Beruflich Dokumente
Kultur Dokumente
CONTENTS
1.
Introduction __________________________________________________________ 3
2.
3.
Principles_____________________________________________________________ 3
4.
5.
6.
Apparatus____________________________________________________________ 4
7.
Extraction ____________________________________________________________ 4
8.
Determination ________________________________________________________ 4
LC -MS/MS: Instrumentation and settings __________________________________________4
GC-MS/MS: Instrumentation and settings __________________________________________5
9.
Figure1. The analytical flow scheme of the ethyl acetate method ________ 7
10.
11.
Precision-repeatability ________________________________________________ 8
12.
13.
14.
Robustness ___________________________________________________________ 9
15.
References __________________________________________________________11
16.
17.
Acknowledgements _________________________________________________11
18.
19.
20.
21.
1. Introduction
The Swedish National Food Administration has since 1989 employed a multi residue method
that is based on extraction with ethyl acetate followed by LC and GC determination1. The
multi residue method has been revised continuously resulting in an improved and simplified
methodology for analysis of pesticides residues. For example, the need of clean up has
been eliminated entirely and to improve the recovery of basic pesticides the addition of
sodium hydrogen carbonate has been used to all matrices. The use of LC-MS/MS and GCMS/MS has further enhanced the analytical quality and performance. A previous drawback
of the method has been the relatively large sample size (75 g) and the large volume of
extraction solvent (200 ml), which made the sample preparation rather cumbersome and
limiting to the sample throughput. Recent developments of the method enable the use of a
smaller sample size of 10 g following a volume of 20 ml of ethyl acetate. Before extraction in
50 ml Falcon tubes a reduced amount of NaHCO3 and Na2SO4 was added to all matrices.
Furthermore, in improving the analytical step, the chromatographic aspects were taken
into consideration including the use of columns with small particles (1.7 m UPLC column)
resulting in the reduction of analytical time in LC-MS/MS from 30 minutes to 16 minutes.
Finally, the previously employed solvent switch from ethyl acetate to methanol has been
eliminated saving time and reducing the number of analytical steps.
2. Application area/matrices
The method is used for analysis of pesticide residues in fruit and vegetables by means of LCMS/MS and GC-MS/MS detection and has been validated according to SANCO
10684/20092 for three selected commodity groups (see Annex 1) 1) high water content. 2)
high acid content and high water content and 3) high sugar and low water content.
3. Principles
Residues are extracted from food matrix with ethyl acetate. Sodium hydrogen carbonate is
added to well homogenised crop sample which is extracted with ethyl acetate. After
centrifugation and filtration the extract is injected to GC-MS/MS and LC-MS/MS. No clean
up is needed.
For more details see Figure 1 Analytical flow scheme.
4. Limit of Quantification
The Limit of Quantification (LOQ) of the method is 0.01 mg/kg for most of the analytes.
Appendix 3.
6. Apparatus
7. Extraction
1) Weigh 3.0 g sodium hydrogen carbonate (NaHCO3) to 10 0.1g sample in a 50 mL
centrifuge tube
2) Add 10 g sodium sulphate (Na2SO4) and 20 0.1ml ethyl acetate and extract by
shaking (30 sec) and ultrasonication (3 min), max 35C
3) Centrifuge 3 minutes at 3200 g.
4) Filtrate the crude extract through a 0.20 m PTFE filter
5) Inject to GC-MS/MS and LC-MS/MS
For analysis of dried fruits (water content of ca 20%) addition of water is needed before
extraction. Add 750 g cold water (4 C) to 500 g dried fruits and homogenate the sample.
Weigh 25 g sample corresponding 10 g dried fruit and add 20 ml ethyl acetate as
described above.
8. Determination
LC -MS/MS: Instrumentation and settings
Any suitable LC -MS/MS conditions may be used. More detailed information of the LCMS/MS measurement conditions is available in the validation report below.
Instrumentation
Agilent 6410 triple quad LC-MS system
Agilent 1200 HPLC
Proposed settings for mass spectrometry
Cycle time
Total MRMs
Concurrent MRM
Min/Max Dwell
Pressure start
Pressure max
Gas Temp:
500ms
212
60
4.83ms/246.50ms
600bar
880bar
3500C
Gas flow:
Nebulizer:
Sheath Gas Temp:
Sheath Gas Flow:
Capillary:
Nozzle voltage:
5 l/min
45 psi
2500C
11 l/min
3500 V
500 V
Flow Rate
(l/min)
450
450
450
450
450
A
(%)
95
5
5
95
95
B
(%)
5
95
95
5
5
90 C
1.0 min
GC oven ramp:
Rate (C/min)
30.00
5.00
Post-run temperature:
Post-run time:
320 C
10 min
170 C
0.10 min
Centrifugation
in 3 min, (3200 g)
Filtration
Filtrate the crude extract
0.20 m PTFE filter
Mean recovery for all included analytes at 0.05 mg/kg (n=5 per analyte).
Orange
94 %
Raisins 99 %
Leek
99 %
Mean recovery for all analytes in all matrices at 0.05 mg/kg was found to be 97 %, n=15 per
analyte.
11. Precision-repeatability
Detection with LC-MS/MS
Repeatability is expressed as the relative standard deviation (RSD %) on the results from five
replicates for all included analytes.
Orange
Raisin
Leek
RSD calculated for all matrices 9.1 % at 0.01 mg/kg (n=15) and 8.4 % at 0.05 mg/kg (n=15).
Detection med GC-MS/MS
Repeatability is expressed as the relative standard deviation (RSD %) on the results from five
replicates for all included analytes.
Orange
Raisin
Leek
RSD calculated for all matrices is 16 % at 0.01 mg/kg (n=15) and 15 % at 0.05 mg/kg (n=15).
14. Robustness
The proposed method is a multi residue method for different type of pesticides and
matrices. In order to test the robustness of the method the matrix effect was studied. The
matrix effect, expressed as the signal from the standard in matrix compared to the signal in
generic matrix was tested at 0.05 mg/kg. In general, the measured matrix effect is small
(<20% suppression or enhancement of the signal). As shown in Figure 2 and Table 2, only 6%
of analytes in raisin with LC-MS/MS showed matrix effects >20% (suppression of the signal).
