IEC 62321-9:2021

IEC 62321-9 ®
Edition 1.0 2021-08
INTERNATIONAL
STANDARD
NORME
INTERNATIONALE
HORIZONTAL PUBLICATION
PUBLICATION HORIZONTALE
Determination of certain substances in electrotechnical products –
Part 9: Hexabromocyclododecane in polymers by gas chromatography-mass
spectrometry (GC‑MS)
Détermination de certaines substances dans les produits électrotechniques –
Partie 9: Hexabromocyclododécane dans les polymères par chromatographie
en phase gazeuse-spectrométrie de masse (GC‑MS)

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IEC 62321-9 ®
Edition 1.0 2021-08
INTERNATIONAL
STANDARD
NORME
INTERNATIONALE
HORIZONTAL PUBLICATION
PUBLICATION HORIZONTALE
Determination of certain substances in electrotechnical products –

Part 9: Hexabromocyclododecane in polymers by gas chromatography-mass

spectrometry (GC‑MS)
Détermination de certaines substances dans les produits électrotechniques –

Partie 9: Hexabromocyclododécane dans les polymères par chromatographie

en phase gazeuse-spectrométrie de masse (GC‑MS)

INTERNATIONAL
ELECTROTECHNICAL
COMMISSION
COMMISSION
ELECTROTECHNIQUE
INTERNATIONALE
ICS 13.020.01; 43.040.10 ISBN 978-2-8322-9960-9

– 2 – IEC 62321-9:2021 © IEC 2021
CONTENTS
FOREWORD . 4
INTRODUCTION . 6
1 Scope . 7
2 Normative references . 7
3 Terms, definitions and abbreviated terms . 7
3.1 Terms and definitions . 7
3.2 Abbreviated terms . 8
4 Principle . 8
5 Reagents and materials . 8
6 Apparatus . 9
7 Sampling . 9
8 Procedure . 10
8.1 General instructions for the analysis . 10
8.2 Sample preparation . 10
8.2.1 Stock solution . 10
8.2.2 Pre-extraction of the Soxhlet extractors . 10
8.2.3 Soxhlet extraction . 10
8.2.4 Alternative extraction procedure for soluble polymers . 11
8.2.5 Addition of the internal standard (IS) . 11
8.3 Instrumental parameters . 11
8.4 Calibrants . 12
8.5 Calibration . 12
8.5.1 General . 12
8.5.2 Standard solutions . 12
9 Calculation of HBCDD concentration . 13
9.1 General . 13
9.2 Calculation . 13
10 Precision . 15
11 Quality assurance and quality control . 16
11.1 Performance . 16
11.2 Internal control samples and blanks . 17
11.3 Method detection limit (MDL) and reporting limit . 17
12 Test report . 18
Annex A (informative) Determination of HBCDD in polymers by high-pressure liquid
chromatography-mass spectrometry (HPLC-MS) . 19
A.1 Principle . 19
A.2 Reagents and materials . 19
A.3 Apparatus . 19
A.4 Sampling. 20
A.5 Procedure . 20
A.5.1 General instructions for the analysis . 20
A.5.2 Sample preparation . 20
A.5.3 Instrumental parameters . 21
A.5.4 Calibrants . 22
A.5.5 Calibration . 22

A.6 Calculation of HBCDD concentration . 23
A.6.1 General . 23
A.6.2 Calculation . 23
A.7 Precision . 24
A.8 Quality assurance and quality control . 25
A.8.1 Performance . 25
A.8.2 Method detection limit (MDL) and reporting limit . 25
A.9 Test report . 26
Annex B (informative) Examples of chromatograms at suggested conditions . 27
Annex C (informative)  Results of international interlaboratory study (IIS 9) . 29
Bibliography . 31

Figure B.1 – Total ion chromatogram of HBCDD by GC‑MS analysis. 27
Figure B.2 – Mass spectrum of HBCDD by GC‑MS analysis . 27
Figure B.3 – Total ion chromatogram of HBCDD isomers (α-, β-, γ-HBCDD) by HPLC-
MS analysis . 28

