SIST EN 1948-4:2011
(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 of about 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 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.
As a result of their similar chemical behaviour PCBs, as shown in the validation campaign, can be sampled from stationary sources together with the PCDDs/PCDFs. 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
1 Anwendungsbereich
Diese Europäische Norm 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 12 non- und mono-ortho und von der WHO ausgewiesenen PCB anwendbar. Es ist für die Messung von PCB Konzentrationen von etwa 0,01 ng WHO TEQPCB/m3 optimiert.
Zusätzlich zu den 12 non- und mono ortho PCB ist das vorliegende Dokument auch für die Messung weiterer PCB-Kongenere anwendbar, wie die „Indikator PCB“ 28, 52, 101, 138, 153, 180 (siehe Anhang F).
Dieses Dokument legt für jedes zum Einsatz kommende Verfahren zur Probenahme, Extraktion, Reinigung, Identifizierung und Quantifizierung von PCB einen Rahmen für die Anforderungen an die Qualitätssicherung fest.
Wie in der Validierungsmesskampagne gezeigt wurde, können PCB aufgrund ihres ähnlichen chemischen Verhaltens zusammen mit PCDD/PCDF aus stationären Quellen gesammelt werden. Daher ist es möglich, PCB zusammen mit PCDD/PCDF zu messen, indem EN 1948-1, -2, -3 und -4 angewendet werden. 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.
Die Analyse der folgenden PCB-Kongenere wird in dieser Europäischen Norm beschrieben und wurde in der Validierungsmesskampagne validiert:
a) Non-ortho substituierte PCB
1) 3,3’,4,4’-TeCB (77)
2) 3,4,4’,5-TeCB (81)
3) 3,3’,4,4’,5-PeCB (126)
4) 3,3’,4,4’,5,5’-HxCB (169)
b) Mono-ortho substituierte PCB
1) 2,3,3’,4,4’-PeCB (105)
2) 2,3,4,4’,5-PeCB (114)
3) 2,3’,4,4’,5-PeCB (118)
4) 2’,3,4,4’,5-PeCB (123)
Émissions de sources fixes - Détermination de la concentration massique en PCDD/PCDF et PCB de type dioxine - Partie 4: Prélèvement et analyse des PCB de type dioxine
Le présent document spécifie les modes opératoires de prélèvement à partir de sources fixes, d’extraction, de purification, d’identification et de quantification des PCB de type dioxine. Le mode opératoire décrit pose les exigences pour mesurer les congénères des PCB données à l’Annexe A (voir le Tableau A.1). Il est applicable aux 12 PCB non-ortho et mono-ortho désignés par l'OMS. Il est optimisé pour mesurer des concentrations de PCB d'environ 0,01 ng de OMS-TEQPCB/m3.
En plus des 12 PCB non-ortho et mono-ortho, le présent document est également applicable pour mesurer d'autres congénères de PCB comme le « marqueur de PCB » 28, 52, 101, 138, 153, 180 (voir l’Annexe F).
Le présent document spécifie un cadre d'exigences de contrôle qualité qui doivent être satisfaites par toute méthode appliquée de prélèvement, d'extraction, de purification, d’identification et de quantification de PCB.
En raison de leur comportement chimique similaire, les PCB, comme présenté dans la campagne de validation, peuvent être prélevés sur des sources fixes en même temps que les PCDD/PCDF. Le mode opératoire de prélèvement complet est décrit dans l’EN 1948-1. Chacune des trois méthodes de prélèvement spécifiées dans l’EN 1948-1 peut être combinée aux méthodes décrites dans le présent document pour compléter le mode opératoire de mesurage. L’EN 1948-1 fait partie intégrante du mode opératoire de mesurage complet et est nécessaire pour la détermination des PCB.
De plus, il est possible de mesurer les PCB en même temps que les PCDD/PCDF en appliquant les parties 1, 2, 3 de l’EN 1948 et la partie 4 du CEN/TS 1948.
Emisije nepremičnih virov - Določevanje masne koncentracije PCDD/PCDF in dioksinom podobnih PCB - 4. del: Vzorčenje in analiza dioksinom podobnih PCB
Ta dokument določa vzorčenje iz nepremičnih virov, ekstrakcijo, čiščenje, identifikacijo in kvantifikacijo dioksinom podobnih PCB. Opisani postopek določa zahteve za merjenje sorodnih vrst PCB, navedenih v dodatku A (glej preglednico A.1). Velja za dvanajst neorto in monoorto PCB, ki jih je določila SZO. Optimizirana je za merjenje koncentracij PCB okrog 0,01 ng WHO-TEQPCB/m3.
