SIST EN 17346:2020
(Main)Ambient Air Quality - Standard method for the determination of the concentration of ammonia by diffusive sampling
Ambient Air Quality - Standard method for the determination of the concentration of ammonia by diffusive sampling
This European Standard specifies a method for the sampling and analysis of NH3 in ambient air using
diffusive sampling.
It can be used for NH3 measurements at ambient levels but the concentration range and exposure time are sampler dependent and the end user shall use the working conditions for the various devices as recommended by the manufacturer.
Denuders may be used as a surrogate reference method, and for this reason their use is also described in this European Standard.
Außenluftqualität - Messverfahren zur Bestimmung der Konzentration von Ammoniak mit Passivsammlern
Dieses Dokument legt ein Verfahren zur Probenahme und Analyse von NH3 in Außenluft mit Passivsammlern fest.
Es kann für NH3 Messungen bei Außenluftkonzentrationen verwendet werden; Konzentrationsbereich und Expositionszeit sind aber sammlerabhängig. Dem Anwender wird daher empfohlen, einen den Messanforderungen entsprechenden Sammlertyp zu wählen und sich an die Herstellerangaben zu halten.
Air ambiant - Méthode normalisée pour la détermination de la concentration d'ammoniac au moyen d'échantillonneurs par diffusion
Le présent document spécifie une méthode pour l’échantillonnage et l’analyse du NH3 dans l’air ambiant à l’aide d’échantillonneurs par diffusion.
Elle peut être utilisée pour mesurer le NH3 aux niveaux ambiants, mais la gamme de concentrations et la durée d’exposition dépendent de l’échantillonneur. Il est donc conseillé à l’utilisateur final d’adapter le type d’échantillonneur aux exigences de mesure et de se conformer aux instructions d’utilisation fournies par le fabricant.
Kakovost zunanjega zraka - Standardna metoda za določevanje koncentracije amoniaka z difuzijskim vzorčenjem
General Information
Standards Content (Sample)
SLOVENSKI STANDARD
SIST EN 17346:2020
01-julij-2020
Kakovost zunanjega zraka - Standardna metoda za določevanje koncentracije
amoniaka z difuzijskim vzorčenjem
Ambient Air Quality - Standard method for the determination of the concentration of
ammonia by diffusive sampling
Außenluftqualität - Messverfahren zur Bestimmung der Konzentration von Ammoniak mit
Passivsammlern
Air ambiant - Méthode normalisée pour la détermination de la concentration d'ammoniac
au moyen d'échantillonneurs par diffusion
Ta slovenski standard je istoveten z: EN 17346:2020
ICS:
13.040.20 Kakovost okoljskega zraka Ambient atmospheres
SIST EN 17346:2020 en,fr,de
2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.
---------------------- Page: 1 ----------------------
SIST EN 17346:2020
---------------------- Page: 2 ----------------------
SIST EN 17346:2020
EN 17346
EUROPEAN STANDARD
NORME EUROPÉENNE
May 2020
EUROPÄISCHE NORM
ICS 13.040.20
English Version
Ambient air - Standard method for the determination of
the concentration of ammonia using diffusive samplers
Air ambiant - Méthode normalisée pour la Außenluft - Messverfahren zur Bestimmung der
détermination de la concentration en ammoniac au Konzentration von Ammoniak mit Passivsammlern
moyen d'échantillonneurs par diffusion
This European Standard was approved by CEN on 13 April 2020.
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, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway,
Poland, Portugal, Republic of North Macedonia, Romania, Serbia, 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: Rue de la Science 23, B-1040 Brussels
© 2020 CEN All rights of exploitation in any form and by any means reserved Ref. No. EN 17346:2020 E
worldwide for CEN national Members.
---------------------- Page: 3 ----------------------
SIST EN 17346:2020
EN 17346:2020 (E)
Contents Page
European foreword . 4
Introduction . 5
1 Scope . 9
2 Normative references . 9
3 Terms and definitions . 9
4 Description of samplers . 11
4.1 Principle . 11
4.2 Implementation . 11
4.3 Tube-type samplers. 11
4.4 Badge-type samplers . 12
4.5 Radial samplers . 12
5 Calculation of the concentration of NH . 12
3
5.1 Mass concentration . 12
5.2 Conversion to standard conditions of temperature and pressure . 13
6 Quality control/quality assurance . 13
6.1 Quality control . 13
6.2 Quality assurance . 14
7 Report . 14
8 Performance requirements and measurement uncertainty . 15
Annex A (informative) Tube-type samplers . 16
A.1 Sampler design . 16
A.2 Extraction and analysis . 16
A.3 Application range and conditions . 16
Annex B (informative) Badge-type samplers . 18
B.1 Type 1 badge-type sampler . 18
B.2 Type 2 badge-type sampler . 20
B.3 Type 3 badge-type sampler . 23
B.4 Type 4 badge-type sampler . 25
Annex C (informative) Radial samplers . 29
C.1 Sampler design . 29
C.2 Extraction and analysis . 30
C.3 Application range and conditions . 31
Annex D (informative) Summary of passive diffusive sampling rate data . 32
Annex E (normative) Estimation of the sampling rate of the samplers . 33
Annex F (informative) Measurement uncertainty calculation . 35
F.1 Measurement equation . 35
2
---------------------- Page: 4 ----------------------
SIST EN 17346:2020
EN 17346:2020 (E)
F.2 Combined standard uncertainty . 35
F.3 Expanded relative uncertainty . 36
F.4 Uncertainty contributions . 36
Bibliography . 41
3
---------------------- Page: 5 ----------------------
SIST EN 17346:2020
EN 17346:2020 (E)
European foreword
This document (EN 17346:2020) 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 November 2020, and conflicting national standards shall
be withdrawn at the latest by November 2020.
