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NEW TECHNOLOGIES FOR THE SIMULTANEOUS ANALYSIS OF MULTIPLE PESTICIDE RESIDUES IN AGRICULTURAL PRODUCE Catherine Ryan and Gordon Kearney Waters Corporation, Manchester, UK

INTRODUCTION METHOD

Pesticides are often used in the production of foodstuffs. The Sample Preparation, Extraction and Cleanup Procedure concentrations of individual pesticides permitted in our food are The raisin sample, Californian sun-dried seedless raisins controlled by legislation. There is, therefore, a requirement for sur- (Thompson variety) was prepared using a procedure described veillance monitoring of pesticide residues in foodstuffs. Analytical below involving methanolic extraction and ChemElut™ cleanup, methods developed for this purpose must achieve limits of detec- evaporation and reconstitution2. tion at or below the Maximum Residue Limit (MRL). The raisin sample was chopped to avoid loss of juice. A 5 g ali- Given the large number of pesticides in existence and the variety quot of the homogenized sample was transferred to a blender cup, of agricultural produce available, multi-residue pesticide screening to which 9 mL of water was added. After 10 minutes, 20 mL of methods can offer efficiency advantages over single residue and methanol was added and the sample was blended for 2 minutes. class specific methods. However, these multi-residue methods are 6 mL of the resultant extract was mixed with 2 mL of a solution of limited both by the chromatographic separation of the analytes and sodium chloride (20 g in 100 mL water). A 5 mL aliquot was then the speed of data acquisition. transferred to a ChemElut column containing 5 mL of diatomaceous Tandem quadrupole mass spectrometry is often used as a detec- earth. After 5 minutes, the ChemElut column was eluted with 16 mL tion system due to the high selectivity offered in multiple reaction of dichloromethane. The eluate was evaporated to dryness and the monitoring (MRM) mode, which compensates for generic sample dry residue was reconstituted in 250 μL of methanol and further preparation methods involving minimal sample cleanup. Due to diluted with 1 mL of water. The final extract contained the residues the number of potential analytes, the mass spectrometer chosen of 0.5 g dry sample per mL. The extract was filtered through a should be able to rapidly switch both between MRM channels and 0.45 μm filter into a glass sample vial. between positive and negative ionization modes, thereby offering Blank matrix was prepared from organically grown sun-dried the potential to achieve greater efficiency in the analysis of multi- seedless raisins (Thompson variety) using the same extraction component mixtures. Complementing these +/– ionization mode and cleanup procedure described above. Matrix-matched standards switching capabilities in the Waters® Micromass® Quattro Premier® were prepared by spiking all analytes at 0.5, 1, 2.5, 5, 10 pg/L mass spectrometer is the revolutionary Waters ACQUITY UPLC® (equivalent to 1, 2, 5, 10, 20 μg/kg, respectively). system, offering improved chromatographic resolution and shorter analysis times resulting from the use of columns packed with novel LC Conditions 1.7 μm stationary phase particles1. LC system: ACQUITY UPLC Mobile phase A: MeOH/H O (1:4 v/v) In this work, we highlight recent advances in these chromatographic 2 + 5 mM CH CO NH and mass spectrometric technologies via the analysis of a multi- 3 2 4 Mobile phase B: MeOH/H O (9:1 v/v) component mixture for surveillance monitoring of pesticides in 2 + 5 mM CH CO NH agricultural produce. 3 2 4 Column: ACQUITY UPLC BEH C18, 2.1 x 100 mm, 1.7 μm

 LC Conditions (continued) Flow rate: 0.45 mL/min Injection volume: 20 μL Column temp.: 40 °C Gradient elution: Time %B 0 min 0% 8.5 min 100% 11.0 min 100% 11.1 min 0% 13.5 min 0%

MS Conditions MS system: Quattro Premier Ionization mode: ES+/ES- Capillary voltage: 0.8 kV (+/- ionization) Gas flow: 800 L/hr Source temp.: 120 °C Desolvation temp.: 400 °C Cone voltage: See Table 1 MS/MS: Operated in MRM mode Collision voltage: See Table 1 Figure 1. Comparison of UPLC (0.1 min) and HPLC (0.3 min) chromatograms. Data obtained for a) and b) (solvent standard) at 10 pg/μl. METHOD DEVELOPMENT AND PERFORMANCE

The work details the development of a multi-residue method for the analysis of 100 pesticide residues by UPLC/MS/MS. The work is based upon a previously developed HPLC/MS/MS method using a Waters Alliance® HT/Quattro Premier system, which had an overall cycle time of 25 minutes (HPLC conditions: ® XTerra MS C18 Column, 2.1 x 100 mm, 3.5 μm, linear gradient from 0 to 100% B in 17 min).

Comparison of UPLC and HPLC chromatograms is shown below (Figure 1). Peak widths observed for the majority of pesticide resi- dues analyzed under UPLC conditions are approximately 0.1 min (cf 0.3 min under HPLC conditions). The narrower peak widths often resulted in an increase in signal response over that achieved under Figure 2. Increased resolution of UPLC over HPLC. HPLC/MS/MS conditions (Figure 1).

 [application note]

Greater chromatographic resolution is achievable under UPLC con- In order for accurate quantization to be performed, a minimum of 10 ditions (cf. HPLC) and is illustrated in Figure 2. Butoxycarboxim data points across each peak must be acquired. This requirement, sulfoxide and sulfoxide have similar retention properties, coupled with the number of target analytes and narrow chromato- with butoxycarboxim sulfoxide eluting first, and the same MRM graphic UPLC peaks indicated that it would be advantageous if the transition (m/z 207.1>132). MRM functions were arranged into time windows, based on analyte retention times (Figure 4). This system enabled the flexible use It can be seen that UPLC has the ability to separate complex mix- of dwell times (Table 1), such that those peaks with lower intensi- tures. This is confirmed by considering the analysis of 100 pesticide ties can have their S/N ratios increased by employing longer dwell residues in raisin matrix (Figure 3). All 100 pesticides elute within times, while retaining a minimal scan time. 10 minutes, and the overall cycle time is just 13.5 minutes. In addition to the primary MRM traces monitored for each analyte, Since the analytical method is intended for surveillance monitor- confirmation MRM traces were incorporated into the method for the ing, it needs to be able to detect tens of pesticide residues; some of 31 most commonly found residues. In total, 131 MRM transitions which are better detected under negative ES conditions (Table 1). were monitored in 26 time windows (Figure 4). The use of the ACQUITY UPLC system places added demands on the mass spectrometer due to the improved chromatographic resolution and short analysis times. For these reasons, the Quattro Premier tandem quadrupole mass spectrometer was selected as the detector for this application.

Figure 3. UPLC TIC chromatogram for the analysis Figure 4. MRM functions arranged into time windows. of 100 pesticide residues in raisin extract (10 μg/kg).

 Six of the pesticides included within the method ionize under APPLICATION negative ES mode. The Quattro Premier can switch rapidly between The analytical method was applied to the analysis of pesticide positive and negative ionization modes, so that closely eluting ana- residues in raisins. The chromatogram (Figure 3) obtained for the lytes under both modes can be achieved within a single analytical analysis of a raisin sample containing the pesticides spiked at a run as illustrated above right (Figure 5), thereby minimizing the level equivalent to the MRL demonstrates good signal response for need to perform separate analyses. all analytes at this reporting level. Since the analytical method is Analysis of standard solutions enabled LODs (based on 3 x S/N) to intended for surveillance monitoring, it needs to be able to detect be determined (Table 1). All are well below the necessary reporting tens of pesticide residues; some of which are better detected under level of individual pesticides in food (10 μg/kg, 5 pg/L), indicat- ES- conditions (Table 1). ing that this method could be applied to the analysis of pesticide Good linearity in calibration was demonstrated over the range residues in a variety of matrices. analyzed, 1-20 μg/kg (Figure 6).

Inclusion of a second transition within the surveillance method ES+ enables unambiguous confirmation of the presence of a residue within the sample, without the need to perform a second confirma- tory analytical run (Figure 7) resulting in further efficiency gains. Two pesticide residues ( and ) were con- ES+ firmed present within the raisin sample at levels below the MRL, 4.4 and 3.4 μg/kg, respectively.

ES-

Figure 5. Chromatographic traces for and vamido- thion (ES+) and bromoxynil (ES-).

 [application note]

Imidacloprid Carbaryl

Tebufenozide

Carbendazim

Figure 6. Representative calibration graphs for the analysis Figure 7. Confirmation that the Californian raisin sample of carbaryl (top) and (bottom) spiked into blank contained imidacloprid (top) and tebufenozide (bottom). raisin matrix at a range of concentrations.