Poleg 12 neorto in monoorto PCB ta dokument velja tudi za merjenje nadaljnjih sorodnih vrst PCB, kot so označevalci PCB 28, 52, 101, 138, 153, 180 (glej dodatek D).
Ta dokument določa okvir za zahteve nadzora kakovosti, ki morajo biti izpolnjene pri vseh uporabljenih metodah vzorčenja, ekstrakcije, čiščenja, identifikacije in kvantifikacije PCB.
Zaradi podobnih kemijskih lastnosti se PCB, kot je prikazano v validaciji, lahko vzorčijo iz nepremičnih virov skupaj s PCDD/PCDF. Celoten postopek vzorčenja je opisan v EN 1948-1. Vsaka od treh metod vzorčenja iz EN 1948-1 se lahko kombinira z metodami, opisanimi v tem dokumentu, da dopolni postopek merjenja. EN 1948-1 je sestavni del celotnega postopka merjenja in je potreben za določevanje PCB.
Poleg tega je PCB skupaj s PCDDs/PCDF mogoče meriti z uporabo 1. dela, 2. dela in 3. dela EN 1948 ter 4. dela CEN/TS 1948.
General Information
Relations
Standards Content (Sample)
2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.Emissionen aus stationären Quellen - Bestimmung der Massenkonzentration von PCDD/PCDF und dioxin-ähnlichen PCB - Teil 4: Probenahme und Analyse dioxin-ähnlicher PCBÉmissions de sources fixes - Détermination de la concentration massique en PCDD/PCDF et PCB de type dioxine - Partie 4: Prélèvement et analyse des PCB de type dioxineStationary source emissions - Determination of the mass concentration of PCDDs/PCDFs and dioxin-like PCBs - Part 4: Sampling and analysis of dioxin-like PCBs13.040.40Stationary source emissionsICS:Ta slovenski standard je istoveten z:EN 1948-4:2010SIST EN 1948-4:2011en,fr,de01-december-2011SIST EN 1948-4:2011SLOVENSKI
STANDARDSIST-TS CEN/TS 1948-4:20081DGRPHãþD
SIST EN 1948-4:2011
EUROPEAN STANDARD NORME EUROPÉENNE EUROPÄISCHE NORM
EN 1948-4
October 2010 ICS 13.040.40 Supersedes CEN/TS 1948-4:2007English 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
Émissions de sources fixes - Détermination de la concentration massique en PCDD/PCDF et PCB de type dioxine - Partie 4: Prélèvement et analyse des PCB de type dioxine
Emissionen aus stationären Quellen - Bestimmung der Massenkonzentration von PCDD/PCDF und dioxin-ähnlichen PCB - Teil 4: Probenahme und Analyse dioxin-ähnlicher PCB This European Standard was approved by CEN on 28 August 2010.
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 CEN Management Centre 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 CEN Management Centre has the same status as the official versions.
