Adsorption and Desorption Behavior of Spirotetramat in Various Soils

Subscriber access provided by Université de Strasbourg - Service Commun de la Documentation

Agricultural and Environmental Chemistry

Adsorption and Desorption Behavior of Spirotetramat in Various Soils and its Interaction Mechanism Xiaojun Chen, Zhiyuan Meng, Yueyi Song, Qingxia Zhang, Li Ren, Lingjun Guan, Yajun Ren, Tianle Fan, Dianjing Shen, and Yizhong Yang J. Agric. Food Chem., Just Accepted Manuscript • DOI: 10.1021/acs.jafc.8b03424 • Publication Date (Web): 07 Nov 2018 Downloaded from http://pubs.acs.org on November 9, 2018

Just Accepted “Just Accepted” manuscripts have been peer-reviewed and accepted for publication. They are posted online prior to technical editing, formatting for publication and author proofing. The American Chemical Society provides “Just Accepted” as a service to the research community to expedite the dissemination of scientific material as soon as possible after acceptance. “Just Accepted” manuscripts appear in full in PDF format accompanied by an HTML abstract. “Just Accepted” manuscripts have been fully peer reviewed, but should not be considered the official version of record. They are citable by the Digital Object Identifier (DOI®). “Just Accepted” is an optional service offered to authors. Therefore, the “Just Accepted” Web site may not include all articles that will be published in the journal. After a manuscript is technically edited and formatted, it will be removed from the “Just Accepted” Web site and published as an ASAP article. Note that technical editing may introduce minor changes to the manuscript text and/or graphics which could affect content, and all legal disclaimers and ethical guidelines that apply to the journal pertain. ACS cannot be held responsible for errors or consequences arising from the use of information contained in these “Just Accepted” manuscripts.

is published by the American Chemical Society. 1155 Sixteenth Street N.W., Washington, DC 20036 Published by American Chemical Society. Copyright © American Chemical Society. However, no copyright claim is made to original U.S. Government works, or works produced by employees of any Commonwealth realm Crown government in the course of their duties.

Page 1 of 39

Journal of Agricultural and Food Chemistry

1

Adsorption and Desorption Behavior of Spirotetramat in

2

Various Soils and its Interaction Mechanism

3

Xiaojun Chena#, Zhiyuan Menga,b#, Yueyi Songa, Qingxia Zhanga, Li Rena, Lingjun Guana,Yajun

4

Rena, Tianle Fan a, Dianjing Shen a, Yizhong Yanga

5

aSchool

6

Laboratory of Agriculture & Agri-Product Safety (Yangzhou University), Jiangsu Yangzhou,

7

225009, People’s Republic of China

8

bBeijing

9

Applied Chemistry, China Agricultural University, Beijing, 100193, People’s Republic of China

of Horticulture and Plant Protection, Yangzhou University/Joint International Research

Advanced Innovation Center for Food Nutrition and Human Health, Department of

10 11

Correspondence author: Xiaojun Chen

12

E-mail: [email protected]

13

#

These authors contributed equally to this work.

1

ACS Paragon Plus Environment


15

ABSTRACT: Spirotetramat is a pesticide with bidirectional systemicity and can

16

effectively control pests by inhibiting the biosynthesis of fatty acids. In this study,

17

adsorption and desorption behavior of spirotetramat in six soils and its interaction

18

mechanism were studied by using batch equilibrium method and infrared radiation.

19

The results showed that the adsorption and desorption behavior of spirotetramat

20

conformed to the Freundlich isotherm model. The values of adsorption capacities

21

KF-ads of ranged from 2.11 to 12.40, and the values of desorption capacities KF-des

22

varied from 2.97 to 32.90. From the hysteresis coefficient, spirotetramat was easily

23

desorbed from the test soils. The adsorption capacity of the soil to spirotetramat

24

enhanced with increasing temperature. Moreover, the changes in pH values and

25

exogenous addition of humic acid and surfactant could also affect soil adsorption

26

capacity, but for desorption there were no correlation.

27

KEY WORDS: spirotetramat; adsorption; desorption; soils; interaction mechanism

2


Page 2 of 39

Page 3 of 39


29

Introduction

30

Soil is one of the important places that residues and metabolites of pesticide exist

31

and accumulate. The transfer procedure of pesticide in soil is complex and has

32

attracted more and more attention in recent years.1-3 The degradation characteristics of

33

pesticide and the sustainability of pesticide efficacy were related to the adsorption

34

behavior in soil and so adsorption of pesticide in soil has a great influence on

35

ecotoxicological impact, environmental mobility and rate of degradation.2-7

36

Spirotetramat (Fig.1) is a bidirectional systemicity insecticide in both xylem and

37

phloem.8 As an inhibitor of acetyl-CoA carboxylase, spirotetramat can effectively

38

prevent and control piercing-sucking mouthpart insects, such as Aphis citricola,

39

Coffect coccid, Bemisia tabaci, Phylloxera, thrip, acarid, etc, via interfering the fatty

40

acid biosynthesis of insects.8-15 At present, the research on spirotetramat mainly focus

41

on the prevention effect and synthetic process

42

toxicity of spirotetramat.19-20 as well as the analysis of residues and metabolites of

43

spirotetramat inenvironment.21-28 Spirotetramat is generally considered to be

44

innocuous and low toxicity.29-32 However, US Environmental Protection Agency

45

(EPA) reported that spirotetramat is poisonous to bees and aquatic invertebrates such

46

as oysters and it is irritating to eyes and has the potential to cause skin-sensitization in

47

animals and humans.33-34

14,16-18,

cross-resistance and acute

48

The adsorption and desorption characteristics of pesticides are an important part

49

of evaluating the potential environmental risks of pesticides. The adsorption and

50

desorption characteristics of pesticides not only affect the migration and

3



51

transformation behavior of pesticides, but also affect the negative effects of pesticides

52

on succession crops.2-7,35-36 According to the literature, yet there have been no

53

researches on the adsorption and desorption behaviors of spirotetramat in soil. In this

54

research, we made a systematic research to analyze the adsorption and desorption

55

behaviors of spirotetramat in six typical soils of China. Meanwhile, several factors

56

affecting the adsorption efficiency, such as initial pH of solution and temperature

57

were studied in detail. Adsorption and desorption behaviors of spirotetramat has

58

theoretical and practical significance for the safe and reasonable usage of it, as well as

59

for further evaluation of spirotetramat's ecological risk on soil.

