EURL-FV

Multiresidue Method using

QuEChERS followed by
GC-QqQ/MS/MS and
LC-QqQ/MS/MS for
Fruits and Vegetables

CONTENTS
1.
2.
3.
4.
5.

6.
7.
8.
9.

Aim and Scope .. 2

Short Description ..... 2
Apparatus and Consumables . 2
Chemicals
. 3
Procedure
. 3
5.1 Sample Preparation
3
5.2 Recovery Experiments for Method Validation 3
5.3 Extraction ...... 4
5.4 Measurement 5
5.5 Instrumentation and Analytical Conditions for the
LC-MS/MS System ... 5
5.6 Instrumentation and Analytical Conditions for the
GC-MS/MS System .. 5
Calibration Curves 6
Evaluation of Results
7
Conclusion .. 7
References .. 7
Appendix I - Validation Results 8
Appendix II Mass Transitions .. 11

1. Aim and Scope

This report describes a validation data of 138 pesticides included in the
Coordinated Multiannual Community Control Programme for 2010, 2011 and
2012 (Commission Regulation (EC) No 901/2009) using a multiresidue method
by LC-MS/MS and GC-MS/MS in four representative matrices.

2. Short Description
The analysis of pesticide residues was performed by using QuEChERS Method.
The homogeneous sample is extracted with acetonitrile. After salts addition the
mixture is shaken intensively and centrifuged for phase separation. An aliquot of
the organic phase is taken for the clean up with bulk sorbents (PSA) and
MgSO4 anhydrous to remove the residual water. Extracts are shaken by vortex
and a small aliquot is diluted with acetonitrile.

3. Apparatus and Consumables

Sample processing equipment, e.g. Dito Sama-K55 Food Processor.

Automatic pipettes, suitable for handling volumes of 10 to 20 L, 100 to

1000 L, 0.5 to 5 mL and 1 to 10 mL.

50 ml centrifuge tubes with screw caps, for example 50 mL centrifuge tubes

with screw cabs (e.g Sharlab S. L, Spain, article-no 027 409926).

10 mL centrifuge tubes with screw caps.

10 mL solvent-dispenser for acetonitrile.

Test tubes, e.g. 10 mL.

Centrifuge, suitable for the centrifuge tubes employed in the procedure and
capable of achieving at least 4000 rpm.

Syringes, e.g. 2 mL disposable syringes.

Syringes filters, 0.45 m pore size.

Injection vials, 1.5 ml, suitable for LC auto-sampler.

Concentration Workstation, e.g. TurboVap LV, Zymark

4. Chemicals
Acetonitrile, HPLC quality
NaCl pa.
Magnesium sulphate, anhydrous, grit, for example MERCK 1.06067.
Phthalates can be removed in a muffle furnace by heating to 550C.

Disodium hydrogencitratesesquihydrate (e.g. Fluka 71635)

Trisodium citrate dehydrate (e.g. Sigma S4641)

Magnesium sulphate anhydrous coarsely grained.

PSA, for example UCT CUMPS2CT

Pesticides Standards, e.g. Dr. Ehrenstorfer, Scharlab.

Cyclohexane, for GC residue analysis

Acetone, for GC residue analysis

5. Procedure
5.1 Sample preparation
Samples were prepared according to the Quality Control procedure established
in the Method Validation and Quality Control Procedures for Pesticide
Residues Analysis in Food and Feed (Document No. SANCO/10684/2009).
Following this document, the sample was perfectly homogenised by grinding
finely at its arrival to the laboratory.
Sample was frozen for its storage immediately after grinding it.
5.2 Recovery Experiments for Method Validation
Commodities used for fortification were:
Avocado
Carrot
Orange
Pepper

Commodities employed should not contain any of the pesticides analyzed.

Organically grown samples are recommended for the analysis.
The validation method has to be performed at two spiking levels (0.10 mg/Kg
and 0.01 mg/Kg). For each commodity five spiked samples and a blank have to
be analyzed at each level. In total eleven samples per commodity.
The working solutions were prepared adding the 138 pesticides used for the
validation method at two concentrations as follows:

