SIST EN ISO 18857-1:2007

Water quality - Determination of selected alkylphenols - Part 1: Method for non-filtered samples using liquid-liquid extraction and gas chromatography with mass selective detection (ISO 18857-1:2005)

This part of ISO 18857 specifies a method for the determination of 4-nonylphenol (mixture of isomers) and 4-(1,1,3,3-tetramethylbutyl)phenol in non-filtered samples of drinking water, ground water and surface water. The method is applicable in a concentration range from 0,005 µg/l to 0,2 µg/l for 4-(1,1,3,3-tetramethylbutyl)phenol and from 0,02 µg/l to 0,2 µg/l for 4-nonylphenol (mixture of isomers). Depending on the matrix, the method is also applicable to waste water in a concentration range from 0,1 µg/l to 50 µg/l. Higher concentrations may be measured after appropriate dilution of the sample.

Wasserbeschaffenheit - Bestimmung ausgewählter Alkylphenole - Teil 1: Verfahren für nichtfiltrierte Proben mittels Flüssig-Flüssig-Extraktion und Gaschromatographie mit massenselektiver Detektion (ISO 18857-1:2005)

Qualité de l'eau - Dosage d'alkylphénols sélectionnés - Partie 1: Méthode pour échantillons non filtrés par extraction en phase liquide-liquide et chromatographie en phase gazeuse avec détection sélective de masse (ISO 18857-1:2005)

L'ISO 18857-1:2005 spécifie une méthode de dosage du 4-nonylphénol (mélange d'isomères) et du 4-(1,1,3,3-tétraméthylbutyl)phénol dans des échantillons non filtrés d'eaux potables, d'eaux souterraines et d'eaux de surface. La méthode est applicable dans une plage de concentrations comprise entre 0,005 microgramme par litre et 0,2 microgramme par litre pour le 4-(1,1,3,3-tétraméthylbutyl)phénol et entre 0,02 microgramme par litre et 0,2 microgramme par litre pour le 4-nonylphénol (mélange d'isomères). Selon la matrice, cette méthode est également applicable aux eaux résiduaires dans une plage de concentrations de 0,1 microgramme par litre à 50 microgrammes par litre. De plus fortes concentrations peuvent être mesurées après dilution appropriée de l'échantillon.

Kakovost vode - Določevanje izbranih alkilfenolov - 1. del: Metoda s tekočinsko-tekočinsko ekstrakcijo in plinsko kromatografijo z masno selektivnim detektorjem za nefiltrirane vzorce (ISO 18857-1:2005)

General Information

• Status: Published
• Publication Date: 31-Jan-2007
• 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: 01-Feb-2007
• Due Date: 01-Feb-2007
• Completion Date: 01-Feb-2007
• 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 18857-1:2006 - Water quality - Determination of selected alkylphenols - Part 1: Method for non-filtered samples using liquid-liquid extraction and gas chromatography with mass selective detection (ISO 18857-1:2005)

Standards Content (Sample)

SLOVENSKI STANDARD
SIST EN ISO 18857-1:2007
01-februar-2007
.DNRYRVWYRGH'RORþHYDQMHL]EUDQLKDONLOIHQRORYGHO0HWRGDVWHNRþLQVNR
WHNRþLQVNRHNVWUDNFLMRLQSOLQVNRNURPDWRJUDILMR]PDVQRVHOHNWLYQLPGHWHNWRUMHP
]DQHILOWULUDQHY]RUFH,62
Water quality - Determination of selected alkylphenols - Part 1: Method for non-filtered
samples using liquid-liquid extraction and gas chromatography with mass selective
detection (ISO 18857-1:2005)
Wasserbeschaffenheit - Bestimmung ausgewählter Alkylphenole - Teil 1: Verfahren für
nichtfiltrierte Proben mittels Flüssig-Flüssig-Extraktion und Gaschromatographie mit
massenselektiver Detektion (ISO 18857-1:2005)
Qualité de l'eau - Dosage d'alkylphénols sélectionnés - Partie 1: Méthode pour
échantillons non filtrés par extraction en phase liquide-liquide et chromatographie en
phase gazeuse avec détection sélective de masse (ISO 18857-1:2005)
Ta slovenski standard je istoveten z: EN ISO 18857-1:2006
ICS:
13.060.50 3UHLVNDYDYRGHQDNHPLþQH Examination of water for
VQRYL chemical substances
SIST EN ISO 18857-1:2007 en,fr,de
2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.

