EN 17163:2019

Pulp, paper and board - Determination of primary aromatic amines (PAA) in a water extract by a LC-MS method

This document describes two representative methods for the determination of the extractable amount of specific primary aromatic amines (PAA) in a water extract of paper, board and pulp samples by means of HPLC with MS/MS detection which basically differ concerning the choice of the mobile and stationary phases. Deviating from this standard further methods may be applicable if it can be shown that comparable results can be achieved. A validation should be carried out by each laboratory.
It is applicable for the determination of the 22 primary aromatic amines (PAA) mentioned in the annex of Directive 2002/61/EC of 19th July 2002 amending Council Directive 76/769/EEC relating to restrictions on the market and use of certain dangerous substances and preparations (azocolourants) which are classified as carcinogenic categories 1A and 1B according to the CLP regulation and aniline.
The method described by this standard should be also applicable for the determination of further primary aromatic amines (PAA). A validation for every further analyte has to be done by the laboratory using this method.
The extractable amount of a primary aromatic amine (PAA) is expressed in mg PAA per litre water extract. This method is suitable for the determination of PAA with a working range of about 0,001 mg/l - 0,020 mg/l water extract.
Deviating from this standard further methods may be applicable if it can be shown that comparable results can be achieved. A validation should be carried out by each laboratory.

Papier, Pappe und Faserstoff - Bestimmung von primären aromatischen Aminen in Wasserextrakten mittels LC-MS

Dieses Dokument beschreibt zwei repräsentative Verfahren zur Bestimmung der extrahierbaren Menge an spezifischen primären aromatischen Aminen (PAA) in einem Wasserextrakt aus Proben von Papier, Pappe und Faserstoff mittels HPLC mit MS/MS Detektion, die sich grundsätzlich hinsichtlich der Wahl der mobilen und stationären Phasen unterscheiden. Abweichend von dieser Norm können weitere Verfahren angewendet werden, wenn nachgewiesen werden kann, dass vergleichbare Ergebnisse erzielt werden können. Eine Validierung sollte von jedem Laboratorium durchgeführt werden.
Sie gilt für die Bestimmung der 22 primären aromatischen Amine (PAA), die im Anhang der Richtlinie 2002/61/EG vom 19. Juli 2002 zur Änderung der Richtlinie 76/769/EWG des Rates betreffend Beschränkungen des Inverkehrbringens und der Verwendung gewisser gefährlicher Stoffe und Zubereitungen (Azofarbstoffe) aufgeführt sind, die als karzinogene Stoffe der Kategorien 1A und 1B nach der CLP Verordnung eingestuft werden, und von Anilin.
Das in dieser Norm beschriebene Verfahren sollte auch auf die Bestimmung weiterer primärer aromatischer Amine (PAA) anwendbar sein. Eine Validierung für jeden weiteren Analyten ist vom Laboratorium unter Anwendung dieses Verfahrens durchzuführen.
Die extrahierbare Menge eines primären aromatischen Amins (PAA) wird in mg PAA je Liter Wasserextrakt angegeben. Dieses Verfahren eignet sich zur Bestimmung von PAA mit einem Arbeitsbereich von etwa 0,001 mg/l bis 0,020 mg/l Wasserextrakt.
Abweichend von dieser Norm können weitere Verfahren angewendet werden, wenn nachgewiesen werden kann, dass vergleichbare Ergebnisse erzielt werden können. Eine Validierung sollte von jedem Laboratorium durchgeführt werden.

Pâtes, papier et carton - Détermination des amines aromatiques primaires (AAP) dans un extrait aqueux par méthode LC-MS

