SIST EN ISO 18857-2:2012

Water quality - Determination of selected alkylphenols - Part 2: Gas chromatographic-mass spectrometric determination of alkylphenols, their ethoxylates and bisphenol A in non-filtered samples following solid-phase extraction and derivatisation (ISO 18857-2:2009)

This part of ISO 18857 specifies a gas chromatographic-mass spectrometric (GC-MS) determination of selected alkylphenols, their ethoxylates and bisphenol A in non-filtered samples of drinking, ground, surface, and waste waters following solid-phase extraction and derivatisation. The lower limit of the working range depends on the matrix, on the specific compound to be analysed and on the sensitivity of the mass spectrometric detection unit. The method is applicable in a working range from 0,005 μg/l to 0,2 μg/l for 4-(1,1,3,3-tetramethylbutyl)phenol (OP), and its mono- (OP1EO) and diethoxylate (OP2EO), from 0,03 μg/l to 0,2 μg/l for 4-nonylphenol (mixture of isomers) (NP), and its mono- (NP1EO) and diethoxylate (NP2EO), and from 0,05 μg/l to 0,2 μg/l for bisphenol A (BPA). Depending on the matrix, the method is also applicable to waste water in a working range from 0,1 μg/l to 50 μg/l for OP, OP1EO, OP2EO and BPA, and from 0,5 μg/l to 50 μg/l for NP, NP1EO and NP2EO. The working ranges are based on experimental work carried out in ruggedness testing. Water samples containing suspended matter at concentrations of more than 500 mg/l and waste water samples are extracted by passing a 100 ml sample through the cartridge.

Wasserbeschaffenheit - Bestimmung von ausgewählten Alkylphenolen - Teil 2: Gaschromatographische-massenspektrometrische Bestimmung von Alkylphenolen, deren Ethoxylaten und Bisphenol-A für nicht filtrierte Proben unter Verwendung der Festphasenextraktion und Derivatisierung (ISO 18857-2:2009)

Dieser Teil von ISO 18857 legt die gaschromatographisch-massenspektrometrische (GC-MS) Bestimmung
ausgewählter Alkylphenole, ihrer Ethoxylate und Bisphenol A in nichtfiltrierten Trink-, Grund-, Oberflächenund
Abwasserproben nach Festphasenextraktion und Derivatisierung fest.
Die untere Grenze des Arbeitsbereichs hängt von der Matrix, den einzelnen zu analysierenden Verbindungen
und der Empfindlichkeit der massenspektrometrischen Detektionseinheit ab. Das Verfahren ist im
Arbeitsbereich von 0,005 µg/l bis 0,2 µg/l für 4-(1,1,3,3-Tetramethylbutyl)phenol (OP), sein Mono- (OP1EO)
und Diethoxylat (OP2EO), von 0,03 µg/l bis 0,2 µg/l für 4-Nonylphenol (Isomerengemisch) (NP), sein Mono-
(NP1EO) und Diethoxylat (NP2EO) und von 0,05 µg/l bis 0,2 µg/l für Bisphenol A (BPA) anwendbar.
In Abhängigkeit von der Matrix ist das Verfahren auch für Abwasser im Arbeitsbereich von 0,1 µg/l bis 50 µg/l
für OP, OP1EO, OP2EO und BPA und von 0,5 µg/l bis 50 µg/l für NP, NP1EO und NP2EO anwendbar. Die
angegebenen Arbeitsbereiche beruhen auf Robustheitsuntersuchungen. Wasserproben, die mehr als
500 mg/l Schwebstoffe enthalten, und Abwasserproben werden extrahiert, indem 100 ml Probe durch die
Kartusche laufen gelassen werden.

