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Residue distribution, dissipation behavior and removal of four fungicide residues on harvested apple after waxing treatment. Wenqing Jiang, Xiaochu Chen, Fengmao Liu, and Canping Pan J. Agric. Food Chem., Just Accepted Manuscript • DOI: 10.1021/acs.jafc.8b06254 • Publication Date (Web): 08 Feb 2019 Downloaded from http://pubs.acs.org on February 11, 2019
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Journal of Agricultural and Food Chemistry
Residue distribution, dissipation behavior and removal of four fungicide residues on harvested apple after waxing treatment Wenqing Jiang1a, Xiaochu Chen1a, Fengmao Liu1, Canping Pan1 1 College of Science, China Agricultural University, Beijing 100193, China.
Corresponding author: Fengmao Liu, Postal address: College of science, China Agricultural University, No. 2 Yuanmingyuan West Road, Haidian District, Beijing, 100193 China. E-mail:
[email protected], Tel: 0086-10-62731978, Fax: 0086-10-62733620 a Xiaochu Chen and Wenqing Jiang contributed equally to this work
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Abstract
2
The residue distribution and dissipation of pyrimethanil, fludioxonil, cyprodinil and
3
kresoxim-methyl which were introduced during postharvest waxing treatments of
4
apples were investigated. In addition, different residue removal methods were tested
5
for the four fungicides in apples and the removal efficiencies were compared. A multi-
6
residue analytical method was developed based on quick, easy, cheap, effective, rugged,
7
and safe method (QuEChERS) method for the determination of the fungicide residues
8
in apples. The dissipation study demonstrated that there was no significant change of
9
fungicide residues during a 40-day storage process under ambient temperature. Waxing
10
treatment has negative effects on the dissipation of fungicides. The results of residue
11
distribution study demonstrated that waxing treatment may help to reduce the risk of
12
pesticide when only the pulp was consumed. In the residue removal study, results
13
suggested that higher temperature and the addition of acetic acid can improve the
14
residue removal efficiency.
15
Keywords: fungicide residue; apple; dissipation; distribution; waxing treatment
16
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Introduction
18
Apple (Malus pumila), a major fruit crop grown in temperate geographical zone, is rich
19
in vitamins, antioxidants dietary fibers, minerals and other phytochemicals.1-2 Apple is
20
of important dietary value and economic value because of its exceptional flavor and
21
abundant nutrition.3 Moreover, medical studies have shown that the ingestion of apple
22
is beneficial to protect against various chronic diseases including asthma, coronary
23
heart and neurodegenerative diseases due to its anti-inflammatory and antioxidant
24
properties.4-5 The huge market demand has boosted the production of the apples.6
25
However, apple production is affected by various diseases and pests.7-8 A series of
26
pesticides and postharvest treatments are inevitably involved during apple growth,
27
storage and transportation processes to assure the quality and safety of apples.9
28
Pesticide residues may dissipate relatively fast during the preharvest period under
29
severe environments such as intensive sunlight and heavy rains.10 However, the half-
30
lives of pesticides that are applied during postharvest treatments can be much longer
31
because of the cold and mild storage conditions.11
32
Waxing treatment is a common postharvest treatment that has been widely used to
33
control postharvest diseases, to extend shelf life, and to improve fruit quality for
34
a variety of fruits, including clementines,12 rambutan,13 avocado,14 and pineapple.15
35
Waxing treatment is also widely applied in storage of apples owing to its advantages
36
mentioned above.6, 16 In addition, wax has been used as a carrier of fungicides and
37
antioxidants in the postharvest anticorrosive treatments of fruits. Such treatment can
38
help to keep the appearance of apples as well as to prevent the storage diseases such as
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apple scab (Venturia inaequalis) and rots caused by a variety of species (Botrytis
40
cinerea, Monilia fructigena, Gloeosporium spp., Penicillium expansum etc.).1
41
Fungicides such as pyrimethanil, fludioxonil, cyprodinil and kresoxim-methyl, which
42
are used to control these diseases in the field, are thus added to the waxing process.16
43
However, during waxing treatments, the wax can form a membrane which may slow
44
down the air exchange on the surface of the fruits and thus slows down the dissipation
45
of pesticides in the fruits. Also, due to the water proof property of the wax, it may
46
reduce the efficiency of pesticide removal during washing and boiling. To estimate the
47
risk of the postharvest waxing treatments, it is important to investigate the pesticide
48
residues introduced during the waxing process as well as the effects of waxing on the
49
dissipation of the preexisting residues.
