Journal of Environmental Science and Health, Part B (2014) 49, 671678

Copyright Taylor & Francis Group, LLC

ISSN: 0360-1234 (Print); 1532-4109 (Online)
DOI: 10.1080/03601234.2014.922775

Determination of 28 pesticides applied on two tomato

cultivars with a different surface/weight ratio of the berries,
using a multiresidue GC-MS/MS method

FABRIZIO DEDOLA, MADDALENA CABIZZA and MAURIZIO SATTA

Agricultural Research Agency of Sardinia (AGRIS), Cagliari, Italy

The behavior of 28 pesticides on two tomato cultivars with a different surface/weight (S/W) ratio of the berries (S/W, Birikino vs.
Tombola) was studied, in order to provide appropriate indications about their persistence on crops reaching the pre-harvest interval
(PHI). Quantitative analysis was performed using a GC MS/MS method. Birikino cv. (BIR) was a cherry type tomato with a
double S/W ratio compared with Tombola cv. (TOM). The results showed a different pesticide behavior. Azoxystrobin, Boscalid,
Bupirimate, Difenoconazole, Etofenprox, Iprodione, Mepanipyrim, Myclobutanil, Tebuconazole, Zoxamide, Metalaxyl M,
Pyrimethanil, Tetraconazole, Benalaxyl, Cyprodinil, Fenamidone, Famoxadone and Fludioxonil immediately after treatments
showed residues on BIR higher than TOM, and this behavior is consistent with its greater exposed surface. BIR showed higher decay
rates of these pesticides during the whole trial, nevertheless residue averages remained higher than TOM reaching the time of
harvest. Residues at the PHI were all below their Maximum Residue Levels (MRLs), but data indicated that they could exceed their
legal limits especially if the above-mentioned active ingredients were employed more than once per crop cycle on cherry type
tomatoes. As regards to Chlorpyrifos, Chlorpyrifos methyl, Triadimenol, Pyridaben and Tebufenpyrad, no different residual
behavior related to S/W ratio of the cultivars was observed. Even in this case, residues at the PHI were all below MRLs. As for
Cyuthrin, Deltamethrin, Lambda cyhalothrin, Etoxazole and Cyproconazole, residues were lower than the limit of quantitation
(LOQ) of the analytical method just after the treatment, according to their low doses of employment.
Keywords: QuEChERS, tomato cultivar, pesticide residues, surface/weight ratio.

