1、BSI Standards PublicationPD CEN/TS 16645:2014Ambient air Methodfor the measurementof benzaanthracene,benzobfluoranthene,benzojfluoranthene,benzokfluoranthene,dibenza,hanthracene,indeno1,2,3-cdpyrene andbenzoghiperylenePD CEN/TS 16645:2014 PUBLISHED DOCUMENTNational forewordThis Published Document is
2、 the UK implementation of CEN/TS16645:2014.The UK participation in its preparation was entrusted to TechnicalCommittee EH/2/3, Ambient atmospheres.A list of organizations represented on this committee can beobtained on request to its secretary.This publication does not purport to include all the nec
3、essaryprovisions of a contract. Users are responsible for its correctapplication. The British Standards Institution 2014. Published by BSI StandardsLimited 2014ISBN 978 0 580 81790 8ICS 13.040.20Compliance with a British Standard cannot confer immunity fromlegal obligations.This Published Document w
4、as published under the authority of theStandards Policy and Strategy Committee on 30 April 2014.Amendments issued since publicationDate Text affectedPD CEN/TS 16645:2014TECHNICAL SPECIFICATION SPCIFICATION TECHNIQUE TECHNISCHE SPEZIFIKATION CEN/TS 16645 April 2014 ICS 13.040.20 English Version Ambie
5、nt air - Method for the measurement of benzaanthracene, benzobfluoranthene, benzojfluoranthene, benzokfluoranthene, dibenza,hanthracene, indeno1,2,3-cdpyrene and benzoghiperylene Air ambiant - Mthode pour la mesure de benzaanthracne, benzobfluoranthne, benzojfluoranthne, benzokfluoranthne, dibenza,h
6、anthracne, indeno1,2,3-cdpyrne et benzoghiperylne Auenluft - Verfahren zur Messung von Benzaanthracen, Benzobfluoranthen, Benzojfluoranthen, Benzokfluoranthen, Dibenza,hanthracen, Indeno1,2,3-cdpyren und Benzoghiperylen This Technical Specification (CEN/TS) was approved by CEN on 16 December 2013 fo
7、r provisional application. The period of validity of this CEN/TS is limited initially to three years. After two years the members of CEN will be requested to submit their comments, particularly on the question whether the CEN/TS can be converted into a European Standard. CEN members are required to
8、announce the existence of this CEN/TS in the same way as for an EN and to make the CEN/TS available promptly at national level in an appropriate form. It is permissible to keep conflicting national standards in force (in parallel to the CEN/TS) until the final decision about the possible conversion
9、of the CEN/TS into an EN is reached. 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, Luxembour
10、g, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland, Turkey and United Kingdom. EUROPEAN COMMITTEE FOR STANDARDIZATION COMIT EUROPEN DE NORMALISATION EUROPISCHES KOMITEE FR NORMUNG CEN-CENELEC Management Centre: Avenue Marnix 17, B-1000 Brussels 2
11、014 CEN All rights of exploitation in any form and by any means reserved worldwide for CEN national Members. Ref. No. CEN/TS 16645:2014 EPD CEN/TS 16645:2014CEN/TS 16645:2014 (E) 2 Contents Page Foreword 4 Introduction . 5 1 Scope 6 2 Normative references 7 3 Terms and definitions . 7 4 Symbols and
12、abbreviations 9 4.1 Symbols 9 4.2 Abbreviations . 10 5 Principle of the method . 10 6 Requirements . 10 6.1 Siting requirements . 10 6.2 Sampling requirements . 11 6.3 Analysis 11 7 Reagents and gases 13 7.1 Solvents 13 7.2 Gases 13 7.3 External standard 13 7.4 Internal standard 13 7.5 Surrogate sta
13、ndard 13 7.6 Stock standard solution 13 7.7 Certified reference material 13 8 Apparatus . 14 8.1 Sampling equipment . 14 8.2 Sample preparation/extraction . 14 8.3 Laboratory apparatus 14 9 Sampling . 15 9.1 Preparation of the equipment before sampling 15 9.2 Handling of filters 15 9.3 Preparation o
14、f filters 15 9.4 Sample collection, transport and storage . 16 10 Sample preparation . 16 10.1 Cleaning of the laboratory apparatus 16 10.2 Extraction . 16 11 Analysis 17 11.1 General 17 11.2 HPLC/FLD analysis 17 11.3 GC-MS analysis 18 12 Quantification . 19 12.1 HPLC/FLD analysis 19 12.2 GC-MS Anal
15、ysis . 21 12.3 Concentration of the PAH compounds in ambient air . 22 13 Quality control . 23 13.1 Reagent blank check . 23 PD CEN/TS 16645:2014CEN/TS 16645:2014 (E) 3 13.2 Calibration drift check. 23 13.3 Control solutions . 23 13.4 Recovery efficiency check . 23 13.5 Chromatographic interference c
16、heck 23 13.6 Laboratory filter blank check . 24 13.7 Field filter blank check 24 13.8 External quality assessment 24 14 Determination of measurement uncertainty . 24 14.1 Introduction 24 14.2 Parameters contributing to measurement uncertainty . 25 14.3 Recommendations for use . 27 15 Interferences 2
17、7 15.1 General . 27 15.2 HPLC/FLD method . 27 15.3 GC-MS method . 28 16 Reporting of results 28 Annex A (informative) Sampling systems with oxidant denuder . 30 Annex B (informative) Extraction methods (examples of experimental conditions) . 33 Annex C (informative) Example for clean-up procedure .