50
Recently, the effects of food processing on pesticide residues have been extensively
51
studied.17 Food processing is the action of transforming the food to a more edible form
52
before the food is consumed, and the processing can influence the pesticide residue via
53
chemical and physical changes.18, 19 A series of food processing techniques such as
54
blanching, boiling, canning, frying, peeling and washing of fruits and vegetables
55
have been proved to be able to reduce the residue levels effectively.20, 21 The removal
56
efficiency of pesticide residues may be influenced by the physical location of the
57
pesticide residue as well as the physico-chemical properties of the pesticide including
58
solubility, volatility, hydrolytic rate constant, octanol-water partition coefficient and
59
thermal degradation.22 Previous studies have shown that washing can remove loose
60
surface residues and polar pesticide residues on fruit surface,23 and peeling can lead to
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an almost complete removal of non-systemic residues.24
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The study of residue behavior of the pesticide in agricultural commodities and residue
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change
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Previous studies have reported the dissipation and distribution behavior of pesticide in
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natural apples or bagged apples under field conditions and during food processing.17, 25-
66
28
67
waxing treatments, although waxing and other postharvest treatments may lead to a
68
higher pesticide residues as compared with the untreated raw agricultural
69
commodities.29
70
In this study, in order to investigate the effect of waxing treatment on residue
71
distribution and dissipation of fungicide, four commonly used fungicides in apples
72
(pyrimethanil, fludioxonil, cyprodinil and kresoxim-methyl) were applied to apples in
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the postharvest waxing treatments. The fungicide residue distribution and dissipation
74
in waxed apples were determined by a quick, easy, cheap, effective, rugged, and safe
75
(QuEChERS) method. In addition, washing treatments were tested and compared for
76
the waxed apples to investigate the removal efficiency of the four fungicide residues.
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Materials and methods
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Reagents and materials
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Pesticide standards (pyrimethanil, fludioxonil, cyprodinil and kresoxim-methyl, purity
80
above 98.0%) were purchased from National Research Center for Certified Reference
81
Material, China. 40% pyrimethanil suspension concentrate (SC) was obtained from
after
processing
is
essential
for
ensuring
food
safety.
However, little is known about the pesticide residues introduced during postharvest
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Kefeng Agricultural Scientific Co., Ltd. (Shanxi, China), 25% fludioxonil SC was
83
obtained from Syngenta (Switzerland), 40% cyprodinil SC was obtained from Kellion
84
Biochemical Co., Ltd. (Chengdu, China), 50% kresoxim-methyl water dispersible
85
granules (WDG) was obtained from BASF China. Chromatographic pure acetonitrile
86
was obtained from Mairuida Scientific Co., Ltd. (Beijing, China). Primary secondary
87
amine (PSA) was obtained from Agela Technologies (Tianjin, China). Fruit wax
88
(FreShine) was obtained from ChinAgri Scientific Co., Ltd. (USA). The specific variety
89
of apples were “Red Fuji”, obtained from the local market. Table 1 shows the
90
physicochemical characters of pesticides.
91
Standard stock solutions (pyrimethanil, fludioxonil and cyprodinil: 100 mg L-1;
92
kresoxim-methyl: 200 mg L-1) were prepared in acetonitrile and stored at -20°C. The
93
standard working solutions (matrix-matched standards) were prepared daily by
94
appropriate serial dilutions in blank matrix extract.
95
Waxing treatment
96
The preparation of wax solution and procedure of waxing treatment were in accordance
97
with the manual waxing treatment which commonly used in the local market.
98
According to the recommendations of the fungicide product labels and the dosage
99
commonly used in postharvest treatment, fungicide products (1.5g of 40% pyrimethanil
100
SC, 1.5g of 25% fludioxonil SC, 2.0g of 40% cyprodinil SC, and 3.0g of 50% kresoxim-
101
methyl WDG) were simultaneously added into a beaker that contained 20 mL deionized
102
water. The suspension was stirring constantly, and then 100g of liquid fruit wax was
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added slowly to the suspension, the mixture was subjected to ultrasonication for 10 min
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to form uniform suspension. Thereafter, wax treatment was conducted by a sponge
105
brush, the sponge brush was immersed into the mixture and subsequently applied on
106
apple surface. The surface of treated apple was air dried under ventilated condition for
107
2 hour.