Le présent document décrit deux méthodes représentatives pour la détermination de la quantité extractible d’amines aromatiques primaires (AAP) spécifiques dans un extrait aqueux d’échantillons de papier, carton et pâte par CLHP avec détection par SM/SM, qui diffèrent principalement par le choix des phases mobiles et stationnaires. D’autres méthodes s’écartant de la présente norme peuvent être applicables s’il peut être démontré qu’elles conduisent à des résultats comparables. Il convient que chaque laboratoire effectue une validation.
Le présent document est applicable à la détermination de l’aniline et des 22 amines aromatiques primaires (AAP) mentionnées dans l’annexe de la Directive 2002/61/CE du 19 juillet 2002 modifiant la Directive 76/769/CEE du Conseil concernant la limitation de la mise sur le marché et de l’emploi de certaines substances et préparations dangereuses (colorants azoïques) qui sont classées dans les catégories cancérigènes 1A et 1B selon le règlement CLP.
Il convient que la méthode décrite dans la présente norme soit également applicable à la détermination d’autres amines aromatiques primaires (AAP). Tout analyte supplémentaire doit faire l’objet d’une validation par le laboratoire à l’aide de cette méthode.
La quantité extractible d’amine aromatique primaire (AAP) est exprimée en mg d’AAP par litre d’extrait aqueux. Cette méthode convient pour la détermination des AAP dans une plage de travail d’environ 0,001 mg/l à 0,020 mg/l d’extrait aqueux.
D’autres méthodes s’écartant de la présente norme peuvent être applicables s’il peut être démontré qu’elles conduisent à des résultats comparables. Il convient qu’une validation soit effectuée par chaque laboratoire.

Vlaknine, papir, karton in lepenka - Določevanje primarnih aromatičnih aminov (PAA) v vodnem ekstraktu z metodo LC-MS

Ta evropski standard opisuje dve reprezentativni metodi za določevanje količine določenih primarnih aromatičnih aminov (PAA), ki jih je mogoče ekstrahirati iz vodnega ekstrakta vzorcev papirja, kartona, lepenke in vlaknin s HPLC z zaznavanjem MS/MS, ki se v osnovi razlikuje glede na izbiro mobilnih in stacionarnih faz. Ob odstopanju od tega standarda se lahko uporabljajo dodatne metode, če je mogoče dokazati, da se lahko dosega primerljive rezultate. Vsak laboratorij mora izvesti validacijo. Uporablja se za določevanje 22 primarnih aromatičnih aminov (PAA), navedenih v dodatku Direktive 2002/61/ES z dne 19. julija 2002, ki dopolnjuje Direktivo Sveta 76/769/EGS v zvezi z omejitvami pri trženju in uporabi nekaterih nevarnih snovi ter pripravkov (azobarvil), ki so razvrščeni kot rakotvorni kategoriji 1A in 1B v skladu z uredbo CLP, in anilina. Metoda, ki jo opisuje ta standard, se uporablja tudi za določevanje dodatnih primarnih aromatičnih aminov (PAA). Validacijo za vsak nadaljnji analit mora izvesti laboratorij, ki uporablja to metodo. Količina primarnega aromatičnega amina (PAA), ki jo je mogoče ekstrahirati, je izražena v mg primarnih aromatičnih aminov na liter vodnega ekstrakta. Ta metoda je primerna za določevanje primarnih aromatičnih aminov v delovnem razponu približno 0,001–0,020 mg/l vodnega ekstrakta. OPOMBA: Ob odstopanju od tega standarda se lahko uporabljajo dodatne metode, če je mogoče dokazati, da se lahko dosega primerljive rezultate. Vsak laboratorij mora izvesti validacijo.

General Information

• Status: Published
• Publication Date: 12-Feb-2019
• Withdrawal Date: 30-Aug-2019
• ICS: 85.060 - Paper and board
• Technical Committee: CEN/TC 172 - Pulp, paper and board
• Drafting Committee: CEN/TC 172/WG 3 - Analytical methods for the assessment of paper and board in contact with foodstuffs
• Ref Project: SIST EN 17163:2019 - Pulp, paper and board - Determination of primary aromatic amines (PAA) in a water extract by a LC-MS method

Standards Content (Sample)

SLOVENSKI STANDARD
01-april-2019
9ODNQLQHSDSLUNDUWRQLQOHSHQND'RORþHYDQMHSULPDUQLKDURPDWLþQLKDPLQRY
3$$YYRGQHPHNVWUDNWX]PHWRGR/&06
Pulp, paper and board - Determination of primary aromatic amines (PAA) in a water
extract by a LC-MS method
Papier, Pappe und Faserstoff - Bestimmung von primären aromatischen Aminen in
Wasserextrakten mittels LC-MS
Pâtes, papier et carton - Détermination des amines aromatiques primaires (AAP) dans
un extrait aqueux par méthode LC-MS
Ta slovenski standard je istoveten z: EN 17163:2019
ICS:
85.040 Vlaknine Pulps
85.060 Papir, karton in lepenka Paper and board
2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.

