SIST EN 1948-4:2011+A1:2014
(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 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 WHOTEQPCB/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, cleanup, 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)
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)
Emissionen aus stationären Quellen - Bestimmung der Massenkonzentration von PCDD/PCDF und dioxin-ähnlichen PCB - Teil 4: Probenahme und Analyse dioxin-ähnlicher PCB
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)
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)
EN 1948-4:2010+A1:2013 (D)
7
c) Indikator-PCB
1) 2,4,4’-TriCB (28)
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)
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
La présente Norme européenne 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 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 d’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 Annexe F).
Le présent document spécifie un cadre d'exigences de contrôle qualité pour 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. Par conséquent, il est possible de mesurer les PCB en même temps que les PCDD/PCDF en appliquant les modes opératoires de l’EN 1948-1, de l’EN 1948-2, de l’EN 1948-3 et de l’EN 1948-4. 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.
L’analyse des congénères suivants des PCB est décrite dans la présente Norme européenne et a été validée lors d'une campagne de validation :
a) PCB non-ortho substitués
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) PCB mono-ortho substitués
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) Marqueurs de PCB
1) 2,4,4'- TriCB (28)
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)
Emisije nepremičnih virov - Določevanje masne koncentracije PCDD/PCDF in dioksinom podobnih PCB - 4. del: Vzorčenje in analiza dioksinom podobnih PCB (vključno z dopolnilom A1)
Ta evropski standard določa vzorčenје iz nepremičnih virov, ekstrakcijo, čiščenje, identifikacijo in postopke kvantifikacije dioksinom podobnih PCB. Opisani postopek določa zahteve za merjenje sorodnih vrst PCB, navedenih v Dodatku A (glejte tabelo A.1). Velja za 12 neorto in monoorto PCB, ki jih je določila SZO. Optimiziran je za merjenje koncentracij PCB okrog 0,01 ng WHOTEQPCB/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 (glejte 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. Zato je PCB mogoče meriti skupaj s PCDD/PCDF z uporabo standardov EN 1948-1, -2, -3 in -4. 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. V tem evropskem standardu je opisana analiza naslednjih sorodnih vrst PCB in potrjena v validaciji.
a) Neorto substituirani 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) Monoorto substituirani 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)
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) Označevalci PCB
1) 2,4,4'- TriCB (28)
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)
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 1948-4:2010+A1:2013SIST EN 1948-4:2011+A1:2014en,fr,de01-julij-2014SIST EN 1948-4:2011+A1:2014SLOVENSKI
STANDARDSIST EN 1948-4:20111DGRPHãþD
SIST EN 1948-4:2011+A1:2014
EUROPEAN STANDARD NORME EUROPÉENNE EUROPÄISCHE NORM
EN 1948-4:2010+A1
December 2013 ICS 13.040.40 Supersedes EN 1948-4:2010English 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 and includes Amendment 1 approved by CEN on 23 October 2013.
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-CENELEC 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-CENELEC 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, Former Yugoslav Republic of Macedonia, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland, Turkey and United Kingdom.
