1、raising standards worldwideNO COPYING WITHOUT BSI PERMISSION EXCEPT AS PERMITTED BY COPYRIGHT LAWBSI Standards PublicationPD CEN/TR 16468:2013Food analysis Determination of pesticide residues by GC-MS Retention times, mass spectrometric parameters and detector response informationPD CEN/TR 16468:201
2、3 PUBLISHED DOCUMENTNational forewordThis Published Document is the UK implementation of CEN/TR 16468:2013.The UK participation in its preparation was entrusted to TechnicalCommittee AW/275, Food analysis - Horizontal methods.A list of organizations represented on this committee can beobtained on re
3、quest to its secretary.This publication does not purport to include all the necessary provisions of a contract. Users are responsible for its correct application. The British Standards Institution 2013.Published by BSI Standards Limited 2013 ISBN 978 0 580 79327 1 ICS 65.100.01; 67.050 Compliance wi
4、th a British Standard cannot confer immunity fromlegal obligations.This Published Document was published under the authority of theStandards Policy and Strategy Committee on 30 April 2013. Amendments issued since publication Date Text affectedPD CEN/TR 16468:2013TECHNICAL REPORT RAPPORT TECHNIQUE TE
5、CHNISCHER BERICHT CEN/TR 16468 March 2013 ICS 65.100.01; 67.050 English Version Food analysis - Determination of pesticide residues by GC-MS -Retention times, mass spectrometric parameters and detector response information Analyse des produits alimentaires - Dtermination des rsidus de pesticides par
6、 CG-SM - Temps de rtention, paramtres de spectromtrie de masse et information sur la rponse des dtecteurs Lebensmitteluntersuchung - Bestimmung von Pestizidrckstnden mit GC-MS - Retentionszeiten, Parameter fr die Massenspektrometrie und Detektionsempfindlichkeit This Technical Report was approved by
7、 CEN on 3 December 2012. 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, Icela
8、nd, 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 Management Centre:
9、 Avenue Marnix 17, B-1000 Brussels 2013 CEN All rights of exploitation in any form and by any means reserved worldwide for CEN national Members. Ref. No. CEN/TR 16468:2013: EPD CEN/TR 16468:2013CEN/TR 16468:2013 (E) 2 Contents Page Foreword . 3 Introduction 4 1 Scope 5 2 Analyte specific parameters
10、for gas chromatographic determination of pesticides 5 2.1 General . 5 2.2 GC-MS, GC-ECD and GC-NPD Parameters . 5 2.3 Analyte specific retention times and MS parameters . 6 Bibliography 24 PD CEN/TR 16468:2013CEN/TR 16468:2013 (E) 3 Foreword This document (CEN/TR 16468:2013) has been prepared by Tec
11、hnical Committee 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
12、 such patent rights. PD CEN/TR 16468:2013CEN/TR 16468:2013 (E) 4 Introduction Pesticide residue analysis employs multiple methods involving extraction of residues from foods and clean-up of the extract to obtain as many analytes as possible in the purified extracts. Afterwards the extracts can be an
13、alysed by different kinds of instruments. The hyphenation of gas chromatography (GC) and mass spectrometry (MS) is one of the most often used universal and selective analysis techniques for identification and quantification of pesticide residues in food extracts. For the ionisation of the analytes (
14、pesticides and/or their metabolites) in GC-MS, electron impact ionisation (EI) is most commonly used. If the typical electron energy of 70 eV is used, very often molecular ions (cation radicals) and several fragment ions are formed simultaneously. The selective determination of each target analyte i