Attention is drawn to the possibility that some of the elements of this document may be the subject of
patent rights. CEN shall not be held responsible for identifying any or all such patent rights.
According to the CEN-CENELEC Internal Regulations, the national standards organisations of the
following countries are bound to implement this European Standard: 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, Republic of North
Macedonia, Romania, Serbia, Slovakia, Slovenia, Spain, Sweden, Switzerland, Turkey and the United
Kingdom.
4
---------------------- Page: 6 ----------------------
SIST EN 17346:2020
EN 17346:2020 (E)
Introduction
Atmospheric ammonia (NH ) is a pollutant of major environmental concern with adverse effects on
3
forests, species composition of semi-natural ecosystems and soils [1-4]. Emission and deposition of NH
3
can contribute significantly to total nitrogen deposition to the environment, contributing to
eutrophication (nutrient enrichment) and acidification (oxidation of NH to nitrate resulting in release of
3
+
H ions) of land and freshwaters, leading to a reduction in both soil and water quality, loss of biodiversity
and ecosystem change [5-10].
In addition to these effects, NH3 is the major precursor for neutralization of atmospheric acids, affecting
the long-range transport distance of both SO and NO and leading to the formation of secondary particles
2 x
(primarily ammonium sulphate and ammonium nitrate) [11-13]. These particles have multiple impacts
including effects on atmospheric visibility, radiative scattering (and the greenhouse effect) and on human
health.
The recognition of NH as an important air pollutant led to its inclusion in international agreements to
3
reduce air pollutant emissions, first under the 1999 UNECE Gothenburg Protocol and then the National
Emissions Ceilings Directive (NECD) (2001/81/EC) of the EU. The target of both these agreements is that
NH emissions should not exceed emission ceilings set for EU member states, with a particular focus on
3
reducing the extent of critical loads exceedance for acidification and eutrophication effects. Revision of
the Gothenburg Protocol (2012) and the NEC Directive (2016) include new, more stringent emission
ceilings for 2020 that seek more environmental protection and improvement in air quality than has so
far been committed, including the introduction of an emissions ceiling for particulate matter (PM). Under
the 2012 UNECE Gothenburg Protocol, EU member states have to jointly cut their emissions of NH by
3
6 % and particles by 22 % between 2005 and 2020. As a precursor of PM, controlling NH is important to
3
reducing particle emissions of PM and PM . A recent study employing three chemical transport models
2,5 10
found that the models underestimated the formation of ammonium particles and concluded that the role
of NH on PM is larger than originally thought [14]. Thus the implementation of 2020 targets detailed
3
above may not be enough to deliver compliance with proposed particle limit values, and further local
measures may be required to be compliant.
Other legislations to abate NH emissions include the Industrial Emissions Directive (IED) (2010/75/EU)
3
which requires pig and poultry farms (above stated size thresholds) to reduce emissions using Best
Available Techniques. For the protection of vegetation and ecosystems, new revised “Critical Levels” (CL)
3 3
of NH concentrations were adopted in 2007 (see Table 1), of 1 µg/m and 3 µg/m annual mean for the
3
protection of lichens/bryophytes and higher plants under field conditions, respectively, which replaced
3 3
the previous CL annual mean value of 8 µg/m . A monthly critical level of 23 µg /m was retained as a
provisional value in order to deal with the possibility of high peak emissions during periods of manure
application (e.g. in spring) ([15]). In Germany, the recommended exposure limit for the protection of
3
ecosystems is 10 µg/m (TA Luft, Annex 1, [16]).
5
---------------------- Page: 7 ----------------------
SIST EN 17346:2020
EN 17346:2020 (E)
Table 1 — Summary of upper limits of NH concentrations for protection of ecosystems under
3
field conditions
Concentration Specification Types of locality
3
(µg/m )
1 UNECE Critical Level (annual mean) for Sensitive ecosystems in
lower plants (lichens, bryophytes) which the lichens and
bryophytes are important
components, e.g. designated
sites for nature
conservation and protection
of sensitive species, e.g.
Natura 2000 sites
3 UNECE Critical Level (annual mean) for Sensitive ecosystems in
higher plants which the higher plants are
important components, e.g.
designated sites for nature
conservation and protection
of sensitive species, e.g.
Natura 2000 sites
10 German First General Administrative Near installations
Regulation Pertaining the Federal
Immission Control Act Maximum near
installations where ecological
monitoring undertaken.
23 UNECE critical level (monthly mean) – for In close proximity to
peak emission periods such as in months emission sources
where slurry spreading takes place.
Improving knowledge on levels of NH in the ambient air and near sources is therefore important for the
3
assessment of:
— environmental effects on ecosystems (Contribution to eutrophication and acidification processes);
— contributions to the formation of PM and PM ;
10 2,5
— effectiveness of current and future abatement measures to reduce NH emissions.
3
The simplest to the latest state-of–the-art techniques for measurement of atmospheric NH are presented
3
in Table 2.