CEN members are the national standards bodies of Austria, Belgium, Bulgaria, Croatia, 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:
Avenue Marnix 17,
B-1000 Brussels © 2010 CEN All rights of exploitation in any form and by any means reserved worldwide for CEN national Members. Ref. No. EN 1948-4:2010: ESIST EN 1948-4:2011
EN 1948-4:2010 (E) 2 Contents Page Foreword .4Introduction .51Scope .62Normative references .73Terms and definitions .74Symbols and abbreviations . 104.1General . 104.2Polychlorinated biphenyls . 105Principle of the measurement procedure . 116Device, materials and 13C12-labelled standards . 126.1Device and materials . 126.213C12-labelled standards . 127Safety measures . 138Measurement procedure . 138.1Sampling . 138.2Extraction . 138.3Clean-up . 148.4Final concentration of the sample extracts . 148.5Addition of recovery standards . 158.6Principle of identification and quantification . 158.7Calibration of the HRGC/HRMS . 158.8Quantification of HRGC/HRMS results . 178.8.1Quantification of the sample . 178.8.2Calculation of the recovery rates of the extraction standards . 188.8.3Calculation of the recovery rates of the sampling standards . 198.9Calculation of the measurement results . 198.10Analytical report. 209Method validation . 219.1General . 219.2Validation of sampling . 219.3Validation of Analytical Extraction and Clean-up . 229.3.1Extraction . 229.3.2Clean-up . 2210Quality control requirements for the measurement . 2210.1Use of a validated method . 2210.2Use of 13C12-labelled standards . 2210.3Minimum requirements for sampling. 2310.4Minimum requirements for extraction and clean-up . 2310.5Minimum requirements for identification of PCB congeners . 2410.6Minimum requirements for quantification . 2511Quality assurance criteria for extraction/clean-up/quantification procedure blanks . 2511.1Analytical blank. 2511.2If the analytical blank values exceed the values mentioned above, the laboratory specific quantification limit has to be adopted (increased) correspondingly. HRGC/HRMS blank . 2612Performance characteristics . 26SIST EN 1948-4:2011
EN 1948-4:2010 (E) 3 12.1General . 2612.2Results of the validation campaign . 2713Interferences (informative) . 28Annex A (informative)
Toxicity and toxic equivalency . 29Annex B (informative)
Examples of extraction and clean-up procedures . 30Annex C (informative)
Evaluation of the performance characteristics . 41Annex D (informative)
Recommendations for measuring high concentrations of
dioxin-like PCBs . 48Annex E (informative)
Possible interferences in dioxin-like PCB analysis . 49Annex F (informative)
Measurement of the marker PCBs 28, 52, 101, 138, 153, and 180 in addition to the 12 dioxin-like PCBs . 52Annex G (informative)
Measurement of hexachlorobenzene (HCB) . 55Annex H (informative)
Significant technical changes . 56Annex ZA (informative)
Relationship between this European Standard and the essential requirements of EU Directives . 57Bibliography . 58 SIST EN 1948-4:2011
EN 1948-4:2010 (E) 4 Foreword This document (EN 1948-4:2010) 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 April 2011, and conflicting national standards shall be withdrawn at the latest by April 2011. 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 document supersedes CEN/TS 1948-4:2007. Annex H provides details of significant technical changes between this European Standard and the previous document CEN/TS 1948-4:2007 This document has been prepared under a mandate given to CEN by the European Commission and the European Free Trade Association, and supports essential requirements of EU Directive. For relationship with EU Directive(s), see informative Annex ZA, which is an integral part of this document. EN 1948 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
The first three parts are necessary for the performance of the PCDD/PCDF measurements. In addition this document EN 1948-4 describes the sampling, extraction and analyses of dioxin-like PCBs and requires references to EN 1948-1, -2, -3. The precision and the performance characteristics of the measurement of PCBs were determined between 2006 and 2008 in a comparison and validation trial at both a waste incinerator and a shredder plant sponsored by the European Commission and the European Free Trade Association. The basic requirements of the determination of PCBs were first published as CEN/TS 1948-4, which served as a basis for these mandated validation measurements. This document EN 1948-4 additionally includes important guidance for sampling and analysis over a broad concentration range gained during the mandated validation measurements. According to the CEN/CENELEC Internal Regulations, the national standards organizations of the following countries are bound to implement this European Standard: Austria, Belgium, Bulgaria, Croatia, 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.
SIST EN 1948-4:2011
EN 1948-4:2010 (E) 5 Introduction Polychlorinated biphenyls (PCBs) are a group of chlorinated aromatic compounds similar in structure to polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) which consist of 209 individual substances (see Figure 1 for the basic structure). PCBs have been produced intentionally 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. Worldwide, more than one million tons of PCBs were produced. PCBs as well as PCDD/PCDF are emitted from thermal and other processes. PCB can contribute 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 12 PCBs, known as dioxin-like PCBs [9, 10] (see Annex A). These 12 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. In the meanwhile these toxicity equivalent factors were revised (see Annex A). This document deals with the determination of these dioxin-like PCBs in emissions from stationary sources. Additionally informative annexes are provided, describing the analyses of the marker PCBs and hexachlorobenzene (HCB) in the same sample (Annex F and Annex G). Only skilled operators who are trained in handling highly toxic compounds should apply this document.
Figure 1 —Structure of PCB SIST EN 1948-4:2011
EN 1948-4:2010 (E) 6 1 Scope This European Standard 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 12 non- and mono-ortho PCB designated by the WHO. It is optimised to measure PCB concentrations of about 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 "marker PCB" 28, 52, 101, 138, 153, 180 (see Annex F). This document specifies a framework of quality control requirements for any PCB sampling, extraction, clean-up, identification and quantification methods to be applied.
