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Properties and determination of pesticides in fruits and vegetables

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Trends Trends in Analytical Chemistry, Vol. 30, No. 6, 2011

Properties and determination

of pesticides in fruits and vegetables
Jolanta Fenik, Maciej Tankiewicz, Marek Biziuk

The intensive development of agriculture means that more and more toxic organic and inorganic compounds are entering the
environment. Because of their widespread use, stability, selective toxicity and bioaccumulation, pesticides are among the most
toxic substances contaminating the environment. They are particularly dangerous in fruit and vegetables, by which people are
exposed to them. It is therefore crucial to monitor pesticide residues in fruit and vegetables using all available analytical methods.
We set out the problems in the determination of organonitrogen and organophosphorus pesticides in samples of fruit and
vegetables, including the complexity and the diversity of matrices in biological materials, and the very low level of pesticides
present, as a result of which target analytes have to be isolated and then enriched prior to final determination.
We discuss the various stages in the determination of pesticide residues in fruit and vegetables. We present results from the
literature in the context of Maximum Residue Levels (MRLs) of target pesticides in fruit and vegetable samples. We discuss the
merits of the Quick, Easy, Cheap, Effective, Rugged, and Safe (QuEChERS) technique and two-dimensional gas chromatography.
ª 2011 Elsevier Ltd. All rights reserved.

Keywords: Determination; Fruit; Maximum Residue Level (MRL); Pesticide; Quick, Easy, Cheap, Effective, Rugged, and Safe (QuEChERS);
Organonitrogen pesticide; Organophosphorus pesticide; Residue; Two-dimensional gas chromatography; Vegetable

Abbreviations: See Appendix A

1. Introduction  control the numbers of pests destroying

Jolanta Fenik*,
Maciej Tankiewicz,
Marek Biziuk
Department of Analytical
Chemistry, Chemical Faculty,
Gdansk University of
Technology,
Str. G. Narutowicza 11/12,
80-233 Gdansk,
Poland
*
Corresponding author.
Tel.: +58 347 22 10;
Fax: +58 347 17 83;
E-mail: jolanta.fenik@gmail.
com
Pesticides are a numerous and diverse
group of chemical compounds, which are
used to eliminate pests in agriculture and
households. They enable the quantities
and the quality of crops and food to be
controlled, and help to limit the many
human diseases transmitted by insect or
rodent vectors. However, despite their
many merits, pesticides are some of the
most toxic, environmentally stable and
mobile substances in the environment.
Their excessive use has a deleterious effect
on humans and the environment; their
presence in food is particularly dangerous.
With their environmental stability, ability
to bioaccumulate and toxicity, pesticides
may place the human body at greater risk
of disease and poisoning [1].
Pesticides enter the environment in
various forms (e.g., powders, moistened
powders, powders for preparing aqueous
solutions, and concentrates for making up
emulsions or sprays). Pesticides are of
enormous importance in increasing the
yields and quality of agricultural products.
They are used to:
whole plants or their parts;
 increase the production of animal and
plant biomass;
 combat microorganisms causing farm
produce to rot and to decay;
 combat algae, bacteria, fungi and weeds;
 combat animal pests damaging crops
(e.g., mites, aphids, insects, larvae,
and nematodes);
 stimulate or inhibit plant-growth
processes (e.g., remove excess flowers,
destroy foliage or dry out plants);
 make possible the action of other
substances;
 counteract growths on boats and ships;
and,
 kill harmful organisms in farm build-
ings, the home, hospitals, stores and
vehicles.
The widespread use of pesticides not
only contaminates water, soil, and air, but
also causes them to accumulate in crops
(e.g., fruit and vegetables) (Fig. 1). Pesti-
cides are transported mainly by rain and
wind from their points of application to
neighboring crops and land, where their
presence may be undesirable or harmful

