IEC 62321-3-2:2020

IEC 62321-3-2 ®
Edition 2.0 2020-06
INTERNATIONAL
STANDARD
NORME
INTERNATIONALE
HORIZONTAL STANDARD
NORME HORIZONTALE
Determination of certain substances in electrotechnical products –
Part 3-2: Screening – Fluorine, chlorine and bromine in polymers and electronics
by combustion-ion chromatography (C-IC)

Détermination de certaines substances dans les produits électrotechniques –
Partie 3-2: Détection – Fluor, chlore et brome dans les polymères et les produits
électroniques par combustion-chromatographie ionique (C-CI)

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IEC 62321-3-2 ®
Edition 2.0 2020-06
INTERNATIONAL
STANDARD
NORME
INTERNATIONALE
HORIZONTAL STANDARD
NORME HORIZONTALE
Determination of certain substances in electrotechnical products –

Part 3-2: Screening – Fluorine, chlorine and bromine in polymers and

electronics by combustion-ion chromatography (C-IC)

Détermination de certaines substances dans les produits électrotechniques –

Partie 3-2: Détection – Fluor, chlore et brome dans les polymères et les produits

électroniques par combustion-chromatographie ionique (C-CI)

INTERNATIONAL
ELECTROTECHNICAL
COMMISSION
COMMISSION
ELECTROTECHNIQUE
INTERNATIONALE
ICS 13.020.01; 43.040.10 ISBN 978-2-8322-8256-4

– 2 – IEC 62321-3-2:2020 © IEC 2020
CONTENTS
FOREWORD . 5
INTRODUCTION . 7
1 Scope . 8
2 Normative references . 9
3 Terms, definitions and abbreviated terms . 9
3.1 Terms and definitions . 9
3.2 Abbreviated terms . 10
4 Principle . 11
5 Reagents and materials . 11
6 Apparatus . 12
7 Sampling . 13
8 Procedure . 14
8.1 Combustion. 14
8.2 IC analysis . 14
8.3 Blank test . 14
8.4 Cleaning and recalibration . 14
8.5 Calibration . 15
8.6 Measurement of the sample . 15
8.7 Interference . 15
9 Calculation . 15
10 Precision . 16
11 Quality assurance and control . 17
11.1 General . 17
11.2 Limits of detection (LOD) and limits of quantification (LOQ) . 17
12 Test report . 18
Annex A (informative) Screening for fluorine, chlorine, bromine and iodine in polymers
and electronics by oxygen bomb combustion-ion chromatography . 19
A.1 General . 19
A.2 Principle . 19
A.3 Reagents and materials . 19
A.4 Apparatus . 20
A.5 Sampling. 20
A.6 Procedure . 21
A.6.1 General . 21
A.6.2 Choice of the absorption solution . 21
A.6.3 Preparation of the bomb . 21
A.6.4 Combustion . 22
A.6.5 Collection of halides . 22
A.6.6 Cleaning procedure . 23
A.7 Ion chromatographic analysis . 23
A.8 Calculation . 23
A.9 Quality assurance and control and test report . 23
Annex B (informative) Screening for fluorine, chlorine, bromine and iodine in polymers
and electronics by oxygen flask combustion-ion chromatography . 25
B.1 General . 25

B.2 Principle . 25
B.3 Reagents and materials . 25
B.4 Apparatus . 25
B.5 Sampling. 26
B.5.1 General . 26
B.5.2 Solid and paste-like samples . 26
B.5.3 Liquid samples . 26
B.6 Procedure . 26
B.6.1 General . 26
B.6.2 Choice of the absorption solution . 26
B.6.3 Combustion . 27
B.7 Ion chromatographic analysis, calculation, quality assurance and control and
test report . 27
Annex C (informative) Example of a combustion device and IC system . 28
Annex D (informative) Screening for iodine in polymers and electronics by
combustion-ion chromatography (C-IC) . 29
D.1 General . 29
D.2 Principle . 29
D.3 Reagents and materials . 29
D.4 Apparatus . 30
D.5 Sampling. 31
D.6 Procedure . 31
D.6.1 Combustion . 31
D.6.2 IC analysis . 32
D.6.3 Blank test . 32
D.6.4 Cleaning and recalibration . 32
D.6.5 Calibration . 32
D.7 Measurement of the sample . 33
D.8 Interference . 33
D.9 Calculation . 33
Annex E (informative) Results of international interlaboratory study (IIS 4A and IIS 3-2) . 35
Annex F (informative) Additional results of TG 3-2 test . 38
Annex G (informative) Additional validation data . 40
Annex H (informative) Additional IC data . 42
Bibliography . 44