Table 1 – Tested concentration ranges for HBCDD by GC‑MS in various materials . 7
Table 2 – Reference masses for the quantification of HBCDD . 12
Table 3 – Commercially available HBCDD reference materials considered suitable for
GC-MS analysis . 12
Table 4 – Calibration solutions of HBCDD . 13
Table 5 – IIS 9 repeatability and reproducibility . 16
Table A.1 – HPLC-MS liquid phase . 21
Table A.2 – Commercially available HBCDD reference materials considered suitable
for HPLC-MS analysis . 22
Table A.3 – Calibration solutions of HBCDD . 23
Table A.4 – IIS 9 repeatability and reproducibility . 25
Table C.1 – Mean results and recovery rates for HBCDD using GC‑MS . 29
Table C.2 – Statistical data for GC‑MS . 29
Table C.3 – Mean results and recovery rates for HBCDD using HPLC-MS . 29
Table C.4 – Statistical data for HPLC-MS . 30

– 4 – IEC 62321-9:2021 © IEC 2021
INTERNATIONAL ELECTROTECHNICAL COMMISSION
____________
DETERMINATION OF CERTAIN SUBSTANCES
IN ELECTROTECHNICAL PRODUCTS –

Part 9: Hexabromocyclododecane in polymers
by gas chromatography-mass spectrometry (GC‑MS)

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
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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.
IEC 62321-9 has been prepared by IEC technical committee 111: Environmental
standardization for electrical and electronic products and systems. It is an International
Standard.
The text of this International Standard is based on the following documents:
FDIS Report on voting
111/620/FDIS 111/631/RVD
Full information on the voting for its approval can be found in the report on voting indicated in
the above table.
The language used for the development of this International Standard is English.

This document was drafted in accordance with ISO/IEC Directives, Part 2, and developed in
accordance with ISO/IEC Directives, Part 1 and ISO/IEC Directives, IEC Supplement, available
at www.iec.ch/members_experts/refdocs. The main document types developed by IEC are
described in greater detail at www.iec.ch/standardsdev/publications.
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 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.
– 6 – IEC 62321-9:2021 © IEC 2021
INTRODUCTION
The widespread use of electrotechnical products has drawn increased attention to their impact
on the environment. In many countries this has resulted in the adoption of regulations affecting
wastes, substances and energy use of electrotechnical products.
The use of certain substances (e.g. lead (Pb), cadmium (Cd) and polybrominated diphenyl
ethers (PBDEs) in electrotechnical products is a source of concern in current and proposed
regional legislation.
The purpose of this document is therefore to provide test methods that will allow the
electrotechnical industry to determine the levels of certain substances of concern in
electrotechnical products on a consistent global basis.
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.

DETERMINATION OF CERTAIN SUBSTANCES
IN ELECTROTECHNICAL PRODUCTS –

Part 9: Hexabromocyclododecane in polymers
by gas chromatography-mass spectrometry (GC‑MS)

1 Scope
This part of IEC 62321 specifies two techniques for the determination of
hexabromocyclododecane (HBCDD) in polymers of electrotechnical products.
The gas chromatography-mass spectrometry (GC-MS) test method is described in the
normative part of this document. The GC-MS method is suitable for the determination of
hexabromocyclododecane (HBCDD).
A method using high-pressure liquid chromatography-mass spectrometry (HPLC-MS) is given
in informative Annex A.
These test methods have been evaluated for use with EPS (expanded polystyrene foam),
XPS (extruded polystyrene foam) and ABS (acrylonitrile butadiene styrene) within the
concentration ranges as specified in Table 1. 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 HBCDD by GC‑MS in various materials
Substance or element HBCDD
Medium or material tested
Unit of
Parameter
measurement ABS
EPS/XPS
mg/kg
Concentration range tested 6 080 to 11 940 1 000 to 10 000

