BS EN 1948-2-2006 Stationary source emissions - Determination of the mass concentration of PCDDs PCDFs and dioxin-like PCBs - Extraction and clean-up of PCDDs PCDFs《固定源排放 PCDDs PCD.pdf

1、BRITISH STANDARDBS EN 1948-2:2006Stationary source emissions Determination of the mass concentration of PCDDs/PCDFs and dioxin-like PCBs Part 2: Extraction and clean-up of PCDDs/PCDFsThe European Standard EN 1948-2:2006 has the status of a British StandardICS 13.040.40g49g50g3g38g50g51g60g44g49g42g3

2、g58g44g55g43g50g56g55g3g37g54g44g3g51g40g53g48g44g54g54g44g50g49g3g40g59g38g40g51g55g3g36g54g3g51g40g53g48g44g55g55g40g39g3g37g60g3g38g50g51g60g53g44g42g43g55g3g47g36g58BS EN 1948-2:2006This British Standard was published under the authority of the Standards Policy and Strategy Committee on 31 March

3、 2006 BSI ISBN 0 580 48046 1National forewordThis British Standard is the official English language version of EN 1948-2:2006. It supersedes BS EN 1948-2:1997 which is withdrawn.The UK participation in its preparation was entrusted by Technical Committee EH/2, Air quality, to Subcommittee EH/2/1, St

4、ationary source emissions, which has the responsibility to: A list of organizations represented on this committee can be obtained on request to its secretary.Cross-referencesThe British Standards which implement international or European publications referred to in this document may be found in the

5、BSI Catalogue under the section entitled “International Standards Correspondence Index”, or by using the “Search” facility of the BSI Electronic Catalogue or of British Standards Online.This publication does not purport to include all the necessary provisions of a contract. Users are responsible for

6、 its correct application. Compliance with a British Standard does not of itself confer immunity from legal obligations. aid enquirers to understand the text; present to the responsible international/European committee any enquiries on the interpretation, or proposals for change, and keep UK interest

7、s informed; monitor related international and European developments and promulgate them in the UK.Summary of pagesThis document comprises a front cover, an inside front cover, the EN title page, pages 2 to 36, an inside back cover and a back cover.The BSI copyright notice displayed in this document

8、indicates when the document was last issued.Amendments issued since publicationAmd. No. Date CommentsEUROPEAN STANDARDNORME EUROPENNEEUROPISCHE NORMEN 1948-2March 2006ICS 13.040.40 Supersedes EN 1948-2:1996 English VersionStationary source emissions - Determination of the massconcentration of PCDDs/

9、PCDFs and dioxin-like PCBs - Part 2:Extraction and clean-up of PCDDs/PCDFsEmissions de sources fixes - Dtermination de laconcentration massique en PCDD/PCDF et PCB de typedioxine - Partie 2: Extraction et purification de PCDD/PCDFEmissionen aus stationren Quellen - Bestimmung derMassenkonzentration

10、von PCDD/PCDF und dioxin-hnlichen PCB - Teil 2: Extraktion und Reinigung vonPCDD/PCDFThis European Standard was approved by CEN on 23 January 2006.CEN members are bound to comply with the CEN/CENELEC Internal Regulations which stipulate the conditions for giving this EuropeanStandard the status of a

11、 national standard without any alteration. Up-to-date lists and bibliographical references concerning such nationalstandards may be obtained on application to the Central Secretariat or to any CEN member.This European Standard exists in three official versions (English, French, German). A version in

12、 any other language made by translationunder the responsibility of a CEN member into its own language and notified to the Central Secretariat has the same status as the officialversions.CEN members are the national standards bodies of Austria, Belgium, Cyprus, Czech Republic, Denmark, Estonia, Finla

13、nd, 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 STANDARDIZATIONCOMIT EUROPEN DE NORMALISATIONEUROPISCHES KOMITEE

14、 FR NORMUNGManagement Centre: rue de Stassart, 36 B-1050 Brussels 2006 CEN All rights of exploitation in any form and by any means reservedworldwide for CEN national Members.Ref. No. EN 1948-2:2006: EEN 1948-2:2006 (E) 2 Contents Page Foreword 3 Introduction6 1 Scope .7 2 Normative references .7 3 T

15、erms and definitions.7 4 Symbols and abbreviations10 5 Principle of the extraction and clean-up procedure.11 6 Device, materials and 13C12-labelled standards 12 7 Method validation and quality control requirements .13 8 Sample pre-treatment and extraction14 9 Report 16 Annex A (informative) Examples

16、 of operation of extraction and clean-up methods17 Annex B (informative) Relations to EU Directives.35 Bibliography.36 EN 1948-2:2006 (E) 3 Foreword This European Standard (EN 1948-2:2006) has been prepared by Technical Committee CEN/TC 264 “Air quality”, the secretariat of which is held by DIN. Thi