FORT LOW: Pesticides at 1 g/ml acetonitrile

FORT HIGH: Pesticides at 10 g/ml acetonitrile

5.3 Extraction
Pesticides analysed by HPLC-MS/MS
1. Weigh 10 g 0.1g sample in 50 mL centrifuge tube
2. Sample spiking:
Low level concentration (0.01 mg/Kg): add 100 L FORT LOW
High level concentration (0.10 mg/Kg): add 100 L FORT HIGH
3. Shake vigorously for 1 min to allow pesticides distribution
4. Add 10 ml of acetonitrile
5. Salt-mixtures addition for the Partitioning Step:
4 g 0.2 g Magnesium sulphate anhydrous
1 g 0.05 g Sodium chloride
1 g 0.05 g Trisodium citrate dihydrate
0.5 g 0.03 g Disodium hydrogencitrate sesquihydrate
6. Shake vigorously by hand or vortex for 1 min
7. Centrifuge for 5 min at 4000 rpm (Extract I)
8. Clean-up: 6 mL Extract I is transferred into a Polipropilene single
centrifuge tube which contains 150 mg PSA and 900 mg magnesium
sulphate anhydrous (25 mg PSA and 150 mg magnesium sulphate per mL
extract). Shake vigorously by hand or vortex for 1 min
9. Centrifuge for 2 min at 6000 rpm (Extract II)
10. Transfer 1mL Extract II into a test tube. Add 220 L of acetonitrile
11. Vortex sample to mix it properly (Extract III)
12. Filter Extract III into a injection vial suitable for LC
Pesticides analysed by GC-MS/MS
The extraction method is the same until step 10:
10. Transfer 1 mL Extract II into a test tube. Evaporate to dryness
11. Add 1mL cyclohexane: acetone (9:1)
12. Vortex sample to mix it properly (Extract III)
13. Filter Extract III into a injection vial suitable for GC.

5.4 Measurement
Run the system in MRM-mode using the mass transitions presented in
Appendix II.
Pesticides expressed according to the residue definition appear on the table
with the index (RD).
5.5 Instrumentation and Analytical Conditions for the LC/QqQ (MS/MS)
System
LC-MS/MS System 3200 Q TRAP, Applied Biosystem:
- Column: Atlantis T3 2.1x100 mm, 3 m
- Column temperature: 40 C
- Mobile phase A: H2O, 2 mM ammonia formiate, 0.1 1% formic
acid.
- Mobile phase B: methanol
- Injection volume: 10L
- Autosampler temperature: 10 C
- Analysis time: 18 min.
TABLE III: FLOW RATE AND ELUTION GRADIENT

Time (min)
0,0
1,0
1,1
10,0
13,0
13,1

A (%)
95
95
70
0
0
95

B (%)
5
5
30
100
100
5

Flow (L/min)
300
300
300
300
300
300

5.6 Instrumentation and Analytical Conditions for the GC/QqQ (MS/MS)

-

GC: Agilent 7890 Series

Autosampler: Agilent 7683 Injector and sample tray
Inlet: Splitless
Carrier gas: Helium
Inlet pressure: 22.73 psi
Inlet temperature: 250C
Injection volume: 1 L

- Oven temperature program:

Rate
(C/min)
Initial
Ramp 1
Ramp 2
Ramp 3

25
3
8

Value
(C)
70
150
200
280

Hold Time
(min)
2
0
0
10

Run Time
(min)
2
5.2
21.9
41.9

Analytical column: Agilent J&W HP-5ms 30 m x 250 m x 0.25 m

Retention time locking: Chlorpyrifos methyl locked to 16.596 min
Spectrometer: Agilent 7000B Series
Source temperature: 280C
Quadrupole temperature: Q1 and Q2 = 150C
Collision gas flows: Nitrogen at 1.5 mL/min, Helium at 25 ml/min

6 Calibration Curves
A calibration curve was calculated for each pesticide at four calibration levels;
0.01 g/mL, 0.02 g/mL, 0.05 g/mL and 0.1 g/mL. The calibration curves
were best fitted to a linear curve.
Figure 1: Examples of calibration curves

7. Evaluation of results
In the Appendix I are shown the results for the mean recovery and RSD
(Relative Standard Deviation) for the quantified pesticides at both levels.
The majority of validation results are acceptable for the recovery and RSD
values for the representative matrices.
It is worth mentioning that there are some mean and RSD values slightly higher
than the values recommended by the Document No. SANCO/10684/2009.
Nevertheless, these values can be considered as acceptable, in certain justified
cases, as multiresidue methods working at the limit of quantification (0.01
mg/Kg).

