1、BSI Standards PublicationPD CEN/TR 16699:2014Foodstuffs Determinationof pesticide residues by GC-MS/MS Tandem massspectrometric parametersPD CEN/TR 16699:2014 PUBLISHED DOCUMENTNational forewordThis Published Document is the UK implementation of CEN/TR 16699:2014.The UK participation in its preparat
2、ion was entrusted to Technical Committee AW/275, Food analysis - Horizontal methods.A list of organizations represented on this committee can be obtained on request to its secretary.This publication does not purport to include all the necessary provisions of a contract. Users are responsible for its
3、 correct application. The British Standards Institution 2014.Published by BSI Standards Limited 2014ISBN 978 0 580 83729 6ICS 67.050Compliance with a British Standard cannot confer immunity from legal obligations.This Published Document was published under the authority of the Standards Policy and S
4、trategy Committee on 31 July 2014.Amendments/corrigenda issued since publicationDate T e x t a f f e c t e dPD CEN/TR 16699:2014TECHNICAL REPORT RAPPORT TECHNIQUE TECHNISCHER BERICHT CEN/TR 16699 July 2014 ICS 67.050 English Version Foodstuffs - Determination of pesticide residues by GC-MS/MS -Tande
5、m mass spectrometric parameters Produits alimentaires - Dtermination des rsidus de pesticides par CG-SM/SM - Paramtres pour la spectromtrie de masse en tandem Lebensmittel - Bestimmung von Pestizidrckstnden mit GC-MS/MS - Parameter fr die Tandem-Massenspektrometrie This Technical Report was approved
6、 by CEN on 10 May 2014. It has been drawn up by the Technical Committee CEN/TC 275. CEN members are the national standards bodies of Austria, Belgium, Bulgaria, Croatia, Cyprus, Czech Republic, Denmark, Estonia, Finland, Former Yugoslav Republic of Macedonia, France, Germany, Greece, Hungary, Icelan
7、d, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland, Turkey and United Kingdom. EUROPEAN COMMITTEE FOR STANDARDIZATION COMIT EUROPEN DE NORMALISATION EUROPISCHES KOMITEE FR NORMUNG CEN-CENELEC Managem
8、ent Centre: Avenue Marnix 17, B-1000 Brussels 2014 CEN All rights of exploitation in any form and by any means reserved worldwide for CEN national Members. Ref. No. CEN/TR 16699:2014 EPD CEN/TR 16699:2014CEN/TR 16699:2014 (E) 2 Contents Page Foreword 3 Introduction .4 1 Scope 5 2 Parameters for GC-M
9、S/MS determination of pesticides following electron impact ionization 5 2.1 General 5 2.2 General MS/MS Parameters 5 2.3 Analyte specific MS/MS Parameters 5 Bibliography . 17 PD CEN/TR 16699:2014CEN/TR 16699:2014 (E) 3 Foreword This document (CEN/TR 16699:2014) has been prepared by Technical Committ
10、ee CEN/TC 275 “Food analysis - Horizontal methods”, the secretariat of which is held by DIN. Attention is drawn to the possibility that some of the elements of this document may be the subject of patent rights. CEN and/or CENELEC shall not be held responsible for identifying any or all such patent r
11、ights. PD CEN/TR 16699:2014CEN/TR 16699:2014 (E) 4 Introduction Pesticide residues analysis employs multi methods involving extraction of residues from the homogenized sample and clean-up of the extract in order to determine as many components as possible in the extracts. Afterwards the extracts can
12、 be analysed by different kind of instruments. The hyphenation of gas chromatography (GC) and tandem mass spectrometry (MS/MS) is a highly selective technique for identification and quantification of pesticide residues in extracts of plant and animal origin. This technique may be used to replace GC-
