SIST EN 1948-3:2006
(Main)Stationary source emissions - Determination of the mass concentration of PCDDs/PCDFs and dioxin-like PCBs - Part 3: Identification and quantification of PCDDs/PCDFs
Stationary source emissions - Determination of the mass concentration of PCDDs/PCDFs and dioxin-like PCBs - Part 3: Identification and quantification of PCDDs/PCDFs
This European Standard specifies the identification and quantification procedures of the sampled PCDDs/PCDFs. It is an integral part of the complete measurement procedure. The use of the other two parts of this standard, EN 1948-1:2006 and EN 1948-2:2006, describing sampling and extraction and clean-up, respectively, is necessary for the determination of the PCDDs/PCDFs. This European Standard has been designed to measure PCDD/PCDF concentrations at about 0,1 ng ITEQ/ m3 in stationary source emissions. This European Standard specifies both method validation and a framework of quality control requirements which shall be fulfilled by any PCDD/PCDF identification and quantification methods to be applied. Some methods are described in detail in Annex A as examples of proven procedures. Each of the three sampling methods (Part 1) can be combined with the extraction and clean-up (Part 2) and the identification and quantification (Part 3) to complete the measurement procedure. During comparison measurements of the three sampling methods on municipal waste incinerators at the level of about 0,1 ng I-TEQ/m3 these methods have been deemed comparable within the expected range of uncertainty. Validation trials were performed on the flue gas of municipal waste incinerators at the level of about 0,1 ng I-TEQ/m3 and a dust loading of from 1 mg/m3 to 15 mg/m3. Although this European Standard is primarily developed and validated for gaseous streams emitted by waste incinerators, the practical experience shows that it can be applied for wide concentration ranges and various emission sources. The procedure described in the three parts of EN 1948:2006 specifies requirements in order to measure every 2,3,7,8-chlorine substituted PCDD/PCDF congener required to calculate the total I-TEQ (see Table A.1 of EN 1948-1:2006). Besides the determination of PCDDs/PCDFs the described measurement methods are suitable for determination of other low-volatile substances, e.g. of dioxin-like PCBs (details for sampling and analyses see CEN/TS 1948-4), although no validated performance characteristics are available yet.
Emissionen aus stationären Quellen - Bestimmung der Massenkonzentration von PCDD/PCDF und dioxin-ähnlichen PCB - Teil 3: Identifizierung und Quantifizierung von PCDD/PCDF
Diese Europäische Norm legt das Identifizierungs- und Quantifizierungsverfahren für die gesammelten
PCDD/PCDF fest. Sie ist integraler Bestandteil des vollständigen Messverfahrens. Die Anwendung der
anderen beiden Teile dieser Norm EN 1948-1:2006 und EN 1948-2:2006, die die Probenahme bzw. die
Extraktion und Reinigung beschreiben, ist notwendig für die Bestimmung der PCDD und PCDF.
Diese Europäische Norm ist für die Messung von PCDD/PCDF-Emissionskonzentrationen von stationären
Quellen im Bereich von 0,1 ng I-TEQ/m3 konzipiert.
In dieser Europäischen Norm werden sowohl die Verfahrensvalidierung als auch ein Rahmen für die
Qualitätskontrollanforderungen, die von allen anzuwendenden Verfahren zur Identifizierung und
Quantifizierung der PCDD/PCDF erfüllt werden müssen, festgelegt. Im Anhang A werden einige Verfahren als
erprobte Ausführungsbeispiele ausführlich beschrieben.
Jedes der drei Probenahmeverfahren (Teil 1) kann mit der Extraktion und Reinigung (Teil 2) und der
Identifizierung und Quantifizierung (Teil 3) zur Vervollständigung des Messverfahrens kombiniert werden.
Anhand von Vergleichsmessungen, die mit den drei Probenahmeverfahren an städtischen
Müllverbrennungsanlagen bei einer PCDD/PCDF-Emission von 0,1 ng I-TEQ/m3 durchgeführt wurden,
wurden diese drei Verfahren innerhalb des erwarteten Unsicherheitsbereiches für gleichwertig erachtet. Die
Validierungsmessungen wurden im Abgas von städtischen Müllverbrennungsanlagen im PCDD/PCDFEmissionsbereich
von etwa 0,1 ng I-TEQ/m3 und einer Staubbeladung von 1 mg/m3 bis 15 mg/m3
durchgeführt.