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SIST EN ISO 18857-1:2007

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SIST EN ISO 18857-1:2007
EUROPEAN STANDARD
EN ISO 18857-1
NORME EUROPÉENNE
EUROPÄISCHE NORM
August 2006
ICS 13.060.50

English Version
Water quality - Determination of selected alkylphenols - Part 1:
Method for non-filtered samples using liquid-liquid extraction and
gas chromatography with mass selective detection (ISO 18857-
1:2005)
Qualité de l'eau - Dosage d'alkylphénols sélectionnés - Qualité de l'eau - Dosage d'alkylphénols sélectionnés -
Partie 1: Méthode pour échantillons non filtrés par Partie 1 : Méthode pur échantillons non filtrés part
extraction en phase liquide-liquide et chromatographie en extraction en phase liquide-liquide et chromatographie en
phase gazeuse avec détection sélective de masse (ISO phase gazeuse avec détection sélective de masse (ISO
18857-1:2005) 18857-1:2005)
This European Standard was approved by CEN on 3 August 2006.
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 Central Secretariat 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 Central Secretariat has the same status as the official
versions.
CEN members are the national standards bodies of Austria, Belgium, 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: rue de Stassart, 36  B-1050 Brussels
© 2006 CEN All rights of exploitation in any form and by any means reserved Ref. No. EN ISO 18857-1:2006: E
worldwide for CEN national Members.

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SIST EN ISO 18857-1:2007
EN ISO 18857-1:2006 (E)
Foreword
The text of ISO 18857-1:2005 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 18857-1:2006 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 February 2007, and conflicting national standards shall be withdrawn
at the latest by February 2007.
According to the CEN/CENELEC Internal Regulations, the national standards organizations of the following
countries are bound to implement this European Standard: Austria, Belgium, 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.

Endorsement notice
The text of ISO 18857-1:2005 has been approved by CEN as EN ISO 18857-1:2006 without any modifications.
2

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SIST EN ISO 18857-1:2007


INTERNATIONAL ISO
STANDARD 18857-1
First edition
2005-01-15


Water quality — Determination of
selected alkylphenols —
Part 1:
Method for non-filtered samples using
liquid-liquid extraction and gas
chromatography with mass selective
detection
Qualité de l'eau — Dosage d'alkylphénols sélectionnés —
Partie 1: Méthode pour échantillons non filtrés par extraction en phase
liquide-liquide et chromatographie en phase gazeuse avec détection
sélective de masse




Reference number
ISO 18857-1:2005(E)
©
ISO 2005

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SIST EN ISO 18857-1:2007
ISO 18857-1:2005(E)
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©  ISO 2005
All rights reserved. Unless otherwise specified, no part of this publication may be reproduced or utilized in any form or by any means,
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ii © ISO 2005 – All rights reserved

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SIST EN ISO 18857-1:2007
ISO 18857-1:2005(E)
Contents Page
Foreword. iv
1 Scope. 1
2 Normative references . 1
3 Principle . 1
4 Interferences. 2
5 Reagents . 2
6 Apparatus. 3
7 Sampling and sample pretreatment . 4
8 Procedure. 4
9 Calibration. 6
10 Calculation. 10
11 Expression of results. 11
12 Test report. 11
Annex A (informative) Suitable capillary columns. 12
Annex B (informative) Examples of chromatograms. 13
Annex C (informative) Recovery tests — 4-nonylphenol (mixture of isomers). 15
Annex D (informative) Example of a separator. 16
Annex E (informative) Method performance data. 17
Bibliography . 18

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SIST EN ISO 18857-1:2007
ISO 18857-1:2005(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 18857-1 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: Method for filtered samples using solid phase extraction and gas chromatography with mass
selective detection

iv © ISO 2005 – All rights reserved

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SIST EN ISO 18857-1:2007
INTERNATIONAL STANDARD ISO 18857-1:2005(E)

