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Humans in the environment. Comparative analysis and assessment of

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Article in European Journal of Science and Theology · December 2013

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 European Journal of Science and Theology, December 2013, Vol.9, No.6, 79-94

_______________________________________________________________________
HUMANS IN THE ENVIRONMENT
COMPARATIVE ANALYSIS AND ASSESSMENT OF
PESTICIDE RESIDUES FROM FIELD-GROWN
TOMATOES

Manuela Olga Pogăcean1,2, Raluca Maria Hlihor2, Cristina Preda3

and Maria Gavrilescu*2,4
1
Plant Protection Agency Mureş, 80 Dezrobirii Street, Tîrgu Mureş, Romania
2
‘Gheorghe Asachi’ Technical University of Iaşi, Faculty of Chemical Engineering and
Environmental Protection, Department of Environmental and Management, 73 D. Mangeron, Iasi
700050, Romania
3
’Gr. T. Popa’ University of Medicine and Pharmacy of Iasi, Emergency Cinical Hospital ‘Sf.
Spiridon’, Independence Blvd. No.1, 700111, Iasi, Romania
4
Academy of Romanian Scientists, 54 Splaiul Independentei, RO-050094 Bucharest, Romania
(Received 15 July 2013, revised 16 August 2013)

Abstract

This paper aims to provide a perspective on the possibility that consumers could be
exposed to pesticides, by estimating quantities of pesticide residues in tomatoes from
field crops. Twelve pesticides, 7 fungicides and 5 insecticides respectively have been
analyzed in field-grown tomatoes samples within the Mureş Fitosanitary Unit (Romania)
by gas chromatography coupled with mass spectrometer with flight time, using the
multi-residual method. This study highlights the necessity of pesticides monitoring in
field-grown tomatoes, to warrant that their levels do not pose risks to human health. A
number of three treatments were applied at the recommended normal doses to field-
grown tomatoes samples at an interval of 20 days during 2012. The final residual
amounts of pesticides in tomatoes were below the MRLs, except for chlorothalonil and
bifenthrin. The analysis of health risk estimates based on consumption data in Europe
and Romania revealed that the target pesticides do not pose a risk to human health.

Keywords: degradation, pesticides, food consumption, human health risk assessment

1. Introduction

1.1. Short history of pesticides use

Agriculture began to be practiced about 10,000 years ago in the Fertile

Crescent of Mesopotamia as the population became more established and
farming turn out to be to be the way of life. Likewise, rice and millet were

*
Corresponding author, e-mail: mgav@ch.tuiasi.ro
 Pogăcean et al/European Journal of Science and Theology 9 (2013), 6, 79-94

cultivated in China, even as about 7,500 years ago rice and sorghum were
farmed in a region of Africa, the Sahel [1]. During time, the farmed crops began
to endure from pests and diseases causing high production breakdown, so that
people started to find ways of overcome these problems. About 4500 years ago
Sumerians who used sulphur compounds as insecticides to control insects and
mites, whilst about 3200 years ago the Chinese were using mercury and
arsenical compounds for controlling body lice [2]. Persians used the powder of
pyrethrum (derived from the dried flowers of Chrysanthemum cinerariaefolium
‗Pyrethrum daisies‘) as an insecticide for over 2000 years to protect stored grain.
In the 1600s, ants were controlled with mixtures of honey and arsenic [1].

Table 1. Main milestones in the modern era of pesticides development [4].

Period Example Source Characteristics
1800s- Early organics, nitrophenols, Organic chemistry, by- Often lacked specificity
1920s chlorophenols, creosote, products of coal gas and were toxic to users or
naphthalene, petroleum oils production etc. nontarget organisms
1954-1955 Chlorinated organics, DDT, Organic synthesis Persistent, good
hexachlorocyclohexane selectivity, good
(HCCH), chlorinated agricultural properties,
cyclodienes good public health
performance, resistance,
harmful ecological effects
1945-1970 Cholinesterase inhibitors, Organic synthesis, good use Lower persistence, some
organophosporous compounds, of structure-activity user toxicity, some
carbamates relationships environmental problems

1970-1985 Synthetic pyrethroids, juvenile Refinement of structure- Some lack of selectivity,

hormones mimics, biological activity relationship, new resistance, costs, and
pesticides target systems variable persistence
1985- Genetically engineered Transfer of genes from Possible problems with
organisms biological pesticides to other mutations and escapes,
organisms and into disruption of
beneficial plants and microbiological ecology,
animals monopoly
Genetic alteration of plats to
resist non-target effects of
pesticides

The start of the 19th century found scientists working for a better
understanding of fungi behaviour, and sulphur compounds were developed as
fungicides [3, 4]. In 1807, copper sulphate solution was used to control bunt
disease in wheat. In the late 19th century, arsenic compounds were introduced to
control insect attack on fruit and vegetable crops. Paris green, developed in 1867
from a copper & arsenic mixture, was applied broadly to control the potato
beetle and protect grapes from insect damage [2]. Inorganic compounds, such as
sodium chlorate and sulphuric acid, or organic chemicals derived from natural
sources were still extensively used in pest control up to 1940s. Chemical
research was directed toward cheap chemicals with persistence in sunlight and
low toxicity to man, but with the ability to kill insect pests rapidly. In 1938
Muller demonstrated that DDT would certainly meet these requirements. Its