Citrus fruits have a well known matrix effect showing 20-50 % suppression for 11% of analytes,
Figure 2 and Table 3.
However, the majority of analytes detected with GC-MS/MS showed a significant
enhancement of the signal in raisin. As a result, 77 % of the analytes had a matrix effect
>20% and 8% of the analytes have matrix effects >50%. However, orange matrix had no
influence on the signal with GC-MS/MS.
Table 2. Analytes with >20 % suppression in raisin extract with LC-MS/MS-detection
Analyte
Atrazindesisopropyl
DMPF
Etofenprox
Fenazakin
Flufenoxuron
Chlorfluasuron
Quinoxyfen
Lufenuron
Paraoxonmethyl
Pyriproxifen
Teflubensuron
Matrixeffect (%)
-22.7
-41.1
-25.0
-28.4
-22.0
-29.2
-21.2
-20.7
-23.3
-21.3
-29.9
Matrixeffect (%)
Atrazin
-22.0
Atrazindesethyl
-41.7
Azoxystrobin
-38.0
Bentazon
-41.4
Cyproconazole
-33.1
Etofumesate
-44.6
Linuron
-48.2
Mekarbam
-23.7
Methoxyfenozide
-23.2
Propetamphos
-38.5
Pyridafention
-41.5
Tepraloxydim
-33.4
Terbuphossulfon
-37.0
Terbuphossulfoxid
-29.3
Tetraconazole
-20.5
Tiachloprid
-23.9
Tiofanatmethyl
-22.0
Triadimefon
-29.3
Triadimenol
-29.2
10
Figure 3. Histogram of matrix effects of all analytes in raisin and orange with GC-MS/MS
detection.
15. References
1. T. Pihlstrm et al.. Anal Bioanal. Chem. (2007) 389:1773-1789
2. Method Validation and Quality Control Procedures for Pesticide Residues Analysis in
Food and Feed (Document No. SANCO/10684/2009)
17. Acknowledgements
We gratefully acknowledge G. Blomkvist, A. Liedgren, U. Pagard, E. Flygh and J. Redeby for
sharing their knowledge and diligence in experimental work.
11
Pesticide
Abamectin
Acefate
Acetamiprid
AcibenzolarSmetyl
Aldicarb
Aldicarbsulfon
Aldicarb-sulfoxid
Aminocarb
Amitraz
Aspon
Atrazin
Atrazindesethyl
Atrazindesisopropyl
Azoxystrobin
Benalaxyl
Bendiocarb
Benfuracarb
Bitertanol
Boscalid
Bupirimate
Buprofezin
Butocarboximsulfoxid
Butokarboxim Na
Butoxycarboxim
Butralin
Carbaryl
Carbendazim
Carbofenothion
Carbofuran
Carbofuran3OH
Carbosulfan
Carfentrazonethyl
Chlorbromuron
CHlorfenvinfos
Clofentezin
Clomazon
Clothianidin
Coumafos
Cyanazin
Rt
min
12.19
2.57
5.6
9.4
6.56
3.21
3.04
5.3
12.2
11.73
8.47
6.13
4.75
9.09
10.52
7.4
11.24
10.57
9.36
10.21
11.36
2.9
6.46
3.15
11.87
7.76
5.71
11.6
7.47
5.51
12.33
10.25
9.38
10.6
10.67
8.91
5.11
10.61
7.15
Precursor
890.6
184.0
223.0
211.0
208.0
223.0
207.0
209.0
294.2
379.1
216.0
188.1
174.0
404.0
326.0
224.0
411.1
338.0
343.3
317.2
306.0
207.0
213.0
223.0
296.2
202.0
192.1
343.0
222.0
238.0
381.1
412.1
295.0
359.0
303.0
240.0
250.0
363.0
241.0
12
Product
DP
CE
Product
CE
305.2
143.0
126.0
136.2
116.0
148.0
132.0
137.0
163.2
114.9
174.1
146.0
68.0
372.0
148.0
109.0
190.2
70.0
307.0
166.1
201.0
132.0
75.0
166.0
240.4
145.0
160.0
157.1
165.0
163.0
160.1
346.0
206.0
154.9
138.0
125.0
169.0
227.1
214.1
150
100
110
130
70
100
100
100
100
100
120
120
110
100
100
100
100
80
100
150
100
100
100
100
100
100
100
80
100
100
130
150
120
100
80
100
90
150
100
20
0
20
30
0
0
0
20
10
35
15
15
28
10
20
15
5
5
15
20
5
5
10
0
5
5
15
5
10
10
10
20
15
5
10
20
5
25
15
567.1
95.0
99.1
91.1
89.1
86.0
89.0
152.0
122.1
210.9
104.1
104.0
104.1
344.0
294.0
167.0
102.0
269.0
139.9
108.0
116.1
75.0
156.0
106.0
222.1
127.0
132.0
199.1
123.0
181.0
118.0
365.8
125.1
98.8
102.0
89.0
132.0
307.1
104.1
10
20
45
15
10
10
8
10
35
15
30
25
20
23
5
5
25
1
20
25
10
10
10
5
20
25
30
5
20
5
20
15
30
30
40
50
15
15
30
Pesticide
Cyazofamid
Cypermethrin
Cyproconazole
Daniphos
Demeton
DemetonSmethylsulfon
DemetonSmethylsulfoxid
DemetonSmetyl
Desmetryn
Dialiphos
Diazinon
Dichlorvos
Dicrotophos
Dietofencarb
Difenamide
Difenoconazole
Dimethoate
Dimetomorf
Disulfoton
Disulfotonsulfon
DMF
DMPF
DMSA
DMST
Epoxiconazole
Ethion
Ethofumesate
Etiofencarb
EtiofencarbsulfonNH3
Etiofencarbsulfoxid
Etofenprox
Etoprophos
Etrimphos
Famoxadon
Fenamifossulfon
Fenamiphossulfoxid
Fenarimol
Fenazaquin
Fenbuconazole
Fenhexamide
Fenmedifam
Fenothrin
Rt
min
9.96
11.89
9.7
10.42
8.95
3.8
3.6
7.52
8.42
10.8
10.52
7.3
4.7
9.2
8.74
10.75
5.48
9.5
10.72
8.27
7.0
4.0
6.78
7.73
10.02
11.41
9.19
7.97
4.7
5.0
12.51
9.97
10.39
10.42
7.75
7.66
9.89
11.8
9.98
9.9
8.94
12.31
Precursor
325.0
433.0
292.2
327.0
259.1
263.0
247.0
230.9
214.1
394.0
305.0
221.0
238.0
268.0
240.0
406.0
230.0
388.0
275.1
307.0
150.0
163.1
201.1.