6
---------------------- Page: 8 ----------------------
SIST EN 17346:2020
EN 17346:2020 (E)
Table 2 — Measurement methods suitable for determination of atmospheric NH gas and
3
ammonium particle concentrations
Monitoring Methods Time resolution References
Integrative methods: passive
Passive diffusion samplers daily to monthly [17]
[18]
[19]
[20]
Integrative methods: active
Simple denuder systems with offline chemical analysis daily to monthly [17]
[19]
[21]
Annular denuder systems (ADS) with offline chemical hourly to daily [22]
analysis
Conditional sampling with denuders at different heights weekly to monthly [23]
(COTAG)
Continuous: wet chemistry methods
Annular Denuder Systems with online analysis hourly or better [24]
depending on set-
Membrane stripping with online analysis
up
Steam Jet Aerosol Collector Systems for gas and aerosol hourly or better [25]
depending on set-
[26]
up
Continuous: optical methods
Differential Optical Absorption Spectrometry (DOAS) hourly or better [27]
depending on set-
up
Tunable Diode Laser Absorption Spectrometry and hourly or better [28]
Quantum Cascade Laser (TDL and QCL AS, respectively) depending on set-
up
Photoacoustic spectrometry hourly or better [29]
depending on set-
up
Chemiluminescence with catalytic conversion hourly or better [30]
depending on set-
up
7
---------------------- Page: 9 ----------------------
SIST EN 17346:2020
EN 17346:2020 (E)
Integrative atmospheric sampling methods such as passive diffusion samplers and active samplers
provide measurement of concentrations of NH averaged over the chosen sampling time. The diffusive
3
samplers used include those that are available commercially and those that have been developed in-
house by organisations to meet specific research requirements. A full validation of diffusive sampling
methods for NH in accordance with the European Standard (EN 13528-2 [31]) would be costly and
3
would also require specialist facilities only available at well-equipped large metrological institutes.
Validation of the quantitative measurement of NH through comparison with “reference” methods is
3
problematic for NH as there is no currently accepted and defined reference method. Automatic
3
continuous analysers for NH , employing spectroscopic or other techniques (Table 2) are available
3
commercially, but there is a lack of robust published calibration data and procedures for reliable field
measurements under ambient concentrations and conditions [32].
8
---------------------- Page: 10 ----------------------
SIST EN 17346:2020
EN 17346:2020 (E)
1 Scope
This document specifies a method for the sampling and analysis of NH in ambient air using diffusive
3
sampling.
It can be used for NH measurements at ambient levels, but the concentration range and exposure time
3
are sampler dependent, and the end user is therefore advised to match the sampler type to the
measurement requirement and to follow the operating instructions provided by the manufacturer.
2 Normative references
There are no normative references in this document.
3 Terms and definitions
For the purposes of this document, the following terms and definitions apply.
ISO and IEC maintain terminological databases for use in standardization at the following addresses:
— IEC Electropedia: available at http://www.electropedia.org/
— ISO Online browsing platform: available at https://www.iso.org/obp/ui
3.1
combined standard measurement uncertainty
combined standard uncertainty
standard measurement uncertainty that is obtained using the individual standard measurement
uncertainties associated with the input quantities in a measurement model
[SOURCE: JCGM 200:2012, 2.31] [33]
3.2
extraction efficiency
ratio of the mass of analyte extracted from a sampling device to that applied
3.3
diffusive sampler
device which is capable of taking samples of gases or vapours from the atmosphere at a rate controlled
by a physical process such as gaseous diffusion through a static air layer or a porous material and/or
permeation through a membrane, but which does not involve the active movement of air through the
device
Note 1 to entry: Active normally refers to the pumped movement of air.
[SOURCE: EN 13528-2:2002, 3.6] [31]
3.4
diffusive sampling rate
diffusive uptake rate
rate at which the diffusive sampler collects a particular gas or vapour from the atmosphere
3 3
Note 1 to entry: The sampling rate is usually expressed in units of (m /h), (ml/min) or (cm /min).
3 3 –8
Note 2 to entry: cm /min may be converted to SI units of m /s by factor 1,67 × 10 .
9
---------------------- Page: 11 ----------------------
SIST EN 17346:2020
EN 17346:2020 (E)
3.5
expanded measurement uncertainty
product of a combined standard measurement uncertainty and a factor larger than the number one
Note 1 to entry: The factor depends upon the type of probability distribution of the output quantity in a
measurement model and on the selected coverage probability.
Note 2 to entry: The term “factor” in this definition refers to a coverage factor.
[SOURCE: JCGM 200:2012, 2.35]
3.6
field blank
unused sampler, taken from the same batch used for NH monitoring, handled in the same way as a
3
sampler that is used for NH monitoring, except it is not used for collecting a sample
3
Note 1 to entry: Adapted from EN 14902:2005, 3.1.6.
Note 2 to entry: The results from the analysis of field blanks are used to identify contamination of the sample
arising from handling in the field and during transport.
[SOURCE: EN 1540:2011, 3.3.8] [34]
Note 3 to entry: A transport blank is considered to be a special case of a field blank. A transport blank is taken to
the exposure site, left unopened and returned to the laboratory immediately after placement or collection of the
samplers. Transport blanks may be used when regular field blanks reveal an unacceptable level of ammonium to
investigate the possibility of contamination of samplers during transport. This blank is only used for quality control
purposes.