814 0165-9936/$ - see front matter ª 2011 Elsevier Ltd. All rights reserved. doi:10.1016/j.trac.2011.02.008
Trends in Analytical Chemistry, Vol. 30, No. 6, 2011
Figure 1. The circulation of pesticides in nature (including crops).
[2,3]. The quantities of pesticides in any particular re-
gion depend to a large extent on the intensity of pesticide
application and the types of crops grown there.
Pesticides have many advantages, but they also do
much harm to the environment [1–4]. Fig. 2 lists some
of the effects of using pesticides.
In view of both positive and negative effects of
pesticides, we should aim to achieve full selectivity of
their action. Nonetheless, the latest studies show that
pesticides still constitute a hazard to the environment
and human health. Each year, 140,000 tons of pesti-
cides are sprayed onto crops in the European Union (EU)
alone. Fruit and vegetables are the crops most likely to
be contaminated by pesticides, particularly grapes, citrus
fruits and potatoes. According to data from the EUÕs
Pesticide Action Network, as of 2008, some 350 different
pesticides were detected in food produced in the EU. More
than 5% of products contained pesticides at levels
exceeding the EUÕs maximum permitted level (MPL).
The diversity of their chemical structures, actions and
applications makes any classification of pesticides diffi-
cult [1]. There are a number of criteria according to
which they can be categorized:
(1) toxicity;
(2) purpose of application;
(3) chemical structure;
(4) environmental stability; and,
(5) the pathways by which they penetrate target
organisms.
Structurally, they can be divided into inorganic and
organic compounds; the inorganic include arsenic
insecticides, fluoride insecticides, inorganic herbicides
and inorganic fungicides, while the organic comprise
Trends
organochlorine, organophosphorus and organonitrogen
pesticides.
Organophosphorus pesticides (OPPs) (e.g., dichlorvos,
methyl parathion, chlorpyriphos, diazinon, demeton-
S-methyl, phosalone, fonofos, metamidofos, monocroto-
phos, chlorfenvinphos, fenitrothion, malathion) are the
principal group of compounds used to protect plants.
They include all organic compounds containing phos-
phorus [5,6] and are used to combat pests in industrial
plantations, orchards and vegetable cultivation. OPPs
usually have an ester structure, decomposing fairly
easily on the surfaces and interiors of plants, and in the
soil. Their toxicity depends on inhibiting the activity of
enzymes controlling the functions of the nervous system,
mainly acetylcholinesterase. They permanently bind the
group hydroxylating the enzyme, which prevents ace-
tylcholinesterase from decomposing, and act through
contact or systemically. Blockage of cholinesterase
activity causes the amount of acetylcholine at the syn-
apses to increase, leading to a state of hyperarousal, and
paralysis of the muscles and the main respiratory center.
Apart from OPPs, organonitrogen pesticides (ONPs) also
play a major part in combating pests [7,8]. ONPs include
phenylureas, carbamates, and triazines and their deriv-
atives (e.g., aminocarb, propoxur, carbaryl, simazine,
atrazine and propazine). Even though they are less stable
in the environment than OCPs, they can get into the
human digestive system, thus posing a health hazard.
Some carbamate insecticides (e.g., carbaryl) can be ter-
atogenic in large doses and nitrosated to form strongly
carcinogenic nitroso-compounds.
OCPs, including aldrin, chlordane, lindane and DDT,
have been withdrawn from use in many countries
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Trends
Figure 2. The effects of using pesticides [1,4].
because they are very toxic towards humans [9–11].
But, because of their considerable stability in the
environment (as long as 30 years), they may still be
present there and can be transported by air or water
over long distances. While ONPs and OPPs are not
very toxic, their improper application can also lead to
their presence in farm produce (e.g., fruit and vegeta-
bles). Even though they facilitate improvement in crop
yields and quality, they do pose a risk to consumers.
That is why international organizations have estab-
lished maximum residue levels (MRLs) of pesticides in
food.
Plant foods can be contaminated by pesticides under a
great variety of circumstances and at different times
preceding their consumption. Many factors can reduce
such contamination, (e.g., rainfall, wind, chemical
reactions induced by oxygen, moisture, light or plant
enzymes) [1]. Pesticides sprayed in liquid form contam-
inate plants to a greater extent than preparations applied
in powder form. The structure of the plant in question is
also important because, for example, OCP insecticides
accumulate in the waxy layer of the rind of many fruits,
especially citrus fruits. It is therefore a matter of urgency
that pesticide residues in fruit and vegetables are moni-
tored, because they can put human health at greater risk
of various diseases. Any assessment of the state of
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Trends in Analytical Chemistry, Vol. 30, No. 6, 2011
contamination of fruit and vegetables by pesticides
requires knowledge of MRLs. The MRLs of pesticides
contained in fruit and vegetables are laid down by the
EU. The limit of detection (LOD) of particular pesticides
(acephate, aldrin, dichlorvos, fenthion) is 0.01–0.05 mg/
kg. The LOD of simazine is slightly higher – 0.1 mg/kg,
rising to 0.25 mg/kg for cherries. An LOD of 5 mg/kg is
permissible for malathion in grapes and of 7 mg/kg in
samples of tomatoes and tangerines [12].
2. Determining pesticides in fruit and vegetable
samples
Despite considerable progress in the development of
methods for preparing samples for analysis and for the
final determination of analytes, the analysis of pesticides
in biological samples continues to present challenges to
analysts. A number of problems crop up in the analysis
of pesticide residues:
(1) the complexity and the diversity of matrices in
biological materials; and,
(2) the low concentrations of pesticides in samples of
fruit and vegetables.
Target analytes must, therefore, be isolated from
matrices and then be enriched before the final
Trends in Analytical Chemistry, Vol. 30, No. 6, 2011 Trends

