BS EN 1948-4:2010+A1:2013 BSI Standards Publication Stationary source emissions — Determination of the mass concentration of PCDDs/PCDFs and dioxin-like PCBs Part 4: Sampling and analysis of dioxin-like PCBs BS EN 1948-4:2010+A1:2013 BRITISH STANDARD National foreword This British Standard is the UK implementation of EN 1948-4:2010+A1:2013 It supersedes BS EN 1948-4:2010 which is withdrawn The start and finish of text introduced or altered by amendment is indicated in the text by tags Tags indicating changes to CEN text carry the number of the CEN amendment For example, text altered by CEN amendment A1 is indicated by The UK participation in its preparation was entrusted by Technical Committee EH/2, Air quality, to Subcommittee EH/2/1, Stationary source emission A list of organizations represented on this subcommittee can be obtained on request to its secretary This publication does not purport to include all the necessary provisions of a contract Users are responsible for its correct application © The British Standards Institution 2014 Published by BSI Standards Limited 2014 ISBN 978 580 81791 ICS 13.040.40 Compliance with a British Standard cannot confer immunity from legal obligations This British Standard was published under the authority of the Standards Policy and Strategy Committee on 30 April 2012 Amendments/corrigenda issued since publication Date Text affected Implementation of CEN amendment A1:2013 EUROPEAN STANDARD EN 1948-4:2010+A1 NORME EUROPÉENNE EUROPÄISCHE NORM December 2013 ICS 13.040.40 Supersedes EN 1948-4:2010 English Version Stationary source emissions - Determination of the mass concentration of PCDDs/PCDFs and dioxin-like PCBs - Part 4: Sampling and analysis of dioxin-like PCBs 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 dioxinähnlichen PCB - Teil 4: Probenahme und Analyse dioxinähnlicher PCB This European Standard was approved by CEN on 28 August 2010 and includes Amendment 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 E BS EN 1948-4:2010+A1:2013 EN 1948-4:2010+A1:2013 (E) Contents Page Foreword Introduction Scope Normative references Terms and definitions 4.1 4.2 Symbols and abbreviations 10 General 10 Polychlorinated biphenyls 11 Principle of the measurement procedure 11 6.1 6.2 Device, materials and C12-labelled standards 12 Device and materials 12 13 C12-labelled standards 12 Safety measures 13 8.1 8.2 8.3 8.4 8.5 8.6 8.7 8.8 8.8.1 8.8.2 8.8.3 8.9 8.10 Measurement procedure 13 Sampling 13 Extraction 13 Clean-up 14 Final concentration of the sample extracts 15 Addition of recovery standards 15 Principle of identification and quantification 15 Calibration of the HRGC/HRMS 16 Quantification of HRGC/HRMS results 18 Quantification of the sample 18 Calculation of the recovery rates of the extraction standards 18 Calculation of the recovery rates of the sampling standards 19 Calculation of the measurement results 20 Analytical report 20 9.1 9.2 9.3 9.3.1 9.3.2 Method validation 21 General 21 Validation of sampling 22 Validation of Analytical Extraction and Clean-up 22 Extraction 22 Clean-up 22 10 10.1 10.2 10.3 10.4 10.5 10.6 Quality control requirements for the measurement 22 Use of a validated method 22 13 Use of C12-labelled standards 23 Minimum requirements for sampling 23 Minimum requirements for extraction and clean-up 24 Minimum requirements for identification of PCB congeners 24 Minimum requirements for quantification 25 11 11.1 11.2 Quality assurance criteria for extraction/clean-up/quantification procedure blanks 26 Analytical blank 26 HRGC/HRMS blank 26 13 BS EN 1948-4:2010+A1:2013 EN 1948-4:2010+A1:2013 (E) 12 12.1 12.2 Performance characteristics 27 General 27 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 BS EN 1948-4:2010+A1:2013 EN 1948-4:2010+A1:2013 (E) 