Single SPE-step method for the simultaneous

Single SPE-step method for the simultaneous

3rd Latin American Pesticide Residue Workshop Food and Environment,
Uruguay 8-11 May 2011
Single SPE-step method for the
simultaneous determination of GCMS and LC-MS amenable pesticides
in water
Ε.N. Papadakis1, A. Tsaboula1, Z.
Vryzas2 & E. PapadopoulouMourkidou1
1Aristotle University of Thessaloniki, Faculty of
Agriculture, Pesticide Science Laboratory, P.O.Box
1678, 54124 Thessaloniki, Greece
2Democritus
University of Thrace, Faculty of
Agricultural Development, Laboratory of
Agricultural Pharmacology and Ecotoxicology, 193
Pantazidou, 682 00 Orestias, Greece,
[email protected]
Uruguay vs Greece:6/2
Uruguayan have visited Greece in
the frame of APFA project
Horacio Heinzen
Veronica Cesio
Lucia Pareja
Silvina Niell
Gabriel Gonzalez
Joaquin Gonzalez
Requite Visit
Marios Zortas
And now Zisis Vryzas
We feel we owe you more visits
6/6/2011
3rd Latin American Pesticide Residue
Workshop Food and Environment, Uruguay
8-11 May 2011
2
Universities
2Democritus University of Thrace, Faculty of Agricultural
Development, Laboratory of Agricultural Pharmacology and
Ecotoxicology, 193 Pantazidou, 682 00 Orestias, Greece,
[email protected]
Orestiada
Thessaloniki
6/6/2011
1Aristotle
University of Thessaloniki, Faculty of Agriculture,
Pesticide Science Laboratory, P.O.Box 1678, 54124
Thessaloniki, Greece
3rd Latin American Pesticide Residue
Workshop Food and Environment, Uruguay
8-11 May 2011
3
Equipment
1 Thermo TSQ Quantum Discovery MAX LC/MS/MS
5 HPLC systems with various
detectors
6/6/2011
3rd Latin American Pesticide Residue
Workshop Food and Environment, Uruguay
8-11 May 2011
3 GC-MSn (ion trap)
3 GC systems with various
4
detectors
Background experience in water analysis
Ε
Ε
Ε
Ε
Past Projects:
INTERREG
Surface water quality of Macedonia-Thrace
Automated sampling and analysis of industrial wastes
Study of leaching mechanisms of herbicides in the major maize crowing areas in Greece
Transboundary river contamination with pesticides
6/6/2011
3rd Latin American Pesticide Residue
Workshop Food and Environment, Uruguay
5
Target analysis of the past projects
Analytical Methods
•
in-house
metabolites
method
for
160
pesticides
•
7 inorganic anions (Standard methods of American Public
association/American Water Works Association/ Water Environment)
•
19 metals
•
pH, T, DO, TDS, Cond, Sal, Redox, BOD5
6/6/2011
and
health
3rd Latin American Pesticide Residue
Workshop Food and Environment, Uruguay
8-11 May 2011
6
New Project for monitoring pesticide residues
in surface and groundwater of Northern Greece
2010-2013
Single SPE-step method for the simultaneous
determination of GC-MSn (151 pesticides and
metabolites) and LC-MS/MS (124 pesticides and
metabolites) amenable pesticides in water.
Target analysis for 275 pesticides and metabolites
Non target screening from NIST library in the GC-MS
system
6/6/2011
3rd Latin American Pesticide Residue
Workshop Food and Environment, Uruguay
8-11 May 2011
7
Sampling of Surface water bodies
Sampling sites: riparian drainage
canals, lakes, rivers, ponds,
surface water tank
6/6/2011
3rd LatinΠΜΣ
American
Pesticide Residue
25-11-09
Workshop Food and Environment, Uruguay
8
8
Groundwater sampling
Samples from field
were brought to the
Lab within 24 h and
SPE was performed a
day later
6/6/2011
3rd Latin American Pesticide Residue
Workshop Food and Environment, Uruguay
8-11 May 2011
9
•
•
SPE
LiChrolut EN 500 mg Cartridge
– Conditioning
• 5 ml MeOH
• 5 ml H2O
– Sample application
• Load 1 L water sample
– Elution of absorbed pesticides
• 5 ml Ethyl acetate/MeOH (90/10)
• 6ml Hexane
– Reduce to ~ 200 μL (in ethyl acetate)
• 100 μL GC-MS analysis
• 100 μL concentrate to dry, reconstitute to 1000 μL initial mobile phase :
MeOH (90:10%), LC-MS/MS analysis
Recovery studies
– 5 and 2 stock solutions for GC and LC respectively (properties and retention
time)
– Each stock recoveries were studied separately
6/6/2011
3rd Latin American Pesticide Residue
Workshop Food and Environment, Uruguay
8-11 May 2011
10
GC-MS method
GC - Ion Trap Mass Spectrometer
operational conditions
