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Food Control
journal homepage: www.elsevier.com/locate/foodcont
Screening of fresh fruit and vegetables for pesticide residues on Croatian market
Zorka Knezevic *, Maja Serdar
Environmental Health Service, Croatian National Institute of Public Health, Rockefellerova 7, 10000 Zagreb, Croatia
a r t i c l e
i n f o
Article history:
Received 6 February 2008
Received in revised form 4 July 2008
Accepted 11 July 2008
Keywords:
Pesticides
Fruit
Vegetables
a b s t r a c t
The aim of this study was to investigate pesticide residues in market foods in Croatia. A total of 240 samples of fresh fruit and vegetables from import and domestic production were analyzed. Pesticide resides
were determined by gas chromatography with mass selective detector (GCMSD). Sample extract was
cleaned up using gel permeation chromatography (GPC). In 66.7% of the samples no residues were found,
25.8% of samples contained pesticide residues at or below MRL, and 7.5% of samples contained pesticide
residues above MRL. Most frequently found pesticides were imazalil (found in 35 samples) and chlorpyrifos (found in 24 samples). The ndings of this study pointed to the following recommendations: the need
for a monitoring program for pesticide residues in food crops, especially imported food crops.
2008 Elsevier Ltd. All rights reserved.
1. Introduction
Fresh fruit and vegetables are an important part of a healthy
diet as they are a signicant source of vitamins and minerals. However, fresh fruits and vegetables can also be a source of noxious
toxic substances pesticides. Fruit and vegetables are traded
worldwide and the list of pesticides that might have been applied
in their agricultural production is usually not known (Stan, 2000).
Pesticides constitute a very important group of chemical compounds that have to be controlled due to their high toxicity and
their widespread use in agricultural practice for eld and post-harvest protection. The presence of pesticide residues in food is a direct result of pesticide use on crops. Over 1000 compounds may
be applied to agricultural crops in order to control undesirable
moulds, insects and weeds (Ortelli, Edder, & Corvi, 2006). The levels of pesticide residues in foodstuffs are generally legislated so as
to minimize the exposure of the consumer to harmful or unnecessary intakes of pesticides, to ensure the proper use of pesticides in
terms of granted authorization and registration (application rates
and pre-harvested intervals) and to permit the free circulation of
pesticide-treated products, as long as they comply with the xed
maximum residue level (MRLs). MRL for pesticide residues represents the maximum concentration of that residue (expressed
in mg/kg) that is legally permitted in specic food items. The
establishment of MRL is based on good agricultural practice 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 good agricultural practices (Nasreddine & Parent-Massin, 2002).
* Corresponding author. Tel.: +385 1 4863 323; fax: +385 1 4683 907.
E-mail address: zorka.knezevic@hzjz.hr (Z. Knezevic).
0956-7135/$ - see front matter 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.foodcont.2008.07.014
Table 1
Selected pesticides, use and purity of reference materials
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.
14.
15.
16.
17.
18.
19.
20.
21.
22.
23.
24.
25.
26.
27.
28.
29.
30.
31.
32.
33.
34.
35.
36.
37.
38.
39.
40.
41.
42.
43.
44.
45.
46.
47.
48.
49.
50.
51.
52.
53.
54.
55.
56.
57.
58.
59.
60.
61.
62.
63.
64.
65.
66.
67.
68.
69.
70.
71.
72.
73.
74.