Emissions de sources fixes - Détermination de la concentration massique en PCDD/PCDF et PCB de type dioxine - Partie 3: Identification et quantification de PCDD/PCDF
La présente Norme européenne spécifie les modes opératoires d’identification et de quantification des PCDD/PCDF prélevés. Elle fait partie intégrante du mode opératoire complet de mesurage. L’utilisation des deux autres parties de la présente Norme (EN 1948 1:2006 et EN 1948 2:2006), décrivant d’une part le prélevement et d’autre part l’extraction et la purification, est nécessaire pour déterminer les PCDD et les PCDF.
La présente Norme européenne a été élaborée pour mesurer des concentrations en PCDD/PCDF de l’ordre de 0,1 ng I-TEQ/m3 dans les émissions de sources fixes.
Elle spécifie a la fois les exigences de validation de la méthode et un ensemble d’exigences de contrôle qualité qui doivent etre respectées dans toute méthode d’identification et de quantification des PCDD/PCDF utilisée. L’Annexe A présente quelques méthodes détaillées a titre d’exemples de modes opératoires éprouvés.
Chacune des trois méthodes de prélevement (Partie 1) peut etre combinée avec les méthodes d’extraction et de purification (Partie 2) et d’identification et de quantification (Partie 3) afin de compléter le mode opératoire de mesurage.
A la suite de mesurages comparatifs des trois méthodes de prélevement effectués sur les fumées d’un incinérateur d’ordures ménageres a un niveau d’émission d’environ 0,1 ng l-TEQ/m3, ces trois méthodes ont été jugées comparables dans la plage d’incertitude attendue. Des essais de validation ont été effectués sur les fumées d’incinérateurs d’ordures ménageres a un niveau d’émission d’environ 0,1 ng I-TEQ/m3 et a une concentration en poussieres allant de 1 mg/m3 a 15 mg/m3. Bien que la présente Norme européenne ait été élaborée et validée a l’origine pour des effluents gazeux émis par des incinérateurs, la pratique montre qu’elle peut s’appliquer a des plages de concentrations larges et a diverses sources d’émission.
Emisije nepremičnih virov – Določevanje masne koncentracije PCDD/PCDF in dioksinu podobnih PCB – 3. del: Identifikacija in kvantifikacija PCDD/PCDF
General Information
Relations
Standards Content (Sample)
SLOVENSKI STANDARD
SIST EN 1948-3:2006
01-maj-2006
1DGRPHãþD
SIST EN 1948-3:1999
(PLVLMHQHSUHPLþQLKYLURY±'RORþHYDQMHPDVQHNRQFHQWUDFLMH3&''3&')LQ
GLRNVLQXSRGREQLK3&%±GHO ,GHQWLILNDFLMDLQNYDQWLILNDFLMD3&''3&')
Stationary source emissions - Determination of the mass concentration of
PCDDs/PCDFs and dioxin-like PCBs - Part 3: Identification and quantification of
PCDDs/PCDFs
Emissionen aus stationären Quellen - Bestimmung der Massenkonzentration von
PCDD/PCDF und dioxin-ähnlichen PCB - Teil 3: Identifizierung und Quantifizierung von
PCDD/PCDF
Emissions de sources fixes - Détermination de la concentration massique en
PCDD/PCDF et PCB de type dioxine - Partie 3: Identification et quantification de
PCDD/PCDF
Ta slovenski standard je istoveten z: EN 1948-3:2006
ICS:
13.040.40 (PLVLMHQHSUHPLþQLKYLURY Stationary source emissions
SIST EN 1948-3:2006 en,fr,de
2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.