Introduction by a high variability of the fruit size among different culti-

Pesticide residues in food represent one of the most impor-
tant causes of concern in the eld of food safety. Although
most farmers use pesticides properly, following the instruc-
tions on the ministerial label and minimizing the number
of treatments, there is always the possibility that a residue
might be found on food. Some pesticides can have toxic
effects even in very low doses. Some of them act as endo-
crine disruptors, showing adverse effects at doses of few
nanograms per kilo.[1] In any case, the toxic effect of a pes-
ticide is dose dependent, therefore the only way to improve
food safety is reducing the amount of residues as much as
possible. It is well-known that a pesticide can be used only
on specic crops indentied by law. When allowed, it can
be used on any variety and cultivar belonging to the same
species. In the case of crops such as tomato, characterized
Address correspondence to Fabrizio Dedola, Agricultural
Research Agency of Sardinia (AGRIS), viale Trieste, 111,
09123, Cagliari, Italy; E-mail: fdedola@agrisricerca.it
Received February 27, 2014.
vars, the exposed surface can strongly inuence the initial
pesticide deposition, and so the risk to obtain a residue. In
a previous work,[2] residual behavior of some fungicides
on two different cultivars of tomato was studied and, for
almost all the analyzed pesticides, a higher initial residue
on little cherry tomatoes compared to big size fruits cv.
was observed. The aim of this paper was to extend the
investigation on 28 pesticides commonly used in tomato
pest management strategies, applied on two cultivars with
different surface/weight (S/W) ratio of fruits (Birikino
and Tombola), in order to provide appropriate informa-
tion to avoid high residues on crops. The evaluated pesti-
cides were Bupirimate, Ciproconazole, Difenoconazole,
Myclobutanil, Tebuconazole, Tetraconazole and Triadi-
menol, effective against powdery mildew (Oidiopsis taur-
ica, Oidium neolycopersici); Azoxystrobin, Benalaxyl,
Metalaxyl M, Famoxadone, Fenamidone and Zoxamide,
effective against late blight (Phytophthora infestans);
Boscalid, Cyprodinil, Fludioxonil, Iprodione, Mepani-
pyrim and Pyrimethanil, effective against gray mold
(Botrytis cinerea); and Chlorpyrifos, Chlorpyrifos methyl,
Cyuthrin, Deltamethrin, Etofenprox, Etoxazole, Lambda
672
cyhalothrin, Pyridaben and Tebufenpyrad, effective
against various insects and mites. All the studied pesticides
were included in Annex I of Directive 91/414/EEC and
their use was registered in Italy on tomato. A GC MS/MS
method for the analysis and quantitation of the pesticides
was set up to determine the residue levels in greenhouse
tomatoes.
Material and methods
Field trials
Trials were carried out in a farm owned by Agricultural
Research Agency of Sardinia (AGRIS), located in Uta
(Italy), into an iron glass greenhouse of 600 m2, equipped
with a hot blast heating system. Tomatoes (Solanum lyco-
persicum cv. Birikino and Tombola) were planted in twin
rows at intervals of 40 20 cm. Each twin row was sepa-
rated by a 2.0 m alley, and plants were irrigated using a
drip system. Birikino cv. had an average weight of fruits
of about 19 g, whereas Tombola cv. about 307 g. No
growth of the fruits was observed from the day of treat-
ments to the end of the experiments for both cultivars.
The trial was set up in a randomized block design with
four replicates, where each block contained 128 plants.
Three treatments were carried out as reported in Table 1,
with a Robin 5.0 EY20 portable motor sprayer (Subaru,
Japan) on January 2013, using about 8 hl ha1 of water.
Commercial formulations were used at the doses recom-
mended by the manufacturers. Treatment periods were
chosen considering the PHI of every single studied pesti-
cide, and the ripening of the fruits. Fully grown tomatoes
were harvested at time 0 (about 1 h after treatment,
immediately analyzed after sampling), and at time 1, 3, 7,
14 and 21 days. Samples were composed of 6 berries
(TOM) or 20 berries (BIR).
Chemicals
Analytical standards of Azoxystrobin, Benalaxyl,
Boscalid, Bupirimate, Chlorpyrifos, Chlorpyrifos methyl,
Ciproconazole, Cyutrin, Cyprodinil, Deltamethrin,
Difenoconazole, Etofenprox, Etoxazole, Famoxadone,
Fenamidone, Fludioxonil, Iprodione, Lambda cyhalo-
thrin, Mepanipyrim, Metalaxyl, Myclobutanil, Pyrida-
ben, Pyrimethanil, Tebuconazole, Tebufenpyrad,
Tetraconazole, Triadimenol and Zoxamide were Fluka
and Riedel-de Haen (Milan, Italy), purity over 99.8%.
Internal standard for GC-MS/MS analysis was tri-
phenyl-phosphate (Sigma-Aldrich, Milan, Italy), purity
over 99.0%. Acetone and acetonitrile were HPLC sol-
vents (Baker, Deventer, Holland). Citrate extraction mix
(4 g of MgSO4, 1 g of NaCl, 1 g of Na3Citrat 2H2O and
0.5 g of Na2HCitrate 1.5H2O) and PSA clean up mix
(0.9 g of MgSO4 and 0.15 g of primary and secondary
Dedola et al.
amine) were Chromabond (Macherey-Nagel, Duren,
Germany). Stock standard solutions of active ingredients
were prepared in acetone. Working standard solutions
for GC-MS/MS analysis were prepared by evaporating
to dryness 1 mL of organic extract from untreated
tomato and taking up the residue in 1 mL of standard
solutions (obtained by diluting stock solutions with ace-
tone) containing internal standard.
Extraction procedure
A QuEChERS method was used for the extraction step.[3,4]
After harvesting, tomatoes samples were chopped and
homogenized with a semi-industrial blender (Malavasi,
Bologna, Italy). A 10 g aliquot of homogenous sample
was weighed in a 50 mL screw capped centrifuge tube and
10 mL of acetonitrile were added. After shaking for
1 min, the citrate extraction mix was added. The tube was
shaken for 1 min and then centrifuged for 5 min. An ali-
quot of 6 mL of the acetonitrile phase was transferred into
a polypropylene single-use centrifuge tube containing the
PSA clean-up mix. The tube was shaken and centrifuged.
The cleaned-up extract was transferred in a screw cup stor-
age vial and acidied with 0.05 mL of a 5% formic acid
solution in acetonitrile. Finally, 1 mL of the acetonitrile
solution was evaporated under a gentle nitrogen stream,
the residue was taken up with 1 mL of acetone containing
internal standard and injected in the GC-MS/MS system
for the analysis.
Apparatus and chromatography
The analysis were carried out with a GC system 7890A gas
chromatograph (Agilent, Santa Clara, CA, USA) coupled
with an Agilent 7693 autosampler, and a MS/MS 7000
Triple Quad detector (Agilent). The column was a fused
silica capillary HP 5 MS (30 m 0.25 mm i.d., lm
0.25 mm) Agilent. The multi-mode injector (MMI) tem-
perature was set at 50 C (hold 0.15 min) raised to 280 C
(720 C min1). Four mL of sample were injected in PTV
solvent vent mode. The oven temperature was pro-
grammed as follows: 50 C (hold 0.2 min) raised to 70 C
(100 C min1), hold 1.5 min, raised to 150 C (25 C
min1), to 200 C (3 C min1), to 280 C (8 C min1), hold
10 min. Helium was the carrier gas at 3.4 mL min1. The
mass spectrometer was operated in electron impact (70 eV
of ion energy), with 4 min solvent delay, the interface tem-
perature was kept at 280 C, the ion source was kept at
280 C, the quadrupoles were at 150 C. Collision gas was
N2 (1.5 mL min1), and He as quench gas (2.25 mL
min1). Multiple reaction monitoring (MRM) mode was
used. Retention times and specic transitions are reported
in Table 2. Calibration graphs were calculated plotting
area ratio peak/internal standard vs. concentration (mg
kg1). A good linearity was achieved between 0.005 and
Determination of pesticides applied on tomato cultivars 673

