Current trends in solid phase based extr

J. Biochem. Biophys. Methods 70 (2007) 117 – 131
www.elsevier.com/locate/jbbm

Review

Current trends in solid-phase-based extraction techniques for the
determination of pesticides in food and environment
Yolanda Picó, Mónica Fernández, Maria Jose Ruiz, Guillermina Font ⁎
Laboratori de Bromatologia i Toxicologia, Facultat de Farmácia, Universitat de Valencia, Av. Vicent Andrés Estellés s/n, 46100 Burjassot, Valencia, Spain
Received 30 May 2006; accepted 27 October 2006

Abstract
Solid-phase extraction (SPE) procedures for pesticide residues in food and environment are reviewed and discussed. The use of these
procedures, which include several approaches such as: matrix solid-phase dispersion (MSPD), solid-phase micro-extraction (SPME) and stir-bar
sorptive extraction (SBSE), represents an opportunity to reduce analysis time, solvent consumption, and overall cost. SPE techniques differ from
solvent extraction depending on the interactions between a sorbent and the pesticide. This interaction may be specific for a particular pesticide, as
in the interaction with an immunosorbent, or non-specific, as in the way a number of different pesticides are adsorbed on apolar or polar materials.
A variety of applications were classified according to the method applied: conventional SPE, SPME, hollow-fiber micro-extraction (HFME),
MSPD and SBSE. Emphasis is placed on the multiresidue analysis of liquid and solid samples.
© 2006 Elsevier B.V. All rights reserved.
Keywords: Solid-phase extraction; Solid-phase micro-extraction; Hollow-fiber micro-extraction; Stir-bar sorptive extraction; Matrix solid-phase dispersion; Food

Contents
1.
2.

Introduction . . . . . . . . . . . . . . . . .
Solid-phase-based extraction techniques . .
2.1. Solid-phase extraction . . . . . . . .
2.2. Solid-phase micro-extraction . . . .
2.3. In-tube solid-phase micro-extraction.

2.4. Matrix solid-phase dispersion . . . .
2.5. Stir-bar sorptive extraction . . . . .
3. Applications . . . . . . . . . . . . . . . .
4. Conclusions. . . . . . . . . . . . . . . . .
Acknowledgments . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . .

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1. Introduction
The analysis of pesticide residues in food and environmental
samples has received increasing attention in the last few decades, as can be deduced from the great number of papers

⁎ Corresponding author. Tel.: +34 96 3544295; fax: +34 96 3544954.
E-mail address: (G. Font).
0165-022X/$ - see front matter © 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.jbbm.2006.10.010

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117
118
118
119
121
121
122
128
129
129
129

published dealing with this subject [1–4]. These compounds are
usually determined by gas chromatography (GC), liquid

chromatography (LC) or capillary electrophoresis (CE),
depending on their polarity, volatility, and thermal stability
[5–9]. Regulatory authorities provide assurance that any
pesticide remaining in or on the food is within safe limits
through monitoring programs or random sampling and analysis
of raw or processed food on the market. In response to this
requirement a number of methods have been developed and


118

Y. Picó et al. / J. Biochem. Biophys. Methods 70 (2007) 117–131

applied routinely for the control of pesticide residues in food
and environment [4,10,11].
In general, food and environmental samples cannot be
analyzed without some preliminary sample preparation, because
contaminants are too diluted and the matrix is rather complex
[2,4]. Due to the low detection levels required by regulatory
bodies and the complex nature of the matrices in which the
target compounds are present, efficient sample preparation and
trace-level detection and identification are important aspects of
analytical methods [4]. Sample preparation, such as extraction,
concentration, and isolation of analytes, greatly influences the
reliability and accuracy of their analysis [2]. In recent years,
many innovations in the analytical processes that can be applied
to prepare food and environmental samples for extraction
and determination of pesticide residues have been developed
[12–20]. This has resulted in the recognition that classical
methods can now be replaced with procedures that are faster,

less expensive, and equal to or better than classical methods.
Although most officially methods for the analysis of pesticides use liquid/liquid extraction (LLE), solid-phase extraction
(SPE) has been developed as an alternative, owing to its
simplicity and economy in terms of time and solvent needs
[21,22]. This technique has gained wide acceptance because of
the inherent disadvantages of LLE, e.g., it is unable to extract
polar pesticides, it is laborious and time-consuming, expensive,
and apt to form emulsions, it requires the evaporation of large
volumes of solvents and the disposal of toxic or flammable
chemicals. In addition, recent regulations pertaining to the use
of organic solvents have made LLE techniques unacceptable.
Alternative solid-phase-based extraction techniques, which
reduce or eliminate the use of solvents, can be employed to
prepare samples for chromatographic analysis. These include
SPE, solid phase micro-extraction (SPME), matrix solid-phase
dispersion (MSPD), and stir-bar sorptive extraction (SBSE)
[15,17–20]. The ideal sample preparation methodology should
be fast, accurate, precise, and consumes little solvent. Further-

more, this sample preparation should be easily adapted for field
work and employs less costly materials [2]. The solid-phasebased extraction techniques could be the isolation techniques
capable of meeting these expectations.
The extraction of analytes from solid matrices is an active
development area in sample preparation technology [21]. Moreover, there has been an increasing demand for new extraction
techniques amenable to automation with shortened extraction
times and reduced organic solvent consumption [23]. Several
other sample preparation methods for organic compounds are
supercritical-fluid extraction (SFE) [13] and solid–fluid–
fluidizing series extraction procedures, named fluidized-bed
extraction (FBE) [23]. However, the application of SPE

technology to the isolation of pesticides and related compounds
has grown enormously [15,17,21].
The aim of this review is to describe the current trends of
SPE of pesticides with special emphasis on articles published in
the last three years. The solid-phase-based extraction procedures developed to isolate and pre-concentrate pesticide residues as well as the principles and relative merits of each
procedure are summarized and discussed. Isolation and pretreatment steps in SPE of pesticide residues in food and
environmental matrices are outlined. An overview of practical
application is given for SPE, SPME, in-tube SPME, MSPD, and
SBSE methods.
2. Solid-phase-based extraction techniques
2.1. Solid-phase extraction
The SPE technique was first introduced in the mid-1970s
[16]. It became commercially available in 1978, and now SPE
cartridges and disks are available from many suppliers. Conventional SPE is generally performed by passing aqueous
samples through a solid sorbent in a column. Pesticides are
eluted from the solid medium with an appropriate organic

Fig. 1. GC/MS chromatogram of pesticide-spiked lemon essential oil (from Barrek et al. [43]).