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 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 BS EN 1948-4:2010+A1:2013 EN 1948-4:2010+A1:2013 (E) 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 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 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 —Structure of PCB BS EN 1948-4:2010+A1:2013 EN 1948-4:2010+A1:2013 (E) 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 WHO3 TEQPCB/m 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) b) c) 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) 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) Marker PCBs 1) 2,4,4'- TriCB (28) BS EN 1948-4:2010+A1:2013 EN 1948-4:2010+A1:2013 (E) 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) 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 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, cleanup, 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 2,3,7,8substituted PCDDs/PCDFs according to WHO [9] 3.4 extraction standard quantification standard 13 C12-labelled PCBs, added before extraction and used for calculating results BS EN 1948-4:2010+A1:2013 EN 1948-4:2010+A1:2013 (E) 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 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 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) LOD = bave + sb (1) where LOD is the detection limit; bave is the mean analytical blank value; sb is standard deviation of the analytical blank NOTE 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) BS EN 1948-4:2010+A1:2013 EN 1948-4:2010+A1:2013 (E) Annex E (informative) Possible interferences in dioxin-like PCB analysis The following figures show examples of interferences that can occur as result of insufficient performance of the chromatography during the simultaneous measurement of PCDD/PCDF and PCB within one single fraction, e.g when using too short columns The mass chromatograms were received as an example under the following analytical conditions 9): Gas Chromatograph: HP 5890 Injector: Cooled Injection System (Gerstel), àl Column: HT-5, 25 m ì 0,2 mm, film thickness: 0,1 µm Carrier Gas: Helium Mass Spectrometer: VG AutoSpec Resolution: > 000 9) All trade names of products are examples of suitable products available commercially This information is given for the convenience of users of this European Standard and does not constitute an endorsement by CEN of these products 52 BS EN 1948-4:2010+A1:2013 EN 1948-4:2010+A1:2013 (E) Figure E.1 — Interference of TCDDs in the ion traces of PeCB and 13 C12-PeCB 53 BS EN 1948-4:2010+A1:2013 EN 1948-4:2010+A1:2013 (E) Figure E.2 — Interference of PeCDDs in the ion traces of HxCB and 54 13 C12-HxCB BS EN 1948-4:2010+A1:2013 EN 1948-4:2010+A1:2013 (E) Key X HxCB O HpCB Figure E.3 — Interference of HxCBs and HpCBs in the ion trace of PeCB 55 BS EN 1948-4:2010+A1:2013 EN 1948-4:2010+A1:2013 (E) Annex F (informative) Measurement of the marker PCBs 28, 52, 101, 138, 153, and 180 in addition to the 12 dioxin-like PCBs PCBs may have other toxic effects than through the Ah-receptor In consequence the Commission of the European Communities (COM 2001,593 final; 24.10.2001) recommends to monitor non-dioxin-like PCBs as well as dioxin-like PCBs The marker PCBs are a group of significant congeners used in some countries for estimating the total PCB concentrations 10) In most European countries the surveillance of PCB concentrations in air, food, feedstuff, soil and waste e.g is done by regulations based on a set of “marker PCB” and there are a lot of data for comparison In order to have further on the opportunity to compare with existing data it is necessary and useful to enlarge this document by the determination of the congeners PCB 28, 52, 101, 138, 153, and 180 Analysis