215.0.
330.1
385.0
287.0
226.0
275.0
242.2
394.0
243.1
293.1
392.2
336.1
337.2
331.0
307.0
337.0
302.0
318.1
351.1
13
Product
DP
CE
Product
CE
108.0
191.0
70.0
157.0
89.0
169.0
169.0
89.0
172.0
208.0
169.0
108.9
112.0
225.9
134.0
251.0
125.0
165.0
89.0
97.0
107.2
107.1
92.1
106.0.
121.1
199.0
121.0
107.0
107.0
107.0
177.0
130.9
124.9
331.0
266.0
320.1
268.2
57.0
70.0
96.9
168.2
183.1
90
70
120
90
70
120
90
70
120
100
150
135
100
100
100
150
70
130
60
100
120
120
100
100
130
100
130
100
80
80
100
100
100
80
100
80
150
120
150
100
100
110
10
10
15
5
10
10
10
0
15
10
20
12
5
5
20
25
20
30
15
30
20
20
15
10
25
5
10
10
15
15
10
15
25
5
15
5
20
25
15
25
5
15
261.0
193.0
125.0
121.2
61.0
125.0
109.0
61.0
82.0
187.0
153.0
79.1
127.0
124.0
167.0
337.0
199.0
301.0
60.9
125.0
106.2
122.2
137.1
151.2
100.9
143.0
259.0
77.05
201.0
185.0
359.0
173.0
264.9
238.0
308.0
171.1
81.1
161.1
125.0
55.0
301.1
333.4
5
10
30
35
40
20
25
30
35
5
20
24
15
35
20
15
5
20
45
10
35
15
5
5
50
20
5
50
5
5
5
10
10
10
10
20
30
15
40
30
5
5
Pesticide
Fenoxycarb
Fenpiclonil
Fenpropimorf
Fenpyroximate
Fensulfothionoxon
Fensulfothionoxonsulfon
Fensulfothionsulfon
Fenthion
Fenthion-oxon
Fenthion-oxon-sulfone
Fenthion-oxon-sulfoxide
Fenthionsulfon
Fenthionsulfoxid
FluazifopPbutyl
Flucytrinate
Fludioxonil
Flumetralin
Fluquinkonazole
Flusilazole
Fonophos
Furalaxyl
Furathiocarb
Haloxyfop
Haloxyfop2etoxyethyl
HaloxyfopRmetyl_
Heptenophos
Hexaconazole
Hexazinon
Hexythiasox
Imazalile
Imidacloprid
Indoxacarb
Iprovalicarb
Isocarbofos
Isofenfosmetyl
Isofenphos
Isoprocarb
Isopropalin
Isoproturon
Isoxaben
Kresoximmetyl
Linuron
Rt
min
10.07
8.9
11.24
11.78
6.6
6.8
8.69
10.42
8.93
5.91
5.7
7.99
7.68
11.13
11.59
9.32
11.77
9.86
10.05
10.51
9.19
11.26
9.5
11.12
10.82
8.65
10.49
7.58
11.52
9.36
5.03
10.78
9.81
8.56
10.35
10.71
8.3
11.91
8.54
9.39
10.3
9.11
Precursor
302.0
254.0
305.0
422.2
293.1
309.0
325.1
279 .0
263.1
295.1
279.1
311.0
295.0
384.0
469.2
266.0
422.0
376.0
316.0
247.0
302.2
383.0
362.0
434.0
376.0
251.0
314.0
253.0
353.0
297.0
256.1
528.0
321.0
312.1
332.1
346.1
194.0
310.3
207.1
333.1
314.0
248.9
14
Product
DP
CE
Product
CE
88.0
202.0
147.3
366.2
236.9
253.0
268.9
168.9
231.3
217.2
264.2
125.0
280.0
282.0
412.3
158.0
143.0
307.1
247.0
109.1
94.9
195.0
316.2
91.0
316.0
126.9
70.1
171.1
228.0
201.0
175.1
150.0
119.0
270.0
231.1
244.8
95.0
226.1
72.1
165.1
116.0
181.9
90
80
150
130
100
100
100
120
140
150
130
150
140
120
120
90
100
100
120
70
100
90
130
100
120
100
130
120
120
140
100
120
80
120
80
70
100
120
100
100
90
110
15
25
30
10
15
10
10
15
10
15
15
20
15
20
5
35
35
25
15
15
25
15
15
40
15
10
20
10
10
12
15
20
15
10
5
5
10
15
20
15
10
10
116.0
140.1
117.2
135.0
265.0
174.9
297.0
247.0
216.1
78.1
104.2
109.1.