Figure A.1 – Example of oxygen bomb combustion device . 24
Figure B.1 – Example of oxygen flask combustion device . 27
Figure B.2 – Example of wrapping of sample . 27
Figure C.1 – Example of a combustion device connected to an ion chromatograph (IC) . 28
Figure C.2 – Example of ion chromatographic system . 28
Figure H.1 – Example of a chromatogram of the standard solution (4 mg/l of each
standard) by IC . 42

Table 1 – Tested concentration ranges for fluorine by C-IC in various materials . 8
Table 2 – Tested concentration ranges for chlorine by C-IC in various materials . 8
Table 3 – Tested concentration ranges for bromine by C-IC in various materials . 8

– 4 – IEC 62321-3-2:2020 © IEC 2020
Table 4 – Fluorine results of international inter-laboratory study (IIS 4A) . 16
Table 5 – Chlorine results of international inter-laboratory study (IIS 4A) . 16
Table 6 – Bromine results of international inter-laboratory study (IIS4A and IIS 3-2) . 16
Table 7 – Acceptance criteria of items for quality control . 17
Table 8 – Student’s t values used for calculation of method detection limit (MDL = t ×
s ) . 18
n–1
Table E.1 – Mean results and recovery rates for bromine obtained in the IIS4A study
using C-IC . 35
Table E.2 – Statistical bromine data for IIS 4A results using C-IC . 35
Table E.3 – Mean results and recovery rates for fluorine obtained in the IIS 3-2 study
using C-IC . 36
Table E.4 – Statistical fluorine data for IIS 3-2 results using C-IC . 36
Table E.5 – Mean results and recovery rates for chlorine obtained in the IIS 3-2 study
using C-IC . 36
Table E.6 – Statistical for chlorine data for IIS 3-2 results using C-IC . 37
Table F.1 – Mean results and recovery rates for bromine obtained in the TG 3-2
internal test study by using C-IC . 38
Table F.2 – Mean results and recovery rates for bromine obtained in the TG 3-2
internal test study by using oxygen bomb-IC . 39
Table G.1 – General conditions for the combustion furnace and the absorption solution . 40
Table G.2 – Additional information – Difference in sample sizes and measured bromine
values in solder paste with burning aid (WO powder) . 40
Table G.3 – Additional information – Difference in combustion temperatures and
measured bromine values in solder paste with burning aid (WO3 powder) . 40
Table G.4 – Additional information – Difference in recovery rate of iodine according to
adsorbents (H O , hydrazine) . 41
2 2
Table H.1 – Typical operating conditions for IC . 42
Table H.2 – Example of fluorine calibration solutions for IC . 43
Table H.3 – Example of chlorine calibration solutions for IC . 43
Table H.4 – Example of bromine calibration solutions for IC . 43

INTERNATIONAL ELECTROTECHNICAL COMMISSION
____________
DETERMINATION OF CERTAIN SUBSTANCES
IN ELECTROTECHNICAL PRODUCTS –

Part 3-2: Screening – Fluorine, chlorine and bromine in polymers and
electronics by combustion-ion chromatography (C-IC)

FOREWORD
1) The International Electrotechnical Commission (IEC) is a worldwide organization for standardization comprising
all national electrotechnical committees (IEC National Committees). The object of IEC is to promote international
co-operation on all questions concerning standardization in the electrical and electronic fields. To this end and
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6) All users should ensure that they have the latest edition of this publication.
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8) Attention is drawn to the Normative references cited in this publication. Use of the referenced publications is
indispensable for the correct application of this publication.
9) Attention is drawn to the possibility that some of the elements of this IEC Publication may be the subject of patent
rights. IEC shall not be held responsible for identifying any or all such patent rights.
International Standard IEC 62321-3-2 has been prepared by IEC technical committee 111:
Environmental standardization for electrical and electronic products and systems.
This second edition cancels and replaces the first edition published in 2013. This edition
constitutes a technical revision.
This edition includes the following significant technical changes with respect to the previous
edition:
a) In the previous edition, a screening test method for bromine (Br) content only was provided.
In this edition, a screening test method by C-IC for fluorine (F), chlorine (Cl) and bromine
(Br) has been added to the normative part of the document.
b) A screening test method by C-IC for iodine (I) has been added in Annex D (informative).