of additional PCBs can be included after a corresponding method validation In case of the additional measurement of the “marker PCBs” this document can be used as described but with 13 an enlarged C12-labelled PCB congener set, which includes the marker PCB (see Table F.1 based on 13 Table with additional C12-labelled PCB congeners for the determination of the marker PCBs) Table F.1 13 shows a selection of available C 12-labelled PCBs suitable as recovery standards At least one shall be added for each dioxin-like PCB containing fraction An example for the clean-up of PCB and the separation from PCDD/PCDFs is described in B.1 Table F.2 shows the concentrations of the calibration solution for the concentration range of 0,01 ng 3 WHO-TEQPCB/m For the determination of significantly higher concentrations than 0,01 ng WHO-TEQPCB/m 13 the solution std and std should be used Table F.2 is based on Table with additional C12-labelled PCB congeners for the determination of the marker PCBs Further recommendations for the measurement of very high concentrations are given in Annex D NOTE If only the marker PCBs is to be analysed, it is also possible to use lower resolution than 10 000 if the absence of interferences is documented and the sensitivity is reached NOTE The results of the determination of the marker PCBs during the validation campaign are given in Table C.2 to Table C.6 10) In Germany a DIN-LAGA-method was established to estimate total PCB concentrations with the six significant congeners (PCB 28, 52, 101, 138, 153, 180) multiplied with a factor of five This method became standard in Germany and other countries for estimating the total PCB in air (indoor and ambient air), technical products, soil, sediments, plants, waste e.g (EN 12766-1:2000 [19], EN 12766-2:2001 [20], EN ISO 16000-12:2008 [21], VDI 2310 Part 32:1995-11 [22], VDI 2464 Part 1:2009-09 [23]) 56 BS EN 1948-4:2010+A1:2013 EN 1948-4:2010+A1:2013 (E) 13 Table F.1 — C12-labelled PCBs congeners to be added to the sample at different stages of the 3 procedure for measurement of about 0,01 ng WHO-TEQPCB/m (dioxin-like PCB) and of about µg/m (total PCB) assuming 10 m of sampling volume Solution: Sampling Extraction GC Injection Total volume in microlitres: sampling standard extraction standard recovery standard (e.g toluene, n-nonane) 100 100 at least 10 Congeners added 13 a Total amount in picograms added before: C12-2,3,4,4'-TeCB (60) 000 13 C12-3,3’,4,5,5’-PeCB (127) b 000 13 C12-2,3,3',4,5,5'-HxCB (159) 000 Marker PCBs 13 C12-2,4,4'- TriCB (28) 5000 13 C12-2,2',5,5'-TeCB (52) 5000 13 C12-2,2',4,5,5'- PeCB (101) 5000 13 C12-2,2',3,4,4',5'- HxCB (138) 5000 13 C12-2,2',4,4',5,5'- HxCB (153) 5000 13 C12-2,2',3,4,4',5,5'- HpCB (180) 5000 non-ortho PCBs 13 C12-3,3’,4,4’-TeCB (77) 000 13 C12-3,4,4’,5-TeCB (81) 000 13 C12-3,3’,4,4’,5-PeCB (126) 000 13 C12-3,3’,4,4’,5,5’-HxCB (169) 000 mono-ortho PCBs 13 C12-2,3,3’,4,4’-PeCB (105) 13 C12-2,3,4,4’,5-PeCB (114) 000 13 C12-2,3’,4,4’,5-PeCB (118) 000 13 C12-2’,3,4,4’,5-PeCB (123) 000 13 C12-2,3,3’,4,4’,5-HxCB (156) 000 13 C12-2,3,3’,4,4’,5’-HxCB (157) 000 13 C12-2,3’,4,4’,5,5’-HxCB (167) 000 13 C12-2,3,3’,4,4’,5,5’-HpCB (189) 000 13 C12-2,3’,4’,5-TeCB (70) 000 13 C12-2,3,3’,5,5’-PeCB (111) 000 13 C12-2,2’,3,3’,4,4’,5-HpCB (170) a b 000 000 13 Recovery standards: Table F.1 shows a selection of available C12-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 57 BS EN 1948-4:2010+A1:2013 EN 1948-4:2010+A1:2013 (E) Table F.2 — Concentrations of PCB congeners in calibration solutions including the marker PCB Solution concentrations (pg/µl) standard solution std standard solution std standard solution std standard solution std standard solution std 77, 81, 105, 114, 123, 126, 156, 157, 167, 169, 189 0,1 10 50 200 800 118 60 300 