CEN/TS 1948-4:2007

SLOVENSKI STANDARD
01-marec-2008
(PLVLMHQHSUHPLþQLKYLURY'RORþHYDQMHPDVQHNRQFHQWUDFLMH3&''3&')LQ
GLRNVLQXSRGREQLK3&%GHO9]RUþHQMHLQDQDOL]DGLRNVLQXSRGREQLK3&%
Stationary source emissions - Determination of the mass concentration of
PCDDs/PCDFs and dioxin-like PCBs - Part 4: Sampling and analysis of dioxin-like PCBs
Emissionen aus stationären Quellen - Bestimmung der Massenkonzentration von
PCDD/PCDF und dioxin-ähnlichen PCB - Teil 4: Probenahme und Analyse dioxin-
ähnlicher PCB
Emissions de sources fixes - Détermination de la concentration massique en
PCDD/PCDF et PCB de type dioxine - Partie 4 : Prélevement et analyse de PCB de type
dioxine
Ta slovenski standard je istoveten z: CEN/TS 1948-4:2007
ICS:
13.040.40
2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.

TECHNICAL SPECIFICATION
CEN/TS 1948-4
SPÉCIFICATION TECHNIQUE
TECHNISCHE SPEZIFIKATION
July 2007
ICS 13.040.40
English Version
Stationary source emissions - Determination of the mass
concentration of PCDDs/PCDFs and dioxin-like PCBs - Part 4:
Sampling and analysis of dioxin-like PCBs
Emissions de sources fixes - Détermination de la Emissionen aus stationären Quellen - Bestimmung der
concentration massique en PCDD/PCDF et PCB de type Massenkonzentration von PCDD/PCDF und dioxin-
dioxine - Partie 4 : Prélèvement et analyse de PCB de type ähnlichen PCB - Teil 4: Probenahme und Analyse dioxin-
dioxine ähnlicher PCB
This Technical Specification (CEN/TS) was approved by CEN on 16 June 2007 for provisional application.
The period of validity of this CEN/TS is limited initially to three years. After two years the members of CEN will be requested to submit their
comments, particularly on the question whether the CEN/TS can be converted into a European Standard.
CEN members are required to announce the existence of this CEN/TS in the same way as for an EN and to make the CEN/TS available
promptly at national level in an appropriate form. It is permissible to keep conflicting national standards in force (in parallel to the CEN/TS)
until the final decision about the possible conversion of the CEN/TS into an EN is reached.
CEN members are the national standards bodies of Austria, Belgium, Bulgaria, Cyprus, Czech Republic, Denmark, Estonia, Finland,
France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal,
Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland and United Kingdom.
EUROPEAN COMMITTEE FOR STANDARDIZATION
COMITÉ EUROPÉEN DE NORMALISATION
EUROPÄISCHES KOMITEE FÜR NORMUNG
Management Centre: rue de Stassart, 36  B-1050 Brussels
© 2007 CEN All rights of exploitation in any form and by any means reserved Ref. No. CEN/TS 1948-4:2007: E
worldwide for CEN national Members.

Contents Page
Introduction .4
1 Scope .4
2 Normative references .5
3 Terms and definitions .5
4 Symbols and abbreviations .7
5 Principle of the measurement procedure.8
6 Device, materials and C -labelled standards .9
7 Safety measures .10
8 Measurement procedure .11
9 Method validation and quality control requirements.18
10 Quality control requirements for the measurement.20
11 Quality assurance criteria for extraction/clean-up/quantification procedure blanks.22
12 Performance characteristics (informative) .23
13 Interferences (informative) .24
Annex A (informative) Toxicity and toxic equivalency.25
Annex B (informative) Example for clean-up of PCB and the separation from PCDD/PCDFs .27
B.1 General.27
B.2 Method .29
Annex C (informative) Possible interferences in dioxin-like PCB analysis.35
Annex D (informative) Measurement of the marker PCB 28, 52, 101, 138, 153, and 180 in addition
to the 12 non- and mono-ortho-PCB.38
Bibliography .41

Foreword
This document (CEN/TS 1948-4:2007) has been prepared by Technical Committee CEN/TC 264 “Air quality”,
the secretariat of which is held by DIN.
The European Standard EN 1948:2006 consists of several parts dealing with the determination of the mass
concentration of PCDDs, PCDFs and PCBs in stationary source emissions:
Part 1: Sampling of PCDDs/PCDFs
Part 2: Extraction and clean-up of PCDDs/PCDFs
Part 3: Identification and quantification of PCDDs/PCDFs
Part 4: Sampling and analysis of dioxin-like PCBs (Technical Specification CEN/TS)
The first three parts are necessary for the performance of the dioxin measurements. In addition this Technical
Specification, CEN/TS 1948-4, describes the sampling, extraction and analyses of dioxin-like PCBs and will
be transferred to a European Standard after corresponding validation measurements.