18、35 Annex D (informative) Parameters for analysis (examples) . 36 Annex E (informative) Assessment of performance indicators and uncertainty contributions . 38 Annex F (informative) Calculation of uncertainty using interlaboratory comparison and field validation data . 47 Bibliography 51 PD CEN/TS 16
19、645:2014CEN/TS 16645:2014 (E) 4 Foreword This document (CEN/TS 16645:2014) has been prepared by Technical Committee CEN/TC 264 “Air quality”, the secretariat of which is held by DIN. Attention is drawn to the possibility that some of the elements of this document may be the subject of patent rights.
20、 CEN and/or CENELEC shall not be held responsible for identifying any or all such patent rights. According to the CEN-CENELEC Internal Regulations, the national standards organizations of the following countries are bound to announce this Technical Specification: Austria, Belgium, Bulgaria, Croatia,
21、 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 U
22、nited Kingdom. PD CEN/TS 16645:2014CEN/TS 16645:2014 (E) 5 Introduction The measurement methods specified in this document are based on methods that were worked out during the laboratory and field validation tests for the European Standards EN 15549 5 (determination of BaP in ambient air) and EN 159
23、80 6 (determination of the deposition of several particle bound PAH compounds). Many data on the performance of the extraction and analysis of benzaanthracene (BaA), benzobfluoranthene (BbF), benzojfluoranthene (BjF), benzokfluoranthene (BkF), dibenza,hanthracene (DBahA), indeno1,2,3-cdpyrene (INP)
24、and benzoghiperylene (BghiP) in deposition or PM10 samples were gathered. These data do not cover the complete measurement procedure including sampling and consequently enable publication of a Technical Specification instead of a European Standard. It is the long-term goal to combine this document w
25、ith EN 15549 5, once adequate progress has been made in the development of reliably working oxidant denuders. PD CEN/TS 16645:2014CEN/TS 16645:2014 (E) 6 1 Scope This Technical Specification specifies a measurement method for the determination of the particle bound polycyclic aromatic hydrocarbon (P
26、AH) compounds benzaanthracene (BaA), benzobfluoranthene (BbF), benzojfluoranthene (BjF), benzokfluoranthene (BkF), dibenza,hanthracene (DBahA), indeno1,2,3-cdpyrene (INP) and benzoghiperylene (BghiP) in ambient air, which can be used in the framework of Council Directive 2008/50/EC 10 and Directive
27、2004/107/EC 11. This document specifies performance characteristics and performance criteria for this measurement method. The performance characteristics of the measurement method are based on a sampling period of 24 h. This Technical Specification describes a measurement method which comprises samp
28、ling of the selected PAH compounds as part of the PM10 particles, sample extraction and analysis by high performance liquid chromatography (HPLC) with fluorescence detector (FLD) or by gas chromatography with mass spectrometric detection (GC-MS). The method is applicable for the measurement of the P
29、AH compounds in the concentration range from approx. 0,04 ng/m3to approximately 20 ng/m3for BaA, BbF, BjF, BkF, BaP, INP and BghiP and 0,02 ng/m3to approximately 2 ng/m3for DBahA. Table 1 shows examples for concentrations of the compounds (annual mean values) for sampling sites with different charac
30、teristics. Table 1 Examples of annual mean values of PAH compounds in PM10 at sampling sites with different characteristics (in ng/m3) Compound Industrial aUrban background bTraffic cRural background dBaA 0,85 0,24 0,24 0,06 BbF 2,44 0,62 0,48 e0,16 eBjF 0,89 0,27 BkF 0,89 0,24 0,17 0,15 BaP 1,15 0,
31、29 0,27 0,13 BghiP 1,31 f0,20 g0,34 0,09 DBahA 0,20 0,10 0,05 f0,07 hINP 1,60 0,43 0,23 0,08 aBottrop (Germany, 2010), HPLC/FLD. bMlheim-Styrum (Germany, 2010), HPLC/FLD. cLondon Crystal Palace Parade (UK, 2010), GC-MS. dHarwell (UK, 2010), GC-MS. e(Bbf+BjF). fWijk aan Zee (The Netherlands, 2011), G
32、C-MS. gRotterdam (The Netherlands, 2011), GC-MS. h(DBacA+DBahA). The lower limit of the applicable range depends on the noise level of the detector and the variability of the laboratory filter blank. PD CEN/TS 16645:2014CEN/TS 16645:2014 (E) 7 2 Normative references The following documents, in whole
33、 or in part, are normatively referenced in this document and are indispensable for its application. For dated references, only the edition cited applies. For undated references, the latest edition of the referenced document (including any amendments) applies. EN 12341, Ambient air Standard gravimetr
34、ic measurement method for the determination of the PM10 or PM2,5 mass concentration of suspended particulate matter ENV 13005, Guide to the expression of uncertainty in measurement EN ISO 20988, Air quality Guidelines for estimating measurement uncertainty (ISO 20988) EN ISO/IEC 17025, General requi