80
 Humans in the environment

accessibility for the period of World War II led to early use as a 10% dust on
humans, for example in Naples, to repress a typhus outbreak [5].
After the World War II, the production of synthetic pesticides accelerated,
with the discovery of the effects of DDT, BHC, aldrin, dieldrin, endrin,
chlordane, parathion, captan and 2,4-D [K.S. Delaplane, Pesticide Usage in the
United States: History, Benefits, Risks, and Trends, 1996, online at
http://ipm.ncsu.edu/safety/factsheets/pestuse.pdf]. A new chemical age began,
and farmers were the main reason for the new age. By 1952, there were almost
10,000 separate new pesticide products registered with the USDA [B. Ganzel,
Farming in the 1940s. The Chemical Age Dawns in Agriculture, online at
http://www.livinghistoryfarm.org/farminginthe40s/pests_01.html].
A chronology of the modern era of pesticide development is shown in
Table 1 [4].
Pesticides have certainly facilitated to increase agricultural production and
control vectors of disease over the past decades. Farmers consider pesticides as
an indispensable means to guarantee that they can preserve production of crops
of quality and quantity to satisfy an increasing human population. Latest
approximations of crop losses due to insect pests, diseases generated by a variety
of pathogens and rivalry from weeds, in spite of present control practices, range
from 26 to 40% for major crops, with weeds causing the highest potential loss
[5, 6]. Unfortunately, some pests became genetically resistant to pesticides under
constant chemical pressure, while non-target plants and animals were harmed,
and pesticide residues appeared in unexpected places [5]. In 1962, Rachel
Carson, in her well-known book, ‗Silent spring‘, due to which public confidence
in pesticide use was shaken, said that ―…. man is a part of nature, and his war
against nature is inevitably a war against himself‖ [7].
Nowadays, pesticides are among the most extensively used chemicals in
the world, being also among the most hazardous compounds to the environment
and humans. The pathways of humans‘ exposure to pesticides are numerous,
since pesticide residues can be found virtually everywhere. Pesticides have also
posed a number of problems for agriculture, since they kill beneficial insects and
assist in developing pesticide-resistant pests [3]. In this context, a regulatory
framework was developed during time, but, despite of this, the adverse impacts
of agricultural pesticide use continue to be serious concern. Simultaneously,
incomplete knowledge of existing and potential effects of pesticides continues to
influence people perception on the dangers and benefits of pesticide use [8, 9].

1.2. Pesticides in environment and foods

Pesticides are chemical compounds with a structure and mode of action

which have rendered them serious pollutants of the environment in general.
Some pesticides (in particular organochlorine compounds) are classified as
persistent organic pollutants (POPs), with a good ability to volatilize and travel
long distances through atmosphere, and then deposited in remote regions. They
also have the ability to accumulate and biomagnify, and bioconcentrate up to

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 Pogăcean et al/European Journal of Science and Theology 9 (2013), 6, 79-94

70,000 times their original concentration [4]. They are not biodegradable or very
little biodegradable. The pesticide degradation needs particular reaction
conditions] [10-14].
The U.S. Environmental Protection Agency (USEPA) defines pesticides
as [2, http://www.epa.gov/kidshometour/pest.htm]: ―A pesticide is a chemical
used to prevent, destroy, or repel pests. Pests can be insects, mice and other
animals, weeds, fungi, or microorganisms such as bacteria and viruses. Some
examples of pests are termites causing damage to our homes, dandelions in the
lawn, and fleas on our dogs and cats. Pesticides also are used to kill organisms
that can cause diseases‖. USEPA [http://www.epa.gov/kidshometour/pest.htm]
made a classification of pesticides, according to their types, purposes and uses,
as presented in Table 2.
The Food and Agriculture Organization (FAO) has defined pesticide as
[http://www.fao.org/docrep/018/a0220e/a0220e00.pdf]: ―Any substance or
mixture of substances intended for preventing, destroying or controlling any
pest, including vectors of human or animal disease, unwanted species of plants
or animals causing harm during or otherwise interfering with the production,
processing, storage, transport or marketing of food, agricultural commodities,
wood and wood products or animal feedstuffs, or substances which may be
administered to animals for the control of insects, arachnids or other pests in or
on their bodies. The term includes substances intended for use as a plant growth
regulator, defoliant, desiccant or agent for thinning fruit or preventing the
premature fall of fruit. Also used as substances applied to crops either before or
after harvest to protect the commodity from deterioration during storage and
transport‖.
Pesticides are designed to be toxic to living bodies, so that they inevitably
pose risks and need to be used safely and disposed properly [15-20]. During
years, the intensive use of pesticides led to serious environmental problems such
as perturbation of the natural balance, widespread pest resistance, environmental
pollution, hazards to non-target organisms and wildlife, and hazards to humans.
Unfortunately, due to their impacts, the use of pesticide contributed to
biodiversity loss, along with habitat loss and climate change, since they affect
wildlife directly and indirectly by means of food sources [16, 17, 21-23].
The use of pesticide in agriculture is the subject to permanent monitoring
due to possible risk for human health [24-27]. Intake of active ingredients
through food ingestion has been shown to be up to five orders of magnitude
higher than other exposure routes like air inhalation and ingestion of drinking
water. Furthermore, because fruits and vegetables are consumed raw or semi-
processed, it is expected to contain higher pesticide residue levels than other
food groups like milk or meat [28, 29]. The consumption of pesticides
contaminated food can seriously deplete some essential nutrients in the body that
are further responsible for serious damage associated with health risks [9, 22, 23,
27, 30-34]. Fresh vegetables and fruits are representing some of the most
important commodities in human diet due to the presence of meaningfully
amounts of nutrients and minerals. However, at the same time, due to

82
 Humans in the environment

agricultural practices they can also turn out to be a source of toxic substances
such as pesticides [35-38].