17、s European Standard shall be given the status of a national standard, either by publication of an identical text or by endorsement, at the latest by September 2006, and conflicting national standards shall be withdrawn at the latest by September 2006. Attention is drawn to the possibility that some

18、of the elements of this document may be the subject of patent rights. CEN and/or CENELEC shall not be held responsible for identifying any or all such patent rights. This European Standard supersedes EN 1948-2:1996. This European Standard has been prepared under a mandate given to CEN by the Europea

19、n Commission and the European Free Trade Association to support Essential Requirements of EU Directive 94/67/EC of 16 December 1994 i on the incineration of hazardous waste. This directive is now replaced by EU Directive 2000/76/EC of 4 December 2000 on the incineration of waste ii and this European

20、 Standard also supports the Essential Requirements of the new EU Directive 2000/76/EC (see also Annex B). The precision and the performance characteristics were determined between 1992 and 1995 in four comparative and validation trials at waste incinerators sponsored by the European Commission, the

21、European Free Trade Association and the German Federal Environment Agency. The revision of this EN between 2001 and 2004 only refers to the normative part. The information given in the informative annexes as examples of operation are kept unchanged, as they represent the state of the art at time of

22、the validation measurements of EN 1948:1996 between 1992 and 1995. This European Standard EN 1948:2006 consists of three parts dealing with the determination of the mass concentration of PCDDs and PCDFs in stationary source emissions: Part 1: Sampling of PCDDs/PCDFs; Part 2: Extraction and clean-up

23、of PCDDs/PCDFs; Part 3: Identification and quantification of PCDDs/PCDFs. All three parts are necessary for the performance of the dioxin measurements. In addition for the sampling, extraction and analyses of dioxin-like PCBs the Technical Specification CEN/TS 1948-41is developed and will be transfe

24、rred to a European Standard after corresponding validation measurements or after an approval time of three years respectively. Important changes made in the revision of EN 1948-2: 1. Title: Broadening of the title with regard to the future EN 1948-4 for the determination of dioxin-like PCBs 2. Forew

25、ord: 1) To be published. EN 1948-2:2006 (E) 4 Deletion of all precursor documents which were basis for elaboration of EN 1948 as well as the names of the standardisation bodies involved in the elaboration of EN 1948 Update of the hint regarding mandate of the standardisation project and regarding fu

26、lfilment of the Essential Requirements of EU Directives 94/67/EC and 2000/76/EC Addition of a hint, that the revision only refers to the normative parts of the standard. The Informative Annex A “Examples of operation” is kept unchanged and represents the state of the art at time of the validation me

27、asurements of EN 1948:1996 between 1992 and 1995 Addition of hint with regard to the future document EN 1948-4 dealing with the analyses of dioxin-like PCBs 3. Scope: Addition of a hint, that EN 1948 can be applied for wide concentration ranges and various emission sources Addition of a hint, that t

28、he described measurement methods are suitable for determination of other low-volatile substances, e.g. of dioxin-like PCBs 4. Normative references: Update of the references to EN 1948-1:2006, EN 1948-3:2006 5. Clause 3 Terms and definitions: Distinction between Clause 3 “Terms and definitions“ and C

29、lause 4 “Symbols and abbreviations“ resulting in a different numbering of the following chapters Corrected definition of “field blank“ for clarification Corrected definition of “analytical blank“ for clarification Corrected definition of “sampling standard“: only furans “Syringe standard“ renamed to

30、 read “recovery standard“ Corrected definition of “recovery standard“: only dioxins Additional definition of “dioxin-like PCBs“ “Sampling volume“ renamed to read “volume of the sampling extract“ Corrected definition and requirement of isokinetic sampling according to EN 13284-1:2001 Additional defin

31、ition and calculation of limit of detection Additional definition and calculation of limit of quantification Additional definition of WHO-TEF/WHO-TEQ 6. Clause 5 Principle of the extraction and clean-up procedure: Additional subclause 5.2 “Minimum information prior to analyses“ 7. Clause 7.2 Sample

32、pre-treatment: Correction of the requirements regarding sample pre-treatment for better comprehensibility EN 1948-2:2006 (E) 5 8. Clause 8.1 Addition of extraction standards: Correction for better comprehensibility 9. Clause 8.2 Sample storage: Requirement to store the samples 320 C) vapour phase tr

33、ansfer mechanisms and aerosol formation during solvent evaporation might lead to substantial losses when concentrating volumes below 10 ml). Depending on the method to be used for solvent volume reduction the following precautions shall be taken into consideration: a) Rotary evaporators Losses might

34、 be substantial when reducing solvent volumes below 10 ml. Counter measures are the use of controlled vacuum conditions according to the vapour pressure and boiling point of the solvent, addition of a high-boiling solvent as a keeper as well as the use of specially shaped vessels (e.g. V-shaped). EN

