Water quality - Determination of dissolved anions by liquid chromatography of ions - Part 1: Determination of bromide, chloride, fluoride, nitrate, nitrite, phosphate and sulfate (ISO 10304-1:2007)

This part of ISO 10304 specifies a method for the determination of dissolved bromide, chloride, fluoride, nitrate, nitrite, orthophosphate and sulfate in water, e.g. drinking water, ground water, surface water, waste water, leachates and marine water by liquid chromatography of ions. The lower limit of application is ≥ 0,05 mg/l for bromide and for nitrite, and ≥ 0,1 mg/l for chloride, fluoride, nitrate, orthophosphate and sulfate. The lower limit application depends on the matrix and the interferences encountered. The working range may be expanded to lower concentrations (e.g. ≥ 0,01 mg/l) if an appropriate pre treatment of the sample (e.g. conditions for trace analyses, pre-concentration technique) is applied, and/or if an ultraviolet (UV) detector (for bromide, nitrate and nitrite) is used.

Wasserbeschaffenheit - Bestimmung von gelösen Anionen mittels Flüssigkeits-Ionenchromatographie - Teil 1: Bestimmung von Bromid, Chlorid, Fluorid, Nitrat, Nitrit, Phosphat und Sulfat (ISO 10304-1:2007)

Dieser Teil von ISO 10304 legt ein Verfahren zur Bestimmung von gelöstem Bromid, Chlorid, Fluorid, Nitrat,
Nitrit, Orthophosphat und Sulfat in Wasser, z. B. Trinkwasser, Grundwasser, Oberflächenwasser, Abwasser,
Sickerwasser und Meerwasser mittels Flüssigkeits-Ionenchromatographie fest.
Der untere Arbeitsbereich beträgt für Bromid und Nitrit ≥ 0,05 mg/l und ≥ 0,1 mg/l für Chlorid, Fluorid, Nitrit,
Orthophosphat und Sulfat. Die untere Anwendungsgrenze hängt von der Matrix und den beobachteten
Störungen ab.
Der Arbeitsbereich kann zu geringeren Konzentrationen (z. B. ≥ 0,01 mg/l) hin erweitert werden, wenn eine
geeignete Probenvorbereitung (z. B. Arbeiten unter spurenanalytischen Bedingungen, Einsatz von
Anreicherungstechniken) angewandt wird und/oder ein UV-Detektor (UVD) (für Bromid, Nitrat und Nitrit)
eingesetzt wird.

Qualité de l'eau - Dosage des anions dissous par chromatographie des ions en phase liquide - Partie 1: Dosage du bromure, chlorure, fluorure, nitrate, nitrite, phosphate et sulfate (ISO 10304-1:2007)

L'ISO 10304-1:2007 spécifie une méthode pour le dosage des ions bromure, chlorure, fluorure, nitrate, nitrite, orthophosphate et sulfate dissous dans l'eau, par exemple l'eau potable, les eaux souterraines, les eaux de surface, les eaux usées, les lixiviats et l'eau de mer, par chromatographie des ions en phase liquide.
La limite inférieure d'application est plus grande que ou égale à 0,05 mg/l pour les ions bromure et nitrite, et plus grande que ou égale à 0,1 mg/l pour les ions chlorure, fluorure, nitrate, orthophosphate et sulfate. La limite inférieure d'application dépend de la matrice et des interférences rencontrées.
Le domaine de travail peut être étendu à des concentrations plus faibles (par exemple plus grande que ou égale à 0,01 mg/l) si un prétraitement approprié de l'échantillon (par exemple conditions en vue d'analyses de traces, technique de préconcentration) est appliqué, et/ou si un détecteur ultraviolet (UV) est utilisé (pour les ions bromure, nitrate et nitrite).