Table 2. Main classes of pesticides and areas of application

[http://www.epa.gov/kidshometour/pest.htm].
Class of pesticides Main use
Algicides Control algae in swimming pools and water tanks
Antimicrobials Kill microorganisms (such as bacteria and viruses)
Attractants Attractants are traps containing a pesticide and
food to lure insects or rodents inside. However,
food is not a pesticide even though it certainly
attracts pests
Disinfectants and Kill disease-producing microorganisms in the
sanitizers kitchen and bathroom
Fumigants Produce gas or vapor intended to destroy pests in
the house or in the ground
Fungicides Kill fungi (including blights, mildews, molds, and
rusts)
Herbicides Kill weeds
Insecticides Kill insects and other arthropods
Miticides Kill mites that feed on plants and animals
Microbial pesticides Microorganisms that kill or inhibit pests, including
insects or other microorganisms. Sometimes
microorganisms get rid of pests simply by growing
larger in numbers, using up the pests' food supply,
and invading the pests' environment
Molluscicides Kill snails and slugs
Nematicides Kill nematodes (microscopic, worm-like
organisms that feed on plant roots)
Pheromones Biochemicals used to disrupt the mating behavior
of insects
Repellents Repel pests, including insects (such as mosquitoes)
and birds
Rodenticides Control mice and other rodents

Maximum Residue Limits (MRLs) encourage food safety by restricting the

concentration of a residue allowed on a commodity, and by limiting the type of
commodity on which it is allowed. The establishment of MRLs is based on good
agricultural practices (GAP) data on food derived from commodities. MRLs are
not toxicological limits, but they must be toxicologically acceptable. Exceeded
MRLs are strong indicators of violations of GAP [39-41].
Tomatoes represent one of the most appreciated and consumed vegetables.
However, the intensive crops could suffer by high infestation of the tomatoes
cultures by pests and diseases, causing major losses and depreciations of the
quality of the vegetables [42, 43]: this is why the pesticides are used on a large
scale to control the infestation [44-46]. The chemical protection used in the case

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 Pogăcean et al/European Journal of Science and Theology 9 (2013), 6, 79-94

of the tomatoes is usually done by using two or three treatments with different
types of pesticides.

Table 3. Target pesticides commercial name and use.

Products
Active Recommended MRLs**
commercial Chemical Group Use*
substance dose (%) (mg/kg)
name
Merpan 80
WDG (grains
80% captan Phthalimide 0.15 Fungicide <2
dispersible in
water)
Shavit F 72 70% folpet Phthalimide <2
WDG (grains
0.2 Fungicide
dispersible in 2% triadimenol Triazole <1
water)
Systhane
Forte 240 g/L
Triazole 0.02 Fungicide <0.3
(soluble myclobutanil
concentrate)
Bravo 500
SC 500 g/L
Chloronitrile 0.2 Fungicide <2
(concentrated chlorothalonil
suspension)
Orius 25 EW
250 g/L
(emulsion – Triazole 0.05 Fungicide <1
tebuconazole
oil in water)
Ridomil 4% metalaxyl-
Phenylamide
Gold MZ 68 M
WG (grains 0.25 Fungicide <0.2
dispersible in 64% mancozeb Ditiocarbamati
water)
Nurelle D 500 g/L
50/500 EC Chlorpyrifos Organophosphate
(emulsifiable ethyl
concentrate) 0.06 Insecticide <0.5
50 g/L
Pyrethroids
cypermethrin

Talstar 10
EC 100 g/L
Pyrethroids 0.05 Insecticide <0.2
(emulsifiable bifenthrin
concentrate)
Fastac 10 EC
100 g/L alfa-
(emulsifiable Pyrethroids 0.02 Insecticide <0.5
cypermethrin
concentrate)
Karate Zeon
50 g/L lambda
(concentrated Pyrethroids 0.02 Insecticide <0.1
Cyhalothrin
suspension)
Decis 2.5 EC
25 g/L
(emulsifiable Pyrethroids 0.05 Insecticide <0.3
deltamethrin
concentrate)
* [48]
**MRLs - maximum residue limits set by European Union legislation
[https://secure.pesticides.gov.uk/MRLs]

The constant usage of the pesticides increases the possibility of finding

multiple residuals of these compounds in the tomatoes that result, beyond the
legal prescribed limits, creating a significant risk for the human health [45, 46].

84
 Humans in the environment

The pesticides residuals from the food products have to be low and under the
MRLs established by each country [24, 44, 46, 47]. Table 3 includes the MRLs
established by the European Union, for each of the analyzed pesticides.
Analysis of multiple pesticide residues in fruits and vegetables is often a
time-consuming, labour-intensive, and expensive process due to the complexity
of the many analytes and matrices involved [49]. A large variety of methods
have been used in the determination of different pesticides in these foods. The
most frequently used technique for analysis of pesticide residues in fruits and
vegetables is gas chromatography with different selective detectors as flame
photometric (FPD) (Ueno, et al, 2003) [50, 51], pulsed flame photometric
(PFPD) [52], nitrogen–phosphorus (NPD) [53], and electron-capture detectors
(ECD) ( [54, 55]. Numerous method use gas chromatography coupled with mass
spectrometry (GC-MSD) [51, 56, 57], due to the possibility of confirming
pesticide identity in these matrices.
In this context, the main objectives of this paper consists in the
investigation of the occurrence and distribution of residues of 11 pesticides in
tomatoes cultivated within the Mureş Fitosanitary Unit (Romania), during a
vegetation period, using a rapid multi-residue method for the analysis based on
by gas chromatography with mass-selective detection (GC-MSD). Human health
risk estimations due to pesticides presence in tomatoes at harvest has been done
based on food consumption rate for vegetables in Europe and in Romania.

Captan Folpet Triadimenol Myclobutanil Chlorothalonil

Tebuconazole Metalaxyl-M Chlorpyrifos ethyl Alpha- cypermethrin Bifenthrin

RZ-1S-cis-isomer SZ-1R-cis-isomer

Lambda-cyhalothrin Deltamethrin

Figure 1. Chemical structure of the selected pesticides for the present study.