Qualité de l'eau - Dosage d'alkylphénols sélectionnés - Partie 2: Dosage par chromatographie en phase gazeuse-spectrométrie de masse d'alkylphénols, de leurs éthoxylates et de bisphénol A dans des échantillons non filtrés après extraction en phase solide et dérivation (ISO 18857-2:2009)

L'ISO 18857-2:2009 spécifie le dosage par chromatographie en phase gazeuse-spectrométrie de masse (CG‑SM) d'alkylphénols sélectionnés, de leurs éthoxylates et du bisphénol A dans des échantillons non filtrés d'eau potable, d'eaux souterraines, d'eaux de surface et d'eaux résiduaires après extraction en phase solide et dérivation.
La limite inférieure du domaine de travail dépend de la matrice, du composé spécifique à analyser et de la sensibilité de l'unité de détection de spectrométrie de masse. La méthode est applicable dans un domaine de travail allant de 0,005 µg/l à 0,2 µg/l pour le 4‑(1,1,3,3‑tétraméthylbutyl)phénol (OP) et ses mono- (OP1EO) et diéthoxylates (OP2EO), de 0,03 µg/l à 0,2 µg/l pour le 4‑nonylphénol (mélange d'isomères) (NP) et ses mono- (NP1EO) et diéthoxylates (NP2EO), et de 0,05 µg/l à 0,2 µg/l pour le bisphénol A (BPA).
Selon la matrice, la méthode est également applicable aux eaux résiduaires dans un domaine de travail allant de 0,1 µg/l à 50 µg/l pour les composés OP, OP1EO, OP2EO et BPA, et de 0,5 µg/l à 50 µg/l pour les composés NP, NP1EO et NP2EO. Les domaines de travail se fondent sur des travaux expérimentaux menés au cours d'essais de robustesse. Les échantillons d'eau contenant des matières en suspension à des concentrations supérieures à 500 mg/l et les échantillons d'eaux résiduaires sont extraits en faisant circuler un échantillon de 100 ml dans la cartouche.

Kakovost vode - Določevanje izbranih alkilfenolov - 2. del: Metoda plinske kromatografije z masno selektivnim detektorjem za določevanje alkilfenolov, njihovih etoksilatov in bisfenola-A v nefiltriranih vzorcih po ekstrakciji na trdni fazi in derivatizaciji (ISO 18857-2:2009)

Ta del standarda ISO 18857 obravnava določevanje izbranih alkilfenolov, njihovih etoksilatov in bisfenola A s plinsko kromatografijo z masno selektivnim detektorjem (GC-MS) v nefiltriranih vzorcih pitne, podzemne, površinske in odpadne vode po ekstrakciji na trdni fazi in derivatizaciji. Spodnja meja delovnega razpona je odvisna od matriksa, specifične spojine za analizo in občutljivosti masno selektivnega detektorja. Metoda se za 4-(1,1,3,3-tetrametilbutil) fenol (OP) ter njegov mono- (OP1EO) in dietoksilat (OP2EO) uporablja v delovnem razponu 0,005 μg/–0,2 μg/l, za 4-nonilfenol (mešanica izomerov) (NP) ter njegov mono- (NP1EO) in dietoksilat (NP2EO) v razponu 0,03 μg/l–0,2 μg/l ter za bisfenol A (BPA) v razponu 0,05 μg/l–0,2 μg/l. Metoda se, odvisno od matriksa, uporablja tudi za odpadno vodo v delovnem razponu 0,1 μg/l–50 μg/l za 4-(1,1,3,3-tetrametilbutil) fenol, njegov mono- in dietoksilat in bisfenol A ter 0,5 μg/l–50 μg/l za 4-nonilfenol ter njegov mono- in dietoksilat. Delovni razponi temeljijo na eksperimentalnem delu, izvedenem med preskusom robustnosti. Ekstrakcija vzorcev vode, ki vsebujejo lebdečo snov v koncentracijah, višjih od 500 mg/l, in vzorcev odpadne vode se izvaja s pretočenjem 100 ml vzorca skozi filter.

