1、raising standards worldwideNO COPYING WITHOUT BSI PERMISSION EXCEPT AS PERMITTED BY COPYRIGHT LAWBSI Standards PublicationPD CEN/TR 16243:2011Ambient air quality Guidefor the measurement ofelemental carbon (EC) andorganic carbon (OC) depositedon filtersPD CEN/TR 16243:2011 PUBLISHED DOCUMENTNational
2、 forewordThis Published Document is the UK implementation of CEN/TR16243:2011.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
3、 not purport to include all the necessaryprovisions of a contract. Users are responsible for its correctapplication. BSI 2011ISBN 978 0 580 74012 1ICS 13.040.20Compliance with a British Standard cannot confer immunity fromlegal obligations.This Published Document was published under the authority of
4、 theStandards Policy and Strategy Committee on 30 September 2011.Amendments issued since publicationDate Text affectedPD CEN/TR 16243:2011TECHNICAL REPORT RAPPORT TECHNIQUE TECHNISCHER BERICHT CEN/TR 16243 August 2011 ICS 13.040.20 English Version Ambient air quality - Guide for the measurement of e
5、lemental carbon (EC) and organic carbon (OC) deposited on filters Qualit de lair ambiant - Guide pour le mesurage du carbone lmentaire (EC) et du carbone organique (OC) dposs sur filtre Auenluftqualitt - Leitfaden zur Messung von auf Filtern abgeschiedenem elementarem Kohlenstoff (EC) und organisch
6、gebundenem Kohlenstoff (OC) This Technical Report was approved by CEN on 18 June 2011. It has been drawn up by the Technical Committee CEN/TC 264. CEN members are the national standards bodies of Austria, Belgium, Bulgaria, Croatia, Cyprus, Czech Republic, Denmark, Estonia, Finland, France, Germany,
7、 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 STANDARDIZATION COMIT EUROPEN DE NORMALISATION EUROPISCHES KOMITEE FR NORMUNG Man
8、agement Centre: Avenue Marnix 17, B-1000 Brussels 2011 CEN All rights of exploitation in any form and by any means reserved worldwide for CEN national Members. Ref. No. CEN/TR 16243:2011: EPD CEN/TR 16243:2011CEN/TR 16243:2011 (E) 2 Contents Page Foreword 3Introduction .41 Scope 62 Terms, definition
9、s and abbreviations 63 Principle 74 Materials and instruments 85 Sampling .96 Transport and storage 107 Analysis . 108 Artefacts and interferences . 129 Quality assurance/quality control (QA/QC) 1410 Calculation of concentrations of EC and OC . 1611 Data reporting . 17Annex A (informative) Example o
10、f a logbook . 18Annex B (informative) An example of a standard operating procedure for analysing EC and OC . 19Annex C (informative) Methods for the assessment of carbonate carbon 24Annex D (informative) Preparation of stock sucrose solutions and calibration standards 28Bibliography . 29PD CEN/TR 16
11、243:2011CEN/TR 16243:2011 (E) 3 Foreword This document (CEN/TR 16243:2011) 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.
12、 CEN and/or CENELEC shall not be held responsible for identifying any or all such patent rights. PD CEN/TR 16243:2011CEN/TR 16243:2011 (E) 4 Introduction For air quality across the European Union to be assessed on a consistent basis, Member States need to employ standard measurement techniques and p
13、rocedures. The aim of this Technical Report is to present guidance on the measurement procedures to be followed when monitoring elemental carbon (EC) and organic carbon (OC) deposited on filters, following Council Directive 2008/50/EC on ambient air quality and cleaner air for Europe 1. This require
14、s the chemical speciation of the sub-2,5 m size fraction of suspended particulate matter (PM2,5) in ambient air, as described in Annex IV: MEASUREMENTS AT RURAL BACKGROUND LOCATIONS IRRESPECTIVE OF CONCENTRATION A. Objectives The main objectives of such measurements are to ensure that adequate infor
15、mation is made available on levels in the background. This information is essential to judge the enhanced levels in more polluted areas (such as urban background, industry related locations, traffic related locations), assess the possible contribution from long-range transport of air pollutants, sup
16、port source apportionment analysis and for the understanding of specific pollutants such as particulate matter. It is also essential for the increased use of modelling in urban areas. B. Substances Measurement of PM2,5shall include at least the total mass concentration and concentrations of appropri
17、ate compounds to characterise its chemical composition. At least the list of chemical species given below shall be included. SO42, Na+,NH4+, Ca2+, elemental carbon (EC), NO3, K+, Cl, Mg2+, organic carbon (OC) C. Siting Measurements should be taken in particular in rural background areas in accordanc
18、e with parts A, B and C of Annex III The method described in this Technical Report is focused primarily on harmonization and improvement of the data quality of thermal-optical measurement method for EC and OC used in monitoring networks, with guidance regarding the different protocols (analytical pa