60

MATERIALS AND METHODS

61

Soil samples

62

The six typical soil samples were collected from Haidian District Beijing city,

63

Guangzhou City Guangdong Province, Chengdou City Sichuan Province, Pingxiang

64

City Jiangxi Province, Changchun City Jilin Province and Yangzhou City Jiangsu

65

Province, representing different regions with spirotetramat usage in China. In

66

addition, the physical and chemical properties of the six typical soils are diverse and

67

typical (Tab.1). Fresh soils from 0-15 cm depth were collected, air-dried, gently

68

ground, and passed through a 2 mm mesh sieve. The methods for soil characteristics

69

analysis were referred to previous research.38-40

70

Reagents and materials

71

Spirotetramat (99.2% purity) was purchased from Sigma-Aldrich, USA. The

72

molecular structure of spirotetramat is shown in Fig.1. HPLC grade acetonitrile were

4


Page 4 of 39

Page 5 of 39


73

obtained from DIKMA Technology, Inc., USA. Other chemicals used in the study

74

were all purchased from Sinopharm Chemical Reagent CO., Ltd, China. Water was

75

obtained from a Direct-Q Water Purification System, France. Stock solution of 20.0

76

mg/L of spirotetramat was prepared in acetonitrile.

77

Adsorption experiments of spirotetramat in various typical soils

78

Equilibrium time of adsorption of spirotetramat in various typical soils

79

Adsorption experiments were carried out using a batch equilibration method 37. 2

80

g soil samples (< 2mm size) were added to 50 mL conical flasks containing 20 mL

81

spirotetramat solution (0.2 mg/L) prepared in 0.01 mol/L CaCl2 which was used to

82

keep the ionic strength of the soil solution constant and to facilitate flocculation.

83

Meanwhile, NaN3 of 0.01 mol/L was added to restrain the microbial degradation.

84

These studies were conducted in triplicate. The mixtures were shaken on a horizontal

85

shaker at 200 r/min for a period of 0, 2, 4, 6, 8, 12, 16, 24, 36 and 48 h at 25±1 °C.

86

Then, the mixtures were transferred into 50 mL centrifuge tubes and centrifuged at

87

6000 r/min for 8 min. Then 10 mL supernatant solutions were collected for the

88

determination of spirotetramat by liquid chromatography-triple quadrupole tandem

89

mass spectrometry (LC-MS/MS).

90

Adsorption kinetics of spirotetramat in various typical soils

91

Adsorption kinetics were conducted for all the six typical soils. 2.0 g soil

92

samples in triplicates were added to 50 mL conical flasks containing 20 mL

93

spirotetramat solution at concentrations of 0.05, 0.10, 0.20, 0.50, 1.00 and 2.00 mg/L,

94

respectively. After the addition of soil samples, the conical flasks were shaken for 24

5



95

h at 200 r/min at 25 ± 1°C using a horizontal shaker. Then, the mixtures were

96

transferred into 50 mL centrifuge tubes and centrifuged at 6000 r/min for 8 min. 10

97

mL supernatant solutions were collected for the determination of spirotetramat by

98

LC-MS/MS.

99

Effect of different environmental factors on adsorption of spirotetramat in various

100

typical soils

101

Effect of temperatures on adsorption behavior of spirotetramat in various typical

102

soils

103

The adsorption processes were performed under three temperatures (288K, 298K

104

and 308K). The adsorption parameters of spirotetramat in the six typical soils were

105

determined using the batch experiments as described in 2.3.1.

106

Effect of pH values on adsorption behavior of spirotetramat in various typical soils

107

The effects of solution pH values on spirotetramat adsorption were examined.

108

Prior to the test, the pH values of spirotetramat solutions were adjusted to 5.0 and 7.0

109

with HCl or NaOH. The experiments were performed in the same way as the kinetic

110

study described in 2.3.1.

111

Effect of humic acid contents on adsorption behavior of spirotetramat in various

112

typical soils

113

The effects of humic acid contents of soils on spirotetramat adsorption were

114

studied. Prior to the test, the humic acid contents of the six typical soils were adjusted

115

to 0.1%, 1.0% and 10% (g/g). The experiments were performed in the same way as

116

described in 2.3.1.

6


Page 6 of 39

Page 7 of 39


117

Effect of surfactants on adsorption behavior of spirotetramat in various typical soils

118

The effects of three typical surfactants (1-hexadecylsulfonic acid sodium salt

119

(AS), hexadecyl trimethyl ammonium bromide (CTAB) and Tween 80 on the

120

influences of spirotetramat adsorption were also studied. 20 mL of spirotetramat

121

surfactant (AS, CTAB, Tween 80) solution of different concentrations (Cspirotetramat: C

122

Surfactant

123

described in 2.3.1.

124

Desorption experiments of spirotetramat in various typical soils

= 10:1) were added. The experiments were performed in the same way as

125

Desorption experiments were carried out immediately after the adsorption

126

experiments. The supernatant of the adsorption step was removed and equal volume

127

of fresh 0.01 mol/L CaCl2 solution was added. The mixtures equilibrated on a

128

horizontal shaker for 24 h at 25±1°C. Then, the mixtures were transferred into 50 mL

129

centrifuge tubes and centrifuged at 6000 r/min for 8 min. Then, 10 mL supernatant

130

solutions were collected for the determination of spirotetramat by LC-MS/MS.

