SIST EN 16913:2017

SLOVENSKI STANDARD
SIST EN 16913:2017
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Ta slovenski standard je istoveten z: EN 16913:2017
ICS:
13.040.20 Kakovost okoljskega zraka Ambient atmospheres
SIST EN 16913:2017 en,fr,de
2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.

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SIST EN 16913:2017

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SIST EN 16913:2017


EN 16913
EUROPEAN STANDARD

NORME EUROPÉENNE

June 2017
EUROPÄISCHE NORM
ICS 13.040.20
English Version

Ambient air - Standard method for measurement of NO₃ˉ,
SO₄²ˉ, Clˉ, NH₄⁺, Na⁺, K⁺, Mg²⁺, Ca²⁺ in PM2,5 as deposited
on filters
Air ambiant - Méthode normalisée pour le mesurage de  Außenluft - Messverfahren zur Bestimmung von NO₃ˉ,
NO₃ˉ, SO₄²ˉ, Clˉ, NH₄⁺, Na⁺, K⁺, Mg²⁺, Ca²⁺ dans la SO₄²ˉ, Clˉ, NH₄⁺, Na⁺, K⁺, Mg²⁺, Ca²⁺ in PM2,5 nach
fraction PM2,5 telle que déposée sur des filtres Abscheidung auf Filtern
This European Standard was approved by CEN on 27 February 2017.

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-CENELEC 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-CENELEC Management
Centre has the same status as the official versions.

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, Serbia, Slovakia, Slovenia, Spain, Sweden, Switzerland,
Turkey and United Kingdom.





EUROPEAN COMMITTEE FOR STANDARDIZATION
C OM I TÉ E U R O P É E N D E N OR M A L I S A TI O N

E U R OP ÄI S C H E S K OM I TE E F Ü R N OR M U N G

CEN-CENELEC Management Centre: Avenue Marnix 17, B-1000 Brussels
© 2017 CEN All rights of exploitation in any form and by any means reserved Ref. No. EN 16913:2017 E
worldwide for CEN national Members.

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SIST EN 16913:2017
EN 16913:2017 (E)
Contents Page
European foreword . 4
Introduction . 5
1 Scope . 6
2 Normative references . 7
3 Terms and definitions . 7
4 Symbols and abbreviations . 7
5 Principle . 8
6 Equipment . 8
7 Sampling . 9
8 Transport and storage . 10
9 Analysis . 10
10 Calculation of results . 12
11 Quality control . 14
12 Measurement uncertainty . 17
13 Artefacts and interferences . 18
14 Data recording . 19
Annex A (informative) Statistical analysis of anion and cation concentrations collected on
filters from field validation exercise . 20
A.1 General . 20
A.2 Analysis methodology . 20
A.2.1 General . 20
A.2.2 Calculating between- and within-laboratory variability . 20
A.2.2.1 Notation . 20
A.2.2.2 Data processing . 21
A.2.2.3 Outlier rejection . 21
A.2.2.4 Data normalization . 22
A.2.2.5 Analysis of variance . 22
A.2.2.6 Calculation of standard deviations . 23
A.2.3 Calculating between-sampler variability . 23
A.2.3.1 Notation . 23
A.2.3.2 Data processing . 24
A.2.4 Combined standard uncertainty . 25
A.3 Remarks . 25
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A.4 Results . 25
A.4.1 Data set 1 – Between laboratory and internal laboratory variability . 25
A.4.2 Data set 2 – Between sampler variability . 26
A.4.3 Data set 3 – Uncertainty over the measured concentration range . 27
A.4.4 Detection limit . 31
A.4.5 Field Blanks . 31
Annex B (informative) Uncertainty budget . 33
Annex C (informative) Reagents . 36
C.1 General . 36
C.2 Anion determination by ion chromatography . 36
C.3 Cation determination by ion chromatography . 37
C.4 Cation determination by inductively coupled plasma optical emission spectrometry
(ICP-OES) . 38
C.5 Ammonium determination by photometry . 39
Annex D (informative) Other analysis methods used in the validation programme . 41
D.1 Inductively coupled plasma optical emission spectrometer system (ICP-OES). 41
D.2 Conductometry . 41
D.3 Photometry . 42
D.3.1 Equipment . 42
D.3.2 Preparation of calibration curve. 42
D.3.3 Analytical procedure . 42
Annex E (informative) Preparation of stock standard solution . 43
Annex F (informative) Sampling artefacts . 44
F.1 General . 44
F.2 Ammonium nitrate . 44
F.3 Chloride . 45
Bibliography . 46