19、rameters) used currently within that method. The method is seen to be suitable for practical use in routine monitoring networks. There are no traceable primary reference materials available for EC and OC analysis and there is no absolute scientific distinction between EC and OC. Therefore, the metho
20、d set out in this Technical Report provides operational definitions of the measured quantities. In February 2009, a workshop took place to provide an overview of the measurements made in Europe and worldwide. The workshop was organised by the Joint Research Centre in Ispra, Italy. The report of this
21、 workshop is available 2. Consensus was reached for the following ranking of measurement techniques: a) thermal method with optical correction for EC and OC for samples collected on filters, b) other off-line analysis techniques for EC and OC for samples collected on filters, c) other on-line analys
22、is techniques for EC and OC for samples collected on filters, d) other analysis techniques for either EC and/or OC, e) other analysis techniques measuring surrogates for either EC and/or OC (i.e. light absorption). Due to the fact that the networks of the EU member countries have to measure EC and O
23、C starting in June 2010 and CEN/TC 264/WG 35 “EC/OC in PM” has neither a mandate nor other funding available to perform necessary validation trials, WG 35 agreed on the following resolutions: PD CEN/TR 16243:2011CEN/TR 16243:2011 (E) 5 1) Resolution 35 Given the urgent need for Member States to have
24、 a standardised method for EC and OC, as they are due to start sampling from June 2010, and in the absence of a mandate from the Commission, the WG agrees that they will work on a CEN Technical Report for EC and OC as a priority. The text of the Technical Report will be made available to interested
25、people (e.g. network operators) when it is ready. This TR will describe several protocols for thermal-optical methods that will give different results for EC and OC, because validation data is needed both to specify one standard method and to properly characterise that method. If a mandate is given,
26、 the priorities will be reconsidered at the time. 2) Resolution 36 WG 35 agrees that the Commission shall be formally informed that the Technical Report will be an unsatisfactory substitute for a full standard, as it will delay the start of comparable data across the EU variations of more than 100 %
27、 for EC can be expected. It may also have financial consequences for some Member States who have to change their method when the standard is produced. 3) Resolution 37 WG 35 agrees that the Technical Report shall include optical charring correction using both transmittance and reflection data, and r
28、ecording of results using both sets of data shall be encouraged. There are some open issues on the measurement procedure that can only be decided after further validation, e.g.: the applicable concentration ranges of the proposed method are limited by the optical correction and thermal protocols app
29、lied in the analysis of EC and OC; since the latter is dependent on the instrument as well as the chosen protocols no definitive values can be given; temperature measurement in the instrument ovens: location and reproducibility; influence of sampling artefacts on the data quality; provision and use
30、of reference materials. Attention is given to harmonizing the sampling with that for anions and cations in PM2,5as far as possible. The measurements for anions and cations are described in prCEN/TR 264125:2010 3 and those for PM2,5in EN 14907:2005 4. NOTE: EN 14907:2005 is under revision and will be
31、 incorporated in the revision of EN 12341:1998 Ambient air quality Standard gravimetric measurement method for the determination of the PM10 mass fraction of suspended particulate matter. PD CEN/TR 16243:2011CEN/TR 16243:2011 (E) 6 1 Scope This Technical Report gives guidance on the measurement of e
32、lemental carbon (EC) and organic carbon (OC) following the requirement for the networks of all EU member countries to measure EC and OC in particulate matter from June 2010 at background sites according to the Council Directive 2008/50/EC on ambient air quality and cleaner air for Europe. The Techni
33、cal Report describes the analytical procedures for determining EC and OC on quartz fibre filters as g/cm2, and the subsequent calculation of concentrations as g/m. Sampling onto filters is to be done in accordance with EN 14907 for PM2,5. The sampling process determines the size fraction of the part
34、iculate matter, the retention of semi-volatile material, and ab/desorption of volatile organic compounds on the filter at the time of sampling. The same analysis method may also be used for other size fractions. Any possible additional artefacts e.g. due to charring or higher concentrations of carbo