OVEN PROGRAM
oC
INITIAL TEMPERATURE
80
o
RATE 1
4
C/MIN
oC
FINAL TEMPERATURE
200
HOLD TIME
3 min
oC/MIN
RATE 2
6
oC
FINAL TEMPERATURE
230
HOLD TIME
10 min
oC/MIN
RATE 3
20
oC
FINAL TEMPERATURE
270
HOLD TIME
14 min
INJECTOR
BASE TEMPERATURE
MODE
SPLIT FLOW
SPLITLESS TIME
SURGE PRESSURE
SURGE DURATION
STOP PURGE AT
SAMPLE VOLUME
220 oC
SPLITLESS WITH SURGE
70 ml/min
2 min
92 kPa
0.5 min
2 min
2 μl
CARRIER METHOD
MODE
CONSTANT FLOW
FLOW
1 ml/min
GAS SAVER
ON
GAS SAVER FLOW
10 ml/min
GAS SAVER TIME
10 min
6/6/2011
MS METHOD
ELECTRON IONISATION
ION SOURCE TEMPERATURE
TRANSFER LINE TEMPERATURE
POLARITY
MICRO SCANS
MAX ION TIME
ELECTRON IMPACT
EMISSION CURRENT
EI
220 oC
280 oC
POSITIVE
3
25 ms
70 eV
250 μΑ
GC CAPILLARY COLUMNS
VARIAN WCOT FUSED SILICA (30 m×0.25 mm I.D. with a 0.25-μm)
COATING CP-CIL 8 CB LOW BLEED /MS
3rd Latin American Pesticide Residue
Workshop Food and Environment, Uruguay
8-11 May 2011
11
GC detection mode (Full Scan and MS/MS)
No COMPOUND
1 ACLONIFEN
2 ACRINATHRIN
3 a-HCH
4 alachlor
5 aldrin
6 alphamethrin
7 ametryne
8 ANTHRACENE
9 atrazine
10 azinphos ethyl
11 azinphos methyl
12 BENFLURALIN
13 b-HCH
14 bifenthrin
15 bromacil
16 bromophos ethyl
17 bromopropylate
18 bupirimate
19 buprofezin
20 butachlor
21 cadusaphos
22 caffeine
23 captafol
24 captan
25 c-HCH (lindane)
26 chinomethionate
27 chlorfevinphos
28 chlorobenzilate
29 chloropropylate
30 chlorothalonil
31 chlorpyriphos ethyl
32 chlorpyriphos-Methyl
CHLORTHAL
33 DIMETHYL
34 chlorthion
35 cis- chlordane
36 COUMAPHOS
37 cyanazine
38 cyanophos
39 cycloate
40 cyfluthrin
41 cypermetrin
42 DEA
43 deltamethrin
44 DEMETON O&S
45 desmetryn
46 d-HCH
47 dialifos
48 diazinon
49 dichlofluanid
50 dichlorvos
6/6/2011
full scan
ms 181
full scan
ms 160
full scan
ms 181
full scan
full scan
ms 200
ms 160
ms 160
ms 292
ms 181
ms 181
full scan
full scan
full scan
ms 193
full scan
ms 160
ms 159
ms 194
full scan
ms 149
ms 181
ms 234
full scan
ms 251
ms 251
ms 266
ms 314
ms 286
Quantitation
264
181
181
160
263
181
227
178
200
132
132
292
145
166
205
359
341
193
175
160
131
194
79
105
145
206
267
251
251
266
286
286
1st
212
152
183
132
293
152
212
152
122
104
104
264
146
165
207
303
183
165
172
132
97
193
77
107
146
148
269
139
139
231
258
271
2nd
194
ms 301
ms 297
full scan
full scan
ms 225
ms 243
full scan
ms 226
ms 181
ms 172
ms 181
full scan
full scan
full scan
ms 208
ms 179
full scan
full scan
301
280
375
362
225
148
154
199
181
172
181
88
213
181
208,1
179
167
109
273
250
373
226
189
210
55
206
152,1
105
152
60
198
183
181,1
137
123
185
258
267
266
334
172
211
83
226
219
117
257
170
164
105
105
206
181
181
190
357
185
105
130
125
165
276
149
181
174
323
179
314
241
130
137
126
171
219
167,1
164
224
79
No COMPOUND
51 dieldrin
52 DIFLUBENZURON
53 diphenylamine
54 DISULFOTON SULFON
55 DISULFOTON SULFOXIDE
56 endosulfan I
57 endosulfan II
58 endosulfan sulfate
59 endrin
60 ETHALFLURALIN
61 ethion
62 ETRIDIAZOLE
63 fenamiphos
64 FENAMIPHOS SULFON
65 FENAMIPHOS SULFOXIDE
66 fenarimol
67 fenazaquin
68 fenchlorphos
69 fenitrothion
70 fenoxycarb
71 fenpropimorph
72 fensulfothion
73 fenthion
74 FENTHION SULFONE
75 FENTHION SULFOXIDE
76 fenvalerate
77 flutriafol
78 FLUVALINATE
79 folpet
80 fonofos
81 furalaxyl
82 HCB
83 heptachlor
84 heptachlor-exo- epoxide
85 ISODRINE
86 isophenphos
87 isopropalin
88 L-cyhalothrin
89 malaoxon
90 malathion
91 mecarbam
92 methacrifos
93 methidathion
94 methoxychlor
95 mevinphos cis/trans
96 mirex
97 napropamide
98 nuarimol
99 o,p-DDD
100 o,p-DDE
full scan
ms 157
ms 169
full scan
full scan
full scan
full scan
full scan
full scan
ms 316
full scan
ms 211
ms 303
full scan
full scan
ms 139
ms 145
full scan
ms 260
ms 255
ms 128
ms 293
ms 278
full scan
full scan
ms 225
ms 219
ms 250
full scan
full scan
full scan
ms 284
full scan
full scan
full scan
full scan
full scan
ms 181
full scan
ms 173
full scan
full scan
full scan
full scan
ms 127
full scan
full scan
full scan
full scan
full scan
Quantitation
79
141
169
213
97
195
195
272
209
276
231
183
195
320
304
139
117
285
260
186
110
293
278
310
279
147
123
250
260
137
95
284
272
353
193
213
280
181
127
127
160
208
145
227
109
272
72
139
235