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SIST EN 1948-3:2006
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SIST EN 1948-3:2006
EUROPEAN STANDARD
EN 1948-3
NORME EUROPÉENNE
EUROPÄISCHE NORM
March 2006
ICS 13.040.40 Supersedes EN 1948-3:1996
English Version
Stationary source emissions - Determination of the mass
concentration of PCDDs/PCDFs and dioxin-like PCBs - Part 3:
Identification and quantification of PCDDs/PCDFs
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 3: Identification et quantification de ähnlichen PCB - Teil 3: Identifizierung und Quantifizierung
PCDD/PCDF von PCDD/PCDF
This European Standard was approved by CEN on 23 January 2006.
CEN members are bound to comply with the CEN/CENELEC Internal Regulations which stipulate the conditions for giving this European
Standard the status of a national standard without any alteration. Up-to-date lists and bibliographical references concerning such national
standards may be obtained on application to the Central Secretariat or to any CEN member.
This European Standard exists in three official versions (English, French, German). A version in any other language made by translation
under the responsibility of a CEN member into its own language and notified to the Central Secretariat has the same status as the official
versions.
CEN members are the national standards bodies of Austria, Belgium, 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
© 2006 CEN All rights of exploitation in any form and by any means reserved Ref. No. EN 1948-3:2006: E
worldwide for CEN national Members.
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SIST EN 1948-3:2006
EN 1948-3:2006 (E)
Contents Page
Foreword .3
Introduction.6
1 Scope .7
2 Normative references .7
3 Terms and definitions.7
4 Symbols and abbreviations.10
5 Principles of identification and quantification.11
6 Reagents, materials and equipment.11
7 Safety measures .11
8 Quality control requirements for identification and quantification.11
9 Quality assurance criteria for extraction/clean-up/quantification procedure blanks .13
10 Calibration of the HRGC/HRMS.14
11 Quantification of HRGC/HRMS results .15
12 Calculation of the measurement results .18
13 Analytical report.18
14 Performance characteristics.19
15 Interferences .21
Annex A (informative) Examples of operation of gas chromatography / mass spectrometry
analysis of PCDDs/PCDFs in emission samples .22
Annex B (informative) Estimation of the measuring uncertainty and precision of the
determination of polychlorinated dibenzo-p-dioxins and dibenzofurans.31
Annex C (informative) Mass of ions monitored for PCDDs and PCDFs .35
Annex D (informative) Relative abundance of chlorine isotope ions and their ratio for
PCDD/PCDF congeners containing 4 to 8 chlorine substituents .36
Annex E (informative) Further general recommendations for separation, detection and
quantification of PCDDs/PCDFs .37
Annex F (informative) Variability determination based on the results of the validation tests.39
Annex G (informative) Relation to EU Directives .47
Bibliography.48
2
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SIST EN 1948-3:2006
EN 1948-3:2006 (E)
Foreword
This European Standard (EN 1948-3:2006) has been prepared by Technical Committee CEN/TC 264 “Air
quality”, the secretariat of which is held by DIN.
This European Standard shall be given the status of a national standard, either by publication of an identical
text or by endorsement, at the latest by September 2006, and conflicting national standards shall be
withdrawn at the latest by September 2006.
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.
This European Standard supersedes EN 1948-3:1996.
This European Standard has been prepared under a mandate given to CEN by the European Commission
and the European Free Trade Association to support Essential Requirements of EU Directive 94/67/EC of
16 December 1994 [i] on the incineration of hazardous waste. This directive is now replaced by EU Directive
2000/76/EC of 4 December 2000 on the incineration of waste [ii] and this European Standard also supports
the Essential Requirements of the new EU Directive 2000/76/EC (see also Annex G).
The precision and the performance characteristics were determined between 1992 and 1995 in four
comparative and validation trials at waste incinerators sponsored by the European Commission, the European
Free Trade Association and the German Federal Environment Agency.
The revision of this EN between 2001 and 2004 only refers to the normative part. The information given in the
informative annexes as examples of operation are kept unchanged, as they represent the state of the art at
the time of the validation measurements of EN 1948:1996 between 1992 and 1995.
This European Standard EN 1948:2006 consists of three parts dealing with the determination of the mass
concentration of PCDDs and PCDFs 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.
