EN 15741:2020

Animal feeding stuffs: Methods of sampling and analysis - Determination of OCPs and PCBs by GC-MS

This document specifies a gas chromatographic mass spectrometric (GC/MS) method for the determination of organochlorine pesticides (OCPs) and polychlorinated biphenyls (PCBs) in animal feeding stuffs and oil.
The method is applicable to animal feeding stuffs consisting of less than 20 % by mass and oil/fatty samples containing residues of one or more of the following OCPs and PCBs and some of their isomers and degradation products:
   aldrin;
   dieldrin;
   chlordane, as the sum of chlordane isomers and oxychlordane;
   dichlorodiphenyltrichloroethane (DDT), as the sum of isomers op'-DDT, pp'-DDT, pp'-TDE (pp'-DDD), and pp'-DDE;
   endosulfan, as the sum of α-/β-isomers and endosulfan-sulphate;
   endrin, as the sum of endrin and delta-keto-endrin;
   heptachlor, as the sum of heptachlor and heptachlor epoxide;
   hexachlorobenzene (HCB);
   hexachlorocyclohexane isomers α-HCH (α-BHC), β-HCH (β-BHC), γ-HCH (γ-BHC or lindane);
   photo heptachlor;
   cis- and trans-nonachlor;
   non dioxin-like PCBs (ndl-PCBs), as the sum of PCB 28, 52, 101, 138, 153 and 180.
The method has been fully validated by a collaborative trial for the substances and corresponding ranges (ng/g) noted in Table 1.
The method has not been fully validated for oxychlordane, endrin ketone, cis- and trans-nonachlor and photo heptachlor in all matrices.
The method is not applicable to chlorocamphene (toxaphene), a complex mixture of polychlorinated camphenes. Chlorocamphene has a very distinctive chromatographic profile and is easily recognisable by GC/ECD. Positive identification of the toxaphene isomers can be performed by negative chemical ionisation mass spectrometry (NCI-MS), electron impact tandem mass spectrometry (EI MS × MS) or electron impact high resolution mass spectrometry (EI-HRMS), which is not within the scope of this method.
A limit of quantification (LOQ) for the mentioned organochlorine pesticides of 5 ng/g should normally be obtained. However, 10 ng/g applies for heptachlor aldrin, endrin, dieldrin, and endosulfan (α-, β- and sulphate). For the ndl-PCBs an LOQ of 0,5 to 1,0 ng/g should be obtained. The LOQs mentioned apply to the individual compounds (i.e. not the sum of two or more compounds). Individual laboratories are responsible for ensuring that the equipment that they used will achieve these LOQs. On customers' demand the standard may be applied to solely the analysis of PCBs or OCPs.

Futtermittel: Probenahme- und Untersuchungsverfahren - Bestimmung von OCP und PCB mittels GC-MS