246
1st
279
129
167
153
168
207
207
274
245
232
153
140
180
292
160
111
145
287
217
255
128
265
245
106
278
225
219
200
130
109
242
249
274
355
263
185
238
152
99
99
131
180
85
209
127
274
128
107
237
248
3rd Latin American Pesticide Residue
Workshop Food and Environment, Uruguay
2nd
263
157
166
125
125
160
160
229
263
248
384
211
260
214
196
75
115
289
228
157
237
169
125
294
198
215
104
246
152
214
337
351
293
255
264
173
145
296
125
228
79
237
271
235
165
318
No COMPOUND
101 o,p-DDT
102 omethoate
103 OXYFLUORFEN
104 p,p-DDD
105 p,p-DDE
106 p,p-DDT
107 paraoxon ethyl
108 paraoxon methyl
109 parathion ethyl
110 parathion methyl
111 PCNB
112 pebulate
PENTACHLORO
113 BENZENE
114 permethrin
115 phenthoate
116 phorate
117 phorate sulfone
118 phorate sulfoxide
119 phosalone
120 phosmet
121 pirimiphos ethyl
122 pirimiphos methyl
123 procymidone
124 profenofos
125 prometon
126 prometryne
127 propachlor
128 propanil
129 propazine
130 propham
131 PROQUINAZIDE
132 prothoate
133 pyrazophos
134 quinalphos
135 SILTHIOFAM
136 simazine
137 simetryne
138 TEFLUTHRIN
139 terbacil
140 terbufos
TERBUFOS
141 SULFONE
142 terbumeton
143 terbutryn
144 tetrachlorvinphos
145 tetradifon
146 thiobencarb
147 tolyfluanid
148 TRALCOXYDIM
149 triazofos
150 trifluralin
151 vinclozolin
full scan
ms 156
full scan
full scan
full scan
full scan
ms 149
ms 230
ms 291
ms 263
ms 295
ms 128
Quantitation
235
141
252
235
246
235
119
136
263
246
237
128
1st
237
110
317
237
318
237
91
200
235
153
265
72
2nd
165
126
300
165
248
165
132
full scan
ms 183
full scan
ms 260
ms 199
ms 199
full scan
ms 160
full scan
full scan
ms 283
full scan
full scan
ms 241
full scan
ms 161
ms 214
full scan
ms 288
ms 115
full scan
full scan
ms 252
ms 201
full scan
ms 177
ms 161
full scan
250
183
274
231
171
171
182
160
168
290
255
339
168
199
120
161
172
93
245
73
221
156
252
173
213
177
144
231
215
168
121
260
143
143
184
133
318
276
254
337
210
226
176
134
214
137
288
97
232
157
197
186
170
127
161
203
108
165
246
203
199
199
367
105
333
180
283
208
183
184
93
126
full scan
full scan
full scan
full scan
full scan
full scan
full scan
ms 283
ms 285
ms 264
full scan
199
169
185
329
159
100
137
227,1
257
264
178
153
210
226
331
229
72
181
265,2
162
206
212
125
154
170
109
356
125
238
226,1
172
160
285
12
233
216
295
100
179
217
115
265
146
210
138
155
137
133
233
LC-MS/MS method
Mobile phase
Gradient
Column: Thermo HyPURITY C18
(150x2.1 mm, 5 μm)
Injection Volume: 20 μL Full loop injection
Column Temperature: 40 oC
Autosampler Tray Temperature : 20 oC
Mobile phase A: 90:10 water:acetonitrile
+ 5 mM ammonium acetate
Mobile phase B: 10:90 water:acetonitrile
+ 5 mM ammonium acetate
Optimization of MS/MS
parameters for each analyte
separately
Parent M/Z
Product M/Z
Collision energy
Probe Position
6/6/2011
Time (min)
%A
0
80
20
0
35
0
40
80
59
80
Flow rate: 0.2
mL/min
MS Parameters
Mode: Electro-Spray Ionization
Spray voltage: 4000 V
Seath gas pressure: 30
Aux gas pressure: 10
Capillary temperature: 325 oC
Collision pressure: 1.5 mTorr
3rd Latin American Pesticide Residue
Workshop Food and Environment, Uruguay
8-11 May 2011
13
LC-MS/MS optimization
A/A
COMPOUND
1 acetamiprid
2 abamectin
3 acetochlor
acibenzolar-S4 methyl
5 aminocarb
6 azoxystrobin
7 beflubutamid
8 benalaxyl
9 bitertanol
10 boscalid
11 carbendazim
carfentrazone
12 ethyl
13 chloridazone
14 chlorotoluron
15 cinidon-ethyl
16 clofentezine
17 clomazone
18 cyazofamid
19 cyhalofop-butyl
20 cyproconazole
21 cyromazine
22 diclofop-methyl
23 difenoconazole
24 diflufenican
25 dimethenamid
26 dimethoate
27 dimethomorph
28 dimoxystrobin
29 diuron
30 dodemorph
31 epoxyconazole
32 ethofumasate
33 ethoprophos
34 etofenprox
35 etoxazole
36 famoxadone
37 fenamidone
38 fenbuconazole
39 fenhexamid
fenoxaprop-p40 ethyl
41 fenpropimorph
6/6/2011
1st transition
2nd transition polarity
1st transition
2nd transition
polarity
A/A COMPOUND
Q1
Q3
CE
Q1
Q3
CE
A/A COMPOUND
Q1
Q3
CE
Q1
Q3
CE
42 fenpyroximate 422,2 134,9
33 422,2 366
15
+
83 oxadiazon
223 90,1
32 223 126
22
+
43 fipronil
434,9 249,8
32 434,9 329,8
18
890,6 305
24 890,6 567
15
+
84 penconazole
44 flonicamid
230 173,9
19 230 202,9
