prEN 17813

Environmental matrices - Halogens and sulfur by oxidative pyrohydrolytic combustion followed by ion chromatography detection and complementary determination methods

This document specifies a method for the simultaneous direct determination of the total fluorine, chlorine, bromine and sulfur content in environmental solid matrices. 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 depend on system blank levels of instrumentation and capacity of the chromatographic separation column used for determination.
NOTE    Simultaneous determination of total iodine content is possible but currently not validated.

Feststoffe in der Umwelt - Halogene und Schwefel durch oxidative pyrohydrolytische Verbrennung, gefolgt von ionenchromatographischer Detektion und komplementären Bestimmungsmethoden

Dieses Dokument legt ein Verfahren für die gleichzeitige direkte Bestimmung des Gesamtgehalts an Fluor, Chlor, Brom und Schwefel in Feststoffen in der Umwelt fest. Das Verfahren gilt für die Bestimmung von Konzentrationen jedes Elements von ≥ 10 mg/kg, bezogen auf die Trockenmasse. Die Höchstgrenze und der exakte Konzentrationsbereich, der abgedeckt wird, hängen von den Blindwerten der Geräte und der Kapazität der für die Bestimmung verwendeten chromatographischen Trennsäule ab.
ANMERKUNG   Die gleichzeitige Bestimmung des Gesamtjodgehalts ist möglich, aber derzeit nicht validiert.

Matrices environnementales - Méthode de dosage des halogènes et du soufre par combustion pyrohydrolytique oxidative suivie d’une détection par chromatographie ionique et méthodes de dosage complémentaires

Le présent document spécifie une méthode de dosage, directe et simultanée, du fluor total, chlore total, brome total et soufre total dans des matrices environnementales solides. Cette méthode s’applique à la détermination, pour chaque élément, de concentrations supérieures ou égales à 10 mg/kg, en masse de matière sèche. La limite supérieure et la plage de concentration exacte couverte dépendent des niveaux de blanc des appareils et de la capacité de la colonne de séparation chromatographique utilisée pour le dosage.
NOTE   Le dosage simultané de l’iode total est possible, mais non validé à l’heure actuelle.

Matriksi z vidika okolja - Določevanje halogenov in žvepla z ionsko kromatografijo in primerljivimi (komplementarnimi) metodami po oksidativnem pirohidrolitskem sežigu

General Information

• Status: Not Published
• Publication Date: 04-Mar-2024
• ICS: 71.040.40 - Chemical analysis
• ICS: 71.040.50 - Physicochemical methods of analysis
• Technical Committee: CEN/TC 444 - Environmental characterization
• Drafting Committee: CEN/TC 444/WG 3 - Inorganic analysis
• Current Stage: 4599 - Dispatch of FV draft to CMC - Finalization for Vote
• Start Date: 10-Mar-2023
• Due Date: 07-Jun-2022
• Completion Date: 10-Mar-2023
• Directive: 2000/76/EC - Directive 2000/76/EC of the European Parliament and of the Council of 4 December 2000 on the incineration of waste
• Directive: 99/31/EC - Landfill of waste
• Ref Project: oSIST prEN 17813:2022 - Environmental matrices - Halogens and sulfur by oxidative pyrohydrolytic combustion followed by ion chromatography detection and complementary determination methods

Standards Content (Sample)

SLOVENSKI STANDARD
oSIST prEN 17813:2022
01-januar-2022

Matriksi z vidika okolja - Določevanje halogenov in žvepla z ionsko kromatografijo

ali komplementarnimi/dopolnilnimi metodami po pirohidrolitskem sežigu

Environmental matrices - Halogens and sulfur by oxidative pyrohydrolytic combustion

followed by ion chromatography detection and complementary determination methods
Umweltbezogene Charakterisierung fester Matrices - Halogene und Schwefel durch
oxidative pyrohydrolytische Verbrennung, gefolgt von ionenchromatographischer
Detektion und komplementären Bestimmungsmethoden
Ta slovenski standard je istoveten z: prEN 17813
ICS:
71.040.40 Kemijska analiza Chemical analysis
71.040.50 Fizikalnokemijske analitske Physicochemical methods of
metode analysis
oSIST prEN 17813:2022 en,fr,de

2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.

