CEN/TR 17345:2019

SLOVENSKI STANDARD
01-julij-2019
Odpadki - Dokument o stanju tehnike - Določevanje halogenov in žvepla z ionsko
kromatografijo po pirohidrolitskem sežigu
Waste - State-of-the-art document - Halogens and sulfur by oxidative pyrohydrolytic
combustion followed by ion chromatography detection
Abfall - Dokument zum Stand der Technik - Bestimmung von Halogenen und Schwefel
mittels oxidativer pyro-hydrolytischer Verbrennung mit Ionenchromatographie Detektion
Caractérisation des déchets - État de l’art - Halogènes et soufre par combustion
pyrohydrolytique oxydative suivie d’une détection par chromatographie ionique
Ta slovenski standard je istoveten z: CEN/TR 17345:2019
ICS:
13.030.01 Odpadki na splošno Wastes in general
71.040.50 Fizikalnokemijske analitske Physicochemical methods of
metode analysis
2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.

CEN/TR 17345
TECHNICAL REPORT
RAPPORT TECHNIQUE
February 2019
TECHNISCHER BERICHT
ICS 13.030.40
English Version
Waste - State-of-the-art document - Halogens and sulfur by
oxidative pyrohydrolytic combustion followed by ion
chromatography detection
Caractérisation des déchets - État de l'art - Halogènes Abfall - Dokument zum Stand der Technik -
et soufre par combustion pyrohydrolytique oxydative Bestimmung von Halogenen und Schwefel mittels
suivie d'une détection par chromatographie ionique oxidativer pyro-hydrolytischer Verbrennung mit
Ionenchromatographie Detektion

This Technical Report was approved by CEN on 4 February 2019. It has been drawn up by the Technical Committee CEN/TC 444.

CEN members are the national standards bodies of Austria, Belgium, Bulgaria, Croatia, Cyprus, Czech Republic, Denmark, Estonia,
Finland, Former Yugoslav Republic of Macedonia, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania,
Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Serbia, Slovakia, Slovenia, Spain, Sweden, Switzerland,
Turkey 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
© 2019 CEN All rights of exploitation in any form and by any means reserved Ref. No. CEN/TR 17345:2019 E
worldwide for CEN national Members.

Contents Page
European foreword . 3
Introduction . 4
1 Scope . 5
2 Normative references . 5
3 Terms and definitions . 5
4 Description of the combustion-IC technique . 5
4.1 Principle . 5
4.2 Configuration of the system . 6
4.2.1 Sample introduction . 6
4.2.2 Combustion system . 6
4.2.3 Gas absorption unit . 6
4.2.4 Ion chromatography system . 6
5 Available standard methods . 7
6 Evaluation study of the C-IC technique . 8
6.1 General . 8
6.2 Description of the samples . 8
6.3 Description of the applied C-IC systems . 9
6.4 Results for certified reference materials (CRM) . 10
6.5 Results of the waste samples . 15
7 Conclusions . 22
Bibliography . 24

