Analytical Letters, 47: 22092220, 2014

Copyright # Taylor & Francis Group, LLC

ISSN: 0003-2719 print=1532-236X online
DOI: 10.1080/00032719.2014.902462

Preconcentration Techniques
DETERMINATION OF ORGANOCHLORIDE AND
TRIAZINE PESTICIDES IN NATURAL WATERS
BY SOLVENT BAR MICROEXTRACTION
C. Vergel, E. J. Guerrero, C. Mendigucha, and C. Moreno
Department of Analytical Chemistry, Faculty of Marine and
Environmental Sciences, University of Cadiz, Puerto Real, Spain
A new analytical methodology based on solvent bar microextraction has been developed to
preconcentrate two triazine and two organochloride pesticides in natural waters prior to
analysis by gas chromatography. The method was optimized for the organic solvent, sample
pH, sample agitation, length of the ber, extraction time, and salt concentration. The
optimized methodology provides high enrichment factors, ranging between 40.2 (aldrin) to
107.0 (lindane). Since no salinity effects were observed, this method may be used to analyze
fresh and salt water. Thus, three real samples with different salinities were analyzed with
pesticide recoveries higher than 80%. As this methodology agreed with the principles of
green analytical chemistry, it offers low solvent and sample consumption, simplicity, and
compatibility with current analytical techniques.
Keywords: Hollow ber; Liquid phase microextraction; Natural waters; Organochloride pesticides;
Triazines

INTRODUCTION
Over the past decades, the extensive use of chemical reagents to exterminate
insects in agriculture has been an increasing source of contamination to natural
waters. Once these compounds have reached the environment, they may be adsorbed
by organisms and accumulated in the food chain. Therefore, most of these
compounds have been prohibited in the majority of developed countries, reducing
their concentrations in the aquatic environment. However, several current analysis
carried out in natural waters have shown the presence of these prohibited
reagents, so that their identication and quantication continues to be an important
task (Belmonte, Garrido, and Martnez 2005).
Among these organic compounds, triazine and organochloride pesticides are
a cause of concern because of their toxicity. In fact, a high number of these
Received 8 January 2014; accepted 3 March 2014.
Address correspondence to C. Mendigucha, Department of Analytical Chemistry, Faculty of
Marine and Environmental Sciences, University of Cadiz, 11510 Puerto Real, Spain. E-mail: carolina.
mendiguchia@uca.es
2209

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C. VERGEL ET AL.

compounds are listed as persistent, bioaccumulative, and toxic reagents (PBT), as

dened in the EPAs Toxic Release Inventory (EPA 2012). Their presence in natural
waters is regulated by Directive 2008=105=CE on environmental quality standards in
the eld of water policy (Directive 2008=105=CE). Specically, triazines present high
mobility, great solubility in water, and tendency to be absorbed in soils (Shen and
Lee 2003). In addition, one of these compounds, atrazine, has been classied as
a possible human carcinogen (Shen and Lee 2002). Organochloride pesticides have
also shown great toxicity for humans, showing a modulating effect on the human
endocrine system (Li et al. 2008).
Although several techniques are available to extract and determine these
pesticides from natural waters, liquid=liquid extraction continues being the most
popular in routine sample preparation (Lambroupoulou and Albanis 2007). However, this technique presents several disadvantages mainly related to the high volumes
of organic solvent needed, moving it away of the principles of Green Chemistry
(Armenta, Garrigues, and de la Guardia 2008; Anastas and Warner 1998). To
overcome this drawback, miniaturized extraction techniques have been developed
to reduce the volume of organic solvents and the waste generated. High enrichment
factors have been obtained with minimum consumption of sample (Ghambarian,
Yamini, and Esrali 2012). The use of a hollow ber as support for the organic
solvent has been widely used recently to avoid the loss of solvent observed in other
microextraction approaches (Psillakis and Kalogerakis 2003; Rasmussen and PedersenBjergaard 2004; Lambroupoulou and Albanis 2007; Pena-Pereira, Lavilla, and
Bendicho 2009; Dadfarnia and Shabani 2010; Tankiewicz, Fenik, and Biziuk 2011).
The two phase mode is the most extensively used for pesticide analysis, because the
organic solvent is placed in the lumen of a microporous polymeric support and the
extraction is performed through the organic phase lling the pores. Once the extraction is complete, the organic solvent is extracted from the lumen and directly injected
into a chromatography system for analysis. Although several congurations are
available, the so-called solvent bar microextraction has been presented as a simple
mode of microextraction (Jiang and Lee 2004). The preparation of the extraction unit
is very easy and requires minimal manipulation of the sample. As it consists in
a solvent bar tumbling freely in the solution, this methodology allows the analysis
of organic compounds in different samples with complex matrices, such as slurries,
wine, and wastewater (Jiang and Lee 2004; Chia and Huang 2006; Kamarei,
Ebrahimzadeh, and Yamini 2010). Jiang and Lee (2004) obtained better relative
standard deviations for the analysis of slurry samples with this technique than by
solid phase microextraction. Moreover, the solvent bar microextraction agrees with
the principles of green chemistry because the solvent volume is drastically reduced
in comparison with traditional extraction. However, the reduction in solvent is
insufcient for the technique to be considered green (Keith, Gron, and Young 2007).
Although solvent bar microextraction and similar approaches have been
previously used to determine organochloride pesticides in wine and triazines in water
(Chia and Huang 2006; Peng et al. 2007; Hu et al. 2009) usually other hollow ber
liquid phase microextraction congurations has been used to determine these
compounds. None of these approaches allowed their simultaneous analysis
(Lambroupoulou and Albanis 2007; Basheer, Lee, and Obbard 2002; Shen and Lee
2002; Yan and Wu 2004).