8. Conclusion
This survey provides validation data for the pesticides included in the
Community Control Programme for 2010, 2011 and 2012 for four representative
matrixes.
The results obtained are considered acceptable within the studied range. As
this multiresidue method is used at the present time by a large number of
laboratories within the European Pesticides Residues Monitoring Programme
for fruit and vegetables, this survey can help to improve the analysis of
pesticides mentioned above.

9. References

Multiannual Community Control Programme for 2010, 2011 and 2012

(Commission Regulation (EC) No 901/2009)
Method Validation and Quality Control Procedures for Pesticide Residues
Analysis in Food and Feed (Document No. SANCO/10684/2009)
http://www.quechers.com
http://www.crl-pesticides.eu

APPENDIX I: VALIDATION RESULTS

RD= Average or all compounds included in the residue definition
PESTICIDE
ACEPHATE
ACETAMIPRID
ACRINATHRIN
ALDICARB(RD)
AMITRAZ(RD)
DMPF
DMF
AZINPHOS-METHYL
AZOXYSTROBIN
BIFENTHRIN
BITERTANOL
BOSCALID
BROMOPROPYLATE
BUPIRIMATE
BUPROFEZIN
CADUSAFOS
CAPTAN
CARBARYL
CARBENDAZIM(RD)
CARBOFURAN(RD)
CHLORFENVINPHOS
CHLOROTALONIL
CHLORPROPHAM(RD)
CHLORPYRIPHOS
CHLORPIRIPHOS-METHYL
CLOFENTEZIN(RD)
CLOTHIANIDIN
CYFLUTHRIN(RD)
CYPERMETHRIN(RD)
CYPROCONAZOLE
CYPRODINIL
DELTAMETHRIN
DIAZINON
DICHLOFLUANID
DICHLORVOS
DICLORAN
DIFENOCONAZOLE
DIMETHOATE(RD)
DIMETHOMORPH
DIPHENYLAMINE
ENDOSULFAN(RD)
EPOXICONAZOLE
ETHION
ETOFENPROX
ETOPROFOS
FENARIMOL

MEAN%
RSD%
(0,01 mg/Kg) (0,01 mg/Kg)
88
84
103
105
89
84
75
86
87
95
118
98
95
96
87
88
76
110
96
91
99
56
99
98
96
93
109
104
109
97
97
106
99
68
85
111
94
86
107
101
92
86
114
95
98
98

7
10
12
13
8
7
5
17
6
9
11
8
11
6
8
16
11
9
6
14
8
4
7
6
5
27
8
13
11
13
7
14
7
5
9
17
9
11
10
8
10
8
9
13
4
12

MEAN%
(0,1 mg/Kg)

RSD%
(0,1 mg/Kg)

TECHNIQUE

89
102
91
98
80
92
103
100
104
92
103
100
94
94
89
96
85
97
95
103
86
67
95
92
93
88
98
97
109
95
91
95
91
71
98
97
99
99
97
86
89
101
102
94
92
90

3
4
13
5
7
5
7
5
4
10
8
4
12
10
8
6
9
5
5
4
27
3
7
7
7
9
7
16
16
5
9
16
7
2
6
8
5
5
5
7
10
3
10
14
6
13

HPLC/QqQ (MS/MS)
HPLC/QqQ (MS/MS)
GC/QqQ (MS/MS)
HPLC/QqQ (MS/MS)
HPLC/QqQ (MS/MS)
HPLC/QqQ (MS/MS)
HPLC/QqQ (MS/MS)
HPLC/QqQ (MS/MS)
HPLC/QqQ (MS/MS)
GC/QqQ (MS/MS)
HPLC/QqQ (MS/MS)
HPLC/QqQ (MS/MS)
GC/QqQ (MS/MS)
GC/QqQ (MS/MS)
GC/QqQ (MS/MS)
HPLC/QqQ (MS/MS)
GC/QqQ (MS/MS)
HPLC/QqQ (MS/MS)
HPLC/QqQ (MS/MS)
HPLC/QqQ (MS/MS)
GC/QqQ (MS/MS)
GC/QqQ (MS/MS)
GC/QqQ (MS/MS)
GC/QqQ (MS/MS)
GC/QqQ (MS/MS)
HPLC/QqQ (MS/MS)
HPLC/QqQ (MS/MS)
GC/QqQ (MS/MS)
GC/QqQ (MS/MS)
HPLC/QqQ (MS/MS)
GC/QqQ (MS/MS)
GC/QqQ (MS/MS)
GC/QqQ (MS/MS)
GC/QqQ (MS/MS)
HPLC/QqQ (MS/MS)
GC/QQQ (MS/MS)
HPLC/QqQ (MS/MS)
HPLC/QqQ (MS/MS)
HPLC/QqQ (MS/MS)
GC/QqQ (MS/MS)
GC/QqQ (MS/MS)
HPLC/QqQ (MS/MS)
GC/QqQ (MS/MS)
GC/QqQ (MS/MS)
GC/QqQ (MS/MS)
GC/QqQ (MS/MS)

