SIST-TS CEN/TS 1948-4:2008
(Main)Stationary source emissions - Determination of the mass concentration of PCDDs/PCDFs and dioxin-like PCBs - Part 4: Sampling and analysis of dioxin-like PCBs
Stationary source emissions - Determination of the mass concentration of PCDDs/PCDFs and dioxin-like PCBs - Part 4: Sampling and analysis of dioxin-like PCBs
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-TEQPCB/m3.
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.
Emissionen aus stationären Quellen - Bestimmung der Massenkonzentration von PCDD/PCDF und dioxin-ähnlichen PCB - Teil 4: Probenahme und Analyse dioxin-ähnlicher PCB
Dieses Dokument legt die Verfahren zur Probenahme an stationären Quellen, zur Extraktion, Reinigung, Identifizierung und zur Quantifizierung von dioxin-ähnlichen PCB fest. Das beschriebene Verfahren legt die Anforderungen zur Messung der in Anhang A aufgeführten PCB-Kongenere fest (siehe Tabelle A.1). Das Verfahren ist für die zwölf non- und mono-ortho und von der WHO ausgewiesenen PCB anwendbar. Es ist für die Messung von PCB Konzentrationen im Bereich von 0,01 ng WHO TEQPCB/m3 optimiert.
Zusätzlich zu den zwölf non- und mono ortho PCB ist das vorliegende Dokument auch für die Messung weiterer PCB-Kongenere anwendbar, wie die so genannten Indikator PCB 28, 52, 101, 138, 153, 180 (siehe Anhang D).
Dieses Dokument legt einen Rahmen für die Qualitätskontrollanforderungen fest, die von jedem Verfahren zur Probenahme, Extraktion, Reinigung, Identifizierung und Quantifizierung von PCB erfüllt werden müssen.
Aufgrund ihres ähnlichen chemischen Verhaltens wird angenommen, dass PCB zusammen mit PCDD/PCDF unter Verwendung desselben Verfahrens aus stationären Quellen gesammelt werden dürfen. Das vollständige Probenahmeverfahren wird in EN 1948-1 beschrieben. Jedes der drei in EN 1948-1 beschriebenen Probenahmeverfahren kann mit dem in diesem Dokument beschriebenen Verfahren kombiniert werden, um das Messverfahren zu vervollständigen. EN 1948-1 ist wesentlicher Bestandteil des vollständigen Messverfahrens und ist für die Bestimmung von PCB erforderlich.
Weiterhin ist es möglich, PCB zusammen mit PCDD/PCDF zu messen, indem EN 1948 Teil 1, Teil 2, Teil 3 und CEN/TS Teil 4 angewendet werden.
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
Le présent document spécifie les procédures de prélevement de sources fixes, d’extraction, de purification, d’identification et de quantification des PCB de type dioxine. La procédure décrite présente les exigences relatives au mesurage des congéneres PCB donnés dans l’Annexe A (voir le Tableau A.1). Elle s’applique aux douze PCB non-ortho et mono-ortho désignés par l’OMS. Cette procédure est particulierement adaptée au mesurage des concentrations de PCB dans la fourchette de 0,01 ng OMS-TEQPCB/m3.
Outre les 12 PCB non-ortho et mono-ortho, le présent document s’applique également au mesurage des autres congéneres PCB, comme les PCB qualifiés d’« indicateurs » 28, 52, 101, 138, 153, 180 (voir l’Annexe D).
Le présent document spécifie un cadre d’exigences de contrôle qualité qui doivent etre satisfaites par toute méthode de prélevement, d’extraction, de purification, d’identification et de quantification des PCB a appliquer.
En raison de leur comportement chimique similaire, il est admis que les PCB puissent etre prélevés sur des sources fixes avec les PCDD/PCDF, en utilisant les memes méthodes. Le mode opératoire d’échantillonnage est décrit dans l’EN 1948-1. Chacune des trois méthodes de prélevement de l’EN 1948-1 peut etre combinée avec les méthodes décrites dans le présent document, afin de compléter la procédure de mesurage. L’EN 1948-1 fait partie intégrante de la procédure de mesurage complete et est nécessaire a la détermination des PCB.
En outre, il est possible de mesurer les PCB avec les PCDD/PCDF en appliquant les parties 1, 2 et 3 de l’EN 1948 ainsi que le prCEN/TS 1948 partie 4.