General Information

• Status: Published
• Public Enquiry End Date: 09-Jul-2011
• Publication Date: 07-Dec-2011
• ICS: 13.060.50 - Examination of water for chemical substances
• Technical Committee: KAV - Water quality
• Current Stage: 6060 - National Implementation/Publication (Adopted Project)
• Start Date: 02-Dec-2011
• Due Date: 06-Feb-2012
• Completion Date: 08-Dec-2011
• Directive: TP128 - Pravilnik o prvih meritvah in obratovalnem monitoringu odpadnih voda
• Directive: TRRTP064 - Rules on initial measurements and operational monitoring of wastewater
• Ref Project: EN ISO 18857-2:2011 - Water quality - Determination of selected alkylphenols - Part 2: Gas chromatographic-mass spectrometric determination of alkylphenols, their ethoxylates and bisphenol A in non-filtered samples following solid-phase extraction and derivatisation (ISO 18857-2:2009)

Standards Content (Sample)

SLOVENSKI STANDARD
SIST EN ISO 18857-2:2012
01-februar-2012
.DNRYRVWYRGH'RORþHYDQMHL]EUDQLKDONLOIHQRORYGHO0HWRGDSOLQVNH
NURPDWRJUDILMH]PDVQRVHOHNWLYQLPGHWHNWRUMHP]DGRORþHYDQMHDONLOIHQRORY
QMLKRYLKHWRNVLODWRYLQELVIHQROD$YQHILOWULUDQLKY]RUFLKSRHNVWUDNFLMLQDWUGQLID]L
LQGHULYDWL]DFLML,62
Water quality - Determination of selected alkylphenols - Part 2: Gas chromatographic-
mass spectrometric determination of alkylphenols, their ethoxylates and bisphenol A in
non-filtered samples following solid-phase extraction and derivatisation (ISO 18857-
2:2009)
Wasserbeschaffenheit - Bestimmung von ausgewählten Alkylphenolen - Teil 2:
Gaschromatographische-massenspektrometrische Bestimmung von Alkylphenolen,
deren Ethoxylaten und Bisphenol-A für nicht filtrierte Proben unter Verwendung der
Festphasenextraktion und Derivatisierung (ISO 18857-2:2009)
Qualité de l'eau - Dosage d'alkylphénols sélectionnés - Partie 2: Dosage par
chromatographie en phase gazeuse-spectrométrie de masse d'alkylphénols, de leurs
éthoxylates et de bisphénol A dans des échantillons non filtrés après extraction en phase
solide et dérivation (ISO 18857-2:2009)
Ta slovenski standard je istoveten z: EN ISO 18857-2:2011
ICS:
13.060.50 3UHLVNDYDYRGHQDNHPLþQH Examination of water for
VQRYL chemical substances
SIST EN ISO 18857-2:2012 en,fr,de
2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.

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SIST EN ISO 18857-2:2012

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SIST EN ISO 18857-2:2012


EUROPEAN STANDARD
EN ISO 18857-2

NORME EUROPÉENNE

EUROPÄISCHE NORM
November 2011
ICS 13.060.50
English Version
Water quality - Determination of selected alkylphenols - Part 2:
Gas chromatographic-mass spectrometric determination of
alkylphenols, their ethoxylates and bisphenol A in non-filtered
samples following solid-phase extraction and derivatisation (ISO
18857-2:2009)
Qualité de l'eau - Dosage d'alkylphénols sélectionnés - Wasserbeschaffenheit - Bestimmung von ausgewählten
Partie 2: Dosage par chromatographie en phase gazeuse- Alkylphenolen - Teil 2: Gaschromatographische-
spectrométrie de masse d'alkylphénols, de leurs massenspektrometrische Bestimmung von Alkylphenolen,
éthoxylates et du bisphénol A dans des échantillons non deren Ethoxylaten und Bisphenol A für nichtfiltrierte Proben
filtrés après extraction en phase solide et dérivation (ISO unter Verwendung der Festphasenextraktion und
18857-2:2009) Derivatisierung (ISO 18857-2:2009)
This European Standard was approved by CEN on 15 October 2011.

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, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland and United Kingdom.





EUROPEAN COMMITTEE FOR STANDARDIZATION
COMITÉ EUROPÉEN DE NORMALISATION

EUROPÄISCHES KOMITEE FÜR NORMUNG

Management Centre: Avenue Marnix 17, B-1000 Brussels
© 2011 CEN All rights of exploitation in any form and by any means reserved Ref. No. EN ISO 18857-2:2011: E
worldwide for CEN national Members.

