ISO 17211:2015
(Main)Stationary source emissions — Sampling and determination of selenium compounds in flue gas
Stationary source emissions — Sampling and determination of selenium compounds in flue gas
ISO 17211:2015 describes the method for the sampling and determination of selenium compounds in both vapour phase and solid phase that are entrained in flue gases carried in stacks or ducts. The selenium content in flue gas is expressed as a mass concentration of elemental selenium in the stack gas. Particulate and gaseous selenium compounds are captured by a filter and an absorber solution, respectively. The total concentration of selenium compounds in flue gas is expressed as the sum of both concentrations. The concentrations of selenium in both samples are determined using inductively coupled plasma optical emission spectrometry (ICP-OES), inductively coupled plasma mass spectrometry (ICP-MS) or graphite furnace atomic absorption spectrometry (GFAAS). Hydride generation (HG) techniques coupled to atomic spectrometry can also be used such as HG-AAS, HG-AFS (atomic fluorescence spectrometry), HG-ICP-OES and HG-ICP-MS. The detection limit for gaseous selenium compounds is 0,3 μg/m3 using HG-ICP-MS at a sampling volume of 0,12 m3. The detection limit for particulate selenium compounds is 0,001 2 μg/m3 using this technique at a sampling volume of 2,0 m3.
Émission des sources fixes — Échantillonnage et détermination des composés de sélénium dans les effluents gazeux
L'ISO 17211:2015 décrit la méthode de prélèvement et de détermination des composés de sélénium, en phase vapeur et en phase solide, qui sont entraînées dans les effluents gazeux circulant dans les cheminées ou les conduits. La teneur en sélénium dans un effluent gazeux est exprimée sous forme de masse de sélénium élémentaire dans le gaz du conduit. Les composés gazeux et particulaires du sélénium sont respectivement capturés par une solution d'absorption et un filtre. La concentration totale des composés de sélénium dans l'effluent gazeux est exprimée comme la somme des deux concentrations. Les concentrations en sélénium dans les deux échantillons sont déterminées par spectroscopie d'émission optique avec plasma induit par haute fréquence (ICP-OES), spectrométrie de masse avec plasma à couplage inductif (ICP-MS) ou spectrométrie d'absorption atomique en four graphite (GFAAS). Les techniques de génération d'hydrures (HG) couplées à la spectrométrie atomique peuvent également être utilisées, telles que HG-AAS, HG-AFS (spectrométrie de fluorescence atomique), HG-ICP-OES et HG‑ICP-MS. La limite de détection pour les composés de sélénium gazeux sera de 0,3 μg/m3 en utilisant la technique HG-ICP-MS pour un volume de prélèvement de 0,12 m3. La limite de détection pour les composés de sélénium particulaires sera de 0,001 2 μg/m3 en utilisant la même technique HG-ICP-MS pour un volume de prélèvement de 2,0 m3.
Emisije nepremičnih virov - Vzorčenje in določevanje selenovih spojin v odpadnih plinih
Ta mednarodni standard opisuje metodo za vzorčenje in določevanje selenovih spojin v parni in trdni fazi, ki jih vsebujejo odpadni plini v dimnikih ali ceveh. Vsebnost selena v odpadnem plinu je izražena kot masna koncentracija elementarnega selena v dimnem plinu.
Delci in plinaste selenove spojine so zajete s filtrom oziroma z raztopino absorberja. Skupna koncentracija selenovih spojin v odpadnih plinih je izražena kot vsota obeh koncentracij.
Koncentracije selena v obeh vzorcih določimo z uporabo optične spektrometrije
z induktivno sklopljeno plazmo (ICP-OES), masne spektrometrije z induktivno sklopljeno plazmo (ICP-MS)
ali elektrotermične atomske absorpcijske spektrometrije (GFAAS). Uporabijo se lahko tudi tehnike pridobivanja hidrida (HG)
skupaj z atomsko spektrometrijo, kot so HG-AAS, HG-AFS (atomska fluorescenčna spektrometrija), HG-ICP-OES in HG-ICP-MS.
Meja zaznavnosti plinastih spojin selena je 0,3 μg/m3 z uporabo HG-ICP-MS pri vzorčni
prostornini 0,12 m3. Meja zaznavnosti za delce selenove spojine je 0,001 2 μg/m3 z uporabo te tehnike pri vzorčni prostornini 2,0 m3.