200 800 10 100 500 000 000 10 10 10 100 100 100 100 10 10 10 10 10 10 10 10 Congeners standard solution std IUPAC, PCB Native “dioxin-like” PCBs 0,6 Native “marker PCBs” 28, 52, 101, 138, 153, 180 Labelled “dioxin-like” PCBs (extraction standards) 77, 81, 105, 114, 118, 123, 126, 156, 157, 167, 169, 189 10 10 10 Labelled “marker PCBs” (extraction standards) 28, 52, 101, 138, 153, 180 100 100 Labelled PCBs (sampling standards) 60, 127, 159 10 10 Labelled PCBs (recovery standards) 70, 111, 170 58 10 10 BS EN 1948-4:2010+A1:2013 EN 1948-4:2010+A1:2013 (E) Annex G (informative) Measurement of hexachlorobenzene (HCB) Hexachlorobenzene was widely used as a pesticide until 1965 Currently hexachlorobenzene can be formed as a by-product during the manufacture of other chemicals (e.g solvents, pesticides) and consequently be released to the environment Because of its persistency and lipophilicity it bio-accumulates through the food chain It has been classified by the International Agency for Research on Cancer (IARC) as a Group B carcinogen (possible carcinogenic to humans) In case of the additional measurement of hexachlorobenzene this document can be used as described with an 13 addition of C6-labelled HCB standard solution Proposed addition: 100 ng of 13 C6-labelled HCB prior sample extraction HCB elutes on alumina and carbon clean up together with mono- and di-ortho PCBs Proposed final sample volume prior injection on GC-MS: 000 µl Table G.1 — Ion mass list for HCB HRMS analysis Native HCB Ion mass Relative abundance Labelled HCB Ion mass Relative abundance % 12 C6 35 Cl6 12 C6 35 Cl5 Cl1 C6 35 37 Cl4 Cl2 C6 35 37 Cl3 Cl3 C6 35 37 Cl2 Cl4 C6 35 37 Cl1 Cl5 C6 37 12 12 12 12 12 37 Cl6 % 281,812 52,15 13 C6 35 Cl6 283,809 100,00 13 C6 35 79,90 13 34,05 13 8,16 13 1,04 13 0,06 13 285,806 287,803 289,800 291,797 293,794 287,832 52,15 Cl5 Cl1 37 289,829 100,00 C6 35 37 Cl4 Cl2 291,826 79,90 C6 35 37 Cl3 Cl3 293,823 34,05 C6 35 37 Cl2 Cl4 295,820 8,16 C6 35 37 Cl1 Cl5 297,817 1,04 C6 37 Cl6 299,815 0,06 Depending on resolution there can be an interference of native HCB ((M+6; M+8) ion mass 287,803 7; 13 289,797 8) on the ion trace of C6 labelled HCB ((M, M+2) ion mass 287,832 7, 289,929 7) Table G.2 — Example of calibration solution concentration Solution concentration pg/µl Standard solution Native HCB 13 C6-labelled HCB Standard solution Standard solution Standard solution Standard solution Standard solution 20 100 400 000 000 100 100 100 100 100 100 Calibration should be carried out with at least five calibration solutions Only when the expected concentration of HCB is low, solution should be used instead of solution 59 BS EN 1948-4:2010+A1:2013 EN 1948-4:2010+A1:2013 (E) Annex H (informative) Significant technical changes The following significant technical changes with regard to CEN/TS 1948-4:2007 are performed: Clause/Annex Change Clause Clause Method validation is revised, the requirements are clarified and substantiated Clause 10 Clause 10 Quality control requirements for the measurement is revised, the requirements are clarified and substantiated Clause 12 Clause 12 Performance characteristics is all newly created based on the results of the validation measurement Annex B Annex B Examples of extraction and clean-up procedures complemented by the experiences of the validation measurements Annex C Annex C Evaluation oft he performance characteristics is all newly created based on the results of the validation measurement Annex D Annex D Recommendations for measuring high concentrations of dioxinlike PCB is all newly created based on the results of the validation measurement at the shredder plant Annex G Annex G Measurement of hexachlorobenzene (HCB) is all newly created based on the results of the validation measurement is NOTE: