1、raising standards worldwideNO COPYING WITHOUT BSI PERMISSION EXCEPT AS PERMITTED BY COPYRIGHT LAWBSI Standards PublicationPD CEN/TR 16269:2011Ambient air Guide for themeasurement of anions andcations in PM2,5PD CEN/TR 16269:2011 PUBLISHED DOCUMENTNational forewordThis Published Document is the UK im
2、plementation of CEN/TR16269:2011.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 not purport to include all the necessaryprov
3、isions of a contract. Users are responsible for its correctapplication. BSI 2011ISBN 978 0 580 74622 2ICS 13.040.20Compliance with a British Standard cannot confer immunity fromlegal obligations.This Published Document was published under the authority of theStandards Policy and Strategy Committee o
4、n 30 September 2011.Amendments issued since publicationDate Text affectedPD CEN/TR 16269:2011TECHNICAL REPORT RAPPORT TECHNIQUE TECHNISCHER BERICHT CEN/TR 16269 September 2011 ICS 13.040.20 English Version Ambient air - Guide for the measurement of anions and cations in PM2,5 Air ambiant - Guide pou
5、r le mesurage des anions et des cations dans la fraction PM2,5 Auenluft - Leitfaden zur Messung von Anionen und Kationen in PM2,5 This Technical Report was approved by CEN on 8 August 2011. It has been drawn up by the Technical Committee CEN/TC 264. CEN members are the national standards bodies of A
6、ustria, Belgium, Bulgaria, Croatia, Cyprus, Czech Republic, Denmark, Estonia, Finland, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland and United Kingdom. E
7、UROPEAN COMMITTEE FOR STANDARDIZATION COMIT EUROPEN DE NORMALISATION EUROPISCHES KOMITEE FR NORMUNG Management 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 16269:2011: EPD CEN/T
8、R 16269:2011CEN/TR 16269:2011 (E) 2 Contents Page Foreword 3Introduction .41 Scope 52 Terms and definitions .53 Symbols and abbreviations 64 Principle 85 Apparatus .86 Sampling, transport and storage 117 Analysis . 118 Calculation of results . 129 Quality control . 1510 Measurement uncertainty 1711
9、Artefacts and interferences . 1712 Reporting of results 18Annex A (informative) Example of a closed vessel microwave digestion procedure to determine elements in the water-insoluble fraction of PM2,519Annex B (informative) Preparation of stock standard solution . 21Annex C (informative) Uncertainty
10、budget. 22Annex D (informative) Data quality objectives 24Annex E (informative) Reagents . 26Bibliography . 31PD CEN/TR 16269:2011CEN/TR 16269:2011 (E) 3 Foreword This document (CEN/TR 16269:2011) has been prepared by Technical Committee CEN/TC 264 “Air quality”, the secretariat of which is held by
11、DIN. 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. PD CEN/TR 16269:2011CEN/TR 16269:2011 (E) 4 Introduction This CEN Technical Repor
12、t describes how to measure a specified range of anions and cations in PM2,5. The new EU Air Quality Directive 2008/50/EC on ambient air quality and cleaner air for Europe requests the measurements of concentrations of NO3-, SO42-, Cl-, NH4+, Na+, K+, Mg2+, Ca2+in PM2,5at rural background locations.
13、In Annex IV of the Directive, guidance for these measurements is given (see Annex D). Until now measurements of anions and cations in PM have been performed by the EMEP programme, mainly by using a filterpack with limited size selectivity. The Cooperative programme for monitoring and evaluation of l
14、ong-range transmission of air pollutants in Europe (EMEP) was launched in 1977 as a response to the growing concern over the effects on the environment caused by acid deposition. EMEP was organized under the auspices of the United Nations Economic Commission for Europe (UNECE). Today EMEP is an inte
15、gral component of the cooperation under the Convention on Long-range Transboundary Air Pollution. Directive 2008/50/EC requires that measurements at rural sites, where appropriate, shall be coordinated with the monitoring strategy and measurement programme of EMEP. Although, there are different samp
16、ling procedures involved, a common approach is used for the analytical procedure. In order to keep the agreement between existing EMEP data and data to be produced using this CEN technical report as close as possible, the EMEP protocol has been taken as starting point for this CEN technical report.