131

Interaction mechanism experiments of spirotetramat with humic acid in the various

132

typical soils

133

The Infrared radiation (IR) spectra of spirotetramat, spirotetramat-soil (S-S) and

134

spirotetramat-humic acid (S-HA) were analyzed by using infrared radiation. Soil and

135

humic acid were weighed separately in 50 mL centrifuge tubes, and spirotetramat

136

solution in acetonitrile (20 mL of 200 mg/L) was added into it. Then the mixtures

137

were shaken for 24 h at 200 r/min at 25±1°C. After centrifuged at 6000 r/min for 8

138

min, the supernatants were removed. The study was repeated twice in accordance with

7



Page 8 of 39

139

the operation process in order to ensure the fully combination of spirotetramat with

140

the soil and humic acid. The mixtures were washed twice with 5 mL of distilled water

141

to remove spirotetramat that was not adsorbed by soil and humic acid. Finally, the

142

samples (S-S and S-HA) were freeze dried and subjected to IR spectra analysis.

143

Data analysis

144

Freundlich isotherm adsorption equation

145

The amount of spirotetramat adsorbed after equilibrium was calculated according

146

to the difference between the initial and final equilibrium solution concentrations by

147

the following equation (1).38 (1)

Cs＝(C0－Ce)×V/m 148

In the equation, Cs (mg/kg) is the amount of spirotetramat adsorbed by a soil; C0

149

(mg/L) and Ce (mg/L) are the initial and equilibrium aqueous concentrations,

150

respectively. V (mL) is the solution volume; m (g) is the mass of the soil.

151

Adsorption-desorption data were fitted to the Freundlich model (equation (2)) in

152

log format. logKF and 1/n are the adsorption parameters calculated from the liner

153

regression (equation (3)).39 Cs = KF Ce1/n

(2)

log Cs＝log KF＋1/n log Ce

(3)

154

In the equation, KF is the adsorption coefficient characterizing the

155

adsorption-desorption capacity, and n is the Freundlich equation exponent related to

156

adsorption intensity that is used as an indicator of the adsorption isotherm

157

nonlinearity. KF-ads is the adsorption coefficient and KF-des is the desorption coefficient

8


Page 9 of 39

158 159 160


of the Freundlich equation. The OM normalized adsorption constant (KOM) was calculated by normalizing KF-ads to fraction of OM according to equation (4):39 (4)

KOM＝KF-ads/OM×100% 161 162 163

Adsorption thermodynamic equation The free energy of adsorption of the herbicide in soil is calculated using the thermodynamic equation (5):40 (5)

△G＝－RT ln KOM 164

In the equation, △ G (kJ/mol) is the free energy of adsorption, R (8.314×10-3

165

kJ/(K mol)) is the mol gas constant, and T (K) is the absolute temperature.

166

Hysteresis coefficient（H）

167 168

The hysteresis coefficient (H), for the adsorption and desorption isotherms was calculated according to equation (6).41 (6)

H＝(1/nF-des)/(1/nF-ads) 169 170 171

In the equation, 1/nf-ads and 1/nf-des are the Freundlich constants obtained from the adsorption and desorption isotherms, respectively. All data analysis and model development were run by SPSS13.0 (IBM, USA) for

172

Windows.

173

RESULTS

174

The adsorption equilibrium time of spirotetramat in various typical soils

175

Through preliminary adsorption experiment, the adsorption equilibrium time was

176

determined, and the results are presented in Fig.2. The adsorption kinetics exhibited

9



177

two distinct stages, a very rapid adsorption in the initial stages (within 3 h) followed

178

by a slow adsorption (Fig.2). The equilibrium were reached within 24 h. Then 24 h

179

was selected as the equilibrium time for the six typical soils in the next study.

180

The adsorption isotherm of spirotetramat in various typical soils

181

In this study, spirotetramat in the supernatant did not significantly degrade

182

during adsorption procession. Thus, the reduced spirotetramat in solution was

183

considered to be the only reason for soil adsorption. Adsorption equilibrium data of

184

spirotetramat were fitted well using the Freundlich model (R2 ＞0.87). The Freundlich

185

adsorption isotherms were shown in Fig.S1 and their parameters are shown in Tab.2.

186

The Freundlich isotherm constant, KF-ads, represents the adsorption affinity between

187

spirotetramat and the six typical soils. The KF-ads of spirotetramat to the six typical

188

soils ranged from 2.11±1.25 (S4) to 12.40±1.43 (S2), and the order of KF-ads was S4

189

＞S3＞S5＞S1＞S6＞S2. The highest KF-ads value was obtained for S2, which suggests

190

that S2 has the highest affinity with spirotetramat within the six typical soils. Tab.2

191

shows that the values of 1/nF-ads ranged from 0.62±0.11 to 1.10±0.15. In soils S3,

192

the values of 1/nF-ads were close to 1, indicating that these soils exhibited a C-type

193

isotherm. While in others soils, the values of 1/nF-ads were less than 1, which reflected

194

decreasing availability of adsorption sites at the increasing concentration of sorbate,

195

indicating that these soils exhibited an L-type isotherm.

196

Effect of temperatures on adsorption behavior of spirotetramat in various typical

197

soils

198

The effects of temperature on the adsorption of spirotetramat were shown in

10


Page 10 of 39

Page 11 of 39


199

Fig.S2 and Tab.3. The cumulative adsorption of spirotetramat in soils S1, S2, S5 and S6

200

were increased significantly with the increase of temperature, but reduced in soil S4.

201

Thus, the high temperatures promoted the adsorption of spirotetramat in some soils

202

(S1, S2, S5 and S6). In all soils, the △G values ranged from -16.61 to -10.35 kJ/mol

203

(288k), -16.61 to -11.72 kJ/mol (298k) and -16.18 to -11.21 kJ/mol (308K). The △G

204

values for all measures were less than 0 kJ/mol which showed that the adsorption

205

behavior of spirotetramat in the six typical soils was spontaneous. The absolute values

206

of △G were less than 40 kJ/mol, therefore, the adsorption behavior of spirotetramat

207

on the six typical soils belongs to physical adsorption.