Table 1. Commercial formulations, PHIs, MRLs, and active ingredients (a.i.) concentration in the sprayed solution according to
doses recommended by manufacturers.
Commercial Active PHI MRL Commercial a.i. Concentration
formulations ingredients (a.i.) (days) (mg kg1) formulation a.i (%) in the sprayed solution (g L1)
Treatment 1
Quadris Azoxystrobin 3 3 22.90% 0.23
Signum Boscalid 3 3 50.00% 0.20
Nimrod Bupirimate 3 2 23.80% 0.71
Trebon Star Etofenprox 3 3 30.00% 0.15
Rovral Iprodione 3 5 25.00% 0.75
Frupica Mepanipyrim 3 1 50.00% 0.40
Hunter Cyutrin 3 0.05 5.00% 0.05
Decis jet Deltamethrin 3 0.3 2.80% 0.01
Karate Xpress Lambda cyhalothrin 3 0.1 1.47% 0.02
Treatment 2
Score 25 Difenoconazole 7 2 23.90% 0.12
Thiocur forte Myclobutanil 3 0.3 4.50% 0.07
Dedalus 25 WDG Tebuconazole 3 1 25.00% 0.13
Emerald Tetraconazole 4 0.1 4.00% 0.07
Zoran Zoxamide 3 0.5 2.85% 0.09
Galben 8 65M Benalaxyl 7 0.5 4.00% 0.10
Ridomil gold MZ Metalaxyl m 3 0.2 3.90% 0.10
Scala Pyrimethanil 3 1 37.40% 0.75
Switch Fludioxonil 7 1 25.00% 0.20
Oracle Fenamidone 7 0.5 4.00% 0.12
Treatment 3
Dursban Chlorpyrifos 21 0.5 44.53% 0.49
Runner M22 Chlorpyrifos methyl 15 0.5 22.10% 0.44
Switch Cyprodinil 7 1 37.50% 0.30
Nexter Pyridaben 7 0.3 19.40% 0.19
Oscar Tebufenpyrad 14 0.5 25.00% 0.16
Equation pro Famoxadone 10 1 22.50% 0.09
Borneo Etoxazole 3 0.1 10.68% 0.05
Baydan Combi Triadimenol 14 1 2.50% 0.05
Atemi 10 Pepite Ciproconazole 10 0.05 10.00% 0.01

