Ambient air - Standard method for measurement of NO3¯, SO4²¯, Cl¯, NH4+, Na+, K+, Mg²+, Ca²+ in PM2,5 as deposited on filters

This European Standard specifies a method for the determination of the mass concentration of water soluble NO3- (nitrate), SO42- (sulphate), Cl- (chloride), NH4+ (ammonium), Na+ (sodium), K+ (potassium), Mg2+ (magnesium), Ca2+ (calcium) in PM2,5 as deposited on filters.
This European Standard describes the analytical procedures for determining anions and cations as part of the PM2,5 particulate phase, sample extraction and analysis of anions and cations by ion chromatography. Sampling onto filters will be done in accordance with EN 12341 for PM2,5.
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 PM2,5. NO3-, NH4+, Cl- are usually 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 PM2,5 samples corresponding to PM2,5 mass concentrations between approximately 1 μg/m3 (i.e. the limit of detection of the standard measurement method (EN 12341) expressed as its uncertainty) up to 120 μg/m3.
The validated range of the anion and cation concentrations based on the field validation measurements is presented in Table 1.
(...)
See Annex A for the statistical analysis of the field validation measurements.

Außenluft — Messverfahren zur Bestimmung von NO₃⁻, SO₄2⁻, Cl⁻, NH₄⁺, Na⁺, K⁺, Mg2⁺, Ca2⁺ in PM2,5 wie auf Filtern abgeschieden

Diese Europäische Norm legt ein Verfahren zur Bestimmung der Massenkonzentration von wasserlöslichem NO3- (Nitrat), SO42- (Sulfat), Cl- (Chlorid), NH4+ (Ammonium), Na+ (Natrium), K+ (Kalium), Mg2+ (Magnesium) und Ca2+ (Calcium) in PM2,5, wie auf Filtern abgeschieden, fest.
Die vorliegende Europäische Norm beschreibt die Analyseverfahren zur Bestimmung von Anionen und Kationen als Anteil der Partikelfraktion PM2,5, die Probenextraktion und die Analyse der Anionen und Kationen durch Ionenchromatographie. Die Probenahme auf den Filtern für PM2,5 erfolgt nach EN 12341.
ANMERKUNG 1   Alternativ können die Kationen, mit Ausnahme von Ammonium, mithilfe der optischen Emissionspektrometrie mit induktiv gekoppeltem Plasma (ICP-OES) analysiert werden. Ammonium kann auch durch Photometrie oder Konduktometrie analysiert werden.
Diese Europäische Norm kann zur Messung von Anionen und Kationen entsprechend den Anforderungen der Richtlinie 2008/50/EG angewendet werden. Das Verfahren berücksichtigt keine Verluste während der Probenahme aufgrund von Verflüchtigung.
ANMERKUNG 2   NO3-, Cl-, NH4+ sind Teil der flüchtigen Fraktion von PM2,5, und die unter Anwendung dieser Norm bestimmten Konzentrationen können als Mindestwerte für die Konzentrationen dieser Ionen in PM2,5 angesetzt werden. Die Konzentrationen an NO3-, Cl-, NH4+ werden üblicherweise aufgrund von Verlusten vom Filter während der Probenahme um bis zu 30 % unterschätzt.
Die vorliegende Europäische Norm darf an Standorten mit ländlichem und städtischem Hintergrund sowie an Straßen eingesetzt werden, die den Standortkriterien nach der Richtlinie 2008/50/EG entsprechen.
Diese Europäische Norm ist für die Messung von Anionen und Kationen in PM2,5 im Massenkonzentrationsbereich von PM2,5 zwischen etwa 1 μg/m3 (d. h. der Nachweisgrenze des Standardmessverfahrens (EN 12341), angegeben als dessen Unsicherheit) bis zu 120 μg/m3 anwendbar.
Der auf Validierungsmessungen im Feld beruhende validierte Bereich der Anionen- und Kationen-Konzentrationen ist in Tabelle 1 dargestellt

Air ambiant - Méthode normalisée pour le mesurage de NO3¯, SO4²¯, Cl¯, NH4+, Na+, K+, Mg²+, Ca²+ dans la fraction PM2,5 telle que déposée sur des filtres

