SIST EN 17813:2024

SLOVENSKI STANDARD
01-junij-2024
Trdni matriksi v okolju - Določanje halogenov in žvepla z ionsko kromatografijo po
oksidativnem pirohidrolitskem sežigu
Environmental solid matrices - Determination of halogens and sulfur by oxidative
pyrohydrolytic combustion followed by ion chromatography
Feststoffe in der Umwelt - Bestimmung von Halogenen und Schwefel durch oxidative
pyrohydrolytische Verbrennung, gefolgt von Ionenchromatographie
Matrices environnementales solides - Méthode de dosage des halogènes et du soufre
par combustion pyrohydrolytique oxydative suivie d’une analyse par chromatographie
ionique
Ta slovenski standard je istoveten z: EN 17813:2023
ICS:
71.040.40 Kemijska analiza Chemical analysis
71.040.50 Fizikalnokemijske analitske Physicochemical methods of
metode analysis
2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.

EN 17813
EUROPEAN STANDARD
NORME EUROPÉENNE
October 2023
EUROPÄISCHE NORM
ICS 71.040.40; 71.040.50
English Version
Environmental solid matrices - Determination of halogens
and sulfur by oxidative pyrohydrolytic combustion
followed by ion chromatography
Matrices environnementales solides - Méthode de Feststoffe in der Umwelt - Bestimmung von Halogenen
dosage des halogènes et du soufre par combustion und Schwefel durch oxidative pyrohydrolytische
pyrohydrolytique oxydative suivie d'une analyse par Verbrennung, gefolgt von Ionenchromatographie
chromatographie ionique
This European Standard was approved by CEN on 23 July 2023.

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, Republic of North Macedonia, Romania, Serbia, Slovakia, Slovenia, Spain, Sweden, Switzerland, Türkiye and
United Kingdom.
EUROPEAN COMMITTEE FOR STANDARDIZATION
COMITÉ EUROPÉEN DE NORMALISATION

EUROPÄISCHES KOMITEE FÜR NORMUNG

CEN-CENELEC Management Centre: Rue de la Science 23, B-1040 Brussels
© 2023 CEN All rights of exploitation in any form and by any means reserved Ref. No. EN 17813:2023 E
worldwide for CEN national Members.

Contents Page
European foreword . 3
1 Scope . 4
2 Normative references . 4
3 Terms and definitions . 4
4 Principle . 4
5 Interferences . 5
5.1 Interferences during combustion . 5
5.2 Interferences during absorption . 5
5.3 Interferences during ion chromatography . 5
6 Reagents and gases. 5
6.1 General. 5
6.2 Reagents for ion chromatography . 5
6.3 Reagents and gases for combustion . 7
6.4 Control standard . 7
6.5 Reagents for absorption . 8
7 Apparatus . 8
7.1 Combustion apparatus . 8
7.2 Ion chromatography (IC) system . 9
8 Sampling and sample preparation . 11
9 Procedure . 11
9.1 Combustion . 11
9.2 Absorption . 12
9.3 Ion chromatography . 12
9.4 Initial and daily checks . 13
10 Calculation . 14
11 Expression of result . 14
12 Test report . 14
Annex A (informative) Performance characteristics . 15
Bibliography . 20

