CEN/TS 1948-4:2007

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 : Prélèvement et analyse de PCB de type dioxine

Le présent document spécifie les procédures de prélèvement 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 congénères 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 particulièrement 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 congénères 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 être satisfaites par toute méthode de prélèvement, d’extraction, de purification, d’identification et de quantification des PCB à appliquer.
En raison de leur comportement chimique similaire, il est admis que les PCB puissent être prélevés sur des sources fixes avec les PCDD/PCDF, en utilisant les mêmes méthodes. Le mode opératoire d’échantillonnage est décrit dans l’EN 1948-1. Chacune des trois méthodes de prélèvement de l’EN 1948-1 peut être 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 complète et est nécessaire à 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

• Status: Withdrawn
• Publication Date: 24-Jul-2007
• Withdrawal Date: 05-Oct-2010
• ICS: 13.040.40 - Stationary source emissions
• Technical Committee: CEN/TC 264 - Air quality
• Drafting Committee: CEN/TC 264/WG 1 - Dioxins - emissions
• Current Stage: 9960 - Withdrawal effective - Withdrawal
• Start Date: 06-Oct-2010
• Completion Date: 06-Oct-2010
• Mandate: M/388 - Standardisation Mandate to CEN for Standard Measuring methods for the determination of dioxin-like PCBs from stationary sources
• Ref Project: SIST-TS CEN/TS 1948-4:2008 - Stationary source emissions - Determination of the mass concentration of PCDDs/PCDFs and dioxin-like PCBs - Part 4: Sampling and analysis of dioxin-like PCBs

Relations

• Replaced By: EN 1948-4:2010 - Stationary source emissions - Determination of the mass concentration of PCDDs/PCDFs and dioxin-like PCBs - Part 4: Sampling and analysis of dioxin-like PCBs
• Effective Date: 22-Dec-2008

Standards Content (Sample)

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
...