EN 15549:2008

SLOVENSKI STANDARD
01-julij-2008
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Air quality - Standard method for the measurement of the concentration of benzo[a]
pyrene in ambient air
Luftbeschaffenheit - Messverfahren zur Bestimmung der Konzentration von Benzo[a]
pyren in Luft
Méthode de mesurage de la concentration du benzo [a] pyrene dans l'air ambiant
Ta slovenski standard je istoveten z: EN 15549:2008
ICS:
13.040.20 Kakovost okoljskega zraka Ambient atmospheres
2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.

EUROPEAN STANDARD
EN 15549
NORME EUROPÉENNE
EUROPÄISCHE NORM
March 2008
ICS 13.040.20
English Version
Air quality - Standard method for the measurement of the
concentration of benzo[a]pyrene in ambient air
Qualité de l'air - Méthode normalisée pour le mesurage de Luftbeschaffenheit - Messverfahren zur Bestimmung der
la concentration de benzo[a]pyrène dans l'air ambiant Konzentration von Benzo[a]pyren in Luft
This European Standard was approved by CEN on 2 February 2008.
CEN members are bound to comply with the CEN/CENELEC Internal Regulations which stipulate the conditions for giving this European
Standard the status of a national standard without any alteration. Up-to-date lists and bibliographical references concerning such national
standards may be obtained on application to the CEN Management Centre or to any CEN member.
This European Standard exists in three official versions (English, French, German). A version in any other language made by translation
under the responsibility of a CEN member into its own language and notified to the CEN Management Centre has the same status as the
official versions.
CEN members are the national standards bodies of Austria, Belgium, Bulgaria, 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: rue de Stassart, 36  B-1050 Brussels
© 2008 CEN All rights of exploitation in any form and by any means reserved Ref. No. EN 15549:2008: E
worldwide for CEN national Members.

Contents Page
Foreword.3
Introduction.4
1 Scope .5
2 Normative references .5
3 Terms and definitions .5
4 Symbols and abbreviations.7
5 Principle of the method.8
6 Requirements.9
7 Reagents and gases.11
8 Apparatus .12
9 Sampling.13
10 Sample preparation .14
11 Analysis .15
12 Quantification.17
13 Quality control .21
14 Determination of measurement uncertainty .23
15 Interferences .25
16 Reporting of results.26
Annex A (informative) Sampling systems .27
Annex B (informative) Extraction methods (examples of experimental conditions) .30
Annex C (informative) Example for clean-up procedure.32
Annex D (informative) Parameters for analysis (examples) .33
Annex E (informative) Assessment of performance indicators and uncertainty contributions .35
Annex F (informative) Results of laboratory and field tests .44
Bibliography.50

