much
lower LODs for the determination of carbamate pesticides.
Real water sample analysis
In order to validate the applicability of the developed
method, four environmental water samples such as melted
snow water, tap water, wastewater and lake water samples
were analyzed with the developed method. These samples

Table 2 Spiked recoveries of

four environmental water Compounds Melted snow water Tap water Xiaoshangzhuang Shouxihu Lake water
samples wastewater

blank spiked blank spiked blank spiked blank spiked

Isoprocarb 82.61.8a 104.44.1 93.42.0 95.01.7

No detection Diethofencarb 95.83.9 101.03.1 99.62.5 99.643.7

a
spiked recovery, mean value (%) Fenothiocarb 108.72.0 95.57.6 97.43.4 84.43.0
standard deviation
Ultratrace determination of carbamate pesticides in water samples 481

Table 3 Figures of merits of

comparable methods for deter- Method Matrix Analytical range LOD Ref.
mination of carbamate
pesticides Matrix -SPE LC-MS Fruits vegetables 0.0110 mgkg-1 0.0010.01 mgkg-1 [17]
C18 SPE HPLC-UV Soil 2200 ngg-1 0.010.4 ngg-1 [32]
In-tube SPME HPLC-UV water 510,000 gL-1 1.015 gL-1 [33]
LLE-LTPa HPLC-UV Water 0.03310 mgL-1 510 gL-1 [34]
a
liquidliquid extraction with low DLLME HPLC-DAD vegetables 10300, 20600 gkg-1 0.53.0 gkg-1 [35]
temperature partitioning DLLME-sweeping MEKC apples 6500, 9500 ngg-1 2.03.0 ngg-1 [36]
b
temperature controlled ionic liq- TCILDLPMEb-HPLC-UV water 5.01,000, 3.1625, 0.451.40 gL-1 Present study
uid dispersive liquid phase 3.8750 gL-1
microextraction

were spiked with isoprocarb, diethofencarb and fenothio- of 82.56108.70% with the precisions of 1.77.6%. The
carb at the concentration of 200, 125 and 150 g L-1, typical chromatograms of target analytes in spiked water
respectively. The results were listed in Table 2. It can be samples versus the blank water samples were shown in
seen that the spiked recoveries were satisfied over the range Fig. 4.

Fig. 4 The representative

spiked chromatogram from
Melted snow water sample.
Conditions: sample volume,
10 mL; [C6MIM][PF6] volume,
40 L; pH 6; extraction
temperature, 70 C; extraction
time, 20 min; centrifuging time,
15 min; salt addition, 15%. 1,
isoprocarb; 2, diethofencarb;
3, fenothiocarb
482
Conclusions
Although there also have a few reports on investigating
their toxicity, ionic liquid has been regarded as green
solvent due to low vapor pressure and other properties. In
present work, ionic liquid was utilized as the alternative of
the extraction solvent and dispersing solvent in traditional
DLLME and developed a simple, rapid, sensitive and cheap
method for the analysis of carbamate pesticides based on
the temperature controlled ionic liquid dispersive liquid
phase microextraction. The detection limits of this method
were in the range of 0.451.40 gL-1 (S/N=3), and the
excellent spiked recoveries of carbamate pesticides in real
water samples was obtained, which proved that this method
was a potential alternative for such contaminants in the
routine anylysis.
Acknowledgements This work was financially supported by the
National Natural Science Foundation of China (20877022) and the
Personal Innovation Foundation of Universities in Henan Province
([2005]126).
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