– 6 – IEC 62321-3-2:2020 © IEC 2020
The text of this International Standard is based on the following documents:
FDIS Report on voting
111/573/FDIS 111/577/RVD
Full information on the voting for the approval of this International Standard can be found in the
report on voting indicated in the above table.
This document has been drafted in accordance with the ISO/IEC Directives, Part 2.
A list of all parts in the IEC 62321 series, published under the general title Determination of
certain substances in electrotechnical products can be found on the IEC website.
The committee has decided that the contents of this document will remain unchanged until the
stability date indicated on the IEC website under "http://webstore.iec.ch" in the data related to
the specific document. At this date, the document will be
• reconfirmed,
• withdrawn,
• replaced by a revised edition, or
• amended.
INTRODUCTION
The widespread use of electrotechnical products has drawn increased attention to their impact
on the environment. In many countries all over the world this has resulted in the adaptation of
regulations affecting wastes, substances and energy use of electrotechnical products.
The use of certain substances (e.g. lead (Pb), cadmium (Cd), polybrominated diphenyl ethers
(PBDEs) and phthalates) in electrotechnical products is a source of concern in current and
proposed regional legislation.
The purpose of the IEC 62321 series is therefore to provide test methods that will allow the
electrotechnical industry to determine the levels of certain substances in electrotechnical
products on a consistent global basis.
The first edition of IEC 62321-3-2 (2013) was published to address screening for total bromine.
This document (revised edition of IEC 62321-3-2) describes the test methods to quantify
halogen (fluorine, chlorine and bromine) in polymers and electronics by C-IC in the normative
section and to quantify iodine (I) in an informative Annex D.
In addition, information on oxygen bomb combustion-ion chromatography and oxygen flask-ion
chromatography is provided in Annex A (informative) and Annex B (informative).
WARNING – Persons using this document should be familiar with normal laboratory practice.
This document 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.

– 8 – IEC 62321-3-2:2020 © IEC 2020
DETERMINATION OF CERTAIN SUBSTANCES
IN ELECTROTECHNICAL PRODUCTS –

Part 3-2: Screening – Fluorine, chlorine and bromine in polymers and
electronics by combustion-ion chromatography (C-IC)

1 Scope
This part of IEC 62321 specifies the screening analysis of fluorine, chlorine and bromine in
polymers and electronics using combustion-ion chromatography (C-IC). A C-IC screening
analysis procedure for iodine can be found in Annex D.
This test method has been evaluated for ABS (acrylonitrile butadiene styrene), EMC (epoxy
moulding compound), PE (polyethylene) and PC (polycarbonate) within the concentration
ranges as specified in Table 1, Table 2 and Table 3. (Detailed results are shown in Table E.1
to Table E.6, and in Annex F (Table F.1 and Table F.2).
The use of this method for other types of materials or concentration ranges outside those
specified below has not been evaluated.
Table 1 – Tested concentration ranges for fluorine by C-IC in PC
Substance/element Fluorine
Polymer PC
Unit of
measure
Concentration or
mg/kg
concentration range tested
Table 2 – Tested concentration ranges for chlorine by C-IC in PE
Substance/element Chlorine
Polymer PE
Unit of
measure
Concentration or
mg/kg 102,2
concentration range tested
Table 3 – Tested concentration ranges for bromine by C-IC in various materials
Substance/element Bromine
Polymer ABS EMC PE
Unit of
measure
Concentration or
124 to 890 195 to 976 96
mg/kg
concentration range tested
This horizontal standard is primarily intended for use by technical committees in the preparation
of standards in accordance with the principles laid down in IEC Guide 108.
One of the responsibilities of a technical committee is, wherever applicable, to make use of
horizontal standards in the preparation of its publications. The contents of this horizontal
standard will not apply unless specifically referred to or included in the relevant publications.