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SIST EN ISO 18857-2:2012
EN ISO 18857-2:2011 (E)
Contents Page
Foreword .3

2

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SIST EN ISO 18857-2:2012
EN ISO 18857-2:2011 (E)
Foreword
The text of ISO 18857-2:2009 has been prepared by Technical Committee ISO/TC 147 “Water quality” of the
International Organization for Standardization (ISO) and has been taken over as EN ISO 18857-2:2011 by
Technical Committee CEN/TC 230 “Water analysis” 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 May 2012, and conflicting national standards shall be withdrawn at the
latest by May 2012.
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.
According to the CEN/CENELEC Internal Regulations, the national standards organizations 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, Romania, Slovakia, Slovenia, Spain,
Sweden, Switzerland and the United Kingdom.
Endorsement notice
The text of ISO 18857-2:2009 has been approved by CEN as a EN ISO 18857-2:2011 without any
modification.

3

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SIST EN ISO 18857-2:2012

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SIST EN ISO 18857-2:2012

INTERNATIONAL ISO
STANDARD 18857-2
First edition
2009-09-15

Water quality — Determination of
selected alkylphenols —
Part 2:
Gas chromatographic-mass
spectrometric determination of
alkylphenols, their ethoxylates and
bisphenol A in non-filtered samples
following solid-phase extraction and
derivatisation
Qualité de l'eau — Dosage d'alkylphénols sélectionnés —
Partie 2: Dosage par chromatographie en phase gazeuse-spectrométrie
de masse d'alkylphénols, de leurs éthoxylates et de bisphénol A dans
des échantillons non filtrés après extraction en phase solide et
dérivation




Reference number
ISO 18857-2:2009(E)
©
ISO 2009

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SIST EN ISO 18857-2:2012
ISO 18857-2:2009(E)
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ii © ISO 2009 – All rights reserved

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SIST EN ISO 18857-2:2012
ISO 18857-2:2009(E)
Contents Page
Foreword .iv
Introduction.v
1 Scope.1
2 Normative references.1
3 Principle.2
4 Interferences .2
5 Reagents.3
6 Apparatus.4
7 Sampling and sample pretreatment .5
8 Procedure.5
9 Calibration and analysis of samples .8
10 Expression of results.9
11 Test report.10
Annex A (informative) Example of a sorbent .11
Annex B (informative) Suitable capillary columns .12
Annex C (informative) Examples of chromatograms .13
Annex D (informative) Performance data .17
Bibliography.18

© ISO 2009 – All rights reserved iii

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SIST EN ISO 18857-2:2012
ISO 18857-2:2009(E)
Foreword
ISO (the International Organization for Standardization) is a worldwide federation of national standards bodies
(ISO member bodies). The work of preparing International Standards is normally carried out through ISO
technical committees. Each member body interested in a subject for which a technical committee has been
established has the right to be represented on that committee. International organizations, governmental and
non-governmental, in liaison with ISO, also take part in the work. ISO collaborates closely with the
International Electrotechnical Commission (IEC) on all matters of electrotechnical standardization.
International Standards are drafted in accordance with the rules given in the ISO/IEC Directives, Part 2.
The main task of technical committees is to prepare International Standards. Draft International Standards
adopted by the technical committees are circulated to the member bodies for voting. Publication as an
International Standard requires approval by at least 75 % of the member bodies casting a vote.
Attention is drawn to the possibility that some of the elements of this document may be the subject of patent
rights. ISO shall not be held responsible for identifying any or all such patent rights.
ISO 18857-2 was prepared by Technical Committee ISO/TC 147, Water quality, Subcommittee SC 2, Physical,
chemical and biochemical methods.
ISO 18857 consists of the following parts, under the general title Water quality — Determination of selected
alkylphenols:
⎯ Part 1: Method for non-filtered samples using liquid-liquid extraction and gas chromatography with mass
selective detection
⎯ Part 2: Gas chromatographic-mass spectrometric determination of alkylphenols, their ethoxylates and
bisphenol A in non-filtered samples following solid-phase extraction and derivatisation
iv © ISO 2009 – All rights reserved

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SIST EN ISO 18857-2:2012
ISO 18857-2:2009(E)
Introduction
The user should be aware that particular problems could require the specifications of additional marginal
conditions.

