Residue distribution, dissipation behavior and removal of four

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Food Safety and Toxicology

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

ACS Paragon Plus Environment


1

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



39

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

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before the food is consumed, and the processing can influence the pesticide residue via

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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

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have been proved to be able to reduce the residue levels effectively.20, 21 The removal

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efficiency of pesticide residues may be influenced by the physical location of the

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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

64

Previous studies have reported the dissipation and distribution behavior of pesticide in

65

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

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In this study, in order to investigate the effect of waxing treatment on residue

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distribution and dissipation of fungicide, four commonly used fungicides in apples

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(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



82

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

104

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

121

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.

146

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.



165

Results and discussion

166

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



205

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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227

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,



248

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.

273



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Environmental

Additives

&

Science

&

Contaminants:

Technology,

Part

404


A,

47(8),

29(8),

3548–3562.

1280–1287.


405

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))

420


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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



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 -


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 -


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).



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)).



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)



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)



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)


Residue distribution, dissipation behavior and removal of four

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