PESTICIDE
FENAZAQUIN
FENBUTATIN OXIDE
FENBUCONAZOLE
FENHEXAMID
FENITROTHION
FENOXYCARB
FENPROPATHRIN
FENPROPIMORPH
FENTHION(RD)
FENTHION SULFOXIDE
FENVALERATE
FIPRONIL(RD)
FLUDIOXONIL
FLUFENOXURON
FLUQUINCONAZOLE
FLUSILAZOLE
FLUTRIAFOL
FOLPET
FORMETANATE(RD)
FOSTHIAZATE
HEXACONAZOLE
HEXYTHIAZOX
IMAZALIL
IMIDACLOPRID
INDOXACARB(RD)
IPRODIONE
IPROVALICARB
KRESOXIM-METHYL
LAMBDA-CYHALOTHRIN(RD)
LINURON
LUFENURON
MALATHION(RD)
MEPANIPYRIM(RD)
METALAXYL(RD)
METCONAZOLE
METHAMIDOPHOS
METHIDATHION
METHIOCARB(RD)
METHOMYL(RD)
METHOXYFENOZIDE
MONOCROTOPHOS
MYCLOBUTANIL
OXADIXYL
OXAMYL
OXYDEMETON-METHYL(RD)
PACLOBUTRAZOLE
PARATHION
PARATHION-METHYL(RD)

MEAN%
RSD%
MEAN%
(0,01 mg/Kg) (0,01 mg/Kg) (0,1 mg/Kg)
89
9
88
78
106
12
100
79
9
94
116
10
103
105
24
98
99
10
96
81
7
99
92
7
90
86
15
92
96
15
93
98
5
91
132
3
96
83
18
110
94
21
99
98
8
93
99
8
102
59
21
65
87
10
95
79
20
114
95
12
96
104
15
97
88
6
97
96
17
100
90
40
113
106
13
94
105
8
99
103
14
107
108
12
96
97
29
99
132
16
110
107
6
100
103
12
95
111
11
94
101
9
95
91
13
89
115
6
101
109
33
104
109
7
106
125
12
99
79
10
98
89
11
91
94
12
88
96
8
96
94
7
97
91
13
100
119
6
101
109
6
100

RSD%
(0,1 mg/Kg)
11
4
5
5
7
8
11
3
8
10
15
11
2
10
7
10
5
13
4
8
4
12
6
6
9
13
4
5
13
6
12
9
12
8
4
6
9
15
5
13
6
11
9
5
4
5
9
7

TECHNIQUE
GC/QqQ (MS/MS)
HPLC/QqQ (MS/MS)
HPLC/QqQ (MS/MS)
HPLC/QqQ (MS/MS)
GC/QqQ (MS/MS)
HPLC/QqQ (MS/MS)
GC/QqQ (MS/MS)
HPLC/QqQ (MS/MS)
GC/QqQ (MS/MS)
HPLC/QqQ (MS/MS)
GC/QqQ (MS/MS)
GC/QqQ (MS/MS)
HPLC/QqQ (MS/MS)
HPLC/QqQ (MS/MS)
HPLC/QqQ (MS/MS)
GC/QqQ (MS/MS)
HPLC/QqQ (MS/MS)
GC/QqQ (MS/MS)
HPLC/QqQ (MS/MS)
HPLC/QqQ (MS/MS)
HPLC/QqQ (MS/MS)
HPLC/QqQ (MS/MS)
HPLC/QqQ (MS/MS)
HPLC/QqQ (MS/MS)
HPLC/QqQ (MS/MS)
GC/QqQ (MS/MS)
HPLC/QqQ (MS/MS)
HPLC/QqQ (MS/MS)
GC/QqQ (MS/MS)
HPLC/QqQ (MS/MS)
HPLC/QqQ (MS/MS)
GC/QqQ (MS/MS)
GC/QqQ (MS/MS)
GC/QqQ (MS/MS)
HPLC/QqQ (MS/MS)
HPLC/QqQ (MS/MS)
GC/QqQ (MS/MS)
HPLC/QqQ (MS/MS)
HPLC/QqQ (MS/MS)
HPLC/QqQ (MS/MS)
HPLC/QqQ (MS/MS)
GC/QqQ (MS/MS)
GC/QqQ (MS/MS)
HPLC/QqQ (MS/MS)
HPLC/QqQ (MS/MS)
HPLC/QqQ (MS/MS)
GC/QqQ (MS/MS)
GC/QqQ (MS/MS)