17、This CEN technical report differs from the EMEP protocol in the sense that measurement of anions and cations are done in PM2,5, and that a number of critical parameters (e.g. choice of filter materials) are fixed. Additional attention is given to harmonizing these critical parameters with elemental
18、carbon/organic carbon (EC/OC) measurements and with PM2,5measurements as well, as the sampling usually is done simultaneously. Finally, it should be noted that this CEN Technical Report has been produced in order to give assistance to those making measurements in accordance with Directive 2008/50/EC
19、 as rapidly as possible. However, there are still some open issues, including the influence of various sampling artefacts on the data quality, which can only be answered via validation work. This CEN Technical Report is not intended to supersede existing (inter)national standards or harmonized metho
20、ds. PD CEN/TR 16269:2011CEN/TR 16269:2011 (E) 5 1 Scope This CEN Technical Report specifies a method for the determination of the mass of water soluble NO3-, SO42-, Cl-, NH4+, Na+, K+, Mg2+, Ca2+in PM2,5 samples which can be used to comply with Directive 2008/50/EC. This CEN Technical Report describ
21、es a measurement method which comprises sampling of anions and cations as part of the PM2,5particulate phase, sample extraction and analysis of anions and cations by ion chromatography. Alternately, cations, excluding ammonium can be analysed by inductively coupled plasma optical emission spectromet
22、ry (ICP-OES). This CEN Technical Report may be used at rural background monitoring sites that are in accordance with the requirements of Directive 2008/50/EC. However, since this CEN Technical Report has not been validated in the field for these, or any other, monitoring site types, it may be consid
23、ered equally applicable to all site types. NOTE The detection limits described in this CEN technical report method will be limited by the noise level of the detector and the variability of the mass in laboratory blank filters rather than by the concentrations of anions and cations in ambient air. 2
24、Terms and definitions For the purposes of this document, the following terms and definitions apply. 2.1 ambient air outdoor air in the troposphere excluding workplace air EN 14907 2.2 high volume sampling method HVS method for sampling particulate matter with a flow rate of 30 m3/h EN 14907 2.3 low
25、volume sampling method LVS method for sampling particulate matter with a flow rate of 2,3 m3/h EN 14907 2.4 PM2,5fraction of suspended particulate matter which passes through a size-selective inlet with a 50 % cut-off efficiency at 2,5 m aerodynamic diameter EN 14907 2.5 PM10fraction of suspended pa
26、rticulate matter which passes through a size-selective inlet with a 50 % cut-off efficiency at 10 m aerodynamic diameter PD CEN/TR 16269:2011CEN/TR 16269:2011 (E) 6 2.6 suspended particulate matter SPM notion of all particles surrounded by air in a given, undisturbed volume of air EN 14907 2.7 measu
27、rement uncertainty non-negative parameter characterizing the dispersion of the quantity values being attributed to a measurand, based on the information used JGCM 200:2008 (VIM) 3 Symbols and abbreviations For the purposes of this document, the following symbols and abbreviated terms apply. 3.1 Symb
28、ols amb mass concentration of anions or cations in ambient air, in g/m3i deviation of the ithcalibration point from the best-fit calibration relationship iI peak area on the ion chromatogram for the relevant ion generated from measurement i samI peak area on the ion chromatogram for the relevant ion
29、 measured on the sampled filter I average of n measurements of iI blkI average peak area on the ion chromatogram for the relevant ion measured on a given number of blank filters k coverage factor to provide a 95 % level of confidence, usually assumed to be equal to 2 blk,im mass of anions or cations
30、 measured on the ithblank filter in a set of n , in g blkm average of n measurements of blkm extmtmass of extraction solution, in g ionm filter blank corrected mass of anions or cations measured in the PM on the sampled filter, in g MDLm method detection limit, expressed in g r ratio of sub-sampled
31、filter area to the total filter area, in m2/m2R peak resolution PD CEN/TR 16269:2011CEN/TR 16269:2011 (E) 7 R relative standard deviation of a set of n measurements s relative standard deviation of the measured analytical response in the centre of the application range based on 10 repeat measurement
32、s Ds relative standard deviation of the measurements of multiple extractions of sub-samples from the same filter is standard deviation of the measured analytical response for the ithcalibration point 1t retention time, in seconds, of the first peak 2t retention time, in seconds, of the second peak (
33、)ux estimated standard uncertainty in x rU relative expanded uncertainty of the measurement result ambV volume of ambient air sampled, in m3calVpore size 0,45 m) together with single use medical syringes can be used. 5.2.6 Ion chromatography system In general, it consists of the following components