Kakovost vode - Določevanje raztopljenih anionov z ionsko kromatografijo - 1. del: Določevanje bromida, klorida, fluorida, nitrata, nitrita, fosfata in sulfata (ISO 10304-1:2007)

General Information

Status
Published
Public Enquiry End Date
19-Jan-2009
Publication Date
14-Apr-2009
Technical Committee
Current Stage
6060 - National Implementation/Publication (Adopted Project)
Start Date
27-Mar-2009
Due Date
01-Jun-2009
Completion Date
15-Apr-2009

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Standards Content (Sample)

SLOVENSKI STANDARD
SIST EN ISO 10304-1:2009
01-maj-2009
1DGRPHãþD
SIST EN ISO 10304-1:1998
SIST EN ISO 10304-2:1998
.DNRYRVWYRGH'RORþHYDQMHUD]WRSOMHQLKDQLRQRY]LRQVNRNURPDWRJUDILMRGHO
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Water quality - Determination of dissolved anions by liquid chromatography of ions - Part
1: Determination of bromide, chloride, fluoride, nitrate, nitrite, phosphate and sulfate (ISO
10304-1:2007)
Wasserbeschaffenheit - Bestimmung von gelösen Anionen mittels Flüssigkeits-
Ionenchromatographie - Teil 1: Bestimmung von Bromid, Chlorid, Fluorid, Nitrat, Nitrit,
Phosphat und Sulfat (ISO 10304-1:2007)
Qualité de l'eau - Dosage des anions dissous par chromatographie des ions en phase
liquide - Partie 1: Dosage du bromure, chlorure, fluorure, nitrate, nitrite, phosphate et
sulfate (ISO 10304-1:2007)
Ta slovenski standard je istoveten z: EN ISO 10304-1:2009
ICS:
13.060.50 3UHLVNDYDYRGHQDNHPLþQH Examination of water for
VQRYL chemical substances
SIST EN ISO 10304-1:2009 en,fr,de
2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.

---------------------- Page: 1 ----------------------

SIST EN ISO 10304-1:2009

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SIST EN ISO 10304-1:2009
EUROPEAN STANDARD
EN ISO 10304-1
NORME EUROPÉENNE
EUROPÄISCHE NORM
March 2009
ICS 13.060.50 Supersedes EN ISO 10304-1:1995, EN ISO 10304-2:1996

English Version
Water quality - Determination of dissolved anions by liquid
chromatography of ions - Part 1: Determination of bromide,
chloride, fluoride, nitrate, nitrite, phosphate and sulfate (ISO
10304-1:2007)
Qualité de l'eau - Dosage des anions dissous par Wasserbeschaffenheit - Bestimmung von gelösen Anionen
chromatographie des ions en phase liquide - Partie 1: mittels Flüssigkeits-Ionenchromatographie - Teil 1:
Dosage du bromure, chlorure, fluorure, nitrate, nitrite, Bestimmung von Bromid, Chlorid, Fluorid, Nitrat, Nitrit,
phosphate et sulfate (ISO 10304-1:2007) Phosphat und Sulfat (ISO 10304-1:2007)
This European Standard was approved by CEN on 1 March 2009.
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 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 Management Centre has the same status as the
official 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 STANDARDIZATION
COMITÉ EUROPÉEN DE NORMALISATION
EUROPÄISCHES KOMITEE FÜR NORMUNG
Management Centre: Avenue Marnix 17, B-1000 Brussels
© 2009 CEN All rights of exploitation in any form and by any means reserved Ref. No. EN ISO 10304-1:2009: E
worldwide for CEN national Members.

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SIST EN ISO 10304-1:2009
EN ISO 10304-1:2009 (E)
Contents Page
Foreword .3

2

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SIST EN ISO 10304-1:2009
EN ISO 10304-1:2009 (E)
Foreword
The text of ISO 10304-1:2007 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 10304-1:2009 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 September 2009, and conflicting national standards shall be
withdrawn at the latest by September 2009.
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.
This document supersedes EN ISO 10304-1:1995, EN ISO 10304-2:1996.
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, 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 10304-1:2007 has been approved by CEN as a EN ISO 10304-1:2009 without any
modification.