3.7
laboratory blank
sealed sampler drawn from the same batch as the samplers being used for NH monitoring which is stored
3
for the duration of the sampling period and is analysed at the same time as the exposed samplers
3.8
measurement uncertainty
uncertainty of measurement
non-negative parameter characterizing the dispersion of the quantity values being attributed to a
measurand, based on the information used
Note 1 to entry: For notes to the definition the reader is referred to the parent document JCGM 200:2012.
[SOURCE: JCGM 200:2012, 2.26]
3.9
standard measurement uncertainty
standard uncertainty
measurement uncertainty expressed as a standard deviation
[SOURCE: JCGM 200:2012, 2.30]
10
---------------------- Page: 12 ----------------------
SIST EN 17346:2020
EN 17346:2020 (E)
4 Description of samplers
4.1 Principle
The diffusive sampler is exposed in air for a measured time period. NH migrates through the sampler
3
along a diffusion path of defined dimensions and is collected by reaction onto an acid sorbent.
Determining the sampling rate is essential when deploying diffusive NH samplers in the field, either by:
3
— calculation based on Fick’s first law of diffusion (see EN 13528-3 [35] and Annex E),
— calibration by exposure to standard atmospheres, or
— co-located calibration studies against another well characterized NH measurement method in the
3
field.
NOTE Denuders can be used as a cost effective surrogate reference method until there are improvements in
the continuous optical methods.
Details of these approaches shall be documented.
Samplers can be provided with manufacturer measured sampling rates. Samplers in networks often have
on-going measurements of sampling rates. Users can calculate a locally derived sampling rate. Sampling
rates are also documented in literature [see [36], and Annex D].
The sampling rate in the field is a function of local meteorology. Samplers can be deployed with protective
shelters to minimize meteorological influences. When doing so, the user shall apply a suitable protocol to
ensure a consistent approach for all samplers. Ideally, the effect of the shelter on the sampler
performance should be characterized.
4.2 Implementation
Samplers shall be sealed and stored under cool conditions, for example at temperatures between 0 °C and
4 °C, in the dark, in order to minimize any undesired reactions before and after deployment. After
deployment, samplers shall be analysed as soon as possible, according to manufacturer’s specifications.
Disposable gloves shall be worn at all times, including during deployment in the field. This serves to
protect the samples from contamination by contact with the skin. It is also advised to avoid breathing
directly on the samples, as exhaled breath contains NH .
3
Since there are different sampler designs, each common sampler type is briefly described below.
4.3 Tube-type samplers
The tube-type samplers are hollow cylindrical tubes oriented vertically. A cap at the top end holds in
place either a cellulose filter paper, glass fibre filter or stainless steel grid, which is coated with a sorbent
that collects the gas of interest. This type of sampler is characterized by a high length to cross sectional
area ratio [15, 37]. To collect NH , sorbents used include citric, phosphoric, phosphorous, sulphuric and
3
tartaric acid [38]. The analysis is carried out using various methods including ion chromatography, flow
injection analysis with detection of conductivity and spectrophotometry.
There is one commonly used design of tube type samplers, the 3,5 cm short membrane diffusion tube.
For more information, see Annex A.
11
---------------------- Page: 13 ----------------------
SIST EN 17346:2020
EN 17346:2020 (E)
4.4 Badge-type samplers
The badge-type samplers have a lower length to area ratio of the sample body, with enhanced sensitivity
over the tube-type samplers [15, 37]. There are many badge-type samplers in use with different
geometry. Due to the short diffusion path length, they have a gas permeable barrier at the inlet to prevent
wind-induced turbulent diffusion (wind shortening effect on sampling rate). The sorbents used to collect
ammonia are the same as employed with tube-type samplers, and the following analytical assessment is
performed by using the same techniques.
For more information, see Annex B.
4.5 Radial samplers
The radial-type sampler has a cylindrical outer surface that acts as a permeation barrier through which
NH diffuses [39]. NH molecules move axially parallel towards an absorbent bed that is also cylindrical
3 3
and coaxial to the diffusive surface. This type of sampler uses phosphoric acid as a sorbent. Exposed
samplers are analysed using various methods, including spectrophotometry, and ion chromatography.
For more information, see Annex C.
5 Calculation of the concentration of NH
3
5.1 Mass concentration
The concentration of NH in ambient air under actual conditions of sampling is calculated using
3
Formula (1):
M
mm−
NH
3 sb
c= .
M e⋅⋅υ t
+
NH
4
(1)
where
3
c is the concentration of NH at ambient conditions in µg/m ;
3
is the molar mass of NH in g/mol;
M 3
NH
3
+
is the molar mass of NH in g/mol;
M 4
+
NH
4
m is the mass of ammonium found in the sample in µg;
s
m is the mass of ammonium found in the mean laboratory blank in µg;
b
NOTE 1 In normal operations the transport and field blanks are expected to record similar masses of
ammonium compared to the laboratory blank. In cases where the transport and/or field blank is higher than
the laboratory blank the transport or field blank can be used for the subtraction. This information needs to be
clearly documented.
υ 3
is the sampling rate at ambient conditions during sampling in m /h;
e is the efficiency of extraction of ammonium;
NOTE 2 It is not necessary to include the efficiency of extraction of ammonium if this efficiency is shown not
be significantly different from 100 % or if it is already included into the estimation of the sampling rate.
t is the sampling time in h.
