EN 15741:2009

Animal feeding stuffs - Determination of OC-pesticides and PCB’s by GC/MS

This European Standard specifies a gas chromatographic/mass spectrometric method for the determination of organochlorine pesticides (OC’s) and polychlorinated biphenyls (PCBs) in animal feeding stuffs and oil.
The method is applicable to animal feeding stuffs with a water content up to about 20 wt% and oil/fatty samples containing residues of one or more of the following OC’s and PCBs and some of their isomers and degradation products:
   Aldrin;
   Dieldrin;
   Chlordane (= sum of Chlordane isomers and Oxychlordane);
   DDT (= sum of isomers op'-DDT, pp'-DDT, pp'-TDE (pp'-DDD), and pp'-DDE);
   Endosulfan (sum of -/-isomers and Endosulphanesulphate);
   Endrin;
   Heptachlor (= sum of Heptachlor and -Heptachlorepoxide);
   Hexachlorobenzene (HCB);
   Hexachlorocyclohexane isomers -HCH (-BHC), -HCH (-BHC), -HCH (-BHC or lindane);
   PCB 28, 52, 101, 138, 153 and 180 (“Indicator PCBs”) and PCB-198, 209.
The method is not yet 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-MSxMS) or electron impact high resolution mass spectrometry (EI-HRMS) [1], which is not within the scope of this method.
The limit of quantification for the mentioned organochlorine pesticides and PCBs is 5 ng/g in general. However, 10 ng/g applies for Heptachlor Aldrin, Endrin, Dieldrin, and Endosulfan (-, - and sulphate). Individual laboratories are responsible to ensure that the equipment they used will achieve these limits of quantifications.

Futtermittel - Bestimmung der OC-Pestizide und PCB's mittels GC/MS-Verfahren

Diese Europäische Norm legt ein gaschromatographisches/massenspektrometrisches Verfahren für die Be¬stimmung von Organochlorpestiziden (OC-Pestizide) und polychlorierte Biphenyle (PCB) in Futtermitteln und Öl fest.
Das Verfahren ist auf Futtermittel mit einem Wassergehalt bis zu etwa 20 % (m/m) und öl-/fetthaltige Proben anwendbar, die Rückstände von einem oder mehreren der folgenden OC Pestiziden und PCB und einige von deren Isomeren und Abbauprodukten enthalten:
   Aldrin;
   Dieldrin;
   Chlordan (= Summe von Chlordanisomeren und Oxychlordan);
   DDT (= Summe der Isomere von op'-DDT, pp'-DDT, pp'-TDE (pp'-DDD) und pp'-DDE);
   Endosulfan (Summe von -/-Isomeren und Endosulfansulfat);
   Endrin;
   Heptachlor (= Summe von Heptachlor und -Heptachlorepoxid);
   Hexachlorbenzen (HCB);
   Hexachlorcyclohexan-Isomere -HCH (-BHC), -HCH (-BHC), -HCH (-BHC oder Lindan);
   PCB 28, 52, 101, 138, 153 und 180 („Indikator-PCB“) und PCB 198, 209.
Das Verfahren ist jedoch nicht anwendbar auf Chlorcamphen (Toxaphen), eine komplexe Mischung von poly¬chlorierten Champhenen. Chlorocamphen hat ein sehr ausgeprägtes chromatographisches Profil und ist leicht erkennbar durch GC/ECD. Eine positive Identifizierung der Toxaphen-Isomere kann mit einer Massenspektro¬metrie mit negativen Ionen bei chemischer Ionisation (NCI-MS), einer Elektronenstoß-Tandem-Massen¬spektrometrie (EI-MSMS) oder einer hochauflösenden Elektronenstoß-Massenspektrometrie (EI-HRMS) [1] durchgeführt werden, die nicht im Rahmen des Anwendungsbereichs dieses Verfahrens sind.
Die Bestimmungsgrenze der betreffenden Organochlorpestizide und PCB’s beträgt gewöhnlich 5 ng/g. Jedoch gilt bei Heptachlor, Aldrin, Endrin, Dieldrin und Endosulfan (-, - und Sulfat) 10 ng/g. Einzelne Laboratorien sind verantwortlich für die Absicherung, dass die von ihnen verwendeten Laborgeräte die quantitativen Bestimmungsgrenzen erreichen.