 CONCLUSION n Given the chromatographic improvements afforded by the n A rapid multi-residue UPLC/MS/MS method has been devel- ACQUITY UPLC system coupled to the advances in data oped for surveillance monitoring of 100 pesticide residues and acquisition methods seen with the Quattro Premier mass has been applied to the analysis of raisins. spectrometer, it is feasible that this method could be extended n Improved efficiency and increased sample throughput has to over three hundred compounds (provided efficient been realized through the combination of these UPLC and MS sample extraction). technologies which offer: References n enhanced chromatographic resolution and short 1. Plumb R., Castro-Perez J., Granger J., Beattie I., Joncour K., Wright A. Rapid analysis times. Commun. Mass Spectrom. 2004; 18: 2331-7. n the ability to group MRM functions into time windows, 2. Waters Application Note 720000686EN: A multi-residue LC/MS/MS method enabling the incorporation of confirmatory MRM traces. for the determination of 81 pesticide residues in fruit and vegetables: Part 1, Method Overview. n the capability to switch rapidly between MRM channels 3. Waters Application Note 720000686EN: A multi-residue LC/MS/MS method and between positive and negative ionization modes. for the determination of 81 pesticide residues in fruit and vegetables: Part 1, Method Overview. n The sensitivity achieved for the majority of pesticide residues indicates that this UPLC/MS/MS method could be applied to the analysis of pesticides in different matrices over the range analyzed.

Retention Time Precursor Ion Product Ion Cone Voltage Collision Voltage Dwell Time LOD Pesticide Residue (min) m/z m/z (V) (V) (ms) (ppb) Daminozid 0.50 161.1 143.1 18 12 200 0.01 93.8 22 14 80 0.79 141.8 0.02 124.9 22 13 80 Acephate 0.89 184.1 143.0 16 8 40 0.04 Butoxycarboxim-sulfoxide 1.00 207.1 132.1 17 6 30 0.05 183.0 20 12 30 1.01 214.0 0.01 154.9 20 15 30 132.0 16 10 30 Aldicarb-sulfoxide 1.11 207.1 0.1 89.0 16 14 30 Butoxycarboxim 1.20 240.1 106.1 10 14 30 0.04 Aldoxycarb 1.26 240.1 86.0 15 20 30 0.005 1.32 237.1 71.9 12 10 30 0.003 102.0 25 17 30 1.36 189.1 0.01 144.0 25 12 30 Oxydemeton -methyl 1.49 247.0 169.0 20 13 10 0.002 Pymetrozin 1.57 218.0 105.0 25 17 10 0.02

6-chloro -4-hydroxy -3-phenyl- 77.0 35 30 10 1.60 207.1 0.04 pyridazin 104.0 35 21 10 87.8 15 8 10 1.60 162.9 0.01 105.9 15 10 10 169.1 28 16 10 -S-methyl -sulfon 1.61 263.1 0.02 121.2 28 16 10 Quinmerac 1.69 222.0 141.0 22 33 10 0.008 Table 1. MRMMonocrotophos method parameters, UPLC1.78 retention times224.0 and LODs126.9 achievable from20 solvent standards.15 10 0.005 109.0 18 18 10 1.78 224.1 0.01 167.1 18 9 10 Nicosulfuron 1.80 411.0 182.1 22 18 10 0.05 Amidosulfuron 1.84 370.0 261.2 18 14 10 0.02 Metsulfuron -methyl 2.00 382.0 167.0 22 15 10 0.02 Thifensulfuron -methyl 2.00 388.0 167.1 22 15 10 0.02 Ethiofencarbsulfon 2.04 275.1 107.1 10 20 10 0.006 Rimsulfuron 2.05 431.9 182.1 30 22 10 0.02 Ethiofencarbsulfoxide 2.13 242.1 107.0 18 18 10 0.003 -sulfoxide 2.14 252.1 104.0 10 12 10 0.3 209.2 22 16 10 Imidacloprid 2.14 256.1 0.02 175.1 22 20 10 Florasulam 2.28 360.1 129.0 30 20 10 0.09 5 Hydroxy-clethodim -sulfon 2.29 408.2 204.2 22 16 10 0.1 Thiofanox -sulfon 2.32 268.1 76.0 10 10 10 0.02 Clethodim -imin -sulfon 2.35 302.2 98.1 35 30 10 0.04 Metamitron 2.37 203.0 175.1 28 16 10 0.02 Cinosulfuron 2.42 414.1 183.1 25 18 10 0.05 141.1 25 16 10 Chlorsulfuron 2.43 358.1 0.08 167.1 25 16 10 Bromoxynil * 2.45 273.9 78.9 40 25 30 0.2 125.1 17 20 10 Dimethoate 2.48 230.1 0.03 199.1 17 10 10 Clethodim -imin -sulfoxide 2.49 286.2 208.2 25 17 10 0.03 Vamidothion 2.51 288.1 146.1 17 12 10 0.005 -3-hydroxy 2.56 220.1 163.1 25 10 10 0.007 Flazasulfuron 2.66 408.1 182.1 25 22 10 0.5 167.1 25 17 10 Triasulfuron 2.85 402.0 0.2 141.0 25 20 10 Clethodim-sulfon 2.90 392.1 300.2 20 12 10 0.04 Clethodim -sulfoxide 2.95 376.1 206.2 22 15 10 0.05 160.1 25 18 10 Carbendazim 2.98 192.1 0.05 132.1 25 30 10 3.05 253.0 126.0 28 22 10 0.01 Difenzoquat methylsulfate 3.12 249.2 193.1 45 28 10 0.03 3.32 213.1 75.0 20 14 10 0.005 Aldicarb 3.39 208.1 116.0 7 7 10 0.3 Ioxynil * 3.40 369.8 126.9 40 30 20 0.1 Carbofuran 3.41 222.3 165.2 25 15 10 0.1 Iodosulfuron 3.63 508.2 167.2 25 18 30 1 175.1 40 25 20 Thiabendazol 3.78 202.0 0.07 131.0 40 32 20 4.17 210.1 111.0 14 15 10 0.01 4.23 222.1 165.2 20 12 10 0.005 141.1 25 20 10 Prosulfuron 4.46 420.0 0.2 167.0 25 18 10 Carbaryl 4.60 202.1 145.0 18 10 10 0.005 Bensulfuron-methyl 4.67 411.1 149.1 25 22 10 0.05 107.1 15 15 10 4.76 226.1 0.01 164.1 15 8 10 Primisulfuron - methyl* 4.84 466.9 226.2 20 15 10 1 Triflusulfuron-methyl 4.86 493.0 264.2 28 20 10 0.8 Thiodicarb 4.88 355.1 87.9 15 16 10 0.02 Thiofanox 4.92 219.0 56.9 15 18 10 0.01 72.0 28 18 10 4.97 239.1 0.005 182.1 28 15 10 Atrazin 5.08 216.1 174.1 30 17 10 0.01 Isoproturon 5.26 207.1 72.1 25 18 10 0.008 Isoxaflutole 5.31 377.1 251.2 15 20 10 0.3 220.2 20 13 10 Metalaxyl 5.34 280.1 0.01 192.2 20 17 10 Diuron 5.35 233.1 72.1 25 18 10 0.02 3,4,5 -Trimethacarb 5.41 194.1 137.1 18 10 10 0.01 Clethodim 5.52 360.2 164.1 20 19 10 0.05 Desmedipham 5.56 318.2 182.2 17 12 10 0.01 Phenmedipham 5.69 301.1 168.0 25 10 10 2 160.0 28 16 10 Linuron 5.92 249.1 0.02 182.1 28 15 10 107.0 42 22 10 Pyrimethanil 5.93 200.1 0.1 82.0 42 25 10 372.2 22 15 10 Azoxystrobin 5.97 404.1 0.02 329.2 22 30 10 6.06 243.1 121.0 10 22 10 0.3 180.1 45 28 20 Fludioxonil * 6.20 247.0 0.1 126.1 45 35 20 151.0 20 9 10 6.23 208.1 0.03 109.0 20 15 10 Iprovalicarb 6.55 321.2 119.1 15 18 10 0.1 97.0 35 25 10 Fenhexamid 6.61 302.1 0.05 55.1 35 35 10 176.1 20 25 10 Metolachlor 6.81 284.1 0.01 252.1 20 15 10 133.0 13 20 10 Tebufenozide 7.01 353.2 0.4 297.2 13 8 10 7.04 302.1 88.0 20 20 10 0.05 93.1 45 33 10 Cyprodinil 7.19 226.2 0.08 108.1 45 25 10 Tebuconazol 7.23 308.1 70.0 30 20 10 0.02 159.0 30 20 10 Imazalil 7.24 297.1 0.3 69.1 30 20 10 156.0 25 18 10 Triflumuron 7.49 359.1 0.2 139.0 25 37 10 Haloxyfop -methyl 7.73 376.1 316.2 30 18 10 0.03 7.80 527.9 218.1 28 20 10 0.5 Hexaflumuron * 7.85 459.1 276.1 22 22 30 5 Quizalofop -ethyl 8.00 373.1 299.2 30 19 10 0.03 282.2 32 22 10 Fluazifop -P-butyl 8.07 384.1 0.02 328.2 32 16 10 Haloxyfop -ethoxyethyl 8.07 434.0 316.2 25 20 10 0.05 Spiroxamine 8.11 298.3 144.1 30 20 10 0.03 Furathiocarb 8.12 383.1 195.1 20 16 10 0.04 8.14 311.0 158.1 30 14 10 0.1 196.0 18 25 10 Teflubenzuron* 8.31 379.0 0.8 339.1 18 15 10 8.68 488.9 158.1 25 18 10 0.05 Pyridate 379.1 207.1 25 16 120 0.05 Fenpropimorph 9.38 304.2 147.2 45 30 120 0.02 Retention Time Precursor Ion Product Ion Cone Voltage Collision Voltage Dwell Time LOD Pesticide Residue (min) m/z m/z (V) (V) (ms) (ppb) Daminozid 0.50 161.1 143.1 18 12 200 0.01 93.8 22 14 80 Methamidophos 0.79 141.8 0.02 124.9 22 13 80 Acephate 0.89 184.1 143.0 16 8 40 0.04 Butoxycarboxim-sulfoxide 1.00 207.1 132.1 17 6 30 0.05 183.0 20 12 30 Omethoate 1.01 214.0 0.01 154.9 20 15 30 132.0 16 10 30 Aldicarb-sulfoxide 1.11 207.1 0.1 89.0 16 14 30 Butoxycarboxim 1.20 240.1 106.1 10 14 30 0.04 [applicaAldoxycarb tion no1.26 te] 240.1 86.0 15 20 30 0.005 Oxamyl 1.32 237.1 71.9 12 10 30 0.003 102.0 25 17 30 Propamocarb 1.36 189.1 0.01 144.0 25 12 30 Oxydemeton -methyl 1.49 247.0 169.0 20 13 10 0.002 Pymetrozin 1.57 218.0 105.0 25 17 10 0.02