Sampling

Fixing, transport and storage

Extraction of pesticides from the sample

and/or enrichment of the sample

Extract cleanup and it is

preparation for analysis

Identification and determination of

analytes

Figure 3. The main stages in analytical procedures for determining pesticides in samples of fruit and vegetables.

determination can be undertaken [13]. The complete
procedure for determining pesticide residues in biological
materials is complex and consists of several stages,
which are summarized in Fig. 3.
It is extremely important that the several stages of the
analytical procedure and the procedure as a whole are
validated in order to ensure compliance with the
requirements defining the procedure and to assess its
usefulness.
2.1. Preparation of samples for analysis
The sample-preparation stage and the operations in-
volved in it can affect the final result. Whether the
analysis provides the desired information about the
sample therefore depends on its proper, correct prepa-
ration. It is extremely important that the sample of
material for analysis is homogeneous and representative.
A representative sample has a chemical composition that
resembles as closely as possible the average composition
of the entirety of the analyzed material. The sample
should be stored frozen and in the dark. Generally
speaking, the sample-preparation process consists of a
number of steps. In the case of fruit and vegetables, one
such step is the removal of surface contaminants by
washing the samples in distilled water. The sample is
then dried at elevated or ambient temperature or with
the aid of a desiccant. In the next step, the sample is
broken up and crushed, or ground in a mill or with a
pestle and mortar, after which the sample is homoge-
nized. The exact preparation procedure depends on the
nature of the material under investigation, and every
combination of operations in this procedure can lead to
loss of analytes and/or cause additional contamination
of the sample [14].
2.2. Isolation (extraction) of pesticides from samples
The next stage involves isolation and/or enrichment of
target analytes – this is necessary because pesticide
concentrations in the various compartments of the
environment are low. This stage is essential, as in
many cases the available analytical methods are not
sufficiently sensitive to carry out a final determination
of the trace constituents directly from the sample. Iso-
lation and/or preconcentration mean the transfer of
analytes from the primary matrix to a secondary one
with the simultaneous removal of interferents and
increase in target-analyte concentrations to levels
above the LOD of the analytical technique applied.
Because pesticide levels in fruit and vegetables are
generally low, enrichment of target analytes is common
[15,16].
With fruit and vegetables, the solid matrix often has to
be replaced by a liquid one. This is done using a suitable
extraction method. Fig. 4 shows those usually used for
extracting pesticides from such samples [17–21]. Solvent
extraction with agitation is easy to carry out, is cheap