2. Materials and methods

2.1. Chemicals and solvents

Reference pesticide analytical standards were purchased from Chem

Service (West Chester, SUA) and Sigma Aldrich Laborchemikalien GmbH

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 Pogăcean et al/European Journal of Science and Theology 9 (2013), 6, 79-94

(Seelze, Germany) with the purity certified between 95.1% and 99.7%. Acetone,
petroleum ether, dichloromethane, toluene and isooctane were Super Purity
Solvents supplied by Fluka& Riedel-deHaën (Sigma-Aldrich, UK). The distilled
water used was provided by a Thermo Scientific TKA system (Niederelbert
Germany). All samples were stored in a refrigerator at 40C until further use. The
standard solutions were dissolved in toluene and later stored in a refrigerator at
40C. The commercial pesticide products used in the study (Figure 1, Table 3)
were purchased from Dafcochim SRL (Tg. Mures, Romania) and Chemark Rom
SRL (Tg. Mures, Romania).

2.2. Gas chromatography-mass spectrometry analysis

The pesticide residues were analyzed by a gas chromatograph coupled

with a mass spectrometer with flight time, CG*GC-TOF-MS Pegasus 4.21
(LECO, SUA). The system consists of an Agilent 7890 gas chromatograph with
2 ovens. The conditions used for the gas chromatography analysis were:
capillary column Rxi-Ms (30m*0.25mm*0.25µm) – main oven, and BPX-50
(1.6m*0.1mm*0.1µm) – secondary oven. Helium was used as carrier gas and
make-up gas at a flow rate of 1.0 mL/min. The injector temperature was set at
2500C. The oven temperature was programmed as follows: main oven, 700C held
for 1 min; ramp at 200C/min to 1400C, held for 1min; ramp at 50C /min to 3100C,
held for 4 min; secondary oven, 950C held for 1 min; ramp at 200C/min to
1650C, held for 1min; ramp at 50C /min to 3300C, held for 4 min. The injection
volume of the GC was 1.0µL. The mass spectrometer operated in the following
conditions: ion source temperature, 2200C; ionization mode EI, 70 eV; detector
Voltage 1800; Start mass 40; End start 450; Acquisition Rate *spectre/second, 5;
temperature of transfer, 2800C; time of analysis, 43 min. The high-performance
auto sampler software enables the syringe washing with several solvents (at least
four different solvents in the same washing phase) to end the contamination.

Table 4. Conditions for pesticide identification.

MS
Pesticides tR, (min)
Selected ions (m/z)
Captan 16.38 117, 149, 264
Folpet 16.31 104, 260, 262
Triadimenol 16.14 112, 128, 168
Myclobutanil 17.29 179, 181, 245
Chlorothalonil 12.39 109, 264, 268
Tebuconazole 18.24 125, 250, 252
Metalaxyl-M 13.50 132, 160, 206
Chlorpyrifos ethyl 14.51 197, 199, 314
Bifenthrin 19.09 165, 181, 182
Alpha-cypermethrin 21.33 127, 163, 165
Lambda-cyhalothrin 19.47 141, 181, 208
Deltamethrin 23.50 135, 173, 350

86
 Humans in the environment

The major ions (m/z) and retention time (tR) were considered for pesticide
identification (Table 4). To evaluate the efficiency of the analytical procedures, a
recovery assay was accomplished. The method was validated by determining the
limits of quantification (LOQ), recovery percentages and coefficient of variation.
In all cases, regression coefficients (R2) resulted were higher than 0.99.
Recoveries were found from 80% to 110%.

2.3. Field experiments and sample preparation

A field survey was conducted within the Mureş Fitosanitary Unit

(Romania) during 2012. Tomatoes plants were transplanted in the open field in
mid May 2012, on two rows to 0.6 m wide and 0.3 m distance between tomato
plants on the same row, at a density of 45-50 thousand plants/ha. A number of 3
treatments were applied to field-grown tomatoes samples at an interval of 20
days between treatments, in the period 3rd of August 2012 and 29th of September
2012. Buffer areas have been ensured between the tomatoes plants subjected to
the experiment. Each applied treatment contains a fungicide and an insecticide.
Fungicides were based on Chlorothalonil, Captan, Folpet, Tebuconazole,
Triadimenol, Myclobutanil, Metalaxyl-M and insecticides were based on
Deltamethrin, Alpha-cypermethrin, Lambda-cyhalothrin, Chlorpyrifos ethyl and
Biphenthrin. Each sample contains tomatoes of approximately the same size,
randomly picked, after 2, 5 and 12 days following the application of the
treatment. All tomatoes samples were put in sterile bags and stored at 4 0C until
further use.
A known quantity of whole tomatoes picked from different areas of the
plant were cut in quarters and mixed at a speed of 6,000 rpm. From the mixed
sample, 15g were weighed. For the extraction procedure dichloro-methane,
acetone and petrol ether were used as solvents. The vial which contains the
sample and the solvents was blended in an ultraturax shaker at 15,000 rpm and
centrifuged at 4,000 rot/min. In order to ensure an advanced homogenization of
the sample, 15 mL were pipetted into a Heidelph balloon of 100 mL attached to
a Heidolph rotoevaporator coupled with a vacuum pump at a rotation of the
balloon of 120 rpm. After solvent evaporation, the sample was sonicated for 5
minutes, at room temperature and analyzed through the GC-MS (CG*GC-TOF-
MS Pegasus 4.21).