Pesticide
Purity (%)
Obtained
Acephate
Allethrine
Azinphos-ethyl
Azinphos-methyl
Bifenthrin
Bioallethrin
Bromophos-ethyl
Bromophos-methyl
Brompropylate
Captan
Carbaryl
Chlordane cis
Chlordane trans
Chlormephos
Chlorfeninphos cis
Chlorfeninphos trans
Chlorothalonil
Chlorpropham
Chlorpyrifos
Chlorpyrifos-methyl
Coumaphos
Cyuthtin I
Cyuthtin II
Cyuthtin III
Cyuthtin IV
Cyhalothrin Lambda
Cypermethrin I
Cypermethrin II
Cypermethrin III
Cypermethrin IV
Cyphenothrin I
Cyphenothrin II
DDD-p,p
DDE-p,p
DDT-o,p
DDT-p,p
Deltamethrin
Demeton S
Demeton-S-Methyl
Demeton-S-Methyl-sulfon
Dialifos
Diazinon
Dichlouanid
Dichlorvos
Dicofol
Dimethoate
Endosulfane-alpha*
Endosulfane-beta*
Endosulfanesulfat
Ethion
Fenamiphos
Fenchlorphos
Fenitrothion
Fenprpathrin
Fenthione
Fonofos
HCB
HCH alpha
HCH beta
HCH delta
HCH gama (Lindan)
Heptachlorepoxid-egzo
Heptachlorepoxid-endo
Heptenophos
Imazalil
Iprodione
Isofenphos
Malaoxon
Malathion
Methamidophos
Methidathion
Metoksiklor
Mevinphos cis
Monocrotophos
96.0
95.3
99.9
98.5
99.5
99.5
99.3
99.8
99.2
99.4
99.8
98.4
98.4
99.2
97.2
97.2
99.2
99.9
99.5
99.7
99.7
98.3
98.3
98.3
98.3
99.7
96.7
96.7
96.7
96.7
97.2
97.2
99.2
99.5
99.1
98.2
99.8
99.0
95.4
95.4
99.6
98.9
98.8
99.4
97.6
99.4
70.0
30.0
97.7
97.9
99.5
99.0
95.4
98.4
96.8
98.6
99.6
99.7
98.1
99.7
99.8
99.7
99.9
97.1
99.8
99.9
98.9
96.3
97.3
98.4
96.0
98.8
98.6
99.9
Riedel-de
Riedel-de
Riedel-de
Riedel-de
Riedel-de
Riedel-de
Riedel-de
Riedel-de
Riedel-de
Riedel-de
Riedel-de
Riedel-de
Riedel-de
Riedel-de
Riedel-de
Riedel-de
Riedel-de
Riedel-de
Supelco
Riedel-de
Riedel-de
Riedel-de
Riedel-de
Riedel-de
Riedel-de
Riedel-de
Riedel-de
Riedel-de
Riedel-de
Riedel-de
Riedel-de
Riedel-de
Riedel-de
Riedel-de
Supelco
Supelco
Riedel-de
Supelco
Supelco
Riedel-de
Riedel-de
Supelco
Riedel-de
Riedel-de
Riedel-de
Riedel-de
Riedel-de
Riedel-de
Riedel-de
Riedel-de
Supelco
Supelco
Riedel-de
Riedel-de
Riedel-de
Supelco
Riedel-de
Riedel-de
Riedel-de
Riedel-de
Riedel-de
Riedel-de
Riedel-de
Riedel-de
Riedel-de
Riedel-de
Riedel-de
Riedel-de
Riedel-de
Riedel-de
Riedel-de
Riedel-de
Riedel-de
Riedel-de
Use
Han
Han
Han
Han
Han
Han
Han
Han
Han
Han
Han
Han
Han
Han
Han
Han
Han
Han
Han
Han
Han
Han
Han
Han
Han
Han
Han
Han
Han
Han
Han
Han
Han
Han
Han
Han
Han
Han
Han
Han
Han
Han
Han
Han
Han
Han
Han
Han
Han
Han
Han
Han
Han
Han
Han
Han
Han
Han
Han
Han
Han
Han
Han
Han
Han
I
I
A,I
A,I
A,I
I
I
I
I,A
F
I
I
I
I
A,I
A,I
F
H,PR
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
A,I
I
F
A,I
A
A,I
I
I
I
A,I
I,N
I
I
I
I
I
F
I
I
I
I
I
I
I
F
F
I
A,I
A,I
A,I
I
I
A,I
A
75.
76.
77.
78.
79.
80.
81.
82.
83.
84.
85.
86.
87.
88.
89.
90.
91.
92.
93.
94.
95.
96.
97.
98.
99.
100.