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Trends
Figure 4. Techniques for extracting pesticides from samples of fruit and vegetables.
and does not need any expensive, complicated appara-
tus. However, it requires large amounts of toxic solvents
and is poorly selective.
In order to speed up sample preparation, new extrac-
tion methodologies [e.g., accelerated solvent extraction
(ASE) and microwave-assisted solvent extraction (MAE)],
based on the use of high temperature and pressure to
heat the sample-solvent mixture, have been developed
recently. MAE is a process of heating with microwave
energy the solvent in contact with a sample to partition
compounds of analytical interest from the sample matrix
into the solvent.
The relatively new technique ASE is a promising
alternative. In short, ASE extracts samples under ele-
vated temperature, while elevated pressure ensures that
volatile extractants remain liquid. ASE can be completely
automated. It employs very small extractant volumes
and has typical extraction times of less than 1 h.
As such, the technique has the potential to overcome
the main shortcoming of Soxhlet extractions. Solvent
extraction in a Soxhlet apparatus is simple to perform
and separates extract from the residue, but the long
extraction time, the need to use large quantities of sol-
vent and the ability to obtain an extract from only one
sample at a time are disadvantages.
The Soxtec method is an improved version, which
gives better recoveries and is quicker, and several
samples can be extracted at the same time, but the
apparatus is very expensive. Solvent-extraction tech-
niques are often assisted with microwaves or ultrasound
to improve analyte recoveries. The usual solvents are
acetone, acetonitrile and ethyl acetate.
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Trends in Analytical Chemistry, Vol. 30, No. 6, 2011
Table 1 lists the most commonly used solvents or their
mixtures for solvent extraction with agitation.
2.3. Extract clean up
The isolation of analytes from biological samples in-
volves a certain clean-up effect, and, like every clean-up
process ensures a certain degree of isolation. Extraction
yields not only the target analytes but also interferents
(e.g., sugars, fats and chlorophyll), which may distort
the result of the analysis. Hence, extract clean up is
essential and should always precede analysis of the
extract. The usual techniques for cleaning up fruit and
vegetable extracts are:
(1) solid-phase extraction (SPE);
(2) solid-phase microextraction (SPME);
(3) matrix solid-phase dispersion extraction (MSPDE);
(4) stir-bar sorption extraction (SBSE);
(5) adsorption chromatography; and,
(6) gel-permeation chromatography (GPC).
SPE is the most popular clean-up technique [31]. As
the sample passes through a column of sorbent, the
target analytes are adsorbed on the sorbent particles.
The compounds retained are then liberated with a sol-
vent and analyzed. A salt, usually NaCl or Na2SO4, is
often added to the solution to increase its ionic strength,
and that increases the proportion of analytes extracted to
the sorbent. Sorbents used for SPE include C18, poly-
mers, graphitized non-porous carbon, and ion-
exchangers.
The B15C5 sorbent is the best one for determining
organophosphorus pesticides. The method is simple and
can be readily automated. However, against that, the
Trends in Analytical Chemistry, Vol. 30, No. 6, 2011 Trends

Table 1. The solvents normally used to extract pesticides from samples of fruit and vegetables

Analyte Sample Solvent Ref.

Pesticide residues Fat vegetable (e.g., avocado) Ethyl acetate-cyclohexane (1:1) [2]
Organochlorine pesticides Fruits, vegetables and tubers Acetone, hexane [11]
90 pesticides of various classes Fresh fruit and vegetables Acetone [16]
Organophosphorus pesticides Apples, tomatoes, apple juice Acetone [19]
Pesticide residues Green leafy vegetables (spinach, Ethyl acetate [20]
komatsuna, qing geng cai,
broccoli, cauliflower, green
pepper, and okra)
Insecticide (OCPS, OPPS, Date palm Methanol [22]
pyrethroids), fungicide, acaricide,
herbicide
Organochlorine, organophosphate Carrots, oranges Acetonitrile [23]
pesticides and fungicides
Pesticide residues Lettuce, tomatoes, grapes, Acetone [24]
strawberries
Pesticides of various classes Fruits and vegetables Methanol [25]
Pesticide residues Fresh fruit (oranges, apples, Acetone, cyclohexane/ [26]
peaches, pears and grapefruits) ethyl acetate (1:1)
and vegetables (lettuce, tomato,
cabbage, potato, onion and leek)
Pesticide residues Oranges Methanol [27]
Cyromazine and its metabolites Beetroot Methanol [28]
Pesticide residues Oranges Methanol, ethyl acetate [29]
Fungicides, acericides, insecticides Oranges Ethyl acetate [30]