6-chloro -4-hydroxy -3-phenyl- 77.0 35 30 10 1.60 207.1 0.04 pyridazin 104.0 35 21 10 87.8 15 8 10 Methomyl 1.60 162.9 0.01 Table 1. (continued) 105.9 15 10 10 169.1 28 16 10 Retention Time Precursor Ion Product Ion Cone Voltage Collision Voltage Dwell Time LOD DemetonPesticide-S-methyl Residue-sulfon 1.61 263.1 0.02 (min) m/z 121.2m/z (V)28 (V)16 (ms)10 (ppb) DaminozidQuinmerac 0.501.69 161.1222.0 143.1141.0 1822 1233 20010 0.0080.01 1.78 224.0 126.993.8 2220 1415 8010 0.005 Methamidophos 0.79 141.8 0.02 124.9109.0 2218 1318 8010 Bendiocarb 1.78 224.1 0.01 Acephate 0.89 184.1 143.0167.1 1618 89 4010 0.04 ButoxycarboximNicosulfuron-sulfoxide 1.001.80 207.1411.0 132.1182.1 1722 186 3010 0.05 Amidosulfuron 1.84 370.0 183.0261.2 2018 1214 3010 0.02 Omethoate 1.01 214.0 0.01 Metsulfuron -methyl 2.00 382.0 154.9167.0 2022 15 3010 0.02 Thifensulfuron -methyl 2.00 388.0 132.0167.1 1622 1015 3010 0.02 Aldicarb-sulfoxide 1.11 207.1 0.1 Ethiofencarbsulfon 2.04 275.1 107.189.0 1610 1420 3010 0.006 ButoxycarboximRimsulfuron 1.202.05 240.1431.9 106.1182.1 1030 1422 3010 0.040.02 EthiofencarbsulfoxideAldoxycarb 1.262.13 240.1242.1 107.086.0 1518 2018 3010 0.0050.003 ThiofanoxOxamyl-sulfoxide 1.322.14 237.1252.1 104.071.9 1210 1012 3010 0.0030.3 102.0209.2 2522 1716 3010 PropamocarbImidacloprid 1.362.14 189.1256.1 0.010.02 144.0175.1 2522 1220 3010 OxydemetonFlorasulam-methyl 1.492.28 247.0360.1 169.0129.0 2030 1320 10 0.0020.09 5 HydroxyPymetrozin-clethodim -sulfon 1.572.29 218.0408.2 105.0204.2 2522 1716 10 0.020.1