All three parts are necessary for the performance of the dioxin measurements.
In addition for the sampling, extraction and analyses of dioxin-like PCBs the Technical Specification
1
CEN/TS 1948-4 is developed and will be transferred to a European Standard after corresponding validation
measurements or after an approval time of three years respectively.
Important changes made in the revision of EN 1948-3:
1. Title: Broadening of the title with regard to the future EN 1948-4 for the determination of dioxin-like
PCBs
2. Foreword:
1
) To be published.
3
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SIST EN 1948-3:2006
EN 1948-3:2006 (E)
• Deletion of all precursor documents which were basis for elaboration of EN 1948 as well as the
names of the standardisation bodies involved in the elaboration of EN 1948
• Update of the hint regarding mandate of the standardisation project and regarding fulfilment of
the Essential Requirements of EU Directives 94/67/EC and 2000/76/EC
• Addition of a hint, that the revision only refers to the normative parts of the standard. The
Informative Annex A “Examples of operation” is kept unchanged and represents the state of the
art at time of the validation measurements of EN 1948:1996 between 1992 and 1995
• Addition of hint with regard to the future document EN 1948-4 dealing with the analyses of dioxin-
like PCBs.
3. Scope:
• Addition of a hint, that EN 1948 can be applied for wide concentration ranges and various
emission sources
• Addition of a hint, that the described measurement methods are suitable for determination of
other low-volatile substances, e.g. of dioxin-like PCBs
4. Normative references: Update of the references to EN 1948-1:2006, EN 1948-2:2006
5. Clause 3 Terms and definitions:
• Distinction between Clause 3 "Terms and definitions" and Clause 4 "Symbols and abbreviations"
resulting in a different numbering of the following chapters
• Corrected definition of "field blank" for clarification
• Corrected definition of "analytical blank" for clarification
• Corrected definition of "sampling standard": only furans
• "Syringe standard" renamed to read "recovery standard"
• Corrected definition of "recovery standard": only dioxins
• Additional definition of "dioxin-like PCBs"
• Corrected definition and requirement of isokinetic sampling according to EN 13284-1:2001
• Additional definition and calculation of limit of detection
• Additional definition and calculation of limit of quantification
• Additional definition of WHO-TEF/WHO-TEQ
6. Clause 8.1 Minimum requirements for identification of PCDF/PCDD congeners:
• Deletion of the permission that resolution in the range of 6 000 to 10 000 might be acceptable if
the absence of interferences is documented.
• Deletion of the permission that other techniques which show that they meet the requirements
described in this Standard may be used for identification.
4
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SIST EN 1948-3:2006
EN 1948-3:2006 (E)
• Uniform specification of retention times for all native congeners of +3 s to 0 s relative to the
13
C-labelled congeners.
• Clarification of the requirement, that the signal-to-noise ratio of the raw data as documented in
Figure 1 shall be at least 3 : 1 for the native signal used for identification.
• Correction of the measurement of the base line noise
7. Clause 8.3 Minimum requirements for quantification:
• Correction of the requirements for quantification in 8.3.a, c, e, f, g, h, i
• h) Calculation of the quantification limit according to new definition
• i) Additional requirement to carry out quantification based on two isotopes
8. Clause 11 Quantification of HRGC/HRMS results:
13
• Correction of the quantification scheme (Table 1): Quantification of dioxins with C-labelled
13
dioxins, quantification of furans with C-labelled furans
• Correction of calculation scheme for recovery rate of the sampling standards (Table 3):
13 13
C-labelled furan sampling standards are related to C-labelled furan extraction standards
9. Clause 12 Calculation of measurement results: Combination of formerly two formulas to one
formula for calculating the concentration of the emitted PCDD/PCDF and adaptation of the formula
caption
10. Annex B: Additional Annex B for estimation of the measurement uncertainty and the accuracy of
polychlorinated PCDD/PCDF determination
11. Annex G: Update of the hint regarding mandate of the standardisation project and regarding fulfilment
of basic requirements of EU Directives 94/67/EC and 2000/76/EC
12. : Update
Bibliography
According to the CEN/CENELEC Internal Regulations, the national standards organizations of the following
countries are bound to implement this European Standard: Austria, Belgium, 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.
