SIST-TP CEN/TR 16699:2014

Foodstuffs - Determination of pesticide residues by GC-MS/MS - Tandem mass spectrometric parameters

CEN/TR 16699 lists the mass spectrometric parameters which are useful for the application of European Standards for the determination of pesticide 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 pesticide 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 transitions suitable for identification and quantification, which can be used.

Lebensmittel - Bestimmung von Pestizidrückständen mit GC-MS/MS - Parameter für die Tandem-Massenspektrometrie

Im vorliegenden Technischen Bericht werden die Parameter für die Massenspektrometrie aufgeführt, die bei der Anwendung von Europäischen Normen zur Bestimmung von Pestizidrückständen in pflanzlichen Lebensmitteln, bei denen GC MS eingesetzt wird, hilfreich sind. Diese Normen sind:
-   EN 1528:    „Fettreiche Lebensmittel — Bestimmung von Pestiziden und polychlorierten Biphenylen (PCB)“
-   EN 12393:    “Pflanzliche Lebensmittel - Multiverfahren zur Bestimmung von Pestizidrückständen mit GC oder LC-MS/MS”;
-   EN 15662    “Pflanzliche Lebensmittel - Bestimmung von Pestizidrückständen mit GC-MS und/oder LC-MS/MS nach Acetonitril-Extraktion/Verteilung und Reinigung mit dispersiver SPE - QuEChERS-Verfahren”.
Zur Erleichterung der Bestimmung von Pestiziden und/oder deren Metaboliten mit GC MS/MS sind die für die Identifizierung und quantitative Bestimmung geeigneten und anwendbaren Übergänge von diagnostischen Ionen in Tabelle 2 festgelegt.

Produits alimentaires - Détermination des résidus de pesticides par CG-SM/SM - Paramètres pour la spectrométrie de masse en tandem

Le présent Rapport technique répertorie les paramètres de spectrométrie de masse qui sont utiles pour l’application des Normes européennes traitant de la détermination des résidus de pesticides dans les aliments d’origine végétale par CG-SM. Ces normes sont les suivantes :
-   EN 1528, Aliments gras — Dosage des pesticides et des polychlorobiphényles (PCB) ;
-   EN 12393, Aliments d’origine végétale — Méthodes multirésidus de détermination de résidus de pesticides par CPG ou CL-SM/SM ;
-   EN 15662, Aliments d’origine végétale — Méthode polyvalente de détermination des résidus des pesticides par CG-SM et CL/SM/SM avec extraction/partition avec de l’acétonitrile et nettoyage par SPE dispersés — Méthode QuEchERS.
Pour faciliter la détermination des pesticides et/ou de leurs métabolites par CG-SM/SM, le Tableau 2 spécifie les transitions d’ions de diagnostic adaptées à l’identification et à la quantification, qui peuvent être utilisées.

Živila - Določevanje ostankov pesticidov z GC-MS/MS - Parametri tandemske masne spektrometrije

CEN/TR 16699 navaja parametre masne spektrometrije, ki so uporabni za evropske standarde za določevanje ostankov pesticidov v živilih rastlinskega izvora, ki uporabljajo GC-MS. Ti evropski standardi so naslednji: EN 1528 (vsi deli), Živila, ki vsebujejo maščobe – Določevanje pesticidov in polikloriranih bifenilov (PCB); EN 12393 (vsi deli), Živila brez maščob – Multirezidualne metode za določevanje ostankov pesticidov s plinsko kromatografijo; EN 15662, Hrana rastlinskega izvora – Določanje ostankov pesticidov z uporabo GC-MS in/ali LC-MS(/MS) po delitvi in izpiranju acetonitrila z disperzivno SPE – Metoda QuEChERS. Za lažje določevanje pesticidov in/ali metabolitov z uporabo GC-MS/MS so v preglednici 2 navedeni diagnostični ioni, primerni za kvantifikacijo, ki jih je mogoče uporabiti.

General Information

• Status: Published
• Public Enquiry End Date: 30-Mar-2014
• Publication Date: 03-Sep-2014
• ICS: 65.100.01 - Pesticides and other agrochemicals in general
• ICS: 67.050 - General methods of tests and analysis for food products
• Technical Committee: KŽP - Agricultural food products
• Current Stage: 6060 - National Implementation/Publication (Adopted Project)
• Start Date: 06-Aug-2014
• Due Date: 11-Oct-2014
• Completion Date: 04-Sep-2014
• Ref Project: CEN/TR 16699:2014 - Foodstuffs - Determination of pesticide residues by GC-MS/MS - Tandem mass spectrometric parameters

Standards Content (Sample)

SLOVENSKI STANDARD
SIST-TP CEN/TR 16699:2014
01-oktober-2014
äLYLOD'RORþHYDQMHRVWDQNRYSHVWLFLGRY]*&06063DUDPHWULWDQGHPVNH
PDVQHVSHNWURPHWULMH
Foodstuffs - Determination of pesticide residues by GC-MS/MS - Tandem mass
spectrometric parameters
Lebensmittel - Bestimmung von Pestizidrückständen mit GC-MS/MS - Parameter für die
Tandem-Massenspektrometrie
Produits alimentaires - Détermination des résidus de pesticides par CG-SM/SM -
Paramètres pour la spectrométrie de masse en tandem
Ta slovenski standard je istoveten z: CEN/TR 16699:2014
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
SIST-TP CEN/TR 16699:2014 en,fr,de
2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.