Y. Picó et al. / J. Biochem. Biophys. Methods 70 (2007) 117–131

solvent. One highly important aspect in SPE is the selection of
the sorbent. C-18 bonded silicas and styrene/divinyl benzene
co-polymers are the most frequently used. This technique is
widely applied to water samples [14,16,22,24–39]. For liquid
foods, such as fruit juices, wine, and milk, acceptable recoveries
can be obtained. Before SPE can be applied to a solid matrix
(soil, vegetables and fruits), a separate homogenization step
and, often, filtration, sonication, centrifugation, and liquid/

liquid clean-up are required [34,40–56]. However, the presence
of interfering substances, such as salts, humic acids, and other
humic substances in water; or proteins, lipids, and carbohydrates in food; makes the determination of polar or early-eluted
pesticides, difficult or impossible. The use of selective solid
phases, such as immunosorbents or molecularly imprinted
polymers (MIPs) can solve these problems. MIPs are used
preferentially, because of their low cost compared with immunosorbents [25,57].
Compatibility of reversed-phase (RP) LC systems with
aqueous samples allows on-line coupling of SPE with the
analytical system. This on-line system is generalized for water
samples and typically handles the pre-concentration of analytes
from 50- to 250-ml aqueous samples on a small cartridge,
packed with a suitable sorbent. Subsequent gradient elution of
the trapped analytes into an analytical column or detection
system is carried out. Automated SPE on-line sample handling
can be performed with commercially available equipment, with
hand-made cartridges, and six-port switching valves [31,58,59].
The advantages of on-line systems are: analyte enrichment,
automated sample preparation and analysis, and minimized
losses. The disadvantages of the on-line pre-concentration are
the reduced sample throughput, since only small sample
volumes can be processed, and lack of versatility of the system.
The direct coupling of SPE with GC is more difficult, because it
requires effective elimination of traces of water. There are some
analytical methodologies that use automated SPE, followed by
large-volume injection (LVI) by injectors with programmable
temperature vaporization (PTV), in combination with GC/MS
[28]. This system provides a fast, reproducible, and sensitive
technique for pesticide determination in drinking water.
The use of fully automated on-line RP–LC/GC has also been

reported, mainly for the determination of pesticide residues in
olive oil. This procedure, in conjunction with the through-oven
transfer adsorption/desorption (TOTAD) interface can be carried out without any other sample pre-treatment than a simple
filtration [44]. Automated, coupled on-line LC/GC systems
have numerous advantages, especially when a large number of
samples is to be analyzed. High sample throughput, as practiced
routinely in pharmacokinetic screening, is now expanding
rapidly in other sectors, such as environmental and food
analysis. However, the majority of reports on the application of
on-line SPE describe environmental monitoring of aqueous
samples with only a few for food analysis, e.g., mepiquat and
chlormequat in pears, tomatoes, and wheat flour [60], and Nmethylcarbamates and their metabolites in soil and food [61].
Fig. 1 shows a gas chromatogram in SIM mode for a spiked
sample of lemon essential oil, previously extracted with a
Florisil cartridge. The temperature ramp is an important step,

119

because it allowed elimination of residual volatile constituents
of the matrix, remaining after SPE extraction [43].
2.2. Solid-phase micro-extraction
SPME was first developed in 1989 by Pawliszyn and coworkers and has been marketed by Supelco since 1993. Subsequently, the technique has grown enormously [18–20]. It can
integrate sampling, extraction, pre-concentration, and sample
introduction into a single uninterrupted process resulting in high
sample throughput. A large number of fiber coatings based on
solid sorbents are now available, in addition to the original
general-purpose poly(dimethylsiloxane) (PDMS) and poly(acrilate) (PA) coated fibers, namely: PDMS/divinylbenzene (DVB),
Carbowax/DVB, Carbowax/template resin (TR), Carboxen/
PDMS, and DVB/Carboxen/PDMS-coated fibers. Extraction of

Fig. 2. SPME/GC/AED chromatograms obtained from a honey sample,
previously fortified with a standard mixture of pesticides: (A) S-181 nm;
(B) Cl-479 nm; (C) Br-478 nm. 1 = 100 ng/g chlordimeform, 2 = 150 ng/g
dimethoate, 3 = 2 ng/g aldrin, 4 = 20 ng/g parathion-ethyl, 5 = 80 ng/g captan,
6 = 20 ng/g chlorfenvinphos, 7 = 3 ng/g dieldrin, 8 = 2 ng/g p,p'-DDE, 9 =
0.5 ng/g p,p'-DDD, 10 = 1 ng/g p,p'-DDT, 11 = 10 ng/g bromopropylate, 12 =
3 ng/g tetradifon, 13 = 60 ng/g azinphos-methyl, 14 = 20 ng/g λ-cyalothrin, 15 =
5 ng/g cumaphos, 16 = 100 ng/g deltamethrin (from Campillo et al. [67]).


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Y. Picó et al. / J. Biochem. Biophys. Methods 70 (2007) 117–131

analytes by the new porous polymer SPME fibers with mixed
coating is primarily based on adsorption rather than absorption.
Some of these porous polymer SPME fibers with bipolar characteristics can be very useful for the simultaneous analysis of
pesticides, enlarging the spectrum of SPME applications [62–65].
Since its introduction, SPME has gained popularity as a simple
solvent-free, reliable, and flexible tool for the sampling of a variety
of volatile and semi-volatile compounds. SPME has extensively
been used for the direct extraction of pesticides from aqueous
samples [63,66–74]. On the other hand, fruit and vegetables, being
mostly in solid or heterogeneous form, do not allow direct
extraction. However, it is possible to analyze them by SPME after
a previous solvent extraction [62,75,76]. The SPME fiber can also
be suspended in the headspace above the homogenized sample.
This option, named headspace-SPME (HS-SPME), eliminates
interferences, because the fiber is not in contact with the complex
matrices of fruits and vegetables. Several classes of pesticide

residues have been extracted from complex matrices with HSSPME [77–82]. In contrast to the more conventional extraction
methods, SPME does not endeavour to extract all or even most of
the analytes from a sample. It is this aspect of SPME that can make
calibration problematic. Calibration in SPME is usually performed
by spiking standards, prepared in pure water. For typical
heterogeneous environmental samples, the assumption is that an
SPME fiber would come to equilibrium with only the freely
dissolved analytes in the water phase or the analytes in the vapor
phase, depending on the methodology used. However, in such a
sample the fiber actually directly interacts with each phase in the
sample. For example, as an analyte is depleted from the dissolved
phase by sorption on the fiber, the analyte is subsequently
replenished via re-equilibration in the other phases in the sample.
Although recoveries are usually low (ca. 30%), the good
repeatability and reproducibility of the methods allows satisfactory quantification of the analytes [66,69,70,83].