2 Normative references
The following documents are referred to in the text in such a way that some or all of their content
constitutes requirements 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.
IEC 62321-2, Determination of certain substances in electrotechnical products – Part 2:
Disassembly, disjunction and mechanical sample preparation
ISO 3696, Water for analytical laboratory use – Specification and test methods
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 10304-1:2007, Water quality – Determination of dissolved anions by liquid chromatography
of ions – Part 1: Determination of bromide, chloride, fluoride, nitrate, nitrite, phosphate and
sulfate
3 Terms, definitions and abbreviated terms
3.1 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 http://www.electropedia.org/
• ISO Online browsing platform: available at http://www.iso.org/obp
3.1.1
accuracy
closeness of agreement between a test result and an accepted reference value
Note 1 to entry: The term accuracy, when applied to a set of test results, involves a combination of random
components and a common systematic error or bias component.
[SOURCE: ISO 5725-1:1994, 3.6]
3.1.2
precision
closeness of agreement between independent test results obtained under stipulated conditions
[SOURCE: ISO 5725-1:1994, 3.12, modified – The notes have been deleted.]
3.1.3
repeatability
precision under repeatability conditions
[SOURCE: ISO 5725-1:1994, 3.13]
3.1.4
repeatability limit
r
value less than or equal to which the absolute difference between two test results obtained
under repeatability conditions may be expected to be with a probability of 95 %

– 10 – IEC 62321-3-2:2020 © IEC 2020
[SOURCE: ISO 5725-1:1994, 3.16]
3.1.5
reproducibility
precision under reproducibility conditions
[SOURCE: ISO 5725-1:1994, 3.17]
3.1.6
reproducibility limit
R
value less than or equal to which the absolute difference between two test results obtained
under reproducibility conditions may be expected to be with a probability of 95 %
[SOURCE: ISO 5725-1:1994, 3.20]
3.1.7
screening
analytical procedure to determine the presence or absence of substances in the representative
part or section of a product, relative to the value or values chosen as the criterion for presence,
absence or further testing
Note 1 to entry: If the screening method produces values that are not conclusive, then additional analysis or other
follow up actions may be necessary to make a final presence/absence decision
[SOURCE: IEC 62321-1:2013, 3.1.10]
3.1.8
test sample
sample prepared from the laboratory and from which test portions will be taken
[SOURCE: ISO 6206:1979, 3.2.13]
3.1.9
test portion
quantity of material drawn from the test sample (or from the laboratory sample if both are the
same) and on which the test or observation is actually carried out
[SOURCE: ISO 6206:1979, 3.2.14]
3.2 Abbreviated terms
ABS acrylonitrile butadiene styrene
CCV continuing calibration verification
CD conductivity detector
C-IC combustion-ion chromatography
CRM certified reference material
EMC epoxy moulding compound
IC ion chromatography
ICV initial calibration verification
IS internal standard
IUPAC International Union of Pure and Applied Chemistry
KRISS Korea Research Institute of Standards and Science
LCS laboratory control sample
LCSD laboratory control sample duplicate
LOD limit of detection
LOQ Limit of quantification
MDL method detection limit
PC polycarbonate
PE polyethylene
PP polypropylene
SOP standard operation procedure
US EPA United States Environmental Protection Agency
4 Principle
A sample of known weight or volume is placed into a sample boat and introduced at a controlled
rate into a high-temperature combustion tube. There the sample is combusted in an oxygen-
rich pyrohydrolytic environment. The gaseous by-products of the combusted sample are trapped
in an absorption medium where the hydrogen halide (HF, HCl, HBr) formed during the
- - - +
combustion dissociates into its specific anion (F , Cl , and Br ) and cation (H 0 ). An aliquot of
known volume of the absorbing solution is then manually or automatically injected into an ion
chromatograph (IC) by means of a sample injection valve. The halide anions, including fluoride,
chloride and bromide are separated into individual elution bands on the separation column of
the IC. The conductivity of the eluent is reduced with an anion suppression device prior to the
ion chromatograph’s conductivity detector, where the anions of interest are measured.
Quantification of halogen in the original combusted sample is achieved by calibrating the system
with a series of standards containing known amounts of fluoride, bromide and chloride and then
analysing unknown samples under the same conditions as the standards. The combined system
of pyrohydrolytic combustion followed by ion chromatographic detection is referred to as
combustion-ion chromatography (C-IC).
5 Reagents and materials
WARNING – All recognized health and safety precautions shall be in effect when carrying out
the operations specified in this document. Failure to heed the directions contained in this
document, or those of the manufacturer of the devices used, may result in injury or equipment
damage.
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 Clause 5 b) and g) to k)
may be considered representative examples for the preparation of eluents (Clause 5 i)). All
reagents used shall not contain an amount of halides above the limit of detection (LOD).
a) Water, complying with grade 1 as defined in ISO 3696.
b) Hydrogen peroxide, a mass fraction of 30 % (H O )
2 2
Hydrogen peroxide is caustic; thus the operator shall wear goggles and gloves and work
under a fume hood when handling this reagent. As this method uses a gas (oxygen) at high
temperature under pressure, precautions shall be taken by the operator.
c) Quartz wool, fine grade or other suitable medium.
d) Argon, carrier gas minimum of 99,9 % purity
Purification scrubbers to ensure the removal of contaminants are recommended such as
moisture (molecular sieve) and hydrocarbon trap filters (activated charcoal or equivalent).
e) Oxygen, combustion gas, minimum 99,6 % purity.