European foreword
This document (EN 17813:2023) has been prepared by Technical Committee CEN/TC 444
“Environmental characterization of solid matrices”, the secretariat of which is held by NEN.
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 April 2024, and conflicting national standards shall be
withdrawn at the latest by April 2024.
Attention is drawn to the possibility that some of the elements of this document may be the subject of
patent rights. CEN shall not be held responsible for identifying any or all such patent rights.
Any feedback and questions on this document should be directed to the users’ national standards body.
A complete listing of these bodies can be found on the CEN website.
According to the CEN-CENELEC Internal Regulations, the national standards organisations of the
following countries are bound to implement this European Standard: Austria, Belgium, Bulgaria, Croatia,
Cyprus, Czech Republic, Denmark, Estonia, Finland, France, Germany, Greece, Hungary, Iceland, Ireland,
Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Republic of North
Macedonia, Romania, Serbia, Slovakia, Slovenia, Spain, Sweden, Switzerland, Türkiye and the United
Kingdom.
1 Scope
This document specifies an empirical method for the simultaneous direct determination of the fluorine,
chlorine, bromine, and sulfur content in environmental solid matrices by oxidative pyrohydrolytic
combustion at (1 050 ± 50) °C, followed by ion chromatography. The method is applicable for the
determination of concentrations ≥ 10 mg/kg of each element based on dry matter. The upper limit and
exact concentration range covered depends on the blank levels of the instrumentation and the capacity
of the chromatographic separation column used for determination.
NOTE 1 Simultaneous determination of iodine content is possible but currently not validated.
NOTE 2 Other detection methods can be applied if validated.
2 Normative references
There are no normative references in this document.
3 Terms and definitions
For the purposes of this document, the following terms and definitions apply.
ISO and IEC maintain terminological databases for use in standardization at the following addresses:
— IEC Electropedia: available at https://www.electropedia.org/
— ISO Online browsing platform: available at https://www.iso.org/obp
3.1
pyrohydrolysis
high temperature chemical reaction with water
3.2
test portion
analytical portion
quantity of material, of proper size, for measurement of the concentration or other property of interest,
removed from the test sample
Note to entry 1: The test portion can be taken from the primary sample or from the laboratory sample directly if
no preparation of sample is required (e.g. with liquids), but it is usually taken from the prepared test sample.
Note to entry 2: A unit or increment of proper homogeneity, size, and fineness, needing to further preparation, can
be a test portion.
[SOURCE: EN ISO 11074:2015, definition 4.3.15]
4 Principle
The homogenized sample is combusted under oxidative conditions. For the determination of fluorine, the
combustion is performed under pyrohydrolytic conditions. The combustion gases are absorbed in an
aqueous solution. For the determination of sulfur the absorption solution contains an oxidizing agent to
ensure complete conversion to sulfate. Changes in the volume of the absorption solution are considered
for concentration calculations.
The anions of interest (bromide, chloride, fluoride, and sulfate) are separated by ion chromatography,
and detected with a conductivity detector. To reduce the total conductivity caused by the eluent a
suppressor unit (cation exchange unit) is used [4].
NOTE A UV detector is not required to carry out this analysis, but can be used for the detection of bromide, if a
higher detection selectivity is required or in case of a matrix interference observed in conductivity detection.
Bromide can be detected directly at λ = 205 nm.
NOTE Additional information is available in [3].
5 Interferences
5.1 Interferences during combustion
Pyrohydrolytic conditions during fluorine determination are required to avoid a negative bias.
Sulfur present in inorganic compounds with melting points higher than 1 050 °C (e.g. earth alkali metal
sulfates) can lead to a negative bias. In this case the determination of the sulfur content can be carried
out by dry combustion in an oxygen stream at a temperature ≥ 1 250 °C [7].
5.2 Interferences during absorption
For the determination of sulfur an oxidizing agent in the absorption solution is required to avoid a
negative bias.
For the determination of bromine a reducing agent in the absorption solution is required, as elemental
bromine can be formed during combustion, which may not be completely absorbed.
5.3 Interferences during ion chromatography
Any substance which generates a detector signal and from which the peak resolution R between the
analyte ion and that substance is less than 1,3, can cause interference. A high concentration of ions can
influence the peak resolution and the retention time of the analyte. A gradient elution can help to prevent
these kind of interferences.
6 Reagents and gases
6.1 General
Use only reagents of recognized analytical grade. The purity of water, reagents and gases shall be
confirmed. Unless otherwise specified, reagents shall be weighed to an accuracy of ± 1 % of nominal
mass. Commercially available solutions may be used. If necessary, alternative volumes and
concentrations may be prepared for the solutions described in this section.
Relevant reagents should be tested for their contribution to the blank value.
6.2 Reagents for ion chromatography
6.2.1 Eluents
Degas all water used for eluent preparation. During operation, the gas intake shall be purged, e.g. by
applying an inert gas to the eluent bottles or use of an inline degasser.
Carbonate, hydrogen carbonate, or hydroxide salts can be used to prepare eluents. Eluents can be
prepared manually, by mixing from stock solutions or electrochemically in situ. The choice of the eluent
depends on the column chosen and the detector. Follow instructions of the column manufacturer. The
selected combination of separation column and eluent shall fulfil the requirement for resolution
according to 7.2.9. The eluents may be used as long as the requirements of 7.2.9 are met. An example of a
suitable eluent is described in 6.2.3.2.
6.2.2 Water, with a resistivity of ≥ 18 MΩ cm (25 °C)
6.2.3 Sodium carbonate (anhydrous), Na CO
2 3
6.2.3.1 Sodium carbonate concentrate, c(Na CO ) = 0,09 mol/l
2 3
Dissolve 9,54 g anhydrous sodium carbonate (6.2.3) in water in a 1 000 ml volumetric flask and bring to
volume with water.
The soluti
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