13、MS detection in existing methods without the need for additional validation provided that calibration was successful and has demonstrated the required sensitivity and precision. For the ionization of the analytes (pesticides and/or their metabolites) in GC-MS/MS, electron impact ionization (EI) is w
14、idely used because it offers sufficient ionization of most compound classes. However, very often molecular ions (cation radicals) and several fragment ions are formed simultaneously. For that reason, a rich variety of potential parent ions for MS/MS transitions exists compared to the soft ionization
15、 techniques applied in LC-MS/MS. This results in a greater freedom for the selection of an appropriate transition for a given situation. Such freedom is useful and often necessary in GC-MS/MS because a higher number of (fragment) ions are often produced by the matrix, which may interfere with the si
16、gnal of the target analyte. On the other hand, this higher number of options may be a bit confusing for less experienced analysts. To simplify the selection of suitable GC-MS/MS transitions in that situation, this Technical Report lists those MS/MS transitions, which have been reported most often in
17、 the scientific literature or are most often proposed by suppliers of GC-MS/MS instruments. PD CEN/TR 16699:2014CEN/TR 16699:2014 (E) 5 1 Scope This Technical Report lists the mass spectrometric parameters which are useful for the application of European Standards for the determination of pesticide
18、residues in foods of plant origin that use GC-MS. These European Standards are as follows: EN 1528 (all parts), Fatty food Determination of pesticides and polychlorinated biphenyls (PCBs) EN 12393 (all parts), Foods of plant origin Multiresidue methods for the gas chromatographic determination of pe
19、sticide residues EN 15662, Foods of plant origin Determination of pesticide residues using GC-MS and/or LC-MS/MS following acetonitrile extraction/partitioning QuEChERS-method To facilitate the determination of pesticides and/or metabolites using GC-MS/MS, Table 2 specifies the diagnostic ion transi
20、tions suitable for identification and quantification, which can be used. 2 Normative References None. 3 Parameters for GC-MS/MS determination of pesticides following electron impact ionization 3.1 General All parameters given in Table 2 were carefully selected from different sources (open literature
21、, application notes of instrument providers or tested by experts of CEN/TC 275/WG 4). Only transitions that were applicable on instruments of at least two different manufacturers (e.g. Agilent Technologies, Bruker Daltonics, Thermo Scientific, former Varian Inc., Waters Corporation) were selected. G
22、C parameters and retention times are not described in this Technical Report. If needed, this information can be taken from CEN/TR 16468 “Food analysis - Determination of pesticide residues by GC-MS - Retention times, mass spectrometric parameters and detector response information“. 3.2 General MS/MS
23、 Parameters All listed MS/MS transitions were obtained from measurements with electron impact ionization at 70 eV. Other parameters (e.g. ion source temperature, ion source voltages, source pressure and the type of carrier gas) were not identical. It is well recognized that variations of these param
24、eters may influence the intensity of selected precursor ions and individual optimization may be necessary. However, despite these differences very often the same preferred precursor ions were reported. This demonstrates that in many cases parameters can be transferred between instruments of other ty