3

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SIST EN ISO 10304-1:2009

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SIST EN ISO 10304-1:2009

INTERNATIONAL ISO
STANDARD 10304-1
Second edition
2007-08-15

Water quality — Determination
of dissolved anions by liquid
chromatography of ions —
Part 1:
Determination of bromide, chloride,
fluoride, nitrate, nitrite, phosphate
and sulfate
Qualité de l'eau — Dosage des anions dissous par chromatographie
des ions en phase liquide —
Partie 1: Dosage du bromure, chlorure, fluorure, nitrate, nitrite,
phosphate et sulfate





Reference number
ISO 10304-1:2007(E)
©
ISO 2007

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SIST EN ISO 10304-1:2009
ISO 10304-1:2007(E)
PDF disclaimer
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All rights reserved. Unless otherwise specified, no part of this publication may be reproduced or utilized in any form or by any means,
electronic or mechanical, including photocopying and microfilm, without permission in writing from either ISO at the address below or
ISO's member body in the country of the requester.
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Published in Switzerland

ii © ISO 2007 – All rights reserved

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SIST EN ISO 10304-1:2009
ISO 10304-1:2007(E)
Contents Page
Foreword. iv
Introduction . v
1 Scope. 1
2 Normative references. 1
3 Interferences. 2
4 Principle. 2
5 Reagents. 2
6 Apparatus. 4
7 Sampling and sample pre-treatment. 7
8 Procedure. 8
9 Calculation. 9
10 Expression of results. 9
11 Test report. 9
Annex A (informative) Performance data. 10
Annex B (informative) Checked interferences . 14
Bibliography . 15

© ISO 2007 – All rights reserved iii

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SIST EN ISO 10304-1:2009
ISO 10304-1:2007(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 10304-1 was prepared by Technical Committee ISO/TC 147, Water quality, Subcommittee SC 2, Physical,
chemical and biochemical methods.
This second edition of ISO 10304-1 cancels and replaces ISO 10304-1:1992 and ISO 10304-2:1995, which
have been technically revised.
ISO 10304 consists of the following parts, under the general title Water quality — Determination of dissolved
anions by liquid chromatography of ions:
⎯ Part 1: Determination of bromide, chloride, fluoride, nitrate, nitrite, phosphate and sulfate
⎯ Part 3: Determination of chromate, iodide, sulfite, thiocyanate and thiosulfate
⎯ Part 4: Determination of chlorate, chloride and chlorite in water with low contamination
iv © ISO 2007 – All rights reserved

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SIST EN ISO 10304-1:2009
ISO 10304-1:2007(E)
Introduction
The user should be aware that particular problems could require the specification of additional conditions not
provided for in this part of ISO 10304.

© ISO 2007 – All rights reserved v

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SIST EN ISO 10304-1:2009

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SIST EN ISO 10304-1:2009
INTERNATIONAL STANDARD ISO 10304-1:2007(E)

Water quality — Determination of dissolved anions by liquid
chromatography of ions —
Part 1:
Determination of bromide, chloride, fluoride, nitrate, nitrite,
phosphate and sulfate
WARNING — Persons using this International Standard should be familiar with normal laboratory
practice. This 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 according to this International Standard
be carried out by suitably trained staff.
1 Scope
This part of ISO 10304 specifies a method for the determination of dissolved bromide, chloride, fluoride,
nitrate, nitrite, orthophosphate and sulfate in water, e.g. drinking water, ground water, surface water, waste
water, leachates and marine water by liquid chromatography of ions.
The lower limit of application is W 0,05 mg/l for bromide and for nitrite, and W 0,1 mg/l for chloride, fluoride,
nitrate, orthophosphate, and sulfate. The lower limit of application depends on the matrix and the interferences
encountered.
The working range may be expanded to lower concentrations (e.g. W 0,01 mg/l) if an appropriate
pre-treatment of the sample (e.g. conditions for trace analyses, pre-concentration technique) is applied, and/or
if an ultraviolet (UV) detector (for bromide, nitrate and nitrite) is used.
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 5667-3, 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 8466-2, Water quality — Calibration and evaluation of analytical methods and estimation of performance
characteristics — Part 2: Calibration strategy for non-linear second-order calibration functions
© ISO 2007 – All rights reserved 1