208

Effect of pH values on adsorption behavior of spirotetramat in various typical soils

209

The initial pH value of the solution is one of the key factors influence the

210

adsorption capacity of spirotetramat. As shown in Fig.3, the adsorption of the six

211

typical soils were increased with the increasing pH values of the suspension. The pH

212

values of the solution changed the structure of the tested soil

213

effective adsorption sites of soils, leading to increasing the adsorption capability for

214

spirotetramat. However, there were large difference between the changes of

215

adsorption capacity in different soils, The KF-ads of spirotetramat for S4 had little

216

change with the increasing pH values. The values of KF-ads increased from 2.55 (pH 5)

217

to 2.67 (pH 7). However, the values of KF-ads for S2 increased from 9.56 (pH 5) to

218

18.79 (pH 7). These differences may came from the different pH values of soils. S4

219

with lower pH (4.42) may have a better buffer capacity for pH change.

220

Effect of humic acid contents on adsorption behavior of spirotetramat in various

11


39.

It increased the


221

typical soils

222

Humic acid is one of the most important soil organic matter (OM) and their

223

amount varied greatly in different sites.42 The effects of humic acid contents on

224

spirotetramat adsorption were shown in Fig.4. When the content of humic acid was

225

0.1%, the adsorption capacity of the six typical soils did not significantly changed.

226

When the content of humic acid in the soil was 1%, the adsorption capacity of

227

spirotetramat on five typical soils increased significantly, except S2. However, when

228

the content of humic acid was up to 10%, the adsorption capacity of spirotetramat on

229

all soils decreased slightly comparing with the blank controls (CK). The addition of

230

humic acid changed the original adsorption equilibrium in the reaction system, then

231

caused the differences. The humic acid could combine with soil and help the soil

232

adsorb spirotetramat from the water phase. With the increase of the content of humic

233

acid, soil effective adsorption sites will continue to decrease and reach saturation

234

eventually. A part of humic acid could enter into water phase, and combine with

235

spirotetramat in water phase. Thus, the adsorption ability of spirotetramat on tested

236

soils was reduced.

237

Effect of surfactants on adsorption behavior of spirotetramat in various typical soils

238

As an important compound in the production and processing of pesticide

239

formulations, surfactants have the ability to increase the solubility of hydrophobic

240

organic contaminants.43 Effects of surfactants on the adsorption behavior of

241

spirotetramat in six soils were shown in Tab.4. The adsorption capacities of the

242

spirotetramat in S2, S5, S6 were reduced, while the adsorption capacities of the

12


Page 12 of 39

Page 13 of 39


243

spirotetramat in S1, S3, S4 were improved slightly with the addition of surfactant. The

244

reason for this phenomenon may be that there are some differences in the interaction

245

between soil and surfactant. The effect of surfactants is related to their capability for

246

the enhancement of the apparent water solubility of compounds through the inclusion

247

in micelles and, consequently, a decrease of the sorption capacity of soils is produced.

248

Thus, the concentration used for each surfactant is a very important factor to be

249

discussed. On the other hand, the adsorption of surfactants can be also an important

250

reason for the increase of the sorption capacity of compounds on soils. So, if the

251

sorption parameters of surfactants on soils are unknown, the discussion could be

252

speculative, however it could be improved if a bibliographic reference regarding the

253

subject is included. According to these antecedents, more in-depth studies should be

254

carried out regarding the interactions in the ternary soil-surfactant-contaminant system

255

to more accurately describe the effects of the addition of these in the soils.

256

The desorption behavior of spirotetramat in various typical soils

257

The hysteresis index (H) and Freundlich desorption parameters are shown in

258

Tab.5. Desorption equilibrium data of spirotetramat were fitted well using the

259

Freundlich model (R2 ≥ 0.89). The values of desorption capacities KF-des varied from

260

2.97 ±1.24 (S4) to 32.90±1.38 (S2). The hysteresis index of five typical soils were

261

above 1, which means that spirotetramat could desorb from soils easily. So it’s not

262

easy for spirotetramat to accumulate in soil and spirotetramat can move in the soil,

263

which may further increases the potential environmental risks.

264

Interaction mechanism analyses of spirotetramat with humic acid in the various

13



265

typical soils

266

The infra-red spectrograms of spirotetramat, blank soil, S-S, HA and S-HA were

267

shown in Fig.5. The main characteristic absorption peak is the stretching vibration

268

band of C=O (1692.3 cm-1 、1785.9 cm-1). As can be seen from Fig.6, it is illustrated

269

in infrared spectra that there are stretching vibration bands of carbanyl group at the

270

wave numbers 1691.6 cm-1 and 1785.1 cm-1 (S-S2), 1691.5 cm-1 and 1784.9 cm-1

271

(S-S5), 1691.8 cm-1 and 1785.1 cm-1(S-S6). Therefore, S2, S5 and S6 have stronger

272

molecular adsorption force than S1, S3 and S4. Spirotetramat has stretching vibration

273

band of carboxyl group of C=O in 1784.1 cm-1 which was showed in Fig.7 so that

274

humic acid molecules have a certain adsorption capacity for spirotetramat molecules.

275

DISSCUSION

276

Spirotetramat is a pesticide with bidirectional systemicity in both xylem and

277

phloem and can effectively control sucking mouthpart pests by inhibiting the

278

biosynthesis of fatty acids. In this study, we systematically explored the adsorption

279

and desorption behavior of spirotetramat in different soils. The Linear regression

280

analysis was used to evaluate the relationship between the adsorption and desorption

281

behavior of spirotetramat and soil properties Tab.6~7. There is a significant linear

282

positive correlation between the Freundlich sorption constant (KF) and clay content,

283

pH value, organic carbon content and organic content of soils. The P values

284

were0.0225, 0.0189, 0.0209 and 0.0208, respectively. The correlation coefficient (r)

285

was 0.8747, 0.8854, 0.8796, 0.8796, respectively. The linear correlation between

286

desorption hysteresis coefficient (H) and properties of soils was not significant. The

14


Page 14 of 39

Page 15 of 39


287

linear notable standard (P) and correlation coefficient(r) were 0.1396~0.6153,

288

0.2412~0.6770, respectively.

289

The higher organic content and clay content is, the stronger ability to absorb

290

pesticides the soils have while the adsorption capacity of soil to pesticide improved

291

with the decrease of pH value. The following conclusions can be drawn from this

292

study that Freundlich sorption constant (KF) of spirotetramat in the six typical soils

293

has a significant linear positive correlation with clay content and organic content of

294

soils, the linear notable standard (P) was 0.0225 and 0.0208, respectively(P＜0.05).