19
+
270 148,1
20 270 224
10
+
85 pencycuron
fluazifop-P86 pendimethalin
45 butyl
384,2 282
21 384,2 328,1
13
+
211,1 136
30 211,1 140
24
+
87 pethoxamid
46 fluazinam
462,9 397,8
10 462,9 415,8
10
209,2 137,1
23 209,2 152,1
14
+
88 picolinafen
47 fludioxonil
247,1 126,1
33 247,1 169,1
37
404 344
23 404 372
13
+
89 picoxystrobin
373,1
91
19 373,1 162
32
+
48 flufenacet
364,1 151,9
17 364,1 194,2
10
+
90 pirimicarb
326,2 148,1
21 326,2 208,1
15
+
49 flufenoxuron
489 140,8
47 489 157,8
21
+
91 prochloraz
338,1 70,1
21 338,1 269,1
10
+
50 flumioxazin
372,1 299
35 372,1 327
18
+
92 promecarb
343 139,8
18 343 306,9
19
+
51 fluometuron
233 72,1
36 233 160
29
+
93 propaquizafop
192,2 132,1
31 192,2 160
18
+
52 fluopicolid
382,9 144,8
52 382,9 172,8
32
+
94 propargite
53 fluoxastrobin 458,9 187,9
33 458,9 426,9
16
+
95 propiconazole
412 345,8
21 412 365,8
18
+
54 fluquinconazole 376 306,8
28 376 348,9
19
+
96 propyzamide
221,9
92
28 221,9 104
20
+
55 flurochloridone 311,9 145
46 311,9 292
21
+
97 prosulfocarb
213,1 72,1
16 213,1 140
24
+
56 flusilazole
316,2 165
31 316,2 247,1
18
+
98 pymetrozine
411 106,9
39
411 347,9
21
+
57 flutolanil
324,1 241,9
24 324,1 261,9
18
+
99 pyraclostrobin
303 101,9
33 303 137,9
15
+
58 fosthiazate
284 103,9
19 284 227,9
10
+
100 pyraflufen ethyl
240,1
89
47 240,1 125
19
+
59 fuberidazole
185,1
65
43 185,1 157
21
+
101 pyridaben
325,2 108
12 325,2 261,2
10
+
60 hexythiazox
353,1 167,9
24 353,1 227,9
14
+
102 pyridate
375,1 119,9
30 375,1 255,9
13
+
61 imazalil
297,1 158,9
32 297,1 200,9
17
+
103 pyrimethanil
292 70,1
25 292 125
32
+
62 imidachloprid
256 175
21 256 209
17
+
104 pyriproxyfen
167,1 108,1
20 167,1 125
18
+
63 indoxacarb
528,1 149,8
24 528,1 202,8
41
+
105 quinoxyfen
357,9 120,1
28 357,9 280,9
18
+
64 iprovalicarb
321,1 119
19 321,1 203,1
10
+
106 quizalofop-ethyl
406 251
29 406 337
14
+
65 isoproturon
207,3 72,1
16 207,3 165,1
12
+
107 S-metolachlor
395 245,9
41 395 265,9
21
+
66 isoxaflutol
377 219,7
51 377 250,9
22
+
108 spirodiclofen
276 168
26 276 243,9
15
+
kresoxym109 spiromesifen
229,9 124,9
22 229,9 198,9
10
+
67 methyl
314 116
33 314 206,1
10
+
110 tebuconazole
388,2 165
33 388,2 301,1
18
+
68 lenacil
235 136
33 235 153
13
+
111 tebufenozide
327,1 115,9
23 327,1 204,9
11
+
69 linuron
248,9 159,9
18 248,9 182
13
+
112 tebufenpyrad
233,1 133
44 233,1 160
29
+
70 mepanipyrim
224,1
77
36 224,1 106
26
+
113 teflubenzuron
282,4 98,1
24 282,4 116,1
21
+
71 metaflumizone
505 284,9
52 505 301,9
20
114 tepraloxydim
330 100,9
41 330
121
20
+
72 metalaxyl
280,1 160,1
23 280,1 220,1
13
+
115 terbuthylazine
304
121
24 304
161
18
+
73 metamitron
203 104
29 203 175
16
+
116 tetraconazole
243
97
29 243 130,9
19
+
74 metazachlor
278,1 134
23 278,1 209,9
11
+
117 thiacloprid
394,2 107
36 394,2 177
14
+
75 metconazole
320,1
70
21 320,1 124,9
35
+
118 thiamethoxam
360,2 112,9
52 360,2 140,9
34
+
76 methiocarb
226,1 121,1
17 226,1 169,1
10
+
119 thiofanox sulfone
392,1 238
18 392,1 331,1
10
+
77 methomyl
163,1
88
10 163,1 106,1
10
+
thiofanox
312,1
92
26 312,1 235,9
15
+
methoxyfenozi
120 sulfoxide
337,1
70
19 337,1 124,9
33
+
78 de
369,2 132,9
24 369,2 148,9
17
+
121 triadimenol
302
55
38 302
97
24
+
79 metrafenone
409,2 209,1
15 409,2 226,9
24
+
122 trifloxystrobin
80 metribuzin
215 84,1
20 215 187,1
18
+
123 triticonazole
362,1
121
31 362,1 287,9
17
+
81 molinate
188,1 83,2
19 188,1 126,1
13
+
124 zoxamide
304,2 117,1
59 304,2 147,1
28
+
82 myclobutanil
289,1 70,1
20 289,1 124,9
32
+
3rd Latin American Pesticide Residue
Workshop Food and Environment, Uruguay
8-11 May 2011
1st transition
Q1
Q3
CE
362 176,9
32
284,1
70
15
329,1 98,9
51
282,1 193,9
12
296,1 130,9
20
377,1 144,9
48
368,1 144,9
20
239,1 72,1
22
375,9 265,9
10
208,2 109,1
16
444,1 99,9
16
368,1 231,2
10
342 69,2
12
256 172,9
23
252,1
91
21
218 79,1
48
388,1 162,9
23
413 252,8
31
365,1
147
25
379,2 206,9
17
200,3 82,2
23
322,1 95,9
15
307,9 161,9
42
373
271
24
284 176,1
22
411 212,8
32
371,1
273
14
308,2
70
20
353,1 132,9
21
334,1 116,9
39
379 338,9
13
342,1
166
24
230,1 104,2
38
371,9 70,1
20
253
126
23
291,9
181
16
268,1 57,1
15
2nd
Q1
362
284,1
329,1
282,1
296,1
377,1