Fig. 3. Chromatogram obtained by using a proposed procedure for the new SPME fiber on the spiked samples of 10 ng ml− 1 of each organophosphorus pesticide.
(A) water and (B) apple juice. Peak identification: 1 = dichlorvos, 2 = phorate, 3 = diazinon, 4 = methyl parathion, 5 = fenitrotion, 6 = malathion, 7 = parathion, 8 =
ethion (from Linghsuang et al. [62]).


Y. Picó et al. / J. Biochem. Biophys. Methods 70 (2007) 117–131

The most common procedure for desorbing analytes from the
fiber in SPME is thermal desorption in the injector of a gas
chromatograph, because this desorption method completely
eliminates the use of organic solvents [66,69,79,83]. The
analytes adsorbed on the fibers can also be desorbed by using
a polar organic solvent, such as MeOH or acetonitrile [84]. This

approach is used to combine this extraction technique with LC or
CE. For LC, there is a commercial device that allow desorption
of all analytes accumulated in the fiber directly into the LC
injector. This system provides enhanced sensitivity [85]. There
are two ways of desorbing analytes from the fiber [83]. When the
analytes are not strongly adsorbed on the fiber, the dynamic
mode of desorption by a moving stream of mobile phase is
sufficient. But when the analytes are more strongly adsorbed on
the fiber, the fiber is dipped in the mobile phase or other strong
solvent for a specified time. Desorption performed in this way is
known as static desorption. Fig. 2 illustrates the elution profiles
obtained at different channels from fortified honey, using a nonpolar (100-μm) PDMS. As can be observed, the lack of
interfering peaks provides unequivocal identification [67]. The
sample matrix can affect the SPME extraction efficiency. Fig. 3
shows the chromatogram of apple juice compared with that of
pure water containing the same concentration of organophosphorus pesticides, obtained with a vinyl crown ether polar fiber.
The amounts of dichlorvos, malathion, and ethion extracted
from apple juice were much less than those from pure water [62].
2.3. In-tube solid-phase micro-extraction
In-tube SPME is a relatively new micro-extraction and preconcentration technique, which can be easily coupled on-line

121

with LC. An open-tubular capillary column with cross-linked
PDMS coating can be used to trap the analytes. A drying step is
necessary before the enriched compounds can be analyzed by
thermodesorption and GC [12,86,87]. When a sample contains
non-volatile high-molecular interfering compounds, such as
proteins, humics acids, and fatty material, analysis by means
of in-tube SPME is difficult. To overcome this difficulty, a

porous cellulose filter, protecting the coating, has been used
to determine pesticides [88,89]. On-line in-tube SPME
continuous extraction, concentration, desorption, and injection with an autosampler, is commonly used in combination
with LC and LC/MS.
2.4. Matrix solid-phase dispersion
In 1989, MSPD, a process for the extraction of solid samples
was introduced by Barker et al. [17]. MSPD performs sample
disruption while dispersing its components into a solid support.
MSPD combines sample homogenization with preliminary
clean-up of the analytes [15]. The method involves the dispersion of the sample in a solid sorbent, followed by preliminary
purification and the elution of the analytes with a relative small
volume of solvent. The extracts obtained are generally ready for
analysis, but, if necessary, they can easily be subjected to direct
extract purification [90].
MSPD has demonstrated its usefulness in several difficult
determinations [91–93]. The most widely used procedure for
separating pesticides from the olive oil matrix has been sizeexclusion chromatography (SEC). However, the main pitfalls
associated with this methodology are the use of large amounts
of organic solvents and the lack of flexibility to change from

Fig. 4. Comparison of GC/MS full-scan olive oil matrix chromatograms, obtained by size-exclusion chromatography (SEC) and matrix solid-phase dispersion (MSPD)
extraction (from Ferrer et al. [92]).


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Y. Picó et al. / J. Biochem. Biophys. Methods 70 (2007) 117–131

one method to another. Moreover, the separation of the
pesticide fraction (which has a low molecular weight) from the

whole fatty matrix (mainly triglycerides) is very difficult to
accomplish by SEC, because those two fractions are partially
overlapping. Normally, a compromise between purity of the
extract (minimizing the amount of fat in the pesticide fraction)
and acceptable pesticide recoveries must be made. This
usually involves the lost of some of the pesticides [92], thus
yielding lower mean percentage recoveries. These drawbacks
can be partially circumvented with the use of the MSPD,
which involves less reagent consumption and waste generation
and provides more flexibility. In addition, the resultant
extracts are cleaner than those obtained by SEC, as can be
seen in Fig. 4, where the full-scan GC/MS olive oil matrix
chromatogram obtained by means of SEC is compared with
that obtained with MSPD. The chromatogram obtained by
extraction with the MSPD method was much cleaner than that
obtained with SEC at two different collection times of the

pesticide fraction. This illustrates the capabilities of MSPD to
provide clean extracts of such complex matrices with a high
fat content.
2.5. Stir-bar sorptive extraction
In 1999, a new extraction technique was developed by
Baltusen et al. [94]. In this extraction technique, known as stirbar sorptive extraction (SBSE), a magnetic stir bar, coated
with 50–300 μl of polydimethylsiloxane (PDMS), is used. The
extraction mechanisms and advantages are similar to those of
SPME, but the enrichment factor, which is determined by the
amount of extractive phase is up to 100 times higher. In
SBSE, analytes are adsorbed on a magnetic rod, coated with
PDMS, by stirring with it for a given time. After that, the stir
bar is either thermally desorbed on-line with capillary GC/MS

or by organic solvents to be subsequently injected into an LC
system [95].