The technical changes referred include the significant technical changes from revision and transfer of TS to EN but is not a exhaustive list of all modifications from the previous version 60 BS EN 1948-4:2010+A1:2013 EN 1948-4:2010+A1:2013 (E) Annex ZA (informative) Relationship between this European Standard and the essential requirements of EU Directives This European Standard has been prepared under a mandate given to CEN by the European Commission and the European Free Trade Association and supports Essential Requirements of the following legal acts — Regulation (EC) No 850/2004 on persistent organic pollutants (POPs) includes PCBs as one of 16 substances or group of substances to be subject for prohibition and/or release reduction provisions — Regulation (EC) No 166/2006 concerning the establishment of a European Pollutant Release and Transfer Register includes PCBs as one of 91 parameters of which releases to air, water and land from industrial facilities have to be reported — Council Conclusions on the Dioxin Strategy (COM(2001) 593)) emphasizes that WHO has derived toxicity equivalency factors for dioxin-like PCBs and has stressed the importance of integrated standards for dioxins and dioxin-like PCBs Furthermore, this European Standard supports directly or indirectly Essential Requirements of the following Directives: — Directive 2000/76/EC of the European Parliament and of the Council of December 2000 on the incineration of waste — Directive 2008/1/EC of the European Parliament and of the Council of 15 January 2008 concerning integrated pollution prevention and control (Codified version) — Proposal for a Directive on industrial emissions [24] WARNING — Other requirements and other EU Directives may be applicable to the product(s) falling within the scope of this standard 61 BS EN 1948-4:2010+A1:2013 EN 1948-4:2010+A1:2013 (E) Bibliography [1] SCHRAMM K.-W., KLIMM C., HOFMAIER A., KETTRUP A Comparison of dioxin-like-response in vitro and chemical analysis of emissions and materials Chemosphere 2001, 42 pp 551–557 [2] Luthardt, P., J Mayer, J Fuchs: Total TEQ emission (PCDD/F and PCB) from industrial sources Chemosphere 46 (2002) pp.1303/1308 [3] ALCOCK R.E., BEHNISCH P.A., JONES K.C., HAGENMAIER H Dioxin-like PCBs in the environment – human exposure and the significance of sources Chemosphere 1998, 37 (8) pp 1457–1472 [4] Grochowalski, A., C Lassen, M Holtzer, M Sadowski, T Hudyma: Determination of PCDDs, PCDFs, PCBs and HCB Emissions from the Metallurgical Sector in Poland ESPR – Environ Sci & Pollut Res 2006 (OnlineFirst), pp 1-7 [5] ABAD E., MARTINEZ K., CAIXACH J., RIVERA J Polychlorinated dibenzo-p-dioxins, dibenzofurans, and “dioxin-like” PCBs in flue gas emissions from municipal waste management plant Chemosphere 2006, 63 pp 570–580 [6] SAKAI S.-S., HAYAKAWA K., TAKATSUKE H., KWAKAMI I Dioxin-like PCBs released from waste Incineration and their deposition flux Environ Sci Technol 2001, 35 pp 3601–3607 [7] SAKURAI T., W EBER R., UENO S., NISHINO J., TANAKA M Relevance of coplanar PCBs for TEQ emission of fluidized bed incineration and impact of emission control devices Chemosphere 2003, 53 pp 619– 625 [8] YOON-SEOK CHANG Seat-Byul Kong, Michael G Ikono: PCBs contributions to the total TEQ Release from Korean municipal and industrial waste incinerators Chemosphere 1999, 39 (15) pp 2629–2640 [9] VAN DEN [10] VAN DEN [11] NATO/CCMS (North Atlantic Treaty Organisation/Committee on the Challenge of Modern Society) International Toxicity Equivalence Factor (I-TEF) method of risk assessment for complex mixtures of dioxins and related compounds, 186, 1988 [12] EN ISO 9169:2006, Air quality - Definition and determination of performance characteristics of an automatic measuring system (ISO 9169:2006) [13] KOOKE