NOTE 3 The sampling rate can be in µg/(nmol/mol)/min, in which case c is expressed in units of nmol/mol.
12
---------------------- Page: 14 ----------------------
SIST EN 17346:2020
EN 17346:2020 (E)
5.2 Conversion to standard conditions of temperature and pressure
The mass concentration of NH in air is calculated at the ambient temperature and pressure during
3
exposure using Formula (1). This mass concentration shall be referred to at standard conditions of
temperature and pressure, as required in Directive 2008/50/EC [40] and defined e.g. by EN 16339 [41],
using Formula (2):
T 101,3
cc=⋅⋅
STP
293 P
(2)
where
3
c is the concentration of NH at standard temperature and pressure in µg/m ;
STP 3
3
c is the concentration of NH at ambient conditions in µg/m ;
3
T is the average temperature during exposure in K;
P is the average pressure during exposure in kPa.
NOTE Temperature and pressure data can be obtained from nearby meteorological stations.
6 Quality control/quality assurance
6.1 Quality control
For each series of analyses, the following control checks shall be performed and recorded:
a) inspection of each sampler before and after exposure, reject those with visible damage or
contamination and record this information in the report;
b) analysis for each batch of samplers, field blanks, transport blanks and/or laboratory blanks to detect
contamination of samplers during transport, in the field and during subsequent storage and
handling;
c) analysis of calibration solutions to determine instrument drift and appropriate re-calibration at
regular intervals, e.g. at the start of each day . If a check of the calibration response is outside the
expected performance criteria of the instrument, then a further investigation is required to
demonstrate that it is functioning correctly.
NOTE For a linear calibration curve, a check can be carried out using at least 3 points (zero, 50 % of calibration
range and full scale).
At regular intervals, the following control checks shall be performed and registered:
d) analysis of reagent solutions to determine variations of reagent blank levels;
e) determination of extraction efficiency by spik
...
SLOVENSKI STANDARD
oSIST prEN 17346:2019
01-marec-2019
.DNRYRVW]XQDQMHJD]UDND6WDQGDUGQDPHWRGD]DGRORþHYDQMHNRQFHQWUDFLMH
DPRQLDND]GLIX]LMVNLPY]RUþHQMHP
Ambient Air Quality - Standard method for the determination of the concentration of
ammonia by diffusive sampling
Außenluftqualität - Messverfahren zur Bestimmung der Konzentration von Ammoniak mit
Passivsammlern
Air ambiant - Méthode normalisée pour la détermination de la concentration d'ammoniac
au moyen d'échantillonneurs par diffusion
Ta slovenski standard je istoveten z: prEN 17346
ICS:
13.040.20 Kakovost okoljskega zraka Ambient atmospheres
oSIST prEN 17346:2019 en,fr,de
2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.
---------------------- Page: 1 ----------------------
oSIST prEN 17346:2019
---------------------- Page: 2 ----------------------
oSIST prEN 17346:2019
DRAFT
EUROPEAN STANDARD
prEN 17346
NORME EUROPÉENNE
EUROPÄISCHE NORM
January 2019
ICS 13.040.20
English Version
Ambient Air Quality - Standard method for the
determination of the concentration of ammonia by
diffusive sampling
This draft European Standard is submitted to CEN members for enquiry. It has been drawn up by the Technical Committee
CEN/TC 264.
If this draft becomes a European Standard, 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.
This draft European Standard was established by CEN 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.
Recipients of this draft are invited to submit, with their comments, notification of any relevant patent rights of which they are
aware and to provide supporting documentation.
Warning : This document is not a European Standard. It is distributed for review and comments. It is subject to change without
notice and shall not be referred to as a European Standard.
EUROPEAN COMMITTEE FOR STANDARDIZATION
COMITÉ EUROPÉEN DE NORMALISATION
EUROPÄISCHES KOMITEE FÜR NORMUNG
CEN-CENELEC Management Centre: Rue de la Science 23, B-1040 Brussels
© 2019 CEN All rights of exploitation in any form and by any means reserved Ref. No. prEN 17346:2019 E
worldwide for CEN national Members.