Fig. 5. GC/TSD chromatograms of organophosphorus pesticides, obtained by an optimized SBSE method from: (A) water solution (800 ng/l); (B) spiked cucumber
sample (0.5 ng/g) and (C) a potato incurred sample. 1 = monocrotophos, 2 = phorate, 3 = dimethoate, 4 = parathion-methyl, 5 = malathion, 6 = fenitrothion, 7 =
fenthion, 8 = chlorpyrifos, 9 = parathion, 10 = methidathion, 11 = triazophos, 12 = ethion (from Liu et al. [96]).


Table 1
SPE methods for pesticides
Matrices

Pre-treatment

Characteristics

Elution

Recovery (%)

Detection

LOD's (μg/l)

LOQ's (mg/kg)

Reference

Fruits and vegetables

Aqueous sample extract passed through
the C18 column

CE

–

0.2–0.5

[97]

Samples homogenized with water:MeCN
(50:50) for 15 min. acetone was evaporated.
Extract passed through the C18 column
Samples passed through tC18 cartridge

58–99

CE/MS

50–200 (CE–MS)

–

[40]

64–85

GC/MS

0.02–0.038

–

[24]

Triazines (6) and metabolites (5)

River and tap water

Pesticides eluted with DCM.
Concentrated to dryness and redisolved
in 0.5 ml of buffer
Pesticides eluted with DCM.
Concentrated to dryness and
redisolved in 0.5 ml of buffer
Carbamates eluted with 2 ml MeCN.
Concentrated to dryness and redisolved in
0.5 ml of MeCN
Triazines eluted with MeCN:acetic acid (9:1).
Concentrated to dryness and redisolved
in 0.5 ml of water: MeCN (9:1)

31–106

Peach and nectarine

MFE C18 solid phase (45- to 55-μm
particle diameter and 60 Å
pore diameter)

C18 solid phase

LC/DAD UV

0.03–0.2

–

[25]

Organochlorine pesticides (13)

Surface water

72–119

LC/MS/MS

0.0008–
0.083

–

[26]

Neonicotinoid pesticides (4)

Pesticides eluted with ethyl acetate.
Evaporated to dryness and redissolved
in 250 μl of 40 ng/ml 2,4-dichlorophenol

in MeCN as internal standard
Pesticides eluted with DCM.
Evaporated at 40 °C under vacuum and
redissolved in 1 ml of MeOH
Pesticides eluted with MeCN. Evaporated
to dryness under vacuum and redissolved
in 1 ml MECN and 200 μl of 16 mM
ammonium carbonate solution

75–105

LC/ESI/MS

–

0.1–0.5

[41]

50–84

CE/UV

18–34 (μg/kg)

–

[42]

Pesticides eluted with MeCN.

Evaporated to dryness at 40 °C and
redissolved in 1 ml MeCN
n-hexane:DCM (1:1, v/v), concentrated
to dryness and redissolved in
0.5 ml n-hexane
Pesticides eluted with DCM.
Extracts concentrated at 30 °C
Pesticides eluted with DCM.
Extracts concentrated at 30 °C.
Pesticides desorbed with 0.5 ml
of ethyl acetate.
MeCN.
MeOH
Mobile phase of LC

55–110

CE/UV

0.13–0.34

–

[27]

69–96

GC/ECD;
GC/MS

–

0.004–0.09

[98]

67–107

GC/MS

30–400

–

[43]

50–115

LC/MS

20–60

–

[43]

–

GC/MS

10–50 (ng/l)

[28]

LC/UV
TLC plates
LC/ESI–
MS/MS

10–30
10
0.011–7.4 (ng/l)

33–166
(ng/l)
35–100 (μg/l)
30 (μg/l)
0.004–2.8 (ng/l)

GC/FID

0.18–0.38 mg/l

LC/
Fluorescence

0.01–0.02 (μg/l)

Water

Sep-Pak tC18 cartridges.

Pre-concentration of water. Prior the SPE,
high-hardness water (40 °f) washed with HCl.
SPE with propazine-MIP and mixtures
of LiChrolut EN propazine-MIP
Water samples containing 1% MeCN were
pre-concentrated through C18E cartridges

Selective MIP cartridges for triazines
and related metabolites Metabolites
extracted by SPE with a mixture of
propazine-MIP and LiChrolut EN
Strata C18E cartridges

Apricot, celery,
courgette, peach, pear

Samples homogenized with acetone for
2 min. in mixer at 9500 rpm

Extrelut-NT20 cartridge

Triazolopyrimidine pesticides (5)

Soils

Sep-Pak Plus C18 cartridges

Triazolopyrimidine

pesticides (5)

Water

Organochlorines (11),
pyretroids (5)

Tea

Pesticides (12)

Oils of citrus fruit

Pesticides (12)

Oils of citrus fruit

Organochlorine pesticides

Drinking water

Soil samples extracted with water and
0.1 M NaOH in ultrasonic bath for 20 min.
Centrifuged at 4000 rpm for 10 min to
separate the supernatant. Added HCl and
passed to C18 SPE cartridge
Water samples containing hydrochloric
acid were pre-concentrated through C18
SPE cartridges
Samples extracted by vortex gyrator a full speed

for 2 min. Centrifuged at 3000 rpm for 5 min.
Supernatant layers were extracted
Samples homogenized in an ultrasonic bath for
15 min. Extract passed through a Florisil cartridge
Samples homogenized in an ultrasonic bath for
15 min. Extract passed through a Florisil cartridge
Samples passed through C18 cartridge

Urea (3), 2,4-D and amitrine
Triazines (6)
Triazines, phenylureas,
organophosphorus, anilines,
acidic, propnil, molinate
Organophosphorus (4)

Water
Water
Water

Samples passed through C18 cartridge.
Samples passed through C18 cartridge
None

1.0 g C18 bonded silica phase
Backerbond SPE C-18 polar
On-line trace enrichment

Olives

Filtering of the olive oil

Benzoylureas (5)

Water

Filtering

LC/GC on-line LC
column C4,Chromasil
C-18 short column

Sep-Pak Plus C18 cartridges.