Attention is drawn to the possibility that some of the elements of this document may be the subject of patent
rights. CEN [and/or CENELEC] shall not be held responsible for identifying any or all such patent rights.
According to the CEN/CENELEC Internal Regulations, the national standards organizations of the following
countries are bound to announce this Technical Specification: Austria, Belgium, Bulgaria, Cyprus, Czech
Republic, Denmark, Estonia, Finland, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia,
Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain,
Sweden, Switzerland and the United Kingdom.

Introduction
A group of chlorinated aromatic compounds similar to polychlorinated dibenzodioxins (PCDDs) and polychlori-
nated dibenzofurans (PCDFs) is known as polychlorinated biphenyls (PCBs) which consists of 209 individual
substances (see Figure 1 for the basic structure).
PCBs have been produced over approximately 50 years until the end of the 1990s with different uses in open
and closed systems, e.g. as electrical insulators or dielectric fluids in capacitors and transformers, specialised
hydraulic fluids, as a plasticiser in sealing material etc. World-wide, more than one million tons of PCBs were
produced.
PCDD/PCDF as well as PCBs are emitted during thermal processes. PCB can contribute considerably to the
total WHO-TEQ as reported for Germany;[1] [2], Great Britain [3], Poland [4], Spain [5], Japan [6]; [7], Korea
[8].
In 1997 a group of experts of the World Health Organisation (WHO) defined toxicity equivalent factors (TEFs)
for PCDDs/PCDFs and twelve PCBs, known as dioxin-like PCBs [9;10] (see Annex A). These twelve dioxin-
like PCBs consist of four non-ortho PCBs and eight mono-ortho PCBs (no or only one chlorine atoms in 2-, 2’-,
6- and 6’-position), having a planar or mostly planar structure, see Figure 1.
This document deals with the determination of these dioxin-like PCBs in emissions from stationary sources.
Only skilled operators who are trained in handling highly toxic compounds should apply this document.

Figure 1 —Structure of PCB
1 Scope
This document specifies sampling from stationary sources, extraction, clean-up, identification and
quantification procedures of the dioxin-like PCBs. The procedure described lays down requirements to
measure the PCB congeners given in Annex A (see Table A.1). It is applicable to the twelve non- and mono-
ortho PCB designated by the WHO. It is optimised to measure PCB concentrations in the range of 0,01 ng
WHO-TEQ /m .
PCB
In addition to the 12 non- and mono-ortho-PCB the present document is also applicable to measure further
PCB-congeners like the so-called “marker PCB” 28, 52, 101, 138, 153, 180 (see Annex D).
This document specifies a framework of quality control requirements which have to be fulfilled by any PCB
sampling, extraction, clean-up, identification and quantification methods to be applied.
It is assumed that due to their similar chemical behaviour PCBs may be sampled from stationary sources
together with the PCDDs/PCDFs by the same methods. The complete sampling procedure is described in the
EN 1948-1. Each of the three sampling methods of EN 1948-1 can be combined with the methods described
in this document to complete the measurement procedure. EN 1948-1 is an integral part of the complete
measurement procedure and is necessary for the determination of PCBs.
In addition it is possible to measure PCBs together with PCDDs/PCDFs by applying EN 1948 Part 1, Part 2,
Part 3 and CEN/TS 1948 Part 4.
2 Normative references
The following referenced documents are indispensable for the application 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.
EN 1948-1:2006, Stationary source emissions - Determination of the mass concentration of PCDDs/PCDFs
and dioxin-like PCBs - Part 1: Sampling of PCDDs/PCDFs
EN 1948-2:2006, Stationary source emissions - Determination of the mass concentration of PCDDs/PCDFs
and dioxin-like PCBs - Part 2: Extraction and clean-up of PCDDs/PCDFs
EN 1948-3:2006, Stationary source emissions - Determination of the mass concentration of PCDDs/PCDFs
and dioxin-like PCBs - Part 3: Identification and quantification of PCDDs/PCDFs
EN 13284-1, Stationary source emissions – Determination of low range mass concentration of dust – Part 1:
Manual gravimetric method
3 Terms and definitions
For the purposes of this document, the terms and definitions given in EN 1948-1:2006, EN 1948-2:2006, EN
1948-3:2006 and the following apply.
3.1
analytical blank value
value determined by a blank sample covering the complete analytical procedure including extraction, clean-up,
identification and quantification including all the relevant reagents and materials
3.2
congener
one of the 209 individual PCBs
3.3
dioxin-like PCBs
non- and mono-ortho PCB with an affinity to the Ah-receptor, showing similar toxical effects as the 2,3,7,8-
substituted PCDDs/PCDFs according to WHO [Error! Bookmark not defined.]
