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Chinese Chemical Letters 19 (2008) 89–91

www.elsevier.com/locate/cclet

Rapid determination of atrazine in environmental water

samples by a novel liquid phase microextraction
Qing Xiang Zhou a,*, Guo Hong Xie b, Long Pang a
a
School of Chemistry and Environmental Sciences, Henan Normal University, Henan Key Laboratory for Environmental Pollution Control, Key
Laboratory for Yellow River and Huaihe River Water Environment and Pollution Control, Ministry of Education, Xinxiang 453007, China
b
College of Resources and Environment, Henan Institute of Science and Technology, Xinxiang 453003, China
Received 3 July 2007

Abstract
A novel method was described for the rapid determination of atrazine using dispersive liquid phase microextraction in
combination with high performance liquid chromatography (HPLC). Possible impact parameters such as sample pH, extraction and
disperser solvents, salting-out effect, and extraction time were investigated. The experimental results indicated that proposed
method possessed an excellent analytical performance. The linear range, detection limit, and precision (R.S.D.) were 0.1–
50 ng mL 1 (R2 = 0.9955), 0.601 ng mL 1 and 6.4%, respectively. The proposed method was validated with the real water samples,
and the spiked recoveries were in the range of 69.9–89.8%, respectively. These results indicated that the established method with
high enrichment factor, short extraction time was an excellent alternative for the routine analysis of atrazine in environmental
samples.
# 2007 Qing Xiang Zhou. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved.

Keywords: Liquid phase microextraction; Atrazine; High performance liquid chromatography; Water samples

Herbicides are extensively used in the world nowadays, and atrazine is one of the often-used herbicides. It is present
in surface and ground waters, and considered to be a potential risk for water quality due to the heavy use and its
persistence. Atrazine has been proven to be an environmental endocrine disruptor. The limited level is set at 3 ng mL 1
in the WHO and United States Environmental Protection Agency. In many countries, its use is increasingly restricted.
Hence, rapid and sensitive methods are needed for monitoring the widespread distribution of trace atrazine, and
especially the green methods.
Most of the developed methods for atrazine determination involve separation by HPLC [1,2] after liquid–liquid
extraction or solid phase extraction (SPE). Up to now, many new sample pretreatment methods have been developed
for the enrichment and cleanup of complex samples such as SPE with molecularly imprinted polymers (MIPs) [3,4],
and liquid phase microextraction [5–7]. Recently, Rezaee et al. developed a new liquid phase microextraction based on
the homogeneous liquid–liquid extraction and cloud point extraction, named dispersive liquid–liquid microextraction
(DLLME) with the merits such as simplicity of operation, rapidity, low cost, high recovery and enrichment factors [8].
This method has been applied to the determination of polycyclic aromatic hydrocarbons, organochlorine pesticides,

* Corresponding author.
E-mail address: zhouqx@henannu.edu.cn (Q.X. Zhou).

1001-8417/$ – see front matter # 2007 Qing Xiang Zhou. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved.
doi:10.1016/j.cclet.2007.10.036
90 Q.X. Zhou et al. / Chinese Chemical Letters 19 (2008) 89–91

organophosphorus pesticides, and benzene, toluene, volatile phenols, antioxidants [9–11], and triazene herbicides
[12]. However, the method developed by Nagaraju and Huang [12] could not enrich atrazine with carbon tetrachloride
as the extraction solvent and acetone as the disperser solvent. This paper established a new method for the sensitive
determination of atrazine based on the same principle.