This document has the status of a horizontal standard in accordance with IEC Guide 108.
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 62321-1:2013, Determination of certain substances in electrotechnical products – Part 1:
Introduction and overview
3 Terms, definitions and abbreviated terms
3.1 Terms and definitions
For the purposes of this document, the terms and definitions given in IEC 62321-1 apply.
ISO and IEC maintain terminological databases for use in standardization at the following
addresses:
– 8 – IEC 62321-9:2021 © IEC 2021
• IEC Electropedia: available at http://www.electropedia.org/
• ISO Online browsing platform: available at http://www.iso.org/obp
3.2 Abbreviated terms
ABS acrylonitrile butadiene styrene
API-ES atmospheric pressure-electrospray
BFR brominated flame retardant
BSA N,O-Bis(trimethylsilyl)acetamide
BSTFA N,O-Bis(trimethylsilyl)trifluoroacetamide
CCC continuing calibration check
C-IC combustion-ion chromatography
EI electron ionization
EPS expanded polystyrene foam
HBCDD hexabromocyclododecane
HPLC-MS high-pressure liquid chromatography-mass spectrometry
ID internal diameter
IS internal standard
GC‑MS gas chromatography-mass spectrometry
LOD limit of detection
LOQ limit of quantification
MDL method detection limit
PTFE polytetrafluoroethylene
QC quality control
RSD relative standard deviation
SIM single (or "selected") ion monitoring
THF tetrahydrofuran
TIF tentatively identified compound
XPS extruded polystyrene foam
XRF X-ray fluorescence
UV ultraviolet
4 Principle
HBCDD is determined using ultrasonic or Soxhlet extraction followed by gas chromatography
separation and mass spectrometry determination. This technique is suitable to determinate total
HBCDD instead of separated HBCDD isomers.
NOTE The thermal stability of HBCDD is poor. The results can be influenced by the temperature testing conditions.
5 Reagents and materials
All reagent chemicals shall be tested for contamination and blank values prior to application.
a) toluene (guaranteed reagent, purity of greater than a volume fraction of 99 %);
b) tetrahydrofuran (THF) (guaranteed reagent, purity of greater than a volume fraction of 99 %);
c) acetonitrile (guaranteed reagent, purity of greater than a volume fraction of 99 %);
d) methanol (guaranteed reagent, purity of greater than a volume fraction of 99 %);

e) mixed solvent solution (tetrahydrofuran and acetonitrile or methanol),
– add 500 ml tetrahydrofuran and 1 000 ml acetonitrile or methanol to a 2 000 ml beaker
and mix;
f) calibrants hexabromocyclododecane (guaranteed reagent, purity of greater than a volume
fraction of 99 %): see 8.4;
g) helium (purity of greater than a volume fraction of 99,999 %);
h) internal standard used to correct for injection errors (e.g. CB 209 (2,2’,3,3’,4,4’,5,5’,6,6’-
decachlorobiphenyl)).
6 Apparatus
The following items shall be used for the analysis:
a) analytical balance capable of measuring accurately to 0,000 1 g;
b) 10 ml, 20 ml, 500 ml, 1 000 ml volumetric flasks;
c) Soxhlet device, Soxhlet extractor of 200 ml or suitable volume;
d) extraction thimble;
e) heating jackets;
f) funnel (non plastic);
g) aluminium foil;
h) ultrasonic bath;
i) Pasteur pipette;
j) glass wool;
k) 1,5 ml sample vials with 100 µl glass insert and a screw cap with polytetrafluoroethylene
(PTFE) gasket or, depending on the analytical system, a comparable sample receptacle;
l) a gas chromatograph with a capillary column coupled to a mass spectrometric detector
(electron ionization, EI). The mass spectrometric detector shall be able to perform selective
ion monitoring. The use of an autosampler is strongly recommended to ensure repeatability.
A column length of approximately 30 m is suitable for sufficient separation efficiency for
HBCDD;
m) rotary evaporator with water bath;
n) milling equipment;
o) 0,45 µm PTFE filter membrane.
p) No. 5A filter paper.
7 Sampling
As described in IEC 62321-2, unless indicated otherwise, the following procedure a) is
recommended.
a) Cut samples approximately to a size of 2 mm × 2 mm, and mix them well.
NOTE 1 When using the alternative ultrasonic dissolution procedure for polymers that are difficult to dissolve,
cryogenic grinding with liquid nitrogen cooling is necessary. The samples are ground to pass through a 500 µm
sieve.
NOTE 2 Contact with polymer material are avoided during sampling.