2.4. Human health risk assessment

The human health risk estimation due to pesticides presence in tomatoes

at harvest has been done based on food consumption rate for vegetables in
Europe, 0.166 kg/person/day [58] and in Romania, 0.284 kg/person/day [59].
The estimated lifetime exposure dose (mg/kg/day) was obtained by multiplying
the residual pesticide concentration (mg/kg) in the tomatoes samples times the
food consumption rate (kg/day), and dividing the product by the body weight
(kg) [58]. The study used the U.S Environmental Protection Agency‘s

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guidelines: (a) a hypothetical body weights 70 kg for adults and (b) maximum
absorption rate is 100% and bioavailability rate is 100% [60, 61]. The hazard
indices for adults were calculated as the ratio between pesticide exposure doses,
and the reference doses which are considered to be safe levels of exposure over
the lifetime [60].

1,2
12 1st treatment
1st treatment
Concentration (mg/kg)

2nd treatment
10 2nd treatment 1
3rd treatment

Concentration (mg/kg)
3rd treatment MRLs, mg/kg
MRLs, mg/kg
8 0,8

6 0,6

4 0,4

2 0,2

0
0
2 5 12 Harvest 2 5 12 Harvest

Tim e (Days) Time (Days)

(a) Chlorothalonil degradation (b) Myclobutanil degradation

7 7
Concentration (mg/kg)

1st treatment 1st treatment

6 2nd treatment 6 2nd treatment
Concentration (mg/kg)

3rd treatment
5 MRLs, mg/kg 5 3rd treatment
MRLs, mg/kg
4 4

3 3

2 2
1
1
0
0
2 5 12 Harvest 2 5 12 Harvest

Time (Days) Time (Days)

(c) Captan degradation (d) Folpet degradation

3 1,2
Concentration (mg/kg)

1st treatment
2,5 2nd treatment
1
Concentration (mg/kg)

3rd treatment
MRLs, mg/kg 1st treatment
2 0,8 2nd treatment
3rd treatment
1,5 0,6 MRLs, mg/kg

1 0,4
0,5 0,2
0 0
2 5 12 Harvest 2 5 12 Harvest

Time (Days) Time (Days)

(e) Tebuconazole degradation (f) Triadimenol degradation

Figure 2. Dynamics of the degradation of Chlorothalonil, Myclobutail, Captan, Folpet,
Tebuconazole, Triadimenol in tomatoes

88
 Humans in the environment

3. Results and discussions

3.1. Pesticides degradation in tomatoes

The pathway of pesticides degradation has been monitored for each

compound and during various episodes of treatment (Figures 2, 3). In the case of
all three treatments carried out with Chlorothalonil (Figure 2a) it was found that
the MRLs (2 mg/kg) have been overrun. As it can be seen in Figure 2a, after 12
days, and the third treatment applied the chlorothalonil residues were higher than
MRLs, reaching 2.83 mg/kg at harvesting.

1,2 1,2
1st treatment

Concentration (mg/kg)
Concentration (mg/kg)

2nd treatment 1st treatment

1 3rd treatment 1 2nd treatment
MRLs, mg/kg 3rd treatment
0,8 0,8 MRLs, mg/kg

0,6
0,6
0,4
0,4
0,2
0,2
0
2 5 12 Harvest 0
2 5 12 Harvest
Time (Days)
Time (Days)

(a) Deltamethrin degradation (b) Alpha - cypermethrin degradation

1,2 1,4
Concentration (mg/kg)

Concentration (mg/kg)

1st treatment 1st treatment

1 2nd treatment
1,2 2nd treatment
3rd treatment
3rd treatment
0,8 1 MRLs, mg/kg
MRLs, mg/kg
0,8
0,6
0,6
0,4
0,4
0,2
0,2
0 0
2 5 12 Harvest 2 5 12 Harvest
Time (Days)
Time (Days)

(c) Lambda-cyhalothrin in tomatoes (d) Chlorpyrifos ethyl degradation

1,2 1,6
Concentration (mg/kg)

Concentration (mg/kg)

1st treatment 1st treatment

1,4
1 2nd treatment 2nd treatment
3rd treatment 1,2 3rd treatment
0,8 MRLs, mg/kg
1
MRLs, mg/kg

0,6 0,8
0,6
0,4
0,4
0,2 0,2
0 0
2 5 12 Harvest 2 5 12 Harvest

Time (Days) Time (Days)

(e) Metalaxyl-M degradation (f) Bifenthrin degradation

Figure 3. Dynamics of degradation of Deltamethrin, Alpha – cypermethrin, Lambda-

cyhalothrin, Chlorpyrifos ethyl, Metalaxyl-M, Bifenthrin in tomatoes

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 Pogăcean et al/European Journal of Science and Theology 9 (2013), 6, 79-94