1. Experimental

Atrazine was purchased from Ying Tian Yi standard solution company in Beijing, China. HPLC grade acetonitrile
and methanol were obtained from Scharlau Chemie SA (Barcelona, Spain). Ultrapure water was prepared in the lab
using a water treatment device ‘‘Ultra-Clear’’ (SG Wasseraufbereitungsanlagen, Barsbüttel, Germany) and all the
other solvents were analytical reagent grade unless stated.
A high performance liquid chromatography system, which consisted of two LC-10ATvp pumps and an SPD-
10Avp, ultraviolet detector (Shimadzu, Japan) was used for the analysis and separation. A reversed-phase VP-ODS
C18 column (250 mm  4.6 mm ID, particle size 5 mm) was used for separation at ambient temperature and
Chromato Solution Light Chemstation for LC system was employed to acquire and process chromatographic data. The
mobile phase was acetonitrile/water (62/38, v/v) at 0.5 mL min 1, and the injection volume and detection wavelength
were 20 mL and 223 nm, respectively.
The experimental procedure was as followed, a 10 mL of ultrapure water was placed in a 10 mL glass test tube
with conical bottom and spiked with atrazine at a concentration of 10 mg L 1, and 10 g sodium chloride was
added in the solution, and the pH was adjusted to pH 5 with HCl. 550 mL methanol (as disperser solvent) containing
60 mL carbon tetrachloride (as extraction solvent) was rapidly injected in the sample solution and then the
mixture was gently shaken. A cloudy solution was formed. Further, the solution was centrifuged for 2 min at
5000 rpm, the dispersed fine droplets were settled to the bottom of the test tube. The upper phase was removed, and
the extraction solvent phase was then blown to near dryness with a mild nitrogen stream and 100 mL acetonitrile
was added to the test tube for dissolving the enriched analyte. 20 mL of the final solvent was injected into HPLC
system for analysis.

2. Results and discussion

In this new enrichment system, many factors maybe influence the trapping performance such as the kind of
extraction solvent, reasonable disperser solvent, pH value, salting-out effect, extraction time and centrifuging time.
These possible effects were investigated in detail.
Carbon tetrachloride, dichloromethane and trichloromethane were tested for obtaining the best extraction solvent.
The results indicated that dichloromethane and trichloromethane provided very low enrichment factor, so carbon
tetrachloride was used in the followed experiments. The volume of carbon tetrachloride was also an important factor
for the extraction of atrazine, and it was optimized in the range of 10–80 mL. The experimental data demonstrated that
there was no markedly change in the range of 10–40 mL, but the peak area of atrazine increased markedly at 60 mL,
and then decreased. Hence, 60 mL extraction solvent was employed. Disperser solvent was one of the key factors for
the best enrichment, its selection was very important. In this paper, methanol was used as the disperser solvent and
better performance was achieved, and the experimental data indicated that the best extraction performance was
obtained when methanol was 550 mL.
Sample pH played another great role in the extraction of atrazine, and it was investigated in the range of 3–11. The
experimental results showed that the extraction performance was the best at pH 5, and the peak area decreased when
the pH value over or below pH 5. A series of experiments were designed for the optimization to gain optimal extraction
time and centrifuging time. The final results exhibited that better extraction was achieved when extraction time and
centrifuging time were 5 and 2 min, respectively. Salting-out effect is often faced in the liquid phase microextraction
procedure. In general, reasonable amount of sodium chloride added into the sample solution would result in the
increase of extraction efficiency. Here, it was investigated in the concentration range of 0–20% (w/v), and the
experimental data proved that 10% salt adding gave the best extraction performance.
A series of experiments were employed for achieving the parameters of analytical performance. These procedures
were carried at the optimum conditions. The linear range, correlation coefficient, detection limit and precision (R.S.D.,
n = 6) of proposed method were 0.5–50 ng mL 1, 99.55%, 0.6 ng mL 1, and 6.4%, respectively.
 Q.X. Zhou et al. / Chinese Chemical Letters 19 (2008) 89–91 91

Table 1
1
Determination of atrazine in environmental samples spiked at 1 ng mL
Samples Blank (ng mL 1) Spiked recovery (%)
Tap water – 84.7
Groundwater – 69.9
Reservoir – 89.8

In order to validate the proposed method, three real water samples such as the tap water, the groundwater, water
sample from Shimeng reservoir were used. The results demonstrated in Table 1. For the sake of the wide use of
proposed method in the future, spiked recoveries were also investigated for four real water samples. The obtained data
were very excellent and the spiked recoveries in the range of 69.9–89.8%.
This paper demonstrated that proposed liquid microextraction utilizing methanol as the disperser solvent resulted in
the marked increase of enrichment factor, and was better than that with acetone as the disperser solvent. The
experimental results indicated that the proposed method was very simple and rapid, and could be used for the atrazine
routine analysis in the environmental monitoring with some improvement.

Acknowledgments

This work was supported by the Personal Innovation Foundation of Universities in Henan Province (No.
[2005]126), Natural Science Foundation of Henan Province (No. 072300460010) and the Fund of Henan Normal
University (No. 2006PL06), and the grants from the Henan Key Laboratory for environmental pollution control.

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