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EN 16913:2017 (E)
European foreword
This document (EN 16913:2017) 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 December 2017, and conflicting national standards
shall be withdrawn at the latest by December 2017.
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.
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,
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, Serbia, Slovakia, Slovenia, Spain, Sweden, Switzerland,
Turkey and the United Kingdom.
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Introduction
This European Standard describes how to measure a specified range of anions and cations in PM as
2,5
deposited on filters.
The EU Air Quality Directive 2008/50/EC [1] on ambient air quality and cleaner air for Europe requests
- 2- - +, + + 2+ 2+
the measurements of concentrations of NO , SO , Cl, NH Na , K , Mg , Ca in PM at rural
3 4 4 2,5
background locations. In Annex IV of the Directive, guidance for these measurements is given.
Measurements of anions and cations in PM are being performed by the EMEP programme, mainly by
using a filterpack with limited particle 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, are 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
European Standard as close as possible, the EMEP protocol has been taken as starting point for this
European Standard. This European Standard 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
2,5
(e.g. choice of filter material) 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 sampling is usually done
2,5
simultaneously.
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1 Scope
This European Standard specifies a method for the determination of the mass concentration of water
- 2- - + + +
soluble NO (nitrate), SO (sulphate), Cl (chloride), NH (ammonium), Na (sodium), K (potassium),
3 4 4
2+ 2+
Mg (magnesium), Ca (calcium) in PM as deposited on filters.
2,5
This European Standard describes the analytical procedures for determining anions and cations as part
of the PM particulate phase, sample extraction and analysis of anions and cations by ion
2,5
chromatography. Sampling onto filters will be done in accordance with EN 12341 for PM .
2,5
NOTE 1 Alternatively, cations, excluding ammonium, can be analysed by inductively coupled plasma optical
emission spectrometry (ICP-OES). Ammonium can also be analysed by photometry or conductometry.
This European Standard can be used for the measurements of anions and cations as required by
Directive 2008/50/EC. The method does not take into account the possible losses during sampling due
to evaporation.
- - +
NOTE 2 NO3 , Cl , NH4 are part of the volatile fraction of PM2,5, and the concentrations determined using this
- + -
standard can be used as minimum values for the concentrations of these ions in PM . NO , NH , Cl are usually
2,5 3 4
up to 30 % underestimated due to evaporational losses from the filter during sampling.
This European Standard may be used at rural and urban background sites and road sites that are in
accordance with the siting criteria of Directive 2008/50/EC.
This European Standard is applicable to the measurement of anion/cations in PM samples
2,5
3
corresponding to PM mass concentrations between approximately 1 μg/m (i.e. the limit of detection
2,5
3
of the standard measurement method (EN 12341) expressed as its uncertainty) up to 120 μg/m .
The validated range of the anion and cation concentrations based on the field validation measurements
is presented in Table 1.
Table 1 — Validated range of anions and cations
Component Minimum Maximum
3 3
μg/m μg/m
-
Cl 0,001 1,4
-
NO 0,002 29
3
2-
SO 0,05 13
4
+
Na 0,003 1,9
+
NH 0,04 11
4
+
K 0,003 0,49
2+
Mg 0,001 0,38
2+
Ca 0,002 0,72