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SIST EN ISO 10304-1:2009
ISO 10304-1:2007(E)
3 Interferences
3.1 Organic acids
Aliphatic organic acids such as mono- or dicarboxylic acids may interfere with the separation of the anions.
3.2 Sulfite
Sulfite may cause a positive bias for sulfate due to autooxidation. In this case the sample may be adjusted to
pH 10 and formaldehyde solution is added in order to stabilize sulfite, if necessary.
3.3 Metals
The presence of metals (e.g. alkaline earth metals, transition metals, heavy metals) possibly interfering with
the anions of interest, should be checked and can be eliminated with the aid of special cation exchangers (e.g.
cartridge in the H-form or Na-form).
NOTE Depending on the sample matrix, the use of cation exchangers in the H-form can cause losses of fluoride and
nitrite.
4 Principle
The sample is pretreated in order to remove solids (see Clause 7), sulfite and metal ions, if necessary. The
anions of interest (bromide, chloride, fluoride, nitrate, nitrite, orthophosphate and sulfate), are separated by
liquid chromatography, applying an anion exchange resin as stationary phase, and aqueous solutions of salts
of weak mono- and dibasic acids as eluents for isocratic or gradient elution (e.g. carbonate,
hydrogencarbonate, hydroxide eluent) (5.10). Detection is carried out using a conductivity detector (CD).
When using CDs it is essential that the eluents show a sufficiently low conductivity. For this reason, CDs are
usually combined with a suppressor device (cation exchanger), which will reduce the conductivity of the eluent
and transform the sample species into their respective acids.
NOTE A UV detector is not required to carry out this analysis, but can be used for bromide, nitrate or nitrite if a higher
sensitivity is required and/or in case of a matrix interference to the CD. If used, bromide, nitrate and nitrite can be
measured at λ = 200 nm to λ = 215 nm.
Check resolution, R, to ensure that it complies with the required separation conditions (6.2). UV may be used
in combination with a CD. UV measures the absorption directly.
Calibration is carried out as specified in ISO 8466-1 or ISO 8466-2 (8.2). In special cases, extended working
ranges (e.g. two concentration decades) may be applied.
Control experiments are necessary to check the validity of the calibration function. Replicate determinations
may be necessary. Use of the method of standard addition may be required when matrix interferences are
expected (8.3).
5 Reagents
Use only reagents of recognized analytical grade. Weigh the reagents with an accuracy of ± 1 % of the
nominal mass, unless stated otherwise. The reagents listed in 5.2 to 5.5 may be considered representative
examples for the preparation of eluents (5.10).
5.1 Water, complying with grade 1, as defined in ISO 3696.
5.2 Sodium hydrogencarbonate, NaHCO .
3
2 © ISO 2007 – All rights reserved

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SIST EN ISO 10304-1:2009
ISO 10304-1:2007(E)
5.3 Sodium carbonate, Na CO .
2 3
5.4 Sodium hydroxide, NaOH.
5.5 Potassium hydroxide, KOH.
5.6 Bromide, chloride, fluoride, nitrate, nitrite, orthophosphate and sulfate stock standard solutions,
ρ = 1 000 mg/l each.
Single anion and mixed anion stock solutions with adequate and required specification are commercially
available. These solutions are considered to be stable for several months.
For an alternative preparation of stock solutions see Table 1. Dissolve the salts accordingly, after appropriate
treatment.
Table 1 — Mass portion and pre-treatment for stock solutions
Mass
a
Anion to be determined Salt to be used Pre-treatment by drying at (105 ± 5) °C for at least
g
Bromide NaBr 1,287 7 6 h
Chloride NaCl 1,648 4 2 h
Fluoride NaF 2,210 0 1 h
Nitrate NaNO 1,370 7 24 h
3
Nitrite NaNO 1,499 8 1 h
2
Orthophosphate KH PO 1,433 0 1 h
2 4
Sulfate Na SO 1,478 6 1 h
2 4
a
Alternative salts with adequate and required specification may be used.

5.7 Bromide, chloride, fluoride, nitrate, nitrite, orthophosphate and sulfate standard solutions
5.7.1 General
Depending on the concentrations expected, prepare single or mixed standard solutions, of bromide, chloride,
fluoride, nitrate, nitrite, orthophosphate and sulfate concentrations from the stock standard solution (5.6).
Store the standard solutions in polyethene bottles.
5.7.2 Example for a bromide, chloride, fluoride, nitrate, nitrite, orthophosphate and sulfate mixed
standard solution, ρ = 10 mg/l each.
Pipette 1,0 ml of each of the stock standard solutions (5.6) into a 100 ml volumetric flask, and dilute to volume
with water (5.1).
The solutions are stable for 1 week, if stored in the dark at 2 °C to 8 °C in polyethene bottles.
5.8 Bromide, chloride, fluoride, nitrate, nitrite, orthophosphate and sulfate calibration solutions
Depending on the concentrations expected in the sample, use the standard solution (5.7.2) to prepare e.g. 5
to 10 calibration solutions distributed as evenly as possible over the expected working range.
For example, proceed as follows for the range 0,05 mg/l to 0,5 mg/l:
© ISO 2007 – All rights reserved 3