Aliments des animaux - Détermination des pesticides organochlorés (OC) et des polychlorobiphényles (PCB) par GC/MS

La présente Norme européenne décrit une méthode de chromatographie en phase gazeuse couplée à la spectrométrie de masse (CPG-SM), pour la détermination des pesticides organochlorés (OC) et des polychlorobiphényles (PCB) , dans les aliments pour animaux et huiles.
La méthode est applicable aux aliments pour animaux dont la teneur en eau s'élève jusqu’ à environ 20 % du poids et dont la teneur en matières grasses peut s'élever jusqu’à 10 % du poids, ainsi qu'aux échantillons d'huile/gras contenant des résidus d'un ou de plusieurs OC et PCB suivants, ou certains de leurs isomères et produits de dégradation :
Aldrine
Dieldrine
Chlordane ( somme des isomères de chlordane et d'oxychlordane)
DDT ( somme des isomères de op'-DDT, pp'-DDT, pp'-TDE (pp'-DDD), et pp'-DDE)
Endosulfan (somme des isomères -/ et sulfate d'endosulfan)
Endrine
Heptachlore ( somme d'heptachlore et d'heptachlore époxyde )
Hexachlorobenzène (HCB)
Isomères d'hexachlorocyclohexane -HCH (-BHC), -HCH (-BHC), -HCH (-BHC ou lindane)
PCB 28, 52, 101, 118, 138, 153 et 180 ("PCB indicateurs") et PCB-198, 209
La méthode ne s'applique pas encore 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 (CPG/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-MSxMS) ou par spectrométrie de masse haute résolution par impact d'électrons (EI-HRMS), qui ne relève pas du domaine de la présente méthode.
La limite de quantification des pesticides organochlorés et des PCB mentionnés est en général de 5 ng/g.

Krma - Določevanje OC-pesticidov in PCB z GC/MS

General Information

• Status: Withdrawn
• Publication Date: 24-Feb-2009
• Withdrawal Date: 10-Mar-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: 9960 - Withdrawal effective - Withdrawal
• Completion Date: 11-Mar-2020
• Directive: 70/373/EC - Council Directive 70/373/EEC of 20 July 1970 on the introduction of Community methods of sampling and analysis for the official control of feeding-stuffs
• Mandate: M/315 - Mandate to CEN for standardization in the field of methods of analysis for animal feedingstuffs
• Ref Project: SIST EN 15741:2009 - Animal feeding stuffs - Determination of OC-pesticides and PCB’s by GC/MS

Relations

• Replaced By: EN 15741:2020 - Animal feeding stuffs: Methods of sampling and analysis - Determination of OCPs and PCBs by GC-MS
• Effective Date: 15-Jul-2015

Standards Content (Sample)

2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.Futtermittel - Bestimmung der OC-Pestizide und PCB's mittels GC/MS-VerfahrenAliments des animaux - Détermination des pesticides organochlorés (OC) et des polychlorobiphényles (PCB) par GC/MSAnimal feeding stuffs - Determination of OC-pesticides and PCB’s by GC/MS65.120KrmilaAnimal feeding stuffsICS:Ta slovenski standard je istoveten z:EN 15741:2009SIST EN 15741:2009en,fr,de01-maj-2009SIST EN 15741:2009SLOVENSKI
STANDARD
EUROPEAN STANDARDNORME EUROPÉENNEEUROPÄISCHE NORMEN 15741February 2009ICS 65.120 English VersionAnimal feeding stuffs - Determination of OC-pesticides andPCB's by GC/MSAliments des animaux - Détermination des pesticidesorganochlorés (OC) et des polychlorobiphényles (PCB) parGC/MSFuttermittel - Bestimmung der OC-Pestizide und PCB'smittels GC/MS-VerfahrenThis European Standard was approved by CEN on 24 January 2009.CEN members are bound to comply with the CEN/CENELEC Internal Regulations which stipulate the conditions for giving this EuropeanStandard the status of a national standard without any alteration. Up-to-date lists and bibliographical references concerning such nationalstandards may be obtained on application to the CEN 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 translationunder the responsibility of a CEN member into its own language and notified to the CEN Management Centre has the same status as theofficial versions.CEN members are the national standards bodies of Austria, Belgium, Bulgaria, Cyprus, Czech Republic, Denmark, Estonia, Finland,France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal,Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland and United Kingdom.EUROPEAN COMMITTEE FOR STANDARDIZATIONCOMITÉ EUROPÉEN DE NORMALISATIONEUROPÄISCHES KOMITEE FÜR NORMUNGManagement Centre:
Avenue Marnix 17,
B-1000 Brussels© 2009 CENAll rights of exploitation in any form and by any means reservedworldwide for CEN national Members.Ref. No. EN 15741:2009: ESIST EN 15741:2009