0.15 mg kg1 (linear range) with correlation coefcient
between 0.9987 and 0.9995, and coefcient of variation
(CV%) <3%.
Method validation
Samples of untreated tomato were fortied using pesticides
standard solutions at three concentrations: 0.01, 0.05, and
0.10 mg kg1. Before the extraction, the fortied samples
were allowed to settle for 30 min, then they were processed
according to the above extraction procedures. Twelve
replicates for each concentration were analyzed. The
QuEChERS method showed good recoveries, according
to Document no. SANCO/12495/2011 principles,[5] with
values ranging from 74 to 119%, and CV% from 1 to 12%
in the most unfavorable case. The values obtained for
CV% (n D 12) demonstrate good repeatability for all pesti-
cides of the method. The limit of quantitation (LOQ) was
calculated as 10-fold the signal-to-noise ratio and set at
0.01 mg kg1 for all the pesticides. Mean recoveries and
CV% for each pesticide are reported in Table 3.
Statistical analysis
Analysis of variance ANOVA was performed by Genstat
10th edition, when appropriate. Analysis was followed by
the Tukey post hoc test (P < 0.05).
Results and discussion
All fungicides showed just after treatment (day 0) resi-
due levels on fruits below their MRLs, established in
EU for tomatoes (Table 1), with the exception of Pyri-
methanil, found above its legal limit on one sample
(residue level D 1.31 mg kg1; MRL D 1.00 mg kg1).
The BIR cv. S/W ratio, calculated as 4pr2, was double
considering BIR vs. TOM (Table 4). The 28 studied
pesticides were divided into four groups according to
674 Dedola et al.

Table 2. Retention times (RT) and specic transitions of analyzed pesticides.

Name RT Transition Type Transition qualier 1 CE* Transition qualier 2 CE*
Azoxystrobin 36.67 344.0 -> 329.0 Target 344.0 -> 183.0 25 344.0 -> 172.0 35
Benalaxyl 26.68 148.0 -> 133.0 Target 148.0 -> 105.0 5
Boscalid 32.73 140.0 -> 112.0 Target 140.0 -> 76.0 25 342.0 -> 140.0 10
Bupirimate 24.74 273.0 -> 193.0 Target 273.0 -> 108.0 15
Chlorpyrifos 19.15 196.9 -> 168.9 Target 196.9 -> 107.0 40
Chlorpyrifos Methyl 16.50 286.0 -> 93.0 Target 286.0 -> 270.9 20
Cyuthrin 32.22 163.0 -> 91.0 Target 163.0 -> 127.0 5 206.0 -> 151.0 25
Cyhalothrin (lambda) 30.34 197.0 -> 141.0 Target 197.0 -> 161.0 10
Cyproconazole 24.83 222.0 -> 125.0 Target 222.0 -> 82.0 10
Cyprodinil 20.48 225.0 -> 224.0 Target 224.0 -> 208.0 20
Deltamethrin 35.92 253.0 -> 93.0 Target 253.0 -> 174.0 5 253.0 -> 172.0 10
Difenoconazole 35.15 323.0 -> 265.0 Target 265.0 -> 202.0 20
Etofenprox 33.17 163.0 -> 135.0 Target 164.0 -> 136.0 5
Etoxazole 29.03 204.0 -> 176.0 Target 300.0 -> 270.0 20 359.0 -> 340.0 15
Famoxadone 36.65 330.0 -> 196.0 Target 330.0 -> 224.0 8
Fenamidone 29.03 238.0 -> 237.0 Target 238.0 -> 103.0 25 268.0 -> 180.0 25
Fludioxonil 24.01 248.0 -> 127.0 Target 248.0 -> 154.0 25
Iprodione 28.35 314.0 -> 56.0 Target 314.0 -> 245.0 10
Mepanipyrim 22.99 222.0 -> 220.0 Target 222.0 -> 193.0 25
Metalaxyl 17.26 249.0 -> 146.0 Target 206.0 -> 162.0 5 206.0 -> 132.0 5
Myclobutanil 24.37 179.0 -> 125.0 Target 179.0 -> 152.0 5
Pyridaben 31.49 147.0 -> 117.0 Target 147.0 -> 132.0 10 309.0 -> 147.0 10
Pyrimethanil 14.04 199.0 -> 198.0 Target 199.0 -> 183.0 30
Tebuconazole 27.39 250.0 -> 125.0 Target 252.0 -> 127.0 25
Tebufenpyrad 29.03 333.0 -> 171.0 Target 333.0 -> 276.0 5
Tetraconazole 19.79 336.0 -> 218.0 Target 336.0 -> 204.0 30 336.0 -> 164.0 35
Triadimefon 19.33 208.0 -> 181.0 Target 208.0 -> 127.0 15
Triadimenol 21.60 128.0 -> 65.0 Target 168.0 -> 70.0 10
Zoxamide 27.97 258.0 -> 187.0 Target 258.0 -> 159.0 30
Tff 27.67 326.0 -> 233.0 Target 326.0 -> 77.0 30 326.0 -> 169.0 30
*Collision Energy (Volt).