See Annex A for the statistical analysis of the field validation measurements.
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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 12341:2014, Ambient air — Standard gravimetric measurement method for the determination of the
PM10 or PM2,5 mass concentration of suspended particulate matter
3 Terms and definitions
For the purposes of this document, the terms and definitions given in EN 12341:2014 and the following
apply.
NOTE In particular, the following terms of EN 12341 are used in this document: calibration, combined
standard uncertainty, coverage factor, expanded uncertainty, PM, standard uncertainty, uncertainty (of
x
measurement).
3.1
field filter blank
filter that is taken through the same procedure as a sample, including transport to and from, and
storage in the field, and analysis, but is not used for sampling air
Note 1 to entry: The filter is taken from the same batch as used for sampling.
3.2
laboratory filter blank
unused filter that does not leave the laboratory and is taken through the same procedure as a sample
Note 1 to entry: The filter is taken from the same batch as used for sampling.
3.3
reagent blank
solution that contains all the reagents used during the analysis of the sample, but without the sample
and filter matrix
4 Symbols and abbreviations
For the purposes of this document, the following abbreviations apply.
EMEP Cooperative programme for monitoring and evaluation of long-range transmission of air
pollutants in Europe
CD Conductivity Detector
FEP Fluorinated Ethylene Propylene
HDPE High Density PolyEthylene
HPLC High Performance Liquid Chromatography
ICP-MS Inductively Coupled Plasma Mass Spectrometry
ICP-OES Inductively Coupled Plasma Optical Emission Spectrometry
NIST National Institute for Standards and Technology
PE Polyethylene
7

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PFA Perfluoroalkoxy
PM particulate matter
PP Polypropylene
PTFE Polytetrafluoroethylene
5 Principle
- - 2- + + + 2+
This method allows the determination of anions (Cl , NO and SO ) and cations (Na , NH , K , Mg and
3 4 4
2+
Ca ) in PM collected on filters used for sampling ambient air. The method is divided into two main
2,5
parts: the sampling in the field and the analytical procedure in the laboratory.
During 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
2,5
particulate matter. The loaded filter is transported to the laboratory, where the anions and cations are
extracted deionized water by ultrasonic extraction. The extraction solution is analysed separately for
anions and cations by ion chromatography.
NOTE Alternatively, cations, excluding ammonium can be analysed by inductively coupled plasma optical
emission spectrometry (ICP-OES). Ammonium can also be analysed by photometry or conductometry.
6 Equipment
6.1 Sampling equipment
The performance requirements of the sampling instrument are described in EN 12341, including
Annex B.
6.2 Laboratory equipment
6.2.1 General requirements
All surfaces in contact with the sample filters, sample and calibration solutions shall be made of inert
material with respect to the analytes measured. High density polyethylene (HDPE) is normally a
suitable material. However, always check the material with respect to the specific purpose, e.g. for the
storage of standard solutions as well as for the determination of elements at an ultra-trace level,
fluorocarbon polymer materials such as perfluoroalkoxy (PFA) or hexafluoro ethylene propene (FEP)
may be advantageous. If cations are to be analysed, do not use glassware.
Wash all labware thoroughly and rinse with deionized water before use.
NOTE Contaminated labware can be cleaned with hot tap water and alkaline detergent before being taken
through the normal cleaning procedure.
6.2.2 General labware
Ordinary labware like volumetric flasks, pipettes, dispensers, PE vessels for sample extraction, storage
bottles (PE) for standard solutions and test tubes.
6.2.3 Filtration equipment
Use syringe filters (e.g. cellulose acetate or nylon; pore size 0,45 μm) together with single use medical
syringes.
Alternatively, membrane filtration equipment (PE, PP or PTFE) and membrane filters of a median pore
size 0,45 μm can be used.
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6.2.4 Ion chromatography system
In general, it consists of the following components:
— eluent reservoir, and a degassing unit;
— metal-free high performance liquid chromatography (HPLC) pump;
— sample injection system, incorporating a sample loop of appropriate volume (e.g. 0,02 ml) or
autosampler device;
— separator column, with the specified separating performance;
— conductivity detector (CD);
— recording device, e.g. a computer with software for data acquisition and evaluation;
— precolumns, if necessary;
— suppressor, if necessary.
7 Sampling
7.1 Filter material.
Quartz fibre filters shall be used for sampling.
It is recommended that filters used should be from a manufacturer who has determined the separation
efficiency of the filter material according to standard methods such as EN 13274-7 [10] or
EN 1822-1 [9].
The anion and cation content of the filter should be as low as possible because it is usually the case that
higher filter blank values lead to higher variability of the blank values.
Brand related restrictions cannot be made, because brand specific qualities are bound to change in time.
1)
+
Currently the use of Whatman® QMA should be discouraged because of the high Na blanks and the
1)
+
uncertainty to what level the water soluble Na per batch may vary. Pallflex® Tissuequartz and
1)
Munktell® MK360 are advised [2].
7.2 Sampling time.
Samples shall be taken for 24 h periods. In case of regulatory measurements filter exchange at midnight
is required in order to obtain a calendar daily basis.
+ - -
Due to evaporational losses, the yield of NH , NO and Cl on the filter is dependent on the start and
4 3
stop time of the 24 h sampling period [2, 3, 4]. With respect to the diurnal variation of temperature, the
lowest yield can be expected when filters are exchanged during relatively high temperature conditions
(afternoon) and the highest yield at cold conditions (early in the morning). Therefore, it is at
least important to have equal daily filter exchange times for sites that measure also PM mass
concentration.