ORGANOCHLORIDE AND TRIAZINE PESTICIDES IN WATER

2211

In the present work, a solvent bar microextraction technique was developed to

determine triazines and organochloride pesticides in natural waters with different salinities. As examples of these contaminants, atrazine, terbuthylazine, lindane, and aldrin
were selected due to their extensive use and their persistence in the environment. Atrazine and lindane are included as priority hazardous substances in the Water Frame
Directive (Directive 2008=105=CE). The most inuent parameters in the extraction
process were studied, such as organic solvent used, the sample pH, stirring rate, ber
length, extraction time, and sample salinity. Once the conditions were optimized, the
method was employed for the analysis of real samples.
EXPERIMENTAL
Materials and Chemicals
Toluene, octanol, octane, hexane, and the pesticides were obtained from SigmaAldrich (Steinheim, Germany). The preparation of the pesticide standards was carried
out by weighing the appropriate amount of each pesticide followed by dissolution in
methanol (Scharlab, Barcelona, Spain). Sodium hydroxide and sodium chloride were
also obtained from Scharlab (Barcelona, Spain) (analytical-reagent grade).
The solvent bar microextraction experiments were performed using an Accurel
PP S6=2 polypropylene hydrophobic capillary ber with the following characteristics:
wall thickness 450 mm, porosity 72% and inner diameter 1800 mm. It was purchased
from Membrane (Wuppertal, Germany).
All synthetic solutions were prepared with Milli-Q water. For optimization
purposes, the concentration of pesticides in the source solution was 1 mg  L1 of
lindane and aldrin, 20 mg  L1 of terbuthylazine, and 50 mg  L1 of atrazine. In
addition, a simulated seawater matrix was produced by adding 35 g  L1 of sodium
chloride to the samples. The pH of the samples was controlled by a model 2001
pH-meter with a combined glass Ag=AgCl electrode (Crison, Spain).
Solvent Bar Microextraction
A piece of the hollow ber was cut to the desired length. One end of the ber
was sealed with heat before immersing it in the solvent. It was then introduced freely
in the sample placed in tubes stirred in a model Reax 2 tubing stirrer (Heidolph,
Germany) that allowed agitation rates between 20 and 100 rpm. In this conguration, loss of solvent is avoided due to the hydrophobic characteristics of the support
material and the surface tension. After the selected extraction time, the solvent was
extracted from the ber with a microsyringe and 1 mL was injected in a gas chromatograph with an electron capture detector.
The effects of the solvent, sample pH, stirring rate, ber length, and extraction
time were studied using a univariate optimization. The parameter to be maximized
was the enrichment factor dened as follows (Pedersen-Bjergaard, Rasmussen, and
Jonsson 2010):
Ee