Foreword
This document (EN 15549:2008) has been prepared by Technical Committee CEN/TC 264 “Air quality”, the
secretariat of which is held by DIN.
This 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 2008, and conflicting national standards shall be
withdrawn at the latest by September 2008.
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.
This document has been prepared under a mandate given to CEN by the European Commission and the
European Free Trade Association, and supports essential requirements of EU Directive(s).
According to the CEN/CENELEC Internal Regulations, the national standards organizations of the following
countries are bound to implement this European Standard: Austria, Belgium, Bulgaria, 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 the United Kingdom.
Introduction
The European Directive 2004/107/EC prescribes the reference methodology for the measurement of
benzo[a]pyrene (BaP) in ambient air and states that the method shall be a method based on manual PM10
sampling systems described in EN 12341 or equivalent.
Hence, this European Standard describes a method in which the sampling systems fulfil this requirement.
However, in the course of drafting this European Standard it became clear that in certain circumstances, in the
presence of oxidants such as ozone, BaP may be degraded. In specific situations this may result in losses of
BaP of > 50 %. It has been shown that the degradation due to ozone can be substantially reduced by
including an ozone denuder in the sampling system.
To date only a limited number of experiments has been performed in order to evaluate the particular
conditions under which the denuder systems can be efficiently used. Consequently, the application of ozone
denuders lacks sufficient validation to be a normative part of this European Standard.
In order to have a complete picture of the performance of ozone denuder systems further information is
required on:
• efficiency under variable atmospheric conditions,
• regeneration time after exposure to high humidity,
• maximum capacity for ozone,
• maximum sample volume and maximum sampling period,
• stability of catalyst,
• maximum period of use,
• particle losses.
Examples of sampling using an ozone denuder are given in Annex A.
The experimental evidence collected so far is presented in Annex F.
It is recommended that further work is undertaken to provide data of BaP comparisons with and without ozone
denuders.
1 Scope
This document specifies a measurement method for the determination of particulate benzo[a]pyrene (BaP) in
ambient air, which can be used in the framework of the Council Directive 96/62/EC [1] and the Directive
2004/107/EC [2]. This document specifies performance characteristics and performance criteria for the
measurement method when it is used as a reference method. The performance characteristics of the
measurement method are based on a sampling period of 24 h.
This document describes a measurement method which comprises sampling of BaP 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 BaP in the concentration range from approx. 0,04 ng/m to
approximately 20 ng/m .
The lower limit of the applicable range depends on the noise level of the detector and the variability of the
laboratory filter blank.
NOTE If the BaP concentration exceeds the calibration range the extract can be diluted.
2 Normative references
The following referenced documents are indispensable for the application of this document. For dated
references, only the edition cited applies. For undated references, the latest edition of the referenced
document (including any amendments) applies.
EN 12341:1998, Air quality – Determination of the PM 10 fraction of suspended particulate matter – Reference
method and field test procedure to demonstrate reference equivalence of measurement methods
ENV 13005:1999, Guide to the expression of uncertainty in measurement
ISO 8258, Shewhart control charts (including ISO 8258:1993 Technical Corrigendum 1)
3 Terms and definitions
For the purposes of this document, the following terms and definitions apply.
3.1
calibration solution
solution used for calibration of the analytical instrument, containing the analyte of interest at a suitable
concentration, prepared by dilution of the stock standard solution
3.2
certified reference material (CRM)
reference material one or more of whose property values are certified by a technically valid procedure,
accompanied by or traceable to a certificate or other documentation that is issued by a certifying body
3.3
external standard solution
solution of the analyte of known concentration
3.4
field blank filter
filter that is taken through the same procedure as a sample, except that no air is drawn through it
3.5
internal standard solution
solution of a known substance of known concentration, added to the 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
3.7
PM10
target specification for sampling the thoracic particles
[EN 12341:1998]
3.8
reagent blank solution
solution that contains all the reagents used during analysis of the sample, but without the sample and filter
matrix
[EN 14902:2005] [27]
3.9
stock standard solution
solution used for preparing calibration solutions, containing the analyte of interest at a concentration traceable
to national or international standards
3.10
surrogate standard solution
solution of a known substance and of known concentration, used to spike filters before extraction in order to
check the recovery efficiency
3.11
target value
concentration in the ambient air fixed with the aim of avoiding, preventing or reducing harmful effects on
human health and the environment, as a whole, to be attained where possible over a given period
NOTE This definition originates from [2]. The current value for BaP is 1 ng/m for the total content in the PM10
fraction averaged over a calendar year.
3.12
uncertainty (of measurement)
parameter associated with the result of a measurement, that characterises the dispersion of the values that
could reasonably be attributed to the measurand
[ENV 13005:1999]
4 Symbols and abbreviations
4.1 Symbols
a is the slope of linear calibration function;
A is the peak area or peak height of BaP or of its characteristic ion in the chromatogram of the
C
calibration solution;
A is the peak area or peak height of BaP or of its characteristic ion in the chromatogram of the sample
E
extract;
A is the peak area or peak height of the internal standard or of its characteristic ion in the chromatogram
IS
of the calibration solution;
A is the peak area or peak height of the internal standard or of its characteristic ion in the chromatogram
ISE
of the sample extract;
b is the intercept of the linear calibration function;
C is the concentration of BaP in ambient air in ng/m³;
D is the detection limit, expressed in ng/m³;
C
D is the absolute detection limit in the sample in ng;
M
f is the response factor of BaP;
m is the mean of laboratory filter blanks in ng;
m is the mass of BaP in the calibration solution in ng;
C
m is the certified mass in the CRM in ng;
CRM
m is the mass of BaP in the sample extract in ng;
E
m is the mass of BaP on the filter sample in ng;
F
m is the individual filter blank in ng;
i
m is the mass of the internal standard in the calibration solution in ng;
IS
m is the mass of
...