– 10 – IEC 62321-9:2021 © IEC 2021
8 Procedure
8.1 General instructions for the analysis
The following general instructions shall be followed:
In order to reduce blank values, ensure the cleanliness of all glass equipment (excluding
volumetric flasks) and deactivate the glass wool by subjecting it to 450 °C for at least 30 min.
To avoid decomposition and/or debromination of HBCDD by UV light during extraction and
analysis, glass equipment made from brown or amber glass shall be used.
NOTE If no brown or amber glass is available, aluminium foil can be used for protection from light.
If the amount of Br in the sample (determined by XRF, C-IC or other means) is considerably
above the 0,1 % range, it will be necessary to carry out the analysis using an adjusted sample
size or by repeating the analysis using an extract that has been appropriately diluted prior to
internal standard addition.
8.2 Sample preparation
8.2.1 Stock solution
a) Standard mixture solution: Prepare a standard mixture solution containing α, β, γ-HBCDD
in an organic solvent at a concentration of 10 µg/ml made from each 100 µg/ml standard
solution.
b) Internal standard (to correct for injection error): 50 µg/ml in toluene or an organic solvent
(e.g. CB 209).
8.2.2 Pre-extraction of the Soxhlet extractors
To clean the Soxhlet extractors (Clause 6, c)), a 2 h pre-extraction is carried out with 70 ml of
toluene. The washing solvent is discarded.
8.2.3 Soxhlet extraction
The following steps shall be followed for sample extraction:
a) Weigh 0,5 g of the crushed sample to the nearest 0,000 1 g. The sample is transferred
through a funnel into the extraction thimble. Put the extraction thimble into the Soxhlet
extractor. Toluene shall be used as the extraction solvent.
b) In order to ensure a quantitative transfer, the funnel is rinsed with approximately 10 ml of
extraction solvent.
c) In order to prevent the sample from floating, the extraction thimble is closed with glass wool
(Clause 6, j)). Approximately 80 ml of solvent is placed in the 200 ml round-bottomed flask,
the equipment is covered with aluminium foil to exclude light and the sample is extracted
for at least 2 h with each cycle being approximately 2 min to 3 min.
NOTE Sample amount and volume of extraction can be reduced in the same ratio to keep the same cycle rate.
d) After Soxhlet extraction, allow it to cool down at room temperature.
e) Evaporate the extracted solution in the round-bottomed flask on a rotary evaporator until
approximately 10 ml remains.
f) Transfer the contents into a 20 ml volumetric flask and then bring to volume using solvent.
g) Filter the sample solution through a 0,45 µm syringe filter (Clause 6, o)) and transfer into a
vial for GC‑MS analysis.
8.2.4 Alternative extraction procedure for soluble polymers
As an alternative to Soxhlet extraction, an ultrasonic dissolution procedure is applicable for
polymers soluble in tetrahydrofuran as described in the following steps:
a) Weigh 0,5 g of the sample to the nearest 0,000 1 g into a suitable glass vessel.
b) Quantitatively add 30 ml of tetrahydrofuran, and put the sample in an ultrasonic bath at
40 °C for approximately one hour or until dissolved.
c) Slowly add 70 ml of methanol dropwise to precipitate the polymer resin portion of the
polymer from the solution.
d) Allow the solution and sample mixture to stand for 30 min at room temperature (the
precipitated polymer resin will settle in the solution). Filter with No. 5A filter paper.
e) Evaporate the extracted solution in the round-bottomed flask on a rotary evaporator until
approximately 10 ml remains.
f) Transfer the contents into a 20 ml volumetric flask and then bring to volume using solvent.
g) Filter the sample solution through a 0,45 µm syringe filter (Clause 6, o)) and transfer into a
vial for GC‑MS analysis.
8.2.5 Addition of the internal standard (IS)
Prepare a 1 ml aliquot of each sample and standard to be analysed and place it in an
appropriate sample vial. Add 20 µl of internal standard solution (8.2.1, b)) to the vial and cap
the vial. Invert the vial twice to mix.
Inject 1 µl of the sample solution into the GC‑MS and analyse it according to the parameters
described in 8.3.
8.3 Instrumental parameters
Different conditions might be necessary to optimize a specific GC‑MS system to achieve
effective separation of all calibration congeners and meet the QC and MDL requirements. The
following parameters have been found suitable and are provided as an example:
a) GC column: non-polar (phenyl-arylene-polymer equivalent to 5 % phenyl-methyl-
polysiloxane), length 30 m; internal diameter 0,25 mm; film thickness 0,25 µm;
b) injector liner: 4 mm single taper glass liner with glass wool (deactivated);
c) carrier: helium (5 g), 1,0 ml/min, constant flow;
d) oven temperature: 70 °C for 2 min, 20 °C/min to 300 °C for 5 min;
e) injection temperature: 250 °C;
f) transfer line: 300 °C;
g) injection volume: 1 µl;
h) injection mode: split (10:1);
i) ionization method: electron ionization (EI);
j) solvent delay time: 4 min;
k) ion source temperature: 250 °C;
l) scan range: m/z 50 ~ m/z 1 000 ;
m) dwell time: 80 ms.
Table 2 shows reference masses for confirmation ions and a quantification ion of HBCDD.