Cacceptor
Csample

2212

C. VERGEL ET AL.

where Cacceptor and Csample are the concentration of pesticides in the solvent and
sample, respectively. The effects of sample salinity, analytical characteristics, and
applicability to real sample analysis were investigated.
Chromatographic Analysis
The analysis of the pesticides extracts was performed by an Agilent 7820A gas
chromatograph (GC) (USA), equipped with a micro electron capture detector. The
capillary column was a HP-5 (5% phenyl and 95% methylpolysiloxane)
30 m  0.32 mm  0.25 mm (Agilent Technologies, DE, USA). The injection of 1 mL
of sample was carried out in splitless mode, using nitrogen as carrier gas at a ow
of 25 psi. The GC temperature program was as follows: initial temperature 150 C,
held for 1 minute, and then increased by 5 C  min1 to 190 C. The detector temperature was maintained at 300 C.
Sample Collection
Three real samples were used to test the applicability of the method. Two were
collected from Cadiz (SW, Spain), one of seawater from the San Pedro River and the
other freshwater from the Guadalete River. The third was tap water. The samples
were passed through a 0.7 mm pore size glass lter prior to the extraction.
RESULTS AND DISCUSSION
Optimization of the method was performed using a univariate approach for the
organic solvent, the sample pH, the stirring rate, the ber length, the extraction time,
and the sample salinity.
Selection of Organic Solvent
The rst parameter studied was the type of solvent used as extractant. The
solvents from most to least polar included octanol, toluene, hexane, and iso-octane.
As shown in Figure 1, different behaviors were observed for the different pesticides.
In general, the enrichments increased when the polarity of solvent decreased, as
expected due to the low polarity of these pesticides. However, atrazine showed minor
extraction for iso-octane and hexane, probably due to the higher polarity of this
pesticide (Perez-Carrera et al. 2007). However, a low enrichment factor for atrazine
was also observed for octanol, the most polar solvent. This could be related to the
high viscosity of octanol (6.49  103 Pa  s), in comparison with the other solvents
(between 3.72  104 5.90  104 Pa  s), which could affect the diffusion coefcients
of the analytes and the kinetics of mass transfer (Kokosa Przyjazny, and Jeannot
2009). For this reason, toluene was selected as the most appropriate solvent for
the extraction of the analytes. This solvent has been widely used in other techniques
for pesticides because of its suitable immobilization in the hollow ber pores and
its high solubility for the analytes (Basheer et al. 2002; Shen and Lee 2002;
Lambroupoulou and Albanis 2007; Sanagi et al. 2010; Young et al. 2011; SarafrazYazdi, Assadi, and Ibrahim 2012).

ORGANOCHLORIDE AND TRIAZINE PESTICIDES IN WATER

2213

Figure 1. Effect of extraction solvent on the enrichment factor. Aqueous solution: pH 8; 35 g  l1 NaCl.
Fiber length: 4 cm; stirring rate: 40 rpm; extraction time: 30 min.

Effect of Sample pH
The pH of the sample plays an important role to modify the ionic form of the
analytes, inuencing the solubility and extraction efciency. The pH should allow
the analytes to remain in neutral states to achieve better extraction (Lambroupoulou
and Albanis 2007). The effect of the pH on the enrichment factor was evaluated in
the range from 2 to 8. As Figure 2 shows, the triazine herbicides presented higher
enrichment factors in the intermediate range of pH values probably due to the
possible hydrolysis of these compounds at extreme values. Similar behavior was
observed by Trtic-Petrovic et al. (2010) for atrazine, although Shen and Lee (2002)
observed the same extraction efciency for this pesticide regardless of the pH value.
Although other authors have observed a reduction in the extraction efciency for
organochloride pesticides at alkaline pH range due to decomposition (Basheer et al.
2002), Figure 2 shows slight differences in the enrichment factors of lindane and aldrin
at basic pH. A small increase was observed for lindane at pH values greater than 6. A
pH of 6 was selected as optimum.

Figure 2. Effect of sample pH on the enrichment factor. (^) Atrazine, (&) Terbutylazine, (~) Lindane, (x)
Aldrin. Aqueous solution: 35 g  l1 NaCl. Fiber length: 4 cm; stirring rate: 40 rpm; extraction time: 30 min.

2214

C. VERGEL ET AL.

Figure 3. Dependence of enrichment factor on the stirring rate. (^) Atrazine, (&) Terbuthylazine, (~)
Lindane, (x) Aldrin. Aqueous solution: pH 6; 35 g  l1 NaCl. Fiber length: 4 cm; stirring rate: 40 rpm;
extraction time: 30 min.