European foreword
This document (CEN/TR 17345:2019) has been prepared by Technical Committee CEN/TC 444 “Test
methods for environmental characterization of solid matrices”, the secretariat of which is held by NEN.
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.
Introduction
The content of sulfur, chlorine, fluorine and/or bromine has to be determined in various waste streams
such as refuse derived fuel, rubber granulates, post-shredder residue and plastics from wastes of
electrical and electronic equipment (WEEE).
At the moment the determination of these elements is performed according to EN 14582. This
European standard specifies a combustion method for the determination of halogen and sulfur contents
in materials by combustion in a closed system containing oxygen (calorimetric bomb), and the
subsequent analysis of the combustion product using different analytical techniques. Because the
combustion has to be conducted for each sample separately and no automation is possible, this method
is time-consuming and labour- intensive compared to combustion ion chromatography (C-IC).
The use of the combustion ion chromatography (C-IC) instrument would allow in one single run the
combustion of the material and the simultaneous determination of fluorine, chlorine, bromine, and
sulfur by ion chromatography. Moreover, the combustion module enables the sample digestion of
different type of samples under pyrolysis and oxidation conditions. The instrument may also be
equipped with automatic sample introduction modules for solids and liquids, which will benefit the
automation and reduce significantly the labour-intensive process. The system is already offered
commercially by different manufacturers.
Many laboratories are using none coupled customized hydropyrolysis systems for different kind of
applications. Offline systems can be used as sample preparation systems for IC measurement, too.
Coupling is no requirement for using the C-IC technique.
This document provides a technical description of the C-IC technique, an overview of available
commercial instruments, the strengths and limitations of this technique, and analytical results for
halogens and sulfur obtained on waste samples.
1 Scope
In the framework of EU Directive 99/31/EC [1] and EU Directive 2000/76/EC [2] halogens and sulfur
need to be determined on waste samples. The implementation of the combustion-IC technique would
allow in one single run the combustion of the sample followed by the determination of the halogens and
sulfur with ion chromatography. Moreover, this instrument may be provided with a sample carrousel
for both solids and liquids, allowing an automation of these type of analyses.
Recent developments of the C-IC technology have made this technique interesting for the determination
of halogens and sulfur in waste samples. Therefore, a document on the current progress of the C-IC
technology was prepared, including the evaluation of the performance of different commercially
available systems and the presentation of analytical results obtained on certified reference materials
and waste samples.
2 Normative references
There are no normative references in this document.
3 Terms and definitions
No terms and definitions are listed in this document.
ISO and IEC maintain terminological databases for use in standardization at the following addresses:
• IEC Electropedia: available at http://www.electropedia.org/
• ISO Online browsing platform: available at http://www.iso.org/obp
4 Description of the combustion-IC technique
4.1 Principle
Samples are introduced in the combustion tube using an automatic boat control device. First samples
are thermally combusted under argon atmosphere, followed by a combustion at 800 °C to 1 100 °C with
oxygen under pyrohydrolytic conditions. Sulfur in the samples converts to SO and halogens to
x
hydrogen halide. These volatile compounds are trapped in an aqueous absorbing solution and
subsequently injected for ion chromatographic analysis. The basic equipment configuration is shown in
Figure 1.
Figure 1 — Basic configuration of a C-IC system
4.2 Configuration of the system
4.2.1 Sample introduction
All the systems have the ability to measure both solids and liquids. Automation is available for boat
trays as well as liquids in vials. Solid analysis is performed by weighing the sample into a sample boat.
Alternative to sampling liquids from vials, they can also be injected into sample boats placed on the boat
tray. In this case there should be no volatile compounds present due to possible losses by evaporation.
The intake will depend on the sample type, density and concentration. Upper limits are approximately
100 mg for solids and 100 µl for liquids. The sample shall be homogeneous with respect to sample
amount.
4.2.2 Combustion system
The furnace is provided with a quartz or ceramic pyrolysis tube. Alkali metals such as sodium, calcium
and magnesium have a tendency to react with SiO . Same effect can be seen when measuring silicium
bearing samples. The reactions cause devitrification of the quartz pyrolysis tube, which will result in
cracking of the tube. This can be overcome by working with a ceramic tube. Using a combustion
improver (e.g. WO , Fe O ), which binds with calcium and magnesium [4] will increase lifetime of glass
4 3 4
parts. Analogously the sample boat consists of quartz or ceramic material.
To achieve complete combustion of the sample and full recovery of analytes, choosing suitable
combustion temperatures, timings of boat movement, addition of water to the combustion gases
(hydropoyrolysis) and possibly addition of combustion improver is required. Special attention is
needed if organic matrices are analysed to prevent soot formation.
Combustion process
The sample boat is introduced under inert gas atmosphere. Samples are pyrolysed following the
temperature gradient at the inlet of the furnace. To prevent soot formation, this pyrolysis shall be
controlled by suitable means to ensure complete transformation of organic matter to CO . After
complete pyrolysis, the inner tube is flushed with oxygen to mobilize remaining analytes.
Hydropyrolysis
To ensure complete mobilization of fluorine during pyrolysis, addition of water to the inert gas is
required. The amount added depends on sample type and analyte concentrations.
4.2.3 Gas absorption unit
The combustion gases are fed into an absorption vessel and passed through an aqueous absorption
solution. Hydrogen halides absorbed as halide anions, SOx is converted to sulfite and sulfate. To unify
analytes for quantification, H O (or a suitable oxidant) is added to the absorption solution to oxidize all
2 2
species to SO . H O also acts as reducing agent if halogens, especially bromine, are combusted to
4 2 2
halogen gas (Br ).
The absorption unit is equipped with measures to quantify total absorption solution volume after
combustion, accounting for water addition by hydropyrolysis. Such measures can be automatic or
manual adjustment to a known volume, calculation of volume changes or addition of an internal
standard.
Sample transfer and loading to ion chromatography sample loop can be fully automatic or manual.
4.2.4 Ion chromatography system
The ion chromatography system uses chromatographic columns based on ion exchange materials to
achieve separation of anionic analytes. To achieve good signal to noise ratio, peak separation and peak
resolution, different setups may be used.
Elution from the column may be performed by isocratic or gradient elution. As H O is creating an
2 2
interference with fluoride detection, additional measures are necessary if very low contents of fluorine
are analysed. Suitable measures may be gradient elution to achieve better separation or physical
separation of H O by a matrix elimination/preconcentration column.
2 2
5 Available standard methods
A range of standard methods are available describing the determination of halogens and sulfur in a
variety of matrices. In Table 1 a non-limited list is given of relevant standard methods containing a
...