La présente Norme européenne spécifie une méthode pour la détermination de la concentration massique de NO3- (nitrate), SO42- (sulfate), Cl- (chlorure), NH4+ (ammonium), Na+ (sodium), K+ (potassium), Mg2+ (magnésium), Ca2+ (calcium) solubles dans l'eau dans la fraction PM2,5 telle que déposée sur filtre.
La présente Norme européenne décrit les procédures d'analyse permettant de déterminer les anions et cations faisant partie de la phase particulaire PM2,5, l'extraction des échantillons et l'analyse des anions et cations par chromatographie ionique. L'échantillonnage sur filtre sera effectué conformément à l'EN 12341 pour PM2,5.
NOTE 1   En variante, les cations, sauf l'ammonium, peuvent être analysés par spectroscopie d'émission optique à plasma induit par haute fréquence (ICP-OES). L'ammonium peut également être analysé par photométrie ou conductimétrie.
La présente Norme européenne peut être utilisée pour le mesurage des anions et cations requis par la Directive 2008/50/CE. La méthode ne prend pas en compte les pertes éventuelles par évaporation pendant le prélèvement.
NOTE 2   NO3-, Cl-, NH4+ font partie de la fraction volatile de PM2,5, et les concentrations déterminées selon la présente norme peuvent être utilisées comme valeurs minimales pour les concentrations de ces ions dans la fraction PM2,5. NO3-, NH4+, Cl- sont généralement sous-estimés jusqu’à 30 % en raison des pertes par évaporation du filtre pendant le prélèvement.
La présente Norme européenne peut être utilisée au niveau de sites caractéristiques de la pollution de fond rurale et urbaine et de sites de proximité automobile conformes aux critères d’implantation de la Directive 2008/50/CE.
La présente Norme européenne s'applique au mesurage d'anions/cations dans des échantillons de la fraction PM2,5 pour des concentrations massiques comprises entre environ 1 µg/m3 (correspondant à la limite de détection de la méthode de mesurage normalisée (EN 12341) exprimée en tant qu'incertitude) et 120 µg/m3.
La plage de validité des concentrations en anions et cations basées sur les mesurages lors de la validation de terrain est présentée dans le Tableau 1.
(...)
Voir l'Annexe A pour l'analyse statistique des mesurages lors de la validation de terrain.

Zunanji zrak - Standardna metoda za merjenje NO₃ˉ, SO₄²ˉ, Cl¯, NH₄⁺, Na⁺, K⁺, Mg²⁺, Ca²⁺ v delcih PM2,5, zbranih na filtru

Ta evropski standard določa metodo za merjenje masne koncentracije vodotopnih NO3-, SO42-, Cl-, NH4+, Na+, K+, Mg2+, Ca2+ v delcih PM2,5, zbranih na filtru.
Ta evropski standard opisuje metodo za merjenje, ki zajema vzorčenje anionov in kationov kot del faze delcev PM2,5, odvzem vzorcev in analizo anionov ter kationov z ionsko kromatografijo.
OPOMBA 1: Alternativno je mogoče analizirati katione, brez amonija, z optično emisijsko spektrometrijo z induktivno sklopljeno plazmo (ICP-OES). Amonij je mogoče analizirati s fotometrijo ali konduktometrijo.
Ta evropski standard se lahko uporablja za meritve anionov in kationov v skladu z Direktivo 2008/50/ES. Metoda ne upošteva morebitnih izgub med vzorčenjem zaradi izhlapevanja.
OPOMBA 2: NO3-, Cl-, NH4+ so del hlapnih frakcij delcev PM2,5 in koncentracije, določene z uporabo tega standarda, se lahko uporabijo kot najmanjše vrednosti za koncentracije teh ionov v delcih PM2,5. Vrednosti NO3-, NH4+, Cl- so običajno 0–30 % pod ocenjeno vrednostjo zaradi izhlapevanja s filtra med vzorčenjem.
Ta evropski standard se lahko uporabi za neizpostavljena podeželska in urbana okolja ter obcestna mesta, ki so v skladu z merili za umestitev Direktive 2008/50/ES.
Ta evropski standard se uporablja za merjenje anionov/kationov v vzorcih delcev PM2,5, ki ustrezajo masnim koncentracijam med približno 1 μg/m3 (tj. mejo zaznavanja standardne merilne metode (EN 12341), izraženo kot negotovost) do 120 μg/m3.
Potrjeni razpon koncentracij anionov in kationov na podlagi terenskih validacijskih meritev je prikazan v preglednici 1.
Za statistično analizo terenskih validacijskih meritev glej dodatek F.

General Information

Status
Published
Publication Date
06-Jun-2017
Current Stage
9020 - Submission to 2 Year Review Enquiry - Review Enquiry
Due Date
15-Jul-2022
Completion Date
15-Jul-2022

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SLOVENSKI STANDARD
SIST EN 16913:2017
01-julij-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.

---------------------- Page: 1 ----------------------
SIST EN 16913:2017
---------------------- Page: 2 ----------------------
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.
---------------------- Page: 3 ----------------------
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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SIST EN 16913:2017
EN 16913:2017 (E)

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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SIST EN 16913:2017
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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SIST EN 16913:2017
EN 16913:2017 (E)
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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SIST EN 16913:2017
EN 16913:2017 (E)
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

corresponding to PM mass concentrations between approximately 1 μg/m (i.e. the limit of detection

2,5

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
SO 0,05 13
Na 0,003 1,9
NH 0,04 11
K 0,003 0,49
Mg 0,001 0,38
Ca 0,002 0,72
See Annex A for the statistical analysis of the field validation measurements.
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SIST EN 16913:2017
EN 16913:2017 (E)
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

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
---------------------- Page: 9 ----------------------
SIST EN 16913:2017
EN 16913:2017 (E)
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

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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SIST EN 16913:2017
EN 16913:2017 (E)
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.

Currently the use of Whatman® QMA should be discouraged because of the high Na blanks and the

uncertainty to what level the water soluble Na per batch may vary. Pallflex® Tissuequartz and

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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EN 16913:2017 (E)
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
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