6-chloroThiofanox-4-hydroxy-sulfon-3-phenyl- 2.32 268.1 77.076.0 3510 3010 10 0.02 1.60 207.1 0.04 Clethodimpyridazin-imin -sulfon 2.35 302.2 104.098.1 35 2130 10 0.04 Metamitron 2.37 203.0 175.187.8 1528 168 10 0.02 Methomyl 1.60 162.9 0.01 Cinosulfuron 2.42 414.1 105.9183.1 1525 1018 10 0.05 169.1141.1 2825 16 10 DemetonChlorsulfuron-S-methyl -sulfon 1.612.43 263.1358.1 0.020.08 121.2167.1 2825 16 10 BromoxynilQuinmerac * 1.692.45 222.0273.9 141.078.9 2240 3325 1030 0.0080.2 Monocrotophos 1.78 224.0 126.9125.1 2017 1520 10 0.005 Dimethoate 2.48 230.1 0.03 109.0199.1 1817 1810 10 Bendiocarb 1.78 224.1 0.01 Clethodim -imin -sulfoxide 2.49 286.2 167.1208.2 1825 179 10 0.03 NicosulfuronVamidothion 1.802.51 411.0288.1 182.1146.1 2217 1812 10 0.0050.05 CarbofuranAmidosulfuron-3-hydroxy 1.842.56 370.0220.1 261.2163.1 1825 1410 10 0.0070.02 MetsulfuronFlazasulfuron-methyl 2.002.66 382.0408.1 167.0182.1 2225 1522 10 0.020.5 Thifensulfuron -methyl 2.00 388.0 167.1 2225 1517 10 0.02 Triasulfuron 2.85 402.0 0.2 Ethiofencarbsulfon 2.04 275.1 107.1141.0 1025 20 10 0.006 ClethodimRimsulfuron-sulfon 2.052.90 431.9392.1 182.1300.2 3020 2212 10 0.020.04 EthiofencarbsulfoxideClethodim -sulfoxide 2.132.95 242.1376.1 107.0206.2 1822 1815 10 0.0030.05 Thiofanox-sulfoxide 2.14 252.1 104.0160.1 1025 1218 10 0.3 Carbendazim 2.98 192.1 0.05 209.2132.1 2225 1630 10 Imidacloprid 2.14 256.1 0.02 Thiacloprid 3.05 253.0 175.1126.0 2228 2022 10 0.01 DifenzoquatFlorasulammethylsulfate 2.283.12 360.1249.2 129.0193.1 3045 2028 10 0.090.03 5 HydroxyButocarboxim-clethodim -sulfon 2.293.32 408.2213.1 204.275.0 2220 1614 10 0.0050.1 ThiofanoxAldicarb-sulfon 2.323.39 268.1208.1 116.076.0 107 107 10 0.020.3 ClethodimIoxynil-imin*-sulfon 2.353.40 302.2369.8 126.998.1 3540 30 1020 0.040.1 MetamitronCarbofuran 2.373.41 203.0222.3 175.1165.2 2825 1615 10 0.020.1 CinosulfuronIodosulfuron 2.423.63 414.1508.2 183.1167.2 25 18 1030 0.051 141.1175.1 2540 1625 1020 ThiabendazolChlorsulfuron 2.433.78 358.1202.0 0.080.07 167.1131.0 2540 1632 1020 BromoxynilPropoxur * 2.454.17 273.9210.1 111.078.9 4014 2515 3010 0.010.2 Formetanate 4.23 222.1 125.1165.2 1720 2012 10 0.005 Dimethoate 2.48 230.1 0.03 Table 1. (continued) MRM method parameters, UPLC retention times199.1141.1 and LODs achievable1725 from solvent1020 standards. 10 Prosulfuron 4.46 420.0 0.2 Clethodim -imin -sulfoxide 2.49 286.2 208.2167.0 25 1718 10 0.03 VamidothionCarbaryl 2.514.60 288.1202.1 146.1145.0 1718 1210 10 0.005 CarbofuranBensulfuron-3--hydroxymethyl 2.564.67 220.1411.1 163.1149.1 25 1022 10 0.0070.05 Flazasulfuron 2.66 408.1 182.1107.110 2515 2215 10 0.5 Ethiofencarb 4.76 226.1 0.01 167.1164.1 2515 178 10 Triasulfuron 2.85 402.0 0.2 Primisulfuron - methyl* 4.84 466.9 141.0226.2 2520 2015 10 1 TriflusulfuronClethodim-sulfon-methyl 2.904.86 392.1493.0 300.2264.2 2028 1220 10 0.040.8 ClethodimThiodicarb-sulfoxide 2.954.88 376.1355.1 206.287.9 2215 1516 10 0.050.02 Thiofanox 4.92 219.0 160.156.9 2515 18 10 0.01 Carbendazim 2.98 192.1 0.05 132.172.0 2528 3018 10 Pirimicarb 4.97 239.1 0.005 Thiacloprid 3.05 253.0 126.0182.1 28 2215 10 0.01 DifenzoquatAtrazinmethylsulfate 3.125.08 249.2216.1 193.1174.1 4530 2817 10 0.030.01 ButocarboximIsoproturon 3.325.26 213.1207.1 75.072.1 2025 1418 10 0.0050.008 IsoxaflutoleAldicarb 3.395.31 208.1377.1 116.0251.2 157 207 10 0.3 Ioxynil * 3.40 369.8 126.9220.2 4020 3013 2010 0.1 Metalaxyl 5.34 280.1 0.01 Carbofuran 3.41 222.3 165.2192.2 2520 1517 10 0.1 IodosulfuronDiuron 3.635.35 508.2233.1 167.272.1 25 18 3010 0.021 3,4,5 -Trimethacarb 5.41 194.1 175.1137.1 4018 2510 2010 0.01 Thiabendazol 3.78 202.0 0.07 Clethodim 5.52 360.2 131.0164.1 4020 3219 2010 0.05 DesmediphamPropoxur 4.175.56 210.1318.2 111.0182.2 1417 1512 10 0.01 PhenmediphamFormetanate 4.235.69 222.1301.1 165.2168.0 2025 1210 10 0.0052 141.1160.0 2528 2016 10 ProsulfuronLinuron 4.465.92 420.0249.1 0.020.2 167.0182.1 2528 1815 10 Carbaryl 4.60 202.1 145.0107.0 1842 1022 10 0.005 Pyrimethanil 5.93 200.1 0.1 Bensulfuron-methyl 4.67 411.1 149.182.0 2542 2225 10 0.05 107.1372.2 1522 15 10 AzoxystrobinEthiofencarb 4.765.97 226.1404.1 0.010.02 164.1329.2 1522 308 10 PrimisulfuronMethiocarb- methyl* 4.846.06 466.9243.1 226.2121.0 2010 1522 10 0.31 Triflusulfuron-methyl 4.86 493.0 264.2180.1 2845 2028 1020 0.8 Fludioxonil * 6.20 247.0 0.1 Thiodicarb 4.88 355.1 126.187.9 1545 1635 1020 0.02 Thiofanox 4.92 219.0 151.056.9 1520 189 10 0.01 Promecarb 6.23 208.1 0.03 109.072.0 2820 1815 10 Pirimicarb 4.97 239.1 0.005 Iprovalicarb 6.55 321.2 182.1119.1 2815 1518 10 0.1 Atrazin 5.08 216.1 174.197.0 3035 1725 10 0.01 Fenhexamid 6.61 302.1 0.05 Isoproturon 5.26 207.1 72.155.1 2535 1835 10 0.008 Isoxaflutole 5.31 377.1 251.2176.1 1520 2025 10 0.3 Metolachlor 6.81 284.1 0.01 220.2252.1 20 1315 10 Metalaxyl 5.34 280.1 0.01 192.2133.0 2013 1720 10 Tebufenozide 7.01 353.2 0.4 Diuron 5.35 233.1 297.272.1 2513 188 10 0.02 3,4,5Fenoxycarb-Trimethacarb 5.417.04 194.1302.1 137.188.0 1820 1020 10 0.010.05 Clethodim 5.52 360.2 164.193.1 2045 1933 10 0.05 Cyprodinil 7.19 226.2 0.08 Desmedipham 5.56 318.2 182.2108.1 1745 1225 10 0.01 PhenmediphamTebuconazol 5.697.23 301.1308.1 168.070.0 2530 1020 10 0.022 160.0159.0 2830 1620 10 ImazalilLinuron 5.927.24 249.1297.1 0.020.3 182.169.1 2830 1520 10 107.0156.0 4225 2218 10 PyrimethanilTriflumuron 5.937.49 200.1359.1 0.10.2 139.082.0 4225 2537 10 Haloxyfop -methyl 7.73 376.1 372.2316.2 2230 1518 10 0.03 Azoxystrobin 5.97 404.1 0.02 Indoxacarb 7.80 527.9 329.2218.1 2228 3020 10 0.5 HexaflumuronMethiocarb * 6.067.85 243.1459.1 121.0276.1 1022 22 1030 0.35 Quizalofop -ethyl 8.00 373.1 180.1299.2 4530 2819 2010 0.03 Fludioxonil * 6.20 247.0 0.1 126.1282.2 4532 3522 2010 Fluazifop -P-butyl 8.07 384.1 0.02 151.0328.2 2032 169 10 Promecarb 6.23 208.1 0.03 Haloxyfop -ethoxyethyl 8.07 434.0 109.0316.2 2025 1520 10 0.05 SpiroxamineIprovalicarb 6.558.11 321.2298.3 119.1144.1 1530 1820 10 0.030.1 Furathiocarb 8.12 383.1 195.197.0 3520 2516 10 0.04 Fenhexamid 6.61 302.1 0.05 Diflubenzuron 8.14 311.0 158.155.1 3530 3514 10 0.1 176.1196.0 2018 25 10 TeflubenzuronMetolachlor * 6.818.31 284.1379.0 0.010.8 252.1339.1 2018 15 10 Flufenoxuron 8.68 488.9 133.0158.1 1325 2018 10 0.05 Tebufenozide 7.01 353.2 0.4 Pyridate 379.1 297.2207.1 1325 168 12010 0.05 FenpropimorphFenoxycarb 7.049.38 302.1304.2 147.288.0 2045 2030 12010 0.050.02 93.1 45 33 10 Cyprodinil 7.19 226.2 0.08 108.1 45 25 10 Tebuconazol 7.23 308.1 70.0 30 20 10 0.02 159.0 30 20 10 Imazalil 7.24 297.1 0.3 69.1 30 20 10 156.0 25 18 10 Triflumuron 7.49 359.1 0.2 139.0 25 37 10 Haloxyfop -methyl 7.73 376.1 316.2 30 18 10 0.03 Indoxacarb 7.80 527.9 218.1 28 20 10 0.5 Hexaflumuron * 7.85 459.1 276.1 22 22 30 5 Quizalofop -ethyl 8.00 373.1 299.2 30 19 10 0.03 282.2 32 22 10 Fluazifop -P-butyl 8.07 384.1 0.02 328.2 32 16 10 Haloxyfop -ethoxyethyl 8.07 434.0 316.2 25 20 10 0.05 Spiroxamine 8.11 298.3 144.1 30 20 10 0.03 Furathiocarb 8.12 383.1 195.1 20 16 10 0.04 Diflubenzuron 8.14 311.0 158.1 30 14 10 0.1 196.0 18 25 10 Teflubenzuron* 8.31 379.0 0.8 339.1 18 15 10 Flufenoxuron 8.68 488.9 158.1 25 18 10 0.05 Pyridate 379.1 207.1 25 16 120 0.05 Fenpropimorph 9.38 304.2 147.2 45 30 120 0.02 Retention Time Precursor Ion Product Ion Cone Voltage Collision Voltage Dwell Time LOD Pesticide Residue (min) m/z m/z (V) (V) (ms) (ppb) Daminozid 0.50 161.1 143.1 18 12 200 0.01 93.8 22 14 80 Methamidophos 0.79 141.8 0.02 124.9 22 13 80 Acephate 0.89 184.1 143.0 16 8 40 0.04 Butoxycarboxim-sulfoxide 1.00 207.1 132.1 17 6 30 0.05 183.0 20 12 30 Omethoate 1.01 214.0 0.01 154.9 20 15 30 132.0 16 10 30 Aldicarb-sulfoxide 1.11 207.1 0.1 89.0 16 14 30 Butoxycarboxim 1.20 240.1 106.1 10 14 30 0.04 Aldoxycarb 1.26 240.1 86.0 15 20 30 0.005 Oxamyl 1.32 237.1 71.9 12 10 30 0.003 102.0 25 17 30 Propamocarb 1.36 189.1 0.01 144.0 25 12 30 Oxydemeton -methyl 1.49 247.0 169.0 20 13 10 0.002 Pymetrozin 1.57 218.0 105.0 25 17 10 0.02