solvent bed has to be conditioned before each use, and
analyte recovery is small.
In SPME, analytes are adsorbed on a fiber coated with
a suitable solid phase that is pushed out from a micro-
syringe [32]. The analyte is then thermally desorbed and
transferred to the GC injector. The benefits of this
method are that solvents can be eliminated and that it is
impossible to overload the column because of the limited
volume of adsorbent. Depending on where the fiber is
placed in relation to the sample, SPME can be divided
into:
(1) direct immersion (DI-SPME),
(2) headspace (HS-SPME).
GPC is just as frequently used as a clean-up technique
[33–35]. It enables micromolecular pesticides to be
separated from macromolecular substances present in
the matrix. While the long lifetime of the columns is an
advantage, the poorer resolution compared to adsorption
techniques, especially when gradient-elution techniques
are used, is a disadvantage.
Approaches are being sought to develop pesticide-
determination techniques that are quick, easy, cheap,
effective, rugged and safe (QuEChERS) [43–54], which is
a combination of liquid-liquid extraction (LLE) and SPE.
It is based on a number of stages (see Fig. 5).
Table 2 lists the most commonly used techniques for
cleaning up extracts prior to the final determination of
pesticides in samples of fruit and vegetables. The con-
sumption of sample and toxic solvents with the
QuEChERS method is minimal. By applying QuEChERS
to the determination of pesticides in fruit and vegetables,
matrix effects are eliminated and high recoveries of
target analytes are possible. The method can be modified
depending on the type of sample and the target analytes.
To improve the extraction of polar organophosphorus
pesticides, the method is modified by the addition of
acetic acid. When samples of citrus fruit are under
investigation, protective wax coatings can be removed
by freezing the samples for at least one hour. For the
analysis of citrus fruits, blackcurrants and raspberries, it
is recommended to add aq NaOH to reach pH = 5 and to
improve the analysis. Work is in progress to optimize this
method for the analysis of pesticides of various classes.
The last stage in the QuEChERS method is the final
determination of analytes by GC or LC.
2.4. Identification and determination of analytes
The last stage in the analytical procedure is identification
of compounds and their quantitative determination
using appropriate instrumentation. The choice of final
determination technique depends above all on the
properties of the analytes. Pesticides cannot be treated as
a homogeneous group of specific environmental con-
taminants, because they differ in their physicochemical
properties. The usual techniques for final determinations
of pesticides include capillary gas chromatography (GC)
and high-performance liquid chromatography (HPLC)
(usually in reversed-phase mode) for determining pesti-
cides that are unsuitable for determination by GC. Pes-
ticides to be determined by GC should be volatile and

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Trends Trends in Analytical Chemistry, Vol. 30, No. 6, 2011

Single-phase extraction of pesticides from the

sample with a small amount of acetonitrile

Addition of MgSO4 and NaCl to separate

the phases into an aqueous and an organic one

Solid phase extraction (SPE) to remove any

remaining water, and the addition of an amine sorbent

Sample enrichment

Analysis of pesticides using

capillary GC-MS or LC/MS
Figure 5. Stages in the determination of pesticides using the Quick, Easy, Cheap, Effective, Rugged, and Safe (QuEChERS) method.

Table 2. Techniques for cleaning up extracts prior to the final determination of pesticides in samples of fruit and vegetables

Analyte Sample Extract clean-up technique Ref.

Organophosphorus pesticides Apples, tomatoes, apple juice SPME, HS-SPME [19]
Pesticide residues Lettuce, tomatoes, grapes, strawberries SPE, SBSE [24]
Pesticides of various classes Fruits and vegetables SBSE [25]
Pesticide residues Fresh fruit (oranges, apples, GPC [26]
peaches, pears and grapefruits)
and vegetables (lettuce, tomato,
cabbage, potato, onion and leek)
Pesticide residues Vegetables SPME [34]
Organophosphorus insecticide Strawberries and cherries HS-SPME [35]
residues
10 pesticide residues Oranges, tangerines SPE [36]
Organophosphorus pesticides Cucumber, potato SBSE [37]
Pesticide residues Oranges, tangerines, grapefruits, lemons MSPD [38]
Volatile compounds Peaches, oranges HS-SPME [39]
Pesticide residues Fruit and vegetables MSPD, SFE [40]
Pesticide residues Grapes SPE [41]
Pyrethroid residues Strawberries SPME [42]

thermally stable. For determining OPPs, GC equipped
with a suitable column and detector is used. GC can be
used to determine the residues of all classes of pesticides.
The choice of chromatographic column is extremely
important for separating analytes and for their qualita-
tive and quantitative determination. The chromato-
graphic column should be highly efficient and resistant
to changes in the parameters of the separation process.
The solid (stationary) phase should be thermally stable
and highly selective with respect to the constituents of
the mixture being analyzed. The multi-residue determi-
nation of pesticides in fruits and vegetables is generally
carried out by GC-MS, due to its excellent characteristics
of efficient chromatographic separation, sensitivity and
confirmation power based on electron-impact ionization
mass spectra. However, LC-MS allows rapid, efficient
determination of many compounds that have rarely
been investigated in food or determined with difficulty by
using laborious, time-consuming GC or conventional LC
procedures.