368,1
239,1
375,9
208,2
444,1
368,1
342
256
252,1
218
388,1
413
365,1
379,2
200,3
322,1
307,9
373
284
411
371,1
308,2
353,1
334,1
379
342,1
230,1
371,9
253
291,9
268,1
transition
polarity
Q3
CE
219,9
20
+
158,9
32
+
125
33
+
212
11
+
250
14
+
237,9
29
+
205,2
10
+
182,1
16
+
308
10
+
151,1
10
+
298,9
25
+
175
15
+
159
33
+
190
15
+
128
12
+
105,1
18
+
194
12
+
338,8
20
+
308,9
13
+
351,1
11
+
107,2
25
+
128,9
34
+
196,8
32
+
298,9
17
+
252
15
+
312,8
10
+
255
22
+
124,9
35
+
296,9
11
+
144,9
28
+
358,8
11
250
11
+
174,1
17
+
158,9
34
+
186
15
+
211
13
+
76
10
+
252,2 57,1
296,1
70
409,1 185,9
318,1 70,1
335,9 186,8
252,2
296,1
409,1
318,1
337,9
104
227,2
205,9
124,9
188,8
36
10
20
40
23
12
10
13
31
22
+
+
+
+
+
14
Results
6/6/2011
3rd Latin American Pesticide Residue
Workshop Food and Environment, Uruguay
8-11 May 2011
15
Pesticide Recoveries with GC-MSn
No Compound
1 aclonifen
2 acrinathrin
3 a-HCH
4 alachlor
5 aldrin
6 alphamethrin
7 ametryne
8 anthracene
9 atrazine
10 azinphos ethyl
11 azinphos methyl
12 benfluralin
13 b-HCH
14 bifenthrin
15 bromacil
16 bromophos ethyl
17 bromopropylate
18 bupirimate
19 buprofezin
20 butachlor
21 cadudaphos
22 caffeine
23 captafol
24 captan
25 c-HCH
26 chinomethionate
27 chlordane
28 chlorfenvinphos
29 chlorobenzilate
30 chloropropylate
31 chlorothalonil
32 chlorpyriphos ethyl
33 chlorpyriphos methyl
34 chlorthal dimethyl
35 chlorthion
36 coumaphos
37 cyanazine
38 cyanophos
39 cycloate
40 cyfluthrin
41 cypermethrin
42 DEA
43 deltamethrin
44 demeton O & S
45 desmetryne
46 d-HCH
47 dialifos
48 diazinon
49 dichlofluanid
50 dichlorvos
*n=8
6/6/2011
LOD
0,01
0,01
0,01
0,005
0,01
0,01
0,01
0,01
0,005
0,01
0,025
0,01
0,01
0,001
0,01
0,005
0,01
0,01
0,01
0,01
0,005
0,01
0,025
0,01
0,005
0,001
0,01
0,01
0,01
0,01
0,01
0,001
0,001
0,001
0,025
0,01
0,01
0,01
0,01
0,01
0,01
0,01
0,01
0,025
0,01
0,01
0,01
0,005
0,01
0,025
LOQ* % RECOVERY LOQ %RSD
0,025
98
9
51
12
0,025
82
17
0,025
94
10
61
16
0.025
79
19
0,025
96
10
0,025
98
3
0,025
92
9
0,025
99
13
0,1
120
15
0,025
88
19
0,025
100
11
0,025
82
21
0,025
91
16
0,025
88
18
0,025
102
9
0,025
110
9
0,025
104
7
0,025
99
7
0,025
109
11
0,025
97
6
0,1
94
18
0,025
95
8
0,025
87
10
0,01
110
11
0,025
95
13
0,025
95
6
0,025
100
10
0,025
104
13
0,025
92
14
0,01
85
20
0,01
100
13
0,01
108
10
0,1
114
5
0,025
106
3
0,025
94
8
0,025
84
12
0,025
79
18
0,025
82
12
0,025
87
15
0,025
102
9
0.025
79
16
65
21
0,025
96
12
0,025
97
6
0,025
88
12
0,025
104
12
0,025
99
12
49
14
No Compound
51 dieldrin
52 diflubenzuron
53 diphenylamine
54 disulfoton sulfone
55 disulfoton sulfoxide
56 endosulfan I
57 endosulfan II
58 endosulfan sulfate
59 endrin
60 ethalfluralin
61 ethion
62 etridiazole
63 fenamiphos
64 fenamiphos sulfone
65 fenamiphos sulfoxide
66 fenarimol
67 fenazaquin
68 fenchlorphos
69 fenitrothion
70 fenoxycarb
71 fenpropimorph
72 fensulfothion
73 fenthion
74 fenthion sulfone
75 fenthion sulfoxide
76 fenvalerate
77 flutriafol
78 fluvalinate
79 folpet
80 fonofos
81 furalaxyl
82 HCB
83 heptachlor
84 heptachlor epoxide
85 isodrin
86 isophenphos
87 isopropalin
88 L-cyhalothrin
89 malaoxon
90 malathion
91 mecarbam
92 methacrifos
93 methidathion
94 methoxychlor
95 mevinphos
96 mirex
97 napropamide
98 nuarimol
99 o,p DDD
100 o,p DDE
LOD
0,01
0,025
0,005
0,01
0,01
0,01
0,01
0,005
0,01
0,005
0,01
0,001
0,01
0,01
0,01
0,001
0,01
0,001
0,01
0,01
0,005
0,01
0,01
0,01
0,01
0,01
0,001
0,01
0,01
0,01
0,005
0,001
0,01
0,001
0,01
0,001
0,01
0,01
0,025
0,005
0,01
0,01
0,01
0,001
0,01
0,01
0,01
0,01
0,001
0,001
LOQ* % RECOVERY LOQ %RSD
0,025
98
14
0,1
102
6
0,025
99
16
0,025
104
5
0,025
104
5
0,025
91
19
0,025
93
9
0,025
95
10
0,025
90
11
0,025
107
11
0,025
100
10
0,025
108
0
0,025
90
5
0,025
90
16
0,025
96
6
0,01
96
17
0,025
95
8
0,01
103
8
0,025
105
15
0,025
93
12
0,025
88
19
0,025
90
16
0,025
88
4
0,025
86
10
0,025
98
9
53
13
0,025
85
15
0,025
81
12
0,025
86
19
0,025
112
8
0,025
96
12
0,025
81
15
0,025
81
15
0,025
94
11
0,025
92
12
0,01
99
12
0,025
84
7
57
18
0,1
103
13
0,025
102
16
0,025
97
9
0,025
91
12
0,025
106
9
0,025
101
10
0,025
98
14
65
6
0,025
109
11
0,025
102
10
0,01
94
16
0,01
94
18
Recovery: 70-120% Quantitative?