108
Distribution and dissipation of fungicide residues in waxed apples
109
To investigate the dissipation pattern at room temperature (monitoring temperature
110
ranged from 18 to 25°C), the waxed apples were stored under shady conditions. The
111
apple samples (three replicates, each including three apples) were randomly collected
112
at 2 hour, 1, 3, 5, 13, 22, 40 days after waxing. Then, the apple samples were
113
homogenized and divided into small amounts by using quartering before sample
114
pretreatment.
115
To investigate the distribution pattern of fungicide residues on waxed apple, the
116
samples (four replicates, each including three apples) of waxed apple were stored for 1
117
day. And then each of the apples was divided into four parts as shown in Fig. 1. The
118
process operated as follows, (i) apples were peeled by a household peeler, and peels
119
(approximately 2 mm thick) were collected and weighted; (ii) the core, stalk and calyx
120
were removed from the peeled apple by a seeder, the core, pulp, stalk and calyx were
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collected and weighted, respectively. All samples were homogenized and stored at
122
−20°C until pretreatment.
123
The average weight percentage of an apple peel, core, pulp, stalk and calyx was used
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to calculate the relative fungicide distribution in a whole apple from the result for
125
fungicide residues in the different portions. Fungicide distribution (D) was expressed
126
in terms of percentage calculated as follows:
127
D(%) = (𝐶𝑝 × 𝑊𝑝)/(𝐶𝑤 × 𝑊𝑤) × 100%
(1)
128
where Cw and Cp are the fungicide concentrations (mg kg-1) in whole apple and different
129
apple portions, respectively. Ww and Wp are the weights of whole apple and different
130
apple portions, respectively.
131
Solution washing treatment
132
To investigate the removal efficiency of fungicide residue, the washing process was
133
carried out on waxed apple; effects of pH and temperature on fungicide residues
134
removal was also optimized. Generally, waxed apple samples after one day’s storage
135
were soaked in different solutions for one hour. The selected solutions including tap
136
water at room temperature, warm water (55°C), warm water with ultrasonics, acetic
137
acid solution (pH=3, 55°C), and sodium carbonate solution (pH=9, 55°C). The treated
138
samples were air dried at room temperature, and then homogenized for analysis.
139
Different solutions including tap water, warm water, warm water with ultrasonics,
140
acetic acid solution and sodium carbonate solution were used to investigate the removal
141
efficiency of fungicide residue. The removal efficiency of washing treatment was
142
expressed by removal rate (R) and calculated with the following equation:
143 144
R(%) = (𝐶0 ―𝐶)/𝐶0 × 100%
(2)
where C0 and C are the fungicide concentrations (mg kg-1) before and after washing
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treatment, respectively.
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Sample pretreatment
147
The apple samples were treated with a modified QuEChERS method. Homogenized
148
samples of apple (5.0 g) and a volume of 10 mL acetonitrile were added into a 50-mL
149
polypropylene centrifuge tube successively. After vortexing vigorously for 1.0 min, 3
150
g of sodium chloride was added into the mixture, the vortexing step was repeated for
151
1.0 min and then centrifuged at 3800 rpm for 5 min. After that, an aliquot of 1.0 mL
152
supernatant was transferred to a 2-mL centrifuge tube in which 30 mg of PSA was
153
preweighed, and then vortexing for 1 min and centrifuged briefly with a mini centrifuge.
154
Finally, the supernatant was filtered with 0.22 μm organic system filters for HPLC-
155
UVD analysis.
156
HPLC-UVD condition
157
Analysis of fungicide residues was performed on an Agilent 1100 series HPLC coupled
158
to a UVD system, an Extend C18 column (150 mm×4.6 mm, 5 μm) was used for the
159
separation of fungicides. The mobile phase was composed of water (A) and acetonitrile
160
(B) and pumped at a flow rate of 1.0 mL min-1. Analytes was separated using gradient
161
elution: inital time, 70% A; time 5.0 min, 55% A; time 20.0 min, 30% A; time 25.0
162
min, 70% A, and the system was re-equilibrated at the initial conditions (70% A) from
163
25.0 to 30.0 min for the next analysis. The injection volume was 10 μL and detection
164
wavelength was set at 254 nm.