As a result of their similar chemical behaviour PCBs, as shown in the validation campaign, can be sampled from stationary sources together with the PCDDs/PCDFs. Therefore, it is possible to measure PCBs together with PCDDs/PCDFs by applying EN 1948-1, -2, -3 and -4. The complete sampling procedure is described in 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.
The analyses of the following PCB congeners is described in this European Standard and is validated in the validation campaign: a) Non-ortho substituted PCBs 1) 3,3’,4,4’-TeCB(77) 2) 3,4,4’,5-TeCB (81) 3) 3,3’,4,4’,5-PeCB (126) 4) 3,3’,4,4’,5,5’-HxCB (169) b) Mono-ortho substituted PCBs 1) 2,3,3’,4,4’-PeCB (105) 2) 2,3,4,4’,5-PeCB (114) 3) 2,3’,4,4’,5-PeCB (118) 4) 2’,3,4,4’,5-PeCB (123) 5) 2,3,3’,4,4’,5-HxCB (156) 6) 2,3,3’,4,4’,5’-HxCB (157) 7) 2,3’,4,4’,5,5’-HxCB (167) 8) 2,3,3’,4,4’,5,5’-HpCB (189) c) Marker PCBs 1) 2,4,4'- TriCB (28) SIST EN 1948-4:2011
EN 1948-4:2010 (E) 7 2) 2,2',5,5'-TeCB (52) 3) 2,2',4,5,5'- PeCB (101) 4) 2,2',3,4,4',5'- HxCB (138) 5) 2,2',4,4',5,5'- HxCB (153) 6) 2,2',3,4,4',5,5'- HpCB (180) 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 13284-1:2001, 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 any one of the 209 individual PCBs 3.3 dioxin-like PCB WHO-PCB non- and mono-ortho PCB with an affinity to the Ah-receptor, showing similar toxic effects as the 2,3,7,8-substituted PCDDs/PCDFs according to WHO [9] 3.4 extraction standard quantification standard 13C12-labelled PCBs, added before extraction and used for calculating results SIST EN 1948-4:2011
EN 1948-4:2010 (E) 8 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 suitable for the task 3.6 I-TEF international toxic equivalent factor defined by NATO/CCMS in 1988 [11] NOTE 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
NOTE 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, 3.5]
3.9 keeper solvent of high boiling point added to the sample in order to avoid evaporation losses 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. [Adapted from EN ISO 9169:2006, 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 (bave) plus three times the standard deviation of the analytical blank (sb). bavesbLOD3+= (1) where
LOD is the detection limit;
bave is the mean analytical blank value;
sb is standard deviation of the analytical blank. NOTE 3 In this document the limit of detection should preferably be calculated from the analytical blank bave. If this is 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. 10.5 of this document). SIST EN 1948-4:2011
EN 1948-4:2010 (E) 9 3.11 limit of quantification
LOQ
limit above which a quantification of the measurand is possible, expressed as the mean analytical blank value plus five to ten times the standard deviation of the analytical blank
NOTE 1 The factor F depends on the accepted measurement uncertainty.
bavesFbLOQ+= (2) where
LOQ is the quantification limit;
bave is the mean analytical blank value;
sb is standard deviation of the analytical blank. NOTE 2 In this document the limit of quantification should preferably be calculated from the analytical blank bave. If this 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 or see 10.5 of this document using the requirement of 8.3, e) of EN 1948-3:2006 or 10.6, d) of this document. NOTE 3 In practice, the Factor F = 10 corresponds to a reasonable measurement uncertainty of approximately 20 %. 3.12 marker PCBs the six PCBs: 28, 52, 101, 138, 153, 180 3.13 PCB isomers PCBs with identical chemical composition but different structure 3.14 recovery standard 13C12-labelled PCBs, added before injection into the GC 3.15 sampling standard 13C12-labelled PCBs, added before sampling 3.16 spiking addition of 13C12-labelled PCB standards 3.17 WHO-TEF toxic equivalent factor first proposed by WHO in 1997 [9; 10] NOTE For detailed description, see Annex A. 3.18 WHO-TEQ toxic equivalent obtained by multiplying the mass determined with the corresponding WHO-TEF including PCDDs, PCDFs and PCBs
NOTE 1 For detailed description, see Annex A.
