CEN/TR 16468:2013

SLOVENSKI STANDARD
01-junij-2013
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Food analysis - Determination of pesticide residues by GC-MS - Retention times, mass
spectrometric parameters and detector response information
Lebensmitteluntersuchung - Bestimmung von Pestizidrückständen mit GC-MS -
Retentionszeiten, Parameter für die Massenspektrometrie und Detektionsempfindlichkeit
Analyse des produits alimentaires - Détermination des résidus de pesticides par CG-SM
- Temps de rétention, paramètres de spectrométrie de masse et information sur la
réponse des détecteurs
Ta slovenski standard je istoveten z: CEN/TR 16468:2013
ICS:
65.100.01 Pesticidi in druge Pesticides and other
agrokemikalije na splošno agrochemicals in general
67.050 Splošne preskusne in General methods of tests and
analizne metode za živilske analysis for food products
proizvode
2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.

TECHNICAL REPORT
CEN/TR 16468
RAPPORT TECHNIQUE
TECHNISCHER BERICHT
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 - Détermination des Lebensmitteluntersuchung - Bestimmung von
résidus de pesticides par CG-SM - Temps de rétention, Pestizidrückständen mit GC-MS - Retentionszeiten,
paramètres de spectrométrie de masse et information sur Parameter für die Massenspektrometrie und
la réponse des détecteurs Detektionsempfindlichkeit

This Technical Report was approved by 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, Iceland, Ireland, Italy, Latvia, Lithuania,
Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland, Turkey and United
Kingdom.
EUROPEAN COMMITTEE FOR STANDARDIZATION
COMITÉ EUROPÉEN DE NORMALISATION

EUROPÄISCHES KOMITEE FÜR NORMUNG

Management Centre: Avenue Marnix 17, B-1000 Brussels
© 2013 CEN All rights of exploitation in any form and by any means reserved Ref. No. CEN/TR 16468:2013: E
worldwide for CEN national Members.

Contents Page
Foreword . 3
Introduction . 4
1 Scope . 5
2 Analyte specific parameters 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

Foreword
This document (CEN/TR 16468:2013) has been prepared by Technical 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 such patent rights.

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
analysed 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 (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 is 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 chromatograms. 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).

1 Scope
This Technical Report lists mass spectrometric parameters which are useful 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 — Multiresidue 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 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-NPD 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 been 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)
Injection 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 µl or 2 µl
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 m, inner diameter 0,25 mm,
film thickness 0,25 µm (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 temperatures 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)

As an alternative to the abovementioned fused silica capillary 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 µm (Agilent Nr. 122-3832)
Carrier gas/MS detection Hydrogen, constant flow 1,1 ml/min (typical 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 technique/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 µl
Purge Gas nitrogen; purge flow 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 impact 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 standard 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 listed 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), which 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.

The RRT data for columns HP-5MS and DB-35MS in Table 1 are relative retention times compared to
parathion (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
RRT RRT
Pesticide name CAS-Nr. Ion1 Ion2 Ion3 Ion4 MSD ECD NPD
HP5MS DB35MS
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 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 0,79 151 150 136 208 xx xx
Amitraz 33089-61-1 1,56 1,46 121 162 132 293 xx x
Amitraz hydrolysis product
95-68-1 0,35 0,41 121 120 106 77 xxx x
(Dimethylaniline, 2,4,-
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 101-05-3 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 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 xx 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
Beflubutamid 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 68505-69-1 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
Table 1 (continued)
RRT RRT
Pesticide name CAS-Nr. Ion1 Ion2 Ion3 Ion4 MSD ECD NPD
HP5MS DB35MS
Bentazone-methyl 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
39811-17-1 0,95 1,01 184 156 199 x x x
(5-Phenyl-o-anisidine)
Bifenox 42576-02-3 1,53 1,46 341 343 310 173 xx 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) 584-79-2 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
...