6-chloro -4-hydroxy -3-phenyl- 77.0 35 30 10 1.60 207.1 0.04 pyridazin 104.0 35 21 10 87.8 15 8 10 Methomyl 1.60 162.9 0.01 105.9 15 10 10 169.1 28 16 10 Demeton-S-methyl -sulfon 1.61 263.1 0.02 121.2 28 16 10 Quinmerac 1.69 222.0 141.0 22 33 10 0.008 Monocrotophos 1.78 224.0 126.9 20 15 10 0.005 109.0 18 18 10 Bendiocarb 1.78 224.1 0.01 167.1 18 9 10 Nicosulfuron 1.80 411.0 182.1 22 18 10 0.05 Amidosulfuron 1.84 370.0 261.2 18 14 10 0.02 Metsulfuron -methyl 2.00 382.0 167.0 22 15 10 0.02 Thifensulfuron -methyl 2.00 388.0 167.1 22 15 10 0.02 Ethiofencarbsulfon 2.04 275.1 107.1 10 20 10 0.006 Rimsulfuron 2.05 431.9 182.1 30 22 10 0.02 Ethiofencarbsulfoxide 2.13 242.1 107.0 18 18 10 0.003 Thiofanox-sulfoxide 2.14 252.1 104.0 10 12 10 0.3 209.2 22 16 10 Imidacloprid 2.14 256.1 0.02 175.1 22 20 10 Florasulam 2.28 360.1 129.0 30 20 10 0.09 5 Hydroxy-clethodim -sulfon 2.29 408.2 204.2 22 16 10 0.1 Thiofanox -sulfon 2.32 268.1 76.0 10 10 10 0.02 Clethodim -imin -sulfon 2.35 302.2 98.1 35 30 10 0.04 Metamitron 2.37 203.0 175.1 28 16 10 0.02 Cinosulfuron 2.42 414.1 183.1 25 18 10 0.05 141.1 25 16 10 Chlorsulfuron 2.43 358.1 0.08 167.1 25 16 10 Bromoxynil * 2.45 273.9 78.9 40 25 30 0.2 125.1 17 20 10 Dimethoate 2.48 230.1 0.03 199.1 17 10 10 Clethodim -imin -sulfoxide 2.49 286.2 208.2 25 17 10 0.03 Vamidothion 2.51 288.1 146.1 17 12 10 0.005 Carbofuran -3-hydroxy 2.56 220.1 163.1 25 10 10 0.007 Flazasulfuron 2.66 408.1 182.1 25 22 10 0.5 167.1 25 17 10 Triasulfuron 2.85 402.0 0.2 141.0 25 20 10 Clethodim-sulfon 2.90 392.1 300.2 20 12 10 0.04 Clethodim -sulfoxide 2.95 376.1 206.2 22 15 10 0.05 160.1 25 18 10 Carbendazim 2.98 192.1 0.05 132.1 25 30 10 Thiacloprid 3.05 253.0 126.0 28 22 10 0.01 Difenzoquat methylsulfate 3.12 249.2 193.1 45 28 10 0.03 Butocarboxim 3.32 213.1 75.0 20 14 10 0.005 Aldicarb 3.39 208.1 116.0 7 7 10 0.3 Ioxynil * 3.40 369.8 126.9 40 30 20 0.1 Carbofuran 3.41 222.3 165.2 25 15 10 0.1 Iodosulfuron 3.63 508.2 167.2 25 18 30 1 Table 1. (continued) 175.1 40 25 20 Thiabendazol 3.78 202.0 0.07 131.0 40 32 20 Retention Time Precursor Ion Product Ion Cone Voltage Collision Voltage Dwell Time LOD Pesticide Residue Propoxur (min)4.17 210.1m/z 111.0m/z (V)14 (V)15 (ms)10 0.01(ppb) FormetanateDaminozid 0.504.23 161.1222.1 143.1165.2 1820 12 20010 0.0050.01 141.193.8 2225 1420 8010 MethamidophosProsulfuron 0.794.46 141.8420.0 0.020.2 124.9167.0 2225 1318 8010 AcephateCarbaryl 0.894.60 184.1202.1 143.0145.0 1618 108 4010 0.0050.04 ButoxycarboximBensulfuron--sulfoxidemethyl 1.004.67 207.1411.1 132.1149.1 1725 226 3010 0.05 183.0107.1 2015 1215 3010 EthiofencarbOmethoate 1.014.76 214.0226.1 0.01 154.9164.1 2015 158 3010 Primisulfuron - methyl* 4.84 466.9 132.0226.2 1620 1015 3010 1 Aldicarb-sulfoxide 1.11 207.1 0.1 Triflusulfuron-methyl 4.86 493.0 264.289.0 1628 1420 3010 0.8 ButoxycarboximThiodicarb 1.204.88 240.1355.1 106.187.9 1015 1416 3010 0.040.02 AldoxycarbThiofanox 1.264.92 240.1219.0 86.056.9 15 2018 3010 0.0050.01 Oxamyl 1.32 237.1 71.972.0 1228 1018 3010 0.003 Pirimicarb 4.97 239.1 0.005 102.0182.1 2528 1715 3010 Propamocarb 1.36 189.1 0.01 Atrazin 5.08 216.1 144.0174.1 2530 1217 3010 0.01 OxydemetonIsoproturon-methyl 1.495.26 247.0207.1 169.072.1 2025 1318 10 0.0020.008 IsoxaflutolePymetrozin 1.575.31 218.0377.1 105.0251.2 2515 1720 10 0.020.3