© ISO 2009 – All rights reserved v

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SIST EN ISO 18857-2:2012

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SIST EN ISO 18857-2:2012
INTERNATIONAL STANDARD ISO 18857-2:2009(E)

Water quality — Determination of selected alkylphenols —
Part 2:
Gas chromatographic-mass spectrometric determination of
alkylphenols, their ethoxylates and bisphenol A in non-filtered
samples following solid-phase extraction and derivatisation
WARNING — Persons using this part of ISO 18857 should be familiar with normal laboratory practice.
This part of ISO 18857 does not purport to address all of the safety problems, if any, associated with
its use. It is the responsibility of the user to establish appropriate safety and health practices and to
ensure compliance with any national regulatory conditions.
IMPORTANT — It is absolutely essential that tests conducted in accordance with this part of ISO 18857
be carried out by suitably qualified staff.
1 Scope
This part of ISO 18857 specifies a gas chromatographic-mass spectrometric (GC-MS) determination of
selected alkylphenols, their ethoxylates and bisphenol A in non-filtered samples of drinking, ground, surface,
and waste waters following solid-phase extraction and derivatisation.
The lower limit of the working range depends on the matrix, on the specific compound to be analysed and on
the sensitivity of the mass spectrometric detection unit. The method is applicable in a working range from
0,005 µg/l to 0,2 µg/l for 4-(1,1,3,3-tetramethylbutyl)phenol (OP), and its mono- (OP EO) and diethoxylate
1
(OP EO), from 0,03 µg/l to 0,2 µg/l for 4-nonylphenol (mixture of isomers) (NP), and its mono- (NP EO) and
2 1
diethoxylate (NP EO), and from 0,05 µg/l to 0,2 µg/l for bisphenol A (BPA).
2
Depending on the matrix, the method is also applicable to waste water in a working range from 0,1 µg/l to
50 µg/l for OP, OP EO, OP EO and BPA, and from 0,5 µg/l to 50 µg/l for NP, NP EO and NP EO. The
1 2 1 2
working ranges are based on experimental work carried out in ruggedness testing. Water samples containing
suspended matter at concentrations of more than 500 mg/l and waste water samples are extracted by passing
a 100 ml sample through the cartridge.
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 3696, Water for analytical laboratory use — Specification and test methods
ISO 5667-1, Water quality — Sampling — Part 1: Guidance on the design of sampling programmes and
sampling techniques
ISO 5667-3, Water quality — Sampling — Part 3: Guidance on the preservation and handling of water
samples
ISO 8466-1, Water quality — Calibration and evaluation of analytical methods and estimation of performance
characteristics — Part 1: Statistical evaluation of the linear calibration function
© ISO 2009 – All rights reserved 1

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SIST EN ISO 18857-2:2012
ISO 18857-2:2009(E)
3 Principle
Extraction of the analytes listed in Table 1 from an acidified water sample by solid-phase extraction, solvent
elution, derivatisation and determination by GC-MS detection.
Table 1 — Analytes determinable by GC-MS following solid-phase extraction and derivatisation
a
Analyte Empirical formula Abbreviation CAS No.
4-(1,1,3,3-Tetramethylbutyl)phenol C HO OP 140-66-9
14 22
4-(1,1,3,3-Tetramethylbutyl)phenol monoethoxylate C H O OPEO —

16 26 2 1
4-(1,1,3,3-Tetramethylbutyl)phenol diethoxylate C H O OPEO —

18 30 3 2
b
4-Nonylphenol (mixture of isomers) C HO NP 84852-15-3
15 24
4-Nonylphenol monoethoxylate (mixture of isomers) C H O NPEO —

17 28 2 1
4-Nonylphenol diethoxylate (mixture of isomers) C H O NPEO —

19 32 3 2
Bisphenol A C H O BPA 80-05-7

15 16 2
a
CAS: Chemical Abstracts Service.
b
The commercially produced nonylphenols are predominantly 4-nonylphenol with a varied and undefined degree of branching in the
alkyl groups. This mixture of isomers falls under the CAS number 84852-15-3, but CAS numbers 104-40-5 (4-nonylphenol, straight
chain) and 25154-52-3 (nonylphenol, straight chain) have also been incorrectly used to denote this isomer mixture.

