Electronic Supplementary Material

Developmentof specific LC-ESI-MS/MS methods to determine bifenthrin, lufenuron and iprodioneresidue levels in green beans, peas and chili peppers under Egyptian field conditions

Anna A. Bletsou,1 Ahmad H. Hanafi,2 Marilena E. Dasenaki,1 Nikolaos S. Thomaidis1,*


1 Laboratory of Analytical Chemistry, Department of Chemistry, Faculty of Science University of Athens, Panepistimiopolis Zographou, 15771 Athens, Greece


2 Plant Protection Department, Faculty of Agriculture Ain Shams Univ. P. O. Box 68 Hadayek Shoubra 11241, Egypt

*Corresponding author:

Tel: +30 210 7274317

Fax: +30 210 7274750

E-mail:


Content

Tables

Table S1 Relative abundances in full scan mode of the three analytes (1 mg/L) in different solvent mixtures...... 3

Table S2 Gradient elution program of bifenthrin...... 4

TableS3 Gradient elution program of lufenuron ...... …...... ….…5

Table S4 Gradient elution program of iprodione ...... 6

Table S5 The optimized ESI parameters for the multi-analyte method...... 7

Table S6 Gradient elution program of the multi-analyte method...... 8

Figures

Fig. S1 Positive ESI mass spectrum of bifenthrin in methanol / ammonium formate (5 mM) media...... 8

Fig. S2 Negative ESI mass spectrum of lufenuron in methanol / ammonium formate (5 mM) media...... 9

Fig.S3 Positive ESI mass spectrum of iprodione in methanol : formic acid (0.1 % v/v)...... 10

Figure S4. Breakdown curves of bifenthrin (precursor ion m/z 440), lufenuron (precursor ion m/z 509), and iprodione (precursor ion m/z 332)...... 11

Fig.S5 Fragmentation pattern of bifenthrin……...... …12

Fig.S6 Fragmentation pattern of lufenuron...... 13

Fig.S7 Fragmentation pattern of iprodione……………...... ……………..…...... 14

Fig. S8 Dissipation curves of pesticides in beans...... 15

Fig. S9 Dissipation curve of bifenthrin in peas...... 16

Fig. S10 Dissipation curves of pesticides in peppers...... 17

Table S1. Relative abundances in full scan mode of the three analytes (1 mg/L) in different solvent mixtures

Positive Ionization / Negative Ionization
Mobile phases / Mobile phases
MeOH: HCOONH4 / MeOH: HCOOH / MeOH: NH3 / MeOH: HCOONH4 / MeOH: NH3 / MeOH: HCOOH
Bifenthrin / 5.1×106 / 1.0×106 / n.d.a / n.d. / n.d. / n.d.
Iprodione / 1.7×106 / 3.6×106 / n.d. / 2.3×104 / 4.0× 104 / n.d.
Lufenuron / 2.0×106 / n.d. / 2.2×106 / 1.9×106 / 1.9×106 / 1.7×106

a n.d.: a signal was not detected

Table S2. Gradient elution program of bifenthrin

Time (min) / % Ammonium Formate 5mM / % MeOH / Flow rate (μL/min)
0 / 10 / 90 / 100
3 / 0 / 100 / 100
5 / 0 / 100 / 100
5.3 / 10 / 90 / 200
8 / 10 / 90 / 200
9 / 10 / 90 / 100
10 / 10 / 90 / 100

Table S3. Gradient elution program of lufenuron

Time (min) / % Ammonium Formate 5mM / % MeOH / Flow rate (μL/min)
0 / 20 / 80 / 100
2 / 0 / 100 / 100
4 / 0 / 100 / 100
4.1 / 20 / 80 / 200
6.1 / 20 / 80 / 200
7.1 / 20 / 80 / 100
8.5 / 20 / 80 / 100

Table S4. Gradient elution program of iprodione

Time (min) / % Formic Acid 0.1% v/v / % MeOH / Flow rate (μL/min)
0 / 30 / 70 / 100
5 / 10 / 90 / 100
5.1 / 0 / 100 / 100
6.1 / 0 / 100 / 100
6.3 / 30 / 70 / 200
8.3 / 30 / 70 / 200
9.3 / 30 / 70 / 100
12 / 30 / 70 / 100

Table S5. The optimized ESI parameters for the multi-analyte method.

Iprodione / Lufenuron / Bifenthrin
Ionization mode / positive / negative / positive
Spray Voltage (V) / 4000 / 4000 / 4000
Sheath gas (psi) / 20 / 40 / 40
Auxiliary gas (a.u.) / 40 / 10 / 30
Capillary temperature (°C) / 270 / 270 / 270

Table S6. Gradient elution program of the multi-analyte method.

Time (min) / % Formic Acid 0.1% v/v / % MeOH / Flow rate (μL/min)
0 / 20 / 80 / 100
6.5 / 10 / 90 / 100
8 / 0 / 100 / 100
15 / 0 / 100 / 100
15.5 / 20 / 80 / 100
21 / 20 / 80 / 100

Fig. S1 Positive ESI mass spectrum of bifenthrin in methanol / ammonium formate (5 mM) media.

Fig. S2 Negative ESI mass spectrum of lufenuron in methanol / ammonium formate (5 mM) media

Fig.S3 Positive ESI mass spectrum of iprodione in methanol : formic acid (0.1 % v/v)

Fig. S4. Breakdown curves of bifenthrin (precursor ion m/z 440), lufenuron (precursor ion m/z 509), and iprodione (precursor ion m/z 332)

Fig. S5. Fragmentation pattern of bifenthrin

Fig. S6. Fragmentation pattern of lufenuron

Fig. S7. Fragmentation pattern of iprodione

Fig. S8 Dissipation curves of pesticides in beans

Fig. S9 Dissipation curve of bifenthrin in peas


Fig. S10 Dissipation curves of pesticides in peppers

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