3.4
extraction standard
C -labelled PCBs, added before extraction and used for calculating results
3.5
field blank value
value determined by a blank sample covering a specific procedure to ensure that no significant contamination
has occurred during all steps of measurement and to check that the operator can achieve a quantification
level adapted to the task
3.6
I-TEF
international toxic equivalent factor defined by NATO/CCMS in 1988 [11] (for detailed description, see EN
1948-1:2006, Annex A)
3.7
I-TEQ
international toxic equivalent obtained by weighting the mass determined with the corresponding I-TEF (for a
detailed description, see EN 1948-1:2006, Annex A)
3.8
isokinetic sampling
sampling at a flow rate such that the velocity and direction of the gas entering the sampling nozzle are the
same as the velocity and direction of the gas in the duct at the sampling point
[EN 13284-1:2001, definition 3.5]
3.9
keeper
solvent of high boiling point added to the sampling standard solution
3.10
Limit of detection (LOD)
minimum value of the measurand for which the measuring system is not in the basic state, with a stated
probability
NOTE 1 The detection limit, also referred to as capability of detection, is defined by reference to the applicable basic
state. But it may be different from "zero", for instance for oxygen measurement as well as when gas chromatographs are
used.
[EN ISO 9169:2006, definition 2.2.10 [12]]
NOTE 2 The measurement value can be distinguished from the analytical blank value with a confidence of 99 %. The
limit of detection is expressed as the mean analytical blank value (b ) plus three times the standard deviation of the
ave
analytical blank (s ).
b
LOD=b + 3s (1)
ave b
where
LOD is the detection limit;
b is the mean analytical blank value;
ave
s is standard deviation of the analytical blank.
b
NOTE 3 In this document the limit of detection should preferably be calculated from the analytical blank b . If this is
ave
not possible, the limit of detection can be calculated from the signal to noise ratio according to 8.1 of EN 1948-3:2006
(resp. 10.3 of this document).
3.11
limit of quantification (LOQ)
limit above which a quantification of the measurand is possible, expressed as the mean analytical blank value
plus, either, five to ten times the standard deviation of the analytical blank. The factor F depends to the
accepted measurement uncertainty
LOQ=b + F s (2)
ave b
where
LOQ is the quantification limit;
b is the mean analytical blank value;
ave
s is standard deviation of the analytical blank
b
NOTE In this document the limit of quantification should preferably be calculated from the analytical blank b . If this
ave
is not possible, the limit of quantification can be calculated from the signal to noise ratio according to 8.1 of EN 1948-
3:2006 (resp. 10.3 this document) using the requirement of Clause 8.3 e) of EN 1948-3:2006 (resp. 10.4 e) of this
document).
3.12
marker PCBs
six PCBs 28, 52, 101, 138, 153, 180
3.13
PCB isomers
PCBs with identical chemical composition but different structure
3.14
PCB profile
graphic presentation of the analysed PCB concentrations
3.15
recovery standard
C -labelled PCBs, added before injection into the GC
3.16
sampling standard
C -labelled PCBs, added before sampling
3.17
spiking
addition of C -labelled PCB standards
3.18
WHO-TEF
toxic equivalent factor proposed by WHO in 1997 [Error! Bookmark not defined.] (for detailed description,
see Annex A)
3.19
WHO-TEQ
toxic equivalent obtained by multiplying the mass determined with the corresponding WHO-TEF including
PCDDs, PCDFs and PCBs (for detailed description, see Annex A)
NOTE WHO-TEQ WHO-TEQ should be used to distinguish different compound classes.
PCB, PCDD/PCDF,
4 Symbols and abbreviations
4.1 General
HRGC
high resolution gas chromatography
HRMS
high resolution mass spectrometry
I-TEF
international toxic equivalent factor (for detailed description, see Annex A of EN 1948-1:2006)
I-TEQ
international toxic equivalent (for detailed description, see Annex A of EN 1948-1:2006)
LOD
limit of detection
LOQ
limit of quantification
PCBs
polychlorinated biphenyls
PCDDs/PCDFs
polychlorinated dibenzo-p-dioxins/dibenzofurans
PTFE
polytetrafluoroethylene
PU foam
polyurethane foam
TDI
tolerable daily intake
WHO-TEF
toxic equivalent factor of the World Health Organisation
WHO-TEQ
toxic equivalent of the World Health Organisation
4.2 Polychlorinated biphenyls
TriCB
Trichlorobiphenyl
TeCB
Tetrachlorobiphenyl
PeCB
Pentachlorobiphenyl
HxCB
Hexachlorobiphenyl
HpCB
Heptachlorobiphenyl
5 Principle of the measurement procedure
Gas is sampled isokinetically in the duct or stack according to the methods described in EN 1948-1. PCBs in
the gas phase and adsorbed on particles are collected in the sampling train together with the PCDDs/PCDFs.