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SIST EN ISO 10304-1:2009
ISO 10304-1:2007(E)
Pipette, into a series of 20 ml volumetric flasks, the following volumes: 100 µl, 200 µl, 300 µl, 400 µl, 500 µl,
600 µl, 700 µl, 800 µl, 900 µl or 1 000 µl of the standard solution (5.7.2) and dilute to volume with water (5.1).
The concentrations of the anions in these calibration solutions are: 0,05 mg/l, 0,1 mg/l, 0,15 mg/l, 0,2 mg/l,
0,25 mg/l, 0,3 mg/l, 0,35 mg/l, 0,4 mg/l, 0,45 mg/l or 0,5 mg/l, respectively.
Prepare the calibration solutions on the day of use.
5.9 Blank
Fill a volumetric flask (e.g. 100 ml flask) with water (5.1).
5.10 Eluents
5.10.1 General
Degas all water used for eluent preparation. In order to minimise the growth of bacteria or algae, prepare
eluents freshly after 3 days.
The choice of eluent depends on the chosen column and detector (e.g. UV or conductivity), seek advice from
the column supplier. The chosen combination of separator column and eluent shall meet the resolution
requirements stated in 6.2.
The example for the eluent composition in 5.10.3 refers to the CD suppressor technique only. Nevertheless,
the non-suppressed CD technique (as well as UV detection) is included in this method.
A selection
...

SLOVENSKI STANDARD
kSIST prEN ISO 10304-1:2008
01-december-2008
.DNRYRVWYRGH'RORþHYDQMHUD]WRSOMHQLKDQLRQRY]LRQVNRNURPDWRJUDILMRGHO
'RORþHYDQMHEURPLGDNORULGDIOXRULGDQLWUDWDQLWULWDIRVIDWDLQVXOIDWD ,62

Water quality - Determination of dissolved anions by liquid chromatography of ions - Part
1: Determination of bromide, chloride, fluoride, nitrate, nitrite, phosphate and sulfate (ISO
10304-1:2007)
Wasserbeschaffenheit - Bestimmung von gelösen Anionen mittels Flüssigkeits-
Ionenchromatographie - Teil 1: Bestimmung von Bromid, Chlorid, Fluorid, Nitrat, Nitrit,
Phosphat und Sulfat (ISO 10304-1:2007)
Qualité de l'eau - Dosage des anions dissous par chromatographie des ions en phase
liquide - Partie 1: Dosage du bromure, chlorure, fluorure, nitrate, nitrite, phosphate et
sulfate (ISO 10304-1:2007)
Ta slovenski standard je istoveten z: prEN ISO 10304-1
ICS:
13.060.50 3UHLVNDYDYRGHQDNHPLþQH Examination of water for
VQRYL chemical substances
kSIST prEN ISO 10304-1:2008 en,fr,de
2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.

---------------------- Page: 1 ----------------------
kSIST prEN ISO 10304-1:2008