Florisil column preconditioned
with n-hexane
FL-PR extraction cartridge
FL-PR extraction cartridge
SPE-LVI

MeOH/water
Mobile phase
(MeOH/water gradient program)

7–91

98–104
88–95
–

–

92–109

Y. Picó et al. / J. Biochem. Biophys. Methods 70 (2007) 117–131

Analyte
Azole (1), insect growth
regulator (1), pyrethroid (1),
pyrrole (1), triazole (4)
Azole (1), insect growth
regulator (1), pyrethroid (1),
pyrrole (1), triazole (4)
Carbamates (7)

[29]
[30]
[31]

[44]
0.04–0.05 (μg/l)

[32]

MIP: molecularly imprinted polymer; °f: French degrees; LiChrolut EN: polymeric sorbent of styrene divinylbenzene; DCM: dichloromethane; LVI: large volume injection; MeCN: acetonitrile; TLC: thin layer chromatography.

123


124

Table 2

SPME methods for pesticides
Analyte

Matrices

Pre-treatment

Characteristics

Elution

Molinate

Rice field and
water
Water

Direct SPME: 5 ml stirred sample with 200 g/l sodium
sulfate and internal standard for 30 min.
HS-SPME: 5 ml sample with 5 ml HOAc/NaOAc buffer
and internal standard solution added. In situ derivation with
300 μl of 1% NaBEt4 sol. Vigorously shaken in ultrasonic
bath for 10 min and extracted for 30 min at 80 °C
Direct SPME: 3 ml stirred sample with 30% NaCl 30 min at 25 °C

DVB/CAR/PDMS

Fenbutatin oxide

Detection

LOD

Reference

Desorption at 220 °C for 5 min.

79–97

GC/FPD

0.48–5.2 μg/l

[70]

100 μm PDMS

Desorption at 250 °C for 1 min.

–

GC/MS

16 ng/l

[99]

85 μm PA

Desorption at 175 °C for 5 min.

–

0.5 μg/l

[66]

85 μm PA

Desorption at 175 °C for 5 min.

–

0.001 mg/kg

[66]

100 μm PDMS

Desorption at 240 °C for 5 min.

–

20–100 ng/l

[68]

100 μm PDMS

–

GC/ECD/
NPD
GC/ECD/
NPD
GC/MS
GC/FID
LC/UV
(254 nm)
LC/DAD
LC/DCAD
GC/MS

1–10 ng/ml

[69]

1.2–11.8 μg/l

[83]

1.3–15 ng/l

[77]

1,3-dichloropropene
methyl isothiocyanate
1,3-dichloropropene
methyl isothiocyanate
Irganrol-1051 related s-triazine

degradation products (M1 and M2)
Nabam thiram azamethiphos

Water

Tap water

HS-SPME:2 g of soil with 400 ml of distilled
water 30 min at 50 °C
Direct SPME: 5 ml stirred sample with 53 ppt of NaCl
in the dark for 90 min.
Direct SPME: Sample with 5 g NaCl for 30 min.

Fenitrothion fenitrooxon
3-methyl-4-nitrophenol
Monobutyltin dibutyltin
tributyltin monophenyltin
diphenyltin triphenyltin

River water

Direct SPME: 3 ml of stirred sample with 15% Na2SO4 60 min.

PDMS/DVB

Desorption by dynamic mode during
5 min.
Desorption by dynamic mode during 5 min

Water

HS-SPME: 5 ml stirred sample with 5 ml buffer,
1 ml EtOH and 6 deuterate internal standards, derivatized with 300 μl
1% NaBEt4 sol. and extracted at 80 °C for 90 min.
0.5 g sample with 1 ml MeOH and 1 ml acetic acid,
placed in ultrasonic bath for 3 h. Deuterate internal
standard and 8 ml buffer solution were added, derivatized
with 500 μL 1% NaBEt4 soln. and extracted at 80 °C for 90 min.
Direct SPME: 6 ml of stirred sample with 31% NaCl (w/v)
at pH 6 extracted for 150 min.

100 μm PDMS

Desorption at 250 °C for 1 min

–

100 μm PDMS

Desorption at 250 °C for 1 min

116–98

GC/MS

1–6.3 μg/kg

[77]

60 μm PDMS/DVB

Desorption with 200 μl MeOH by stirring
for 16 min and added 200 μl acetic
acid 0.4 M before CE injection
Desorption at 300 °C for 6.5 min.

5–46

CE/UV

2.5–47 μg/l

[75]

64–85% GC/MS

0.6–19 μg/l –
[24]
0.02–0.038 μg/l

100 μm PDMS
Vinyl crown ether polar fiber:
80 μm B15C5

Desorption at 250 °C for 7.5 min.
Desorption at 270 °C for 5 min.

76–121
55–105

GC/ECD
GC/FPD

0.1–0.5 ng/g
0.003–0.09
ng/g

[80]
[62]

85 μm PA

Desorption at 280 °C for 3 min.

87–110

GC/MS

LOQ 0.004–
0.03 ng/ml

[64]

100 μm PDMS

Desorption at 240 °C for 5 min.

–

GC/NPD

0.05–8.37 μg/l

[76]

100 μm PDMS

Desorption at 270 °C for 5 min

71–121

GC/ECD

0.029–
0.301 ng/g
0.8–13 ng/l
0.8–504 0.09–
143 ng/l
0.02–3.6 ng/g

[82]

Soil
Coastal water

Sediments

Cyprodinil cyromazine pyrifenox
pirimicarb pyrimethanil

Water apple and
orange juice

Aldicarb Carbetamide Propoxur
Carbofuran Carbaryl Methiocarb
Pirimicarb (7 Carbamates)
Organochlorines (8)
Organophosphorus (8)

Brine water

Phenoxy acid herbicides Dicamba (8)

Treated urban
wastewater

Organophosphorus (9)

Organochlorines (11)
Organophosphorus (11)

Fish water
potatoes guava
coffee
Estuarine surface
sediments
Lake water
River water

Organochlorines (11)

Soil

Pesticides (8) Triazine metabolites (3)
Organochlorines and metabolites (12)

Rain water
Radish

Organochlorines organophosphorus
Pyrethrins (16 pesticides)
Pesticides (20)

Honey

Organochlorines (10)