Minimum requirements for PCDD/PCDF sampling are described in EN 1948-1 and have also to be met for
PCB sampling. There is the choice between three different sampling systems:
 filter/condenser method;
 dilution method;
 cooled probe method.
C -labelled PCB congeners are added at different stages of the whole method (before sampling, extraction
and HRGC/HRMS-measurement). Spiking with C -labelled PCBs according to 6.2 before sampling is
necessary to determine the sampling recovery rate of the PCB congeners. Losses during extraction and
clean-up are detected and compensated by using these added congeners as internal extraction standards for
quantification together with recovery standards which are added just before the HRGC/HRMS analysis.
For the determination of PCBs it is useful to separate them from PCDDs/PCDFs and vice versa (interferences
see Annex C).
The main purpose of the clean-up procedure of the raw sample extract is removal of sample matrix
components, which can overload the separation method, disturb the quantification or severely impact the
performance of the identification and quantification method. Furthermore, enrichment of the analytes in the
final sample extract is achieved. Extraction procedures are normally based on soxhlet extraction of filters and
adsorbents and liquid extraction of the condensate. Sample clean-up is usually carried out by multi-column
liquid chromatographic techniques using different adsorbents.
The method specified in this document is based on using gas chromatography/mass spectrometry combined
with the isotope dilution technique to enable the separation, detection and quantification of PCB in the extracts
of emission samples. These extracts are prepared in accordance with EN 1948-2 and contain at least one of
the recovery standards mentioned in Table 1. The combination of gas chromatography and mass
spectrometry enables the differentiation of twelve dioxin-like PCB congeners and marker PCB congeners by
either retention time and/or mass.
6 Device, materials and C -labelled standards
6.1 Device and materials
For determining dioxin-like PCBs in emission samples the same devices and materials for sampling,
extraction, clean-up, identification and quantification may be used as for determining PCDDs/PCDFs. For a
description, see EN 1948-1, EN 1948-2 and EN 1948-3.
6.2 C -labelled standards
The sampling standards (see Table 1) shall be added to the different sampling media before sampling and the
extraction standards shall be added to the samples after their arrival in the laboratory. These C -labelled
congeners behave in the same way to the native PCBs during sampling and clean-up due to their similar
chemical and physical properties. The sampling standards are only used to verify the sampling quality by
determining their recovery rates versus extraction standard. The extraction standards are used for
quantification. The recovery standards are added just before the injection to measure the recovery rates of the
extraction standards. Table 1 shows a selection of available C -labelled PCBs suitable as recovery
standards. At least one shall be added for each dioxin-like PCB containing fraction.
The quantities of the C -labelled congeners to be added per sample for sampling at a medium PCB
concentration level of 0,01 ng WHO-TEQ /m³ and 10 m³ sampling volume (dry gas) are given in Table 1.
PCB
If a considerably higher or lower mass of native PCBs is expected in the sample, the masses of the C -
labelled standards to be added shall be adapted accordingly.

Table 1 — C -labelled PCBs congeners to be added to the sample at different stages of the
procedure for measurement of about 0,01 ng WHO-TEQ /m assuming 10 m³ of sampling volume
PCB
Sampling Extraction GC Injection
Solution: sampling standard extraction standard recovery standard *)

Total volume in µl: 100 100 at least 10
(eg. toluene, n-nonane)
Congeners added Total amount in pg added before:
C -2,3,4,4'-TeCB (60) 1 000
C -3,3’,4,5,5’-PeCB (127) **) 1 000
C --2,3,3',4,5,5'-HxCB (159) 1 000
C -3,3’,4,4’-TeCB (77) 1 000
C -3,4,4’,5-TeCB (81) 1 000
C -2,3,3’,4,4’-PeCB (105) **) 1 000
C -2,3,4,4’,5-PeCB (114) 1 000
C -2,3’,4,4’,5-PeCB (118) 1 000
C -2’,3,4,4’,5-PeCB (123) 1 000
C -3,3’,4,4’,5-PeCB (126) 1 000
C -2,3,3’,4,4’,5-HxCB (156) 1 000
C -2,3,3’,4,4’,5’-HxCB (157) 1 000
C -2,3’,4,4’,5,5’-HxCB (167) 1 000
C -3,3’,4,4’,5,5’-HxCB (169) 1 000
C -2,3,3’,4,4’,5,5’-HpCB (189) 1 000
C -2,3’,4’,5-TeCB (70)  1 000
C -2,3,3’,5,5’-PeCB (111)  1 000
C -2,2’,3,3’,4,4’,5-HpCB (170)  1 000
Recovery standards:
*) Table 1 shows a selection of available C -labelled PCBs suitable as recovery standards. At least one shall be added
for each dioxin-like PCB containing fraction.