SIST EN 1948-4:2011
EN 1948-4:2010 (E) 10 NOTE 2 WHO-TEQPCB, WHO-TEQPCDD/PCDF and WHO-TEQPCDD/PCDF/PCB should be used to distinguish different compound classes. In this document WHO-TEQPCDD/PCDF/PCB is also defined as Total WHO-TEQ. 4 Symbols and abbreviations 4.1 General GC gas chromatography HCB hexachlorobenzene 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 SIST EN 1948-4:2011
EN 1948-4:2010 (E) 11 TeCB Tetrachlorobiphenyl PeCB Pentachlorobiphenyl HxCB Hexachlorobiphenyl HpCB Heptachlorobiphenyl 5 Principle of the measurement procedure Gas is sampled in the duct or stack according to the methods described in EN 1948-1 taking into account the requirements of isokinetic sampling according to EN 13284-1. 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. 13C12-labelled PCB congeners are added at different stages of the whole method (before sampling, extraction and HRGC/HRMS-measurement). Spiking with 13C12-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 E). 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 12 dioxin-like PCB congeners and marker PCB congeners by either retention time and/or mass.
SIST EN 1948-4:2011
EN 1948-4:2010 (E) 12 6 Device, materials and 13C12-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. The reagents shall be of high purity to meet the criteria of blank analysis to have a low PCB and PCDD/PCDF background concentration. 6.2 13C12-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 before extraction. These 13C12-labelled congeners behave in the same way as 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 injection to measure the recovery rates of the extraction standards. Table 1 shows a selection of available 13C12-labelled PCBs suitable as recovery standards. At least one shall be added for each dioxin-like PCB containing fraction. The quantities of the 13C12-labelled congeners to be added per sample for sampling at a PCB concentration level of 0,01 ng WHO-TEQPCB/m³ and 10 m³ sampling volume (dry gas) are given in Table 1. If a considerably higher mass of native PCBs is expected in the sample, the masses of the 13C12-labelled standards to be added shall be enhanced accordingly taking into account the calibration range.
Table 1 — 13C12-labelled PCBs congeners to be added to the sample at different stages of the procedure for measurement of about 0,01 ng WHO-TEQPCB/m3 assuming 10 m³ of sampling volume.
Solution:
Total volume in microlitres: (e.g. toluene, n-nonane) Sampling sampling standard
100 Extraction extraction standard
100 GC Injection recovery standard a
at least 10
Congeners added Total amount in picograms added before: 13C12-2,3,4,4'-TeCB (60) 1 000
13C12-3,3’,4,5,5’-PeCB (127) b 1 000
13C12-2,3,3',4,5,5'-HxCB (159) 1 000
13C12-3,3’,4,4’-TeCB (77)
1 000
13C12-3,4,4’,5-TeCB (81)
1 000
13C12-2,3,3’,4,4’-PeCB (105) b
1 000
13C12-2,3,4,4’,5-PeCB (114)
1 000
13C12-2,3’,4,4’,5-PeCB (118)
1 000
13C12-2’,3,4,4’,5-PeCB (123)
1 000
13C12-3,3’,4,4’,5-PeCB (126)
1 000
13C12-2,3,3’,4,4’,5-HxCB (156)
1 000
13C12-2,3,3’,4,4’,5’-HxCB (157)
1 000
13C12-2,3’,4,4’,5,5’-HxCB (167)
1 000
13C12-3,3’,4,4’,5,5’-HxCB (169)
1 000
13C12-2,3,3’,4,4’,5,5’-HpCB (189)
1 000
SIST EN 1948-4:2011
EN 1948-4:2010 (E) 13
Solution:
Total volume in microlitres: (e.g. toluene, n-nonane) Sampling sampling standard
100 Extraction extraction standard
100 GC Injection recovery standard a
at least 10
Congeners added Total amount in picograms added before: 13C12-2,3’,4’,5-TeCB (70)
1 000 13C12-2,3,3’,5,5’-PeCB (111)
1 000 13C12-2,2’,3,3’,4,4’,5-HpCB (170)
1 000 a Recovery standards: Table 1 shows a selection of available 13C 12-labelled PCBs suitable as recovery standards. At least one shall be added for each dioxin-like PCB containing fraction.
b Sampling Standards: Attention should be paid to
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