35、rements for the competence of testing and calibration laboratories (ISO/IEC 17025) ISO/IEC Guide 98-3:2008, Uncertainty of measurement Part 3: Guide to the expression of uncertainty in measurement (GUM:1995) ISO 5725-2, Accuracy (trueness and precision) of measurement methods and results Part 2: Bas
36、ic method for the determination of repeatability and reproducibility of a standard measurement method ISO 7870-2, Control charts Part 2: Shewhart control charts 3 Terms and definitions For the purposes of this document, the following terms and definitions apply. 3.1 calibration solution solution use
37、d for calibration of the analytical instrument, containing the analyte of interest at a suitable concentration, prepared by dilution of the stock standard solution SOURCE: EN 15549:2008 5 3.2 certified reference material CRM reference material, accompanied by documentation issued by an authoritative
38、 body and providing one or more specified property values with associated uncertainties and traceabilities, using valid procedures SOURCE: JGCM 200:2012 12 3.3 external standard solution solution of compounds of known concentrations which are analysed separately from the unknown sample under identic
39、al conditions 3.4 field blank filter filter that is taken through the same procedure as a sample, except that no air is drawn through it SOURCE: EN 15549:2008 5 PD CEN/TS 16645:2014CEN/TS 16645:2014 (E) 8 3.5 internal standard solution solution of known compounds of known concentrations, added to th
40、e sample before chromatographic analysis 3.6 laboratory blank filter unused filter that does not leave the laboratory and is taken through the same analytical procedure as the sample SOURCE: EN 15549:2008 5 3.7 PM10 particulate matter suspended in air which is small enough to pass through a size-sel
41、ective inlet with a 50 % efficiency cut-off at 10 m aerodynamic diameter Note 1 to entry: By convention, the size-selective standard inlet designs prescribed in this Technical Specification used at the prescribed flow rates possess the required characteristics to sample the relevant PM fraction susp
42、ended in ambient air. Note 2 to entry: The efficiency of the size selectiveness of other inlets used may have a significant effect on the fraction of PM surrounding the cut-off, and, consequently on the particle bound PAH compounds determined. SOURCE: EN 12341:2014, modified the very end of Note 2 t
43、o entry has been modified. 3.8 reagent blank solution solution that contains all the reagents used during analysis of the sample, but without the sample and filter matrix SOURCE: EN 14902:2005 4 3.9 stock standard solution solution used for preparing calibration solutions, containing the analyte of
44、interest at a concentration traceable to national or international standards SOURCE: EN 15549:2008 5 3.10 surrogate standard solution solution of a compound added to the test material, the chemical and physical behaviour of which is taken to be representative of the native analyte Note 1 to entry: T
45、his solution is used to spike filters before extraction in order to check the recovery efficiency. 3.11 uncertainty (of measurement) parameter associated with the result of a measurement, that characterizes the dispersion of the values that could reasonably be attributed to the measurand SOURCE: ISO
46、/IEC Guide 98-3:2008 PD CEN/TS 16645:2014CEN/TS 16645:2014 (E) 9 4 Symbols and abbreviations 4.1 Symbols a is the slope of linear calibration function ACis the peak area or peak height of a PAH compound or of its characteristic ion in the chromatogram of the calibration solution AEis the peak area o
47、r peak height of a PAH compound or of its characteristic ion in the chromatogram of the sample extract AIS is the peak area or peak height of the internal standard or of its characteristic ion in the chromatogram of the calibration solution AISEis the peak area or peak height of the internal standar
48、d or of its characteristic ion in the chromatogram of the sample extract b is the intercept of the linear calibration function C is the concentration of the PAH compound in ambient air, in ng/m3DCis the detection limit, in ng/m3DMis the absolute detection limit in the sample, in ng f is the response
49、 factor of the PAH compound bm is the mean of laboratory filter blanks, in ng mCis the mass of the PAH compound in the calibration solution, in ng mCRMis the certified mass in the CRM, in ng mEis the mass of the PAH compound in the sample extract, in ng mFis the mass of the PAH compound on the filter sample, in ng miis the individual filter blank, in ng mISis the mass of the internal standard in the calibration solution, in ng mISEis