295

Many studies have shown that the adsorption capacity of soil to pesticide is decided

296

by physical and chemical properties of soils and the ability to adsorb pesticides of

297

soils is decided by the chemical structure of soils and pesticide.39-40 Infrared

298

spectroscopy is the most commonly used method studying the adsorption ability of

299

active component of soils to pesticide. It is illustrated in infrared spectra that there are

300

stretching vibration bands of carbanyl group at the wave numbers 1691.6 cm-1 and

301

1785.1 cm-1 (S-S2), 1691.5 cm-1 and 1784.9 cm-1 (S-S5), 1691.8/cm and 1785.1 cm-1

302

(S-S6), which are close to the stretching vibration band of spirotetramat molecular.

303

Therefore, the adsorption interaction between S2, S5, S6 and spirotetramat molecular is

304

weak interaction like Van Der Waals Force. By comparing infrared spectrums of HA

305

and S-HA, we can find that the stretching vibration bands of carbanyl group of

306

spirotetramat does not shift apparently, but the characteristic peak of HA shifted down

307

apparently. The stretching vibration band of carbanyl group of humic acid molecular

15



Page 16 of 39

308

shifted from 1707.4 cm-1, 1596.0 cm-1 to 1692.5 cm-1, 1592.4 cm-1, so humic acid has

309

strong adsorption ability to spirotetramat.3

310

The

results

showed

that

the

Freundlich

model

can

well

fit

the

311

adsorption-desorption parameters of spirotetramat in the six typical soils. The order of

312

the adsorption capacity of the six typical soils to spirotetramat was: Guangzhou

313

soil >Yangzhou soil >Beijing soil >Changchun soil >Chengdu soil > Pingxiang soil.

314

The adsorption behavior of spirotetramat is spontaneous and adsorption capacity of

315

the soil to spirotetramat enhanced with increasing temperature. The effects of pH

316

value on the adsorption behavior of spirotetramat in soil was significant. Adsorption

317

capacity of the soil to spirotetramat enhanced with the pH rising. The low content of

318

humic acid (0.1% and 1%) increased the adsorption capacity of the soil to

319

spirotetramat. The addition of surfactants (AS, CATB and Tween 80) result in the

320

weakened adsorption capacity of three typical soils (Guangzhou soil, Changchun soil

321

and Yangzhou soil) and increased of the other three typical soils (Beijing soil,

322

Chengdu soil and Pingxiang soil). From the hysteresis coefficient, spirotetramat was

323

easy to desorb from the tested soils, which was difficult to accumulate in the soil for a

324

long time and has certain migration characteristics.

325 326

ACKNOWLEDGEMENTS We gratefully acknowledge the financial support

327

received from Key Research and Development Program of Jiangsu Province

328

(BE2017344), Six Talent Peaks Project in Jiangsu Province (NY-101), Forestry

329

Science and Technology Innovation and Extension Project of Jiangsu Forestry

16


Page 17 of 39

330


Bureau(LYKJ[2017]45).

331 332 333

REFERENCES

334

(1) Liu, W. P. Pesticide environmental chemistry. Beijing: Chemical Industry Press.

335

2006, 165-195.

336

(2) Liu, Y. H.; Xu, Z. Z.; Wu, X. G.; Gui, W. J.; Zhu, G. N. Adsorption and

337

desorption behavior of herbicide diuron on various Chinese cultivated soils. J.

338

Hazard. Mater. 2010, 178, 462-468.

339

(3) Anand, S.; Anjana, S.;Prakash, C. S. Sorption-desorption of fipronil in some soils,

340

as influenced by ionic strength, pH and temperature. Pest Manage. Sci. 2016, 72,

341

1491-1499.

342

(4) Morrica, P.; Barbato, F.; Giodano, A.; Serenella, S.; Francesca, U. Adsorption and

343

desorption of imazosulfuron by soil. J. Agric. Food Chem.2000, 48, 6132-6137.

344

(5) Pusino, A.; Fiori, M. G.; Braschi, I.; Gessa, C. Adsorption and desorption of

345

triasulfuron by soil. J. Agr. Food Chem.2003, 51, 5350-5354.

346

(6) Pusino, A.; Pinna, V. M.; Gessa, C. Azimsulfuron sorption-desorption on soil. J.

347

Agr. Food Chem.2004, 52, 3462-3466.

348

(7) Ma, A. J.; He, R. H.; Zhou, L. X. Behavior and mechanism of napropamide

349

adsorption in soil-water environment. Acta Sci. Circumstantiae.26,(2006)1159-1163.

350

(8) Nauen, R.; Reckmann, U.; Thomzik, J.; Thielert, W. Biological profile of

351

spirotetramat (Movento)–a new two-way systemic (ambimobile) insecticide against

17



352

sucking pest species. Bayer CropSci. J. 2008, 61, 245-278.

353

(9) Cantoni, A.; De Maeyer, L.; Izquierdo, C. J.; Niebes, J. F.; Peeters, D.

354

Development of Movento on key pests and crops in European countries. Bayer

355

CropSci. J. 2008, 61, 349-376.

356

(10) Brück, E.; Elbert, A.; Fischer, R.; Krueger, S.; Kühnhold, J.; Klueken, A. M.;

357

Nauen, R.; Niebes, J. F.; Reckmann, U.; Schnorbach, H. J.; Steffens, R.;

358

Waetermeulen, X. V. Movento, an innovative ambimobile insecticide for sucking

359

insect pest control in agriculture: biological profile and field performance. Crop Prot.

360

2009, 28, 838-844.

361

(11) Kumar, B. V.; Kuttalam, S.; Chandrasekaran, S. Efficacy of a new insecticide

362

spirotetramat against cotton whitefly. Pestic. Res. J. 2009, 21, 45-48.

363

(12) Kumar, B.; Kuttalam, S. Toxicity of spirotetramat 150 OD-a new insecticide

364

molecule against natural enemies of chillies. J. Plant Prot. Environ.2009, 6, 1-5.