109.0
328.0
199.4
185.1
5
50
50
30
10
20
5
5
20
40
25
25
30
15
15
20
349.1
165.0
137.1
242.2
252.0
288.2
316.0
288.0
124.9
159.1
71.1
168.0
159.0
209.0
203.0
203.0
236.0
273.1
286.8
152.0
206.1
165.2
107.0
267.0
160.1
15
25
5
10
5
30
15
25
10
40
35
20
20
10
40
5
10
5
5
5
15
10
50
0
15
Pesticide
Malathion
MalathionOanalog
Mecarbam
Mepanipyrim
Mephosfolan
Metabenztiazuron
Metaflumizone
Metalaxyl
Metamidophos
Metconazole
Methomyl
Methoxyfenozide
Metidathion
Metiocarb
Metiocarbsulfon
Metiokarbsulfoxid
Monocrotophos
Myclobutanil
Napropamid
Omethoate
Oxamyl
Oxamyloxim
Oxydisulfoton
Paclobutrazole
Paraoxon
Paraoxonmethyl
Penconazole
Pencycuron
Phorate
PhorateOanalogue
Phoratesulfon
Phoratesulfoxid
Phosfamidon
Phoxim
Piperonylbutoxid
Pirimicarb
Pirimicarb desmethyl
Prochloraz
Promecarb
Propamocarb
Propaquizafop
Propetamphos
Rt
min
9.43
7.64
9.91
9.78
7.38
8.42
11.23
8.65
2.15
10.3
3.41
9.62
8.8
9.2
5.91
5.45
4.0
9.62
9.89
2.87
3.29
2.89
8.24
9.51
8.35
6.85
10.36
10.72
10.59
8.92
8.3
8.24
7.06
10.5
11.37
8.2
6.7
10.66
9.33
3.0
11.27
9.57
Precursor
331.0
315.0
330.0
224.0
270.0
222.0
507.2
280.1
142.0
320.2
163.1
369.3
303.0
226.0
258.1
242.0
224.0
289.0
272.0
214.0
237.0
163.1
291.0
294.2
276.0
248.0
284.0
329.2
261.1
245.1
293.0
277.0
300.0
299.1
356.2
239.1
225.2
376.0
208.0
189.0
444.1
282.1
15
Product
DP
CE
Product
CE
127.0
99.0
227.0
77.0
139.9
165.0
178.2
220.0
94.0
70.1
88.1
149.1
145.0
121.0
122.2
185.2
127.0
70.0
129.0
125.0
72.0
72.1
185.0
70.1
220.0
202.0
70.1
125.0
75.1
75.0
171.0
143.0
127.0
77.1
149.0
72.1
72.1
308.0
109.0
101.9
100.0
138.1
110
100
90
120
100
90
140
100
100
140
70
90
100
100
130
100
100
120
100
90
80
80
70
130
110
120
120
140
50
70
100
80
130
110
100
110
100
100
100
110
100
100
5
20
5
45
20
10
24
10
10
25
4
10
0
15
15
5
10
15
10
16
10
5
5
15
10
15
15
25
5
5
5
15
15
35
35
20
20
5
10
15
15
10
284.8
127.0
199.0
106.0
196.0
150.0
116.2
191.9
125.0
43.2
106.0
313.3
85.0
169.0
201.2
122.2
193.0
125.0
171.0
183.0
90.0
90.0
157.0
125.1
174.0
90.0
159.0
218.0
46.9
47.0
247.0
199.0
174.0
129.2
147.0
182.1
168.2
266.0
151.0
73.9
370.9
156.0
5
5
10
25
10
35
50
15
10
50
4
0
15
5
0
30
0
40
15
4
5
15
20
40
20
25
30
15
45
35
0
5
10
5
30
10
10
10
5
25
10
5
Pesticide
Propiconazole
Propoxur
Prosulfocarb
Prothioconazoledesthio
Pymetrozine
Pyraclostrobin
Pyrazophos
Pyridafenthion
Pyrifenox
Pyriproxifen
Quinoxyfen
QuisalofopEtyl
Simazin
SpinosynA
SpinosynD
Spiroxamin
Sulfentrazon
Taufluvalinate
Tebuconazole
Tebufenozide
Tebufenpyrad
TEPP
Tepraloxydim
Terbuphos
Terbuphosoxon
Terbuphosoxonsulfon
Terbuphosoxonsulfoxid
Terbuphossulfon
Terbuphossulfoxid
Terbuthylazine
Terbutryn
Tetrachlorvinphos
Tetraconazole
Thiabendazole
Thiachloprid
Thiametoxam
Thiodicarb
Thiofanatmethyl
Thiometon
Thiometonsulfon
Thiometonsulfoxid
Triadimefon
Rt
min
10.51
7.46
11.1
10.1
3.8
10.6
10.67
9.58
9.9
11.46
11.52
11.14
7.47
11.02
11.34
9.35
7.77
12.13
10.39
10.16
11.28
7.05
9.56
11.3
9.95
7.21
6.9
9.06
9.15
9.42
10.0
10.25
9.88
6.63
6.18
4.0
8.18
7.47
8.33
6.93
6.75
9.62
Precursor
342.1
210.0
252.0
312.1
218.0
388.0
374.0
341.1
295.1
322.1
308.0
373.1
202.1
732.4
746.0
298.0
386.9
503.1
308.2
353.0
334.0
291.0
342.1
289.1
273.1
305.1
289.0
321.0
305.0
230.2
242.0
364.9
372.0
202.0
253.0
292.0
355.0
343.1
247.0
279.0
263.0
294.0
16
Product
DP
CE
Product
CE
159.2
111.0
91.1
125.2
105.0
194.1
222.0
189.1
93.2
95.9
197.0
299.0
124.0
142.0
142.0
144.0
306.9
208.1
70.1
133.0
145.0
178.9
250.1
57.1
57.1
203.1
171.1
171.0