4 Interferences
4.1 Sampling and extraction
Sampling containers shall consist of materials that do not change the sample when in contact with it. Avoid
contact with plastics and other organic materials during sampling, sample storage or extraction.
Commercially available adsorbent materials are often of varying quality. Considerable batch-to-batch
differences in quality and selectivity of this material are possible. The recovery of single substances can vary
with the concentration. Therefore, check the recovery regularly at different concentrations and whenever new
batches are used. Perform calibration and analysis with material from the same batch.
4.2 Gas chromatography-mass spectrometry
Substances with retention times or which produce masses similar to the analytes to be determined can
interfere with the determination.
These interferences may lead to incompletely resolved signals and to additional signals in the
chromatographic pattern of NP, NP EO and NP EO. They may, depending on their magnitude, affect
1 2
accuracy and precision of the analytical results, since all three analytes are determined from the sum of a
cluster of eight to ten chromatographic peaks (Table 3 and Annex C). It is important that the interfering peaks
are not included in the calculations.
The presence of interfering compounds can, if necessary, be detected by recording full mass spectra (range
of mass fragments to monitor m/z = 50 to m/z = 350).
Matrix interferences can be caused by contaminants that are co-extracted from the sample. The extent of
matrix interferences varies considerably, depending on the nature of the sample. In drinking water and ground
water, matrix interferences usually do not occur.
2 © ISO 2009 – All rights reserved

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SIST EN ISO 18857-2:2012
ISO 18857-2:2009(E)
5 Reagents
The reagents shall not have blank values that would interfere with the GC-MS analysis.
Use solvents and reagents of sufficient purity, i.e. with negligibly low impurities compared with the
concentration of analytes to be determined. As reagents, use, as far as available, “residual grade” or better in
order to obtain clean blanks. Check blanks regularly and establish proper charge control.
5.1 Water, as specified in ISO 3696, grade 1, or equivalent.
5.2 Acid, e.g. hydrochloric acid, w(HCl) = 37 % mass fraction, or sulfuric acid, c(H SO ) = 1 mol/l.
2 4
5.3 Acetone, C H O.
3 6
5.4 Internal standard solutions.
Examples of suitable internal standards are given in Table 2.
Store solutions 5.4.1 and 5.4.2 in a refrigerator protected from light. Check the solutions weekly prior to use.
Table 2 — Internal standards
No. Name Abbreviation CAS No.
13 13
1 4-(1,1,3,3-Tetramethylbutyl)phenol (ring- C) OP- C —
6 6
13 13
2 4-(1,1,3,3-Tetramethylbutyl)phenol monoethoxylate (ring- C) OP EO- C —
6 6
1
13 13
3 4-(1,1,3,3-Tetramethylbutyl)phenol diethoxylate (ring- C) OP EO- C —
6 2 6
13 13
4 4-(3,6-Dimethyl-3-heptyl)phenol (ring- C) 363 NP- C —
6 6
13 13
5 4-(3,6-Dimethyl-3-heptyl)phenol monoethoxylate (ring- C) 363 NP EO- C —
6 1 6
13 13
6 4-(3,6-Dimethyl-3-heptyl)phenol diethoxylate (ring- C) 363 NP EO- C —
6 2 6

7 Bisphenol A-d16 BPA-d16 96210-87-6

5.4.1 Internal standard stock solution.
Use commercially available internal standard solutions or prepare a solution as follows.
Weigh 10 mg of each internal standard (Table 2) separately in a 100 ml one-mark volumetric flask and make
up to the mark with acetone (5.3) to give a concentration of each internal standard of 100 ng/µl.
5.4.2 Internal standard working solution.
Dilute the solution (5.4.1) with acetone (5.3) 1→100 to give a final concentration of each internal standard of
1 ng/µl.
© ISO 2009 – All rights reserved 3

