SIST-TS CEN/TS 16645:2014

SLOVENSKI STANDARD
SIST-TS CEN/TS 16645:2014
01-julij-2014
=XQDQML]UDN0HWRGD]DGRORþHYDQMHEHQ]R>D@DQWUDFHQDEHQ]R>E@IOXRUDQWHQD
EHQ]R>M@IOXRUDQWHQDEHQ]R>N@IOXRUDQWHQDGLEHQ]R>DK@DQWUDFHQDLQGHQR>FG@
SLUHQDLQEHQ]R>JKL@SHULOHQD
Ambient air - Method for the measurement of benz[a]anthracene, benzo[b]fluoranthene,
benzo[j]fluoranthene, benzo[k]fluoranthene, dibenz[a,h]anthracene, indeno[1,2,3-cd]
pyrene and benzo[ghi]perylene
Außenluft - Verfahren zur Messung von Benz[a]anthracen, Benzo[b]fluoranthen, Benzo[j]
fluoranthen, Benzo[k]fluoranthen, Dibenz[a,h]anthracen, Indeno[1,2,3-cd]pyren und
Benzo[ghi]perylen
Air ambiant - Méthode pour la mesure de benz[a]anthracène, benzo[b]fluoranthène,
benzo[j]fluoranthène, benzo[k]fluoranthène, dibenz[a,h]anthracène, indeno[1,2,3-cd]
pyrène et benzo[ghi]perylène
Ta slovenski standard je istoveten z: CEN/TS 16645:2014
ICS:
13.040.20 Kakovost okoljskega zraka Ambient atmospheres
SIST-TS CEN/TS 16645:2014 en,fr,de
2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.

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SIST-TS CEN/TS 16645:2014

TECHNICAL SPECIFICATION
CEN/TS 16645

SPÉCIFICATION TECHNIQUE

TECHNISCHE SPEZIFIKATION
April 2014
ICS 13.040.20
English Version
Ambient air - Method for the measurement of benz[a]anthracene,
benzo[b]fluoranthene, benzo[j]fluoranthene,
benzo[k]fluoranthene, dibenz[a,h]anthracene, indeno[1,2,3-
cd]pyrene and benzo[ghi]perylene
Air ambiant - Méthode pour la mesure de Außenluft - Verfahren zur Messung von Benz[a]anthracen,
benz[a]anthracène, benzo[b]fluoranthène, Benzo[b]fluoranthen, Benzo[j]fluoranthen,
benzo[j]fluoranthène, benzo[k]fluoranthène, Benzo[k]fluoranthen, Dibenz[a,h]anthracen, Indeno[1,2,3-
dibenz[a,h]anthracène, indeno[1,2,3-cd]pyrène et cd]pyren und Benzo[ghi]perylen
benzo[ghi]perylène
This Technical Specification (CEN/TS) was approved by CEN on 16 December 2013 for 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 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 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,
Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland, Turkey and United
Kingdom.





EUROPEAN COMMITTEE FOR STANDARDIZATION
COMITÉ EUROPÉEN DE NORMALISATION

EUROPÄISCHES KOMITEE FÜR NORMUNG

CEN-CENELEC Management Centre: Avenue Marnix 17, B-1000 Brussels
© 2014 CEN All rights of exploitation in any form and by any means reserved Ref. No. CEN/TS 16645:2014 E
worldwide for CEN national Members.

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Contents Page
Foreword . 4
Introduction . 5
1 Scope . 6
2 Normative references . 7
3 Terms and definitions . 7
4 Symbols and 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 standard . 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 of 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 Analysis . 21
12.3 Concentration of the PAH compounds in ambient air . 22
13 Quality control . 23
13.1 Reagent blank check . 23
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13.2 Calibration drift check. 23
13.3 Control solutions . 23
13.4 Recovery efficiency check . 23
13.5 Chromatographic interference check . 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 . 27
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 . 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
47
validation data .
Bibliography . 51