187.0
174.0
186.0
127.1
159.1
175.0
126.0
211.0
88.0
151.1
89.1
143.1
157.1
197.0
140
80
100
140
120
100
100
100
130
100
120
120
100
150
140
130
150
100
140
90
130
100
100
70
80
130
90
100
80
120
120
130
100
100
90
90
90
100
60
120
80
80
25
10
25
40
20
5
20
20
20
10
35
15
15
30
30
20
20
5
20
15
25
15
5
20
15
10
5
5
5
15
15
10
25
24
20
10
10
15
5
5
10
10
69.0
168.0
128.1
89.1
78.12
163.0
194.0
205.0
263.2
227.0
272.0
271.0
131.9
98.0
98.0
100.0
308.9
181.1
124.9
297.0
117.0
235.0
166.1
103.1
103.1
99.1
115.1
114.9
131.0
68.0
91.0
239.0
70.2
131.0
99.0
210.1
108.0
311.2
61.0
125.1
185.1
225.2
20
5
5
76
48
20
35
20
15
10
30
25
15
50
55
30
20
20
35
0
40
5
15
5
5
20
25
25
25
40
25
15
20
35
50
5
10
5
40
15
5
5
Pesticide
Triadimenol
Triamiphos
Triazamate
Trichlorfon
Trifloxystrobin
Triflumeron
Trimethacarb -2,3,5
Trimethacarb- 3,4,5
Trithiconazole
Vamidothion
Vamidothionsulfon
Vamidothionsulfoxid
Zoxamide
Rt
min
9.74
8.57
9.97
5.4
10.85
10.65
8.58
8.58
9.97
5.5
4.0
3.7
10.58
Precursor
296.0
295.2
315.1
257.0
409.2
359.0
194.0
194.1
318.2
288.2
320.1
304.0
336.1
17
Product
DP
CE
Product
CE
70.0
135.2
72.1
109.2
186.0
156.1
137.0
137.0
70.1
146.1
178.1
169.1
187.1
80
130
90
120
100
100
100
100
110
90
130
90
120
10
20
20
15
15
10
5
5
15
5
10
10
20
43.0
92.1
226.3
221.0
206.1
139.1
122.0
122.0
125.2
118.0
169.0
201.1
159.1
35
45
5
10
10
40
25
25
40
20
15
5
45
Rt
min
Bentazon
2.01
Diflubensuron
Precursor
Product
DP
CE
Product
CE
239.1
197.1
140
15
175.2
15
5.40
309.1
289.0
100
156.1
Dinocap
5.40
295.1
209.2
150
25
193.1
25
Dinoseb
3.80
239.1
193.1
140
20
194.1
15
Dinoterb
4.10
239.1
207.0
150
20
177.0
30
DNOC
2.30
197.1
180.1
120
15
137.0
15
Flufenoxuron
6.73
487.1
156.2
140
10
304.2
15
Hexaflumuron
5.94
460.1
440.2
90
276.2
15
Chlorfluasuron
7.03
538.0
518.1
110
355.0
20
Lufenuron
6.38
509.0
339.1
110
326.1
15
Teflubensuron
6.44
379.1
339.0
90
359.1
18
Pesticide
Rt
min
m/z
quant
Aclonifen
17.73
193.8
Acrinathrin 2
21.20
152.0
Acrinatrin 2
21.47
152.0
Aldrin
12.05
193.0
Azinphos-ethyl
21.95
77.0
Azinphos-methyl
20.86
77.0
Beta-cyfluthrin 1
24.45
91.0
Beta-cyfluthrin 2
24.66
91.0
Beta-cyfluthrin 3
24.66
91.0
Beta-cyfluthrin 4
24.86
91.0
Bifenthrin
19.31
165.0
Binapacryl
15.54
55.0
Biphenyl
5.30
153.1
Bromophos
12.54
316.0
Bromophos-ethyl
13.80
303.0
Bromopropylate
19.48
157.0
Bromuconazole I
19.34
145.0
Bromuconazole II
20.14
145.0
Cadusaphos
7.89
96.9
Captafol
19.92
77.0
Captan
13.57
105.0
Chlorbensilate
16.12
139.0
Chlordan-alpha
14.41
237.0
Chlordan-gamma
13.99
266.0
Chlordimeform
7.66
117.0
Chlorfenapyr
15.57
31.0
Chlorfenson
14.76
111.0
Chlormefos
5.61
121.0
Chlorprofam
7.59
65.0
Chlorpropylate
16.12
139.0
Chlorpyriphos
11.81
258.0
Chlorpyriphos-methyl
10.49
93.0
Chlorpyriphos-O-analogue
11.62
123.0
19
Pesticide
Rt
min
m/z
quant
Chlortaldimetyl
12.00
221.0
Chlorthalonil
9.55
231.0
Chlozolinate
13.51
145.0
Cyanofenphos
17.45
141.0
Cyanophos
9.08
109.0
Cyfluthrin 1
23.82
91.0
Cyfluthrin 2
24.02
91.0
Cyfluthrin 3
24.13
91.0
Cyfluthrin 4
24.22
91.0
Cyprodinil
12.92
208.0
DEET
6.78
91.0
Deltamethrin 1
27.92
152.0
Deltamethrin 2
28.50
152.0
Dichlofluanid
11.63
123.0
224.0>123.0 [-12.0V]
Dichloran
8.61
176.0
Dichloranilin-3.5
5.45
99.0
Dichlorbenzofenon-o.p
11.44
111.0
Diclobenil
5.03
136.0
Diclobenzofenon-p.p
12.39
111.0
Dicofol-o.p
19.47
139.0
Dieldrin
15.32
193.0
Dinobuton
13.21
117.0
Dioxathion 2
23.11
97.0
Dioxathion I
8.95
97.0
Diphenylamine
7.39
167.0
Endosulfan-alpha
14.43
206.0
Endosulfan-beta
16.42