PESTICIDE
PENCYCURON
PENCONAZOLE
PENDIMETHALIN
PERMETHRIN(RD)
PHENTHOATE
PHOSALONE
PHOSMET(RD)
PYRACLOSTROBIN
PIRIMICARB(RD)
PIRIMIPHOS-METHYL
PROCHLORAZ(RD)
PROCYMIDONE
PROFENOFOS
PROPAMOCARB(RD)
PROPARGITE
PROPICONAZOLE
PROPYZAMIDE
PROTHIOCONAZOLE
PYRIDABEN
PYRIMETHANYL
PYRIPROXYFEN
QUINOXYFEN
SPINOSAD(RD)
SPIROXAMINE
TAUFLUVALINATE
TEBUCONAZOLE
TEBUFENOZIDE
TEBUFENPYRAD
TEFLUBENZURON
TEFLUTHRIN
TETRACONAZOLE
TETRADIFON
THIABENDAZOLE
THIAMETHOXAM(RD)
THIACLOPRID
THIOPHANATE-MEHYIL
TOLCLOFOS-METHYL
TOLYFLUANID(RD)
TRIADIMENOL(RD)
TRIAZOPHOS
TRICHLORFON
TRIFLOXYSTROBIN
TRIFLUMURON
TRIFLURALIN
TRITICONAZOLE
VINCLOZOLIN(RD)
ZOXAMIDE

MEAN%
RSD%
MEAN%
(0,01 mg/Kg) (0,01 mg/Kg) (0,1 mg/Kg)
100
18
101
97
11
97
116
8
96
98
12
93
109
7
99
111
14
99
100
10
99
95
11
110
92
6
94
111
8
94
88
8
95
94
8
93
100
10
97
68
9
69
112
10
104
94
9
91
99
5
96
78
24
33
95
14
92
119
13
95
103
16
95
114
8
87
97
11
98
124
15
80
102
13
96
113
11
95
124
45
97
92
11
94
96
31
103
89
5
89
107
10
91
87
12
90
92
9
93
84
16
101
86
8
105
69
13
104
91
4
97
69
9
72
105
117
7
102
75
19
106
93
13
103
121
92
3
88
104
14
97
97
7
95
79
17
112

10

RSD%
(0,1 mg/Kg)
6
5
8
13
8
14
7
4
7
9
5
8
10
6
7
10
7
12
13
6
13
10
4
15
17
11
13
12
14
7
8
13
8
5
4
6
5
10
29
11
7
7
6
6
5
7
5

TECHNIQUE
HPLC/QqQ (MS/MS)
HPLC/QqQ (MS/MS)
GC/QqQ (MS/MS)
GC/QqQ (MS/MS)
GC/QqQ (MS/MS)
GC/QqQ (MS/MS)
HPLC/QqQ (MS/MS)
HPLC/QqQ (MS/MS)
GC/QqQ (MS/MS)
GC/QqQ (MS/MS)
HPLC/QqQ (MS/MS)
GC/QqQ (MS/MS)
GC/QqQ (MS/MS)
HPLC/QqQ (MS/MS)
HPLC/QqQ (MS/MS)
GC/QqQ (MS/MS)
GC/QqQ (MS/MS)
HPLC/QqQ (MS/MS)
GC/QqQ (MS/MS)
GC/QqQ (MS/MS)
GC/QqQ (MS/MS)
HPLC/QqQ (MS/MS)
HPLC/QqQ (MS/MS)
HPLC/QqQ (MS/MS)
GC/QqQ (MS/MS)
GC/QqQ (MS/MS)
HPLC/QqQ (MS/MS)
GC/QQQ (MS/MS)
HPLC/QqQ (MS/MS)
GC/QqQ (MS/MS)
GC/QqQ (MS/MS)
GC/QqQ (MS/MS)
HPLC/QqQ (MS/MS)
HPLC/QqQ (MS/MS)
HPLC/QqQ (MS/MS)
HPLC/QqQ (MS/MS)
GC/QqQ (MS/MS)
GC/QqQ (MS/MS)
HPLC/QqQ (MS/MS)
GC/QqQ (MS/MS)
HPLC/QqQ (MS/MS)
HPLC/QqQ (MS/MS)
HPLC/QqQ (MS/MS)
GC/QqQ (MS/MS)
HPLC/QqQ (MS/MS)
GC/QqQ (MS/MS)
HPLC/QqQ (MS/MS)