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oSIST prEN 17813:2022
DRAFT
EUROPEAN STANDARD
prEN 17813
NORME EUROPÉENNE
EUROPÄISCHE NORM
January 2022
ICS 71.040.40; 71.040.50
English Version
Environmental matrices - Halogens and sulfur by oxidative
pyrohydrolytic combustion followed by ion
chromatography detection and complementary
determination methods

This draft European Standard is submitted to CEN members for enquiry. It has been drawn up by the Technical Committee

CEN/TC 444.

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-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, Turkey and

United Kingdom.

Recipients of this draft are invited to submit, with their comments, notification of any relevant patent rights of which they are

aware and to provide supporting documentation.

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
CEN-CENELEC Management Centre: Rue de la Science 23, B-1040 Brussels

© 2022 CEN All rights of exploitation in any form and by any means reserved Ref. No. prEN 17813:2022 E

worldwide for CEN national Members.
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Contents Page

European foreword ............................................................................................................................................ 4

1 Scope .......................................................................................................................................................... 5

2 Normative references .......................................................................................................................... 5

3 Terms and definitions ......................................................................................................................... 5

4 Principle ................................................................................................................................................... 5

5 Interferences .......................................................................................................................................... 5

5.1 Interferences during combustion ................................................................................................... 5

5.2 Interferences during absorption ..................................................................................................... 6

5.3 Interferences during ion chromatography .................................................................................. 6

6 Reagents and gases............................................................................................................................... 6

6.1 General...................................................................................................................................................... 6

6.2 Reagents for ion chromatography .................................................................................................. 6

6.2.1 Eluents ...................................................................................................................................................... 6

6.2.2 Water, with a resistivity of ≥ 18 MΩ cm (25°C). ......................................................................... 6

6.2.3 Sodium carbonate (anhydrous), Na CO ...................................................................................... 6

2 3

6.2.4 Bromide, chloride, fluoride, and sulfate stock solutions, c = 1 000 mg/l of each

element ..................................................................................................................................................... 6

6.2.5 Bromide, chloride, fluoride and sulfate standard solutions ................................................. 7

6.3 Reagents and gases for combustion ............................................................................................... 7

6.3.1 Inert gas, for example Argon, ≥ 99,9 % purity............................................................................ 7

6.3.2 Oxygen, ≥ 99,9 % purity..................................................................................................................... 7

6.3.3 Control standard ................................................................................................................................... 8

6.4 Reagents for absorption ..................................................................................................................... 8

6.4.1 General...................................................................................................................................................... 8

6.4.2 Hydrogen peroxide solution, H O , approx. 30 %, electronic grade ................................. 8

2 2

6.4.3 Sodium methane sulfonate, CH SO Na ......................................................................................... 9

3 3

7 Apparatus ................................................................................................................................................ 9

7.1 Combustion apparatus ........................................................................................................................ 9

7.1.1 Combustion furnace ............................................................................................................................. 9

7.1.2 Combustion vessel .............................................................................................................................. 10

7.1.3 Absorption vessel ............................................................................................................................... 10

7.2 Ion Chromatography (IC) system .................................................................................................. 10

7.2.2 HPLC pump ............................................................................................................................................ 10

7.2.3 Sample injection system ................................................................................................................... 10

7.2.4 Separation column ............................................................................................................................. 10

7.2.5 Conductivity detector and suppressor device .......................................................................... 11

7.2.6 Guard column ....................................................................................................................................... 11

7.2.7 data handling unit............................................................................................................................... 11

7.2.8 Quality of the separation system ................................................................................................... 11

8 Sampling and sample preparation ............................................................................................... 12

9 Procedure .............................................................................................................................................. 12

9.1 Combustion ........................................................................................................................................... 12

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9.1.1 General ................................................................................................................................................... 12

9.1.2 Blank determination ......................................................................................................................... 12

9.2 Absorption ............................................................................................................................................ 12

9.3 Ion chromatography .......................................................................................................................... 13

9.3.1 General ................................................................................................................................................... 13