5
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SIST EN 1948-3:2006
EN 1948-3:2006 (E)
Introduction
Two groups of related chlorinated aromatic ethers are known as polychlorinated dibenzodioxins (PCDDs) and
polychlorinated dibenzofurans (PCDFs); they consist of a total of 210 individual substances (congeners):
75 PCDDs and 135 PCDFs.
PCDDs and PCDFs can form in the combustion of organic materials; they also occur as undesirable by-
products in the manufacture or further processing of chlorinated organic chemicals. PCDDs/PCDFs enter the
environment via these emission paths and through the use of contaminated materials. In fact, they are
universally present at very small concentrations. The 2,3,7,8-substituted congeners are toxicologically
significant. Toxicologically much less significant than the tetrachlorinated to octachlorinated
dibenzodioxins/dibenzofurans are the 74 monochlorinated to trichlorinated dibenzodioxins/dibenzofurans (for
toxicity equivalent factors, see Annex A of EN 1948-1:2006).
Only skilled operators who are trained in handling highly toxic compounds should apply the method described
in this European Standard.
6
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SIST EN 1948-3:2006
EN 1948-3:2006 (E)
1 Scope
This European Standard specifies the identification and quantification procedures of the sampled
PCDDs/PCDFs. It is an integral part of the complete measurement procedure. The use of the other two parts
of this standard, EN 1948-1:2006 and EN 1948-2:2006, describing sampling and extraction and clean-up,
respectively, is necessary for the determination of the PCDDs/PCDFs.
This European Standard has been designed to measure PCDD/PCDF concentrations at about 0,1 ng I-
3
TEQ/m in stationary source emissions.
This European Standard specifies both method validation and a framework of quality control requirements
which shall be fulfilled by any PCDD/PCDF identification and quantification methods to be applied. Some
methods are described in detail in Annex A as examples of proven procedures.
Each of the three sampling methods (Part 1) can be combined with the extraction and clean-up (Part 2) and
the identification and quantification (Part 3) to complete the measurement procedure.
During comparison measurements of the three sampling methods on municipal waste incinerators at the level
3
of about 0,1 ng I-TEQ/m these methods have been deemed comparable within the expected range of
uncertainty. Validation trials were performed on the flue gas of municipal waste incinerators at the level of
3 3 3
about 0,1 ng I-TEQ/m and a dust loading of from 1 mg/m to 15 mg/m . Although this European Standard is
primarily developed and validated for gaseous streams emitted by waste incinerators, the practical experience
shows that it can be applied for wide concentration ranges and various emission sources.
The procedure described in the three parts of EN 1948:2006 specifies requirements in order to measure every
2,3,7,8-chlorine substituted PCDD/PCDF congener required to calculate the total I-TEQ (see Table A.1 of EN
1948-1:2006).
Besides the determination of PCDDs/PCDFs the described measurement methods are suitable for
determination of other low-volatile substances, e.g. of dioxin-like PCBs (details for sampling and analyses see
CEN/TS 1948-4), although no validated performance characteristics are available yet.
2 Normative references
The following referenced documents are indispensable for the application of this European Standard. 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
3 Terms and definitions
For the purposes of this European Standard, the terms and definitions given in EN 1948-1:2006,
EN 1948-2:2006 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
7
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SIST EN 1948-3:2006
EN 1948-3:2006 (E)
3.2
congener
any one of the 210 individual PCDDs/ PCDFs
3.3
dioxin-like PCBs
any PCB showing similar toxicity as the 2,3,7,8-substituted PCDDs/PCDFs according to WHO [iii]
3.4
extraction standard
13
C -labelled 2,3,7,8-chlorine substituted PCDD/PCDF, added before extraction and used for the calculation
12
of results
3.5
field blank value
value determined by a blank sample covering a specific procedure used to ensure that no significant
contamination has occurred during all steps of the measurement and to check that the operator can achieve a
quantification level adapted to the task
3.6
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 [iv]]
3.7
keeper
high boiling point solvent added to the sampling standard solution
3.8
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 limit of detection, 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.