– 12 – IEC 62321-9:2021 © IEC 2021
Table 2 – Reference masses for the quantification of HBCDD
Confirmation ions Quantification ion
(m/z) (m/z)
HBCDD 319, 401, 561 319
NOTE 1 α-, β-, γ-HBCDD isomers are not separated by GC and therefore appear as a single peak. This is sufficient
for quantification.
NOTE 2 In GC analysis, degradation of HBCDD occurs with an oven temperature above 160 °C, resulting in the
formation of the degradation products, pentabromocyclododecane and tetrabromocyclododecadiene. The three
isomers, α-, β-, γ-HBCDD, were detected on the same retention time. Therefore, they cannot be clearly separated in
the mixed HBCDD peak.
The chromatogram in Annex B (see Figure B.1 and Figure B.2) gives an example of GC-MS
analysis.
8.4 Calibrants
Reference materials are used as calibrants to make stock solutions of 100 µg/ml each in toluene.
Table 3 shows recommended HBCDD reference materials suitable for GC-MS analysis.
Table 3 – Commercially available HBCDD reference
materials considered suitable for GC-MS analysis
Compound name CAS Number
α-Hexabromocyclododecane 134237-50-6
β-Hexabromocyclododecane 134237-51-7
γ-Hexabromocyclododecane 134237-52-8
25637-99-4
Mix standards of α-, β-,γ-Hexabromocyclododecane
and 3194-55-6
8.5 Calibration
8.5.1 General
Wherever possible, the solvent used for the sample and standard solutions shall be the same
to avoid any potential solvent effects. A calibration curve shall be developed for quantitative
analysis. At least five calibration solutions shall be prepared in equidistant concentration steps.
Quantification is made on the basis of the measurement of the peak areas. The linear regression
fit of each calibration curve is required to have a relative standard deviation (RSD) of less than
or equal to 15 % of the linear calibration function.
NOTE If the limiting value of the RSD of 15 % is exceeded, from the point of view of quality assurance, 2nd order
curve fitting does not guarantee any significantly better adjustment. Only statistical tests such as the F-test fulfil
these requirements by comparing linear or 2nd order. That means that although the RSD value is exceeded, the
calibration is linear.
8.5.2 Standard solutions
Stock solutions of HBCDD listed in Table 3 are used to prepare the calibration solution
concentrations shown in Table 4 using the mixed solvent solution (Clause 5, e)) as a diluent.