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Trends in Analytical Chemistry, Vol. 30, No. 6, 2011 Trends

The following techniques are employed to determine
OPPs and ONPs in fruits and vegetables:
 MS (mass spectrometry) – for the determination pesti-
cides of various classes;
 ECD (electron-capture detector) – highly sensitive in
relation to compounds containing electronegative
atoms and generally used for quantification of
OCPs;
 FPD (flame-photometric detector) – applied in the
determination of OPPs;
 NPD (nitrogen-phosphorus detector) – for the simulta-
neous determination of ONPs and OPPs; and,
 TSD (thermionic specific detector) – for the determina-
tion of compounds containing nitrogen or phospho-
rus,
Once a target analyte has been detected quantita-
tively, for example by GC-NPD, the result must be con-
firmed by another independent method. Alternatively,
the conditions of the process can be changed (e.g., by
altering the temperature program, or simply by using a
different detector). It is crucial to obtain confirmation by
another method, as identification based solely on reten-
tion times is not sufficiently reliable.
There are also other techniques available for deter-
mining OPPs and ONPs in fruits and vegetables, e.g.:
 gas liquid chromatography (GLC) [55]; and,
 chemiluminescence method (CL) [56,57].
Table 3 lists information on the most commonly ap-
plied final determination techniques for fruit and vege-
table samples.
EU member states are obliged to organize effective
monitoring of food with the aim of assessing its safety. In
the case of pesticide residues, this task is carried out in
the form of monitoring programs and official inspections
of food to ensure compliance with MRLs.
Table 4 presents data from the literature regarding
final determinations of pesticides in fruit and vegetable
samples. Depending on the type of matrix, different
extraction techniques, different column clean-up proce-
dures and different final determination methods are
used. According to the type of sample, the mean recov-
ery of a method was in the range 55–120%, and relative
standard deviation (RSD%) 1–26%. LODs were 0.003–
100 lg/kg. Analysis of data from the literature shows
that there is no one universal method with which to
determine pesticide residues in a sample. What we are

Table 3. Techniques for the final determination of pesticides in samples of fruit and vegetables

Analyte Sample Final determination Ref.

technique + detector
Organophosphorus pesticides Apples, tomatoes, apple juice GC-FPD [19]
Pesticide residues Fresh fruit (oranges, apples, peaches, GC-MS [26]
pears and grapefruits) and vegetables
(lettuce, tomato, cabbage, potato,
onion and leek)
Pesticide residues Oranges LC-MS [27]
Cyromazine and its metabolites Beetroot LC–ESI–MS2 [28]
Pesticide residues Fruits and vegetables GC–NPD/ECD [32]
Organophosphorus insecticide residues Strawberries and cherries GC-MS [35]
10 pesticides of various classes Oranges, tangerines LC-MS [36]
Organophosphorus pesticides Cucumber, potato GC-TSD [37]
Pesticide residues Oranges, tangerines, grapefruits, LC-MS2 [38]
lemons
Insecticides Peppers GC-MS, [46]
GC-MS2
52 pesticides of various classes Tobacco HPLC-MS2 [58]
234 pesticides of various classes Herbs GC-MS [59]
Pesticide residues Fatty vegetable GC-MS, [60]
LC-MS
Fungicides Fruits (oranges, tangerines, lemons, LC- fluorescence [61]
grapefruits, apples, pears, bananas) detection
and vegetables (potatoes and
lettuces)
Organophosphorus pesticides Olive oil GC-FPD [62]
Pesticide residues Cucumber, strawberries GC-ECD [63]
Pesticides of various classes Grapes, musts, wines GC-MS [64]
Pesticides of various classes Oranges, tangerines, nectarines, GC-NPD, [65]
peaches, khakis GC-ECD,
GC-MS
Organophosphorus pesticides Cabbage, grapes LC-MS2 [66]
160 pesticides of various classes Tomatoes, pears, oranges LC-MS2 [67]