APPENDIX II
MASS TRANSITION FOR HPLC-MS/MS
PESTICIDE

R.T. (min) TRANSITION

ACEPHATE

5.50

184.1 > 143.1

184.1 > 113.2

ACETAMIPRID

8.30

223.1 > 126.2

223.1 > 72.8

ALDICARB

9.20

208.2 > 116.2

208.2 > 89.1

ALDICARB SULFONE

6.70

240.1 > 223.3

240.1 > 86.1

ALDICARB SULFOXIDE

6.50

207.2 > 89.1

207.2 > 132.1

AMITRAZ

13.80

294.1 > 163.2

294.1 > 122.1

6.80

163.1 > 107.1

163.1 > 122.1

8.70

150.2 > 107.1

150.0 > 132.1

AZINPHOS-METHYL

11.10

318.0 > 132.1

318.0 > 105.0

AZOXYSTROBIN

11.30

404.1 > 372.3

404.1 > 344.2

BITERTANOL

12.70

338.2 > 99.1

338.2 > 69.8

BOSCALID

11.60

343.0 > 307.1

343.0 > 140.1

CADUSAFOS

12.90

271.0 > 159.0

271.0 > 131.0

CARBARYL

10.20

202.2 > 145.3

202.2 > 127.0

CARBENDAZIM

6.80

192.1 > 160.2

192.1 > 105.2

CARBOFURAN

9.90

222.0 > 165.1

222.0> 123.0

CARBOFURAN 3OH

8.20

238.0 > 163.2

238.0 > 181.0

CLOTHIANIDIN

7.90

250.0 > 169.1

250.0 > 132.0

CLOFENTEZIN

12.70

303.1 > 138.1

303.1 > 130.1

CYPROCONAZOLE

11.90

292.1 > 69.8

292.1 > 125.0

DMPF
(N-2,4-DIMETHYLPHENYL-NMETHYL.FORMAMIDINE)

DMF
(2,4 DIMETHYLFORMANILIDE)