Table 4 – Calibration solutions of HBCDD
Final concentration of Volume of internal
HBCDD standard
Standard solution No.
(μg/ml) (μl)
1 0,5 20
2 1,0 20
3 2,5 20
4 5,0 20
5 10 20
A linear regression is carried out using Equation (1):
AC
=ab×+ (1)
AC
IS IS
where
A is the peak area of HBCDD in the calibration solution;
A is the peak area of the internal standard;
IS
C is the concentration of HBCDD (μg/ml);
C is the concentration of the internal standard (μg/ml);
IS
a is the slope of the calibration curve;
b is the intercept on the y-axis of the calibration curve.
The internal standard is used for the correction of the injection error. Therefore, the evaluation
of the response factor or ratio is carried out by A/A .
IS
To produce the calibration straight lines the response A/A is plotted against the concentration
IS
ratio C/C .
IS
9 Calculation of HBCDD concentration
9.1 General
In the event that there is no HBCDD compound detected in the sample, HBCDD shall be
reported as a function of the compound with the highest method detection limits.
9.2 Calculation
The final concentration of HBCDD in the sample can be calculated by using Equation (2):
For a linear fit, the equation takes the form of:
y = ax + b (2)
where
y is the response factor or ratio (A/A ) for the HBCDD in the sample;
IS
a is the slope of the line that best fits the calibration obtained in Equation (1);

– 14 – IEC 62321-9:2021 © IEC 2021
x is the instrumental result (C/C where C commonly equals 1) in µg/ml (the concentration
IS IS
of the congener in the extract);
b is the y intercept or the concentration when the response factor equals 0, obtained from
Equation (1).
For a quadratic fit the equation takes the form of Equation (3):
y = ax + bx + c (3)
where
y is the response factor or ratio (A/A ) for the HBCDD in the sample;
IS
a and b are constants that correspond to the curve that best fits the calibration;
x is the instrument result in µg/ml (the concentration of the HBCDD in the extract);
c is the y intercept or the concentration when the response factor equals 0.
If the concentration of HBCDD in a sample does not fall within the range of its respective
calibrants, a serial sample dilution shall be prepared that will bring the concentration of the
HBCDDs to failing within the calibration. Analyse the dilution and use the dilution factor to
quantify the concentration of those HBCDD that were not within the calibration range in the
original analysis. The dilution factor (D) can be calculated by dividing the final volume of the
dilution by volume of the aliquot, per Equation (4):
V
f
(4)
D=
V
a
where
D is the dilution factor;
V is the final volume in ml;
f
V is the volume of the aliquot in ml.
a
Equation (2), which is in the form of a linear equation, can be rewritten in the form of
Equation (5):

A C

IS
Cb−×
 (5)

Aa

IS
where
A is the peak area of HBCDD;
A is the peak area of the internal standard;
IS
C is the (intermediate) concentration of HBCDD in µg/ml;
C is the concentration of the internal standard in µg/ml.
IS
a is the slope of the line that best fits the calibration obtained in Equation (2);
b is the y intercept or the concentration when the response factor equals 0, obtained from
Equation (2).
Equation (5) does not give the final concentration; as the volume of the organic solvent, the
mass of the sample and the volume of the extract and any dilution factor needs to be taken into
account. A conversion factor (F) to convert the units from ng to µg is also needed. The final
concentration of HBCDD in the sample can be calculated by using Equation (6):
=