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SIST EN ISO 18857-2:2012
ISO 18857-2:2009(E)
5.5 Solutions of reference standards of the analytes listed in Table 1.
Store solutions 5.5.1 and 5.5.2 in a refrigerator protected from light. Check the solutions weekly prior to use.
5.5.1 Reference standard stock solution.
Use commercially available reference standard solutions or prepare a solution as follows.
Weigh 10 mg of each reference substance separately in a 100 ml volumetric flask and bring to volume with
acetone (5.3) to give a concentration of each reference standard of 100 ng/µl.
5.5.2 Reference standard working solution.
Dilute the solution (5.5.1) 1→100 with acetone (5.3) to give a final concentration of each reference substance
of 1 ng/µl.
5.6 2,2,2-Trifluoro-N-methyl-N-(trimethylsilyl)acetamide (MSTFA), C H F NOSi.
6 12 3
5.7 Solid-phase material, on styrene-divinylbenzene polymer basis, e.g. commercially available packing
material (see Annex A).
5.8 Sand, e.g. sea sand, acid washed and calcinated for analysis, particle size 0,1 mm to 0,3 mm.
5.9 Nitrogen, N , purity W 99,996 % volume fraction, for drying of the sorbent packing after sample
2
extraction and for concentration by evaporation.
5.10 Sodium thiosulfate pentahydrate, Na S O ⋅ 5 H O.
2 2 3 2
6 Apparatus
Equipment or parts of it which may come into contact with the water sample or the extract should be free from
interfering compounds.
Clean all glassware by rinsing with acetone (5.3). Avoid detergents when using a labware washing machine.
Alternatively, prior to use, heat all glassware, except volumetric ware, to at least 200 °C for a minimum of 2 h.
Usual laboratory equipment, and in particular the following.
6.1 Narrow-neck flat bottomed glass bottles, conical shoulders, preferably brown glass, 1 000 ml, with
glass stoppers or with PTFE-lined screw caps (PTFE = polytetrafluoroethene). Protect samples from light if
brown glass bottles are not available. Wash the bottle, cap liner or glass stopper, then rinse with acetone (5.3),
and dry before use in order to minimise contamination.
6.2 Solid-phase extraction cartridges, of inert non-leaching plastic, e.g. polypropene, or glass. The
cartridges should be packed with a minimum of 200 mg of sorbent (5.7).
6.3 Vacuum or pressure assembly, for the extraction step.
[1]
6.4 One-mark volumetric flasks, ISO 1042 class A, with inert stoppers.
6.5 Quartz wool, rinsed with acetone.
6.6 Pear-shaped flask, 10 ml, with inert stopper.
6.7 Evaporation assembly, e.g. rotary evaporator with vacuum stabiliser and water bath.
6.8 Vials, brown glass with PTFE-lined septa, capacity e.g. 1,5 ml, according to the autosampler.
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SIST EN ISO 18857-2:2012
ISO 18857-2:2009(E)
6.9 Stainless steel cocks, with stainless steel cone.
6.10 Gas chromatograph, temperature-programmable and with all required accessories including gases,
capillary columns, capillary injector and mass spectrometer detector. The mass spectrometer should be
capable of operating in electron impact mode over the mass range of interest and incorporate a data system
capable of quantifying ions using selected m/z values (selected ion monitoring).
7 Sampling and sample pretreatment
Take samples as specified in ISO 5667-1 and ISO 5667-3.
For sampling, use carefully cleaned bottles (6.1). Fill bottles only to the shoulder, in which case the sample
volume is approximately 1 l. This volume is completely used for extraction (8.1). If the presence of free
chlorine is suspected, immediately add approximately 80 mg of sodium thiosulfate (5.10). Other
non-interfering substances may be used for dechlorination as well (e.g. sodium sulfite). Acidify the sample
with acid (5.2) to pH (2 ± 0,2).
If necessary, store the sample in a refrigerator (2 °C to 5 °C) and analyse as soon as possible, but not later
than 2 weeks after sampling.
Weigh the sample bottle with its contents to the nearest 1 g and record the mass for subsequent sample
volume determination (8.1.2).
8 Procedure
8.1 Solid-phase extraction