Recovery: < 70 or >120 or RSD >20 Screening
No Compound
101 o,p DDT
102 omethoate
103 oxyfluorfen
104 p,p DDD
105 p,p DDE
106 p,p DDT
107 paraoxon methyl
108 paraoxon ethyl
109 parathion ethyl
110 parathion methyl
111 PCNB
112 pebulate
113 pentachlorobenzene
114 permethrin
115 phenthoate
116 phorate
117 phorate sulfone
118 phorate sulfoxide
119 phosalone
120 phosmet
121 pirimiphos ethyl
122 pirimiphos methyl
123 procymidone
124 profenofos
125 prometone
126 prometryne
127 propachlor
128 propanil
129 propazine
130 propham
131 proquinazide
132 prothoate
133 pyrazophos
134 quinalphos
135 silthiofam
136 simazine
137 simetryne
138 tefluthrin
139 terbacil
140 terbufos
141 terbufos sulfone
142 terbumeton
143 terbutryn
144 tetrachlorvinphos
145 tetradifon
146 thiobencarb
147 tolyfluanide
148 tralcoxydim
149 triazophos
150 trifluralin
151 vinclozolin
LOD
0,01
0,025
0,01
0,001
0,01
0,01
0,025
0,01
0,01
0,01
0,001
0,01
0,01
0,01
0,005
0,025
0,01
0,01
0,01
0,001
0,001
0,001
0,005
0,001
0,01
0,005
0,01
0,01
0,005
0,01
0,001
0,001
0,01
0,01
0,001
0,01
0,01
0,01
0,025
0,005
0,01
0,01
0,01
0,01
0,01
0,01
0,01
0,01
0,01
0,005
0,01
LOQ* % RECOVERY LOQ %RSD
0,025
74
11
0,1
108
17
0,025
102
8
0,01
90
16
0,025
82
12
0,025
86
9
0,1
88
17
0,025
99
16
67
13
0,025
107
9
0,025
86
10
0,025
99
17
52
22
0,025
92
18
0,025
106
6
59
8
0,025
103
15
0,025
99
8
0,025
103
9
0,025
98
20
0,01
96
19
0,01
107
14
0,025
97
11
0,01
105
11
0,025
92
7
0,025
94
14
0,025
104
16
0,025
94
7
0,025
90
9
0,025
96
12
0,01
93
14
0,01
100
12
0,025
103
7
0,025
96
12
0,025
0.001/103
4
0,1
106
9
0,025
98
3
0,025
78
10
0,1
100
14
0,025
86
18
0,025
104
5
0,025
98
9
0,025
101
10
0,025
101
8
0,025
99
6
0,025
106
11
0,025
99
14
0,025
94
8
0,025
92
13
0,025
77
14
0,025
97
13
16
Pesticide Recoveries with LC-MS/MS
No Compound
1 acetamiprid
2 abamectin
3 acetochlor
acibenzolar-S4 methyl
5 aminocarb
6 azoxystrobin
7 beflubutamid
8 benalaxyl
9 bitertanol
10 boscalid
11 carbendazim
carfentrazone
12 ethyl
13 chloridazone
14 chlorotoluron
15 cinidon-ethyl
16 clofentezine
17 clomazone
18 cyazofamid
19 cyhalofop-butyl
20 cyproconazole
21 cyromazine
22 diclofop-methyl
23 difenoconazole
24 diflufenican
25 dimethenamid
26 dimethoate
27 dimethomorph
28 dimoxystrobin
29 diuron
30 dodemorph
31 epoxyconazole
32 ethofumasate
33 ethoprophos
34 etofenprox
35 etoxazole
36 famoxadone
37 fenamidone
38 fenbuconazole
39 fenhexamid
fenoxaprop-p40 ethyl
41 fenpropimorph
*n=5
6/6/2011
LOQ (μg/L) % RECOVERY LOQ %RSD
0.01
102
2
0.025
59
2
0.01
83
3
0.025
0.025
0.025
0.025
0.025
0.025
0.025
0.025
63
71
85
95
94
86
102
53
6
13
7
2
4
13
1
8
0.025
0.025
0.025
0.025
0.025
0.025
0.025
0.025
0.025
0.025
0.025
0.01
0.025
0.025
0.01
0.025
0.025
0.025
0.025
0.025
0.025
0.025
0.025
0.025
0.025
0.025
0.025
0.025
92
94
106
67
86
73
91
73
95
59
92
102
101
80
93
94
92
94
97
85
89
61
109
89
91
90
84
80
7
2
5
5
10
7
12
7
13
9
7
2
6
3
1
5
9
1
6
14
3
12
5
2
4
7
16
1
0.025
0.01
98
99
3
2
No Compound
LOQ (μg/L) % RECOVERY LOQ %RSD
42 fenpyroximate
0.025
81
11
43 fipronil
0.01
81
8
44 flonicamid
0.025
100
4
fluazifop-P45 butyl
0.025
97
5
46 fluazinam
0.01
89
5
47 fludioxonil
0.025
101
16
48 flufenacet
0.01
89
7
49 flufenoxuron
0.025
70
11
50 flumioxazin
0.025
69
9
51 fluometuron
0.01
108
8
52 fluopicolid
0.025
87
4
53 fluoxastrobin
0.025
87
9
54 fluquinconazole
0.025
92
9
55 flurochloridone
0.025
102
16
56 flusilazole
0.025
94
9
57 flutolanil
0.025
95
1
58 fosthiazate
0.025
48
16
59 fuberidazole
0.025
85
2
60 hexythiazox
0.025
92
2
61 imazalil
0.025
77
3
62 imidachloprid
0.01
92
8
63 indoxacarb
0.025
69
15
64 iprovalicarb
0.025
98
6
65 isoproturon
0.025
98
7
66 isoxaflutol
0.025
65
16
kresoxym67 methyl
0.025
86
7
68 lenacil
0.01
91
1
69 linuron
0.01
103
1
70 mepanipyrim
0.025
92
11
71 metaflumizone
0.025
82
5
72 metalaxyl
0.025
78
15
73 metamitron
0.025
43
23
74 metazachlor
0.025
96
4
75 metconazole
0.025
89
10
76 methiocarb
0.025
53
15
77 methomyl
0.025
61
12
methoxyfenozi
78 de
0.025
89
11
79 metrafenone
0.025
93
8
80 metribuzin
0.025
47
10
81 molinate
0.025
44
23
82 myclobutanil
0.01
96
8
Recovery: 70-120% Quantitative ?