Sampling Standards:
**) Attention should be paid to possible co-elution problems of PCB 127 and PCB 105 on certain commercially available
columns.
7 Safety measures
All relevant national safety regulations shall be observed. The dioxin-like PCBs as well as the 2,3,7,8-chlorine
substituted PCDDs/PCDFs, which can usually be present in emission samples together with PCBs, are
among the most toxic chemicals. All work with PCBs and PCDDs/PCDFs therefore requires the utmost care;
the national safety measures which correspond to those for toxic substances should be strictly adhered to.
8 Measurement procedure
8.1 Sampling
Sampling and storing see EN 1948-1.
The sampling train is spiked with C -labelled PCBs (see Table 1) as described for PCDD/PCDF in EN 1948-
1.
During sample storage, the use of screw-caps with PTFE-lined seals is recommended to avoid contamination.
8.2 Extraction
The extraction procedure is carried out using the following materials and techniques. Detailed descriptions of
some procedures are given in Annex A of EN 1948-2:2006. Other methods can also be used but shall be of
proven equal performance to the techniques below:
a) Pre-treatment of sampled particles with hydrochloric acid shall be part of any extraction procedure
(examples of procedures are given in Annex A of EN 1948-2:2006 see also [13]).
b) Particle collecting media (glass fibre filters, thimbles, glass wool etc.): Soxhlet extraction with toluene or a
comparable method.
c) Solid adsorbents (Polyurethane foam, XAD-2): Soxhlet extraction for 20 h with toluene or comparable
validated method. (Water shall be removed, e.g. via a Dean-Stark water separator or by sodium
sulphate.)
d) Aqueous liquids (condensate and bubbler/impinger solution): Liquid/liquid extraction with toluene or
dichloromethane. The water/toluene volume ratio should not be greater than 20:1. Three consecutive
extractions shall be carried out.
e) Inner surfaces of tubes, vessels or other parts of the sampling device in contact with the sample: Rinsing
with a water-miscible solvent (acetone, methanol) followed by toluene. Reflux boiling with toluene is an
alternative for the second step.
f) When sampling with flow division is performed, the filter part and the condenser/adsorber part may be
analyzed separately. The measured concentrations shall be added at the final stage of calculation.
g) Alternatively an aliquot of the filter extract, corresponding to the proportion of side stream to main stream
gas volume, is combined for analysis with the condenser/adsorber part. In this case, the quantity of
extraction standard solution added to the filter is increased in proportion to the ratio of main stream to
side stream gas volume.
h) If coke or activated carbon is used in the gas cleaning system of the incinerator suitable methods,
including freeze drying or Dean-Stark extraction or the addition of water miscible solvents to the
extraction medium, shall be taken to remove water. Attention shall be paid to the method validation of this
step.
After extraction, the organic solvents containing water shall be dried before the concentration procedure. After
combination of all extraction and rinsing solutions any volume reduction shall be carefully carried out to avoid
evaporation losses of PCBs. In case evaporation to nearly dryness is necessary, use of a small amount (e.g.
50 µl) of a keeper (usually a high-boiling solvent such as tetradecane) is strongly recommended.
8.3 Clean-up
Clean-up methods shall prepare the sample extract in an appropriate manner for subsequent quantitative
determination (see also 8.8). Clean-up procedures have to concentrate PCBs in the extracts and to remove
interfering matrix components present in the raw extract.
Proven clean-up procedures shall be used normally containing two or more of the following techniques which
can be combined in different orders. A detailed description of some of the procedures is given in Annex B.
Other methods can also be used but shall be proven to be of equal performance to the techniques described
below:
a) Gel permeation chromatography.
The interesting molecular weight range for PCBs of 200 g/mol to 500 g/mol can be isolated from larger
molecules and polymers which might overload other clean-up methods.
b) Multilayer column liquid chromatography.
Silica with different activity grades and surface modifications.
Compounds with different chemical properties than PCBs can be removed. If sulphuric acid treatment of
the sample extract is carried out, it has to be checked that losses of PCBs do not occur due to the formed
carboniferous surfaces.
c) Column adsorption chromatography using activated carbon.
Non-ortho PCBs’ molecules are separated from mono- and di-ortho PCBs.
d) Column liquid chromatography on alumina of different activity grade and acidity/basicity.
Interfering compounds with small differences in polarity or structure compared to PCBs can be removed.
8.4 Final concentration of the sample extracts
To achieve sufficient detection limits, the cleaned sample fraction(s) are concentrated to a small volume
before quantification.
Though dioxin-like PCBs have high boiling points, vapour phase transfer mechanisms and aerosol formation
during solvent evaporation might lead to substantial losses when concentrating volumes below 10 ml.
Depending on the method used for solvent volume reduction, the following precautions have to be taken into
consideration:
a) Rotary evaporators.