their different behavior. Table 5 reported comparisons
between residues found on BIR and TOM, referred to
different sampling days (day 0, 1, PHI and day 21). For
every single active ingredient (a.i.), statistical analysis
were performed taking into consideration degradation
rate on BIR vs. TOM (all days of sampling), and on
each day of sampling (day 0 vs. 1st day; day 0 vs. PHI;
day 0 vs. 21st day; Tukey post hoc test).
First group: azoxystrobin, boscalid, bupirimate,
difenoconazole, etofenprox, iprodione, mepanipyrim,
metalaxyl m, myclobutanil, pyrimethanil, tebuconazole
and zoxamide
As regards to the pesticides listed above, at the day of treat-
ments (day 0) BIR cv. showed residues between 3 and
7 times over than TOM cv. After 24 h, they were reduced
on BIR cv. by a percentage between 33 and 53%, and differ-
ences were signicant (P < 0.05) for all the pesticides (day
0 vs. 1st day, Table 5). On the contrary, residues found on
TOM cv. after 24 h showed a low and not signicant degra-
dation rate, reaching a maximum reduction percentage of
21% on Tebuconazole. Residues found at the PHI (3 days
for all the pesticides, except for Difenoconazole, 7 days)
were still higher on BIR cv, but differences were found sta-
tistically signicant only for Boscalid, Difenoconazole,
Myclobutanil and Tetraconazole. In any case, degradation
rates of pesticides expressed as percentage from day 0 to
PHI ranged on BIR from about 79% (Iprodione) to 46%
(Miclobutanil) of reduction. At the same time, on TOM cv.
they ranged from 48% (Boscalid) to 26% (Myclobutanil),
so showing a slower decay time on cv. with big berries. At
the end of the trial (21st day), no signicant differences
between BIR and TOM residues were found, even if residue
averages on BIR have always been higher on all the ana-
lyzed samples and during the whole experiment, suggesting
that an experimental design with more replications could
have carried out a signicative difference even in this case.
The higher residue degradation rate on BIR, even if not
always signicant, was observed during the whole experi-
ment for all the a.i. mentioned above. This fact might be
attributed to its greater surface area exposed which,
although responsible of the much greater initial apposition,
caused at the same time a more rapid disappearance of
these pesticides on BIR, probably due to an increased
photodegradation.[6,7]
Determination of pesticides applied on tomato cultivars 675