34、: 5.2.6.1 Eluent reservoir, and a degassing unit 5.2.6.2 Metal-free high performance liquid chromatography (HPLC) pump 5.2.6.3 Sample injection system, incorporating a sample loop of appropriate volume (e.g. 0,02 ml) or autosampler device 5.2.6.4 Separator column, with the specified separating perfo
35、rmance 5.2.6.5 Conductivity detector (CD) 5.2.6.6 UV detector, e.g. a spectrophotometer, operating over the wavelength range: 190 nm to 400 nm, optionally used in combination with a CD for the determination of nitrate or nitrite 5.2.6.7 Recording device, e.g. a computer with software for data acquis
36、ition and evaluation 5.2.6.8 Precolumns, if necessary 5.2.6.9 Suppressor device, if necessary 5.2.7 Inductively coupled plasma optical emission spectrometer system In general, it consists of the following components: 5.2.7.1 Computer-controlled optical emission spectrometer with background correctio
37、n 5.2.7.2 Radiofrequency generator 5.2.7.3 Mass-flow controller A mass-flow controller on the nebulizer gas supply is recommended. NOTE The plasma is very sensitive to variations in the gas flow rate of the nebulizer gas. PD CEN/TR 16269:2011CEN/TR 16269:2011 (E) 11 5.2.7.4 Nebulizer, with variable
38、speed peristaltic pump Common nebulizers are the concentric nebulizer (e.g., Meinhard), the cross-flow nebulizer, the V-groove nebulizer and a cyclonic chamber with or without baffles. Other types of nebulizers may also be used if it can be shown that they are fit for purpose. 5.2.7.5 Ultrasonic neb
39、ulizer If very low concentration measurements are to be achieved, ultrasonic nebulizers are recommended. In this special type of nebulizer the sample solution is pumped through a tube that ends near the transducer plate that vibrates at an ultrasonic frequency. The amount of aerosol produced (the ef
40、ficiency) is typically 10 % to 20 % of the quantity of the pumped solution. As this is very high, the aerosol needs to be dried (desolvated) before being introduced into the plasma, which otherwise would be extinguished. The aerosol is transported to the plasma by the nebulizer gas. Disadvantages of
41、 the ultrasonic nebulizer include its greater susceptibility to matrix effects, diminished tolerance to high dissolved solid contents (approximately 0,5 % m/v) and a longer rinsing time. Vapour generation apparatus for hydride or cold vapour can also be used for sample introduction. 5.2.7.6 Argon ga
42、s supply Argon gas with a sufficient purity grade, for instance 99,95 %. 6 Sampling, transport and storage Sampling, as well as transport and storage of unloaded filters, should be performed according to EN 14907. NOTE EN 14907 is under revision and will be included in the forthcoming revision of EN
43、 12341. 7 Analysis 7.1 Filter sub-sampling For extraction of water-soluble constituents from the PM2,5filters, the whole filter can be used or a sub-sample, representative of the filter as a whole, may be taken. This can be done by using an appropriate cutting device to obtain an accurately defined
44、part of the exposed area of the sampled filter. 7.2 Sample extraction The filters are put into a sample tube and deionised water is added. The extraction volume should be as small as possible, but enough to completely cover the sample, typically at least 10 ml, for 47 mm filters. The sample tubes sh
45、ould be exposed in an ultrasonic bath for at least 30 minutes to obtain complete extraction. 7.3 Sample preparation If any filter material is expected to be present in the extract, the extracts should be filtered or centrifuged prior to analysis. PD CEN/TR 16269:2011CEN/TR 16269:2011 (E) 12 7.4 Anal
46、ysis of extracts The analysis of NO3-, SO42-, Cl-, NH4+, Na+, K+, Mg2+, Ca2+should follow EN ISO 10304-1 and EN ISO 14911 for ion chromatography or the procedure described in chapter 4.1 of the EMEP manual. A small volume of the sample, typically less than 0,5 ml, is introduced into the injection sy
47、stem of an ion chromatograph. The sample is mixed with an eluent and pumped through a guard column, a separation column, a suppressor device and a detector. The ion chromatograph should be calibrated with standard solutions containing known concentrations of the ions. At least five calibration solut
48、ions and one zero standard (blank solution of only deionized water) should be used to generate a suitable calibration curve. The concentration range depends on the sample; the calibration curve should cover concentrations lower and higher than the measured concentration. NOTE 1 The calibration stand
49、ards may contain 0, 0,5, 1,0, 2,5, 5,0 and 10,0 mg/l of the different ions. An example of the preparation of standard solutions is found in Annex B. Special attention should be paid to control contamination from ammonia in the laboratory air. All reagents should be of recognized analytical grade. The water used for dilution should be deionized and filtered. NOTE 2 Any other analytical method shown to be equivalent using the EC equivalence procedure may be used 11 NOTE 3 Further met