In general, samples are examined without pretreatment, which means that suspended solids are not removed
prior to analysis. Before starting the analysis, homogenise the sample. In cases where blocking of the
cartridge packing is likely to occur, use some filter aid, e.g. quartz wool (6.5) or sand (5.8) e.g. 0,5 cm bed
thickness.
8.1.1 Conditioning of the solid-phase material
The following procedure is described for commercially available 6 ml polypropene cartridges packed with
200 mg of sorbent sandwiched between two polyethene frits.
Rinse the cartridge with two 10 ml aliquots of acetone (5.3). Allow the first aliquot to drain from the cartridge.
Before the acetone level of the second aliquot falls below the top edge of the packing, add 10 ml of water (5.1),
acidified with acid (5.2) to pH (2 ± 0,2), to the cartridge, and make sure that the sorbent packing in the
cartridge does not run dry, e.g. by using a stainless steel cock (6.9). Retain the water in the cartridge (water
level just above the packing) to keep the sorbent activated.
8.1.2 Sample extraction
Start the extraction immediately after conditioning. Make sure that no air bubbles are trapped in the sorbent
bed when changing from conditioning to extraction. Maintain the sorbent material in the cartridge immersed in
water at all times.
Add the internal standard mixture (5.4.2) well below the surface of the water sample (Clause 7) in the sample
bottle [50 µl to 200 µl of the prepared mixture (5.4) dependent on the sample matrix] and mix thoroughly.
Allow this sample to run through the cartridge (8.1.1) at a flow rate between 5 ml/min and 10 ml/min. Water
samples containing suspended matter at a concentration of more than 500 mg/l and waste water samples are
extracted by passing a 100 ml sample through the cartridge. Rinse the cartridge with 10 ml of water (5.1),
acidified with acid (5.2) to pH (2 ± 0,2).
Remove the residual water in the sorbent packing by passing nitrogen at a flow rate of about 500 ml/min
through the cartridge for about 1 h.
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SIST EN ISO 18857-2:2012
ISO 18857-2:2009(E)
NOTE The end of the removal of water from the cartridge can usually be recognised by the change in colour of the
adsorbent. The colour of the moist adsorbent is brown, the dry material is light orange.
Reweigh the empty sample bottle with its original cap or stopper and calculate the net mass of the sample by
difference to the nearest 1 g. For an assumed density of 1 g/ml, this net mass, in grams, is equivalent to the
volume, in millilitres, of water extracted. The volume of the acid (5.2) added to acidify the sample is negligible.
8.1.3 Elution
Add 1 ml of acetone (5.3) to the completely dried cartridge, allow to equilibrate for e.g. 10 min and elute the
cartridge. Then, add five further 1 ml aliquots of acetone (5.3) to the cartridge, but do not allow the acetone to
elute below the top of the sorbent packing during the elution steps.
After these elutions, draw the remaining solvent through the cartridge in order to collect the remaining drops.
Collect all eluates in a pear-shaped flask (6.6). Evaporate the eluates to dryness under a moderate stream of
nitrogen. Dissolve the residue by adding 200 µl of acetone (5.3) and continue with derivatisation (8.2).
8.2 Derivatisation
Add 25 µl of MSTFA (5.6) to the sample extract solution (8.1.3) and mix gently. Allow the mixture to react at
room temperature for at least 30 s. Transfer the solution of the derivatised analytes and internal standards to a
suitable vial (6.8). This acetone solution may be stored for 1 week. Afterwards, decomposition of the
derivatives may take place. The decomposition can be reversed by addition of another portion of MSTFA.
8.3 GC-MS operating conditions
Optimise the operating conditions of the GC-MS system in electron ionisation mode in accordance with the
manufacturer's instructions. The appropriate GC oven temperature programme is determined experimentally
during method development and validation. For the sake of sensitivity, selected ions (T
...