Dieses Dokument legt ein gaschromatographisches massenspektrometisches Verfahren (GC MS) für die Bestimmung von Organochlorpestiziden (OCP) und polychlorierten Biphenylen (PCB) in Mischfuttermitteln und Einzelfuttermitteln (Öle und Fette, Fischmehl) fest.
Das Verfahren ist auf Mischfuttermittel mit einem Massenanteil von weniger als 20 % und für öl /fetthaltige Proben anwendbar, die Rückstände von einem oder mehreren der folgenden OCP und PCB und einige von deren Isomeren und Abbauprodukten enthalten:
—   Aldrin;
—   Dieldrin;
—   Chlordan, als die Summe von Chlordanisomeren und Oxychlordan;
—   Dichlordiphenyltrichlorethan (DDT), als die Summe der Isomere von o,p’ DDT, p,p ’DDT, p,p’ TDE (p,p’ DDD) und p,p’ DDE;
—   Endosulfan, als die Summe von α /β Isomeren und Endosulfan Sulfat;
—   Endrin, als die Summe von Endrin und delta Ketoendrin;
—   Heptachlor, als die Summe von Heptachlor und Heptachlorepoxid;
—   Hexachlorbenzol (HCB);
—   Hexachlorcyclohexan Isomere α HCH (α BHC), β HCH (β BHC), γ HCH (γ BHC oder Lindan);
—   Photoheptachlor;
—   cis  und trans Nonachlor;
—   nicht dioxinähnliche PCB (ndl PCB), als Summe von PCB 28, 52, 101, 138, 153 und 180.
Das Verfahren wurde vollständig durch einen Ringversuch für die in Tabelle 1 aufgeführten Substanzen und entsprechenden Bereiche (µg/kg) validiert.
Das Verfahren wurde für Oxychlordan, Endrin-Keton, cis   und trans Nonachlor und Photoheptachlor in allen Matrices nicht vollständig validiert.
Für die Analyt/Matrix Kombinationen, bei denen die Validierungsdaten als unzureichend angesehen wurden, können die mit diesem Verfahren erzielten Ergebnisse nur als Screening-Ergebnisse betrachtet werden, es sei denn, das Laboratorium führt eine interne Validierung durch, um nachzuweisen, dass zufriedenstellende Ergebnisse erzielt werden können.
Das Verfahren ist nicht anwendbar auf Chlorcamphen (Toxaphen), eine komplexe Mischung von poly-chlorierten Camphenen. Chlorcamphen hat ein sehr ausgeprägtes chromatographisches Profil und ist leicht erkennbar durch GC-ECD. Eine positive Identifizierung der Toxaphen Isomere kann durch eine negative chemische Ionisationsmassen¬spektrometrie (NCI MS), eine Elektronenstoß Tandem-Massenspektrometrie (EI MS × MS) oder eine hochauflösende Elektronenstoß Massenspektrometrie (EI HRMS) durchgeführt werden, die nicht in den Anwendungsbereich dieses Verfahrens fällt.
In der Regel sollte für die genannten Organochlorpestizide eine Bestimmungsgrenze (LOQ) von 6 µg/kg bis 29 µg/kg erreicht werden (siehe Tabelle 1). Für die ndl PCB sollte eine Bestimmungsgrenze von 0,5 µg/kg bis 1,0 µg/kg erreicht werden. Die genannten Bestimmungsgrenzen gelten für die einzelnen Verbindungen (d. h. nicht die Summe von zwei oder mehr Verbindungen). Die einzelnen Laboratorien sind dafür verantwortlich sicherzustellen, dass die von ihnen verwendeten Geräte diese Bestimmungsgrenzen erreichen. Auf Kundenwunsch darf die Norm nur auf die Analyse von PCB oder OCP angewendet werden.

Aliments des animaux - Méthodes d’échantillonnage et d’analyse - Détermination des pesticides organochlorés (POC) et des polychlorobiphényles (PCB) par GC/MS