206.0
Endosulfan-sulfate
17.71
237.0
Endrin
16.43
243.0
EPN
19.48
141.0
Esfenvalerate 1
26.42
89.0
Esfenvalerate 2
26.95
89.0
Fenamiphos
14.49
195.0
Fenitrothion
11.38
109.0
Fenchlorphos
10.97
270.0
Fenpropathrin
19.71
152.0
Fenson
12.60
77.0
20
Pesticide
Rt
min
m/z
quant
Fensulfothion
16.40
97.0
Fenthoate
13.33
125.0
Fenvalerate 2
26.95
89.0
Fenvalerate 1
26.42
89.0
Fluacrypyrim
16.60
189.0
Fluazinam
12.65
372.0
Flutriafol
14.52
123.0
Folpet
13.77
130.0
Formothion
10.09
93.0
Ftalimid
5.95
76.0
HCH-alpha
8.29
145.0
HCH-beta
9.10
145.0
HCH-delta
9.84
145.0
HCH-gamma
9.09
183.0
Heptachlorepoxide
13.38
119.0
Heptachlor
10.98
237.0
Hexachlorbensen
8.41
249.0
Iodofenphos
14.71
362.0
Iprodione
19.15
245.0
Chinomethionate
14.13
148.0
Lambda-cyhalothrin
21.20
152.0
Leptophos
20.69
362.0
Methoxychlor
19.70
115.0
Metribuzin
10.53
82.0
Mevinphos
5.42
127.0
Nitrofen
15.94
162.0
Ortofenylphenol
6.40
141.0
Oxadixyl
16.49
132.0
Parathion
12.07
109.0
Parathion-methyl
10.69
109.0
Pendimethanil
12.85
162.0
Pentachloraniline
10.28
192.0
Pentachloranisole
8.49
237.0
Pentachlorbensen
6.42
212.9
Permethrin 1
22.78
153.0
Permethrin 2
23.03
153.0
Phosalone
20.65
111.0
21
Pesticide
Rt
min
m/z
quant
Phosmet
19.43
133.0
Phosmet-O-analogue
17.78
77.0
Phosthiazate I
12.60
103.0
Phosthiazate II
12.68
103.0
Pirimiphos-ethyl
12.37
166.0
Pirimiphos-methyl
11.20
125.0
pp-DDD
16.52
165.0
pp-DDD/op-DDT
16.52
165.0
pp-DDE
15.08
176.0
pp-DDT
17.79
165.0
235.0>165.0 [-23.0V]
pp-Dicofol
19.88
111.0
Procymidone
13.51
96.0
Profam
5.73
93.0
Profenophos
14.91
267.0
Propargite 1
18.22
107.0
Propargite 2
18.28
107.0
Propyzamide
9.11
145.0
Prothiophos
14.75
239.0
Pyrachlofos
22.18
138.0
Pyridaben
23.09
119.1
Pyrimethanil
9.35
198.0
Quinalphos
13.38
118.0
Quintozene
8.97
237.0
Sulfotep
7.67
146.0
TCNB-2,3,4,5
7.78
178.9
Tecnazene
7.07
179.0
Tefluthrin
9.33
127.0
Tetrachloraniline (2,3,5,6-TCA)
7.47
158.0
Tetradifon
20.50
199.0
Tetrahydroftalimid
6.13
79.1
Tetrasul
17.00
182.0
Thionazin
7.03
106.1
Tolclofos-methyl
10.71
93.0
Tolylfluanid
13.16
137.0
Triazophos
17.00
77.0
Tribromanisole
7.40
301.0
Trichloronate
12.35
269.0
22
Pesticide
Rt
min
m/z
quant
Trichlorphenol
5.10
132.0
Triflumizole
13.49
179.0
Vinclozolin
10.56
124.0
23
24
Detection
LOQ (mg/kg)
LC-MSMS
LC-MSMS
LC-MSMS
LC-MSMS
GC-MSMS
GC-MSMS
LC-MSMS
LC-MSMS
LC-MSMS
LC-MSMS
LC-MSMS
LC-MSMS
LC-MSMS
LC-MSMS
LC-MSMS
GC-MSMS
GC-MSMS
LC-MSMS
LC-MSMS
LC-MSMS
LC-MSMS
LC-MSMS(-)
GC-MSMS
GC-MSMS
GC-MSMS
LC-MSMS
LC-MSMS
GC-MSMS
GC-MSMS
GC-MSMS
GC-MSMS
GC-MSMS
LC-MSMS
LC-MSMS
LC-MSMS
LC-MSMS
LC-MSMS
LC-MSMS
GC-MSMS
GC-MSMS/GC-ECD
GC-MSMS/GC-ECD
LC-MSMS
LC-MSMS
0.05
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.05
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.05
0.05
0.01
0.01
Pesticide
Carbofuran
Carbofuran-3OH
Carbophenothion
Carbosulfan
Carfentrazone-ethyl
Chinomethionat
Chlordane, cisChlordane, transChlordimeform
Chlorfenapyr
Chlorfenson
Chlorfenvinphos
Chlorfluazuron
Chlormephos
Chlorobenzilate
Chlorobromuron
Chloropropylate
Chlorothalonil
Chlorpropham
Chlorpyrifos
Chlorpyrifos-methyl
Chlorpyrifos-O-Analogue
Chlorthal-dimethyl
Chlozolinate
Clofentezine
Clomazone
Clothianidin
Coumaphos
Cyanazin
Cyanofenfos
Cyanofos
Cyazofamid
Cyfluthrin (sum)
Cyfluthrin, beta- (sum)
Cypermethrin
Cyproconazole
Cyprodinil
Danifos
DDD, p,p-/DDT, o,pDDE, p,pDDT, p,pDEET
Deltamethrin 1
Deltamethrin 2
Demeton
Demeton-S-methyl
Demeton-S-methyl-sulfone
25
Detection
LOQ (mg/kg)
LC-MSMS
LC-MSMS
LC-MSMS