1) Whatman® QMA, Pallflex® Tissuequartz and Munktell® MK360 are examples of suitable products available
commercially. This information is given for the convenience of users of this European Standard and does not
constitute an endorsement by CEN of these products.
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NOTE The filter exchange time may differ per application for practical reasons:
— in case of manually operated measurements, which is often the case for EMEP, it is best to synchronize with
other measurement series preferably at a fixed time in the morning, i.e. 8 am;
— in case of PM measurements as part of a scientifically driven study, it is best to exchange filters early in the
morning just after the expected coldest time of the day.
7.3 Field sampling and type of sampler.
The sampling device shall be in accordance with EN 12341. It is acknowledged that the sampling
process determines the size fraction of the particulate matter, the retention of semi-volatile material,
and sorption of inorganic gases to the filter at the time of sampling.
7.4 Site types.
In Directive 2008/50/EC Annex IV the requirement for anions and cations measurements is set to
“rural background areas”. It is also stated in Annex IV that "this information is essential to judge the
enhanced levels in more polluted areas (such as urban back-ground, industry related locations, traffic
related locations)". Hence, in view of consistency and comparability of methods this European Standard
is for the use at rural sites as well as other types of monitoring sites, including suburban, urban
background, urban roadside and industrial sites.
7.5 Filter environment during sampling.
The sampler can be located either indoors or outdoors. At this stage, no specific demands on
temperature control beyond those given in EN 12341 are given.
8 Transport and storage
8.1 Handling
Filters shall be handled with clean tweezers, away from contamination sources.
Transport of filters shall be performed in a clean container. Storage after sampling shall be performed
in individual clean containers.
8.2 Time and temperature limits
Filters shall not be kept longer than 16 days in the field. Transport and any laboratory storage shall be
carried out at temperatures below 23 °C. Within 28 d after sampling, filters shall either be analysed or
transferred to storage at temperatures below 5 °C. Filters can be stored at this condition for a longer
period.
9 Analysis
9.1 Reagents
Use only reagents of recognized analytical grade (see Annex C).
Use deionized water with a resistivity equal to or greater than 18 MΩ.cm at 25 °C, filtered to exclude
particles larger than 0,45 µm.
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9.2 Filter sub-sampling
For extraction of water-soluble constituents from PM samples, the whole filter can be used or a sub-
2,5
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 part of the exposed area of the sampled filter.
If sub-samples are to be analysed, perform a homogeneity check at least once for each type of sampler
and for each type of sampling site (e.g. industrial, urban, traffic, rural).
9.3 Sample extraction
The filters are put into a sample tube and deionized water (9.1) is added.
The extraction volume shall be enough to cover completely the sample, typically at least 10 ml, for
47 mm filters.
The sample tubes shall be exposed in an ultrasonic bath for (30 ± 5) min to obtain complete extraction.
Extraction should be performed at room temperature (no heating or cooling).
9.4 Sample preparation
If any filter material is expected to be present in the extract, the extracts shall be filtered or centrifuged
prior to analysis to avoid problems with the analytical instrument.
NOTE To filter the sample solutions use, e.g. a disposable syringe filter (6.2.3).
9.5 Analysis of extracts
For the ion chromatography method, follow EN ISO 10304-1 [11] and EN ISO 14911 [12] for the
- 2- - + + + 2+ 2+
analysis of NO3 , SO4 , Cl , NH4 , Na , K , Mg , and Ca or the procedure described in chapter 4.1 of the
EMEP manual [5]. For other analytical methods, see Annex D.
The injection system of the ion chromatograph is rinsed with sample solution. A small volume of the
sample solution, typically less than 0,05 ml, is then introduced into the injection system of an ion
chromatograph. The sample i
...