Le présent document décrit une méthode de chromatographie en phase gazeuse couplée à la spectrométrie de masse (GC-MS) pour la détermination des pesticides organochlorés (POC) et des polychlorobiphényles (PCB) dans les aliments composés et les matières premières alimentaires pour animaux (huiles et graisses, farine de poisson).
La méthode est applicable aux aliments composés constitués de moins de 20 % d’eau en masse et aux échantillons d’huile/de graisses contenant des résidus d’un ou de plusieurs des POC et PCB suivants et de certains de leurs isomères et produits de dégradation :
—   aldrine ;
—   dieldrine ;
—   chlordane, correspondant à la somme des isomères de chlordane et d’oxychlordane ;
—   dichlorodiphényltrichloréthane (DDT), correspondant à la somme des isomères de o,p’-DDT, p,p’ DDT, p,p’-TDE (p,p’-DDD) et p,p’-DDE ;
—   endosulfan, correspondant à la somme des isomères α-/β et de l’endosulfan sulfate ;
—   endrine, correspondant à la somme de l’endrine et du delta-keto-endrine ;
—   heptachlore, correspondant à la somme de l’heptachlore et de l’heptachlore époxyde ;
—   hexachlorobenzène (HCB) ;
—   isomères des hexachlorocyclohexanes α-HCH (α-BHC), β-HCH (β-BHC), γ-HCH (γ-BHC ou lindane) ;
—   photoheptachlore ;
—   cis-nonachlore et trans-nonachlore ;
—   PCB qui ne sont pas de type dioxine (NDL-PCB), correspondant à la somme des PCB 28, 52, 101, 138, 153 et 180.
La méthode a été intégralement validée par un essai interlaboratoires au regard des substances et des plages de concentrations correspondantes (ng/g) notées dans le Tableau 1.
La méthode n’a pas été intégralement validée pour l’oxychlordane, l’endrine-cétone, le cis-nonachlore, le trans-nonachlore et le photoheptachlore dans toutes les matrices.
Pour les combinaisons matrice/analyte pour lesquelles les données de validation ont été jugées insuffisantes, les résultats obtenus avec cette méthode ne peuvent être considérés que comme des résultats de dépistage, à moins que le laboratoire ne procède à une validation interne pour montrer que des résultats satisfaisants peuvent être obtenus.
La méthode ne s’applique pas au camphéchlore (toxaphène), mélange complexe de camphènes polychlorés. Le camphéchlore possède un profil chromatographique très particulier et est facilement identifiable par chromatographie en phase gazeuse avec détecteur à capture d’électrons (GC/ECD). L’identification positive des isomères du toxaphène peut être effectuée par spectrométrie de masse par ionisation chimique négative (NCI-MS), spectrométrie de masse en tandem par impact d’électrons (EI MS/MS) ou par spectrométrie de masse haute résolution par impact d’électrons (EI-HRMS), qui ne relèvent pas du domaine d’application de la présente méthode.
Il convient généralement d’obtenir une limite de quantification (LQ) des pesticides organochlorés mentionnés de 6 µg/kg à 29 µg/kg (voir le Tableau 1). Pour les NDL-PCB, il convient d’obtenir une LQ de 0,5 µg/kg à 1,0 µg/kg. Les LQ mentionnées s’appliquent aux composés individuels (c’est-à-dire non applicables à la somme de deux composés ou plus). Il incombe à chaque laboratoire de garantir que les appareils qu’ils utilisent atteignent ces LQ. Sur demande des clients, la norme peut être appliquée uniquement à l’analyse des PCB ou des POC.

Krma: metode vzorčenja in analize - Določevanje OCP in PCB z GC/MS

General Information

• Status: Published
• Publication Date: 10-Mar-2020
• Withdrawal Date: 29-Sep-2020
• ICS: 65.120 - Animal feeding stuffs
• Technical Committee: CEN/TC 327 - Animal feeding stuffs - Methods of sampling and analysis
• Drafting Committee: CEN/TC 327/WG 1 - Minerals and Contaminants
• Current Stage: 6060 - Definitive text made available (DAV) - Publishing
• Start Date: 11-Mar-2020
• Due Date: 18-Apr-2019
• Completion Date: 11-Mar-2020
• Directive: 882/2004 - Regulation (EC) No 882/2004 of the European Parliament and of the Council of 29 April 2004 onofficial controls performed to ensure the verification of compliance with feed and food law, animal health and animal welfare rules
• Mandate: M/522 - Mandate for standardisation addressed to CEN for methods of analysis in the field of animal nutrition - part II
• Ref Project: SIST EN 15741:2020 - Animal feeding stuffs: Methods of sampling and analysis - Determination of OCPs and PCBs by GC/MS

Relations

• Replaces: EN 15741:2009 - Animal feeding stuffs - Determination of OC-pesticides and PCB’s by GC/MS
• Effective Date: 15-Jul-2015

Standards Content (Sample)

SLOVENSKI STANDARD
01-maj-2020
Nadomešča:
SIST EN 15741:2009
Krma: metode vzorčenja in analize - Določevanje OCP in PCB z GC/MS
Animal feeding stuffs: Methods of sampling and analysis - Determination of OCPs and
PCBs by GC/MS
Futtermittel: Probenahme- und Untersuchungsverfahren - Bestimmung von OCP und
PCB mittels GC-MS
Aliments des animaux - Méthodes d’échantillonnage et d’analyse - Détermination des
pesticides organochlorés (POC) et des polychlorobiphényles (PCB) par GC/MS
Ta slovenski standard je istoveten z: EN 15741:2020
ICS:
65.120 Krmila Animal feeding stuffs
2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.