6-chloro -4-hydroxy -3-phenyl- 220.277.0 3520 3013 10 Metalaxyl 1.605.34 207.1280.1 0.040.01 pyridazin 104.0192.2 3520 2117 10 Diuron 5.35 233.1 87.872.1 1525 188 10 0.02 Methomyl 1.60 162.9 0.01 3,4,5 -Trimethacarb 5.41 194.1 105.9137.1 1518 10 10 0.01 Clethodim 5.52 360.2 169.1164.1 2820 1619 10 0.05 Demeton-S-methyl -sulfon 1.61 263.1 0.02 Desmedipham 5.56 318.2 121.2182.2 2817 1612 10 0.01 PhenmediphamQuinmerac 1.695.69 222.0301.1 141.0168.0 2225 3310 10 0.0082 Monocrotophos 1.78 224.0 126.9160.0 2028 1516 10 0.005 Linuron 5.92 249.1 0.02 109.0182.1 1828 1815 10 Bendiocarb 1.78 224.1 0.01 167.1107.0 1842 229 10 Pyrimethanil 5.93 200.1 0.1 Nicosulfuron 1.80 411.0 182.182.0 2242 1825 10 0.05 Amidosulfuron 1.84 370.0 261.2372.2 1822 1415 10 0.02 Azoxystrobin 5.97 404.1 0.02 Metsulfuron -methyl 2.00 382.0 167.0329.2 22 1530 10 0.02 ThifensulfuronMethiocarb-methyl 2.006.06 388.0243.1 167.1121.0 2210 1522 10 0.020.3 Ethiofencarbsulfon 2.04 275.1 107.1180.1 1045 2028 1020 0.006 Fludioxonil * 6.20 247.0 0.1 Rimsulfuron 2.05 431.9 182.1126.1 3045 2235 1020 0.02 Ethiofencarbsulfoxide 2.13 242.1 107.0151.0 1820 189 10 0.003 Promecarb 6.23 208.1 0.03 Thiofanox-sulfoxide 2.14 252.1 104.0109.0 1020 1215 10 0.3 Iprovalicarb 6.55 321.2 209.2119.1 2215 1618 10 0.1 Imidacloprid 2.14 256.1 0.02 175.197.0 2235 2025 10 Fenhexamid 6.61 302.1 0.05 Florasulam 2.28 360.1 129.055.1 3035 2035 10 0.09 5 Hydroxy-clethodim -sulfon 2.29 408.2 204.2176.1 2220 1625 10 0.1 Metolachlor 6.81 284.1 0.01 Thiofanox -sulfon 2.32 268.1 252.176.0 1020 1015 10 0.02 Clethodim -imin -sulfon 2.35 302.2 133.098.1 3513 3020 10 0.04 Tebufenozide 7.01 353.2 0.4 Metamitron 2.37 203.0 175.1297.2 2813 168 10 0.02 CinosulfuronFenoxycarb 2.427.04 414.1302.1 183.188.0 2520 1820 10 0.05 141.193.1 2545 1633 10 ChlorsulfuronCyprodinil 2.437.19 358.1226.2 0.08 167.1108.1 2545 1625 10 TebuconazolBromoxynil * 2.457.23 273.9308.1 78.970.0 4030 2520 3010 0.020.2 125.1159.0 1730 20 10 DimethoateImazalil 2.487.24 230.1297.1 0.030.3 Table 1. (continued) MRM method parameters, UPLC retention times199.169.1 and LODs achievable1730 from solvent1020 standards. 10 Clethodim -imin -sulfoxide 2.49 286.2 208.2156.0 25 1718 10 0.03 Triflumuron 7.49 359.1 0.2 Vamidothion 2.51 288.1 146.1139.0 1725 1237 10 0.005 CarbofuranHaloxyfop-3--methylhydroxy 2.567.73 220.1376.1 163.1316.2 2530 1018 10 0.0070.03 FlazasulfuronIndoxacarb 2.667.80 408.1527.9 182.1218.111 2528 2220 10 0.5 Hexaflumuron * 7.85 459.1 167.1276.1 2522 1722 1030 5 Triasulfuron 2.85 402.0 0.2 Quizalofop -ethyl 8.00 373.1 141.0299.2 2530 2019 10 0.03 Clethodim-sulfon 2.90 392.1 300.2282.2 2032 1222 10 0.04 Fluazifop -P-butyl 8.07 384.1 0.02 Clethodim -sulfoxide 2.95 376.1 206.2328.2 2232 1516 10 0.05 Haloxyfop -ethoxyethyl 8.07 434.0 160.1316.2 25 1820 10 0.05 Carbendazim 2.98 192.1 0.05 Spiroxamine 8.11 298.3 132.1144.1 2530 3020 10 0.03 FurathiocarbThiacloprid 3.058.12 253.0383.1 126.0195.1 2820 2216 10 0.010.04 DifenzoquatDiflubenzuronmethylsulfate 3.128.14 249.2311.0 193.1158.1 4530 2814 10 0.030.1 Butocarboxim 3.32 213.1 196.075.0 2018 1425 10 0.005 Teflubenzuron* 8.31 379.0 0.8 Aldicarb 3.39 208.1 116.0339.1 187 157 10 0.3 FlufenoxuronIoxynil * 3.408.68 369.8488.9 126.9158.1 4025 3018 2010 0.050.1 CarbofuranPyridate 3.41 222.3379.1 165.2207.1 25 1516 12010 0.050.1 FenpropimorphIodosulfuron 3.639.38 508.2304.2 167.2147.2 2545 1830 12030 0.021 175.1 40 25 20 Thiabendazol 3.78 202.0 0.07 131.0 40 32 20 Propoxur 4.17 210.1 111.0 14 15 10 0.01 Formetanate 4.23 222.1 165.2 20 12 10 0.005 141.1 25 20 10 Prosulfuron 4.46 420.0 0.2 167.0 25 18 10 Carbaryl 4.60 202.1 145.0 18 10 10 0.005 Bensulfuron-methyl 4.67 411.1 149.1 25 22 10 0.05 107.1 15 15 10 Ethiofencarb 4.76 226.1 0.01 164.1 15 8 10 Primisulfuron - methyl* 4.84 466.9 226.2 20 15 10 1 Triflusulfuron-methyl 4.86 493.0 264.2 28 20 10 0.8 Thiodicarb 4.88 355.1 87.9 15 16 10 0.02 Thiofanox 4.92 219.0 56.9 15 18 10 0.01 72.0 28 18 10 Pirimicarb 4.97 239.1 0.005 182.1 28 15 10 Atrazin 5.08 216.1 174.1 30 17 10 0.01 Isoproturon 5.26 207.1 72.1 25 18 10 0.008 Isoxaflutole 5.31 377.1 251.2 15 20 10 0.3 220.2 20 13 10 Metalaxyl 5.34 280.1 0.01 192.2 20 17 10 Diuron 5.35 233.1 72.1 25 18 10 0.02 3,4,5 -Trimethacarb 5.41 194.1 137.1 18 10 10 0.01 Clethodim 5.52 360.2 164.1 20 19 10 0.05 Desmedipham 5.56 318.2 182.2 17 12 10 0.01 Phenmedipham 5.69 301.1 168.0 25 10 10 2 160.0 28 16 10 Linuron 5.92 249.1 0.02 182.1 28 15 10 107.0 42 22 10 Pyrimethanil 5.93 200.1 0.1 82.0 42 25 10 372.2 22 15 10 Azoxystrobin 5.97 404.1 0.02 329.2 22 30 10 Methiocarb 6.06 243.1 121.0 10 22 10 0.3 180.1 45 28 20 Fludioxonil * 6.20 247.0 0.1 126.1 45 35 20 151.0 20 9 10 Promecarb 6.23 208.1 0.03 109.0 20 15 10 Iprovalicarb 6.55 321.2 119.1 15 18 10 0.1 97.0 35 25 10 Fenhexamid 6.61 302.1 0.05 55.1 35 35 10 176.1 20 25 10 Metolachlor 6.81 284.1 0.01 252.1 20 15 10 133.0 13 20 10 Tebufenozide 7.01 353.2 0.4 297.2 13 8 10 Fenoxycarb 7.04 302.1 88.0 20 20 10 0.05 93.1 45 33 10 Cyprodinil 7.19 226.2 0.08 108.1 45 25 10 Tebuconazol 7.23 308.1 70.0 30 20 10 0.02 159.0 30 20 10 Imazalil 7.24 297.1 0.3 69.1 30 20 10 156.0 25 18 10 Triflumuron 7.49 359.1 0.2 139.0 25 37 10 Haloxyfop -methyl 7.73 376.1 316.2 30 18 10 0.03 Indoxacarb 7.80 527.9 218.1 28 20 10 0.5 Hexaflumuron * 7.85 459.1 276.1 22 22 30 5 Quizalofop -ethyl 8.00 373.1 299.2 30 19 10 0.03 282.2 32 22 10 Fluazifop -P-butyl 8.07 384.1 0.02 328.2 32 16 10 Haloxyfop -ethoxyethyl 8.07 434.0 316.2 25 20 10 0.05 Spiroxamine 8.11 298.3 144.1 30 20 10 0.03 Furathiocarb 8.12 383.1 195.1 20 16 10 0.04 Diflubenzuron 8.14 311.0 158.1 30 14 10 0.1 196.0 18 25 10 Teflubenzuron* 8.31 379.0 0.8 339.1 18 15 10 Flufenoxuron 8.68 488.9 158.1 25 18 10 0.05 Pyridate 379.1 207.1 25 16 120 0.05 Fenpropimorph 9.38 304.2 147.2 45 30 120 0.02 Retention Time Precursor Ion Product Ion Cone Voltage Collision Voltage Dwell Time LOD Pesticide Residue (min) m/z m/z (V) (V) (ms) (ppb) Daminozid 0.50 161.1 143.1 18 12 200 0.01 93.8 22 14 80 Methamidophos 0.79 141.8 0.02 124.9 22 13 80 Acephate 0.89 184.1 143.0 16 8 40 0.04 Butoxycarboxim-sulfoxide 1.00 207.1 132.1 17 6 30 0.05 183.0 20 12 30 Omethoate 1.01 214.0 0.01 154.9 20 15 30 132.0 16 10 30 Aldicarb-sulfoxide 1.11 207.1 0.1 89.0 16 14 30 Butoxycarboxim 1.20 240.1 106.1 10 14 30 0.04 Aldoxycarb 1.26 240.1 86.0 15 20 30 0.005 Oxamyl 1.32 237.1 71.9 12 10 30 0.003 102.0 25 17 30 Propamocarb 1.36 189.1 0.01 144.0 25 12 30 Oxydemeton -methyl 1.49 247.0 169.0 20 13 10 0.002 Pymetrozin 1.57 218.0 105.0 25 17 10 0.02