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Table 4. Results of final determinations of pesticides in samples of fruit and vegetables

Pesticide class Analyte Type of sample Final determination Result of determination Ref.
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technique
Analyte Limit of detection Limit of quantitation
recovery [%] (LOD) [lg/kg] (LOQ) [mg/kg]
90 pesticides of various Methamidophos, acephate, Fresh fruits and vegetables GC-MS >80 0.01 for nearly all 0.01 [16]
classes omethoate, fenitrothion (apples, oranges, pears) pesticides;
exception: 20 for:
captan, dicofol,
maleoxon,
paraoxon-ethyl,
paraoxon-methyl
Organophosphorus Dichlorvos, phorate, diazinon, Apple juice, apples, GC-FPD 55–106 0.003–0.009 – [19]
pesticides fenitrothion, malathion, tomatoes
parathion, ethion
Organochlorine, Acephate, aldrin, captan, Carrots, oranges GC-MS 72–116 0.1 0.0004–0.09 [23]
organophosphate chlorpyrifos, diazinon,
pesticides and fungicides dichlorvos, dieldrin, disulfoton,
endosulfan, fenthion,
methoxychlor, methyl parathion,
methamidophos and others
Pesticide residues Bitertanol, carbendazim, Oranges LC-MS 8–96 1–50 0.001–0.05 [27]
fenthion, flusilazole,
hexythiazox, imidacloprid,
methidathion, methiocarb,
pyriproxyfen and trichlorfon.
Cyromazine and its Cyromazine, melamine Beetroot LC–ESI–MS2 92, 78 10 0.05 [28]
metabolites

Trends in Analytical Chemistry, Vol. 30, No. 6, 2011

Organophosphorus Thiabendazole, iprodione, Strawberries, cherries GC-MS – 1 0.05–0.5 [35]
insecticides vinclozolin, azinphos-methyl,
methidathion,
malathion and others
Organophosphorus Dimethoate, Cucumber, potato GC-TSD – < 0,15 0.0005–0.05 [37]
pesticides parathion-methyl

Insecticides Isofenphos-methyl, Peppers GC-MS2 85–98 0.1–0.3 - [46]