In the case of systemic fungicide Myclobutanil, the content in residues at

harvest is below 0.3 mg/kg, the maximum limit allowed. As seen in Figure 2b,
myclobutanil residues content were below the MRLs, for the first two treatments
applied, after 12 days. After the first 5 days of application of the 3 treatments
with Captan, the content in residues decreases almost by half the maximum
residue limit value surpassing 2 mg/kg, but reaching a value of 0.79 mg/kg at
harvesting, below the MRLs (Figure 2c).
After 12 days after application of each of the three treatments, Folpet
residues are below the maximum residue limit of 2 mg/kg (Figure 2d).
Tebuconazole degradation is gradual. After 12 days of application of each
treatment, the residue content of the target pesticide is reduced to about half the
content of the residue obtained after 2 days of treatment. The final value reached
0.64 mg/kg at harvesting, below the maximum allowed of 1 mg/kg (Figure 2e).
Triadimenol is the second active substance Folpet along side commercial
product Shavit F 72 WDG. The values obtained in all three treatments applied,
after 2 days, 5 days and 12 days respectively is the maximum residue limits.
Finally, at harvest, the amount obtained being 0.07 mg/kg far below the MRLs
of 1 mg/kg (Figure 2f).
After 5 days in each of the 3 treatments applied, the content of
Deltamethrin residues were higher than the MRLs (0.3 mg/kg). Deltamethrin
degradation occurs gradually, reaching a concentration of 0.1 mg/kg at
harvesting, below the MRLs (Figure 3a). Salghi et al. [62] compared the
contents of Deltamethrin residues in tomatoes grown in the field with those of
tomatoes grown in greenhouses. Tomatoes cultivated under greenhouse
conditions are highly sensitive to pests and need frequent pesticide treatments,
leading to higher residues in the final products.
The content of Alpha-cypermethrin residues is below the maximum
permitted, 0.5 mg/kg, after 12 days for all three treatments applied. Finally the
value obtained at harvest reached 0.19 mg/kg much below the MRLs (Figure
3b).
Compared with Alpha-cypermethrin, Lambda-cyhalothrin was degraded
slowly due to its special structure (Figure 1). After each of the three treatments
applied, the residues content of Lambda-cyhalothrin exceeds the MRLs of 0.1
mg/kg. At harvest the Lambda-cyhalothrin concentration reaches a value of 0.09
mg/kg, below the MRLs (Figure 3c).
The degradation of Chlorpyrifos ethyl exceeds the MRLs value of 0.5
mg/kg, after 2 days and 5 days of the treatments application. After 12 days the
contents in residues were below the MRLs, reaching at harvest a value of 0.13
mg/kg (Figure 3d).
The content of Metalaxyl-M residues falls below the MRLs of 0.2 mg/kg,
after 12 days, considering the application of the first and third treatment. After 5
days from each treatment application the content in residues of Metalaxyl-M
decreases approximately by half compared with the concentration obtained after
2 days of spraying solution applying, reaching at harvest a residue content of 0.1
mg/kg much below the MRLs (Figure 3e).

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 Humans in the environment

As seen in Figure 3f the Bifenthrin residues were below the MRLs, 0.2
mg/kg, after 12 days of applying the second treatment. At harvesting,
considering the third treatment application, the content in residues of bifenthrin
reaches a value of 0.3 mg/kg, above the MRL.

3.2. Health risk estimates

Risk assessment is essential to the process of decision making about

pesticide effects on ecological systems and human health, both new and existing.
The human health risk estimation entails to assess the nature and probability of
adverse health effects in humans potentially exposed to chemicals in
contaminated environmental media. The risk assessment process depends on the
existing suitable data and testing models.

Table 5. Health risk estimation associated with pesticide residues in tomatoes, at

harvesting.
Europe Romania
Reference Concentration Europe Romania
estimated estimated Health
Pesticide dose of pesticides Hazard Hazard
dose dose risk
(mg/kg/day) (mg/kg) Index Index
(mg/kg/day) (mg/kg/day)
Captan 1.3 x10-1 0.79 0.18 x10-2 0.32x10-2 0.0144 0.0246 No
Folpet 1 x10-1 1.03 0.24 x10-2 0.41 x10-2 0.0244 0.0417 No
Triadimenol 5 x 10-2 0.07 0.01 x10-2 0.02 x10-2 0.0033 0.0056 No
Myclobutanil 3.1 x10-1 0.25 0.05 x10-2 0.10x10-2 0.0019 0.0032 No
Chlorothalonil 1.5 x10-2 2.83 0.67 x10-2 1.14x10-2 0.4474 0.7654 No
Tebuconazole 3 x 10-2 0.64 0.15 x10-2 0.25 x10-2 0.0505 0.0865 No
Metalaxyl-M 6 x10-2 0.10 0.02 x10-2 0.04 x10-2 0.0039 0.0067 No
Chlorpyrifos
1 x10-1 0.13 0.03 x10-2 0.05 x10-2 0.0030 0.0052 No
ethyl
Bifenthrin 1.5 x10-2 0.30 0.07 x10-2 0.12 x10-2 0.0474 0.0811 No
Alfa- -2 -2 -2
1 x10 0.19 0.04 x10 0.07 x10 0.0450 0.0770 No
cypermethrin
Lambda-
5 x10-3 0.09 0.02 x10-2 0.03 x10-2 0.0426 0.0730 No
cyhalothrin
Deltamethrin 1 x10-2 0.10 0.02 x10-2 0.04 x10-2 0.0237 0.0405 No

Table 5 summarizes the health risk estimates associated with pesticide

residues in tomatoes, at harvesting. The Table comprises of reference daily dose,
computed average maximum daily intake values and corresponding hazard
indices during the study period for adults. The human health risk estimation has
been performed based on Romanian and Europe consumption data. The health
risk analysis considered hazard indices and showed that the target pesticides
residues available in field-grown tomatoes at harvest do not pose a risk to human
health, although the doses of Chlorothalonil and Bifenthrin exceed the MRLs.
It should be noted that during our study, processing factors were ignored,
since often tomatoes are peeled, cooked or boiled before consumption, resulting
in an overestimation of the actual exposure to pesticide residues. Additionally,
the effect of pesticides on other groups such as children or pregnant women
should be of high interest in future studies.

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 Pogăcean et al/European Journal of Science and Theology 9 (2013), 6, 79-94

4. Conclusions

The present study shows that, despite the high number of treatments with
pesticides applied to field-grown tomatoes during 2012, the contamination level
could not be considered a public health problem. From a group of 12 target
pesticides chosen in our study for tomatoes treatment, only Chlorothalonil and
Bifenthrin concentration exceeded the MRLs allowed by the UE legislation, at
the final of the treatment upon harvesting.
Estimating the degradation of pesticides in tomatoes is important for the
assessment of the diet risks and to ensure continuous monitoring of residues.
Although the study focused on the consumption data both in Europe and
Romania for adults, the human health risk estimates indicated that adults are not
subjected to any health problems due to consumption of tomatoes treated with
pesticides. A future study should aim the health risk assessment from pesticide
treated fruit and vegetable consumption by more vulnerable groups such as
children and pregnant women.