365

(13) Kay, I. R.; Herron, G. A. Evaluation of existing and new insecticides including

366

spirotetramat and pyridalyl to control Frankliniella occidentalis (Pergande)

367

(Thysanoptera:Thripidae) on peppers in Queensland. Aust. J Entomol.2010, 49,

368

175-181.

369

(14) Smiley, R. W.; Marshall, J. M.; Yan, G. P. Effect of foliarly applied spirotetramat

370

on reproduction of Heterodera avenaeon wheat roots. Plant Dis.2011, 95, 983-989.

371

(15) McKenna, C.; Gaskin, R.; Horgan, D.; Dobson, S.; Jia, Y. Efficacy of a

372

postharvest spirotetramat spray against armoured scale insects on kiwifruit vines. N.

373

Z. J. Crop Hortic. Sci.2013, 41, 105-116.

18


Page 18 of 39

Page 19 of 39


374

(16) Deng, X. M.; Tan, X.; Tan, Y. L.; Zhai, G.Y.; Gan, Y.G.; Jiang, J.J.; Lan, B.T.,

375

Wei, W. Field Efficacy trials of spirotetramat 24% SC on Diaphorina citri Kuwayama

376

and Dialeurodes citri Ashmead and other citrus pests. Agrochemicals. 2011, 50,

377

217-222.

378

(17) Guillen, J.; Navarro, M.; Bielza, P. Cross-Resistance and baseline susceptibility

379

of spirotetramat in Frankliniella occidentalis (Thysanoptera: Thripidae). J. Econ.

380

Entomol.2014, 107, 1239-1244.

381

(18) Prabhaker, N.; Castle, S.; Perring, T. M. Baseline susceptibility of Bemisia tabaci

382

B biotype (Hemiptera: Aleyrodidae) populations from California and Arizona to

383

spirotetramat. J. Econ. Entomol.2014, 107, 773-780.

384

(19) Yin, X. H.; Jiang S. J.; Yu J.; Zhu, G. N.; Wu, H. M.; Mao, C. L. Effects of

385

spirotetramat on the acute toxicity, oxidative stress, and lipid peroxidation in

386

Chinesetoad (Bufo bufo gargarizans) tadpoles. Environ. Toxicol. Pharmacol. 2014,

387

37, 1229-1235.

388

(20) Peng, T. F.; Pan, Y. O.; Yang, C.; Gao, X. W.; Xi, J. H.; Wu, Y. Q.; Huang, X.;

389

Zhu, E.; Xin, X. C.; Zhan, C. Over-expression of CYP6A2 is associated with

390

spirotetramat resistance and cross-resistance in the resistant strain of Aphis gossypii

391

Glover. Pestic. Biochem. Physiol.2016, 126, 64-69.

392

(21) Schoning, R. Residue analytical method for the determination of residues of

393

spirotetramat and its metabolites in and on plant material by HPLC-MS/MS. Bayer

394

CropSci. J. 2008, 61, 417-454.

395

(22) Mandal, K.; Chahil, G. S.; Sahoo, S. K.; Battu, R. S.; Singh, B. Dissipation

19



396

kinetics of spirotetramat and imidacloprid in brinjal and soil under subtropical

397

conditions of Punjab, India. Bull. Environ. Contam. Toxicol.2010, 84, 225-229.

398

(23) Pandiselvi, S.; Sathiyanarayanan, S.; Ramesh, A. Determination of spirotetramat

399

and imidacloprid residues in cotton seed, lint, oil and soil by HPLC UV method and

400

their dissipation in cotton plant. Pestic. Res. J.2010, 22, 168-173.

401

(24) Chahil, G. S.; Mandal, K.; Sahoo, S. K.; Singh, B. Risk assessment of mixture

402

formulation of spirotetramat and imidacloprid in chili fruits. Environ. Monit. Assess.

403

2015, 187, 4105.

404

(25) Mohapatra, S.; Kumar, S.; Prakash, G. S. Residue evaluation of imidacloprd,

405

spirotetramat and spirotetramat-enol in/on grapes (Vitis vinifera L.) and soil. Environ.

406

Monit. Assess.2015, 187, 632-644.

407

(26) Li, S. S.; Liu, X. G.; Dong, F. S.; Xu, J.; Xu, H. Q.; Hu, M. F.; Zheng, Y. Q.

408

Chemometric-assisted QuEChERS extraction method for the residual analysis of

409

thiacloprid, spirotetramat and spirotetramat’s metabolites in pepper: application of

410

their dissipation patterns. Food Chem.2016, 192, 893-899.

411

(27) Chen, X. J.; Meng, Z. Y.; Zhang, Y. Y.; Ren, Y. J.; Liu, L.; Ren, L. Degradation

412

kinetics and pathways of spirotetramat in different parts of spinach plant and in the

413

soil. Environ. Sci. Pollut. Res.2016, 23, 15053-15062.

414

(28) Meng, Z. Y.; Ren, L.; Song, Y. Y.; Xu, Z. Y.; Chen, X. J. Simultaneous

415

determination of spirotetramat and its four metabolites in Spinacia oleracea L., soil

416

and water using liquid chromatography-tandem mass spectrometry. Chin. J. Pestic.

417

Sci.2017, 19, 482-490.

20


Page 20 of 39

Page 21 of 39


418

(29) Mohapatra, S.; Deepa, M.; Jagadish, G. K. An efficient analytical method for

419

analysis of spirotetramat and its metabolites spirotetramat-enol by HPLC. Bull.

420

Environ. Contam. Toxicol.2012, 88, 124-128.

421

(30) Mohapatra, S.; Deepa, M.; Lekha, S.; Nethravathi, B.; Radhika, B.;

422

Gourishanker, S. Residue dynamics of spirotetramat and imidacloprid in/on mango

423

and soil. Bull. Environ. Contam. Toxicol.2012, 89, 862-867.

424

(31) Singh, B.; Mandal, K.; Sahoo, S. K.; Bhardwaj, U.; Battu, R. S. Development

425

and validation of an HPLC method for determination of spirotetramat and

426

spirotetramat cis enol in various vegetables and soil. J. AOAC Int.2013, 96,670-676.