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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. 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, 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 United Kingdom.
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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 15980 [6] (determination of the deposition of several particle bound PAH compounds).
Many data on the performance of the extraction and analysis of benz[a]anthracene (BaA),
benzo[b]fluoranthene (BbF), benzo[j]fluoranthene (BjF), benzo[k]fluoranthene (BkF), dibenz[a,h]anthracene
(DBahA), indeno[1,2,3-cd]pyrene (INP) and benzo[ghi]perylene (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 with EN 15549 [5], once adequate progress has been made
in the development of reliably working oxidant denuders.
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1 Scope
This Technical Specification specifies a measurement method for the determination of the particle bound
polycyclic aromatic hydrocarbon (PAH) compounds benz[a]anthracene (BaA), benzo[b]fluoranthene (BbF),
benzo[j]fluoranthene (BjF), benzo[k]fluoranthene (BkF), dibenz[a,h]anthracene (DBahA), indeno[1,2,3-
cd]pyrene (INP) and benzo[ghi]perylene (BghiP) in ambient air, which can be used in the framework of
Council Directive 2008/50/EC [10] and Directive 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 sampling 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 PAH compounds in the
3 3
concentration range from approx. 0,04 ng/m to approximately 20 ng/m for BaA, BbF, BjF, BkF, BaP, INP and
3 3
BghiP and 0,02 ng/m to approximately 2 ng/m for DBahA. Table 1 shows examples for concentrations of the
compounds (annual mean values) for sampling sites with different characteristics.
Table 1 — Examples of annual mean values of PAH compounds in PM10 at sampling sites with
3
)
different characteristics (in ng/m
a b c d
Compound Industrial Urban background Traffic Rural background
BaA 0,85 0,24 0,24 0,06
BbF 2,44 0,62
e e
0,16
0,48
BjF 0,89 0,27
BkF 0,89 0,24 0,17 0,15
BaP 1,15 0,29 0,27 0,13
f g
BghiP 1,31 0,20 0,34 0,09
f h
DBahA 0,20 0,10 0,05 0,07
INP 1,60 0,43 0,23 0,08
a
Bottrop (Germany, 2010), HPLC/FLD.
b
Mülheim-Styrum (Germany, 2010), HPLC/FLD.
c
London Crystal Palace Parade (UK, 2010), GC-MS.
d
Harwell (UK, 2010), GC-MS.
e
(Bbf+BjF).
f
Wijk aan Zee (The Netherlands, 2011), GC-MS.
g
Rotterdam (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.
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2 Normative references
The following documents, in whole 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 gravimetric 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 requirements 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: Basic 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 used 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 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 identical 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]]
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3.5
internal standard solution
solution of known compounds of known concentrations, 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
[SOURCE: EN 15549:2008 [5]]
3.7
PM10
particulate matter suspended in air which is small enough to pass through a size-selective inlet with a 50 %
efficiency cut-off at 10 µm 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 suspended 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 to 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 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: This 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/IEC Guide 98-3:2008]
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4 Symbols and abbreviations
4.1 Symbols
a is the slope of linear calibration function
A is the peak area or peak height of a PAH compound or of its characteristic ion in the chromatogram
C
of the calibration solution
A is the peak area or peak height of a PAH compound or of its characteristic ion in the chromatogram
E
of the sample extract
A is the peak area or peak height of the internal standard or of its characteristic ion in the
IS
chromatogram of the calibration solution
A is the peak area or peak height of the internal standard or of its characteristic ion in the
ISE
chromatogram of the sample extract
b is the intercept of the linear calibration function
3
C is the concentration of the PAH compound in ambient air, in ng/m
3
D is the detection limit, in ng/m
C
D is the absolute detection limit in the sample, in ng
M
f is the response factor of the PAH compound
m is the mean of laboratory filter blanks, in ng
b
m
is the mass of the PAH compound in the calibration solution, in ng
C
m is the certified mass in the CRM, in ng
CRM
m
is the mass of the PAH compound in the sample extract, in ng
E
m is the mass of the PAH compound 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 the internal standard in the sample extract, in ng
ISE
m is the mass of the PAH compound calculated from the regression formula at the level of the
reg
calibration standard, in ng
m is the mass of the surrogate standard in the sample extract, in ng
SSE
m is the mass of the surrogate standard added to the filter, in ng
SSF
m/z is the mass-to-charge ratio;
n
is the number of analysed filters;