Recovery: < 70 or >120 or RSD >20 Screening ?
No Compound
LOQ (μg/L) % RECOVERY
83 oxadiazon
0.025
84 penconazole
0.01
85 pencycuron
0.025
86 pendimethalin
0.025
87 pethoxamid
0.025
88 picolinafen
0.025
89 picoxystrobin
0.025
90 pirimicarb
0.025
91 prochloraz
0.025
92 promecarb
0.025
93 propaquizafop
0.025
94 propargite
0.025
95 propiconazole
0.025
96 propyzamide
0.025
97 prosulfocarb
0.025
98 pymetrozine
0.025
99 pyraclostrobin
0.025
100 pyraflufen ethyl
0.025
101 pyridaben
0.025
102 pyridate
0.025
103 pyrimethanil
0.025
104 pyriproxyfen
0.025
105 quinoxyfen
0.025
106 quizalofop-ethyl
0.025
107 S-metolachlor
0.025
108 spirodiclofen
0.025
109 spiromesifen
0.025
110 tebuconazole
0.025
111 tebufenozide
0.025
112 tebufenpyrad
0.01
113 teflubenzuron
0.025
114 tepraloxydim
0.025
115 terbuthylazine
0.025
116 tetraconazole
0.01
117 thiacloprid
0.01
118 thiamethoxam
0.01
119 thiofanox sulfone
0.025
120 thiofanox sulfoxide
0.025
121 triadimenol
0.025
122 trifloxystrobin
0.01
123 triticonazole
0.01
124 zoxamide
0.025
LOQ
85
91
94
76
98
83
99
83
78
52
76
90
96
71
74
68
85
109
89
108
94
35
82
90
87
89
100
99
85
92
84
97
80
100
98
90
66
56
97
92
90
84
%RSD
5
3
3
3
5
8
3
4
5
11
18
2
4
8
11
6
3
19
2
8
2
16
4
2
4
3
5
4
8
5
14
17
2
3
1
9
13
12
9
2
4
6
17
GC-MSn Chromatographic profile
of Stock A (49 compounds) full
scan TIC
RT: 0.00 - 65.00
38.23
100
NL:
3.61E6
TIC F: + c
Full ms
[50.00500.00]
MS
stA1ppm
38.57
90
80
40.35
70
30.39
60
35.01
42.20
42.41
50
40
27.72
46.83
30
23.43
25.44
50.50
60.77
22.75
43.21
57.76
52.54
54.90
20
17.48
11.76
12.40
10
19.63
64.18
0
0
6/6/2011
5
10
15
20
25
30
35
Time (min)
40
45
3rd Latin American Pesticide Residue
Workshop Food and Environment, Uruguay
8-11 May 2011
50
55
60
65
18
GC-MSn Chromatographic profile
of Stock B (36 compounds)full scan
TIC
RT: 0.00 - 65.03
51.55
100
NL:
2.84E6
TIC F: + c
Full ms
[50.00500.00]
MS
stb1ppm
40.31
53.59
90
31.51
80
50.90
25.39
56.12
29.98
70
39.37
34.21
43.82
60
48.88
26.58
50
45.88
40
59.30
22.24
17.55
63.37
30
20
10
12.54
19.57
0
0
6/6/2011
5
10
15
20
25
30
35
Time (min)
40
45
3rd Latin American Pesticide Residue
Workshop Food and Environment, Uruguay
8-11 May 2011
50
55
60
65
19
GC-MSn Chromatographic profile
of Stock C (33 compounds)full scan
TIC
RT: 0.00 - 65.02
33.89
100
NL:
1.91E6
TIC F: + c
Full ms
[50.00500.00]
MS
stc1ppm
90
38.63
80
38.39
50.20
39.76
70
30.31
60
31.77
50.86
37.65
27.30
50
55.90
27.05
40
55.01
23.78
30
46.11
49.30
20
59.25
63.39
43.84
10
14.23
18.79
0
0
6/6/2011
5
10
15
20
25
30
35
Time (min)
40
45
3rd Latin American Pesticide Residue
Workshop Food and Environment, Uruguay
8-11 May 2011
50
55
60
65
20
GC-MSn Chromatographic profile
of Stock D (18 compounds)full scan
TIC
RT: 0.00 - 65.01
36.09
100
NL:
1.42E6
TIC F: + c
Full ms
[50.00500.00]
MS
std1ppm
90
80
32.01
70
60
50
35.54
40
42.41
26.46
30
53.77 54.14
56.33
50.26
30.22
26.13
20
63.89
17.91
10
17.61
39.34
44.18 49.36
24.80
10.29
0
0
6/6/2011
5
10
15
20
25
30
35
Time (min)
40
45
3rd Latin American Pesticide Residue
Workshop Food and Environment, Uruguay
8-11 May 2011
50
55
60
65
21
GC-MSn Chromatographic profile
of Stock E (15 compounds)full scan
TIC
RT: 0.00 - 65.02
40.37
100
NL:
1.11E6
TIC F: + c
Full ms
[50.00500.00]
MS
ste1ppm
90
28.27
80
70
52.57
40.10
20.06
34.35
60
38.66
45.52
50
35.10
40
18.51
55.83
30
45.18
40.64
26.13
20
10
14.16
43.84
30.01
22.26
59.26
51.51
63.36
0
0
6/6/2011
5
10
15
20
25
30
35
Time (min)
40
3rd Latin American Pesticide Residue
Workshop Food and Environment, Uruguay
8-11 May 2011
45
50
55
60
65
22
GC-MSn (SRM 172)
RT: 0.00 - 65.03
24.44
171.95
100
NL: 1.96E4
m/z=
171.50-172.50 F: +
c SRM ms2
[email protected]
[86.00-200.00] MS
stb1ppm
90
80
70
DEA
60
50
40
30
20
stb1ppm #1769 RT: 24.44 AV: 1 NL: 1.96E4
F: + c SRM ms2 [email protected] [86.00-200.00]
10
171.95
100
0
90
0
5
10
15
20
25
30
35
Time (min)