427

(32) Zhu, Y. L.; Liu, X. G.; Xu, J.; Dong, F. S.;Liang, X. Y.; Li, M. M.; Duan, L. F.;

428

Zheng, Y. Q. Simultaneous determination of spirotetramat and its four metabolites in

429

fruits and vegetables using a modified quick, easy, cheap, effective, rugged, and safe

430

method and liquid chromatography/tandem mass spectrometry. J. Chromatogr. A

431

2013, 1299,71-77.

432

(33) Australian Pesticides and Veterinary Medicines Authority (APVMA). Evaluation

433

of the new active spirotetramat in the product MOVENTO 240 SC insecticide.

434

Canberra, Australia: APVMA, 2009, 9-10.

435

(34) United States Department of Agriculture, Foreign Agricultural Service Pesticide

436

MRL Database (2013). Available from: http://www.mrldatabase.com/default.cfm?

437

Selectvetdrug=0.

438

(35) Wu, C. X.; Zhang, S. Z.; Nie, G.; Zhang, Z. M.; Wang, J.J. Adsorption and

439

desorption of herbicide monosulfuron- ester in Chinese soils. J. Environ. Sci. 2011,

21



440

23, 1524-1532.

441

(36) Li, F. Z.; Feng, D.; Deng, H.; Yu, H. M.; Ge, C.J. Adsorption and desorption of

442

atrazine in five agriculture soils. Ecol. Environ. Sci.2015, 24, 2056-2061.

443

(37) OECD Chemicals Testing-Guidelines 106: Absorption-desorption using a batch

444

equilibrium method (Updated Guideline, adopted 21st January 2000)

445

(38) Li, K. B.;, Liu, W. P.; Zhou, Y.; Wang, H.Y. Factors dominating the sorption of

446

bentazon in soils. Environ Sci, 2003, 24,126-130.

447

(39) Zhang, W.; Wang, J. J.; Zhang, Z. M.; Qin Z. Adsorption of nicosulfuron on soils

448

and its correlation with soil properties. Chin J Pestic Sci, 2006, 8,265-271.

449

(40) Wang, Q, Q.; Liu, W. P. Adsorption and desorption of herbicide imazapyr by

450

soil. China Environ Sci, 1998, 18, 314-318.

451

(41) Cox, L.; Koskinen, W. C.; Yen, P. Y. Sorption−desorption of imidacloprid and

452

its metabolites in soils. J Agric Food Chem, 1997, 45, 1468-1472.

453

(42) Chen, H. F.; Koopal, L. K.; Xiong, J.; Avena, M.; Tan,W. F. Mechanisms of soil

454

humic acid adsorption onto montmorillonite and kaolinite. J. Colloid Interface Sci.

455

2017, 504, 457-467.

456

(43) Cheng, M.; Zeng, G. M.; Huang, D. L.; Yang, C. P.; Lai, C.; Zhang, C.; Liu, Y.

457

Tween 80 surfactant-enhanced bioremediation: toward a solution to the soil

458

contamination by hydrophobic organic compounds. Crit. Rev. Biotechnol.2017,1-14.

459

22


Page 22 of 39

Page 23 of 39


460

Figure legends

461

Fig.1 The molecular structure of spirotetramat

462

Fig.2 Equilibration curves of spirotetramat in the six typical soils

463

Fig.3 The effect of pH values on the adsorption parameters of spirotetramat (Note: CK is Control,

464

which means that the adsorption parameters of spirotetramat in 6 soils without any treatment)

465

Fig.4 The effect of humic acid contents in the soil on the spirotetramat adsorption parameters

466

(Note: CK is Control, which means that the adsorption parameters of spirotetramat in 6 soils

467

without any treatment)

468

Fig.5 The infrared spectroscopy spectra of spirotetramat

469

Fig.6 The infrared spectroscopy spectra of spirotetramat sorbed onto soil (S-S) and soil free

470

Fig.7 The infrared spectroscopy spectra of spirotetramat sorbed onto humic acid (S-HA) and

471

humic acid (HA).

23



473

Table legends

474

Tab.1 The physical and chemical properties of the six typical soils

475

Tab.2 Parameters of adsorption of spirotetramat for the six typical soils

476

Tab.3 Thermodynamic parameters for the adsorption of spirotetramat in the six typical soils

477

Tab.4 The effect of surfactant in the soil on the spirotetramat adsorption parameters

478

Tab.5 Parameters of desorption of spirotetramat for the six typical soils

479

Tab.6 Linear regression analysis for Freundlich sorption constant (KF) and selected properties of

480

soils

481

Tab.7 Linear regression analysis for desorption hysteresis coefficient (H) and selected properties

482

of soils

483

24


Page 24 of 39

Page 25 of 39


484

Tab.1 The physical and chemical properties of the six typical soils Soils

485

Site

Texture

pH

Sand

Silt

Clay

Texture class

(%)

(%)

(%)

(USDA system)

CEC1

OC2

OM3

(cmol kg-1)

(%)

(%)

S1

Haidian, Beijing (N40°01′, E116°16′)

40.68

25.53

33.79

Clay loam

7.25

47.50

0.92

1.59

S2

Guangzhou, Guangdong (N23°11′, E113°21′)

23.92

33.98

42.10

Clay

8.19

39.35

2.48

4.28

S3

Chengdu, Sichuan (N30°42′,E103°51′)

43.62

26.68

29.70

Loam

4.78

25.54

1.25

2.16

S4

Pingxiang, Jiangxi (N27°36′, E113°50′)

33.64

40.62

25.74

Loam

4.42

28.41

1.86

3.21

S5

Changchun, Jilin (N43°52′, E125°18′)

39.35

22.24

38.41

Clay loam

5.49

46.43

0.13

0.23

S6

Yangzhou, Jiangsu (N32°23′, E119°24′)

27.92

34.80

37.28

Clay loam

6.82

38.09

1.27

2.19

1CEC,cation

exchange capacity; 2OC,the content of organic carbon;3OM,the content of organic matter