25、pes of the same or other manufacturers, even if these instruments are operated under slightly different conditions. 3.3 Analyte specific MS/MS Parameters The most often reported analyte specific ion transitions of pesticides are listed in Table 2. Transitions applicable for instruments of three supp
26、liers are reported first and those transitions reported for instruments of two suppliers are written in italics. If available, at least two precursor ions with their transitions have been selected for each analyte. In general, transitions starting from ions with higher mass were preferred to transit
27、ions from low mass precursor ions. Pesticide names (and those of some metabolites) are supplemented by the molecular mass and the CAS number (Chemical Abstracts Service), which is useful for searches in databases. The CAS number is usually taken from 1, but in various cases more than one number exis
28、ts, e.g. for isomers and racemates. PD CEN/TR 16699:2014CEN/TR 16699:2014 (E) 6 In addition to the above mentioned parameters, an indication on the appropriate collision energy for each transition is given. Instead of definitive voltages, a classification into low, medium and high collision energies
29、 was chosen, because transitions are based on data from different instruments, which do not require identical voltages to obtain the optimal intensity for a given transition. Therefore, from each reference (application note, article, etc.) all parameter sets were sorted by the collision energy in or
30、der to obtain the categories. Afterwards, the sorted list was divided in three groups of equal size. The resulting meaning of low, medium and high collision energy is listed in Table 1. Table 1 Categories of collision energy (CE) Instrument Voltage corresponding to low CE V Voltage corresponding to
31、medium CE V Voltage corresponding to high CE V Agilent 7000 Series 21 Bruker SCION TQ 16 Thermo Quantum 19 Varian 1200 (L) 20 Waters Quattro micro 17 PD CEN/TR 16699:2014CEN/TR 16699:2014 (E) 7 Table 2 MS/MS Parameters Pesticide name CAS-Nr. MRM No. 1 CE MRM No. 2 CE MRM No. 3 CE MRM No. 4 CE MRM No
32、. 5 CE Acephate 305-19-1 136 94 m 136 42 l Acetochlor 34256-82-1 146 130 h 223 132 h 223 146 l 224 148 l Aclonifen 74070-46-5 212 182 l 264 194 m 264 211 l 264 182 h 264 212 l Acrinathrin 101007-06-1 181 152 m 208 181 l 289 93 l 181 127 h 208 152 h Alachlor 15972-60-8 188 130 h 188 160 l Aldrin 309-
33、00-2 263 191 h 263 193 h 263 228 m 265 193 h 293 258 h Allethrin 584-79-2 123 81 l 123 79 m 136 108 l Atrazine 1912-24-9 200 94 m 200 104 m 200 122 l 215 173 l 215 200 l Azinphos-ethyl 2642-71-9 132 77 l 160 77 m 160 104 l 160 132 l 132 104 l Azinphos-methyl 86-50-0 132 77 m 160 77 m 160 104 l 160 1
34、32 l Azoxystrobin 131860-33-8 344 156 h 344 329 m 388 345 m 388 300 m Benfluralin 1861-40-1 292 160 m 292 206 m 292 264 l Bifenthrin 82657-04-3 181 115 h 181 165 h 181 166 m 165 115 h 166 165 m Biphenyl 92-52-4 154 152 h 154 153 m 153 152 m 154 128 m Bitertanol 70585-36-3 141 115 m 170 115 h 170 141
35、 m Boscalid (Nicobifen) 188425-85-6 140 76 h 140 112 l 342 140 m 342 112 m Bromophos 2104-96-3 329 314 m 331 286 h 331 316 m 331 93 h Bromophos-ethyl 4824-78-6 303 285 m 359 303 m 359 331 l 357 301 m 358 303 m Bromopropylate 18181-80-1 185 157 h 341 155 h 341 157 h 341 183 m 341 185 m Bupirimate 414