6-chloro -4-hydroxy -3-phenyl- 77.0 35 30 10 1.60 207.1 0.04 pyridazin 104.0 35 21 10 87.8 15 8 10 Methomyl 1.60 162.9 0.01 105.9 15 10 10 169.1 28 16 10 Demeton-S-methyl -sulfon 1.61 263.1 0.02 121.2 28 16 10 Quinmerac 1.69 222.0 141.0 22 33 10 0.008 Monocrotophos 1.78 224.0 126.9 20 15 10 0.005 109.0 18 18 10 Bendiocarb 1.78 224.1 0.01 167.1 18 9 10 Nicosulfuron 1.80 411.0 182.1 22 18 10 0.05 Amidosulfuron 1.84 370.0 261.2 18 14 10 0.02 Metsulfuron -methyl 2.00 382.0 167.0 22 15 10 0.02 Thifensulfuron -methyl 2.00 388.0 167.1 22 15 10 0.02 Ethiofencarbsulfon 2.04 275.1 107.1 10 20 10 0.006 Rimsulfuron 2.05 431.9 182.1 30 22 10 0.02 Ethiofencarbsulfoxide 2.13 242.1 107.0 18 18 10 0.003 Thiofanox-sulfoxide 2.14 252.1 104.0 10 12 10 0.3 209.2 22 16 10 Imidacloprid 2.14 256.1 0.02 175.1 22 20 10 Florasulam 2.28 360.1 129.0 30 20 10 0.09 5 Hydroxy-clethodim -sulfon 2.29 408.2 204.2 22 16 10 0.1 Thiofanox -sulfon 2.32 268.1 76.0 10 10 10 0.02 Clethodim -imin -sulfon 2.35 302.2 98.1 35 30 10 0.04 Metamitron 2.37 203.0 175.1 28 16 10 0.02 Cinosulfuron 2.42 414.1 183.1 25 18 10 0.05 141.1 25 16 10 Chlorsulfuron 2.43 358.1 0.08 167.1 25 16 10 Bromoxynil * 2.45 273.9 78.9 40 25 30 0.2 125.1 17 20 10 Dimethoate 2.48 230.1 0.03 199.1 17 10 10 Clethodim -imin -sulfoxide 2.49 286.2 208.2 25 17 10 0.03 Vamidothion 2.51 288.1 146.1 17 12 10 0.005 Carbofuran -3-hydroxy 2.56 220.1 163.1 25 10 10 0.007 Flazasulfuron 2.66 408.1 182.1 25 22 10 0.5 167.1 25 17 10 Triasulfuron 2.85 402.0 0.2 141.0 25 20 10 Clethodim-sulfon 2.90 392.1 300.2 20 12 10 0.04 Clethodim -sulfoxide 2.95 376.1 206.2 22 15 10 0.05 160.1 25 18 10 Carbendazim 2.98 192.1 0.05 132.1 25 30 10 Thiacloprid 3.05 253.0 126.0 28 22 10 0.01 Difenzoquat methylsulfate 3.12 249.2 193.1 45 28 10 0.03 Butocarboxim 3.32 213.1 75.0 20 14 10 0.005 Aldicarb 3.39 208.1 116.0 7 7 10 0.3 Ioxynil * 3.40 369.8 126.9 40 30 20 0.1 Carbofuran 3.41 222.3 165.2 25 15 10 0.1 Iodosulfuron 3.63 508.2 167.2 25 18 30 1 175.1 40 25 20 Thiabendazol 3.78 202.0 0.07 131.0 40 32 20 Propoxur 4.17 210.1 111.0 14 15 10 0.01 Formetanate 4.23 222.1 165.2 20 12 10 0.005 141.1 25 20 10 Prosulfuron 4.46 420.0 0.2 167.0 25 18 10 Carbaryl 4.60 202.1 145.0 18 10 10 0.005 Bensulfuron-methyl 4.67 411.1 149.1 25 22 10 0.05 107.1 15 15 10 Ethiofencarb 4.76 226.1 0.01 164.1 15 8 10 Primisulfuron - methyl* 4.84 466.9 226.2 20 15 10 1 Triflusulfuron-methyl 4.86 493.0 264.2 28 20 10 0.8 Thiodicarb 4.88 355.1 87.9 15 16 10 0.02 Thiofanox 4.92 219.0 56.9 15 18 10 0.01 72.0 28 18 10 Pirimicarb 4.97 239.1 0.005 182.1 28 15 10 Atrazin 5.08 216.1 174.1 30 17 10 0.01 Isoproturon 5.26 207.1 72.1 25 18 10 0.008 Isoxaflutole 5.31 377.1 251.2 15 20 10 0.3 220.2 20 13 10 Metalaxyl 5.34 280.1 0.01 192.2 20 17 10 Diuron 5.35 233.1 72.1 25 18 10 0.02 3,4,5 -Trimethacarb 5.41 194.1 137.1 18 10 10 0.01 Clethodim 5.52 360.2 164.1 20 19 10 0.05 Desmedipham 5.56 318.2 182.2 17 12 10 0.01 Phenmedipham 5.69 301.1 168.0 25 10 10 2 160.0 28 16 10 Linuron 5.92 249.1 0.02 182.1 28 15 10 107.0 42 22 10 Pyrimethanil 5.93 200.1 0.1 82.0 42 25 10 372.2 22 15 10 Azoxystrobin 5.97 404.1 0.02 329.2 22 30 10 Methiocarb 6.06 243.1 121.0 10 22 10 0.3 180.1 45 28 20 Fludioxonil * 6.20 247.0 0.1 126.1 45 35 20 151.0 20 9 10 Promecarb 6.23 208.1 0.03 [application note] 109.0 20 15 10 Iprovalicarb 6.55 321.2 119.1 15 18 10 0.1 97.0 35 25 10 Fenhexamid 6.61 302.1 0.05 55.1 35 35 10 176.1 20 25 10 Metolachlor 6.81 284.1 0.01 252.1 20 15 10 133.0 13 20 10 Tebufenozide 7.01 353.2 0.4 297.2 13 8 10 Fenoxycarb 7.04 302.1 88.0 20 20 10 0.05 Table 1. (continued) 93.1 45 33 10 Cyprodinil 7.19 226.2 0.08 108.1 45 25 10 Retention Time Precursor Ion Product Ion Cone Voltage Collision Voltage Dwell Time LOD Pesticide Residue Tebuconazol (min)7.23 308.1m/z 70.0m/z (V)30 (V)20 (ms)10 0.02(ppb) Daminozid 0.50 161.1 143.1159.0 1830 1220 20010 0.01 Imazalil 7.24 297.1 0.3 93.869.1 2230 1420 8010 Methamidophos 0.79 141.8 0.02 124.9156.0 2225 1318 8010 Triflumuron 7.49 359.1 0.2 Acephate 0.89 184.1 143.0139.0 1625 378 4010 0.04 ButoxycarboximHaloxyfop --methylsulfoxide 1.007.73 207.1376.1 132.1316.2 1730 186 3010 0.050.03 Indoxacarb 7.80 527.9 183.0218.1 2028 1220 3010 0.5 Omethoate 1.01 214.0 0.01 Hexaflumuron * 7.85 459.1 154.9276.1 2022 1522 30 5 Quizalofop -ethyl 8.00 373.1 132.0299.2 1630 1019 3010 0.03 Aldicarb-sulfoxide 1.11 207.1 0.1 282.289.0 1632 1422 3010 Fluazifop -P-butyl 8.07 384.1 0.02 Butoxycarboxim 1.20 240.1 106.1328.2 1032 1416 3010 0.04 HaloxyfopAldoxycarb-ethoxyethyl 1.268.07 240.1434.0 316.286.0 1525 20 3010 0.0050.05 SpiroxamineOxamyl 1.328.11 237.1298.3 144.171.9 1230 1020 3010 0.0030.03 Furathiocarb 8.12 383.1 102.0195.1 2520 1716 3010 0.04 Propamocarb 1.36 189.1 0.01 Diflubenzuron 8.14 311.0 144.0158.1 2530 1214 3010 0.1 Oxydemeton -methyl 1.49 247.0 169.0196.0 2018 1325 10 0.002 Teflubenzuron* 8.31 379.0 0.8 Pymetrozin 1.57 218.0 105.0339.1 2518 1715 10 0.02