EN 17163
EUROPEAN STANDARD
NORME EUROPÉENNE
February 2019
EUROPÄISCHE NORM
ICS 85.060
English Version
Pulp, paper and board - Determination of primary
aromatic amines (PAA) in a water extract by a LC-MS
method
Pâtes, papier et carton - Détermination des amines Papier, Pappe und Faserstoff - Bestimmung von
aromatiques primaires (AAP) dans un extrait aqueux primären aromatischen Aminen in Wasserextrakten
par méthode LC-MS mittels LC-MS
This European Standard was approved by CEN on 26 November 2018.

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, Former Yugoslav Republic of Macedonia, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania,
Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, 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
© 2019 CEN All rights of exploitation in any form and by any means reserved Ref. No. EN 17163:2019 E
worldwide for CEN national Members.

Contents Page
European foreword . 3
Introduction . 4
1 Scope . 5
2 Normative references . 5
3 Terms and definitions . 5
4 Principle . 5
4.1 General . 5
4.2 Interferences . 6
5 Apparatus . 6
6 Reagents . 6
7 Sample preparation . 10
8 HPLC conditions . 10
8.1 General . 10
8.2 System example 1 . 11
8.3 System example 2 . 11
8.4 Example of MS conditions . 12
8.5 HPLC calibration . 12
8.6 Quality control . 13
8.7 Confirmation of Identity . 13
9 Calculation of the PAA concentrations in the Sample Extracts . 13
10 Test report . 13
Annex A (informative) Precision data . 14
Bibliography . 16

European foreword
This document (EN 17163:2019) has been prepared by Technical Committee CEN/TC 172 “Pulp, paper
and board”, the secretariat of which is held by DIN.
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 August 2019, and conflicting national standards shall
be withdrawn at the latest by August 2019.
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.
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, Former Yugoslav Republic of Macedonia,
France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta,
Netherlands, Norway, Poland, Portugal, Romania, Serbia, Slovakia, Slovenia, Spain, Sweden, Switzerland,
Turkey and the United Kingdom.
Introduction
Primary aromatic amines (PAAs) can occur in paper and board materials as residual basic chemicals for
the production of azodyes and azo pigments. Furthermore, hydrolysis products of isocyanates
especially from paper laminates may be a possible source.
A draft of a European Standard EN 13130-XX concerning the “Determination of Primary Aromatic
Amines (PAAs) in Food Simulants” has been prepared by the standardization committee
CEN/TC 194/SC1/TG9.
When preparing this standard it has been assessed by the laboratories participating that the
photometric screening method described in part A of the draft of standard EN 13130-XX is not
applicable for the examination of water extracts of paper and board materials due to interferences of
extractable paper components which caused irreproducible test results.
Due to the advantages of the MS/MS-detection regarding selectivity and sensitivity the determination of
primary aromatic amines by means of LC-MS/MS was found to be capable for water extracts of paper
and board materials when preparing this standard.
1 Scope
This document describes two representative methods for the determination of the extractable amount
of specific primary aromatic amines (PAA) in a water extract of paper, board and pulp samples by
means of HPLC with MS/MS detection which basically differ concerning the choice of the mobile and
stationary phases. Deviating from this standard further methods may be applicable if it can be shown
that comparable results can be achieved. A validation should be carried out by each laboratory.
It is applicable for the determination of the 22 primary aromatic amines (PAA) mentioned in the annex
of Directive 2002/61/EC of 19th July 2002 amending Council Directive 76/769/EEC relating to
restrictions on the market and use of certain dangerous substances and preparations (azocolourants)
which are classified as carcinogenic categories 1A and 1B according to the CLP regulation and aniline.
The method described by this standard should be also applicable for the determination of further
primary aromatic amines (PAA). A validation for every further analyte has to be done by the laboratory
using this method.
The extractable amount of a primary aromatic amine (PAA) is expressed in mg PAA per litre water
extract. This method is suitable for the determination of PAA with a working range of about
0,001 mg/l – 0,020 mg/l water extract.
Deviating from this standard further methods may be applicable if it can be shown that comparable
results can be achieved. A validation should be carried out by each laboratory.
2 Normative references
The following documents are referred to in the text in such a way that some or all of their content
constitutes requirements 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.
EN 645, Paper and board intended to come into contact with foodstuffs — Preparation of a cold water
extract
EN 647, Paper and board intended to come into contact with foodstuffs — Preparation of a hot water
extract
3 Terms and definitions
No terms and definitions are listed in this document.
ISO and IEC maintain terminological databases for use in standardization at the following addresses:
• IEC Electropedia: available at http://www.electropedia.org/
• ISO Online browsing platform: available at http://www.iso.org/obp
4 Principle
4.1 General
The primary aromatic amines (PAA) are extracted with water according to EN 645 or EN 647. The
corresponding extracts can generally be used for the HPLC-MS quantification without further
preparation steps.
4.2 Interferences
As some of the PAAs are sensitive to light, it has to be ensured that the samples are protected from light
at all stages of treatment.
5 Apparatus
5.1 An instrument or item of apparatus is listed only if it is special, or made to a particular
specification, usual laboratory glassware and equipment which is assumed to be available.
5.2 High performance liquid chromatograph with a MS-detector and electro spray ionization
6 Reagents
6.1 General
All reagents shall be of recognized analytical quality unless otherwise stated.
6.2 Acetonitrile; [75-05-8]; LC-MS-grade
6.3 Deionized water
6.4 Pentafluoropropionic acid; [422-61-0] (for system-example 1)
6.5 Formic acid; [64-18-6] (for system-example 2)
6.6 Reference substances
Table 1 — Reference Substances
No. Name Abbreviation CAS No. Structure MW
1 4-Aminobiphenyl 4-ABP 92–67–1 169,2