[prEN ISO 9169:2004, definition 3.2.6 [v]]
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 European Standard the limit of detection should preferably be calculated from the analytical blank b .
ave
If this is not possible, the limit of detection can be calculated from the signal to noise ratio according to 8.1.
8
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SIST EN 1948-3:2006
EN 1948-3:2006 (E)
3.9
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 European Standard the limit of quantification should preferably be calculated from the analytical blank
b . If this is not possible, the limit of quantification can be calculated from the signal to noise ratio according to 8.1 using
ave
the requirement of Clause 8.3e.
3.10
pattern
defined as a chromatographic print of any series of PCDD/PCDF isomers
3.11
PCDD/PCDF isomers
PCDDs or PCDFs with identical chemical composition but different structure
3.12
profile
graphic representation of the sums of the isomer concentrations of the PCDDs and the PCDFs
3.13
recovery standard
13
C -labelled 2,3,7,8-chlorine substituted PCDD, added before injection into the GC
12
3.14
sampling standard
13
C -labelled 2,3,7,8-chlorine substituted PCDF, added before sampling
12
3.15
spiking
13
addition of C -labelled PCDD/PCDF standards
12
3.16
WHO-TEF
toxic equivalent factor proposed by WHO [iii] (for detailed description see EN 1948-1:2006, Annex A)
3.17
WHO-TEQ
toxic equivalent obtained by multiplying the mass determined with the corresponding WHO-TEF including
PCDDs, PCDFs, and PCBs (for detailed description see EN 1948-1:2006, Annex A)
NOTE WHO-TEQ , WHO-TEQ should be used to distinguish different compound classes.
PCB PCDD/PCDF
9
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SIST EN 1948-3:2006
EN 1948-3:2006 (E)
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 obtained by weighting the mass determined with the corresponding I-TEF (for
detailed description, see Annex A of EN 1948-1:2006)
LOD
limit of detection
LOQ
limit of quantification
PCB
polychlorinated biphenyl
PCDD/PCDF
polychlorinated dibenzo-p-dioxin/dibenzofuran
PTFE
polytetrafluoroethylene
WHO-TEF
toxic equivalent factor of the World Health Organisation
WHO-TEQ
toxic equivalent of the World Health Organisation
4.2 Congeners of PCDD/PCDF
TCDD
Tetrachlorodibenzo-p-dioxin
PeCDD
Pentachlorodibenzo-p-dioxin
HxCDD
Hexachlorodibenzo-p-dioxin
HpCDD
Heptachlorodibenzo-p-dioxin
OCDD
Octachlorodibenzo-p-dioxin
TCDF
Tetrachlorodibenzofuran
10
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SIST EN 1948-3:2006
EN 1948-3:2006 (E)
PeCDF
Pentachlorodibenzofuran
HxCDF
Hexachlorodibenzofuran
HpCDF
Heptachlorodibenzofuran
OCDF
Octachlorodibenzofuran
5 Principles of identification and quantification
This European Standard is based on the use of the gas chromatography/mass spectrometry combined with
the isotope dilution technique to enable the separation, detection and quantification of PCDD/PCDF in the
extracts of emission samples. These extracts are prepared in accordance with EN 1948-2 and contain the two
recovery standards. The gas chromatographic parameters offer information which enables the identification of
isomers (position of Cl substituents) whereas the mass spectrometric parameters enable the differentiation
between congeners with different numbers of chlorine substituents and between
dibenzo-p-dioxins and furans.
6 Reagents, materials and equipment
See examples of operation in Annex A.
7 Safety measures
All relevant national safety regulations shall be observed. The 2,3,7,8-chlorine substituted PCDDs/PCDFs are
among the most toxic of chemicals. All work with PCDDs/PCDFs requires therefore the utmost care; the
national safety measures which correspond to those for toxic substances shall be strictly adhered to.