Acknowledgement

This paper was elaborated with the support of a grant of the Romanian
National Authority for Scientific Research, CNCS – UEFISCDI, project number
PN-II-ID-PCE-2011-3-0559, Contract 265/2011 and with the support of Plant
Protection Agency Mureş, Romania.

References

[1] J. Unsworth, History of Pesticide Use, International Union of Pure and Applied
Chemistry (IUPAC), Research Triangle Park, North Carolina, 2010, online at
http://agrochemicals.iupac.org/index.php?option=com_sobi2&sobi2Task=sobi2Det
ails&catid=3&sobi2Id=31
[2] E.L. Taylor, A.G. Holey and M. Kirk, Southern Regional Extension Forestry,
SREF-FM-0 10 (2007) 1-7.
[3] M.J. Levine, Pesticides: A Toxic Bomb in Our Midst, Greenwood Publishing
Group, New York, 2007.
[4] M.F. Mahmoud and N. Loutfy, Uses and Environmental Pollution of Biocides, in
Pesticides: Evaluation of Environmental Pollution, H.S. Ratore & L.M.L. Nollet
(eds.), CRC Press – Taylor and Francis Group, Boca Raton, 2012, 3-28.
[5] G.A. Matthews, Pesticides: Health, Safety and the Environment, Blackwell
Publishing, Chichester, 2006.
[6] E.-C. Oerke and H.-W. Dehne, Crop Protection, 23 (2004) 275–285.
[7] R. Carson, Silent Spring, Fortieth Anniversary Edition, Houghton Mifflin Hartcourt
Company, Boston, 2002, 256-312.
[8] F. de Hond, P. Groenewegen and N.M. van Straalen, Questions around the
Persistence of the Pesticide Problem, In: Pesticides: Problems, Improvements,
Alternatives, F. den Hond, P. Groenewegen & N.M. van Straalen (eds.), Blackwell
Publishing, Malden, Massachusetts, 2003, 1-15.

92
 Humans in the environment

[9] B. Dibi, K.I. Kouame, A.B. Donan-Waidhet, I. Savane, J. Biemi, V. Nedeff and G.
Lazar, Environ. Eng. Manag. J., 11 (2012) 2175-2184.
[10] I. Iordache, S. Wilson, E. Lundanes, M. Iordache, V.L. Pavel and N. Aelenei,
Environ. Eng. Manag. J., 9 (2010) 519-525.
[11] S. Motoc, F. Manea, A, Pop, R. Pode and C. Teodosiu, Environ. Eng. Manag. J., 11
(2012) 627-634.
[12] V. Andrew and Y. Pico, TrAC, 23 (2004) 772-789.
[13] S. Chiron, A. Fernandez-Alba, A. Rodriguez and E. Garcia-Calvo, Water Res, 34
(2000) 366-377.
[14] D. Barcello, Trace Determination of Pesticides and Their Degradation Products in
Water, Elsevier, Amsterdam, 1977.
[15] C. Preda, M.C. Ungureanu and C. Vulpoi, Environ. Eng. Manag. J., 11 (2012)
1697-1706.
[16] F.A. Căliman, B.M. Robu, C. Smaranda, V.L. Pavel and M. Gavrilescu, Persistent
pollutants in the environment II. Persistent organic pollutants and dyes (in
Romanian), Politehnium, Iasi, 2009.
[17] M. Gavrilescu, Eng. Life Sci., 5 (2005) 497–526.
[18] M. Miclean, O. Cadar, C. Roman, C. Tanaselia, L. Stefanescu, C.I. Stezar and I.S.
Groza, Environ. Eng. Manag. J., 10 (2011) 37-42.
[19] A.M. Mocanu, C. Luca, L. Odochian, C. Zaharia and C. Iordache, Environ. Eng.
Manag. J., 11 (2012) 413-420.
[20] A.E. Gurzau, C.D. Roman, I. Dumitrascu and E.S. Gurzau, Environ. Eng. Manag.
J., 11 (2012) 257-263.
[21] M.E. Fortună, I.M. Simion, C. Ghinea, M. Petraru, P. Cozma, L.C. Apostol, R.M.
Hlihor, D.T. Fertu and M. Gavrilescu, Environ. Eng. Manag. J., 11 (2012) 333-350.
[22] S. Khan, Q. Cao, Y.M. Zheng, Y.Z. Huang and Y.G. Zhu, Environ. Pollut., 152
(2008) 686-692.
[23] A. Soceanu, S. Dobrinas, V. Coatu and E. Chirila, Pesticide residues determination
in vegetables from Romania by GC-ECD, in Exposure and risk assessment of
chemical pollution — contemporary methodology, NATO Science for Peace and
Security Series C: Environmental Security, Springer, Netherlands, 2009, 423-430.
[24] K.A. Osman, A.M. Al-Humaid, S.M. Al-Rehiayani and K.N. Al-Redhaiman,
Ecotoxicol. Environ. Saf., 73 (2010) 1433–1439.
[25] M.H.S. Kurz, F.F. Goncalves, M.B. Adaime, I.F.D. da Costa, E.G. Primel and R.
Zanella, J. Braz. Chem. Soc., 19 (2008) 1129–1135.
[26] I. Mukherjee, Environ. Monit. Assess., 86 (2003) 265–271.
[27] A. Dragus, M.S. Beldean-Galea, R. Mihaiescu, T. Mihaiescu and R. Ristoiu,
Environ. Eng. Manag. J., 11 (2012) 319-323.
[28] R. Juraske, C.L. Mutel, F. Stoessel and S. Hellweg, Chemosphere, 77 (2009) 939–
945.
[29] V.L. Pavel, D.-L. Sobariu, I.D. Tudorache Fertu, F. Stătescu and M. Gavrilescu,
Eur. J. Sci. Theol., 9(4) (2013) 211-224.
[30] L.C. Apostol, R.M. Hlihor, C. Smaranda, V.L. Pavel, B. M. Robu, F.A. Căliman
and M. Gavrilescu, Bulletin of the Polytechnic Institute of Iasi, Chemistry and
Chemical Engineering, 55 (2009) 67-83.
[31] M. Arienzo, D. Cataldo and L. Ferrara, Food Control, 31 (2013) 108-115.
[32] K. Hjorth, K. Johansen, B. Holen, A. Andersson, H.B. Christensen, K. Siivinen and
M. Toome, Food Control, 22 (2011) 1701-1706.
[33] A.D. Soceanu, S. Dobrinas, V. Popescu, G. Stanciu and D.T. Epure, Environ. Eng.
Manag. J., 11 (2012) 457-462.