Water quality — Determination of selected alkylphenols —
Part 1:
Method for non-filtered samples using liquid-liquid extraction
and gas chromatography with mass selective detection
WARNING — Persons using this International Standard should be familiar with normal laboratory
practice. This International Standard 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 method for the determination of 4-nonylphenol (mixture of isomers) and
4-(1,1,3,3-tetramethylbutyl)phenol in non-filtered samples of drinking water, ground water and surface water.
The method is applicable in a concentration range from 0,005 µg/l to 0,2 µg/l for
4-(1,1,3,3-tetramethylbutyl)phenol and from 0,02 µg/l to 0,2 µg/l for 4-nonylphenol (mixture of isomers).
Depending on the matrix, the method is also applicable to waste water containing the analyzed compounds in
the concentration range from 0,1 µg/l to 50 µg/l. Higher concentrations can be measured after appropriate
dilution of the sample.
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 reference document
(including any amendments) applies.
ISO 3696:1987, Water for analytical laboratory use — Specification and test methods
ISO 5667-1, Water quality — Sampling — Part 1: Guidance on the design of sampling programmes
ISO 5667-2, Water quality — Sampling — Part 2: Guidance on sampling techniques
ISO 5667-3, Water quality — Sampling — Part 3: Guidance on the preservation and handling of water
samples
3 Principle
The compounds 4-(1,1,3,3-tetramethylbutyl)phenol and 4-nonylphenol (mixture of isomers) are extracted from
the acidified water sample with toluene. The extract is cleaned, if necessary, with silica and the alkylphenols
are separated by gas chromatography using capillary columns. The alkylphenols are identified by mass
spectrometry and quantified using an internal standard over the total procedure. The response factor using
4-(1,1,3,3-tetramethylbutyl)phenol and a technical mixture of isomers of 4-nonylphenol is determined daily.
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SIST EN ISO 18857-1:2007
ISO 18857-1:2005(E)
4 Interferences
The extent and the importance of interferences are sample-dependent.
There are many sources of sample contamination, including contamination of reagents during storage,
contamination of equipment reused in the sequential extraction of samples and standards and carryover
contamination from the septum seal on a sample bottle or vial and GC septa. Organic polymers can form alkyl
phenols thus leading to elevated values. Avoid direct contact with plastics material as these can contain
alkylphenols that can contaminate the sample.
5 Reagents
Use reagents with negligibly low concentrations of target alkyl phenols compared with the concentration to be
determined and verify by blank determinations.
5.1 Water, grade 1, as specified in ISO 3696:1987.
5.2 Acid, e.g. hydrochloric acid, c(HCl) = 37 %, or sulfuric acid, c(H SO ) = 1 mol/l.
2 4
5.3 Silica, medium pore size 6 nm (60 Å), grain-size 0,063 mm to 0,2 mm (230 mesh to 70 mesh).
Purify about 100 g of silica in a quartz beaker (6.5) by heating to 550 °C ± 20 °C in a muffle furnace (6.6) for at
least 10 h. Let the silica cool to about 100 °C and transfer it to a wide-necked glass bottle. Let it cool to room
temperature in a desiccator. Add water (5.1) to the silica to produce a concentration of about 3 % mass
fraction. Homogenize on a shaking device for 2 h. Store tightly sealed.
5.4 Hexane, C H .
6 14
5.5 Toluene, C H .
7 8
Other extracting solvents may be used if equivalent recoveries can be achieved (see Annex C).
5.6 Sodium sulfate, Na SO , anhydrous, powdered.
2 4
5.7 Acetone, C H O.
3 6
13 13
5.8 4-n-nonylphenol(ring- C ) solution, C H -[ C ]H -OH, 1 ng/µl, used as an internal standard.
6 9 19 6 4
13
Weigh 10 mg of 4-n-nonylphenol(ring- C ) in a 100 ml measuring flask and bring to volume with acetone
6
(5.7). Dilute this solution with acetone (5.7) in the ratio 1:100.
Alternative internal standards (e.g. 4-n-nonylphenol) that meet the internal standard requirements are
acceptable. An internal standard should have the following characteristics: It should be stable and should not
interfere with the analyte. It should be as similar in structure to the analyte as possible, to ensure that it will
show the same properties relative to, for example, adsorption on glass surfaces, extraction, concentration as
the analyte. It should not be present in the sample matrix.
5.9 4-nonylphenol solution, 1 ng/µl, used as a calibration standard.
Weigh 10 mg of 4-nonylphenol, C H O (technical mixture of isomers), CAS No 84852-15-3, in a 100 ml
15 24
measuring flask and bring to volume with toluene (5.5). Dilute this solution in the ratio 1:100 with toluene (5.5)
or acetone (5.7) if a calibration over the total procedure (9.3, 9.4) is applied.
2 © ISO 2005 – All rights reserved