Results of interlaboratory tests . 22 Annex B Description of PTV injection system (in case this is available). . 23 Bibliography . 25
 Aldrin;  Dieldrin;  Chlordane (= sum of Chlordane isomers and Oxychlordane);  DDT (= sum of isomers op'-DDT, pp'-DDT, pp'-TDE (pp'-DDD), and pp'-DDE);  Endosulfan (sum of α-/β-isomers and Endosulfan-sulphate);  Endrin;
 Heptachlor (= sum of Heptachlor and β-Heptachlorepoxide);  Hexachlorobenzene (HCB);  Hexachlorocyclohexane isomers α-HCH (α-BHC), β-HCH (β-BHC), γ-HCH (γ-BHC or lindane);  PCB 28, 52, 101, 138, 153 and 180 (“Indicator PCBs”) and PCB 198, 209. The method is not yet 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-MSxMS) or electron impact high resolution mass spectrometry (EI-HRMS) [1], which is not within the scope of this method. The limit of quantification for the mentioned organochlorine pesticides and PCBs is 5 ng/g in general. However, 10 ng/g applies for Heptachlor Aldrin, Endrin, Dieldrin, and Endosulfan (α-, β- and sulphate). Individual laboratories are responsible to ensure that the equipment they used will achieve these limits of quantifications. 2 Normative references The following referenced documents are indispensable for the application of this document. For dated references, only the edition cited applies. For undated references, the latest edition of the referenced document (including any amendments) applies. ISO 6498, Animal feeding stuffs – Preparation of test samples SIST EN 15741:2009

3.2 limit of quantification lowest content of the analyte which can be measured with reasonable statistical certainty NOTE If both accuracy and precision are constant over a concentration range around the limit of detection, then the limit of quantification is numerically equal to 6 times the standard deviation of the mean of blank determinations (n>10). 3.3 feed Additives substances are feed additives when they comply with the definition of feed additives given in the Regulation 1831/2003 4 Principle A test portion of animal feeding stuff is fortified with internal standard (PCB 198), and is extracted with ethylacetate. The extract is concentrated and subsequently purified by:  Gel permeation chromatography (GPC), with cyclohexane/ethylacetate as eluting solvent
 chromatography on partially deactivated silica gel. The collected fraction containing the compounds of interest is concentrated and re-dissolved in a solution containing another internal standard (PCB 209) as a reference standard. After concentration an aliquot of the extract is injected into a GC-MS, using a splitless injector (an alternative here is PTV injection, see Note below).
NOTE In case more sensitivity is necessary or less volume reduction is wanted, injection of a larger volume by PTV is possible (an example is described in Annex B). 5 Reagents and materials 5.1 General Use only reagents of recognized analytical grade and with a purity suitable for OC and PCB residue analysis. Check the purity of the reagents by performing a blank test under the same conditions as used in the method. The chromatogram should not show any interfering impurity at the retention time of compounds of interest. WARNING — The use of this European Standard 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. SIST EN 15741:2009