– 12 – IEC 62321-3-2:2020 © IEC 2020
f) Burning aids, tungsten oxide (WO ) or iron oxide (Fe O ) with < 50 µm particle size and
3 3 4
purity > 90 %. Before using burning aids, it is necessary to check that the halogen content
is below the MDL level and in addition always use a method blank.
g) Blank solution, fill a volumetric flask (e.g. 100 ml flask) with water (Clause 5 a)).
h) Calibration standard solutions
Certified calibration standards from commercial sources, or calibration standards prepared
in the laboratory, containing the elements of interest at the concentrations of interest are
used. Depending on the concentrations expected in the sample, use the standard solution
to prepare 5 to 10 calibration solutions with concentrations distributed evenly over the
expected working range.
NOTE The solution is either prepared from a primary standard solution or calibration solution.
i) Eluents
The choice of eluent depends on the chosen column and detector (seek advice from IC
manufacturer or column supplier). Eluent preparation is carried out as specified in
ISO 10304-1:2007, 5.10.
1) Sodium hydrogen carbonate, NaHCO .
2) Sodium carbonate, Na CO .
2 3
3) Sodium hydroxide, NaOH.
4) Potassium hydroxide, KOH.
j) Internal standard (IS) solution (optional)
An internal standard can be used to correct analytical errors.
The internal standard used in the absorption solution shall not contain any of the sample
components, and is to be selected based on the condition of column and mobile phase (e.g.
phosphate, citric acid, oxalic acid, methane sulfonic acid). The internal standard solution
should be prepared by selecting a middle range of concentration in the calibration curve
range when preparing the calibration solution. (e.g. 1 mg/l).
k) Absorption solution, used for trapping halogen – 3 ml of H O (Clause 5 b)), is poured into
2 2
a 1 000 ml volumetric flask, brought to volume with water and mixed. This solution contains
O .
900 mg/kg of H
2 2
Very careful use of H O is required when handling especially high concentrations of
2 2
fluorine-containing samples. When analysing samples containing a high concentration of
fluorine, a minimum amount of hydrogen peroxide to diminish IC peak identification issues
shall be used.
l) Laboratory control sample (LCS) – Reference materials can be used to ensure recovery
rates of the halogen fall within 90 % to 110 %. A certified reference material is the best one
for that purpose. If a certified reference material is not available, a reference material can
be prepared by mixing certain amounts of the halogen (fluorine, chlorine and bromine)
compounds, diluting with cellulose or aluminium oxides to obtain a suitable concentration,
and then pulverizing the mixture to homogenize.
6 Apparatus
The following apparatuses shall be used. See also Annex C.
a) Balance – analytical, with sensitivity to 0,000 1 g (0,1 mg).
b) Scissors or shears.
c) Combustion system – in general, consists of the following components (see Figure C.1):
1) Auto sampler (optional) – an auto sampler is capable of accurately delivering 1 mg to
100 mg of sample into the sample boat.
2) Sample boat – made of quartz, nickel, ceramic, platinum or stainless steel.