---------------------- Page: 3 ----------------------
oSIST prEN 17346:2019
prEN 17346:2019 (E)
Contents Page
European foreword . 5
Introduction . 6
1 Scope . 10
2 Normative references . 10
3 Terms and definitions . 10
4 Description of samplers . 11
4.1 General . 11
4.2 Tube-type samplers. 12
4.3 Badge-type samplers . 12
4.4 Radial samplers . 12
5 Calculation of the concentration of ammonia . 12
5.1 Mass concentration . 12
5.2 Conversion to standard conditions of temperature and pressure . 13
6 Quality control/quality assurance . 13
6.1 Quality control . 13
6.2 Quality assurance . 14
7 Report . 14
8 Performance requirements and measurement uncertainty . 15
8.1 Parameters to be assessed and performance requirements . 15
Annex A (informative) Tube-type samplers . 17
A.1 Type 1 tube-type sampler . 17
A.1.1 Sampler design . 17
A.1.2 Extraction and analysis . 17
A.1.3 Application range and conditions . 17
Annex B (informative) Badge-type samplers . 19
B.1 Type 1 badge-type sampler . 19
B.1.1 Sampler design . 19
B.1.2 Extraction and analysis . 20
B.1.3 Application range and conditions . 20
B.2 Type 2 badge-type sampler . 21
B.2.1 Sampler design . 21
B.2.2 Extraction and analysis . 22
B.2.2.1 General . 22
B.2.2.2 Extraction of acid coated filter paper . 22
B.2.2.3 Analysis of ammonium . 22
B.2.2.3.1 Flow Injection Conductivity Ammonium Analysers . 22
2
---------------------- Page: 4 ----------------------
oSIST prEN 17346:2019
prEN 17346:2019 (E)
B.2.2.3.2 Spectrophotometry . 23
B.2.2.3.3 Ion Chromatography . 24
B.2.3 Application range and conditions . 24
B.3 Type 3 badge-type sampler . 24
B.3.1 Sampler design . 24
B.3.2 Extraction and analysis . 25
B.3.3 Application range and conditions . 25
B.4 Type 4 badge-type sampler . 26
B.4.1 Sampler design . 26
B.4.2 Application Range and Conditions . 28
Annex C (informative) Radial samplers . 30
C.1 Type 1 radial sampler . 30
C.1.1 Sampler design . 30
C.1.2 Extraction and analysis . 32
C.1.2.1 General . 32
C.1.2.2 Spectrophotometry . 32
C.1.2.3 Flow injection analysis . 32
C.1.2.4 Ion chromatography . 32
C.1.3 Application range and conditions . 32
Annex D (informative) Summary of passive diffusive sampling rate data. 34
Annex E (normative) Estimation of the sampling rate of the samplers . 35
Annex F (informative) Measurement uncertainty . 37
F.1 Uncertainty calculation . 37
F.1.1 Measurement equation. 37
F.1.2 Combined standard uncertainty . 37
F.1.3 Expanded relative uncertainty . 37
F.1.4 Uncertainty contributions . 38
F.1.4.1 Sampling rate . 38
F.1.4.2 Mass of ammonium in sample . 38
F.1.4.2.1 General . 38
F.1.4.2.2 Mass of ammonium in calibration standards . 39
F.1.4.2.3 Lack of fit of the calibration function . 39
F.1.4.2.4 Analytical repeatability . 39
F.1.4.2.5 Response drift between calibrations . 39
F.1.4.3 Mass of ammonium in blank . 39
F.1.4.4 Exposure time . 40
3
---------------------- Page: 5 ----------------------
oSIST prEN 17346:2019
prEN 17346:2019 (E)
F.1.4.5 Average temperature and pressure during exposure . 40
F.1.4.6 Worked example . 40
Bibliography . 43
4
---------------------- Page: 6 ----------------------
oSIST prEN 17346:2019
prEN 17346:2019 (E)
European foreword
This document (prEN 17346:2019) has been prepared by Technical Committee CEN/TC 264 “Air quality”,
the secretariat of which is held by DIN.
This document is currently submitted to the CEN Enquiry.
5
---------------------- Page: 7 ----------------------
oSIST prEN 17346:2019
prEN 17346:2019 (E)
Introduction
Atmospheric ammonia (NH ) is a pollutant of major environmental concern with adverse effects on
3
forests, species composition of semi-natural ecosystems and soils [1-4]. Emission and deposition of NH
3
can contribute significantly to total nitrogen deposition to the environment, contributing to
eutrophication (nutrient enrichment) and acidification (oxidation of NH to nitrate resulting in release
3
+
of H ions) of land and freshwaters, leading to a reduction in both soil and water quality, loss of
biodiversity and ecosystem change [5-10].
In addition to these effects, NH is the major precursor for neutralization of atmospheric acids, affecting
3
the long-range transport distance of both SO and NO and leading to the formation of secondary
2 x
particles (primarily ammonium sulphate and ammonium nitrate) [11-13]. These particles have multiple
impacts including effects on atmospheric visibility, radiative scattering (and the greenhouse effect) and
on human health.
The recognition of NH as an important air pollutant led to its inclusion in international agreements to
3
reduce air pollutant emissions, first under the 1999 UNECE Gothenburg Protocol and then the National
Emissions Ceilings Directive (NECD) (2001/81/EC) of the EU. The target of both these agreements is that
NH emissions should not exceed emission ceilings set for EU member states, with a particular focus on
3
reducing the extent of critical loads exceedance for acidification and eutrophication effects. Revision of
the Gothenburg Protocol (2012) and the NEC Directive (2016) include new, more stringent emission
ceilings for 2020 that seek more environmental protection and improvement in air quality than has so
far been committed, including the introduction of an emissions ceiling for particulate matter (PM). Under
the 2012 UNECE Gothenburg Protocol, EU member states must jointly cut their emissions of NH by 6 %
3
and particles by 22 % between 2005 and 2020. As a precursor of PM, controlling ammonia is important
to reducing particle emissions of PM and PM . A recent study employing three chemical transport
2.5 10
models found that the models underestimated the formation of ammonium particles and concluded that
the role of NH on PM is larger than originally thought. Thus the implementation of 2020 targets detailed
3
above may not be enough to deliver compliance with proposed particle limit values, and further local
measures may be required to be compliant [14].