40
45
50
55
60
65
80
Selected reaction monitoring of the 172
m/z characteristic for (DEA)
DEA was used as an indicator for GC
system maintenance
6/6/2011
Relative Abundance
70
60
50
40
30
20
10
94.06
0
88.01
3rd Latin American Pesticide Residue
Workshop Food and Environment, Uruguay
8-11 May 2011
90
105.02
103.97
102.97
100
129.99
111.05
110
136.04 145.04
172.97
128.99
120
130
140
m/z
150
160
170
180
23
190
200
RT: 0.00 - 38.63
100
LC-MS/MS Chromatographic
profile
95
NL:
3.13E6
TIC MS
Fort
A+C+E 0,1
ugL
90
85
80
75
70
65
60
55
50
45
40
35
30
25
20
15
10
5
0
0
6/6/2011
5
10
15
20
Time (min)
25
30
35
24
LC-MS/MS chromatogram
RT: 0.00 - 38.62
100
S-metolachor-positive
NL: 8.67E5
TIC F: + c ESI SRM
ms2 284.000
[176.099-176.101,
251.999-252.001] MS
fort a+c+e 0,025 ugl
95
90
85
80
75
70
65
60
55
50
45
Selected reaction monitoring of the 284
m/Z characteristic for S-metolachlor
40
35
30
25
20
15
10
and
5
0
100
NL: 2.27E3
TIC F: - c ESI SRM
ms2 247.000
[124.899-124.901,
160.899-160.901] MS
fort a+c+e 0,025 ugl
95
90
85
80
of 247 m/z characteristic for fludioxonil
75
70
65
60
55
50
45
40
35
fludioxonil-negative
30
25
20
15
10
5
0
0
5
10
6/6/2011
15
20
Time (min)
25
30
35
3rd Latin American Pesticide Residue
Workshop Food and Environment, Uruguay
8-11 May 2011
25
Analysis of surface and ground
water samples
• Up to now
– More than 1000 samples were analyzed (plan for
10.000 in 3 years period)
• rivers
• lakes
• ground water
• Also the GC-MS and LC-MS instrumental
analytical methods were used for the
determination of pesticide residues in
sediment of the above mentioned surface
water bodies
6/6/2011
3rd Latin American Pesticide Residue
Workshop Food and Environment, Uruguay
8-11 May 2011
26
LC-MS/MS positive detection
(real sample)
thiamethoxam
Sample Conc:
0.012 μg/L
Quant Ion: 211.00
Qual Ion 1: 181.00
Ratio: 18.24% Range:0.00 - 47.02%
MS-Data
Overlay
The parent ion is 291.9 and the
quantitation ion is from the second
transition the 211. While the ion 181 is
used for confirmation.
6/6/2011
3rd Latin American Pesticide Residue
Workshop Food and Environment, Uruguay
8-11 May 2011
27
LC-MS/MS positive detection
(real sample)
imidacloprid
Sample Conc:
0.017 μg/L
Quan Ion: 209.00
Qual Ion 1: 175.00
Ratio: 78.21% Range:55.34 - 95.34%
MS-Data
Overlay
The parent ion is 256 and the quantitation
ion is from the second transition the 209.
The ion 175 is used for confirmation.
6/6/2011
3rd Latin American Pesticide Residue
Workshop Food and Environment, Uruguay
8-11 May 2011
28
LC-MS/MS positive detection (real
sample)
fluometuron
Sample Conc: 0.068 μg/L
Quan Ion: 72.10
Qual Ion 1: 160.00
Ratio: 15.54% Range:0.00 - 42.50%
MS-Data
Overlay
parent ion 233
6/6/2011
3rd Latin American Pesticide Residue
Workshop Food and Environment, Uruguay
8-11 May 2011
29
Preliminary Results
• Most frequently detected pesticides
Chlorpyriphos ethyl
Molinate
Trifluralin
boscalid
Prometryne
Malathion
Caduzaphos
Bubirimate
Alachlor
Phorate sulfone
/sulfoxide
Pirimiphos
methyl
Fensulfothion
Diphenylamine
HCB
Metribuzin
λ-Cyhalothrin
Caffeine
PCNB
Profenofos
Deltamethrin
S-metolachlor
Diazinon
Tralcoxydim
Ethion
Fluometuron
Propazine
Phosmet
Thiamethoxam
Etridiazole
Flutriafol
Fenthion
DEA
Chlorthal Dimethyl
Permethrin
Fenoxycarb
Thiacloprid
Imidacloprid
Bifenthrin
Terbutryn
Therbuthylazine
Atrazine
Fenpropimorph
Prometon
Fenamiphos
Simazine
Captan
Napropimide
C-HCH
6/6/2011
3rd Latin American Pesticide Residue
Workshop Food and Environment, Uruguay
8-11 May 2011
30
Greece Famous for …
• History-Mythology
• Ancient culture
• Hospitality
• Islands
• Mediterranean diet
•
•
Sun and Sea
Deptocracy ?
Parthenon
6/6/2011
Future:
Ninemia
Lull
Ancient
Athens
coins 450400 BC
Ancient
Epidaurus
theater
Thunderbolts
around
Greece:
IMF
“Greece is
going to be
sold at a
bargain
price”
Thank you very much
for your attention