36、83-43-6 273 108 m 273 193 l 316 208 l Buprofezin 69327-76-0 172 57 l 175 132 l 105 77 m 105 104 l Cadusafos 95465-99-9 159 97 m 159 131 l 158 114 m Captafol 2425-06-1 79 51 h 79 77 l 313 79 m 150 79 m 151 79 m Captan 133-06-2 79 77 l 149 70 m 149 79 m 149 105 l PD CEN/TR 16699:2014CEN/TR 16699:2014
37、(E) 8 Pesticide name CAS-Nr. MRM No. 1 CE MRM No. 2 CE MRM No. 3 CE MRM No. 4 CE MRM No. 5 CE Captan metabolite (Tetrahydrophthalimide) 1469-48-3 151 79 l 151 80 l 151 122 l Carbaryl 63-25-2 144 115 h 144 116 m Carbaryl metabolite (1-Naphthol) 90-15-3 144 115 h 115 63 h 115 89 m Carbofuran 1563-66-2
38、 164 131 m 164 149 l Carboxin 5234-68-4 235 87 h 235 143 l Chinomethionat 2439-01-2 206 148 m 234 206 l 234 148 h Chlorbenside 103-17-3 125 89 m 268 125 l Chlordane 5103-71-9 373 266 h 373 301 m 272 237 m 410 375 l Chlorfenapyr 122453-73-0 59 31 l 247 200 h 247 227 m 247 197 m 408 59 l Chlorfenson 8
39、0-33-1 175 111 l 302 175 l 302 111 h Chlorfenvinphos 18708-86-6 267 159 m 323 267 m 267 81 h 269 161 m 325 269 m Chlormephos 24934-91-6 154 121 l 234 121 m Chlorobenzilate 510-15-6 139 111 m 251 139 m 251 111 h 253 141 m Chloroneb 2675-77-6 206 191 l 191 141 l 191 113 m Chloropropylate 5836-10-2 139
40、 111 l 251 111 h 251 139 m 253 141 m Chlorothalonil 1897-45-6 264 133 h 264 168 h 264 229 m 266 133 h 266 231 m Chlorpropham 101-21-3 127 65 h 171 127 l 213 127 m 213 171 l Chlorpyrifos (ethyl) 2921-88-2 197 169 m 199 171 m 314 258 m 314 286 l 316 260 l Chlorpyrifos-methyl 5598-13-0 286 93 m 286 271
41、 m 288 93 h Chlorthal-dimethyl 1861-32-1 299 221 h 301 223 h 301 273 m 332 301 l Chlozolinate 84332-86-5 188 147 m 259 188 m 331 259 l Clomazone 81777-89-1 125 89 m 125 99 m 204 107 m Coumaphos 56-72-4 226 163 m 362 109 m 362 226 m 362 334 l Cyanazine 21725-46-2 198 91 l 225 189 l 240 225 l 212 123
42、m Cyanofenphos 13067-93-1 157 110 l 303 169 l 169 141 l 303 141 m Cyanophos 2636-26-2 243 79 h 243 109 m 243 127 m 109 79 l 125 79 l PD CEN/TR 16699:2014CEN/TR 16699:2014 (E) 9 Pesticide name CAS-Nr. MRM No. 1 CE MRM No. 2 CE MRM No. 3 CE MRM No. 4 CE MRM No. 5 CE Cyfluthrin, beta- 86560-93-2 163 91
43、 m 163 127 l 206 151 h 226 206 l 227 199 l Cyhalothrin, lambda- 91465-08-6 181 152 h 197 141 m 197 161 l 197 91 m Cypermethrin 67375-30-8 163 91 m 163 127 l 181 152 h 165 127 l Cyproconazole 94361-06-5 139 111 m 222 82 l 222 125 m 222 153 l Cyprodinil 121552-61-2 224 197 h 224 208 m 225 224 l 225 20
44、8 m 225 210 m DDD, o,p- 53-19-0 235 165 h 235 199 m 237 165 h DDD, p,p- 72-54-8 235 165 h 235 199 m 237 165 h DDE, o,p- 3424-82-6 246 176 h 318 248 m 248 176 h 318 176 h DDE, p,p- 72-55-9 246 176 h 248 176 h 318 246 h 318 248 h DDT, o,p- 789-02-6 235 165 h 237 165 m DDT, p,p- 50-29-3 235 165 h 235 1
45、99 m 237 165 h DEET 134-62-3 119 91 l 190 91 m 190 145 l 190 117 m 190 119 m Deltamethrin 52918-63-5 181 152 h 253 93 m 253 172 l 253 174 l 181 127 h Di-allate 2303-16-4 234 150 m 234 192 m Diazinon 333-41-5 179 122 h 179 137 m 304 179 m Dichlobenil 1194-65-6 171 100 h 171 136 m 173 138 m Dichlofent
46、hion 97-17-6 223 205 l 279 205 h 279 223 m Dichlofluanid 1085-98-9 167 124 l 224 123 m 226 123 m 123 77 m 167 97 m Dichlorbenzophenone, p,p- 90-98-2 139 75 h 139 111 m 250 139 l 250 215 l Dichloroaniline, 3,4- 95-76-1 161 99 h 161 126 m 161 90 m Dichlorvos 62-73-7 109 79 l 185 93 m 185 109 m Dicloran 99-30-9 176 148 m 206 124 h 206 148 m 206 176 l 208 178 l Dicofol, p,p 115-32-2 139 111 m 251 139 m 253 141 m Dicrotophos 3735-78-3 127 95 m 127 109 l 193 127 l Dieldrin 60-57-1 263 191 h 263 193 h 279 243 m 277 241 l