R is the recovery efficiency of the PAH compound, in %;
R
is the peak resolution
s
S is the standard deviation of laboratory filter blanks, in ng
lfb
s(m ) is the standard deviation of the replicate measurement results of the mass determined, in ng
E
t is the sampling time, in h
t
is the Student factor for n measurements and a 95 % confidence interval
n–1;0,95
t is the retention time for peak 1, in min
R1
t
is the retention time for peak 2, in min
R2
is the volume of the extract, in ml
VE
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3
V is the volume of air sampled in, m
3
V
is the nominal daily sampling volume, in m
n
w is the peak width of peak 1, in min
1
w is the peak width of peak 2, in min
2
X is the measured mass fraction of the PAH compound, in mg/kg
a
X is the certified mass fraction of the PAH compound, in mg/kg
ca
4.2 Abbreviations
BaA Benz[a]anthracene
BaP Benzo[a]pyrene
Benzo[b]fluoranthene
BbF
BghiP Benzo[ghi]perylene
BjF Benzo[j]fluoranthene
BkF Benzo[k]fluoranthene
CRM Certified reference material
DAD Diode array detection
Dibenz[a,h]anthracene
DBahA
FLD Fluorescence detection
GC Gas chromatography
HPLC High performance liquid chromatography
INP Indeno[1,2,3-cd]pyrene
MS Mass spectrometry
PAH Polycyclic aromatic hydrocarbon
PTFE Polytetrafluoroethylene
QA/QC Quality Assurance/Quality Control
TSP Total suspended particulates
5 Principle of the method
The method is divided into two main parts: the sampling of PM10 in the field and the analysis of the specified
PAHs in the laboratory.
The sampling time is 24 h. The filter is transported to the laboratory. The PAH compounds are extracted using
an organic solvent. If necessary, the extract is cleaned up. The resulting solution is analysed by HPLC/FLD or
GC-MS.
6 Requirements
6.1 Siting requirements
Specific siting requirements depend on the objectives of the measurements. For measuring in compliance with
Directive 2004/107/EC [11] then the instructions for siting samplers given in [11] will need to be followed.
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6.2 Sampling requirements
The sampling system shall fulfil the requirements of EN 12341.
In the presence of oxidants (e.g. ozone, OH radicals) PAH compounds may degrade. Whenever these effects
are expected to be significant, the PM10 sampler may be equipped with an oxidant (e.g. ozone) denuder
(see Annex A). However, the application of these denuders lacks sufficient validation to be a normative part of
this Technical Specification.
NOTE The analytical methods are also suitable for PAH determination in other PM particle size fractions (e.g. PM2.5
and TSP).
6.3 Analysis
6.3.1 Recovery efficiency
Using the external or internal standard method for quantification check the recovery efficiency within every
analytical batch by spiking laboratory blank filters with a known amount of the PAH compounds and process
them as usual. The recovery efficiency shall be between 80 % and 120 %.
If the surrogate standard method (see 12.1.3) is used this recovery check is not necessary. The surrogate
recovery for field samples shall not be less than 50 %, otherwise the sample shall be discarded.
If the surrogate recovery is constantly less than 70 %, this indicates problems with the sample preparation
procedure. These problems should be eliminated.
Check the recovery efficiency of the method for the PAH compounds in certified reference material
(e.g. NIST 1649b, ERM-CZ 100) using Formula (1):
X
a
R= ⋅100
(1)
X
ca
where
R is the recovery efficiency of the PAH compound, in %;
X
is the measured mass fraction of the PAH compound, in mg/kg;
a
X is the certified mass fraction of the PAH compound, in mg/kg.
ca
The recovery efficiency shall be between 80 % and 120 %.
NOTE A certified reference material containing the same matrix as ambient PM10 particles collected on filters is not
available at the moment. Interferences occurring to field samples, e.g. chemical reactions of the PAH compounds during
extraction, can be identified, for example, by:
• repeating the extraction step with a different method and comparing the results;
• comparing the ratio of the PAH compounds to at least one more stable and high-boiling PAH like
benzo[e]pyrene or benzo[k]fluoranthene: an indication for problems occurring during the sample preparation procedure is
that deviations (lower ratios) with respect to previous measurements at the same location and in the same season are
observed; changing the sample preparation procedure (different extraction solvent, different purification procedure) can
verify the problem.
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6.3.2 Detection limit
6.3.2.1 General
The detection limit can be calculated either based on laboratory filter blanks or, if no peaks corresponding to
the PAH compounds can be identified in filter blanks, based on the signal-to-noise ratio.
3
In general the detection limit shall be less than 0,04 ng/m . If the 3 benzofluoranthene species are analysed
3
as a sum, their cumulated detection limit shall be less than 0,1 ng/m . If BjF is analysed by HPLC-FLD, its
3
detection limit is about 0,4 ng/m .
6.3.2.2 Determination based on laboratory filter blanks
Determine the detection limit from the standard deviation of at least 10 laboratory filter blanks, analysed like
the real samples, using Formula (2):
n
2
(m − m
...