35、 1948-2:2006 (E) 16 b) Counter gas flow evaporators Volumes should not be reduced to less than 1 ml. c) Nitrogen flow An excessive flow of nitrogen which disturbs the solvent surface should be avoided. The vial shape has also some influence on possible losses. V-shaped vials or vial inserts shall be

36、 used for volume reductions below around 200 l. 8.6 Addition of recovery standards The very last step before quantification is the addition of the recovery standards to measure the recovery rates of the extraction standards. The recovery standards according to Table 1 shall be added under following

37、conditions: a) Recovery standards shall be added just prior to the quantification procedure. Samples with the recovery standard added which could not be analysed due to operational reasons (instrument failure), should be stored as briefly as possible and any further uncontrolled solvent evaporation

38、shall be avoided. b) Recovery standards shall be added after the final volume reduction. Any further direct volume reduction shall be avoided. A slow evaporation at room temperature from the open sample vial to a volume of about 25 l is acceptable. 9 Report The contents of the report for sampling ar

39、e described in EN 1948-1:2006 and for analysis in EN 1948-3:2006. EN 1948-2:2006 (E) 17 Annex A (informative) Examples of operation of extraction and clean-up methods A.1 General The revision of this EN between 2001 and 2004 only refers to the normative part. The information given in this informativ

40、e annex as examples of operation are kept unchanged, as they represent the state of the art at time of the validation measurements of EN 1948:1996 between 1992 and 1995. Polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) are extracted from the sampling media by soxhlet extraction, l

41、iquid/liquid extraction or rinsed with solvents (sampling train surfaces). Selected 13C12-isotope labelled 2,3,7,8-chlorine substituted PCDD/PCDF congeners are added to the different sampling media before extraction. Clean-up of the sample extract is performed by liquid chromatography. 13C12-isotope

42、 labelled congeners are added as recovery standards just before quantification to calculate recovery rates of the sampling and extraction standards. A.2 Method 1 A.2.1 Equipment, chemicals and instruments A.2.1.1 Sampling materials and cleaning of materials A.2.1.1.1 Sampling materials a) XAD-2, pol

43、ystyrene divinylbenzene co-polymer, 0,3 mm to 0,85 mm particle size; b) Polyurethane foam plugs (polyether, open pored type, surface area 330 m2/g, pore size 90 10-8cm, 100 mm diameter, 50 mm thickness, density 25 kg/m3produced from toluene-2.4.-diisocyanate/toluene-2.6.-diisocyanate (TDI) and polyo

44、xypropylene triol; c) glass fibre filters, type AE 2), 142 mm diameter. A.2.1.1.2 Cleaning of XAD-2 350 ml XAD-2 are placed in a 60 mm x 180 mm thimble and cleaned in a soxhlet-extractor of 700 ml volume first with methanol (8 h) followed by acetonitrile (8 h) and diethylether (8 h). Afterwards the

45、adsorbent is air-dried in a fume-hood for 48 h and in an oven at 35 C for at least 8 h. The adsorbent is stored in a borosilicate bottle with a polypropylene cap. A.2.1.1.3 Cleaning of polyurethane foam (PUF) plugs 8 new plugs are placed in a 2 000 ml soxhlet extractor avoiding too much deformation.

46、 They are cleaned with 2 500 ml of the following solvents (see A.2.1.3): toluene (24 h), acetone (24 h) and toluene (8 h). After extraction, the plugs are squeezed manually to remove the remaining solvent (fume hood!) by using solvent 2) Fibre filter, type AE, no. 64878 is the trade-name of a produc

47、t supplied by Gelman, USA, and is an example of a suitable commercially available product. This indication is only made for information of the user of this European Standard and does not mean any approval of the named products by CEN. EN 1948-2:2006 (E) 18 resistant gloves. The moist plugs are trans

48、ferred to a desiccator of 300 mm diameter which is placed into an oven. They are dried at 60 C under vacuum (80 kPa) for 8 h. Afterwards, each plug is wrapped into aluminium foil and stored in a plastic bag. Storage should not exceed 2 months. A.2.1.1.4 Cleaning of glass fibre filters Up to 20 glass

49、 fibre filters are heated in a muffle furnace at 450 C for 8 h. Afterwards they are wrapped into aluminium foil. A.2.1.2 Laboratory equipment A.2.1.2.1 Glassware a) Round bottom flasks, 500 ml and 1 000 ml, joint size 24/29; b) round bottom flasks, 100 ml, with centrifuge tube of 5 ml volume fused to the bottom, joint size 24/29 (see Figure A.1); c) Pasteur pipettes, 150 mm and 230 mm length, d) separation funnels with glass tap and glass stopper, 500 ml, 1 000 ml, 2 000 ml; e) bottles made from borosilicate glass, 50