EN 15741
EUROPEAN STANDARD
NORME EUROPÉENNE
March 2020
EUROPÄISCHE NORM
ICS 65.120 Supersedes EN 15741:2009
English Version
Animal feeding stuffs: Methods of sampling and analysis -
Determination of OCPs and PCBs by GC/MS
Aliments des animaux : Méthodes d'échantillonnage et Futtermittel: Probenahme- und
d'analyse - Détermination des pesticides organochlorés Untersuchungsverfahren - Bestimmung von OCP und
(POC) et des polychlorobiphényles (PCB) par GC/MS PCB mittels GC/MS
This European Standard was approved by CEN on 6 January 2020.

CEN members are bound to comply with the CEN/CENELEC Internal Regulations which stipulate the conditions for giving this
European Standard the status of a national standard without any alteration. Up-to-date lists and bibliographical references
concerning such national standards may be obtained on application to the CEN-CENELEC Management Centre or to any CEN
member.
This European Standard exists in three official versions (English, French, German). A version in any other language made by
translation under the responsibility of a CEN member into its own language and notified to the CEN-CENELEC Management
Centre has the same status as the official versions.

CEN members are the national standards bodies of Austria, Belgium, Bulgaria, Croatia, Cyprus, Czech Republic, Denmark, Estonia,
Finland, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway,
Poland, Portugal, Republic of North Macedonia, Romania, Serbia, 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: Rue de la Science 23, B-1040 Brussels
© 2020 CEN All rights of exploitation in any form and by any means reserved Ref. No. EN 15741:2020 E
worldwide for CEN national Members.