Soil
Apple juice
Apple Tomato

Rain water

–

Direct SPME: 6 ml sample and 4 ml of water for 120 min at 25°C SPE-SPME:
250 ml sample passed through tC-18 SPE cartridge and eluted with 2 ml
of MeCN, evaporated and redisolved in 8 ml aqueous solution with 60% (v/v) of brine
HS-SPME: 0.5 ml of sample and 5 ml of water are stirred for 60 min at 60 °C
HS-SPME (Apple juice) 15 ml of diluted juice (1:30) with 5 g NaCl,

extracted for 45 min at 70 °C. Direct SPME: 15 ml apple (1:50) and
tomato (1:70) dilution with 5 g NaCl, for 60 min at 30 °C
Direct SPME: 20 ml stirred Milli-Q water pH 2, HCl 0.1 M
extracted for 40 min. Postderivatization on the fiber exposing it to
the headspace of a vial containing 1.5 ml with 50 μl of MBTSTFA
for 10 min.
Direct SPME (Solid sample): 0.5 g stirred sample with
16 ml water and for 40 min at 30 °C Direct SPME (water):
16 ml sample 40 min at 30 °C
HS-SPME: 0.5 g stirred sample in 5 ml water and Tween 80,
60 min. at 70 °C.
HS-SPME: 4 ml of stirred sample 30 min. at 80 °C
Direct SPME: 10 ml stirred Milli-Q water with 10% NaCl for 45 min. at 25 °C.

85 μm PA

PMPVS/OH-TSO
100 μm PDMS

Desorption at 270 °C for 2 min
Desorption at 240 °C for 5 min

71–115
71–114

MAE: 5 g sample with 20 ml hexane:acetone (115 °C, 10 min,
200 psi), 15 ml filtered and evaporated to dryness, and redissolved
by 720 μl of ethanol and 40 ml of water. HS-SPME: 60 min. 65 °C.
Direct SPME: 3 ml stirred sample 40 min. 50 °C pH 6 and 70% NaCl
HS-SPME (water): 4 ml stirred radish matrix solution and

1 g K2SO4 30 min. at 70 °C
Direct SPME: 1.5 g stirred sample with 10 ml phosphate buffer
solution at 75 °C for 20 min
Direct SPME: 3 ml of stirred sample with 50% NaCl, extracted
at 40 °C for 45 min.

100 μm PDMS

Desorption at 260 °C for 16 min

8–51

GC/ECD
GC/MS
GC/ICP/ MS
GC/MS/ MS

85 μm PA
C[100]/OH-TSO

Desorption at 290 °C for 5 min
Desorption at 270 °C for 2 min

–
79–119

GC/MS/MS
GC/ECD

0.01–0.05 μg/l

1.27–174 ng/kg

[71]
[78]

100 μm PDMS

Desorption at 280 °C for 5 min.

91

GC/AED

0.02–10 ng/g

[67]

100 μm PDMS

Desorption at 250 °C for 5 min.

GC/ITD/
MS/MS

5–500 ng/l

[65]

–

[79]
[73]
[81]

M1: 2-methylthio-4-tert-butylamino-6-amino-s-triazine; M2: 3-[4-tert-butylamino-6-methylthiol-s-triazin-2-ylamino]-propionaldehyde; DCAD: Direct current amperometric; MBTSTFA N-methyl-N-(tert-butyldimethylsilyl)-trifluoroacetamide; PMPVS/OH-TSO: poly(methylphenylvinylsiloxane)/hydroxyl-terminated silicone oil;C[4]/OH-TSO : sol/gel calyx[4] arene/hydroxy-terminated silicone oil; AED: atomic-emission detection; MAE: microwave-assisted extraction.

Y. Picó et al. / J. Biochem. Biophys. Methods 70 (2007) 117–131

Mean
recovery


Table 3
In-tube SPME methods for pesticides
Matrices

Pre-treatment

Phenylurea (6)
and carbamate
(6) pesticides

Water and
wine

Samples extracted with 15 draw/eject
cycles 60-cm-long capillary,
no buffer solutions or salts were used

Characteristics

PPY coated on inner surface of a
fused-silica capillary (60 cm,
0.25 mm i.d.). Capillary cleaned
with acetone and MeOH, dried
with N2, and coupled to LC
Phenylurea (6)
Water and
Samples extracted with 15 draw/eject
PPY coated on inner surface of a
and carbamate
wine
cycles 60-cm-long capillary,
fused-silica capillary (60 cm, 0.25 mm
(6) pesticides
no buffer solutions or salts were used. i.d.). Capillary cleaned with acetone
and MeOH, dried with N2, and
coupled to LC
Carbamates (6)
Water
Extraction by moving the sample
Coated GC capillary (SPB-1, SPB-5,
in and out of the extraction capillary
PTE-5, Supelcowax, Omegawax 250)
(25 aspirate/dispense steps at a
and retention gap capillary
flow-rate of 63 μl/min)
(fused-silica without coating) were
used in the in-tube SPME
PC-HFME Polymer-coated

Water
1.2 cm of fiber, coated with 1 g/l of
Organochlorine
PH-PPP in toluene. Extraction at 23 °C hollow fiber. 600 μm of i.d.,
pesticides
for 30 min. in 30% NaCl and at pH 10. 200 μm wall; 0.2 μm pore size
(15 OCP)
HFM-SPME Polypropylene
65 μm PDMS/DVB fiber. Extraction
Triazine herbicides Bovine milk
hollow fiber. 600 μm (i.d.),
at 80 °C for 40 min. in 30% NaCl
(6 triazines)
and sewage
200 μm wall; 0.2 μm pore size
sludge samples and at pH 10

Elution

Recovery (%)

Detection LOD (ng/l)

LOQ (ng/l)

Reference

SPME, coupled
95–104 (water)
automated in-tube to 89–97 (wine)

LC desorption with
mobile phases

LC/UV

–

[86]

95–104 (water)
SPME, coupled
automated in-tube to 89–97 (wine)
LC desorption with
mobile phases

L C / E S I / 10–1200
MS

–

[86]

Desorption in-tube
SPME procedure
with MeOH

97–100

LC/UV

1000–
15,000

–

[87]

Sonication with
hexane for 10 min.

85–106

GC/MS

1–8

–

[89]

Desorptions in
splitless mode

88–107 (milk) GC/MS
93–113 (sludge)

380–8200

3–13 (milk) 6–21 (milk) – [88]
1–9 (sludge) (sludge)

Y. Picó et al. / J. Biochem. Biophys. Methods 70 (2007) 117–131

Analytes

i.d.: inner diameter; HF: hollow fiber; HFM: hollow-fiber membrane; PC-HFME: polymer-coated hollow-fiber micro-extraction; HFM-SPME: hollow-fiber membrane protected solid phase-micro-extraction; FTD:
flame-thermoionic detector; PH-PPP: polyhydroxylated polyparaphenylene; PDMS/DVB: polydimethylsiloxane/divinylbenzene; PPY: polypyrrole; PMPY: poly-N-methylpyrrole.