isocarbophos
234 pesticides of various Parathion, parathion-methyl, Herbs GC-MS 62–119 <50 <0.05 [59]
classes phorate, phosalone, phosmet,
phosphamidone, pretilachlor,
propoxur, pymetrozine,
simazine,
terbuthylazine, terrazole,
thifluzamide
 Trends in Analytical Chemistry, Vol. 30, No. 6, 2011
Organophosphorus Dimethoate, parathion-methyl, Olive oil GC-FPD 78–97 – – [62]
pesticides fenthion, parathion-ethyl, and
methidathion
Pesticides of various classes Diazinon, vinclozolin, Grapes, musts GC-MS 57–120 0.02–5 0.02–5 [64]
dicarboxamide, and wines
chlorpyrifos-methyl
organophosphate,
metalaxyl, phenylamide,
malathion organophosphate,
fenthion organophosphate,
ethion, phosmet
organophosphate,
phosalone, azinphos-methyl and
others
Organophosphorus Acephate, methamidophos, Cabbage, grapes LC-MS2 80–101 1–4 0.01 [66]
pesticides monocrotophos, omethoate,
oxydemeton-methyl,
vamidothion
160 pesticides of various Thiabendazole, iprodione, Tomatoes, pears, LC-MS2 70–120 10–100 0.005–0.5 [67]
classes vinclozolin, azinphos-methyl, oranges
methidathion, malathion and
others
Carbamates pesticides Isopropoxyphenol, naphthol, Potatoes GC-NPD 50–73 41–53 0.05 [68]
carbofuran, propham,
methiocarb, propoxur, carbaryl,
aldicarb, sulfoxide, methomyl,
phenanthrene, 4-nitrophenol
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Trends
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Trends
looking for is a method giving the highest recovery of
analytes and simultaneously the lowest possible LOD. It
turns out that there is no universal detector capable of
determining all classes of pesticides at the same time. In
the case of GC-MS, only 17 different pesticides could be
determined in 240 samples [26]; in 66.7% of samples, no
pesticides were detected, in 25.8%, pesticides were
present at levels below the MRL, but 7.5% of samples
contained pesticides in amounts exceeding their MRLs.
More than 5% of the fruit and vegetable samples
analyzed contained five or more different pesticides. In
sweet peppers and grapes, more than 10 such com-
pounds were found. In apricots, grapes, tangerines and
oranges, pesticide levels exceeded EU MRLs, and straw-
berries contained 14 different pesticides. Around 50% of
fruit and vegetable samples contained no pesticides at
all, 45% contained pesticide residues below the MRL, but
5% above the MRL.
Work is in progress to develop analytical methods that
conform to the principles of green analytical chemistry,
that is, they:
 enable a wide range of analytes to be determined in a
single analytical run, using multi-residue methods
(MRMs);
 ensure maximum removal of interferents from ex-
tracts;
 yield high recoveries of compounds, are very sensitive
and guarantee good precision; and,
 consume the smallest possible amounts of chemical
reagents, especially organic solvents.
Tandem mass spectrometry (MS2) improves sensitivity
and selectivity of analytical methods. In this technique,
ions that were separated in the first analyzer are again
fragmented and the derivative ions analyzed in the
second analyzer. The chromatogram background is
reduced, as a result of which the signal value is
enhanced with respect to noise and the LOD of the target
analytes is lowered [69,70]. Improved peak resolution
and smaller influence of the matrix on the final result
can be achieved with two-dimensional GC (GCxGC).
GCxGC separation systems must satisfy a series of basic
requirements [71,72]. Each such system must use two
columns with different retention mechanisms. The
columns must be joined by means of a modulator, which
collects or samples fractions from the first column and
periodically injects them into the second column with a
frequency sufficient to prevent the bands separated in
the first column from recombining in the modulator
[73–76]. The final determination process is as follows:
1) the sample injected into the system is initially sepa-
rated in the first column;
2) on leaving the first column, the sample constituents
go to the modulator, which collects the material
leaving this column for a fixed, unchanging period
of time;
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Trends in Analytical Chemistry, Vol. 30, No. 6, 2011
3) the next step is when the modulator injects the
entire collected material into the second column
in the form of a narrow band;
4) separation in the second column of the constituents
of the preceding fraction takes place at the same
time as the collection of the next fraction in the
modulator following sample injection; and,
5) the constituents leaving the second column are sent
to an appropriate chromatographic detector, which
records a series of very short, sequential chromato-
grams from the second dimension.
The advantage of this method is that the separation
mechanisms in the two columns are independent of each
other, so that constituents that were co-eluted from the
first column can be separated. Moreover, GCxGC can
simplify the preparation of fruit and vegetable samples
for determination of the presence of pesticides. This is
exemplified by the samples of celeriac [68], which were
chopped and mixed with ethyl acetate and sodium
sulfate. The mixture was then comminuted and centri-
fuged. The ethyl-acetate layer was removed and dried
over sodium sulfate before being injected into the GCxGC
system coupled to a time-of-flight mass spectrometer
(TOF-MS). As a result, peaks of all the analytes chro-
matographically separated from the matrix were
obtained; they were correctly identified and determined
quantitatively.
GCxGC is widely used because of its high resolving
power, greater sensitivity and ordered nature of the
chromatograms. Fast GC is equally frequently used to
shorten the time of analysis and to obtain better peak
resolution. Compared to classical GC, it requires shorter
capillary columns with a smaller diameter and solid
phase films 0.1 lm in thickness, as well as faster flow
rate and higher pressure of the carrier gas. These
parameters yield determination results of a better preci-
sion [70,77,78]. The trend at present is to develop
analytical methods enabling a broad spectrum of ana-
lytes to be determined in a single analytical run with
MRMs. But the problem here is that the compounds to be
determined simultaneously are often present at low
concentrations, and have different physicochemical
properties depending on their chemical structure.
3. Summary
The increasingly widespread application of pesticides
– substances with different physical and chemical
properties – means that ever larger amounts of these
compounds are getting into the environment. As a result
of the various processes to which they are subject in the
environment, they may be converted to even more toxic
compounds. They are currently regarded as some of the
most dangerous environmental contaminants because of
Trends in Analytical Chemistry, Vol. 30, No. 6, 2011 Trends

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