35、nates would need to be assessed in those cases. The measurement procedures are applicable for: rural background, urban background, road side and industrial sites. The scope includes non rural site measurements, to allow the assessment of additional exposure of people in urban areas as stated in the
36、objectives of the council directive and to achieve coherence in the European approach. Measurements are made over a nominal sampling period of 24 h, and concentrations are expressed as g/m, where the volume of air is the volume at ambient conditions near the inlet of the sampler at the time of sampl
37、ing. The applicable concentration range of the proposed method is limited by the optical correction, instrument, and thermal protocols applied in the analysis of EC and OC. Therefore no definitive values can be given. The experience from EMEP shows the applicability of the method at regional backgro
38、und sites. 2 Terms, definitions and abbreviations For the purposes of this document, the following terms and definitions apply. 2.1 Terms and definitions 2.1.1 total carbon TC total quantity of carbon atoms in a PM sample, whatever the constituent it belongs to. This includes EC, OC and IC NOTE It i
39、s understood that the measure of TC released from a PM sample in a specified thermal desorption and oxidation process may be different for different protocols, and that it will not necessarily be all of the carbon atoms in the sample. 2.1.2 elemental carbon EC fraction of the non-IC total carbon in
40、a PM sample, characterised by its non-volatility according to a specified thermal / optical protocol. EC evolves from the sample by oxidation only PD CEN/TR 16243:2011CEN/TR 16243:2011 (E) 7 2.1.3 organic carbon OC fraction of the non-IC total carbon in a PM sample that is volatilised or pyrolyzed i
41、n a specified thermal/optical protocol 2.1.4 inorganic carbon IC fraction of carbon belonging to mineral species, including carbonates and other molecules 2.1.5 carbonate carbon CC fraction of carbon belonging to a carbonate group NOTE Carbonate carbon (mainly CaCO3 and MgCO3) is viewed as the only
42、inorganic carbon fraction being released within the temperature range used in the thermal protocols. 2.1.6 sampling artefact ab(d)sorption of gaseous species in (on) a PM sampling substrate (positive sampling artefact), and volatilization of particulate species from a PM sampling substrate (negative
43、 sampling artefact) 2.1.7 PMxparticulate matter suspended in air which passes through a size-selective inlet with a 50 % efficiency cut-off at x m aerodynamic diameter 2.2 Abbreviations PM Particulate Matter EMEP Co-operative Programme for Monitoring and Evaluation of the Long-range Transmission of
44、Air Pollutants in Europe EUSAAR European Super-sites for Atmospheric Aerosol Research NIOSH National Institute for Occupational Safety and Health IMPROVE US-Interagency Monitoring of Protected Visual Environments TOR Thermal Optical Reflectance TOT Thermal Optical Transmission SOP Standard Operating
45、 Procedure PC Pyrolytic carbon 3 Principle The method for measuring EC and OC in ambient PM samples deposited on filters is based on the volatilisation and oxidation of carbon-containing PM components, the quantification of the carbonaceous gases released, with optical correction for the charring of
46、 organic to elemental carbon in the process (the thermal-optical method). The procedure described is a thermal-optical transmittance/reflectance (TOT/TOR) method, which is widely used in networks like EMEP, GAW (Global Atmosphere Watch), STN (US-Speciation Trend Network) and IMPROVE. This method can
47、 be implemented with various commercial instruments. PD CEN/TR 16243:2011CEN/TR 16243:2011 (E) 8 4 Materials and instruments 4.1 Materials 4.1.1 Gases The use of high purity gases, with low moisture content, is recommended: helium at least 99,999 % (% by volume); hydrogen at least 99,997 % (% by vol
48、ume). 4.1.2 Standard solution Carbon-containing standard solutions (typically sucrose), with an accurately determined concentration ranging e.g. from 0,4 g C l-1 to 4 g C l-1. Calibrating standard solutions should be prepared which cover the concentration range of the samples to be analysed. 4.1.3 O
49、ther materials precision puncher, quartz boat for the filter punch, stainless steel tweezers for sample handling, clean cutting surface (e.g. aluminum foil or quartz fibre filter), analytical syringe or pipette for calibration using standard solutions, e.g. 10 l volume. 4.2 Instruments 4.2.1 Sampling instruments The performance requirements of the sampling instrument are given in EN 14907. 4.2.2 Analytical instruments A Thermo-Optical Analyser that all