A C V

IS
Cb−× ×
(6)

final 
A aM

IS
where
C is the concentration of HBCDD in the sample in µg/g;
final
V is the final extraction volume (100 ml);
M is the mass of the sample in grams.
NOTE The calculation example shown above is for linear regression calibration only. A separate calculation can be
required if polynomial regression calibration is utilized.
The HBCDD can be calculated by the measured concentrations of signals identified as an
HBCDD. The HBCDD result shall include the signal with appropriate mass, retention time and
ion ratios for HBCDD.
The calibration solutions can be used to establish an average response factor for each degree
of bromination within the HBCDD. The average response factors can then be used in the
calculation of the measured concentration in the sample that are not included in the calibration
(e.g. tentatively identified compounds or "TICs"). Automatic integration of signals meeting the
criteria for HBCDD is a common function of software used in GC‑MS trace analysis.
The HBCDD isolated from the sample extraction (8.2.3) are quantified by adding the internal
standard (CB 209) (8.2.1, b)) to an extract aliquot, injecting the solution into the GC‑MS,
measuring the area of the analyte peak(s) and the area of the CB 209 peak, and calculating the
concentration of the analyte according to Equations (5) and (6).
10 Precision
When the values of two independent single test results, obtained using the same method on
identical test material in the same laboratory by the same operator using the same equipment
within a short interval of time, lie within the range of the mean values cited in Table 5 below,
the absolute difference between the two test results obtained shall not exceed the repeatability
limit r deduced by statistical analysis of the international interlaboratory study (IIS 9) results in
more than 5 % of cases.
When the values of two single test results, obtained using the same method on identical test
material in different laboratories by different operators using different equipment, lie within the
range of the values cited in Table 5 below, the absolute difference between the two results shall
not be greater than the reproducibility limit R by statistical analysis of the international
interlaboratory study (IIS 9) results in more than 5 % of cases.
=
– 16 – IEC 62321-9:2021 © IEC 2021
Table 5 – IIS 9 repeatability and reproducibility
m r R
Parameter N
mg/kg mg/kg mg/kg
HBCDD 36 4 513,2 881,17 4 427,02
HBCDD 24 10 623,71 3 421,82 7 942,11
HBCDD 24 9 924,00 1 882,62 5 203,60
HBCDD 12 811,83 254,32 616,22
HBCDD 15 7 991,13 2 588,69 4 599,88
Key
N number of test results taken into calculation
m mean value in mg/kg
r repeatability
R reproducibility
See Annex C (results of the international interlaboratory study (IIS 9)) for supporting data.
11 Quality assurance and quality control
11.1 Performance
The following steps are taken for the quality control:
a) One reagent blank shall be extracted with each sequence of samples. The reagent blank is
60 ml of only solvent taken through the entire extraction procedure according to 8.2.3 or
8.2.4. The concentration of HBCDD compounds found in the method blank shall be less than
the method detection limits for each compound.
b) One sample per sequence or one every ten samples, depending on the sample load, shall
be spiked with 10 µg of HBCDD in the matrix spiking solution (see 8.2.1).
Equation (7) shall be used for the calculation:
CC−
m
HR ×100 (7)
C
s
where
HR is the recovery of HBCDD in %;
is the concentration of HBCDD in the matrix spike in µg/ml;
C
m
C is the concentration of HBCDD in the original sample in µg/ml;
C is the concentration of HBCDD spike solution in µg/ml.
s
The percent recovery for HBCDD shall be between 50 % and 150 %. The percent recovery
for each matrix spike shall be recorded and tracked in a spreadsheet to determine possible
matrix effects in the analysis.
c) After every tenth sample run and at the end of each sample set, analyse a continuing
calibration check (CCC) standard. A CCC is an unextracted mid-range calibrant that is
analysed as a sample. The percent recovery for HBCDD shall be between 70 % and 130 %.
If the percent recovery for HBCDD in the CCC standard falls outside of this range, the CCC
standard shall be reinjected within 12 h. If the recovery is still out of range after re-injection
of the CCC standard, the analysis is stopped and maintenance shall be performed on the
system to return it to optimal operating conditions. All samples injected before the last
successful CCC standard may be reported, but all samples after the failing CCC standard
shall be re-analysed with a new calibration.
=
d) The surrogate recovery shall be monitored for each sample. Percent (%) surrogate recovery
shall be calculated by Equation (8):
M
s
SR ×100 (8)
10 µg
where
SR is the surrogate re
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