11

PESTICIDE

R.T. (min) TRANSITION

DICHLORVOS

9.80

221.1 > 127.1

221.1 > 109.2

DIFENOCONAZOLE

12.80

406.1 > 251.1

406.1 > 75.0

DIMETHOATE

8.30

230.1 > 199.1

230.1 > 125.1

DIMETHOMORPH

11.60

388.2 > 301.1

388.2 > 165.2

EPOXICONAZOLE

12.10

330.1 > 121.0

330.1 > 74.9

FENBUCONAZOLE

12.10

337.1 > 125.1

337.1 > 70.1

FENBUTATIN OXIDE

16.00

519.2 > 196.9

519.2 > 120.1

FENHEXAMID

12.00

302.1 > 97.2

302.1 > 55.2

FENOXYCARB

12.20

301.9 > 88.1

301.9 > 116.1

FENPROPIMORPH

10.30

304.0 > 117.0

304.0 > 147.1

FENTION SULFOXIDE

10.10

295.0 > 280.1

295.0 > 109.0

FLUFENOXURON

13.50

488.8 > 158.0

488.8 > 141.0

FLUQUINCONAZOLE

11.90

376.0 > 307.2

376.0 > 108.1

FORMETANATE

6.00

222.3 > 165.5

222.3 > 120.3

FOSTHIAZATE

10.50

284.1 > 104.0

284.1 > 228.2

HEXACONAZOLE

12.60

313.9 > 70.0

313.9 > 159.1

HEXYTHIAZOX

13.50

353.0 > 168.0

353.0 > 228.0

IMAZALIL

9.60

296.9 > 69.2

296.9 > 158.8

IMIDACLOPRID

7.80

255.9 > 208.9

255.9 > 175.0

INDOXACARB

12.80

527.8 > 203.0

527.8 > 217.9

IPROVALICARB

11.90

321.0 > 119.0

321.0 > 90.9

KRESOXIM-METHYL

12.30

314.2 > 131.1

314.2 > 115.8

12

PESTICIDE

R.T. (min) TRANSITION

LINURON

11.50

248.9 > 159.9

248.9 > 132.9

LUFENURON

13.30

510.6 > 141.1

510.6 > 158.2

MALAOXON

10.00

315.0 > 99.0

315.0 > 127.1

METCONAZOLE

12.60

320.1 > 70.1

320.1 > 125.2

METHAMIDOPHOS

3.40

142.0 > 93.9

142.0 > 112.0

METHIOCARB

11.50

225.9 > 169.0

225.9 > 121.1

METHIOCARB SULFONE

8.40

258.0 > 122.0

258.0 > 201.0

METHIOCARB SULFOXIDE

8.00

241.9 > 185.0

241.9 > 122.0

METHOMYL

7.10

163.0 > 88.0

163.0 > 106.0

METHOXYFENOZIDE

11.70

369.2 > 149.0

369.2 > 91.1

MONOCROTOPHOS

7.30

224 .0 > 127.0

224.0 > 193.0

OMETOATE

6.30

213.9 > 125.0

213.9 > 183.0

OXAMYL

6.80

237.0 > 72.1

237.0 > 90.0

OXYDEMETON-METHYL

7.10

263.0 > 169.2

263.0 > 127.2

DEMETON-S-METHYL
SULFONE

7.00

247.1 > 169.1

247.1 > 127.0

PACLOBUTRAZOLE

11.60

294.1 > 70.0

294.1 > 125.0

PARAOXON - METHYL

9.40

248.0 > 202.1

248.0 > 90.1

PENCONAZOLE

12.40

284.0 > 159.2

284.0 > 70.1

PENCYCURON

12.80

329.0 > 125.0

329.0 > 89.0

PHOSMET

11.20

318.0 > 160.2

318.0 > 77.0

PHOSMETOXON

9.30

302.0 > 133.1

302.0 > 160.1

PROCHLORAZ

12.50

375.8 > 307.9

375.8 > 265.9

13

PESTICIDE

R.T. (min) TRANSITION

PROPAMOCARB

6.00

189.2 > 102.2

189.2 > 144.1

PROPARGITE

13.60

368.1 > 175.1

368.1 > 231.2

PROTHIOCONAZOLE

12.60

344.0 > 326.2

344.0 > 125.2

PYRACLOSTROBIN

12.60

387.9 > 194.0

387.9 > 163.0

QUINOXYFEN

13.50

308.0 > 197.0

308.0 > 214.2

SPINOSAD (A)

11.50

732.0 > 142.2

732.0 > 97.6

SPINOSAD (D)

11.70

746.0 > 142.1

746.0 > 98.1

SPIROXAMINE

10.30

298.1 > 144.2

298.1 > 99.9

TEBUFENOZIDE

12.20

353.0 > 132.9

353.0 > 297.0

TEFLUBENZURON

13.30

383.1 > 140.9

383.1 > 158.2

THIABENDAZOLE

7.30

201.9 > 175.0

201.9 > 131.0

THIACLOPRID

8.80

252.9 > 126.0

252.9 > 73.0

THIAMETHOXAM

7.20

291.8 > 211.0

291.8 > 181.0

THIOPHANATE-MEHYIL

9.90

342.9 > 151.1

342.9 > 93.1

TRIADIMEFON

11.80

293.9 > 69.0

293.9 > 197.1

TRICHLORFON

8.30

256.9 > 109.1

256.9 > 127.1

TRIFLOXYSTROBIN

12.80

408.9 > 186.0

408.9 > 145.0

TRIFLUMURON

12.50

359.1 > 156.2

359.1 > 139.0

TRITICONAZOLE

12.00

318.1 > 70.0

318.1 > 125.1

ZOXAMIDE

12.50

336.0 > 187.0

336.0 > 159.0

14

MASS TRANSITION FOR GC-MS/MS

PESTICIDE

R.T. (min)