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SIST EN ISO 18857-1:2007
ISO 18857-1:2005(E)
5.10 4-(1,1,3,3-tetramethylbutyl)phenol solution, 1 ng/µl, used as a calibration standard.
Weigh 10 mg of 4-(1,1,3,3-tetramethylbutyl)phenol, C H O, CAS No 140-66-9, in a 100 ml measuring flask
14 22
and bring to volume with toluene (5.5). Dilute this solution in the ratio 1:100 with toluene (5.5) or acetone (5.7)
if a calibration over the total procedure (9.3, 9.4) is applied.
Store solutions 5.8, 5.9 and 5.10 in the refrigerator protected from light. Check the solutions weekly prior to
use.
NOTE The solutions 5.8, 5.9 and 5.10 are commercially available.
5.11 Nitrogen, N , purity W 99,996 %.
2
6 Apparatus
Clean all glassware by rinsing with acetone (5.7). Avoid detergents when using a labware-washing machine.
Alternatively, prior to use, heat all glassware, except volumetric ware, to at least 250 °C for a minimum of 2 h.
The given volumes are chosen corresponding to the described extraction volume of 1 000 ml. Smaller
volumes are possible.
Usual laboratory equipment, and the following.
6.1 Shaking device.
6.2 Flat-bottomed glass bottles, 1 000 ml, preferably of brown glass, with straight shoulders and a glass
stopper or polytetrafluoroethene- (PTFE-) lined screw cap.
The sampling bottle shall allow direct extraction from the bottle.
6.3 Quartz wool, rinsed with hexane (5.4).
6.4 Clean up column, inner diameter 8 mm, length 120 mm, with glass or PTFE stopcocks.
6.5 Quartz beaker, 100 ml.
6.6 Muffle furnace, capable of maintaining a temperature of at least 600 °C.
6.7 Evaporation device, rotary evaporator, turbo-evaporator or vacuum concentration device.
6.8 Separator, for an example see Annex D, or another suitable device for phase separation.
6.9 Drying column, chromatographic column, length 600 mm, inner diameter 30 mm (or other convenient
size), with coarse frit filter disk.
6.10 Tapered flask, 100 ml.
6.11 Vials, of brown glass, with a capacity of, for example 1,5 ml, compatible with the autosampler.
6.12 Gas chromatograph, temperature-programmable, with all required accessories, including gases,
capillary columns, capillary injector and mass spectrometric detector.
The mass spectrometer should be capable of operating across the mass range of interest and incorporate a
data system capable of quantifying ions using selected m/z values.
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SIST EN ISO 18857-1:2007
ISO 18857-1:2005(E)
7 Sampling and sample pretreatment
Take samples in accordance with ISO 5667-1, ISO 5667-2 and ISO 5667-3.
For sampling, use bottles (6.2), and acidify the sample with acid (5.2) to pH 2.
Do not fill the sample bottles completely (e.g. fill them to the shoulder) in order to allow the addition of the
extracting agent.
If necessary, store the sample in the refrigerator (2 °C to 5 °C) and analyse as soon as possible, but not later
than 2 weeks after sampling.
Carry out the extraction directly from the sampling bottle. Weigh the sample bottle with its contents to the
nearest 1 g and record the mass for subsequent sample volume determination (8.1).
8 Procedure
8.1 Extraction and concentration
Add 100 µl to 1 000 µl of the internal standard (5.8) to 1 000 ml of the sample in the original sample bottle.
Choose the volume of the internal standard according to the matrix-dependent extraction end volume which
may vary between 100 µl and 1 000 µl. The concentration should be approximately in the middle range of the
calibration, e.g. 20 ng/l for ground and surface water or 500 ng/l for wastewater.
Add 40 ml of toluene (5.5) and extract for at least 4 h using the shaking device (6.1). Make sure that the
phases are well mixed.
Let the phases separate and use a separator (6.8) to collect the toluene extract.
If an emulsion forms, break the emulsion by centrifuging the extract and/or by adding sodium sulfate.
Fill the drying column (6.9) with 1 cm to 2 cm with sodium sulfate (5.6) and clean it with 10 ml of toluene (5.5);
discard this toluene portion.
Subsequently let the toluene extract run through the frit into a 100 ml tapered flask (6.10).
Rinse the frit with 10 ml of toluene (5.5) and add this toluene portion to the extract.
Evaporate the extract to about 2 ml using an evaporation device (6.7).
Using a gentle nitrogen (5.11) stream, carefully evaporate, at a temperature of < 40 °C, to 50 µl to 100 µl.
If necessary, e.g. in the case of wastewater and polluted surface water, continue with the clean-up as
described in 8.2.
If a clean up is not necessary, transfer the extract to a vial, rinse using a glass pipette and evaporate the
extract to a suitable volume (in general, 100 µl to 500 µl) using nitrogen
...