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Results and discussion
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Method validation
167
To ensure the quality and the reliability of the pesticide residue data, the performance
168
of the detection method was evaluated before the real apple samples were analyzed
169
(Table 2). The average recoveries for pyrimethanil, fludioxonil, cyprodinil and
170
kresoxim-methyl were 97.0-104.8% at spiking levels of 0.5, 1, and 10 mg kg-1 (except
171
kresoxim-methyl, which was 1, 2 and 20 mg kg-1), and the relative standard deviation
172
(RSDs) were 2.6-6.2%. The linearity of each analyte was performed by matrix-matched
173
standards with five concentration levels, and the obtained correlation coefficients were
174
higher than 0.9953 for all fungicides in the range of 0.25-10 mg L-1 (kresoxim-methyl:
175
0.5-20 mg L-1). The limits of quantification (LOQs) for the analytes, defined as the
176
lowest fortified levels with satisfactory recoveries and RSDs, ranged from 0.5 to 1.0
177
mg kg-1. All the results demonstrated that the proposed method is suitable for the
178
determination of pyrimethanil, fludioxonil, cyprodinil and kresoxim-methyl in apple
179
samples. The typical chromatograms of the non-spiked and spiked apple sample are
180
shown in Fig. 2.
181
Dissipation pattern of fungicide residues in waxed apple
182
Generally, 30% is defined as a critical value to determine whether a pesticide is stable
183
during storge. Residue levels of the four fungicides in waxed apple were detected
184
throughout the storage process, and the results were presented in Fig. 3. The results
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indicate that none of the four fungicides shows a significant change in concentration
186
during the storage period. These results were quite different from those reported on
187
natural apples or other corps with similar potential for pesticide residues. In previous
188
studies, more rapid dissipation rates of these fungicides were observed. The half-life of
189
pyrimethanil was between 11 to 20 days on unwaxed apples.30 Kresoxim-methyl shows
190
a half-life of 6.2 days on strawberrys and 4.8 days on unwaxed apples.25, 31 Fludioxonil
191
shows a maximum half-life of 24 days in peppers, lettuces and grapes. Cyprodinil
192
shows a maximum half-life of 7.3 days for cyprodinil in peppers, lettuces and grapes.32-
193
34
194
were less than 29 days in lettuces and grapes.32
195
The relatively rapid dissipation rates obtained by previous studies for the four
196
fungicides could be attributed to different storage conditions as well as the physical
197
location of fungicides. As opposed to the direct application of pesticide on the apple
198
surface, the fungicides was applied by using the wax as carrier in this work. Wax layer
199
reduced the moisture loss of apples, but its inhibition on cellular respiration also limited
200
the metabolism of fungicides in apple.35 Furthermore, the wax served as a protective
201
layer to avoid fungicide residues exposure to air, reduced the volatilization of residues.
202
These conclusions illstrated that the wax treatment slows the dissipation of fungicides
203
in apples; the residue on waxed apple increasing the exposure of the consumer to the
204
fungicides.
During storage under low temperature, the half-life of fludioxonil and cyprodinil
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Distribution pattern of fungicide residues in waxed apple
206
Residue levels of the four fungicides in different apple portions were shown in Table
207
3. The residue levels of pyrimethanil, fludioxonil, cyprodinil and kresoxim-methyl in
208
whole apple were 5.6, 3.5, 6.6, 11.3 mg kg-1, respectively. The distribution of residues
209
in apple peel ranged from 75.6 to 90.0%, which were significantly higher than that of
210
pulp, core, stalk and calyx due to the wax layer serving as a transport barrier. In addition,
211
about 7.7-8.4% of the residues were accumulated in the stalk and calyx because of the
212
deposition effects of apple stalk and calyx on pesticides.10 None of the residues of
213
fludioxonil, cyprodinil and kresoxim-methyl were detected in pulp and core due to the
214
block effect of epidermal tissue of apple and wax. However, residue level of
215
pyrimethanil was an exception, which was observed in the pulp with a concentration of
216
1.0 mg kg-1. This might due to the special physico-chemical properties of pyrimethanil.
217
As systemic fungicides with lower logKow (logKow of pyrimethanil, fludioxonil,
218
cyprodinil and kresoxim-methyl were 2.6, 3.6, 3.0 and 3.5, respectively), pyrimethanil
219
could translocated in the plant tissue and penetrated the epicuticular wax of the crops.36
220
There were differences in distribution trends compared with previous research studied
221
by Kong.37 In natural apple, the distribution of chlorpyrifos, β-cypermethrin
222
tebuconazole, acetamiprid and carbendazim in apple pulp and core ranged from 15 to
223
66%, concentrations of both non-systemic (chlorpyrifos and β-cypermethrin) and
224
systemic pesticides (tebuconazole, acetamiprid and carbendazim) were higher in the
225
apple pulp and core. Thus, wax treatments reduce transfer of pesticides into the apple,
226
perhaps reducing exposure to consumers, but note that apple peel, stalk and calyx are
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also used in large quantities in jam and vinegar.