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kSIST prEN ISO 10304-1:2008
EUROPEAN STANDARD
FINAL DRAFT
prEN ISO 10304-1
NORME EUROPÉENNE
EUROPÄISCHE NORM
August 2008
ICS 13.060.50 Will supersede EN ISO 10304-1:1995
English Version
Water quality - Determination of dissolved anions by liquid
chromatography of ions - Part 1: Determination of bromide,
chloride, fluoride, nitrate, nitrite, phosphate and sulfate (ISO
10304-1:2007)
Qualité de l'eau - Dosage des anions dissous par Wasserbeschaffenheit - Bestimmung von gelösen Anionen
chromatographie des ions en phase liquide - Partie 1: mittels Flüssigkeits-Ionenchromatographie - Teil 1:
Dosage du bromure, chlorure, fluorure, nitrate, nitrite, Bestimmung von Bromid, Chlorid, Fluorid, Nitrat, Nitrit,
phosphate et sulfate (ISO 10304-1:2007) Phosphat und Sulfat (ISO 10304-1:2007)
This draft European Standard is submitted to CEN members for unique acceptance procedure. It has been drawn up by the Technical
Committee CEN/TC 230.
If this draft becomes a European Standard, 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.
This draft European Standard was established by CEN 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 Management Centre has the
same status as the official 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.
Warning : This document is not a European Standard. It is distributed for review and comments. It is subject to change without notice and
shall not be referred to as a European Standard.
EUROPEAN COMMITTEE FOR STANDARDIZATION
COMITÉ EUROPÉEN DE NORMALISATION
EUROPÄISCHES KOMITEE FÜR NORMUNG
Management Centre: rue de Stassart, 36  B-1050 Brussels
© 2008 CEN All rights of exploitation in any form and by any means reserved Ref. No. prEN ISO 10304-1:2008: E
worldwide for CEN national Members.

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kSIST prEN ISO 10304-1:2008
prEN ISO 10304-1:2008 (E)
Contents Page
Foreword.3

2

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kSIST prEN ISO 10304-1:2008
prEN ISO 10304-1:2008 (E)
Foreword
The text of ISO 10304-1:2007 has been prepared by Technical Committee ISO/TC 147 “Water quality” of the
International Organization for Standardization (ISO) and has been taken over as prEN ISO 10304-1:2008 by
Technical Committee CEN/TC 230 “Water analysis” the secretariat of which is held by DIN.
This document is currently submitted to the Unique Acceptance Procedure.
This document will supersede EN ISO 10304-1:1995.
Endorsement notice
The text of ISO 10304-1:2007 has been approved by CEN as a prEN ISO 10304-1:2008 without any
modification.

3

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kSIST prEN ISO 10304-1:2008

---------------------- Page: 6 ----------------------
kSIST prEN ISO 10304-1:2008

INTERNATIONAL ISO
STANDARD 10304-1
Second edition
2007-08-15

Water quality — Determination
of dissolved anions by liquid
chromatography of ions —
Part 1:
Determination of bromide, chloride,
fluoride, nitrate, nitrite, phosphate
and sulfate
Qualité de l'eau — Dosage des anions dissous par chromatographie
des ions en phase liquide —
Partie 1: Dosage du bromure, chlorure, fluorure, nitrate, nitrite,
phosphate et sulfate





Reference number
ISO 10304-1:2007(E)
©
ISO 2007

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kSIST prEN ISO 10304-1:2008
ISO 10304-1:2007(E)
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©  ISO 2007
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kSIST prEN ISO 10304-1:2008
ISO 10304-1:2007(E)
Contents Page
Foreword. iv
Introduction . v
1 Scope. 1
2 Normative references. 1
3 Interferences. 2
4 Principle. 2
5 Reagents. 2
6 Apparatus. 4
7 Sampling and sample pre-treatment. 7
8 Procedure. 8
9 Calculation. 9
10 Expression of results. 9
11 Test report. 9
Annex A (informative) Performance data. 10
Annex B (informative) Checked interferences . 14
Bibliography . 15

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kSIST prEN ISO 10304-1:2008
ISO 10304-1:2007(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 10304-1 was prepared by Technical Committee ISO/TC 147, Water quality, Subcommittee SC 2, Physical,
chemical and biochemical methods.
This second edition of ISO 10304-1 cancels and replaces ISO 10304-1:1992 and ISO 10304-2:1995, which
have been technically revised.
ISO 10304 consists of the following parts, under the general title Water quality — Determination of dissolved
anions by liquid chromatography of ions:
⎯ Part 1: Determination of bromide, chloride, fluoride, nitrate, nitrite, phosphate and sulfate
⎯ Part 3: Determination of chromate, iodide, sulfite, thiocyanate and thiosulfate
⎯ Part 4: Determination of chlorate, chloride and chlorite in water with low contamination
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kSIST prEN ISO 10304-1:2008
ISO 10304-1:2007(E)
Introduction
The user should be aware that particular problems could require the specification of additional conditions not
provided for in this part of ISO 10304.

