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 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 which should 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. 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
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
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
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
Figure 1 —Structure of PCB SIST EN 1948-4:2011+A1:2014
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
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
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
1 000
13C12-2,3,3’,4,4’,5,5’-HpCB (189)
1 000
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 possible co-elution problems of PCB 127 and PCB 105 on certain commercially available columns. If the co-elution problems cannot be avoided, the sampling standard PCB 127 may be omitted. 7 Safety measures All relevant national safety regulations shall be observed. The dioxin-like PCBs as well as the 2,3,7,8-chlorine substituted PCDDs/PCDFs, which can usually be present in emission samples together with PCBs, are amongst the most toxic chemicals. All work with PCBs and PCDDs/PCDFs therefore requires the utmost care; the national safety measures which correspond to those for toxic substances shall be strictly adhered to. 8 Measurement procedure 8.1 Sampling The sampling and storage shall be performed according to EN 1948-1. The sampling train is spiked with 13C12-labelled PCBs (see Table 1) as described for PCDD/PCDF in EN 1948-1. For sample storage the use of screw caps with aluminium-lined seals is recommended to avoid losses. Alternatively the use of non-greased glass ground necks is recommended. If using plastic sealings, losses have to be expected due to adsorption on the sealing materials. 8.2 Extraction Before extraction the extraction standards shall be added to the sample following EN 1948-2. Pre-treatment of all sampled particles with hydrochloric acid shall be part of any extraction procedure (examples of procedures are given in Annex A of EN 1948-2:2006, see also [13]). The extraction procedure is carried out using the following materials and techniques. Detailed descriptions of some procedures are given in Annex A of EN 1948-2:2006. Other methods can also be used but shall be of proven equal performance to the techniques below: SIST EN 1948-4:2011+A1:2014
Native “dioxin-like” PCBs 77, 81, 105, 114, 123, 126, 156, 157, 167, 169, 189 0,1 1 10 50 200 800 118 0,6 6 60 300 1 200 4 800 Labelled “dioxin-like” PCBs (extraction standards) 77, 81, 105, 114, 118, 123, 126, 156, 157, 167, 169, 189 10 10 10 10 10 10 Labelled PCBs (sampling standards) 60, 127, 159 10 10 10 10 10 10 Labelled PCBs (recovery standards) 70, 111, 170 10 10 10 10 10 10 Calibration frequency depends on the stability of the instrument. Daily calibration checks shall be run with at least one of the standard solutions of Table 2. If the deviation of a single injected calibration standard exceeds 20 % a full five point calibration shall be carried out. This deviation is calculated as the average of the absolute values of the deviation of the relative response factors of the 12 PCBs. A full five point calibration shall also be performed, if the deviation for PCB 126 exceeds 20 %. In addition, a full five point calibration shall be repeated after major changes such as: a) use of new or repaired equipment; b) replacement of GC columns; c) after ion source cleaning. The relative response factors are used together with the 13C12-labelled congeners, added to the sample to quantify the mass of the native PCBs by the isotope dilution method. SIST EN 1948-4:2011+A1:2014
Figure 2 — HRGC/HRMS calibration curve of the mass ratio CCiiQQ1312versus response ratio CCiiAA1312 SIST EN 1948-
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