Emisije nepremičnih virov - Določevanje masne koncentracije PCDD/PCDF in dioksinu podobnih PCB - 4. del: Vzorčenje in analiza dioksinu podobnih PCB
General Information
Relations
Standards Content (Sample)
SLOVENSKI STANDARD
SIST-TS CEN/TS 1948-4:2008
01-marec-2008
(PLVLMHQHSUHPLþQLKYLURY'RORþHYDQMHPDVQHNRQFHQWUDFLMH3&''3&')LQ
GLRNVLQXSRGREQLK3&%GHO 9]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
SIST-TS CEN/TS 1948-4:2008 en,fr,de
2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.
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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.
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CEN/TS 1948-4:2007 (E)
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
13
6 Device, materials and C -labelled standards .9
12
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
2
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CEN/TS 1948-4:2007 (E)
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.
3
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CEN/TS 1948-4:2007 (E)
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
3
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
4
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CEN/TS 1948-4:2007 (E)
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
13
C -labelled PCBs, added before extraction and used for calculating results
12
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)
5
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CEN/TS 1948-4:2007 (E)
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
6
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CEN/TS 1948-4:2007 (E)
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
13
C -labelled PCBs, added before injection into the GC
12
3.16
sampling standard
13
C -labelled PCBs, added before sampling
12
3.17
spiking
13
addition of C -labelled PCB standards
12
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
7
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CEN/TS 1948-4:2007 (E)
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.
13
C -labelled PCB congeners are added at different stages of the whole method (before sampling, extraction
12
13
and HRGC/HRMS-measurement). Spiking with C -labelled PCBs according to 6.2 before sampling is
12
necessary to determine the sampling recovery rate of the PCB congeners. Losses during extraction and
8
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CEN/TS 1948-4:2007 (E)
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.
13
6 Device, materials and C -labelled standards
12
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.
13
6.2 C -labelled standards
12
The sampling standards (see Table 1) shall be added to the different sampling media before sampling and the
13
extraction standards shall be added to the samples after their arrival in the laboratory. These C -labelled
12
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
13
extraction standards. Table 1 shows a selection of available C -labelled PCBs suitable as recovery
12
standards. At least one shall be added for each dioxin-like PCB containing fraction.
13
The quantities of the C -labelled congeners to be added per sample for sampling at a medium PCB
12
concentration level of 0,01 ng WHO-TEQ /m³ and 10 m³ sampling volume (dry gas) are given in Table 1.
PCB
13
If a considerably higher or lower mass of native PCBs is expected in the sample, the masses of the C -
12
labelled standards to be added shall be adapted accordingly.
9
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CEN/TS 1948-4:2007 (E)
13
Table 1 — C -labelled PCBs congeners to be added to the sample at different stages of the
12
3
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:
13
C -2,3,4,4'-TeCB (60) 1 000
12
13
C -3,3’,4,5,5’-PeCB (127) **) 1 000
12
13
C --2,3,3',4,5,5'-HxCB (159) 1 000
12
13
C -3,3’,4,4’-TeCB (77) 1 000
12
13
C -3,4,4’,5-TeCB (81) 1 000
12
13
C -2,3,3’,4,4’-PeCB (105) **) 1 000
12
13
C -2,3,4,4’,5-PeCB (114) 1 000
12
13
C -2,3’,4,4’,5-PeCB (118) 1 000
12
13
C -2’,3,4,4’,5-PeCB (123) 1 000
12
13
C -3,3’,4,4’,5-PeCB (126) 1 000
12
13
C -2,3,3’,4,4’,5-HxCB (156) 1 000
12
13
C -2,3,3’,4,4’,5’-HxCB (157) 1 000
12
13
C -2,3’,4,4’,5,5’-HxCB (167) 1 000
12
13
C -3,3’,4,4’,5,5’-HxCB (169) 1 000
12
13
C -2,3,3’,4,4’,5,5’-HpCB (189) 1 000
12
13
C -2,3’,4’,5-TeCB (70) 1 000
12
13
C -2,3,3’,5,5’-PeCB (111) 1 000
12
13
C -2,2’,3,3’,4,4’,5-HpCB (170) 1 000
12
Recovery standards:
13
*) Table 1 shows a selection of available C -labelled PCBs suitable as recovery standards. At least one shall be added
12
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.
10
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CEN/TS 1948-4:2007 (E)
8 Measurement procedure
8.1 Sampling
Sampling and storing see EN 1948-1.
13
The sampling train is spiked with C -labelled PCBs (see Table 1) as described for PCDD/PCDF in EN 1948-
12
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.
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CEN/TS 1948-4:2007 (E)
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
13
one of the three C -labelled congeners mentioned as recovery standards in Table 1 shall be added to
12
each PCB containing fraction. Recovery standard and the respective extraction standards shall match
together with respect to retention time and mass range.
b) Slow evapor
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