125


126

Table 4
MSPD methods for pesticides
Analyte

Matrices

Pre-treatment

Characteristics

Elution

Recovery
(%)

Detection LOD's LOQ's
(μg/kg) (mg/kg)

Carbamate (1), organophosphate (3),
organochlorine (1), imidazole (1),
triazole (2), insecticide growth
regulator (1), mouse growth
regulator (1)
Insecticide growth regulators (3),
pyrimidine insecticide (1),
pyrazole insecticide (1) and 1
pyrethroid insecticide

Oranges

Unwashed and unpeeled samples
were chopped and homogenized
for 3 min. at high speed

0.5 g of C8
bonded silica

Elution was made with
DCM/MeOH (80:20, v/v) and
vacuum. Eluate was concentrated
to 0.5 ml MeOH

47–96

LC/MS

–

Unwashed and unpeeled samples
were chopped and homogenized.
Sample was blended with C18
bonded silica for 5 min.

0.5 g of C18
bonded silica

Elution was made with
DCM/MeOH (80:20, v/v) and
vacuum. Eluate was concentrated
to 0.5 ml MeOH

51–92

LC/MS/
MS

5–1000 0.2–4
(μg/l)

Organochlorine pesticides (18)

Citrus fruit
(oranges,
tangerines,
grape fruits
and lemons)
Tobacco

5 g of pretreated and
deactivated
Florisil

Extract was concentrated to
1.0 mL

52–99

GC/ECD –

0 . 0 1 – [100]
0.02

Pesticides (226)

Apple juice

43–117

GC/MS

3–18

–

Organophosphates (3),
organochlorines (3),
pyrethroids (2),

triazines (3), urea (1)
Glyphosate and
aminomethylphosphonic
acid (AMPA)

Olive and olive
oil

MSPD-SSEC. Florisil was heated at
550 °C overnight and homogenized
in water in a rotary evaporator for 1 h.
Samples were extracted in Soxhlet
with heat n-hexane for 6 h.
Juice was homogenized with diatomaceous
earth. Sample was blended with C18 bonded
silica for 5 min. before MSPD procedure
samples were kept for 3 h in darkness at 4 °C
Preliminary LLE in olive oil samples with
petroleum ether saturated with MeCN.
Separation of MeCN phase and applying
MSPD
Two aqueous samples were obtained
after MSPD homogenized.
Clean-up with SAX anion exchange silica

81–111
(LC–MS)
73–130
(GC–MS)
86–93

GC/MS;
LC/MS/
MS

0.2–80 –

[92]

LC/FD

30–50

–

[102]

Organochlorine (11), pyretroids (5)

Tea

GC/
ECD;
GC/MS
LC/ESI/
MS/MS

–

0 . 0 0 5 – [98]

0.06

0.03
(μg/l)

0.1
(μg/l)

Homogeneous mixture (sample and
Florisil) was transferred in a glass
cartridge, connected to vacuum and eluted
Juice was adjusted a pH 6 and sonified in
Fruit juice
ultrasonic bath for 15 min. before MSPD
(apple, peach,
cherry, raspberry, procedure
and orange)

1 g of
diatomaceous
earth

DCM

80–96

82–102

SSEC:Soxhlet simultaneous extraction clean-up; LLE: liquid/liquid extraction; FD: fluorescence detection; FMOC-Cl: 9-fluorenylmethylchloroformate; DCM: dichloromethane.

0 . 0 0 8 – [91]
0.3

[93]

[101]

[103]

Y. Picó et al. / J. Biochem. Biophys. Methods 70 (2007) 117–131

Carbendazim

Tomato fruit

Elution was made with
DCM/MeOH (1/1) and evaporated
to dryness in a rotary vacuum.
Eluate was concentrated to 1 ml
Elution with MeCN, evaporated
Aminopropyl
(Bondesil-NH2, until dryness and dissolved with
40 μm particle MeCN/water (1:1). Clean-up step
size).
with Florisil
HNO3 1 M and Elution with HNO3 0.01 M
NH2-silica
extract were evaporated at 40 °C
and pH adjusted to 7–9 for
the derivatization reaction

with FMOC-Cl
2.0 g Florisil
n-hexane/DCM (1:1, v/v)
20 g of
diatomaceous
earth

Reference


Table 5
SBSE methods for pesticides
Matrices

Pre-treatment

Characteristics

Elution

Carbamate (1),
organophosphates (3),
organochlorine (1),
imidazole (1), triazoles (2),
insecticide growth
regulator (1), mouse
growth regulator (1)
Azole (1), insect growth
regulation (1),
pyrethroid (1),

pyrrole (1), triazole (4)

Oranges

Samples homogenized with
MeOH and water by sonication
for 15 min, filtered and washed
with water and extracted with stir
bar for 2 h. Stir bar was filled with
MeCN and conditioned with
MeCN for 5 min. by sonication
Samples were homogenized
with acetone and water by
sonication for 15 min, filtered
and washed with acetone and
extracted with stir bar for 4 h.
at 900 rpm Stir bar was filled
and conditioned with MeOH for
5 min by sonication
Extraction with n-tetradecane,
stirring speed of 600 rpm for
30 min at 25 °C

Stir bar, 10 mm in length and
coated with a 1-mm PDMS
layer

Desorption with MeCN
in an ultrasonic device
for 10 min.

8–84

Stir bar, 10 mm in length and
coated with a 1-mm PDMS
layer

Desorption with
MeOH, concentrated to
dryness and
redissolved with
0.5 ml of buffer

12–47

SBME/HFM impregnated with
n-tetradecane. The ends of the
fiber were sealed, forming a bar
that extracts pesticide by a
magnetic stirrer
20 mm long PDMS stir bar

93–101
Organic extracting
solvent is withdrawn
into a micro-syringe for
injection into the gas
chromatograph
TSD at 280 °C
–

for 6 min.