LC-MSMS
LC-MSMS
GC-MSMS
GC-MSMS
GC-MSMS
GC-MSMS
GC-MSMS
GC-MSMS
LC-MSMS
LC-MSMS(-)
GC-MSMS
GC-MSMS
LC-MSMS
GC-MSMS
GC-MSMS
GC-MSMS
GC-MSMS
GC-MSMS
GC-MSMS
GC-MSMS
GC-MSMS
LC-MSMS
LC-MSMS
LC-MSMS
LC-MSMS
LC-MSMS
GC-MSMS
GC-MSMS
LC-MSMS
GC-MSMS
GC-MSMS
LC-MSMS
LC-MSMS
GC-MSMS
LC-MSMS
GC-MSMS/GC-ECD
GC-MSMS/GC-ECD
GC-MSMS/GC-ECD
GC-MSMS
GC-MSMS
GC-MSMS
LC-MSMS
LC-MSMS
LC-MSMS
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
Pesticide
Demeton-S-methyl-sulfoxid
Desmethyl pirimicarb
Desmetryn
Dialifos
Diazinon
Dichlobenil
Dichlofluanid
Dichloroaniline, 3,5Dichlorobenzophenone, 2,4`Dichlorobenzophenone, 4,4`Dichlorvos
Dicloran
Dicofol
Dicrotophos
Dieldrin
Diethofencarb
Difenoconazole
Diflubenzuron
Dimethoate
Dimethomorph
Dinobuton
Dinocap
Dinoseb
Dinoterb
Dioxathion 1
Dioxathion 2
Diphenamid
Diphenylamine
Disulfoton
Disulfoton-Sulfon
Disulfoton-sulfoxid
DMF
DMPF
DMSA
DMST
DNOC
Endosulfan, alphaEndosulfan, betaEndosulfansulfate
Endrin
EPN
Epoxiconazole
Esfenvalerate
Ethiofencarb
Ethiofencarb-sulfone NH3-add
Ethiofencarb-sulfoxid
Ethion
26
Detection
LOQ (mg/kg)
LC-MSMS
LC-MSMS
LC-MSMS
LC-MSMS
LC-MSMS
GC-MSMS
GC-MSMS
GC-MSMS
GC-MSMS
GC-MSMS
LC-MSMS
GC-MSMS
GC-MSMS/GC-ECD
LC-MSMS
GC-MSMS
LC-MSMS
LC-MSMS
LC-MSMS(-)
LC-MSMS
LC-MSMS
GC-MSMS
LC-MSMS(-)
LC-MSMS(-)
LC-MSMS(-)
GC-MSMS
GC-MSMS
LC-MSMS
GC-MSMS
LC-MSMS
LC-MSMS
LC-MSMS
LC-MSMS
LC-MSMS
LC-MSMS
LC-MSMS
LC-MSMS(-)
GC-MSMS
GC-MSMS
GC-MSMS
GC-MSMS
GC-MSMS
LC-MSMS
GC-MSMS
LC-MSMS
LC-MSMS
LC-MSMS
LC-MSMS
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.05
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
Pesticide
Ethofumesate
Ethoprophos
Etofenprox
Etrimfos
Famoxadone
Fenamiphos
Fenamiphos-Sulfon
Fenamiphos-Sulfoxid
Fenarimol
Fenazaquin
Fenbuconazole
Fenchlorphos
Fenhexamid
Fenitrothion
Fenoxycarb
Fenpiclonil
Fenpropathrin
Fenpropimorph
Fenpyroximate
Fenson
Fensulfothion
Fensulfothion-oxon
Fensulfothion-oxon-sulfone
Fensulfothion-sulfone
Fenthion
Fenthion-oxon
Fenthion-oxon-sulfone
Fenthion-oxon-sulfoxide
Fenthion-sulfon
Fenthion-sulfoxid
Fenvalerate 1
Fenvalerate 2
Fipronil
Fluacrypyrim
Fluazifop-P-butyl
Fluazinam
Flucythrinate
Fludioxinil
Fludioxonil
Flufenoxuron
Flumetralin
Fluquinconazole
Flusilazole
Flutriafol
Folpet
Fonofos
Formothion
27
Detection
LOQ (mg/kg)
LC-MSMS
LC-MSMS
LC-MSMS
LC-MSMS
LC-MSMS
GC-MSMS
LC-MSMS
LC-MSMS
LC-MSMS
LC-MSMS
LC-MSMS
GC-MSMS
LC-MSMS
GC-MSMS
LC-MSMS
LC-MSMS
GC-MSMS
LC-MSMS
LC-MSMS
GC-MSMS
GC-MSMS
LC-MSMS
LC-MSMS
LC-MSMS
LC-MSMS
LC-MSMS
LC-MSMS
LC-MSMS
LC-MSMS
LC-MSMS
GC-MSMS
GC-MSMS
GC-MSMS
GC-MSMS
LC-MSMS
GC-MSMS
LC-MSMS
LC-MSMS(-)
LC-MSMS
LC-MSMS(-)
LC-MSMS
LC-MSMS
LC-MSMS
GC-MSMS
GC-MSMS/GC-ECD
LC-MSMS
GC-MSMS
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.05
0.01
0.01
Pesticide
Fosthiazate 1+2
Ftalimid
Furalaxyl
Furathiocarb
Haloxyfop
Haloxyfop-Ethoxyethylester
Haloxyfop-Methyl
HCH, alphaHCH, betaHCH, deltaHCH, gammaHeptachlor
Heptachlor epoxide
Heptenophos
Hexachlorobenzene
Hexaconazole
Hexaflumuron
Hexazinone
Hexythiazox
Imazalil
Imidacloprid
Indoxacarb
Iprodione
Iprovalicarb
Isofenphos
Isofenphos-methyl
Isoprocarb
Isopropalin
Isoproturon
Isoxaben
Jodfenphos
Kresoxim-methyl
Kvinoxyfen
Lambda-Cyhalothrin 2
Leptophos
Linuron
Lufenuron
Malaoxon
Malathion
Mecarbam
Mepanipyrim
Mephosfolan
Metaflumizone
Metalaxyl
Metconazole
Methabenzthiazuron
Methamidophos
28
Detection
LOQ (mg/kg)
GC-MSMS
GC-MSMS
LC-MSMS
LC-MSMS
LC-MSMS
LC-MSMS
LC-MSMS
GC-MSMS
GC-MSMS
GC-MSMS
GC-MSMS
GC-MSMS
GC-MSMS
LC-MSMS