Contents Page
European foreword . 3
Introduction . 4
1 Scope . 5
2 Normative references . 7
3 Terms and definitions . 7
4 Principle . 7
5 Reagents and materials . 8
6 Apparatus . 14
7 Sampling . 18
8 Preparation of test sample . 19
9 Procedure. 19
9.1 General . 19
9.2 Test portions of animal feed stuff and oil samples . 19
9.3 Extraction of the feed test portion . 20
9.4 Clean-up . 20
9.5 Gas chromatography . 21
10 Calculation and expression of results . 21
10.1 General . 21
10.2 Calibration criteria . 22
10.3 Identification and confirmation. 22
10.4 Calculation . 22
10.5 Recovery . 24
11 Precision . 25
11.1 Interlaboratory test . 25
11.2 Repeatability and precision within participating laboratories . 25
11.3 Reproducibility and precision between participating laboratories . 25
12 Test report . 25
13 Important considerations to this method . 25
13.1 Alternative extraction techniques . 25
13.2 Different amounts of silica . 25
13.3 Different clean-up step . 25
13.4 Different internal standard . 25
13.5 Optimal GC-MS (MS) settings . 26
Annex A (informative) Description of PTV injection system (in case this is available) . 27
Annex B (informative) Collaborative trial. 28
Bibilography . 48
European foreword
This document (EN 15741:2020) has been prepared by Technical Committee CEN/TC 327 “Animal
feeding stuffs: Methods of sampling and analysis”, the secretariat of which is held by NEN.
This European Standard shall be given the status of a national standard, either by publication of an
identical text or by endorsement, at the latest by September 2020, and conflicting national standards shall
be withdrawn at the latest by September 2020.
Attention is drawn to the possibility that some of the elements of this document may be the subject of
patent rights. CEN shall not be held responsible for identifying any or all such patent rights.
This document supersedes EN 15741:2009.
In comparison with the previous edition, the following technical modification has been made:
Regarding non dioxin-like PCBs (ndl-PCBs), this document contains two approaches that can be followed.
Method 1 concerns the original extraction and clean-up methods of the previous edition of this standard,
but combined with more sensitive detection approaches. In method 2, the extraction and clean-up
methods have been modified in order to increase the test portion. The detection of method 2 concerns
the original detection method of the previous edition of this standard.
This document has been prepared under a standardization request given to CEN by the European
Commission and the European Free Trade Association.
According to the CEN-CENELEC Internal Regulations, the national standards organisations of the
following countries are bound to implement this European Standard: Austria, Belgium, Bulgaria, Croatia,
Cyprus, Czech Republic, Denmark, Estonia, Finland, France, Germany, Greece, Hungary, Iceland, Ireland,
Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Republic of North
Macedonia, Romania, Serbia, Slovakia, Slovenia, Spain, Sweden, Switzerland, Turkey and the United
Kingdom
Introduction
WARNING — The use of this document can involve hazardous materials, operations and equipment. This
standard does not purport to address all the safety problems associated with its use. It is the
responsibility of the user of this European Standard to establish appropriate safety and health practices
and determine the applicability of regulatory limitations prior to use.
1 Scope
This document specifies a gas chromatographic mass spectrometric (GC-MS) method for the
determination of organochlorine pesticides (OCPs) and polychlorinated biphenyls (PCBs) in compound
feeds and feed materials (oils and fats, fish meal).
The method is applicable to compound feeds consisting of less than 20 % water by mass and oil/fatty
samples containing residues of one or more of the following OCPs and PCBs and some of their isomers
and degradation products:
— aldrin;
— dieldrin;
— chlordane, as the sum of chlordane isomers and oxychlordane;
— dichlorodiphenyltrichloroethane (DDT), as the sum of isomers o,p'-DDT, p,p'-DDT, p,p'-TDE (p,p'-
DDD), and p,p'-DDE;
— endosulfan, as the sum of α-/β-isomers and endosulfan-sulphate;
— endrin, as the sum of endrin and delta-keto-endrin;
— heptachlor, as the sum of heptachlor and heptachlor epoxide;
— hexachlorobenzene (HCB);
— hexachlorocyclohexane isomers α-HCH (α-BHC), β-HCH (β-BHC), γ-HCH (γ-BHC or lindane);
— photo heptachlor;
— cis- and trans-nonachlor;
— non dioxin-like PCBs (ndl-PCBs), as the sum of PCB 28, 52, 101, 138, 153 and 180.
The method has been fully validated by a collaborative trial for the substances and corresponding ranges
(µg/kg) noted in Table 1.
Table 1 — Residue compound and range of (µg/kg) collaborative trial
Compound Range (µg/kg)
all ndl-PCBs 0,7 to 39
aldrin 10 to 34
dieldrin 12 to 97
endrin 13 to 88
a a
cis-chlordane 16 to 24
trans-chlordane 7 to 25
b b
p,p’-DDT 19 to 200
o,p’-DDT 8 to 87
c c
pp’-TDE 9 to 103
pp'-DDE 21 to 264
α-endosulfan 15 to 165
β-endosulfan 26 to 331
d d
endosulfan sulphate 29 to 61
heptachlor 15 to 365
heptachlor epoxide 15 to 382
e e
HCB 8 to 170
α-HCH 21 to 247
β-HCH 6 to 84
f f
γ-HCH 17 to 186
NOTE  The following information is to be taken into consideration:
a)  Cis-chlordane has not been fully validated for chicken feed, pig feed and fish oil.
b)  p,p’-DDT has not been fully validated for pig feed and vegetable oil.
c)  pp’-TDE has not been fully validated for pig feed and fish meal.
d)  Endosulfan sulphate has not been fully validated for pig feed and vegetable oil.
e)  HCB has not been fully validated for fish oil.
f)  γ-HCH has not been fully validated for fish oil.
The method has not been fully validated for oxychlordane, endrin ketone, cis- and trans-nonachlor and
photo heptachlor in all matrices.
For those matrix-analyte combinations where the validation data were regarded insufficient, the results
obtained with this method can only be regarded as screening results, unless the laboratory performs an
in-house validation to show that satisfactory results can be obtained.
The method is not applicable to chlorocamphene (toxaphene), a complex mixture of polychlorinated
camphenes. Chlorocamphene has a very distinctive chromatographic profile and is easily recognizable by
GC/ECD. Positive identification of the toxaphene isomers can be performed by negative chemical
ionization mass spectrometry (NCI-MS), electron impact tandem mass spectrometry (EI MS × MS) or
electron impact high resolution mass spectrometry (EI-HRMS), which is not within the scope of this
method.
A limit of quantification (LOQ) for the mentioned organochlorine pesticides of 6 to 29 µg/kg should
normally be obtained (see Table 1). For the ndl-PCBs an LOQ of 0,5 to 1,0 µg/kg should be obtained. The
LOQs mentioned apply to the individual compounds (i.e. not the sum of two or more comp
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