15、s performed by simultaneous aquisition of typically three ions formed by the analyte in the selected ion monitoring (SIM) mode. The diagnostic value of an ion depends on its mass. Usually even-numbered, high mass ions are less frequently formed and their recording results in more specific chromatogr
16、ams. A reduction of selectivity may be caused by background ions formed during column bleeding or by sample matrix (e.g. typical ions from fatty of fruit acids or hydrocarbons). PD CEN/TR 16468:2013CEN/TR 16468:2013 (E) 5 1 Scope This Technical Report lists mass spectrometric parameters which are us
17、eful for the application of European Standards for the determination of pesticide residues in foods that use GC-MS, such as the following standards: EN 1528 (all parts), Fatty food Determination of pesticides and polychlorinated biphenyls (PCBs); EN 12393 (all parts), Foods of plant origin Multiresi
18、due methods for the gas chromatographic determination of pesticide residues; EN 15662, Foods of plant origin Determination of pesticide residues using GC-MS and/or LC-MS/MS following acetonitrile extraction/partitioning and clean-up by dispersive SPE QuEChERS-method. To facilitate the determination
19、of pesticides and/or metabolites using GC-MS, Table 1 specifies the diagnostic ions suitable for quantification, which can be used. 2 Analyte specific parameters for gas chromatographic determination of pesticides 2.1 General All values indicated in Table 1 were acquired using GC-MS, GC-ECD or GC-NP
20、D systems under the experimental conditions as outlined in 2.2. Comparative investigations showed that these parameters can be transferred simply on instruments of other types of the same or other manufacturers 1. 2.2 GC-MS, GC-ECD and GC-NPD Parameters The following GC operating conditions have bee
21、n proven to be satisfactory. This is an example for appropriate experimental conditions. Equivalent conditions may be used if they can be shown to lead to the same results. Gas chromatograph Agilent model 6890 Carrier gas Helium, constant flow 1,0 ml/min (typical pressure at 70 C is 61 kPa) Injectio
22、n technique Pulsed splitless, 200 kPa; Pulse time 1,0 min Injector temperature 240 C Injection liner single taper, splitless (Agilent 5181-3316) Injection volume 1 l or 2 l Purge Gas Helium; purge flow to split vent 50 ml/min; Purge time 1,5 min Column Fused silica capillary column HP-5MS, length 30
23、 m, inner diameter 0,25 mm, film thickness 0,25 m (Agilent Nr. 19091S-433) Temperature programme 2 min 70 C, programmed to rise at 25 C/min to 170 C, at 3 C/min to 210 C, at 30 C/min to 290 C, then isothermal for 9 min Transfer Line Temperatur 280 C Mass spectrometer Agilent MSD 5973N inert MS tempe
24、ratures Quadrupole 150 C; Source 230 C; Ionisation Electron impact 70 eV Solvent Delay 4,0 min Retention time of parathion 15,85 min (parathion is used for calculation of relative retention times) PD CEN/TR 16468:2013CEN/TR 16468:2013 (E) 6 As an alternative to the abovementioned fused silica capill
25、ary column HP-5MS a column DB-35MS can be used. This column requires some slightly changed conditions. Column Fused silica capillary column DB-35MS, length 30 m, inner diameter 0,25 mm, film thickness 0,25 m (Agilent Nr. 122-3832) Carrier gas/MS detection Hydrogen, constant flow 1,1 ml/min (typical
26、pressure at 80 C is 15,9 kPa) Carrier gas/NPD and ECD detection Hydrogen, constant flow 1,9 ml/min (typical pressure at 80 C is 88,3 kPa) Temperature programme 1,8 min 80 C, programmed to rise at 30 C/min to 190 C, at 6 C/min to 240 C, at 30 C/min to 290 C, then isothermal for 12 min Injection techn