9.3.2 Calibration............................................................................................................................................. 13

9.3.3 Measurement ....................................................................................................................................... 13

9.4 Initial and daily checks ..................................................................................................................... 13

9.4.1 Initial laboratory capability check ............................................................................................... 13

9.4.2 Daily check ............................................................................................................................................ 14

10 Calculation ............................................................................................................................................ 14

11 Expression of result ........................................................................................................................... 14

12 Reporting ............................................................................................................................................... 15

Bibliography ....................................................................................................................................................... 16

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European foreword

This document (prEN 17813:2022) has been prepared by Technical Committee CEN/TC 444

“Environmental characterization of solid matrices”, the secretariat of which is held by NEN.

This document is currently submitted to the CEN Enquiry.
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1 Scope

This document specifies a method for the simultaneous direct determination of the total fluorine,

chlorine, bromine and sulfur content in environmental solid matrices. 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 depend on system blank levels of instrumentation and capacity of the

chromatographic separation column used for determination.

NOTE Simultaneous determination of total iodine content is possible but currently not 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
4 Principle

The homogenized sample is combusted under oxidative conditions. For the determination of total

fluorine the combustion is performed under pyrohydrolytic conditions. The combustion gases are

absorbed in an aqueous solution. For the determination of total sulfur the absorption solution contains

an additive 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, 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. Detection is carried out using a conductivity

detector (CD). When using a CD the eluents shall show a sufficiently low conductivity. For this reason, a

CD is 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 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.
5 Interferences
5.1 Interferences during combustion

Missing or too low water supply to establish pyrohydrolytic conditions during total fluorine

determination can lead to negative bias. Sulfur present as inorganic compounds with high melting points

(e.g. earth alkali metal sulfates) can lead to negative bias if combustion temperatures are too low.

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5.2 Interferences during absorption

Missing or too low amount of oxidizing agent in the absorption solution can lead to negative bias on the

determination of total sulfur. Missing or too low amount of reducing agent in the absorption solution can

lead to an underestimation of total bromine, as elemental bromine can be formed during combustion.

5.3 Interferences during ion chromatography

Any substance that has a retention time similar to that of the analyte ion and generates a detector signal

can cause interference. A high concentration of ions can influence peak resolution and retention time of

the analyte. A gradient elution can help to prevent many such 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, gas intake shall be prevented, e.g. by

applying inert gas to the eluent bottles or use of an inline degasser.

Carbonate, hydrogen carbonate, or hydroxide salts may be used to prepare eluents. Eluents can be

prepared manually, by low pressure mixing from stock solutions or electrochemically in situ. The choice

of 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 7.2.8. The eluents may be used as long as the requirements of 7.2.8 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 solution is stable for six months if stored at 2 °C to 8 °C
6.2.3.2 Sodium carbonate eluent, c(Na CO ) = 0,009 mol/l
2 3

Pipette 100 ml of sodium carbonate concentrate (6.2.3.1) into a 1 000 ml volumetric flask and bring to

volume with water.

6.2.4 Bromide, chloride, fluoride, and sulfate stock solutions, c = 1 000 mg/l of each element

Single anion and mixed anion stock solutions are commercially available in sufficiently high quality.

These solutions are considered stable for several months. Alternatively, stock solutions may be prepared

manually according to Table 1.
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Salts are dried appropriately and dissolved according to the weights stated in the table. For calibration,

use mixed multi component standard solutions with at least five different concentrations.

Table 1 — Weighing and salt pretreatment for stock solutions
Anion Salt Weighing (g) Dry salt at (105 ± 5) °C
for at least
Fluoride NaF 2,210 1 h
Chloride NaCl 1,648 2 h
Bromide NaBr 1,288 6 h
Sulfate Na SO 4,439 3 h
2 4

Other salts with corresponding weights and pretreatment specifications may be used.

6.2.5 Bromide, chloride, fluoride and sulfate standard solutions
6.2.5.1 General

Depending on the concentrations expected, prepare single or mixed calibration solutions with different

bromide, chloride, fluoride, and sulfate concentrations from the stock standard solution (6.2.4). The

example in 6.2.5.3 describes preparation
...