Pesticide
Purity (%)
Obtained
Omethoate
Paraoxon
Parathion
Parathion-methyl
Permethrin-cis
Permetrin-trans
Phenothrin cis
Phenothrin trans
Phorate
Phosalone
Pirimicarb
Pirimiphos-ethyl
Pitimiphos-methyl
Procymidone
Pyrazophos
Resmethrin cis
Resmethrin trans
Tetrachlovinphos
Tetramethrin cis
Tetramethrin trans
Tolclofos-methyl
Thiabendazole
Tolyluanid
Transuthrin
Trichlorfon
Vinclozolin
98.4
97.2
98.0
99.8
98.0
98.0
94.9
94.9
95.7
99.3
99.0
99.8
99.9
98.7
99.8
94.3
94.3
97.9
98.4
98.4
99.2
99.9
99.6
99.7
97.8
99.6
Riedel-de
Riedel-de
Supelco
Riedel-de
Riedel-de
Riedel-de
Riedel-de
Riedel-de
Riedel-de
Riedel-de
Riedel-de
Riedel-de
Riedel-de
Riedel-de
Riedel-de
Riedel-de
Riedel-de
Riedel-de
Riedel-de
Riedel-de
Riedel-de
Riedel-de
Riedel-de
Riedel-de
Riedel-de
Riedel-de
Use
Han
Han
Han
Han
Han
Han
Han
Han
Han
Han
Han
Han
Han
Han
Han
Han
Han
Han
Han
Han
Han
Han
Han
Han
Han
A,I
A,I
I
I
I
I
I
I
I
A,I
I
I
I
I
F
I
I
I
I
I
F
F
F
I
I
F
stored at 4 C until the analysis. All samples were collected according to the method of taking representative sample (Narodne novine, 58/98). Samples origin is shown in Fig. 1.
2.3. Sample preparation
2.3.1. Sample preparation of material with a water content exceeding
70 g/100 g and a fat content below 2.5 g/100 g
Samples prepared according to this procedure are: apple (water
content 85%), peach (water content 90%), pear (water content 85%),
lettuce (water content 95%), tomato (water content 95%), cabbage
(water content 90%), potato (water content 80%), onion (water content 85%) and leek (water content 85%).
Samples were homogenized in a food cutter and subsamples of
50 g (ms) of the material having a water content of x g/100 g
weighted into a glass jar. Sufcient amount of water was then
added to adjust the total water presence to 100 g. The amount of
water (mw) to be added is calculated as follows: mw = 100
100
86
90
Number of samples
420
80
70
Fruits
61
Vegetables
60
50
40
30
25
22
20
26
20
10
0
Domestic
Import
Unknown
421
Table 2
Pesticides concentration ranges found in the samples
Pesticide type
Fungicide
Insecticide
Other
Chemical name
Imazalil
Thiabendazole
Tolyluanid
Iprodione
Chlorothalonil
Viclozolin
Procymidone
Chlorpyrifos
Chlorpyrifos-methyl
Azinphos-methyl
Methidathion
Malathion
Fenthione
Endosulfane beta
Diazinon
Tetramethrin
Chlorpropham
Fruits
Vegetables
MinMax (mg/kg)
MinMax (mg/kg)
35
17
8
24
4
1
3
1
1
4
3
0.0827.9
0.1210.62
0.0610.74
0.030.67
0.030.14
0.32
0.130.33
0.07
0.05
0.060.08
0.050.82
1
2
1
3
1
1
0.07
10.5711.57
0.51
2.793.27
3.58
0.37
0.010.04
0.73.6
Number of samples
422
10
9
8
7
6
5
4
3
2
1
0
28% ( 5 samples)
Oranges
Apple
Lettuce
Peach
22% (4 samples)
Potato
Commodity
50% (9 samples)
Domestic
Import
Unknown
140
118
Number of samples
120
100
Fruits
Vegetables
80
60
50
42
40
20
12
14
4
0
No reidues found Residues at or below
MRL found
4. Conclusions
Fig. 3. Occurrence of pesticide residues in fruit and vegetables samples.
13% (8 samples)
31% (19
samples)
The present study shows a high incidence rate of pesticide residues (mostly fungicides and insecticides) in analyzed samples,
especially fruits. The most critical commodity is oranges. The contamination level of pesticide residues could be considered a possible public health problem. The results also emphasize the need for
regular monitoring of a greater number of samples for pesticide
residues, especially imported samples.
References
56%(35 samples)
Domestic
Import
Unknown