Effect of Stirring Rate

The agitation of the sample is an important parameter to consider because
mass transfer of the analytes may be improved by agitation (Lambroupoulou and
Albanis 2007; Pena-Pereira, Duarte, and Duarte 2012). However, a negative effect
has been observed for high stirring rates due to a less stability of the organic solvent
in the ber and the appearance of air bubbles on the surface of the hollow ber
(Sanagi et al. 2010; Sarafraz-Yazdi et al. 2012). In this work, different behavior
was observed for the pesticides. As shown in Figure 3, for organochloride pesticides,
the enrichment factor was independent of stirring rate, probably because the
maximum enrichment factor for these pesticides was obtained at lower stirring rates.
However, triazines showed higher enrichment factors at intermediate stirring rates.
A stirring rate of 40 rpm was selected for subsequent experiments.
Effect of Fiber Length
The next parameter studied was the ber length used for the extraction.
A shorter length may improve the enrichment factor due to a higher volume between
the donor and received phases, but may increase the time of sample preparation
due to the lower surface area (Sanagi et al. 2010). In this case, the ber length was
varied from 1 to 9.5 cm, which was the maximum length allowed for the selected
conguration. Figure 4 shows that better enrichment factors were achieved by
reducing the length of the ber. Nevertheless, aldrin showed a minor enrichment
factor for the shortest length (1 cm) so that an optimum length of 2 cm was chosen
for the following experiments.
Selection of Extraction Time
A study of extraction time was performed to evaluate the interval required for
the system to reach equilibrium. Figure 5 shows that the enrichment factor increases
with extraction time up to 60 minutes and remains constant for times up to 400 min.
For longer times, a decrease was observed, probably due to the instability of the

ORGANOCHLORIDE AND TRIAZINE PESTICIDES IN WATER

2215

Figure 4. Effect of the ber length on the enrichment factor. (^) Atrazine, (&) Terbuthylazine, (~)
Lindane, (x) Aldrin. Aqueous solution: pH 6; 35 g  l1 NaCl. Fiber length: 4 cm; stirring rate: 40 rpm;
extraction time: 30 min.

organic phase. Previous studies have suggested that the optimum extraction time
for these systems to be between 15 and 30 min due to instability at longer times
(Lambroupoulou and Albanis 2007; Sanagi et al. 2010). The enrichment factor
obtained in this work was constant from 60 to 400 min, and it was signicantly
higher than at lower times. As instability problems were not observed, a time of
60 min was selected as optimum.
Effect of Sample Salinity
As the system has been developed to extract pesticides from saline waters
(35 g  l1 NaCl), the effect of NaCl concentration was investigated. Although some
authors found an increase in the efciency at high NaCl concentrations, other
behavior has been observed in liquid phase microextraction (Lambroupoulou and
Albanis 2007). In this case, the enrichment factors for the four pesticides were
constant with the salinity over the range from 0 to 35 g  l1, as has been observed
in previous reports of organochloride pesticides and triazines with liquid phase

Figure 5. Effect of extraction time on the enrichment factor. (^) Atrazine, (&) Terbuthylazine, (~)
Lindane, (x) Aldrin. Aqueous solution: pH 6; 35 g  l1 NaCl. Fiber length: 2 cm; stirring rate: 40 rpm.

2216

C. VERGEL ET AL.

microextraction (Shen and Lee 2002; Sarafraz-Yazdi et al. 2012). Lampropoulos

reported two effects when NaCl is added to samples (Lambroupoulou and Albanis
2007). The salting-out effect improves the extraction due to a reduction in the
solubility of the pesticides and a subsequent increase of their partitioning into the
organic phase. The other is related to changes in the physicochemical properties of
the extraction lm reducing the diffusion rates of analytes into the organic phase.
In the present work, the combination of these effects may be responsible for the
constant enrichment factors with different salinities. Therefore, this methodology
allows the simultaneous extraction of pesticides selected in saline or fresh water.