93
 Pogăcean et al/European Journal of Science and Theology 9 (2013), 6, 79-94

[34] D. Nicuta, N. Badaluta, G. Lazar and I.M. Lazar, Environ. Eng. Manag. J., 12
(2013) 85-96.
[35] D. Sharma, A. Nagpal, Y.B. Pakade and J.K. Katnoria, Talanta, 82 (2010) 1077–
1089.
[36] M.O. Pogăcean and M. Gavrilescu, Environ. Eng. Manag. J., 8 (2009) 607-627.
[37] M. Frunza, M.I. Popa and G. Lisa, Environ. Eng. Manag. J., 6 (2007) 319-324.
[38] L. Ghervase, C. Ioja, E. Carstea and D. Savastru, Environ. Eng. Manag. J., 11
(2012) 567-571.
[39] C. Chen, Y. Qian, Q. Chen, C. Tao, C. Li and Y. Li, Food Control, 22 (2011) 1114-
1120.
[40] C. Smaranda and M. Gavrilescu, Environ. Eng. Manag. J., 7 (2008) 743-762
[41] M.-H. Kovacs and D. Ristoiu, Environ. Eng. Manag. J., 11 (2012) 589-595.
[42] L.M. Ravelo-Pérez, J. Hernández-Borges, T.M. Borges-Miquel and M.A.
Rodríguez-Delgado, J. Chromatogr. A, 1185 (2008) 151–154.
[43] J.P. Fife and S.E. Nokes, Crop Prot., 21 (2002) 733–740.
[44] M. Araoud, W. Douki, A. Rhim, M.F. Najjar and N. Gazzah, J. Environ. Sci.
Health B, 42 (2007) 179–187.
[45] M.F. Cengiz, M. Certel, B. Karakas and H. Gocmen, Food Chem, 100 (2007)
1611–1619.
[46] S. Zawiyah, Y.B. Che Man, S.A.H. Nazimah, C.K. Chin, I. Tsukamoto, A.H.
Hamanyza and I. Norhaizan, Food Chem, 102 (2007) 98–103.
[47] A. Columé, S. Cárdenas, M. Gallego and M. Valcárcel, Anal. Chim. Acta, 436
(2001) 153–162.
[48] C.D.S. Tomlin, The Pesticide Manual. A World Compendium, 13th edn., British
Crop Protection Council, Alton, 2009, 876-913.
[49] J. Fenoll, P. Hellin, C.M.tinez, M. Miguel and P. Flores, Food Chem., 105 (2007)
711-719.
[50] E. Ueno, H. Oshima, I. Saito and H. Matsumoto, J. AOAC Int., 86 (2003) 1241–
1251.
[51] L.V. Podhorniak, J.F. Negron and F.D. Griffith, J. AOAC Int., 84 (2001) 873–890.
[52] G. Gambacorta, M. Faccia, C. Lamacchia, A. Di Luccia and E. La Notte, Food
Control, 16 (2005) 629–632.
[53] E. Ueno, H. Oshima, I. Saito and H. Matsumoto, J. Food Hyg. Soc. Jpn., 42 (2001)
385–393.
[54] A. Gelsomino, B. Petrovicova, S. Tiburtini, E. Magnani and M. Felici, J.
Chromatogr. A, 782 (1997) 105–122.
[55] E. Ueno, H. Oshima, I. Saito, H. Matsumoto and H. Nakazawa, J. Food. Hyg. Soc.
Jpn., 45 (2004) 212–217.
[56] M. Gamón, C. Lleó, A. Ten and F. Mocholí, J. AOAC Int., 84 (2001) 1209–1216.
[57] S.J. Lehotay, A. de Kok, M. Hiemstra and P. van Bodegraven, J. AOAC Int., 88
(2005) 595–614.
[58] I. Elmadfa (ed.), European Nutrition and Health Report, Forum of Nutrition. Basel,
Karger, 62 (2009) 60–67.
[59] ***, Population income and consumption in the first quarter (in Romanian),
Statistics National Institute, Bucharest, 2012.
[60] C.K. Bempah, A. Buah-Kwofie, D. Denutsui, J. Asomaning and A.O. Tutu,
Research Journal of Environmental and Earth Sciences, 3 (2011) 761-771.
[61] USEPA, Exposure Factors Handbook, EPA/600/R-09/052F, 2011.
[62] R. Salghi, G. Luis, C. Rubio, A. Hormatallah, L. Bazzi, A.J. Gutierrez and A.
Hardisson, Bull. Environ. Contam. Toxicol., 88 (2012) 358–361.

94

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