27、ique/MS detection Pulsed splitless, 80 kPa; Pulse time 1,5 min Injection technique/NPD and ECD, parallel detection Pulsed splitless, 172 kPa; Pulse time 1,5 min Injector temperature 240 C Injection liner single taper, splitless (Agilent 5181-3316) Injection volume 2 l Purge Gas nitrogen; purge flow
28、to split vent 35 ml/min; Purge time 2,0 min Detector split ratio 1:5 (ECD:NPD; post column) Detector temperature (NPD) 280 C Detector temperature (ECD) 300 C Transfer line temperature (MS) 280 C Mass spectrometer Agilent MSD 5973N MS temperatures Quadrupole 150 C; Source 230 C; Ionisation Electron i
29、mpact 70 eV Solvent Delay/MS 4,0 min Retention time of parathion 14,69 min (RT parathion with GC NPD/ECD is used for calculation of relative retention times) As slight fluctuations in the measurement conditions influence the retention time, usually relative retention times (RRT), related to a standa
30、rd substance, are compared. The standard substance for the calculation of the RRT values in the tables was parathion (RRT = 1,000). 2.3 Analyte specific retention times and MS parameters The analyte specific parameters for selected ion monitoring (SIM) of pesticides by GC-MS with EI ionisation are l
31、isted in Table 1. These data are completed by some indications about the sensitivity of detection, which can be expected if GC-MS with the most intense ion and GC-ECD or GC-NPD are used. The names of the individual active substances are supplemented by the CAS number (Chemical Abstracts Service), wh
32、ich is useful for the search in data bases. It is usually taken from 2, but there can be several numbers in individual cases, e.g. for isomers and racemates. PD CEN/TR 16468:2013CEN/TR 16468:2013 (E) 7 The RRT data for columns HP-5MS and DB-35MS in Table 1 are relative retention times compared to pa
33、rathion (RRT = 1,00). The units for numbers presented in columns Ion 1 to Ion 4 are Da (or m/z). Three crosses in the columns MSD, ECD or NPD indicate a better sensitivity compared to two or one crosses. Table 1 Parameters of 691 analytes Pesticide name CAS-Nr. RRT HP5MS RRT DB35MS Ion1 Ion2 Ion3 Io
34、n4 MSD ECD NPD Acephate 30560-19-1 0,47 0,58 136 94 95 96 xx x xx Aclonifen 74070-46-5 1,40 1,34 264 266 212 77 xxx x x Acrinathrin, 1 101007-06-1 1,57 1,41 207 181 281 208 xx xxx xx Acrinathrin, 2 101007-06-1 1,58 1,46 181 208 207 93 xxx xxx xx Alachlor 15972-60-8 0,89 0,88 160 188 146 237 xxx xxx
35、x Aldicarb, -sulfone 1646-88-4 0,33 0,43 68 80 65 69 xx x x Aldrin 309-00-2 0,97 0,93 263 66 265 261 xxx xxx Allidochlor 93-71-0 0,40 0,47 56 138 132 70 xxx xx xx Ametryn 834-12-8 0,89 0,93 227 212 170 185 xxx xx Amidithion 919-76-6 0,96 1,03 125 131 93 143 x x x Aminocarb 2032-59-9 0,73 0,79 151 15
36、0 136 208 xx xx Amitraz 33089-61-1 1,56 1,46 121 162 132 293 xx x Amitraz hydrolysis product (Dimethylaniline, 2,4,- 95-68-1 0,35 0,41 121 120 106 77 xxx x Amitraz-metabolite (BTS 27271) 33089-74-6 0,55 0,61 162 132 120 106 x xx Ancymidol 12771-68-5 1,36 1,30 228 107 121 215 xx xxx Anilazine 101-05-
37、3 1,09 1,11 239 241 178 143 x xx x Anilofos 64249-01-0 1,53 1,46 226 125 184 334 xx xx xx Aramite, 1 140-57-8 1,32 1,20 185 175 319 334 x x Aramite, 2 140-57-8 1,35 1,22 185 175 319 334 x x Aspon 3244-90-4 0,99 0,90 211 210 253 378 xxx xx xxx Atraton 1610-17-9 0,69 0,74 196 211 169 154 xx x Atrazine
38、 1912-24-9 0,71 0,76 200 215 202 173 xxx x xxx Atrazine, -desethyl 6190-65-4 0,63 0,71 172 174 187 145 xx x x Atrazine, -desethyl-desisopropyl 3397-62-4 0,56 0,66 145 110 68 147 x x xx Atrazine, -desisopropyl 1007-28-9 0,61 0,72 173 158 145 68 x x x Azaconazole 60207-31-0 1,32 1,30 217 219 173 175 x