Other legislations to abate ammonia emissions include the Industrial Emissions Directive (IED)
(2010/75/EU) which requires pig and poultry farms (above stated size thresholds) to reduce emissions
using Best Available Techniques. In Germany, the recommended exposure limit for the protection of
3
ecosystems is 10 µg/m (TA Luft, Annex 1, [15]) For the protection of vegetation and ecosystems, new
3 3
revised “Critical Levels” (CL) of NH concentrations were adopted in 2007, of 1 µg/m and 3 µg/m
3
annual mean for the protection of mosses and vegetation under field conditions, respectively, which
3 3
replaced the previous CL annual mean value of 8 µg/m . A monthly critical level of 23 µg /m was
retained as a provisional value in order to deal with the possibility of high peak emissions during periods
of manure application (e.g. in spring) ([16]).
6
---------------------- Page: 8 ----------------------
oSIST prEN 17346:2019
prEN 17346:2019 (E)
Table 1 — Summary of critical NH values for ecosystems under field conditions
3
Concentration Specification Types of locality
3
(µg/m )
1 UNECE Critical Level for lower plants Natura 2000 sites: Habitats
(lichens, mosses, bryophytes) Directive. Background and
semi-natural areas
3 UNECE Critical Level for higher plants Sensitive habitats
10 German First General Administrative Near installations
Regulation Pertaining the Federal
Immission Control Act Maximum near
installations where ecological
monitoring undertaken.
23 Monthly critical level (only used for In close proximity to
manure spreading) emission sources
Improving knowledge on levels of ammonia in the ambient air and near sources is therefore important
for the assessment of:
— Environmental effects on ecosystems (Contribution to eutrophication and acidification processes);
— Contributions to the formation of PM and PM ;
10 2.5
— Effectiveness of current and future abatement measures to reduce ammonia emissions.
The simplest to the latest state-of–the-art techniques for measurement of atmospheric ammonia are
presented in Table 2.
7
---------------------- Page: 9 ----------------------
oSIST prEN 17346:2019
prEN 17346:2019 (E)
Table 2 — Measurement methods suitable for determination of atmospheric ammonia gas and
ammonium particle concentrations
Time resolution References
Monitoring Methods
Integrative methods: Passive
Passive diffusion samplers daily to monthly [17]
[18]
[19]
[20]
Integrative methods: Active
Simple denuder systems with offline chemical analysis daily to monthly [17]
[21]
[19]
Annular denuder systems (ADS) with offline chemical hourly to daily [22]
analysis
Conditional sampling with denuders at different heights weekly to monthly [23]
(COTAG)
Continuous: wet chemistry methods
Annular Denuder Systems with online analysis hourly or better [24]
depending on set-
Membrane stripping with online analysis
up
Steam Jet Aerosol Collector Systems for gas and aersosol hourly or better [25]
depending on set-
[26]
up
Continuous: optical methods
Differential Optical Absorption Spectrometry(DOAS) hourly or better [27]
depending on set-
up
Tunable Diode Laser Absorption Spectrometry and hourly or better [28]
Quantum Cascade Laser (TDL & QCL AS respectively) depending on set-
up
Photoacoustic spectrometry hourly or better [29]
depending on set-
up
Chemiluminescence with catalytic conversion hourly or better [30]
depending on set-
up
Integrative atmospheric sampling methods such as passive diffusion samplers and active samplers
provide measurement of concentrations of NH averaged over the chosen sampling time. The diffusive
3
samplers used include those that are available commercially and those that have been developed in-
house by organisations to meet specific research requirements. A full validation of diffusive sampling
methods for ammonia in accordance with the European Standard (EN 13528-2 [31]) would be costly and
8
---------------------- Page: 10 ----------------------
oSIST prEN 17346:2019
prEN 17346:2019 (E)
would also require specialist facilities only available at well-equipped larger metrological institutes.
Validation of the quantitative measurement of ammonia through comparison with “reference” methods
is problematic for ammonia as there is no currently accepted and defined reference method. Automatic
continuous analysers, using spectroscopic or other techniques as used for other inorganic gases still
suffer from robust published calibration demonstrated at ambient concentrations and conditions.
9
---------------------- Page: 11 ----------------------
oSIST prEN 17346:2019
prEN 17346:2019 (E)
1 Scope
This document specifies a method for the sampling and analysis of NH in ambient air using diffusive
3
sampling.
It can be used for NH measurements at ambient levels, but the concentration range and exposure time
3
are sampler dependent, and the end user is therefore advised to comply with the operating instructions
provided by the manufacturer.
NOTE Denuders may be used as a surrogate reference method until there are improvements in the continuous
optical methods.
2 Normative references
There are no normative references in this document.
3 Terms and definitions
For the purposes of this document, the following terms and definitions apply.
ISO and IEC maintain terminological databases for use in standardization at the following addresses:
— IEC Electropedia: available at http://www.electropedia.org/
— ISO Online browsing platform: available at http://www.iso.org/obp
3.1
combined standard uncertainty
standard measurement uncertainty that is obtained using the individual standard measurement
uncertainties associated with the input quantities in a measurement model
[SOURCE: JGCM 200:2012] [32]
3.2
extraction efficiency
ratio of the mass of analyte extracted from a sampling device to that applied
3.3
diffusive sampler
device which is capable of taking samples of gases or vapours from the atmosphere at a rate controlled
by a physical process such as gaseous diffusion through a static air layer or a porous material and/or
permeation through a membrane, but which does not involve the active movement of air through the
device
[SOURCE: EN 13528-2:2002] [31]
Note 1 to entry: Active normally refers to the pumped movement of air.