Losses might be substantial when reducing solvent volumes below 10 ml. Counter measures are use of
controlled vacuum conditions according to the vapour pressure and boiling point of the solvent, addition of
a high-boiling solvent as a keeper, as well as use of specially shaped vessels (e.g. V-shaped).
b) Counter gas flow evaporators.
Volumes should not be reduced to less than 1 ml.
c) Nitrogen flow.
An excessive flow of nitrogen which disturbs the solvent surface should be avoided. The vial shape has
also some influence on possible losses. V-shaped vials or vial inserts shall be used for volume reductions
below around 200 µl.
8.5 Addition of recovery standards
The very last step before injection is the addition of the recovery standards to measure the recovery rates of
the extraction standards. The recovery standards shall be added under following conditions:
a) Recovery standards in a minimum volume of 10 µl shall be added just prior to the injection. If the twelve
dioxin-like PCBs are collected and concentrated in several fractions during clean-up procedure, at least
one of the three C -labelled congeners mentioned as recovery standards in Table 1 shall be added to
each PCB containing fraction. Recovery standard and the respective extraction standards shall match
together with respect to retention time and mass range.
b) Slow evaporation to a volume of a minimum of 10 µl is acceptable.
c) Samples with the recovery standard added which could not be analysed due to operational reasons
(instrument failure), should be stored for as brief a time as possible and any further uncontrolled solvent
evaporation shall be avoided.
8.6 Principle of identification and quantification
The method specified in this document is based on using gas chromatography/mass spectrometry combined
with the isotope dilution technique to enable separation, detection and quantification of dioxin-like PCBs in the
extracts of emission samples. The internal standard method is applied to determining the recovery rates of the
labelled PCBs, used as sampling and extraction standards.
The gas chromatographic parameters offer information that enables identification of isomers (position of Cl
substituents), whereas the mass spectrometric parameters enable differentiation between congeners with
different numbers of chlorine substituents.
8.7 Calibration of the HRGC/HRMS
Quantification shall be carried out within the linear range of the system. This range has to be determined
during the calibration procedure.
Calibration itself is carried out with at least five calibration solutions. These solutions contain all native dioxin-
like PCBs in defined amounts and all C -labelled standards (sampling, extraction and recovery standards).
The calibration range should encompass the PCB concentrations of the sample. Table 2 shows the
concentrations of the calibration solution for the concentration range of 0,01 ng WHO-TEQ /m . For
PCB
determining significantly higher concentrations than 0,01 ng WHO-TEQ /m solution std 6 should be used
PCB
instead of solution std 1. The calibration curve is used to calculate the analyte relative response factors.
Table 2 — Concentrations of PCB congeners in calibration solutions
Solution concentrations (pg/µL)
Congeners
standard standard standard standard standard standard
solution std 1 solution std 2 solution std 3 solution std 4 solution std 5 solution std 6
IUPAC, PCB
Native "dioxin-like" PCBs
77, 81, 105, 114, 123, 126, 156,
0,1 1 10 50 200 800
157, 167, 169, 189
0,6 6 60 300 1 200 4 800
Labelled "dioxin-like" PCBs (extraction standards)
77, 81, 105, 114, 118, 123, 126,
10 10 10 10 10 10
156, 157, 167, 169, 189
Labelled PCBs (sampling standards)
10 10 10 10 10 10
60, 127, 159
Labelled PCBs (recovery standards)
10 10 10 10 10 10
70, 111, 170
Calibration frequency depends on the stability of the instrument. Daily calibration checks shall be run with at
least one of the standard solutions of Table 2. If the deviation exceeds 20 % in average, a full five point
calibration shall be carried out. In addition, a full five point calibration shall be repeated after major changes
such as:
a) use of new or repaired equipment;
b) replacement of GC columns;
c) after cleaning of the separation and detection systems.
The relative response factors are used together with the C -labelled congeners, added to the sample to
quantify the mass of the native PCBs by the isotope dilution method.
The relative response factor for congener i is defined and calculated as follows:
A Q
12 13
C C
i i
rrf = ⋅ (3)
i
A Q
13 12
C C
i i
where
rrf is the relative response factor of native congener i relative to C -labelled congener i;
i
A
C
i
is the response ratio of native congener i and C -labelled congener i;
A 13
C
i
Q
C
i
is the inverse mass ratio of C -labelled congener i and native congener i.
Q 12
C
i
Q
12 A
C C
i i
The calibration curve is a plot of the mass ratio (x-axis) versus response ratio (y-axis) (see
A
Q
C
C i
i
Figure 2.)