228
Effect of washing treatment on fungicide residue
229
The removal efficiency by different washing treatments is shown in Fig. 4. In general,
230
washing with tap water at room temperature removed the least residues with removal
231
rates at 8.5-10.7%, acetic acid solution was the most effective in removing residues of
232
the investigated pesticides, with 49.0- 66.7% residues being eliminated. Removal rates
233
ranged from 18.9 to 32.0% for warm water, from 15.3 to 34.7% for warm water with
234
ultrasonics, and from 18.5 to 33.3% for sodium carbonate solution.
235
In addition, the relationship between washing conditions and removal efficiency were
236
explored. It can be found that raising the temperature of tap water increased fungicide
237
removal. This may due to the fact that the solubility of wax in water increases with the
238
increase of temperature, and most of the residues remained in the wax layer
239
and therefore were more easily removed. However, there was no significant difference
240
for the removal efficiency of fungicide residues in the treatment of sodium carbonate
241
solution or an extra ultrasonics compared with warm water treatment. This could
242
illustrate that ultrasonics and sodium carbonate solution had little effect on removal
243
efficiency of these fungicide residues in waxed apple.
244
The effects of physicochemical properties of fungicides on removal efficiency were
245
also discussed. Results show that the removal rates of fungicide during the washing
246
process were positively correlated with water solubility. For example, washing with
247
acetic acid solution removed 66.7, 44.3, 49.0 and 50.6% for pyrimethanil, fludioxonil,
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cyprodinil and kresoxim- methyl, respectively. The water solubility of pyrimethanil,
249
fludioxonil, cyprodinil and kresoxim-methyl were 121, 1.8, 20 and 2 mg L-1,
250
respectively. These results were in accordance with those conducted on the potato,
251
cucumber and strawberry.20, 38
252
Conclusion
253
A simple and quick HPLC-UVD method based on modified QuEChERS method was
254
established for simultaneous determination of pyrimethanil, fludioxonil, cyprodinil and
255
kresoxim-methyl. The proposed method was successfully applied to investigate the
256
dissipation and distribution of fungicide residues in waxed apples. Compared with
257
previous studies, the tested fungicides in waxed apples show different dissipation trends,
258
the wax treatment slows the dissipation of fungicides in apples. Therefore, waxing
259
apples may result in higher residues at the time of consumption than in unwaxed apples.
260
According to the results of the residue distribution study, over 84% of the total
261
fungicide residues were accumulated in the apple peel, stalk and calyx parts due to the
262
blocking effect of the wax. Waxing treatment reduces the amount of fungicide residues
263
consumed only when just the apple pulp is consumed.In the residue removal study,
264
washing with 55°C tap water removed 32%, 19%, 19% and 22% of the pyrimethanil,
265
fludioxonil, cyprodinil and kresoxim-methyl, respectively. Washing with a 55°C acetic
266
acid solution increased removal to 67%, 44%, 49%, and 51% respectively. These
267
results suggest that combining the use of a high temperature wash solution with the
268
addition of acetic acid increases the removal of fungicide residues on waxed apples.
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Acknowledgments
270
This study was supported by National Key Research and Development Program of
271
China (2016YFD0200206).
272
The authors have declared no conflict of interest.
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Environmental
Additives
&
Science
&
Contaminants:
Technology,
Part
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A,
47(8),
29(8),
3548–3562.
1280–1287.
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Figure captions
406 407
Fig.1. Sketch of waxed apple portions
408 409
Fig.2. Typical chromatograms of the spiked apple sample (peak are from left to right
410
pyrimethanil 0.25 mg L-1, fludioxonil 0.25 mg L-1, cyprodinil 0.25 mg L-1 and
411
kresoxim-methyl 0.50 mg L-1).
412 413
Fig. 3. Residue behavior of fungicides in waxed apple during storage at ambient
414
temperature.