R.M.M., LUSTENHOUWER J.W.A., OLIE K., HUTZINGER O Extraction Efficiencies of Polychlorinated Dibenzo-p-dioxins and Polychlorinated Dibenzofurans from fly ash Anal Chem 1981, 53 pp 461–463 [14] van Bavel, Bert: Field test experiments and validation for EN 1948-4; Standardisation mandate to CEN for standard measurement methods for the determination of dioxin-like PCBs from stationary sources; Final report, November 2008 ISBN 987-3-931384-66-1 [15] van Bavel, B et al.: Validation of Method EN 1948 Part 4: Determination of DL-PCB from stationary sources Organohalogen Compounds Vol 71 (2009) pp 2273–2277 (http://www.dioxin20xx.org/pdfs/2009/09-461.pdf) 62 BERG M et al Toxic Equivalency Factors (TEFs) for PCBs, PCDDs, PCDFs for humans and wildlife Environ Health Perspect 1998, ••• p 106 BERG M et al The 2005 World Health Organization Re-evaluation of Human and Mammalian Toxic Equivalency Factors for Dioxins and Dioxin-like Compounds Toxicol Sci 2006, 93 pp 223–241 BS EN 1948-4:2010+A1:2013 EN 1948-4:2010+A1:2013 (E) [16] Schleicher, O et al.: DL-PCB and marker PCB emission from shredder plant processing mixed scrap measured according to EN 1948-4 Organohalogen Compounds Vol 71 (2009) pp 2164-2167 (http://www.dioxin20xx.org/pdfs/2009/09-439.pdf) [17] ISO 4793:1980, Laboratory sintered (fritted) filters — Porosity grading, classification and designation [18] ISO 5725-2:1994, Accuracy (trueness and precision) of measurement methods and results — Part 2: Basic method for the determination of repeatability and reproducibility of a standard measurement method [19] EN 12766-1:2000, Petroleum products and used oils - Determination of PCBs and related products Part 1: Separation and determination of selected PCB congeners by gas chromatography (GC) using an electron capture detector (ECD) [20] EN 12766-2:2001, Petroleum products and used oils - Determination of PCBs and related products Part 2: Calculation of polychlorinated biphenyl (PCB) content [21] EN ISO 16000-12:2008, Indoor air - Part 12: Sampling strategy for polychlorinated biphenyls (PCBs), polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and polycyclic aromatic hydrocarbons (PAHs) (ISO 16000-12:2008) [22] VDI 2310 Part 32:1995-11, Maximum immission values; Maximum immission values for PCBs to protect farm animals Berlin: Beuth Verlag [23] VDI 2464 Part 1:2009-09, Ambient air measurement; Indoor air measurement; Measurement of polychlorinated biphenyls (PCBs); GC-MS method for PCB 28, 52, 101,138, 153, 180 Berlin: Beuth Verlag [24] European Parliament legislative resolution of July 2010 on the Council position at first reading for adopting a directive of the European Parliament and of the Council on industrial emissions (integrated pollution prevention and control) (recast) (11962/2/2009 – C7-0034/2010 – 2007/0286(COD)) (status 2010-07-15) 63 This page deliberately left blank This page deliberately left blank NO COPYING WITHOUT BSI PERMISSION EXCEPT AS PERMITTED BY COPYRIGHT LAW British Standards Institution (BSI) BSI is the national body responsible for preparing British Standards and other standards-related publications, information and services BSI is incorporated by Royal Charter British Standards and other standardization products are published by BSI Standards Limited About us Revisions We bring together business, industry, government, consumers, innovators and others to shape their combined experience and expertise into standards -based solutions Our British Standards and other publications are updated by amendment or revision The knowledge embodied in our standards has been carefully assembled in a dependable format and refined through our open consultation process Organizations of all sizes and across all sectors 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