Q
12 A
C C
i i
Figure 2 — HRGC/HRMS calibration curve of the mass ratio versus response ratio
A
Q
13 C
C i
i
8.8 Quantification of HRGC/HRMS results
8.8.1 Quantification of the sample
The mass of congener i in the sample is calculated as follows:
Q A
13 12
C C
i i
Q = ⋅ (4)
C
i
rrf A
i C
i
where
Q is the mass of the native congener i;
C
i
Q is the mass of the C -labelled congener i added to the sample;
13 12
C
i
A
C
i
is the response ratio of native congener i and C -labelled congener in the sample;
A
C
i
rrf is the relative response factor of congener i relative to C -labelled congener i.
i
The response of all detected masses of the PCBs in the samples shall be within the linear range of the
method (see clause 11). Overlap in the mass window between high isotopic (i.e. M+12, M+14) of the native
PCBs with the lower isotopic ions (M, M+2) of the C -labelled standards, will result in a significant deviation
from linearity beyond a mass ratio of 10, especially for higher chlorinated congeners.
Every native dioxin-like PCB congener is quantified against its corresponding labelled C -PCB congener.
Table 3 shows the theoretical isotope ratio for all PCBs with four to seven chlorine substituents examples for
monitored PCBs.
Table 3 — Mass of ions for PCBs (informative)
Ion Natives Labelled C Relative Abundance
TeCB M 289.9224 301.9626 78
M+2 291.9194 303.9597 100
M+4 293,9165 305.9567 48
PeCB M 323.8834 335.9236 63
M+2 325.8804 337.9207 100
M+4 327.8775 339.9177 64
HxCB M+2 359.8415 371.8817 100
M+4 361.8385 373.8788 80
HpCB M+2 393.8025 405.8428 100
M+4 395.7995 407.8398 96
8.8.2 Calculation of the recovery rates of the extraction standards
The extraction standards are quantified against the recovery standards as given in Table 1 using Equation (5).
Q A
ire ie
R = ⋅ ⋅ (5)
ie
Q rrf A
ie i ire
where
R is the recovery rate of the extraction standard in percent;
i e
Q is the mass of the individual extraction standard added;
ie
Q is the mass of the C -labelled recovery standard added to the sample;
i re
A
ie
is the response ratio of the extraction standard i and the relevant recovery standard in the
A
ire
sample;
rrf is the relative response factor of extraction standard i relative to recovery standard i.
i
If more than one recovery standard is used (see Table 1) the number of chlorine atoms in corresponding
standards should be equal or as similar as possible to the extraction standard.
8.8.3 Calculation of the recovery rates of the sampling standards
The sampling standards are quantified against the extraction standards shown in Table 4 using equation (6).
Q A
ie isa
(6)
R = ⋅ ⋅
isa
Q rrf A
isa i ie
where
R is the recovery rate of the sampling standard in percent;
i sa
Q is the mass of the individual sampling standard added;
i sa
Q is the mass of the extraction standard added to the sample;
i e
A
i sa
is the response ratio of the sampling standard i and the relevant extraction standard in the
A
i e
sample;
rrf is the relative response factor of sampling standard i relative to extraction standard i.
i
Table 4 — Calculation scheme for the recovery rates of the sampling standards
Sampling standard Extraction standard
13 13
C -2,3,4,4'-TeCB (60) C -3,3’,4,4’-TeCB (77)
12 12
13 13
C -3,3’,4,5,5’-PeCB (127) C -2,3’,4,4’,5-PeCB (118)
12 12
13 13
C -2,3,3',4,5,5'-HxCB (159) C -2,3,3’,4,4’,5-HxCB (156)
12 12
8.9 Calculation of the measurement results
PCB emissions are expressed as the mass per dry standard cubic meter of waste gas and reference oxygen
(or carbon dioxide) content.
The WHO-TEQ concentration is calculated by the addition of the concentrations of the twelve individual
PCB
PCBs when multiplied by the appropriate WHO-TEF (see Annex A).
C =()Q ⋅ WHO-TEF (7)
T ∑ i i
C
V
nr
where
Q is the amount of the emitted PCB-congener i;
i12C
C is the concentration of the emitted dioxin-like PCB expressed as WHO-TEQ under
T PCB
standard conditions dry and reference conditions;
V is the waste gas volume of the sample under standard conditions dry and reference
nr
conditions calculated in accordance with equation (5) of EN 1948-1:2006;
WHO-TEF is the WHO-TEF of congener i.
i
The total WHO-TEQ concentration of PCDD/PCDF and PCB can be calculated accordingly.
If the mass of a congener or congeners is below the limit of quantification, then two WHO-TEQ
PCB
concentrations should be reported per sample:
a) with the mass of those congener(s) below the limit of quantification being taken as equal to the limit of
quantification;
b) with the mass of those congener(s) taken as zero.
If the filter/condenser method with flow division is used, and the side stream sample is analysed separately
from the filter, it shall be taken into account that the concentrations and not the masses of the congeners are
used.