486

25



487

Page 26 of 39

Tab.2 Parameters of adsorption of spirotetramat for the six typical soils Soils S1 S2 S3 S4 S5 S6

Freundlich model KF-ads

1/ nF-ads

R2

5.10±1.23 12.40±1.43 2.66±1.31 2.11±1.25 5.04±1.41 6.71±1.01

0.62±0.11 0.73±0.12 1.10±0.15 0.70±0.11 0.84±0.16 0.70±0.05

0.92 0.90 0.93 0.90 0.87 0.98

26


KOC

KOM

554.64 499.86 212.76 1621.30 271.20 528.56

320.92 289.64 123.13 916.39 157.14 306.52

Page 27 of 39

489


Tab.3 Thermodynamic parameters for the adsorption of spirotetramat in the six typical soils Soils S1 S2 S3 S4 S5 S6

KF-ads

△G（kJ/mol）

288K

298K

308K

288K

298K

308K

1.97±1.20 8.13±1.41 1.78±1.32 2.23±1.39 4.03±1.29 4.25±1.20

5.10±1.23 12.40±1.43 2.66±1.31 2.10±1.25 5.04±1.41 6.71±1.01

7.11±1.30 21.04±1.69 1.85±1.17 1.77±1.31 5.95±1.24 10.04±1.34

-11.34 -12.35 -10.39 -16.73 -11.37 -12.40

-14.06 -13.81 -11.72 -16.61 -12.32 -13.95

-15.37 -15.61 -11.21 -16.18 -13.15 -15.44

27



491

Page 28 of 39

Tab.4 The effect of surfactant in the soil on the spirotetramat adsorption parameters Soils

S1

S2

S3

S4

S5

S6

Surfactants

Freundlich model KF-ads

1/ nF-ads

R2

AS

7.41±1.13

1.23±0..24

0.96

CATB

8.27±1.34

1.35±0.27

0.89

Tween80

7.82±1.25

1.13±0.32

0.93

AS

6.92±1.38

0.57±0.12

0.89

CATB

7.04±1.47

0.55±0.14

0.97

Tween80

7.59±1.23

0.57±0.13

0.90

AS

3.04±1.12

0.59±0.05

0.96

CATB

3.45±1.20

0.64±0.08

0.98

Tween80

3.54±1.19

0.64±0.09

0.90

AS

2.44±1.23

0.90±0.11

0.96

CATB

2.03±1.50

0.97±0.22

0.92

Tween80

2.29±1.23

0.88±0.11

0.91

AS

3.00±1.14

0.62±0.06

0.89

CATB

2.86±1.10

0.55±0.04

0.90

Tween80

3.56±1.16

0.75±0.07

0.95

AS

4.56±1.03

0.91±0.01

0.95

CATB

2.79±1.26

0.79±0.12

0.90

Tween80

3.79±1.18

0.81±0.08

0.90

28


Page 29 of 39


493

Tab.5 Parameters of desorption of spirotetramat for the six typical soils Soils S1 S2 S3 S4 S5 S6

Freundlich model KF

1/n

R2

15.93±1.51 32.90±1.38 22.22±1.61 2.97±1.24 24.91±1.23 3.07±1.83

0.93±0.15 1.09±0.13 0.89±0.14 0.93±0.07 0.96±0.04 0.89±0.29

0.93 0.97 0.95 0.97 0.99 0.89

494

29


KOC

KOM

H

1731.86 1326.63 1777.83 2285.92 1339.33 241.54

1002.08 768.70 1028.84 1292.04 776.06 140.07

1.5033 1.4984 0.8029 1.3417 1.1455 1.2781


495

Page 30 of 39

Tab.6 Linear regression analysis for Freundlich sorption constant (KF) and selected properties of soils Property

Sand (%)

Silt (%)

Clay (%)

pH

CEC (cmol kg-1)

OC (%)

OM (%)

Slope

-0.3631

0.0471

0.5392

2.2019

0.1715

4.0657

2.3594

Intercept

18.3256

4.2266

-12.9348

-7.8892

- 0.7710

0.3106

0.2991

Significant level (P)

0.0806

0.8682

0.0225

0.0189

0.4091

0.0209

0.0208

Correlation coefficient (R)

-0.7582

0.0883

0.8747

0.8854

0.4183

0.8796

0.8796

30


Page 31 of 39


497

Tab.7 Linear regression analysis for desorption hysteresis coefficient (H) and selected properties of soils Property

Sand (%)

Silt (%)

Clay (%)

pH

CEC (cmol kg-1)

OC (%)

OM (%)

Slope

- 0.0198

0.01338

0.0150

0.1192

0.0161

0.0791

0.0458

Intercept

1.9510

0.8518

0.7433

0.5274

0.6572

1.1574

1.1574

Significant level (P)

0.2243

0.4924

0.5042

0.1396

0.2537

0.6446

0.6153

Correlation coefficient (R)

- 0.5833

0.3529

0.3441

0.6770

0.5542

0.2417

0.2412

498

31



Fig.1 The molecular structure of spirotetramat 41x55mm (96 x 96 DPI)


Page 32 of 39

Page 33 of 39


Fig.2 Equilibration curves of spirotetramat in the six typical soils 79x56mm (300 x 300 DPI)



Fig.3 The effect of pH values on the adsorption parameters of spirotetramat 162x59mm (300 x 300 DPI)


Page 34 of 39

Page 35 of 39


Fig.4 The effect of humic acid contents in the soil on the spirotetramat adsorption parameters 162x64mm (300 x 300 DPI)



Fig.5 The infrared spectroscopy spectra of spirotetramat 79x56mm (300 x 300 DPI)


Page 36 of 39

Page 37 of 39


Fig.6 The infrared spectroscopy spectra of spirotetramat sorbed onto soil (S-S) and soil free 160x169mm (300 x 300 DPI)



Fig.7 The infrared spectroscopy spectra of spirotetramat sorbed onto humic acid (S-HA) and humic acid (HA). 79x56mm (300 x 300 DPI)


Page 38 of 39

Page 39 of 39



Adsorption and Desorption Behavior of Spirotetramat in Various Soils

Recommend Documents