2 Benzidine BNZ 92–87–5 184,2
3 4-Chloro-o-toluidine 4-CoT 95–69–2 141,6

4 2-Naphthylamine 2-NA 91–59–8 143,2

No. Name Abbreviation CAS No. Structure MW
5 o-Aminoazotoluene o-AAT 97–56–3 225,3

6 2-Amino-4-nitrotoluene 2-ANT 99–55–8 152,2

7 4-Chloroaniline 4-CA 106–47–8 127,6

8 2,4-Diaminoanisole 2,4-DAA 615–05–4 138,2

4,4`-
9 4,4'-DADPM 101–77–9 198,3
Diaminodiphenylmethane
10 3,3`-Dichlorobenzidine 3,3`-DCB 91–94–1 253,1

11 o-Dimethoxybenzidine o-DMB 119–90–4 244,3

12 3,3`-Dimethylbenzidine 3,3`-DMB 119–93–7 212,3

3,3`-Dimethyl-4,4`-
13 3,3`-D-4,4`-DADPM 838–88–0 226,3
diaminodiphenylmethane
No. Name Abbreviation CAS No. Structure MW
14 p-Cresidine p-C 120–71–8 137,2

4,4`-Methylene-bis(2-
15 4,4`-M-2-CA 101–14–4 267,2
chloroaniline)
16 4,4`-Oxydianiline 4,4'-ODA 101–80–4 200,2

17 4,4`-Thiodianiline ASD 139–65–1 216,3

18 o-Toluidine o-T 95–53–4 107,2

19 2,4-Toluylenediamine 2,4-TDA 95–80–7 122,2

No. Name Abbreviation CAS No. Structure MW
20 2,4,5-Trimethylaniline 2,4,5-TMA 137–17–7 135,2

21 o-Anisidine o-ASD 90–04–0 123,2

22 4-Aminoazobenzene 4-AAB 60–09–3 197,2

23 Aniline ANL 62–53–3 93,1
1)
NOTE The standards may be obtained as pure substances, e.g. from Ehrensdorfer or Promochem.
6.7 Solutions
6.7.1 Solvent A (for system-example 1)
Pentafluoropropionic acid 4,7 mmol/l in water
6.7.2 Solvent B (for system-example 1)
Pentafluoropropionic acid 4,7 mmol/l in methanol
6.7.3 Solvent C (for system-example 2)
Deionized water
1)
This information serves as a note for the user of this European standard and does not represent a
recommendation of the product from the part of CEN. Products of e
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