Table 3. Mean recoveries and coefcient of variation (CV%) for each analyzed pesticide.
Pesticide Spike (mg kg1) Mean recoveries % CV %
Azoxystrobin 0.01 110 7
0.05 108 4
0.10 109 6
Benalaxyl 0.01 97 7
0.05 107 5
0.10 101 7
Boscalid 0.01 105 7
0.05 111 5
0.10 106 7
Bupirimate 0.01 99 7
0.05 108 5
0.10 103 6
Chlorpyrifos 0.01 103 8
0.05 106 7
0.10 98 9
Chlorpyrifos Methyl 0.01 95 11
0.05 99 9
0.10 90 12
Cyuthrin 0.01 111 7
0.05 109 5
0.10 108 7
Cyhalothrin (lambda) 0.01 105 7
0.05 103 4
0.10 96 6
Cyproconazole 0.01 104 7
0.05 112 4
0.10 105 5
Cyprodinil 0.01 94 9
0.05 104 7
0.10 99 8
Deltamethrin 0.01 110 11
0.05 82 5
0.10 74 10
Difenoconazole 0.01 116 4
0.05 112 5
0.10 112 8
Etofenprox 0.01 96 5
0.05 104 6
0.10 101 8
Etoxazole 0.01 100 4
0.05 107 6
0.10 101 8
Famoxadone 0.01 119 8
0.05 109 6
0.10 111 10
Fenamidone 0.01 100 9
0.05 109 4
0.10 103 5
Fludioxonil 0.01 100 6
0.05 112 6
0.10 105 8
Iprodione 0.01 112 7
0.05 115 5
0.10 112 6
Mepanipyrim 0.01 95 8

(continued on next page)

676 Dedola et al.

Table 3. Mean recoveries and coefcient of variation (CV%) for each analyzed pesticide. (Continued)
Pesticide Spike (mg kg1) Mean recoveries % CV %
0.05 111 6
0.10 106 8
Metalaxyl 0.01 104 3
0.05 103 1
0.10 98 1
Myclobutanil 0.01 96 8
0.05 106 5
0.10 100 6
Pyridaben 0.01 106 6
0.05 110 5
0.10 105 7
Pyrimethanil 0.01 95 10
0.05 101 5
0.10 96 6
Tebuconazole 0.01 108 6
0.05 114 4
0.10 108 6
Tebufenpyrad 0.01 99 3
0.05 106 6
0.10 101 8
Tetraconazole 0.01 103 6
0.05 106 6
0.10 100 8
Triadimefon 0.01 99 9
0.05 106 5
0.10 100 6
Triadimenol 0.01 107 8
0.05 115 3
0.10 108 3
Zoxamide 0.01 90 11
0.05 99 7
0.10 92 10

Second group: benalaxyl, cyprodinil, famoxadone, signicant reduction only at the 21st day (Table 5). On the
fenamidone, fludioxonil and tetraconazole other hand, residues on TOM cv. remained stable reaching
their PHI with a noticeable degradation (P < 0.05) only
These pesticides on BIR cv., immediately after treatments
for Famoxadone and Fludioxonil (Table 5). Residues at
(day 0), showed residues between 1.2 (Famoxadone) and
PHI were higher on BIR cv., although statistically signi-
3.5 times (Tetraconazole) above than that found on TOM
cant for only Tetraconazole. At the end of the test (day
cv. Even for these groups of pesticides, degradation rates
21st), no signicant differences between BIR and TOM
on little fruits were higher but not so fast as that observed
residues were observed. Even for these pesticides, residue
in the rst group. In fact, after 24 h, BIR showed no signif-
averages on little berries cv. found on the whole experi-
icant differences among pesticide degradation rates (day
ment (taking into account all days of sampling) were
0 vs. 1st day, Table 5). Residues decreased signicantly
higher (P < 0.05).
only reaching the PHI, ranging from 43 to 61% of reduc-
tion on BIR, except for Famoxadone, which showed a

Table 4. Mean weight, surface and S/W ratio of Birikino (BIR) Third group: chlorpyrifos, chlorpyrifos methyl, triadimenol,
and Tombola (TOM) fruits. pyridaben and tebufenpyrad
Mean Radius (r) Surface of S/W ratio As regards to the pesticides listed above, their rates of loss
Cultivar weight (g) of fruits (cm) fruits (cm2)* (S/W) seemed to be not inuenced by the size of the berries. In
fact, no signicant differences between residues on the two
Birikino 19 1.6 32 1.68 cv. were found. Besides, they remained fairly stable until
Tombola 307 4.5 250 0.81
the end of the experiment (day 21st), even if much lower
*Surface is calculated as 4pr2. than their legal limits.
`Table 5. Pesticide residues (mg kg 1 SD). Time 0 (after eld treatment), First day, PHI, and at the end of the experiment (21st day) (n D 4).
Birikino Tombola