8 Quality control requirements for identification and quantification
8.1 Minimum requirements for identification of PCDF/PCDD congeners
High resolution gas chromatography/high resolution mass spectrometry at a resolution of greater or equal to
10 000 is at present required to achieve adequate sensitivity, selectivity and to allow the use of all the
13
C -labelled standards.
12
For each 2,3,7,8-chlorine substituted congener at least two ions of the molecular isotope cluster shall be
13
recorded for both the native and the added C -labelled congeners (see Annex C). A positive identification of
12
a congener is made if all the following requirements are met:
a) the isotope ratio between the ions monitored shall match the theoretical value within ± 20 % (see
Annex D);
b) the retention time of a native 2,3,7,8-chlorine substituted isomer (Cl -Cl -congeners) shall be within a time
4 6
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window of +3 s to 0 s based on the retention time of the corresponding C -labelled isomer in the
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sample. Alternatively, relative retention times based on 1,2,3,7,8-PeCDF can be calculated. The
difference shall not be more than 0,25 % compared with the calibration standard.
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SIST EN 1948-3:2006
EN 1948-3:2006 (E)
c) The signal-to-noise ratio of the raw data as documented in Figure 1 shall be at least 3 : 1 for the native
signal used for identification.
The base line noise shall be measured in front of the signal of the native congener within a signal-free window
corresponding to 10 times the signal width at half height. Peak-to-peak values are taken.
Key
S signal height
N peak-to-peak-noise
W 10 × signal width at half height
Figure 1 — Determination of the signal-to-noise ratio
8.2 Isomer sums of PCDD/PCDF congeners
If the sum of the concentrations of isomer groups are needed the following requirements shall be met:
a) The retention time window for all isomers of an isomer group shall be measured by a solution containing
all native PCDDs/PCDFs. A fly ash extract can be used for this purpose. Each group of isomer (tetra to
octa) should be defined via relative retention times (of the central isomer first). The pattern of overlapping
windows (tetra/penta) should be "constant" during one series of measurements; the changes in the
relative retention times shall not be greater than ± 10 %.
b) The retention times of all congeners attributed to an isomer group shall be within the time window of the
first and last eluting isomer.
8.3 Minimum requirements for quantification
In addition to the requirements for identification, the following points shall be fulfilled as quantification
requirements:
a) At present, there is no chromatographic column available that is able to separate all 2,3,7,8-chlorine
substituted congeners from all other, non-2,3,7,8-chlorine substituted congeners. Complete separation
can be achieved by multi-analysis of the sample on different columns of different nature (polarity). Single
column data may therefore be reported by this method, however in cases where a regulatory emission
limit value is exceeded, a confirmatory analysis should be performed on a second column.
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EN 1948-3:2006 (E)
b) The peak shape of the gas chromatographic signal of a congener shall contain ten or more sampling
points (scanning units).
c) 2,3,7,8-TCDD shall be separated from all other interfering isomers within a 25 % valley below the top of
the minor peak with respect to the height of that peak.
d) The recovery rate of each individual 2,3,7,8-chlorine substituted PCDD/PCDF of the extraction standards
in each sample shall be within:
1) 50 % to 130 % for the tetra- to hexa-chlorinated congeners;
2) 40 % to 130 % for the hepta- and octa-chlorinated congeners.
If the above ranges are exceeded, then provided the sum of the contributions to the total I-TEQ in the
sample from all the congeners with recoveries not within these ranges does not exceed 10 %, the
acceptable ranges shall be:
3) 30 % to 150 % for the tetra- to hexa-chlorinated congeners;
4) 20 % to 150 % for the hepta- and octa-chlorinated congeners.
e) For quantification the signal-to-noise ratio of the native congeners shall be 10 : 1. The signal-to-noise
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ratio of the C -labelled congeners used for quantification shall be > 20 : 1.
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f) The measuring range shall be linear (at least over a concentration range of a factor of a 100). The
standard deviation of the relative response factor shall not exceed 15 % and shall be based on a
minimum of five measuring points over the whole range.
g) An analytical blank shall be taken. The blank of all 2,3,7,8-chlorine substituted congeners shall be equal
or less than the detec
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