TRANSITION

ACRINATHRIN

30.72

289 > 93
181 > 152
208 > 181

BIFENTHRIN

28.84

181 > 166

181 > 165
181 > 153

BROMOPROPYLATE

28.62

341 > 185

183 > 155

BUPIRIMATE

24.81

273 > 193

273 > 108

BUPROFEZIN

24.58

172 > 57
105 > 104

CAPTAN

21.23

79 > 77
79 > 51

CHLORFENVINPHOS

20.98 - 21.57

323 > 267

267 > 159

CHLOROTHALONIL

14.78

266 > 231

266 > 168
264 > 168

CHLORPROPHAM

11.04

213 > 171

213 > 127

CHLORPYRIFOS

19.23

197 > 169

197 > 107

CHLORPYRIFOS METHYL

16.59

286 > 271

286 > 93

CYFLUTHRIN

32.2 - 32.5

206 > 151

163 > 127
163 > 91

CYPERMETHRIN

32.69 - 33.02

181 > 152

163 >127
163 > 91

CYPRODINIL

20.57

225 > 224

224 > 208

DELTAMETHRIN

36.00

253 > 93
181 > 152

15

PESTICIDE

R.T. (min)

TRANSITION

DIAZINON

14.47

304 > 179

179 > 137

DICHLOFLUANID

18.41

332 > 167

224 > 123

DICLORAN

12.56

206 > 176

206 > 124
176 > 148

DIPHENYLAMINE

10.52

169 > 77
169 > 115

ENDOSULFAN
(ALPHA ISOMER)

22.64

241 > 206

239 > 204

ENDOSULFAN
(BETA ISOMER)

26.16

241 > 206

239 > 204

ENDOSULFAN SULFATE

26.76

387 > 253

387 > 217

ETHION

26.00

231 > 175

231 > 129

ETHOFENPROX

33.20

163 > 135

163 > 107

FENARIMOL

30.40

251 > 139

139 > 111

FENAZAQUIN

29.08

160 > 145

145 > 115
145 > 91

FENITROTHION

18.07

277 > 125

277 > 109

FENPROPATHRIN

28.99

265 > 210

181 > 152
181 > 127

FENTHION

19.12

278 > 125

278 > 109

FENVALERATE/
ESFENVALERATE

34.68

125 > 99
125 > 89

FIPRONIL

21.81

367 > 228

367 > 213

16

PESTICIDE

R.T. (min)

TRANSITION

FLUSILAZOLE

24.59

233 > 165

233 > 152

FLUVALINATE-TAU

34.70 - 34.85

250 > 200

250 > 55

FOLPET

21.59

147 >103
147 > 76

IPRODIONE

28.39

314 > 245

314 > 56

LAMBDA - CYHALOTHRIN

30.37

181 > 152

163 > 127
163 > 91

MALATHION

18.80

173 > 117

173 > 99

MEPANIPYRIM

23.06

222 > 220

222 > 193

METALAXYL

17.34

206 > 162

206 > 132

METHIDATHION

22.30

145 > 85
145 > 58

MYCLOBUTANIL

24.44

179 > 152

179 > 125

OXADIXYL

25.90

163 > 132

163 > 117

PARATHION

19.27

291 > 109

291 > 81

PARATHION METHYL

16.59

263 > 109

263 > 81

PENDIMETHALIN

20.99

252 > 162

252 > 161

PERMETHRIN

31.37 - 31.55

183 > 168

183 > 153
183 > 115

PHENTHOATE

21.71

274 > 125

274 > 121

PIRIMICARB

15.68

238 > 166

166 > 96

17

PESTICIDE

R.T. (min)

TRANSITION

PIRIMIPHOS METHYL

18.31

305 > 290

290 > 125

PROCYMIDONE

21.96

283 > 96
283 > 67

PROFENOFOS

23.90

337 > 267

208 > 63

PROPICONAZOLE

26.94 - 27.15

259 > 191

259 > 173
259 > 69

PROPYZAMIDE

13.95

173 > 145

173 > 109

PYRIDABEN

31.53

147 > 132

147 > 117

PYRIMETHANIL

14.13

199 > 184

199 > 158

PYRIPROXYFEN

29.86

136 > 96
136 > 78

TEBUCONAZOLE

27.43

252 > 127

250 > 125

TEBUFENPYRAD

29.09

333 > 276

333 > 171

TEFLUTHRIN, CIS-

15.08

197 > 141

177 > 127

TETRACONAZOLE

18.86

336 > 218

336 > 204

TETRADIFON

29.38

356 > 159

354 > 159
229 > 201

TOLCLOFOS METHYL

16.81

265 > 250

265 > 93

TOLYLFLUANID

21.25

137 > 91
137 > 65

TRIAZOPHOS

26.46

161 > 134

161 > 106

TRIFLURALIN

11.64

306 > 264

264 > 206
264 > 160

VINCLOZOLIN

16.63

212 > 172

212 > 145
212 > 109

18