PHI
Active ingredients (days) Day 0 Day 1 PHI Day 21 Day 0 Day 1 PHI Day 21
Azoxystrobin*** 3 0.118 0.033a 0.057 0.012b 0.033 0.009bc 0.041 0.019bc 0.018 0.004c 0.018 0.008c 0.013 0.001c 0.016 0.005c
Boscalid*** 3 0.213 0.050a 0.118 0.013b 0.049 0.012bc 0.082 0.023cd 0.045 0.011cd 0.044 0.018cd 0.023 0.004d 0.046 0.011cd
Bupirimate*** 3 0.555 0.146a 0.313 0.066b 0.122 0.050c 0.095 0.019c 0.093 0.032c 0.111 0.057c 0.049 0.016c 0.024 0.004c
Difenoconazole*** 7 0.108 0.029a 0.068 0.011b 0.051 0.021b 0.030 0.013c 0.027 0.007c 0.024 0.008c 0.017 0.003c 0.018 0.005c
Etofenprox*** 3 0.123 0.033a 0.067 0.017b 0.034 0.012bcd 0.048 0.011bc 0.019 0.004cd 0.024 0.005cd 0.012 0.005d 0.021 0.003cd
Iprodione*** 3 0.490 0.125a 0.280 0.043b 0.215 0.025c 0.226 0.046bc 0.067 0.019c 0.055 0.022c 0.063 0.035c 0.090 0.021c
Mepanipyrim*** 3 0.355 0.090a 0.200 0.036b 0.084 0.027cd 0.127 0.029bc 0.051 0.018cd 0.058 0.035cd 0.029 0.007d 0.043 0.013cd
Myclobutanil*** 3 0.072 0.020a 0.048 0.009b 0.039 0.006bc 0.017 0.008d 0.019 0.004cd 0.017 0.005d 0.014 0.003d <LOQ
Tebuconazole*** 3 0.142 0.037a 0.066 0.035b 0.072 0.012b 0.027 0.013bc 0.038 0.01bc 0.030 0.013bc 0.027 0.006bc 0.021 0.006c
Zoxamide*** 3 0.065 0.022a 0.042 0.003b 0.031 0.006bc 0.017 0.004cd 0.015 0.003cd 0.016 0.001cd <LOQ <LOQ
Metalaxyl M*** 3
Determination of pesticides applied on tomato cultivars