Analytical Performance
Once the main factors inuencing the extraction process were investigated, the
methods linearity, precision and detection limits were evaluated, as shown in
Table 1. The linearity was studied over the ranges of 2.550 mg  L1 atrazine,
120 mg  L1 terbuthylazine, and 0.051 mg  L1 lindane and aldrin. The calibration
curves were linear for the pesticides, with a linear determination coefcients from
0.964 (aldrin) to 0.997 (lindane). Each measurement was performed three times
under the optimized conditions, obtaining relative standard deviations from 2.8%
(terbuthylazine) to 9.6% (aldrin), comparable with those obtained by other researchers (Basheer et al. 2002; Lambroupoulou and Albanis 2007). The limits of detection
were calculated from the calibration curve as 3 sb=m, where sb is the standard deviation of the y-intercept and m represents the slope of the line (Miller and Miller
2010). The enrichment factor for each pesticide was also considered. These limits
of detection are below the environmental quality standards for priority substances
in the eld of the Water Frame Directive that included atrazine and lindane (Directive 2008=105=CE). Under optimized conditions, the enrichment factors obtained
were between 40.2 (aldrin) and 107.0 (lindane).
In comparison with other similar hollow ber liquid phase microextraction
approaches, the reported method provides low limits of detection for atrazine and
aldrin and also high enrichment factors for atrazine and lindane (Peng et al. 2007;
Basheer et al. 2002). In addition, in some cases, the time necessary to perform the
extraction was reduced (Trtic-Petrovic et al. 2010). In addition, the method may
be presented as a green alternative to the traditional solvent extraction due to the
reduction of the waste generated, although toluene is included in the EPAs Toxic
Release Inventory as a persistent, bioaccumulative, and toxic reagent in the F and
U hazardous waste list of the Resource Conservation and Recovery Act. The
Table 1. Analytical performance of the optimized methodology
Pesticide
Atrazine
Lindane
Terbuthylazine
Aldrin

Linear range (mg  L1)

r2

LOD (mg  L1)

RSD (%)

Ee

2.550
0.051
120
0.051

0.988
0.997
0.996
0.964

0.086
0.001
0.012
0.005

5.6
3.6
2.8
9.6

63.7
107.0
100.1
40.2

LOD: limit of detection; RSD: relative standard deviation; Ee: enrichment factor.

ORGANOCHLORIDE AND TRIAZINE PESTICIDES IN WATER

2217

Figure 6. Typical chromatogram of spiked seawater. Peaks: (1) 5 mg  l1 atrazine, (2) 0.1 mg  l1 lindane,
(3) 2 mg  l1 terbuthylazine, and (4) 0.1 mg  l1 aldrin.

replacement of the organic solvent for other greener alternative could imply
a reduction in the enrichment factors or in the analytical characteristics of the
methodology, which is not recommended.
Real Sample Analysis
Under the optimized conditions, the system was applied to real samples of
varying salinities. Since the analytes were not found in these samples, the samples
were spiked with pesticides at concentrations of 0.1 mg  L1 of lindane and aldrin,
2 mg  L1 of terbuthylazine, and 5 mg  L1 of atrazine. A typical chromatogram for
a spiked seawater sample is shown in Figure 6.
Table 2. Analysis of spiked samples, recoveries, and relative standard deviations (RSD) for ve replicates

Atrazine

Terbuthylazine

Lindane

Aldrin

Spiked, mg  L1
Found, mg  L1
Recovery, %
RSD, %
Spiked, mg  L1
Found, mg  L1
Recovery, %
RSD, %
Spiked, mg  L1
Found, mg  L1
Recovery, %
RSD, %
Spiked, mg  L1
Found, mg  L1
Recovery, %
RSD, %

Seawater

Tap water

River water

5.0
4.34
87
16.6
2.0
1.82
92
15.3
0.1
0.09
93
7.7
0.1
0.1
105
6.2

5.0
5.64
113
6.7
2.0
2.15
109
14.5
0.1
0.11
106
15.9
0.1
0.09
85
20.5

5.0
5.56
111
6.5
2.0
1.95
99
7.4
0.1
0.09
92
4.3
0.1
0.08
79
6.5

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C. VERGEL ET AL.

The recoveries values and relative standard deviations are shown in Table 2
(Lambroupoulou and Albanis 2007; Pena-Pereira et al. 2012). Although previous
methods presented similar analytical characteristics, the application to real seawater
samples has not been performed (Shen and Lee 2002; Yan and Wu 2004; Peng et al.
2007; Basher et al. 2010, Trtic-Petrovic et al. 2010). As acceptable recoveries
and relative standard deviations were obtained, the methodology is an attractive
tool for the determination of pesticides in natural waters.
CONCLUSIONS
A solvent bar microextraction method for pesticide analyses has been reported
as a greener alternative to the traditional liquid-liquid extraction due to the
reduction of solvent and waste. In addition, it presents advantages of simplicity,
low-cost, good stability of organic phase, high enrichment factors, and good
precision. The detection limits are sufciently low to meet the environmental quality
standards for priority substances in the eld of the Water Frame Directive.
Moreover, the application of this methodology to real water samples with different
salinities has been satisfactorily performed.
FUNDING
The authors thank the Spanish Ministry of Economy and Competitiveness
(CTM2010-15618) for support of this work.
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