8.10 Analytical report
The analytical report shall include at least the following information and information as to whether these
requirements have been fulfilled, to demonstrate compliance with this document:
a) Measurement information:
1) institution, person;
2) site, sampling location with the site;
3) date, time; or
4) sample code if appropriate.
b) Statement:
1) analysis was performed in accordance with EN 1948-2 and this document;
2) in the case of deviations from this document, justification(s) shall be given.
c) Precision:
indication of the reproducibility and repeatability which may be expected under similar conditions to the
validation measurements are given in the future European Standard.
d) Sample storage:
1) location of sample storage between sampling and extraction;
2) temperature of the sample storage location;
3) date at which the samples were put into storage.
e) Extraction:
1) sampling train compartments to which the extraction standards were added and in what proportion
and at what date;
2) recovery rate of each sampling standard;
3) recovery rate of each extraction standard.
f) Concentration:
1) final extract volume after concentration.
g) Addition of recovery standards:
1) time and date of recovery standard addition;
2) time and date of injection;
3) extract volume at injection.
9 Method validation and quality control requirements
9.1 Use of C -labelled standards
C -labelled PCBs are added before sampling (sampling standards), before extraction (extraction standards)
and just before the GC injection (recovery standards). The recovery standards are assumed to be transferred
to the analytical system without any loss and allowed to determine the recoveries (or losses) of the congeners
added at earlier stages.
Sampling standards are added to the sampling device before starting sampling. C -labelled congeners
introduced at this stage might not be exposed to completely the same mechanisms of losses as the native
PCBs collected during the sampling period. First, the labelled congeners are exposed to the gas flow during
the entire sampling time while the native PCBs are present, on average, only half the time. Second, a
significant fraction of the sampled native PCBs are bound to particles and, therefore, they can have different
susceptibilities to reactions and mechanisms which might lead to losses. C -labelled congeners added prior
to sampling might be subject to loss mechanisms. Their use as internal standards for quantification can lead
to an overestimation of the found concentrations. Therefore, the only purpose of the isotope labelled
standards added before sampling (see Table 1) is to identify anomalies during sampling. They are not used
for quantification.
9.2 Sampling
a) Particle bound and gas phase PCBs shall be sampled on a representative base.
 Filter efficiency shall be better than 99,5 % on a test aerosol with a mean particle diameter of 0,3 µm,
at the maximum flow rate anticipated, (or 99,9 % on a test aerosol of 0.6 µm mean diameter). This
efficiency shall be certified by the filter supplier (EN 13284-1:2001, 6.2.7).
The filter is placed upstream of the adsorption stage in case of the filter-condenser method and the
dilution method, or before the last adsorption stage in case of the cooled probe method.
 Adsorption stage for collecting the gaseous PCBs shall be part of the sampling train. This can be a
solid adsorbent (XAD, PU, Porapak) or impingers.
b) Breakthrough of each type of the sampling train shall be tested at least once. In this validation trial an
additional ad/absorption stage shall be used at the end of the sampling train.
NOTE Trapping efficiency of the adsorption stage can be lower for PCBs (mainly tri- and tetrachloro PCBs) than
for PCDDs and PCDFs, and has therefore to be demonstrated by these validation trials.
Sufficient sample volume shall be collected during these validation trials to ensure a detection limit lower
than 5 % of the total amount on a TEQ base.
c) According to the sampling prescriptions for the filter/condenser method, the filter should be kept beneath
125 °C, but above the flue gas dew point.
9.3 Extraction
The efficiency of all applied extraction methods shall be documented as part of the method description. It shall
be measured regularly and corrective action taken if the extraction efficiency falls below the acceptable
requirements given in 9.5. This validation criterion shall be fulfilled for all parts of the sampling device that can
contain a part of the sample such as (where applicable) filters, ab/adsorbents, condensate, vessels and
surfaces of the sampling device.
9.4 Clean-up
Sample clean-up depends on the type of sample matrix that shall be removed. Therefore, a single well-
defined clean-up procedure shall not be applied to all sample matrices without a preliminary check.
In contrast to PCDD/PCDF analysis, where the isomer pattern and congener profile of a well characterised
sample extract shall not be altered by the applied clean-up procedure, it is intended within the analysis of
dioxin-like PCB, to separate the lower toxic di-ortho-substituted congeners more or less from the higher toxic
mono- and non-ortho-substituted dioxin-like PCBs. Therefore, isomer pattern and congener profile are not
suitable criteria to check the clean-up procedure in contrast to the dioxin clean-up procedure (EN 1948-2:2006,
7.3.1 a). For the PCB clean-up procedure, it is important to meet the minimum requirements in 9.5.
9.5 Minimum requirements for method validation
a) Sampling:
 Filter efficiency shall be better than
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