0.085 0.021a 0.054 0.011b 0.036 0.006bc 0.016 0.005cd 0.027 0.008cd 0.021 0.006cd 0.017 0.003cd 0.013 0.001d
Pyrimethanil*** 3 0.954 0.246a 0.675 0.148b 0.368 0.085c 0.107 0.035cd 0.283 0.048cd 0.223 0.101cd 0.193 0.041cd 0.057 0.036d
Tetraconazole*** 4 0.049 0.013a 0.035 0.006ab 0.028 0.004bc <LOQ 0.014 0.004cd 0.014 0.005d 0.012 0.002d <LOQ
Benalaxyl*** 7 0.298 0.084a 0.21 0.042ab 0.086 0.029bc 0.045 0.014d 0.088 0.023cd 0.060 0.030d 0.035 0.015cd 0.029 0.016d
Cyprodinil*** 7 0.328 0.092a 0.265 0.053ab 0.104 0.048bc 0.054 0.024d 0.102 0.029cd 0.085 0.053cd 0.049 0.017cd 0.039 0.016d
Fenamidone*** 7 0.128 0.042a 0.086 0.023ab 0.05 0.024bc 0.031 0.013c 0.042 0.012bc 0.028 0.012c 0.020 0.005c 0.020 0.010c
Famoxadone** 10 0.033 0.004a 0.033 0.009a 0.027 0.011abc 0.015 0.003bc 0.027 0.01ab 0.016 0.007abc 0.015 0.006c 0.014 0.004bc
Fludioxonil* 7 0.095 0.025a 0.076 0.019ab 0.049 0.021bc 0.031 0.003c 0.077 0.028ab 0.037 0.018bc 0.025 0.012c 0.025 0.006c
Chlorpyrifos n.s. 21 0.180 0.041 0.110 0.105 0.043 0.006 0.218 0.060 0.135 0.065 0.041 0.023
Chlorpyrifos M. n.s. 15 0.160 0.040 0.077 0.079 0.027 0.013 0.031 0.006 0.205 0.054 0.100 0.045 <LOQ 0.049 0.005
Triadimenol n.s. 14 0.022 0.004 0.017 0.005 0.014 0.004 0.010 0.005 0.02 0.006 0.014 0.003 <LOQ 0.012 0.002
Pyridaben n.s. 7 0.059 0.009 0.055 0.018 0.038 0.017 0.021 0.003 0.068 0.021 0.036 0.018 0.019 0.010 0.019 0.009
Tebufenpyrad n.s. 14 0.085 0.019 0.078 0.026 0.048 0.023 0.044 0.003 0.089 0.026 0.051 0.025 0.020 0.008 0.045 0.025
Values in the same row sharing the same superscript letter do not differ signicantly; P < 0.05.
BIR vs. TOM (all days sampling): *** D P < 0.001; ** D P < 0.01; * D P < 0.05; n.s. D not signicant.
677
678
Fourth group: cyfluthrin, deltamethrin, lambda
cyhalothrin, etoxazole and cyproconazole
These pesticides showed, immediately after treatments,
residues less than their LOQ which did not allow the study
of their degradation behavior. This fact was probably due
to the low active ingredients concentration in the sprayed
solution which, according to label indications of manufac-
turers, ranged between 0.05 to 0.01 g L1 (Table 1).
Conclusions
The analytical method validated in our trial was performed
in GC/MS/MS and allowed the analysis of 28 pesticides
on tomato with high specicity and precision. All pesticides
showed values at PHI below the MRLs set by EU in toma-
toes, thus causing no problems of food safety and market-
ing. The double S/W ratio of Birikino vs. Tombola should
have theoretically led to an initial deposition of pesticides
about twice as much, but in our trial this fact was observed
only for the second group of pesticides. The rst group
showed initial residues on BIR cv. even seven times more
than those found on TOM, while in the third group no
appreciable differences between the two cultivars were
found. Chemical and physical properties of the active ingre-
dients, different formulations applied in the trial, and differ-
ent mobility of pesticides, could have inuenced the
different initial deposition on the tomato fruits, as well as
botanical and physiological differences (e.g., properties of
cuticles, epicuticular waxes composition, etc.).[814] Since
during the trial, no signicant growth of the berries was
observed, no dilution factor affected residues dissipation,
therefore it could be only due to photodegradation, co-
distillation and/or evaporation.[6,7,15] In the rst group,
the disappearance rate of pesticides on BIR was much
higher compared to TOM cv., while degradation of sec-
ond group occurred more slowly. In the third group, no
difference between the two cv. was found. Taking into
consideration the whole experiment, residue averages
found on BIR cv. were higher than TOM cv. (P < 0.05)
for all the pesticides of the rst two groups (Table 5).
Our study highlights that Chlorpyrifos, Chlorpyrifos
methyl, Triadimenol, Pyridaben and Tebufenpyrad did
not show any different residue behavior between BIR
and TOM. On the other hand, more than 50% of the
examined pesticides (Azoxystrobin, Boscalid, Bupirimate,
Difenoconazole, Etofenprox, Iprodione, Mepanipyrim,
Myclobutanil, Tebuconazole, Zoxamide, Metalaxyl M,
Pyrimethanil, Tetraconazole, Benalaxyl, Cyprodinil,
Fenamidone, Famoxadone and Fludioxonil) could deter-
mine, at time of harvest, high residues on cherry type
tomatoes. Even if residues found were below their legal
limits, in case of multiple treatments they could exceed
the MRLs, so leading to unmarketable productions. This
fact suggests that the effect of different cultivars might be
underestimated in xing the EU MRLs, especially when
Dedola et al.
strong differences of S/W ratio of fruits occur. In any
case, the higher residues found on small berries tomato
could be reduced by using minimum doses recommended
by manufacturers, when applicable. The obtained results
showed that the behavior of pesticides can differ so much
among cultivars of the same species, and so more detailed
studies will be required to ensure a better food safety.
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