EUROPEAN COMMITTEE FOR STANDARDIZATION
COMITÉ EUROPÉEN DE NORMALISATION EUROPÄISCHES KOMITEE FÜR NORMUNG
CEN-CENELEC Management Centre:
Avenue Marnix 17,
B-1000 Brussels © 2013 CEN All rights of exploitation in any form and by any means reserved worldwide for CEN national Members. Ref. No. EN 1948-4:2010+A1:2013 ESIST EN 1948-4:2011+A1:2014
EN 1948-4:2010+A1:2013 (E) 2 Contents Page Foreword .4 Introduction .5 1 Scope .6 2 Normative references .7 3 Terms and definitions .7 4 Symbols and abbreviations . 10 4.1 General . 10 4.2 Polychlorinated biphenyls . 11 5 Principle of the measurement procedure . 11 6 Device, materials and 13C12-labelled standards . 12 6.1 Device and materials . 12 6.2 13C12-labelled standards . 12 7 Safety measures . 13 8 Measurement procedure . 13 8.1 Sampling . 13 8.2 Extraction . 13 8.3 Clean-up . 14 8.4 Final concentration of the sample extracts . 15 8.5 Addition of recovery standards . 15 8.6 Principle of identification and quantification . 15 8.7 Calibration of the HRGC/HRMS . 16 8.8 Quantification of HRGC/HRMS results . 18 8.8.1 Quantification of the sample . 18 8.8.2 Calculation of the recovery rates of the extraction standards . 18 8.8.3 Calculation of the recovery rates of the sampling standards . 19 8.9 Calculation of the measurement results . 20 8.10 Analytical report. 20 9 Method validation . 21 9.1 General . 21 9.2 Validation of sampling . 22 9.3 Validation of Analytical Extraction and Clean-up . 22 9.3.1 Extraction . 22 9.3.2 Clean-up . 22 10 Quality control requirements for the measurement . 22 10.1 Use of a validated method . 22 10.2 Use of 13C12-labelled standards . 23 10.3 Minimum requirements for sampling. 23 10.4 Minimum requirements for extraction and clean-up . 24 10.5 Minimum requirements for identification of PCB congeners . 24 10.6 Minimum requirements for quantification . 25 11 Quality assurance criteria for extraction/clean-up/quantification procedure blanks . 26 11.1 Analytical blank. 26 11.2 HRGC/HRMS blank . 26 SIST EN 1948-4:2011+A1:2014
EN 1948-4:2010+A1:2013 (E) 3 12 Performance characteristics . 27 12.1 General . 27 12.2 Results of the validation campaign . 27 13 Interferences (informative) . 28 Annex A (informative)
Toxicity and toxic equivalency . 30 Annex B (informative)
Examples of extraction and clean-up procedures . 32 B.1 Example for clean-up of PCB and the separation from PCDD/PCDFs . 32 B.1.1 General . 32 B.1.2 Chromatography column I . 34 B.1.3 Chromatography column II . 34 B.1.4 Additional clean-up I . 34 B.1.5 Additional clean-up II . 35 B.1.5.1 General . 35 B.1.5.2 Carbon Column . 35 B.1.5.3 Preparation . 35 B.1.6 Addition of the recovery standard . 35 B.1.7 HRGC/HRMS-analysis . 35 B.2 Description of extraction and clean-up procedures used in the validation campaign . 41 Annex C (informative)
Evaluation of the performance characteristics . 43 C.1 General . 43 C.2 Interlaboratory comparison study of the analytical method . 43 C.3 Accuracy. 44 C.4 Limits of detection (LOD) and limits of quantification (LOQ) . 46 C.5 Recovery. 48 C.6 Breakthrough . 49 Annex D (informative)
Recommendations for measuring high concentrations of
dioxin-like PCBs . 51 Annex E (informative)
Possible interferences in dioxin-like PCB analysis . 52 Annex F (informative)
Measurement of the marker PCBs 28, 52, 101, 138, 153, and 180 in addition to the 12 dioxin-like PCBs . 56 Annex G (informative)
Measurement of hexachlorobenzene (HCB) . 59 Annex H (informative)
Significant technical changes . 60 Annex ZA (informative)
Relationship between this European Standard and the essential requirements of EU Directives . 61 Bibliography . 62
SIST EN 1948-4:2011+A1:2014
EN 1948-4:2010+A1:2013 (E) 4 Foreword This document (EN 1948-4:2010+A1:2013) 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 June 2014, and conflicting national standards shall be withdrawn at the latest by June 2014. 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 includes Amendment 1 approved by CEN on 21 October 2013. This document supersedes EN 1948-4:2010. 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. The start and finish of text introduced or altered by amendment is indicated by tags . 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, Former Yugoslav Republic of Macedonia, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland, Turkey and the United Kingdom. SIST EN 1948-4:2011+A1:2014
EN 1948-4:2010+A1:2013 (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+A1:2014
EN 1948-4:2010+A1:2013 (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+A1:2014
EN 1948-4:2010+A1:2013 (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+A1:2014
EN 1948-4:2010+A1:2013 (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+A1:2014
EN 1948-4:2010+A1:2013 (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+A1:2014
EN 1948-4:2010+A1:2013 (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 SIST EN 1948-4:2011+A1:2014
EN 1948-4:2010+A1:2013 (E) 11 4.2 Polychlorinated biphenyls TriCB Trichlorobiphenyl 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+A1:2014
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