415 416
Fig. 4. Reduction of the fungicide residues in waxed apple, washing treatments were
417
conducted by soaking the apple in different solutions for one hour. (A: tap water at
418
room temperature; B: warm water at 55°C; C: warm water with ultrasonics; D: sodium
419
carbonate solution (pH 9, 55°C); E: acetic acid solution (pH 3, 55°C))
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Tables Table 1. Physicochemical characters of pesticides
logKow
Henry constant (Pa m3 mol-1)
Solubility in water (mg L1)
2.2
2.6
3.6×10-3
121.0
3.9×10-4
3.6
5.4×10-5
1.8 20.0 2.0
Compound
Melting point (°C)
Vapor pressure (mPa)
Pyrimethanil
96.3
Fludioxonil
199.8
Cyprodinil
75.9
0.51
3.0
6.6×10-3
Kresoximmethyl
313.4
2.3×10-3
3.5
3.6×10-4
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Table 2. Linearity, LOQ, and recoveries of four fungicides.
Fungicide
Linear range
r
(mg L-1)
LOQ
Spiked level
Recovery
RSD
(mg kg-1)
(mg kg-1)
(%)
(%)
0.5 1 10 0.5 1 10 0.5 1 10
100.4 104.8 102.3 101.4 104.8 102.6 97.9 104.2 102.4
3.8 2.6 3.7 5.8 3.6 3.8 5.6 3.1 3.5
1
97.0
6.2
2 20
104.6 102.2
3.0 3.6
Pyrimethanil
0.25-100
0.9978
0.5
Fludioxonil
0.25-100
0.9977
0.5
Cyprodinil
0.25-100
0.9978
0.5
Kresoximmethyl
0.5-200
0.9976
0.5
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Table 3. Distribution of fungicides introduced during waxing treatment in apples. Pyrimethanil Fludioxonil Cyprodinil Portion of Residue level D* Residue level D Residue level D apple (mg kg-1) (%) (mg kg-1) (%) (mg kg-1) (%) Whole apple 5.6 ± 0.3 3.5 ± 0.2 6.6 ± 0.5 Peel 50.3 ± 5.0 75.6 37.2 ± 4.5 90 73.3 ± 8.0 Stalk and calyx 6.1 ± 1.1 7.7 4.1 ± 0.8 8.4 7.6 ± 1.5 Pulp 1.0 ± 0.2 16.3 < 0.5 < 0.5 Core < 0.5 < 0.5 < 0.5 Note: * Fungicide distribution (D) was expressed in terms of percentage.
88.1 7.7 -
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Kresoxim-methyl Residue level
D
(mg kg-1)
(%)
11.3 ± 1.2 117.3 ± 12.6 13.8 ± 2.6 < 1.0 < 1.0
89.5 8.4 -
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Figure graphics
Fig.1. Sketch of waxed apple portions
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Fig.2. Typical chromatograms of the spiked apple sample (peak are from left to right pyrimethanil 0.25 mg L-1, fludioxonil 0.25 mg L-1, cyprodinil 0.25 mg L-1 and kresoxim-methyl 0.50 mg L-1).
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Fig. 3. Residue behavior of fungicides in waxed apple during stroage at ambient temperature.
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Fig. 4. Reduction of the fungicide residues in waxed apple, washing treatments were conducted by soaking the apple in different solutions for one hour. (A: tap water at room temperature; B: warm water at 55°C; C: warm water with ultrasonics; D: sodium carbonate solution (pH 9, 55°C); E: acetic acid solution (pH 3, 55°C)).
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Table of Contents of Graphic
The residue distribution and dissipation of fungicides which were introduced during postharvest waxing treatments of apples were investigated. In addition, different home processing methods were tested for the fungicides in apples and the removal efficiencies were compared.
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Fig.1. Sketch of waxed apple portions 108x76mm (300 x 300 DPI)
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Fig.2. Typical chromatograms of the spiked apple sample (peak are from left to right pyrimethanil 0.25 mg L-1, fludioxonil 0.25 mg L-1, cyprodinil 0.25 mg L-1 and kresoxim-methyl 0.50 mg L-1). 295x159mm (300 x 300 DPI)
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Fig. 3. Residue behavior of fungicides in waxed apple during storage at ambient temperature. 149x84mm (300 x 300 DPI)
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Fig. 4. Reduction of the fungicide residues in waxed apple, washing treatments were conducted by soaking the apple in different solutions for one hour. (A: tap water at room temperature; B: warm water at 55°C; C: warm water with ultrasonics; D: sodium carbonate solution (pH 9, 55°C); E: acetic acid solution (pH 3, 55°C)) 196x106mm (300 x 300 DPI)
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84x47mm (300 x 300 DPI)
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