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SIST-TP CEN/TR 16699:2014

TECHNICAL REPORT
CEN/TR 16699

RAPPORT TECHNIQUE

TECHNISCHER BERICHT
July 2014
ICS 67.050
English Version
Foodstuffs - Determination of pesticide residues by GC-MS/MS -
Tandem mass spectrometric parameters
Produits alimentaires - Détermination des résidus de Lebensmittel - Bestimmung von Pestizidrückständen mit
pesticides par CG-SM/SM - Paramètres pour la GC-MS/MS - Parameter für die Tandem-
spectrométrie de masse en tandem Massenspektrometrie


This Technical Report was approved 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, 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

CEN-CENELEC Management Centre: Avenue Marnix 17, B-1000 Brussels
© 2014 CEN All rights of exploitation in any form and by any means reserved Ref. No. CEN/TR 16699:2014 E
worldwide for CEN national Members.

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Contents Page

Foreword .3
Introduction .4
1 Scope .5
2 Parameters for GC-MS/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

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Foreword
This document (CEN/TR 16699:2014) 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.
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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 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-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 widely 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 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 signal 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 the scientific literature or are most often proposed
by suppliers of GC-MS/MS instruments.
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1 Scope
This Technical Report lists the mass spectrometric parameters which are useful for the application of
European Standards for the determination of pesticide 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 pesticide 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 transitions 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, 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.
GC 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 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 parameters 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 types 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 suppliers 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
transitions 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 exists, e.g. for isomers and racemates.
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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
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 order 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 Voltage corresponding Voltage corresponding
to low CE [V] to medium CE [V] to high CE [V]
Agilent 7000 Series < 13 13 to 21 > 21
Bruker SCION TQ < 8 8 to 16 > 16
Thermo Quantum < 15 15 to 19 > 19
Varian 1200 (L) < 13 13 to 20 > 20
Waters Quattro micro < 9 9 to 17 > 17
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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. 5 CE
Acephate 305-19-1 136 → 94 m 136 → 42 l
148 l
Acetochlor 34256-82-1 146 → 130 h 223 → 132 h 223 → 146 l 224 →
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 309-00-2 263 → 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 → 132 l
300 m
Azoxystrobin 131860-33-8 344 → 156 h 344 → 329 m 388 → 345 m 388 →
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
152 m 154 128 m
Biphenyl 92-52-4 154 → 152 h 154 → 153 m 153 → →
Bitertanol 70585-36-3 141 → 115 m 170 → 115 h 170 → 141 m
Boscalid (Nicobifen) 188425-85-6 140 → 76 h 140 → 112 l 342 → 140 m 342 → 112 m
93 h
Bromophos 2104-96-3 329 → 314 m 331 → 286 h 331 → 316 m 331 →
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 41483-43-6 273 → 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
79 m 151 79
Captafol 2425-06-1 79 → 51 h 79 → 77 l 313 → 79 m 150 → → m
Captan 133-06-2 79 → 77 l 149 → 70 m 149 → 79 m 149 → 105 l
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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 1563-66-2 164 → 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
237 m 410 375 l
Chlordane 5103-71-9 373 → 266 h 373 → 301 m 272 → →
Chlorfenapyr 122453-73-0 59 → 31 l 247 → 200 h 247 → 227 m 247 → 197 m 408 → 59 l
Chlorfenson 80-33-1 175 → 111 l 302 → 175 l 302 → 111 h
81 h 269 161 m 325 269 m
Chlorfenvinphos 18708-86-6 267 → 159 m 323 → 267 m 267 → → →
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
113 m
Chloroneb 2675-77-6 206 → 191 l 191 → 141 l 191 →
Chloropropylate 5836-10-2 139 → 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 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 m
Cyanofenphos 13067-93-1 157 → 110 l 303 → 169 l 169 → 141 l 303 → 141 m
79 l 125 79 l
Cyanophos 2636-26-2 243 → 79 h 243 → 109 m 243 → 127 m 109 → →
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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 m 163 → 127 l 206 → 151 h 226 → 206 l 227 → 199 l
91 m
Cyhalothrin, lambda- 91465-08-6 181 → 152 h 197 → 141 m 197 → 161 l 197 →
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
208 m 225 210 m
Cyprodinil 121552-61-2 224 → 197 h 224 → 208 m 225 → 224 l 225 → →
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
→ 176 h 31
...