5.5 Hexane
5.6 Decane 5.7 Hexane/Decane = 95+5 part by volume Mix 950 ml of hexane (5.5) with 50 ml of decane (5.6) and mix thoroughly. Store at room temperature in a tightly closed glass bottle. 5.8 Iso-octane 5.9 Toluene 5.10 Silica gel, deactivated with 3,5% water Heat silica gel 60 (63µm to 200µm = 70 mesh to 230 mesh), at 130ºC for at least 5 h, allow to cool in a desiccator, and store in a tightly stopped container in the desiccator. To 96,5 g dried silica gel in a 300 ml Erlenmeyer flask with a ground joint, add 3,5 ml water dropwise from a burette, with continuous swirling. Immediately stopper the flask with a ground stopper and shake vigorously for 5 min until all lumps have disappeared. Next shake for 2 h on a mechanical shaker, and then store in a tightly stoppered container. Deactivated silica gel is tenable during approximately 2 weeks if carefully stored. 5.11 Hexane/toluene = 3+7 parts by volume Mix 30 ml of n-hexane (5.5) with 70 ml of toluene (5.9) and mix thoroughly. Store at room temperature in a tightly closed glass bottle.
5.12 Internal standard (PCB 209) 5.12.1 PCB 209 Stock solution 1, 100 µg/ml Weigh 5-10 mg (± 0,01 mg) of PCB 209 (5.12) in a brown medicine glass bottle of 100 ml and add iso-octane (5.8) to achieve a concentration of 100 µg/ml. Store the solution in a refrigerator at 4°C (± 3°C). The solution is tenable under these conditions during at least 5 years if the weight is carefully controled. Or use a commercially available standard solution of 100 µg/ml. 5.12.2 PCB 209 Stock solution 2, 10,0 µg/ml Dilute 10,0 ml of PCB 209 Stock solution 1 (5.12.1) to 100,0 ml with hexane (5.5). Store the solution in a refrigerator at 4°C (± 3°C). The solution is tenable under these conditions during at least 5 years if the weight is carefully controled. 5.12.3 PCB 209 Work solution, concentration 1 000 ng/ml Dilute 10 ml of PCB 209 Stock solution 2 (5.12.2) to 100,0 ml with hexane (5.5). Store the solution in a refrigerator at 4°C (± 3°C). The solution is tenable under these conditions during at least 5 years if the weight is carefully controled. SIST EN 15741:2009

5.13.1 PCB 198 Stock solution 1, 100 µg/ml Weigh 5-10 mg (± 0,01 mg) of PCB 198 (5.13) in a brown medicine glass bottle of 100 ml and add iso-octane (5.8) to achieve a concentration of 100 µg/ml. Store the solutions in a refrigerator at 4°C (± 3°C). The solutions are tenable under these conditions during at least 5 years if the weight is carefully controled. Or use a commercially available standard solution of 100 µg/ml. 5.13.2 PCB 198 Stock solution 2, 5,0 µg/ml Pipet 5,0 ml of PCB 198 Stock solution 1 (5.13.1) to graduated flask of 100,0 ml with hexane (5.5). Store the solution in a refrigerator at 4°C (± 3°C). The solution is tenable under these conditions during at least 5 years if the weight is carefully controled. 5.13.3 PCB 198 Work solution, 1 000 ng/ml Pipet 2,0 ml of the PCB 198 Stock solution 2 (5.13.2) into a 10,0 ml graduated flask and dilute with hexane (5.5) to 10,0 ml. Store the solution in a refrigerator at 4°C (± 3°C). The solution is tenable under these conditions during at least 5 years if the weight is carefully controled. 5.14 PCB congeners Stock standard solution, 10 µg/ml PCB 28 (2,4,4’ trichlorobiphenyl); CAS Number: 7012-37-5 PCB 52 (2,2’,5,5’ tetrachlorobiphenyl); CAS Number: 35693-99-3 PCB 101 (2,2’,4,5,5’ pentachlorobiphenyl); CAS Number: 37680-73-2 PCB 138 (2,2’,3’,4,4’,5 hexachlorobiphenyl); CAS Number: 35065-28-2 PCB 153 (2,2’,4,4’,5,5’ hexachlorobiphenyl); CAS Number: 35065-27-1 PCB 180 (2,2’,3,4,4’,5,5’ heptachlorobiphenyl); CAS Number: 35065-29-3 Or a Certified Mixture at a concentration of 10 µg/ml. 5.15 PCB congeners Work standard solution, 2,0 µg/ml Dilute 2,0 ml of PCB congeners Stock standard solution (5.14) to 10,0 ml with hexane (5.5). Store the solu
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