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kSIST prEN ISO 10304-1:2008

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kSIST prEN ISO 10304-1:2008
INTERNATIONAL STANDARD ISO 10304-1:2007(E)

Water quality — Determination of dissolved anions by liquid
chromatography of ions —
Part 1:
Determination of bromide, chloride, fluoride, nitrate, nitrite,
phosphate and sulfate
WARNING — Persons using this International Standard should be familiar with normal laboratory
practice. This 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 according to this International Standard
be carried out by suitably trained staff.
1 Scope
This part of ISO 10304 specifies a method for the determination of dissolved bromide, chloride, fluoride,
nitrate, nitrite, orthophosphate and sulfate in water, e.g. drinking water, ground water, surface water, waste
water, leachates and marine water by liquid chromatography of ions.
The lower limit of application is W 0,05 mg/l for bromide and for nitrite, and W 0,1 mg/l for chloride, fluoride,
nitrate, orthophosphate, and sulfate. The lower limit of application depends on the matrix and the interferences
encountered.
The working range may be expanded to lower concentrations (e.g. W 0,01 mg/l) if an appropriate
pre-treatment of the sample (e.g. conditions for trace analyses, pre-concentration technique) is applied, and/or
if an ultraviolet (UV) detector (for bromide, nitrate and nitrite) is used.
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 5667-3, 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 8466-2, Water quality — Calibration and evaluation of analytical methods and estimation of performance
characteristics — Part 2: Calibration strategy for non-linear second-order calibration functions
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kSIST prEN ISO 10304-1:2008
ISO 10304-1:2007(E)
3 Interferences
3.1 Organic acids
Aliphatic organic acids such as mono- or dicarboxylic acids may interfere with the separation of the anions.
3.2 Sulfite
Sulfite may cause a positive bias for sulfate due to autooxidation. In this case the sample may be adjusted to
pH 10 and formaldehyde solution is added in order to stabilize sulfite, if necessary.
3.3 Metals
The presence of metals (e.g. alkaline earth metals, transition metals, heavy metals) possibly interfering with
the anions of interest, should be checked and can be eliminated with the aid of special cation exchangers (e.g.
cartridge in the H-form or Na-form).
NOTE Depending on the sample matrix, the use of cation exchangers in the H-form can cause losses of fluoride and
nitrite.
4 Principle
The sample is pretreated in order to remove solids (see Clause 7), sulfite and metal ions, if necessary. The
anions of interest (bromide, chloride, fluoride, nitrate, nitrite, orthophosphate and sulfate), are separated by
liquid chromatography, applying an anion exchange resin as stationary phase, and aqueous solutions of salts
of weak mono- and dibasic acids as eluents for isocratic or gradient elution (e.g. carbonate,
hydrogencarbonate, hydroxide eluent) (5.10). Detection is carried out using a conductivity detector (CD).
When using CDs it is essential that the eluents show a sufficiently low conductivity. For this reason, CDs are
usually combined with a suppressor device (cation exchanger), which will reduce the conductivity of the eluent
and transform the sample species into their respective acids.
NOTE A UV detector is not required to carry out this analysis, but can be used for bromide, nitrate or nitrite if a higher
sensitivity is required and/or in case of a matrix interference to the CD. If used, bromide, nitrate and nitrite can be
measured at λ = 200 nm to λ = 215 nm.
Check resolution, R, to ensure that it complies with the required separation conditions (6.2). UV may be used
in combination with a CD. UV measures the absorption directly.
Calibration is carried out as specified in ISO 8466-1 or ISO 8466-2 (8.2). In special cases, extended working
ranges (e.g. two concentration decades) may be applied.
Control experiments are necessary to check the validity of the calibration function. Replicate determinations
may be necessary. Use of the method of standard addition may be required when matrix interferences are
expected (8.3).
5 Reagents
Use only reagents of recognized analytical grade. Weigh the reagents with an accuracy of ± 1 % of the
nominal mass, unless stated otherwise. The reagents listed in 5.2 to 5.5 may be considered representative
examples for the preparation of eluents (5.10).
5.1 Water, complying with grade 1, as defined in ISO 3696.
5.2 Sodium hydrogencarbonate, NaHCO .
3
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kSIST prEN ISO 10304-1:2008
ISO 10304-1:2007(E)
5.3 Sodium carbonate, Na CO .
2 3
5.4 Sodium hydroxide, NaOH.
5.5 Potassium hydroxide, KOH.
5.6 Bromide, chloride, fluoride, nitrate, nitrite, orthophosphate and sulfate stock standard solutions,
ρ = 1 000 mg/l each.
Single anion and mixed anion stock solutions with adequate and required specification are commercially
available. These solutions are considered to be stable for several months.
For an alternative preparation of stock solutions see Table 1. Dissolve the salts accordingly, after appropriate
treatment.
Table 1 — Mass portion and pre-treatment for stock solutions
Mass
a
Anion to be determined Salt to be used Pre-treatment by drying at (105 ± 5) °C for at least
g
Bromide NaBr 1,287 7 6 h
Chloride NaCl 1,648 4 2 h
Fluoride NaF 2,210 0 1 h
Nitrate NaNO 1,370 7 24 h
3
Nitrite NaNO 1,499 8 1 h
2
Orthophosphate KH PO 1,433 0 1 h
2 4
Sulfate Na SO 1,478 6 1 h
2 4
a
Alternative salts with adequate and required specification may be used.

