CEN/TR 16269:2011

SLOVENSKI STANDARD
01-december-2011
Kakovost zunanjega zraka - Vodilo za merjenje anionov in kationov v frakciji PM2,5
Ambient air quality - Guide for the measurement of anions and cations in PM2,5
Außenluftqualität - Leitfaden zur Messung von Anionen und Cationen in PM2,5
Qualité de l'air ambiant - Guide pour le mesurage des anions et des cations dans la
fraction PM2,5
Ta slovenski standard je istoveten z: CEN/TR 16269:2011
ICS:
13.040.20 Kakovost okoljskega zraka Ambient atmospheres
2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.

TECHNICAL REPORT
CEN/TR 16269
RAPPORT TECHNIQUE
TECHNISCHER BERICHT
September 2011
ICS 13.040.20
English Version
Ambient air - Guide for the measurement of anions and cations
in PM2,5
Air ambiant - Guide pour le mesurage des anions et des Außenluft - Leitfaden zur Messung von Anionen und
cations dans la fraction PM2,5 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 Austria, 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.

EUROPEAN COMMITTEE FOR STANDARDIZATION
COMITÉ EUROPÉEN DE NORMALISATION

EUROPÄISCHES KOMITEE FÜR NORMUNG

Management Centre: Avenue Marnix 17, B-1000 Brussels
© 2011 CEN All rights of exploitation in any form and by any means reserved Ref. No. CEN/TR 16269:2011: E
worldwide for CEN national Members.

Contents Page
Foreword .3
Introduction .4
1 Scope .5
2 Terms and definitions .5
3 Symbols and abbreviations .6
4 Principle .8
5 Apparatus .8
6 Sampling, transport and storage . 11
7 Analysis . 11
8 Calculation of results . 12
9 Quality control . 15
10 Measurement uncertainty . 17
11 Artefacts and interferences . 17
12 Reporting of results . 18
Annex A (informative) Example of a closed vessel microwave digestion procedure to determine
elements in the water-insoluble fraction of PM . 19
2,5
Annex B (informative) Preparation of stock standard solution . 21
Annex C (informative) Uncertainty budget. 22
Annex D (informative) Data quality objectives . 24
Annex E (informative) Reagents . 26
Bibliography . 31

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 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.
Introduction
This CEN Technical Report describes how to measure a specified range of anions and cations in PM .
2,5
The new EU Air Quality Directive 2008/50/EC on ambient air quality and cleaner air for Europe requests the
- 2- - + + + 2+ 2+
measurements of concentrations of NO , SO , Cl , NH , Na , K , Mg , Ca in PM at rural background
3 4 4 2,5
locations. 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
long-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 integral
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 sampling
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. This CEN technical report differs from the EMEP protocol in the sense that measurement of
anions and cations are done in PM , and that a number of critical parameters (e.g. choice of filter materials)
2,5
are fixed.
Additional attention is given to harmonizing these critical parameters with elemental carbon/organic carbon
(EC/OC) measurements and with PM measurements as well, as the sampling usually is done
2,5
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 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 methods.
1 Scope
- 2-
This CEN Technical Report specifies a method for the determination of the mass of water soluble NO , SO ,
3 4
- + + + 2+ 2+
Cl , NH , Na , K , Mg , Ca in PM samples which can be used to comply with Directive 2008/50/EC.
4 2,5
This CEN Technical Report describes a measurement method which comprises sampling of anions and
cations as part of the PM particulate phase, sample extraction and analysis of anions and cations by ion
2,5
chromatography. Alternately, cations, excluding ammonium can be analysed by inductively coupled plasma
optical emission spectrometry (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 considered 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 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 m /h
[EN 14907]
2.3
low volume sampling method
LVS
method for sampling particulate matter with a flow rate of 2,3 m /h

[EN 14907]
2.4
PM
2,5
fraction of suspended particulate matter which passes through a size-selective inlet with a 50 % cut-off
efficiency at 2,5 µm aerodynamic diameter
[EN 14907]
2.5
PM
fraction of suspended particulate matter which passes through a size-selective inlet with a 50 % cut-off
efficiency at 10 µm aerodynamic diameter
2.6
suspended particulate matter
SPM
notion of all particles surrounded by air in a given, undisturbed volume of air

[EN 14907]
2.7
measurement 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 Symbols
γ  mass concentration of anions or cations in ambient air, in µg/m
amb
th
δ deviation of the i calibration point from the best-fit calibration relationship
i
I peak area on the ion chromatogram for the relevant ion generated from measurement i
i
I peak area on the ion chromatogram for the relevant ion measured on the sampled filter
sam
I average of n measurements of I
i
I  average peak area on the ion chromatogram for the relevant ion measured on a given number of blank
blk
filters
k coverage factor to provide a 95 % level of confidence, usually assumed to be equal to 2
th
m mass of anions or cations measured on the i blank filter in a set of n , in µg
blk,i
m average of n measurements of m
blk blk
m  mass of extraction solution, in g
t
ext
m filter blank corrected mass of anions or cations measured in the PM on the sampled filter, in µg
ion
m method detection limit, expressed in µg
MDL
2 2
r ratio of sub-sampled filter area to the total filter area, in m /m
R peak resolution
σ relative standard deviation of a set of n measurements
R
s relative standard deviation of the measured analytical response in the centre of the application range
based on 10 repeat measurements
s relative standard deviation of the measurements of multiple extractions of sub-samples from the same
D
filter
th
s standard deviation of the measured analytical response for the i calibration point
i
t retention time, in seconds, of the first peak
t retention time, in seconds, of the second peak
ux() estimated standard uncertainty in x
U relative expanded uncertainty of the measurement result
r
V volume of ambient air sampled, in m
amb
&
V gradient of calibration curve (sensitivity) produced by the ion chromatograph, in g/µg
cal
&
V measured sensitivity of the instrument at time t = 0
cal, 0t=
&
V measured sensitivity of the instrument at time t
cal, tt=
&
∆V drift in the sensitivity of the ion chromatograph over a time, t
cal
w peak width on the time axis, in seconds, of the first peak
w peak width on the time axis, in seconds, of the second peak
w  peak width of peak i
i
x filter blank corrected mass fraction of anions or cations in the PM extract, in µg/g
ext
3.2 Abbreviations
CD  conductivity detector
EA  European cooperation for accreditation
FEP  hexafluoroethene propene
HDPE high density polyethene
HPLC high performance liquid chromatography
HVS high volume sampler
ICP-MS inductively coupled plasma atomic mass spectrometry
ICP-OES inductively coupled plasma optical emission spectrometry
LVS  low volume sampler
MLA multi-lateral agreement
NIST national institute for standards and technology
PE  polyethene
PFA  perfluoroalkoxy
PM  particulate matter
PP  polypropylene
PTFE polytetrafluoroethene
SPM suspended particulate matter
UV  ultraviolet
4 Principle
This method allows the determination of anions (chloride, nitrate and sulfate) and cations (sodium,
ammonium, potassium, magnesium and calcium) in PM collected on filters used for sampling ambient air.
2,5
The method is divided into two main parts: the sampling in the field and the analytical procedure in the
laboratory.
During the sampling, particles containing anions and cations are collected by drawing a measured volume of
air through a filter mounted in a sampler designed to collect the PM fraction of suspended particulate matter.
2,5
The sampled filter is transported to the laboratory, where the anions and cations are taken into solution by
ultrasonic extraction with deionised water. The resultant extract is analysed separately for anions and cations
by ion chromatography (for all ions), or ICP-OES (for cations, except ammonium).
5 Apparatus
5.1 Sampling equipment
5.1
...