39、x x xx Azamethiphos 35575-96-3 1,44 1,39 215 155 125 109 x x xx Azinphos-ethyl 2642-71-9 1,55 1,59 132 160 77 105 x xx xxx Azinphos-methyl 86-50-0 1,55 1,55 160 132 77 105 xx xx xxx Azobenzene 103-33-3 0,60 0,66 77 182 105 51 x x xxx Azoxystrobin 131860-33-8 1,82 2,28 344 388 345 372 xx xx x Beflubu
40、tamid 113614-08-7 1,13 1,03 91 176 221 193 xx x x Benalaxyl 71626-11-4 1,45 1,35 148 91 206 204 xxx x Benazolin-ethyl 25059-80-7 1,09 1,13 170 271 198 134 xxx xxx x Benfluralin 1861-40-1 0,64 0,61 292 264 276 335 xx xxx xx Benfuracarb 82560-54-1 1,58 1,50 190 163 164 102 xx x xx Benfuresate 68505-69
41、-1 0,84 0,90 163 256 121 164 xxx x x Benodanil 15310-01-7 1,43 1,38 231 323 203 76 xxx xx x Benoxacor 98730-04-2 0,82 0,87 120 259 261 176 xx xxx xx PD CEN/TR 16468:2013CEN/TR 16468:2013 (E) 8 Table 1 (continued) Pesticide name CAS-Nr. RRT HP5MS RRT DB35MS Ion1 Ion2 Ion3 Ion4 MSD ECD NPD Bentazone-m
42、ethyl 61592-45-8 0,89 0,94 212 105 254 133 xxx x xx Benzoylprop-ethyl 22212-55-1 1,50 1,39 105 77 292 294 xxx xx x Bifenazate 149877-41-8 1,52 1,44 300 258 199 196 xx x Bifenazate-metabolite (5-Phenyl-o-anisidine) 39811-17-1 0,95 1,01 184 156 199 x x x Bifenox 42576-02-3 1,53 1,46 341 343 310 173 xx
43、 xxx x Bifenthrin 82657-04-3 1,52 1,36 181 165 166 182 xxx xxx Binapacryl 485-31-4 1,37 1,22 83 55 84 53 x x x Bioallethrin S-cyclopentyl (Esbiol) 28434-00-6 1,12 1,00 123 136 79 107 xx xxx Bioallethrin, cis- (Allethrin) 584-79-2 1,11 1,00 123 136 79 91 x xxx Bioallethrin, trans- (Allethrin) 584-79-
44、2 1,12 1,00 123 136 79 91 xx xxx Bioresmethrin 28434-01-7 1,49 1,35 123 171 143 128 xxx x Biphenyl 92-52-4 0,45 0,51 154 153 152 155 xxx Bitertanol, 1 70585-36-3 1,60 1,55 170 168 171 112 xx x x Bitertanol, 2 70585-38-5 1,61 1,57 170 168 171 112 xx x x Boscalid 188425-85-6 1,67 1,78 140 342 142 344
45、xx xxx xx Bromacil 314-40-9 0,96 1,05 205 207 206 188 x xx xx Metobromuron-metabolite (4-Bromoaniline) 106-40-1 0,41 0,49 171 173 92 65 xxx x x Bromfenvinfos, (E)- 58580-14-6 1,24 1,13 267 269 323 325 xx xx x Bromfenvinfos, (Z)- 58580-13-5 1,20 1,19 267 269 323 325 x xx x Bromocyclen 1715-40-8 0,81
46、0,80 357 359 361 355 xxx xxx Bromophos 2104-96-3 1,04 1,03 331 329 125 333 xxx xxx xxx Bromophos-ethyl 4824-78-6 1,17 1,09 359 303 357 97 xxx xxx xxx Bromopropylate 18181-80-1 1,51 1,40 341 343 339 183 xxx xxx Bromuconazole, cis- 116255-48-2 1,51 1,44 173 295 175 293 xxx x xx Bromuconazole, trans- 1
47、16255-48-2 1,53 1,48 173 175 295 293 xxx x xx Bupirimate 41483-43-6 1,34 1,24 273 208 316 166 xxx xx xx Buprofezin 69327-76-0 1,31 1,20 105 172 106 175 xxx x x Butachlor 23184-66-9 1,21 1,08 176 160 57 188 xxx xxx xc Butafenacil 134605-64-4 1,63 1,58 331 333 180 332 xx xx x Butamifos 36335-67-8 1,24
48、 1,17 286 200 232 202 x xxx xxx Butralin 33629-47-9 1,05 0,95 266 224 295 267 xx xx x Butylate 2008-41-5 0,47 0,50 57 146 156 174 xx xx Cadusafos 95465-99-9 0,65 0,67 159 158 88 97 xxx xxx xxx Cafenstrole 125306-83-4 1,64 1,68 100 188 72 119 xx xx x Captafol 2425-06-1 1,48 1,43 79 80 77 183 xx x x C
49、aptan 133-06-2 1,11 1,19 79 149 77 80 xx xx x Captan-metabolite (Tetrahydrophthalimide) 1469-48-3 0,50 0,62 79 151 80 77 xxx x x Carbaryl-GC-artifact (1-Naphthol) 90-15-3 0,52 0,53 144 115 116 145 xx Carbetamide 16118-49-3 1,03 1,04 119 120 91 64 x Carbofuran 1563-66-2 0,70 0,80 164 149 131 122 xx x Carbofuran, -phenol 1563-38-8 0,42 0,46 164 149 131 122 xx x Carbophenothion 786-19-6 1,45 1,34 157 342 121 153 xxx xx xxx PD CEN/TR 16468:2013CEN/TR 16468:2013 (E) 9 Table 1 (continued) Pesticide name CAS-Nr. RRT HP5