6-chloro -4Flufenoxuron-hydroxy -3-phenyl- 8.68 488.9 158.177.0 3525 3018 10 0.05 1.60 207.1 0.04 pyridazinPyridate 379.1 104.0207.1 3525 2116 12010 0.05 Fenpropimorph 9.38 304.2 147.287.8 1545 308 12010 0.02 Methomyl 1.60 162.9 0.01 105.9 15 10 10 Table 1. MRM method parameters, UPLC retention times and LODs169.1 achievable from28 solvent standards.16 10 Demeton-S-methyl -sulfon 1.61 263.1 0.02 121.2 28 16 10 Quinmerac 1.69 222.0 141.0 22 33 10 0.008 Monocrotophos 1.78 224.0 126.9 20 15 10 0.005 109.0 18 18 10 Bendiocarb 1.78 224.1 0.01 167.1 18 9 10 Nicosulfuron 1.80 411.0 182.1 22 18 10 0.05 Amidosulfuron 1.84 370.0 261.2 18 14 10 0.02 Metsulfuron -methyl 2.00 382.0 167.0 22 15 10 0.02 Thifensulfuron -methyl 2.00 388.0 167.1 22 15 10 0.02 Ethiofencarbsulfon 2.04 275.1 107.1 10 20 10 0.006 Rimsulfuron 2.05 431.9 182.1 30 22 10 0.02 Ethiofencarbsulfoxide 2.13 242.1 107.0 18 18 10 0.003 Thiofanox-sulfoxide 2.14 252.1 104.0 10 12 10 0.3 209.2 22 16 10 Imidacloprid 2.14 256.1 0.02 175.1 22 20 10 Florasulam 2.28 360.1 129.0 30 20 10 0.09 5 Hydroxy-clethodim -sulfon 2.29 408.2 204.2 22 16 10 0.1 Thiofanox -sulfon 2.32 268.1 76.0 10 10 10 0.02 Clethodim -imin -sulfon 2.35 302.2 98.1 35 30 10 0.04 Metamitron 2.37 203.0 175.1 28 16 10 0.02 Cinosulfuron 2.42 414.1 183.1 25 18 10 0.05 Waters, Micromass, Alliance, ACQUITY UPLC, Oasis, XTerra, 141.1 25 16 10 Chlorsulfuron 2.43 358.1UltraPerformance LC and UPLC are registered trademarks of Waters Corporation 0.08 167.1 25 16 10 Waters Corporation. Quattro Premier and The Science of What’s 34 Maple Street Bromoxynil * 2.45 273.9Possible are trademarks78.9 of Waters Corporation.40 All other trade- 25 Milford, MA30 01757 U.S.A.0.2 marks are the property125.1 of their respective owners.17 20 10 Dimethoate 2.48 230.1 T: 1 508 478 2000 0.03 199.1 17 10 10 ©2004-2007 Waters Corporation. Printed in the U.S.A. F: 1 508 872 1990 Clethodim -imin -sulfoxide 2.49 286.2 208.2 25 17 10 0.03 June 2007 720001172EN RB-AC www.waters.com Vamidothion 2.51 288.1 146.1 17 12 10 0.005 Carbofuran -3-hydroxy 2.56 220.1 163.1 25 10 10 0.007 Flazasulfuron 2.66 408.1 182.1 25 22 10 0.5 167.1 25 17 10 Triasulfuron 2.85 402.0 0.2 141.0 25 20 10 Clethodim-sulfon 2.90 392.1 300.2 20 12 10 0.04 Clethodim -sulfoxide 2.95 376.1 206.2 22 15 10 0.05 160.1 25 18 10 Carbendazim 2.98 192.1 0.05 132.1 25 30 10 Thiacloprid 3.05 253.0 126.0 28 22 10 0.01 Difenzoquat methylsulfate 3.12 249.2 193.1 45 28 10 0.03 Butocarboxim 3.32 213.1 75.0 20 14 10 0.005 Aldicarb 3.39 208.1 116.0 7 7 10 0.3 Ioxynil * 3.40 369.8 126.9 40 30 20 0.1 Carbofuran 3.41 222.3 165.2 25 15 10 0.1 Iodosulfuron 3.63 508.2 167.2 25 18 30 1 175.1 40 25 20 Thiabendazol 3.78 202.0 0.07 131.0 40 32 20 Propoxur 4.17 210.1 111.0 14 15 10 0.01 Formetanate 4.23 222.1 165.2 20 12 10 0.005 141.1 25 20 10 Prosulfuron 4.46 420.0 0.2 167.0 25 18 10 Carbaryl 4.60 202.1 145.0 18 10 10 0.005 Bensulfuron-methyl 4.67 411.1 149.1 25 22 10 0.05 107.1 15 15 10 Ethiofencarb 4.76 226.1 0.01 164.1 15 8 10 Primisulfuron - methyl* 4.84 466.9 226.2 20 15 10 1 Triflusulfuron-methyl 4.86 493.0 264.2 28 20 10 0.8 Thiodicarb 4.88 355.1 87.9 15 16 10 0.02 Thiofanox 4.92 219.0 56.9 15 18 10 0.01 72.0 28 18 10 Pirimicarb 4.97 239.1 0.005 182.1 28 15 10 Atrazin 5.08 216.1 174.1 30 17 10 0.01 Isoproturon 5.26 207.1 72.1 25 18 10 0.008 Isoxaflutole 5.31 377.1 251.2 15 20 10 0.3 220.2 20 13 10 Metalaxyl 5.34 280.1 0.01 192.2 20 17 10 Diuron 5.35 233.1 72.1 25 18 10 0.02 3,4,5 -Trimethacarb 5.41 194.1 137.1 18 10 10 0.01 Clethodim 5.52 360.2 164.1 20 19 10 0.05 Desmedipham 5.56 318.2 182.2 17 12 10 0.01 Phenmedipham 5.69 301.1 168.0 25 10 10 2 160.0 28 16 10 Linuron 5.92 249.1 0.02 182.1 28 15 10 107.0 42 22 10 Pyrimethanil 5.93 200.1 0.1 82.0 42 25 10 372.2 22 15 10 Azoxystrobin 5.97 404.1 0.02 329.2 22 30 10 Methiocarb 6.06 243.1 121.0 10 22 10 0.3 180.1 45 28 20 Fludioxonil * 6.20 247.0 0.1 126.1 45 35 20 151.0 20 9 10 Promecarb 6.23 208.1 0.03 109.0 20 15 10 Iprovalicarb 6.55 321.2 119.1 15 18 10 0.1 97.0 35 25 10 Fenhexamid 6.61 302.1 0.05 55.1 35 35 10 176.1 20 25 10 Metolachlor 6.81 284.1 0.01 252.1 20 15 10 133.0 13 20 10 Tebufenozide 7.01 353.2 0.4 297.2 13 8 10 Fenoxycarb 7.04 302.1 88.0 20 20 10 0.05 93.1 45 33 10 Cyprodinil 7.19 226.2 0.08 108.1 45 25 10 Tebuconazol 7.23 308.1 70.0 30 20 10 0.02 159.0 30 20 10 Imazalil 7.24 297.1 0.3 69.1 30 20 10 156.0 25 18 10 Triflumuron 7.49 359.1 0.2 139.0 25 37 10 Haloxyfop -methyl 7.73 376.1 316.2 30 18 10 0.03 Indoxacarb 7.80 527.9 218.1 28 20 10 0.5 Hexaflumuron * 7.85 459.1 276.1 22 22 30 5 Quizalofop -ethyl 8.00 373.1 299.2 30 19 10 0.03 282.2 32 22 10 Fluazifop -P-butyl 8.07 384.1 0.02 328.2 32 16 10 Haloxyfop -ethoxyethyl 8.07 434.0 316.2 25 20 10 0.05 Spiroxamine 8.11 298.3 144.1 30 20 10 0.03 Furathiocarb 8.12 383.1 195.1 20 16 10 0.04 Diflubenzuron 8.14 311.0 158.1 30 14 10 0.1 196.0 18 25 10 Teflubenzuron* 8.31 379.0 0.8 339.1 18 15 10 Flufenoxuron 8.68 488.9 158.1 25 18 10 0.05 Pyridate 379.1 207.1 25 16 120 0.05 Fenpropimorph 9.38 304.2 147.2 45 30 120 0.02