GC-MSMS
LC-MSMS
LC-MSMS(-)
LC-MSMS
LC-MSMS
LC-MSMS
LC-MSMS
LC-MSMS
GC-MSMS
LC-MSMS
LC-MSMS
LC-MSMS
LC-MSMS
LC-MSMS
LC-MSMS
LC-MSMS
GC-MSMS
LC-MSMS
LC-MSMS
GC-MSMS
GC-MSMS
LC-MSMS
LC-MSMS(-)
LC-MSMS
LC-MSMS
LC-MSMS
LC-MSMS
LC-MSMS
LC-MSMS
LC-MSMS
LC-MSMS
LC-MSMS
LC-MSMS
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
Pesticide
Detection
LOQ (mg/kg)
Methiocarb
Methiocarb-sulfon
Methiocarb-sulfoxid
Methomyl
Methoxychlor
Methoxyfenozide
Metidathion
Metribuzin
Mevinphos
Monocrotophos
Myclobutanil
Napropamide
Nitrofen
Omethoate
Orthophenylphenol
Oxadixyl
Oxamyl
Oxamyl-Oxime
Paclobutrazol
Paraoxon
Paraoxon-Methyl
Parathion
Parathion-methyl
Penconazole
Pencycuron
Pendimethalin
Pentachloroaniline
Pentachloroanisole
Pentachlorobenzene
Permethrin
Phenmedipham
Phenothrin
Phenthoate
Phorate
Phorate-O-Analogue
Phorate-Sulfon
Phorate-Sulfoxid
Phosalone
Phosmet
Phosmet oxon
Phosphamidon
Phoxim
Piperonyl Butoxide
Pirimicarb
Pirimiphos-Ethyl
Pirimiphos-methyl
Prochloraz
LC-MSMS
LC-MSMS
LC-MSMS
LC-MSMS
GC-MSMS
LC-MSMS
LC-MSMS
GC-MSMS
GC-MSMS
LC-MSMS
LC-MSMS
LC-MSMS
GC-MSMS
LC-MSMS
GC-MSMS
GC-MSMS
LC-MSMS
LC-MSMS
LC-MSMS
LC-MSMS
LC-MSMS
GC-MSMS
GC-MSMS
LC-MSMS
LC-MSMS
GC-MSMS
GC-MSMS
GC-MSMS
GC-MSMS
GC-MSMS
LC-MSMS
LC-MSMS
GC-MSMS
LC-MSMS
LC-MSMS
LC-MSMS
LC-MSMS
GC-MSMS
GC-MSMS
GC-MSMS
LC-MSMS
LC-MSMS
LC-MSMS
LC-MSMS
GC-MSMS
GC-MSMS
LC-MSMS
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.05
0.01
0.01
0.01
0.01
0.01
0.01
0.01
29
Pesticide
Procymidone
Profenofos
Promecarb
Propamocarb
Propaquizafop
Propargite (1+2)
Propetamphos
Propham
Propiconazole
Propoxur
Propyzamide
Prosulfocarb
Prothioconazole-desthio
Prothiofos
Pymetrozine
Pyraclofos
Pyraclostrobin
Pyrazophos
Pyridaben
Pyridaphenthion
Pyrifenox
Pyrimethanil
Pyriproxyfen
Quinalphos
Quintozene
Quizalofop
Simazine
Spinosyn A
Spinosyn D
Spiroxamine
Sulfentrazone
Sulfotep
tau-Fluvalinate
TCNB, 2,3,4,5Tebuconazole
Tebufenozide
Tebufenpyrad
Tecnazene
Teflubenzuron
Tefluthrin
TEPP
Tepraloxydim
Terbufos
Terbufos Sulfone
Terbufos Sulfoxide
Terbufos-O-sulfone
Terbufos-oxon
30
Detection
LOQ (mg/kg)
GC-MSMS
GC-MSMS
LC-MSMS
LC-MSMS
LC-MSMS
GC-MSMS
LC-MSMS
GC-MSMS
LC-MSMS
LC-MSMS
GC-MSMS
LC-MSMS
LC-MSMS
GC-MSMS
LC-MSMS
GC-MSMS
LC-MSMS
LC-MSMS
GC-MSMS
LC-MSMS
LC-MSMS
GC-MSMS
LC-MSMS
GC-MSMS
GC-MSMS
LC-MSMS
LC-MSMS
LC-MSMS
LC-MSMS
LC-MSMS
LC-MSMS
GC-MSMS
LC-MSMS
GC-MSMS
LC-MSMS
LC-MSMS
LC-MSMS
GC-MSMS
LC-MSMS(-)
GC-MSMS
LC-MSMS
LC-MSMS
LC-MSMS
LC-MSMS
LC-MSMS
LC-MSMS
LC-MSMS
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
Pesticide
Terbufos-oxon-sulphoxid
Terbuthylazine
Terbutryn
Tetrachloranilin, 2,3,5,6Tetrachlorvinphos
Tetraconazole
Tetradifon
Tetrahydroftalimid
Tetrasul
Thiabendazole
Thiacloprid
Thiametoxam
Thiodicarb
Thiometon
Thiometon-sulfone
Thiometon-sulfoxide
Thionazin
Thiophanate-methyl
Tolclofos-methyl
Tolylfluanid
Triadimefon
Triadimenol
Triamiphos
Triazamate
Triazofos
Tribromoanisole, 2,4,6Trichlorfon
Trichloronat
Trichlorophenol, 2,4,6Trifloxystrobin
Triflumizole
Triflumuron
Trimethacarb, 2,3,5Triticonazole
Vamidothion
Vamidothion-sulfoxide
Vinclozolin
Zoxamide
31
Detection
LOQ (mg/kg)
LC-MSMS
LC-MSMS
LC-MSMS
GC-MSMS
LC-MSMS
LC-MSMS
GC-MSMS
GC-MSMS
GC-MSMS
LC-MSMS
LC-MSMS
LC-MSMS
LC-MSMS
LC-MSMS
LC-MSMS
LC-MSMS
GC-MSMS
LC-MSMS
GC-MSMS
GC-MSMS
LC-MSMS
LC-MSMS
LC-MSMS
LC-MSMS
GC-MSMS
GC-MSMS
LC-MSMS
GC-MSMS
GC-MSMS
LC-MSMS
GC-MSMS
LC-MSMS(-)
LC-MSMS
LC-MSMS
LC-MSMS
LC-MSMS
GC-MSMS
LC-MSMS
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
32
33