3) Sample introduction system – the system provides a sampling port for introduction of the
sample into the sample boat and is connected to the inlet of the pyrohydrolytic
combustion tube. The system is swept by a humidified inert carrier gas and shall be
capable of allowing the quantitative delivery of the material to be analysed into the
pyrohydrolytic oxidation zone at a controlled and repeatable rate.
4) Electric furnace – it can be heated from 900 °C to 1 000 °C and has a quartz or ceramic
tube installed inside and connected to the equipment for injecting the sample. Therefore,
it is designed so that the combustion gas of the sample can be discharged without loss.
5) Pyrohydrolytic combustion tube – the pyrohydrolytic combustion tube is made of quartz
and constructed such that when the sample is combusted in the presence of humidified
oxygen, the by-products of combustion are swept into the humidified pyrohydrolytic
combustion zone. The inlet end shall allow for the stepwise introduction and
advancement of a sample boat into the heated zone and shall have a side arm for the
introduction of the humidified carrier gas and oxygen. The pyrohydrolytic combustion
tube shall be of ample volume, and have a heated zone with quartz wool or other suitable
medium providing sufficient surface area so that the complete pyrohydrolytic combustion
of the sample is ensured. If the sample contains halogen at high concentration (e.g.
samples containing more than one percent concentration of halogen), a trap column
shall be installed between the absorption tube and the combustion tube.
6) Water supply device – capable of delivering grade 1 water (Clause 5 a)) to the
combustion tube at a controlled rate sufficient to provide a pyrohydrolytic environment.
7) Absorption tube – glass pipe of such a total volume that 10 ml to 20 ml of the absorption
solution only occupies about half the total glass tube volume. The discharge of the gas
pipe from the heating furnace is submerged in the absorption solution to absorb the
discharged gas. The absorption solution can be injected into the ion chromatograph
through a connecting device. The absorption tube shall be washed after sample analysis
to avoid contamination from previous samples.
d) Ion chromatographic system – Consisting of the following components (see Figure C.2):
1) eluent reservoir;
2) IC pump;
3) sample injection system – incorporating a sample loop of appropriate volume (e.g. 0,02
ml) or auto sampler device;
4) precolumn or guard column;
5) separation column;
6) suppressor;
7) conductivity detector (CD);
8) recording device – e.g. computer, integrator.
7 Sampling
Sampling shall be carried out as described in IEC 62321-2. It should be done randomly and the
collected segments should represent the entire sample.
a) Solid sample
The sample shall be cut into small pieces (approximately less than 3 mm × 3 mm) using
scissors or shears (Clause 6 b)).
b) Liquid sample
When sampling liquids, the inside of the transfer pipette (or similar vessel) shall be rinsed
several times with the sample liquid.

– 14 – IEC 62321-3-2:2020 © IEC 2020
8 Procedure
8.1 Combustion
a) After a sample boat is heated sufficiently in the electric furnace to remove the contaminants,
remove the sample boat from the furnace with clean tongs, let it cool to room temperature,
then weigh (typically 10 mg to 100 mg) the sample to the nearest 0,1 mg and load into the
sample boat. If samples are difficult to combust (e.g. flux, solder paste), a burning aid (e.g.
WO ) shall be used. Generally, a 5 to 1 ratio of burning aids to sample is sufficient. If any
burning aid is being used, apply approximately 1/4 of its total mass in a thin layer over the
surface of the sample boat, place the weighed sample on it and then cover the sample with
approximately ¾ of the total burning aid mass. Detailed analysis conditions are described
in Annex G (Table G.1, Table G.2, Table G.3)
b) The sample and boat are heated in the combustion furnace for 10 min to 20 min together
with argon, oxygen and water by using the sample injection device located at the centre of
the quartz tube of the combustion furnace. Suitable combustion conditions are described in
Table G.1. I
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