5.7 Bromide, chloride, fluoride, nitrate, nitrite, orthophosphate and sulfate standard solutions
5.7.1 General
Depending on the concentrations expected, prepare single or mixed standard solutions, of bromide, chloride,
fluoride, nitrate, nitrite, orthophosphate and sulfate concentrations from the stock standard solution (5.6).
Store the standard solutions in polyethene bottles.
5.7.2 Example for a bromide, chloride, fluoride, nitrate, nitrite, orthophosphate and sulfate mixed
standard solution, ρ = 10 mg/l each.
Pipette 1,0 ml of each of the stock standard solutions (5.6) into a 100 ml volumetric flask, and dilute to volume
with water (5.1).
The solutions are stable for 1 week, if stored in the dark at 2 °C to 8 °C in polyethene bottles.
5.8 Bromide, chloride, fluoride, nitrate, nitrite, orthophosphate and sulfate calibration solutions
Depending on the concentrations expected in the sample, use the standard solution (5.7.2) to prepare e.g. 5
to 10 calibration solutions distributed as evenly as possible over the expected working range.
For example, proceed as follows for the range 0,05 mg/l to 0,5 mg/l:
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kSIST prEN ISO 10304-1:2008
ISO 10304-1:2007(E)
Pipette, into a series of 20 ml volumetric flasks, the following volumes: 100 µl, 200 µl, 300 µl, 400 µl, 500 µl,
600 µl, 700 µl, 800 µl, 900 µl or 1 000 µl of the standard solution (5.7.2) and dilute to volume with water (5.1).
The concentrations of the anions in these calibration solutions are: 0,05 mg/l, 0,1 mg/l, 0,15 mg/l, 0,2 mg/l,
0,25 mg/l, 0,3 mg/l, 0,35 mg/l, 0,4 mg/l, 0,45 mg/l or 0,5 mg/l, respectively.
Prepare the calibration solutions on the day of use.
5.9 Blank
Fill a volumetric flask (e.g. 100 ml flask) with water (5.1).
5.10 Eluents
5.10.1 General
Degas all water used for eluent preparation. In order to minimise the growth of bacteria or algae, prepare
eluents freshly after 3 days.
The choice of eluent depends on the chosen column and detector (e.g. UV or conductivity), seek advice from
the column supplier. The chosen combination of separator column and eluent shall meet the resolution
requirements stated in 6.2.
The example for the eluent composition in 5.10.3 refers to the CD suppressor technique only. Nevertheless,
the non-suppressed CD technique (as well as UV detection) is included in this method.
A selection of reagents for common eluents is given in 5.2 to 5.5.
NOTE Preparing the eluent from concentrates has proved to be successful.
5.10.2 Sodium carbonate/sodium hydrogencarbonate concentrate
For the eluent concentrate preparation:
Place 28,6 g of sodium carbonate (5.3) and 8,4 g of sodium hydrogencarbonate (5.2) into a 1 000 ml
volumetric flask.
Dissolve in wate
...

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