3.4
diffusive sampling rate
rate at which the diffusive sampler collects a particular gas or vapour from the atmosphere
3 3
Note 1 to entry: The sampling rate is usually expressed in units of (m /h), (ml/min) or (cm /min).
3 3 -10
Note 2 to entry: cm /min may be converted to SI units of m /s by factor 1,67 x 10 .
10
---------------------- Page: 12 ----------------------
oSIST prEN 17346:2019
prEN 17346:2019 (E)
3.5
expanded (measurement) uncertainty
product of a combined standard measurement uncertainty and a factor larger than the number one
[SOURCE: JCGM 200:2012]
Note 1 to entry: The factor depends upon the type of probability distribution of the output quantity in a
measurement model and on the selected coverage probability.
Note 2 to entry: The term “factor” in this definition refers to a coverage factor.
3.6
field blank
sealed sampler drawn from the same batch as the samplers being used for NH monitoring. This sampler
3
is taken unopened to the field and returned together with exposed samplers after the sampling is
completed
Note 1 to entry: A transport blank is considered to be a special case of a field blank. A transport blank is taken to
the exposure site, left unopened and returned to the laboratory immediately after placement or collection of the
samplers. Transport blanks may be used when regular field blanks reveal an unacceptable level of ammonium to
investigate the possibility of contamination of samplers during transport. This blank is only used for quality control
purposes.
3.7
laboratory blank
sealed sampler drawn from the same batch as the samplers being used for NH monitoring which is
3
stored in a refrigerator during sampling of the exposed samplers
3.8
standard (measurement) uncertainty
measurement uncertainty expressed as a standard deviation
[SOURCE: JGCM 200:2012]
3.9
uncertainty (of measurement)
non-negative parameter characterizing the dispersion of the quantity values being attributed to a
measurand, based on the information used
Note 1 to entry: For footnotes to the definition the reader is referred to the parent document JGCM 200:2012.
[SOURCE: JGCM 200:2012]
4 Description of samplers
4.1 General
The diffusive sampler is exposed to air for a measured time period. NH migrates through the sampler
3
diffusion path and is collected by reaction onto the relevant sorbent.
The diffusive sampling rate is determined either by numerical calculation based on Fick’s first law of
diffusion (see EN 13528-3 [33]) through calibration by exposure to standard atmospheres or through co-
located calibration studies against another well characterized method in the field.
Because there are different sampler designs, each common sampler type is briefly described below.
11
---------------------- Page: 13 ----------------------
oSIST prEN 17346:2019
prEN 17346:2019 (E)
4.2 Tube-type samplers
The tube-type samplers are hollow cylindrical tubes oriented vertically. A cap at the top end holds in
place either a cellulose filter paper, glass fibre filter or stainless steel grid, which is coated with a sorbent
that collects the gas of interest. This type of sampler has a large length to area ratio of the tube [15, 34].
To sample ammonia, sorbents used include citric, phosphoric, phosphorous, sulphuric and tartaric acid
[35]. The analysis is done using various methods including ion chromatography, flow injection analysis
with detection of conductivity and spectrophotometry.
There is 1 commonly used design of tube type samplers, the 3,5 cm short membrane diffusion tube.
For more information, see Annex A.
4.3 Badge-type samplers
The badge-type samplers have a lower length to area ratio of the sample body, with enhanced sensitivity
over the tube-type samplers [15, 34]. There are different types of badge-type samplers in use with
different geometry. Due to the short diffusion path length, they have a gas permeable barrier at the inlet
to prevent wind-induced turbulent diffusion (wind shortening effect on sampling rate). This type of
sampler contains a sorbent which could include boric, citric, phosphoric, phosphorous, sulphuric and
tartaric acid. The analysis is done using various methods including ion chromatography, flow injection
analysis with detection of conductivity, and spectrophotometry.
For more information, see Annex B.
4.4 Radial samplers
This type of sampler is a radial-type of diffusive sampler and its cylindrical outer surface acts as a diffusive
membrane [36]. Ammonia molecules move axially parallel towards an absorbent bed which is cylindrical
too and coaxial to the diffusive surface. This type of sampler uses phosphoric acid as a sorbent. Exposed
samplers are analysed using various methods, including spectrophotometry, flow injection analysis, and
ion chromatography.
For more information, see Annex C.
5 Calculation of the concentration of ammonia
5.1 Mass concentration
The concentration of NH in ambient air under actual conditions of sampling is calculated using Formula
3
(1):
M
+
mm−
NH
4 sb
C=
(1)
M et⋅⋅υ
NH
3
where
C 3
is the concentration of NH at ambient conditions in µg/m ;
3
is the molar mass of NH in g/mol;
M
3
NH
3
+ +
M
+ is the molar mass of NH in g/mol;
NH 4
4
m is the mass of ammonium found in the sample in µg;
s
12
---------------------- Page: 14 ----------------------
oSIST prEN 17346:2019
prEN 17346:2019 (E)
m is the mass of ammonium found in the mean laboratory blank in µg;
b
NOTE 1 In normal operations the travel and field blanks are expected to record similar masses of ammonium
compared to the laboratory blank. In cases where the travel and/or field blank is higher th
...
Questions, Comments and Discussion
Ask us and Technical Secretary will try to provide an answer. You can facilitate discussion about the standard in here.