Organochlorine pesticides (6)

Fruits and vegetables

Wine

Organochlorine pesticides (17), Tap water, ground
organophosphorus
water and surface water
pesticides (4), triazines (8)

Organophosphorus
pesticides (12)

Pesticides (68)

Pesticides (85)

Pyrethroid pesticides (8)

Samples were added with
20% NaCl. Stir bar at 900 rpm
for 14 h. at ambient
temperature Na2S2O3·5H2O
was added to tap water to
eliminate chlorine stir bar
conditioned in a thermodesorption
tube at 300 °C for 4 h with He flow

Water, cucumber, potato
Samples were immersed for
30 min with stirring at 600 rpm
at 30 °C with 30% NaCl.
Vegetable samples were extracted
with acetone prior to SBSE
Extracts were concentrated at 2 ml
and diluted to 20 ml with water
River water
Samples were added with 30% NaCl.
Stir bar was stirred at 1000 rpm for
60 min. at room temperature
Samples were extracted with
Grape, tomato, cucumber,
green beans, soybeans, spinach, MeOH and diluted with water
prior to SBSE.
green tea
SBSE performed at 24 °C, for
60 min., stirring at 1000 rpm
Stir bar thermally conditioned
at 300 °C for 30 min. with He flow
Water
SBSE performed with 5% MeOH
as organic modifier, at 20 °C
for 60 min. stirring at 750 rpm,
and MeCN as back-extraction solvent

10-mm stir bar, coated with
PDMS. Dual SBSE

Stir bar coated with PDMS

Reference

–

0.001–0.05

[91]

CE

–

1

[97]

GC/MS/
MS

0.3–17.3

–

[104]

GC/MS

0.1–10.7

0.4–36.1
(ng/l)

[105]

–

GC/TSD

0.06–1.22 (water)
–
4–15 (ng/kg; cucumber)
1.2–98 (ng/kg; potato)

[96]

TSD by programming
from 20 °C (0.5 min)
to 300 °C (5 min.)
TSD by programming
from 20 °C (1 min.) to
280 °C (5 min.)

59–132

GC/MS

0.2–2

[106]

–

GC/MS

0.63–26 (μg/kg)

–

LD with MeCN

67–103

GC/MS

1–2.5

3–7.5 (ng/l) [108]

[107]

127

PDMS: polydimethylsiloxane; ACN: acetonitrile; CE: capillary electrophoresis; TSD: Thermal desorption; LD: liquid desorption.

LOQ's
(mg/kg)

LC/MS

A sol/gel PDMS was used to
TSD at 260 °C
coated bars consisting of an iron for 5 min.
bar inside a glass tube

Stir bar coated with PDMS

Recovery Detection LOD's
(%)
(ng/l)

Y. Picó et al. / J. Biochem. Biophys. Methods 70 (2007) 117–131

Analyte


128

Y. Picó et al. / J. Biochem. Biophys. Methods 70 (2007) 117–131

Fig. 6. LC/MS chromatograms of an orange sample containing 0.02 mg/kg carbendazim, 0.07 mg/kg hexythiazox, 0.1 mg/kg methidathion, and 0.07 mg/kg
pyriproxyfen after (A) ethyl acetate extraction (B) SBSE, and (C) MSPD. Peak identification: 3 = carbendazim, 5 = methidathion, 9 = pyriproxyfen, 10 = hexythiazox
(from Blasco et al. [91]).

Typical chromatograms of organophosphorus pesticides in
standard solution and a spiked cucumber sample, obtained by
SBSE/GC/TSD, are shown in Fig. 5.
3. Applications
Selecting a suitable method of residue analysis will depend

on the problem at hand as well as on the final goal. To quote two
widely different situations, when large sample series have to be
monitored for a group of pesticides, such as organophosphorus
pesticides, sample throughput will be an important criterion
since speed is of the essence. In this situation, a screening
method is selected, because high sample throughput and speed
are the characteristics of such a method. When, on the other
hand, samples are suspected to contain a prohibited pesticide,
such as, e.g., methylparathion in oranges, method selectivity
will no doubt be the main criterion, because avoiding false noncompliant results is now of overriding importance. In this
situation, a confirmatory method is of interest, because it
provides full or complementary information, enabling confirmation of the identity of the substance. Here our discussion will

be limited to method selection and a few comments on SPE that
can be considered relevant in light of recent trends in pesticide
residue analysis.
The applications of the different SPE methods since 2003 for
pesticide residues in food and environmental analysis are
compiled in Table 1 (SPE methods), Table 2 (SPME methods),
Table 3 (in-tube SPME methods), Table 4 (MSPD methods), and
Table 5 (SBSE methods). An evaluation of the scientific literature
of the years 2003–2006 shows that some 100 papers on pesticide/
drug residue analysis have been published. With regard to sample
treatment, SPE and SPME were found to be very popular, being
used in, respectively, 17 and 25% of all studies. The application of
MSPD, in-tube SPME, and SBSE is reported in only a few papers.
In several instances, SPE and SPME were used in combination:
after analyte isolation by means of SPE, the pesticides were
enriched by using a suitable SPME procedure. Fig. 6 displays the
LC/MS chromatogram of an orange sample, extracted by different

procedures: solvent extraction (ethyl acetate), MSPD, and SBSE.
This figure shows differences in sensitivity between the three
extraction methods as well as the absence of a carbendazim signal
when SBSE was used [96].


Y. Picó et al. / J. Biochem. Biophys. Methods 70 (2007) 117–131

4. Conclusions
Comparison of the above procedures applied to the SPE of
pesticide residues indicates:
• Conventional off- and on-line SPE is already a wellestablished and routine technique.
• SPME and SBSE in combination with GC/MS or LC are
solvent-free or almost solvent-free procedures, obviating the
need for further preparation steps.
• One advantage of SPME is the possibility of full automation;
SBSE cannot yet be completely automated.
• SPME is now a widely accepted and reliable technique for
the determination of several organic compounds. In the
headspace mode, it allows attainment of satisfactory LODs
and cleaner chromatograms for volatile analytes.
• SPME has been widely used in recent years, as demonstrated
the large number of applications reported in the literature in
comparison with other SPE procedures.
Acknowledgments
This work was financially supported by the Spanish Ministry
of Science and Technology and the European Regional
Development Funds (ERDF) (Project AGL2003-01407) and
by the Conselleria d’Empresa, Universitat i Ciencia (Project GV
2005-109).

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