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INTERNATIONAL ISO
STANDARD 17211
First edition
2015-08-15
Stationary source emissions —
Sampling and determination of
selenium compounds in flue gas
Émission des sources fixes — Échantillonnage et détermination des
composés de sélénium dans les effluents gazeux
Reference number
ISO 17211:2015(E)
©
ISO 2015
---------------------- Page: 1 ----------------------
ISO 17211:2015(E)
COPYRIGHT PROTECTED DOCUMENT
© ISO 2015, Published in Switzerland
All rights reserved. Unless otherwise specified, no part of this publication may be reproduced or utilized otherwise in any form
or by any means, electronic or mechanical, including photocopying, or posting on the internet or an intranet, without prior
written permission. Permission can be requested from either ISO at the address below or ISO’s member body in the country of
the requester.
ISO copyright office
Ch. de Blandonnet 8 • CP 401
CH-1214 Vernier, Geneva, Switzerland
Tel. +41 22 749 01 11
Fax +41 22 749 09 47
copyright@iso.org
www.iso.org
ii © ISO 2015 – All rights reserved
---------------------- Page: 2 ----------------------
ISO 17211:2015(E)
Contents Page
Foreword .v
Introduction .vi
1 Scope . 1
2 Normative references . 1
3 Terms and definitions . 2
4 Symbols and abbreviated terms . 2
4.1 Symbols . 2
4.2 Abbreviated terms . 4
5 Principle . 4
6 Reagents . 5
7 Apparatus . 6
8 Sampling . 9
8.1 General . 9
8.2 Sampling position and sampling point . 9
8.3 Minimum sampling duration and minimum sample volume . 9
8.4 Other measurements to be made prior to sampling . 9
8.4.1 Volumetric gas flow through duct at the sampling plane . 9
8.4.2 Moisture content of gas . 9
8.4.3 Oxygen content of gas .10
8.5 Assembly of sampling apparatus .10
8.6 Sampling .10
8.7 Checking for leaks .10
8.8 Quality assurance.10
8.9 Sample recovery .11
8.9.1 Sample recovery for gaseous selenium .11
8.9.2 Sample recovery for particulate selenium .11
8.10 Field blank .11
9 Sample preparation .12
9.1 General .12
9.2 Sample preparation for analysis with hydride generation .12
9.2.1 Sample preparation for gaseous selenium analysis .12
9.2.2 Sample preparation for particulate selenium analysis .12
9.3 Sample preparation for analysis without hydride generation .12
9.3.1 Sample preparation for gaseous selenium analysis .12
9.3.2 Sample preparation for particulate selenium analysis .12
10 Analytical procedure .13
11 Expression of results .13
11.1 Calculation of the volume of dry flue gas sampled at sampling conditions, V .13
m
11.2 Calculation of the volume of dry flue gas sample normalized to standard
temperature and pressure, V .14
d
11.3 Mass concentration of selenium expressed as elemental selenium in the flue gas
on a dry basis at STP, ρ .14
Se,dry
11.4 Mass concentration of selenium expressed as elemental selenium in the flue gas
on a dry basis at STP and reference oxygen volume fraction, ρ .16
Se,dry,O
11.5 Rate of mass discharge of selenium expressed as elemental selenium, q .17
m,Se
11.6 Mass concentration of selenium expressed as elemental selenium in the flue gas
on a wet basis at STP, ρ .17
Se,wet
11.7 Mass concentration of selenium expressed as elemental selenium in the flue gas
on a wet basis at STP and reference oxygen concentration, ρ .17
Se,wet,O
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ISO 17211:2015(E)
12 Performance characteristics .18
12.1 Detection limits .18
12.2 Evaluation of measurement uncertainty .18
13 Test report .18
Annex A (informative) Results of evaluation of measurement uncertainties.20
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ISO 17211:2015(E)
Foreword
ISO (the International Organization for Standardization) is a worldwide federation of national standards
bodies (ISO member bodies). The work of preparing International Standards is normally carried out
through ISO technical committees. Each member body interested in a subject for which a technical
committee has been established has the right to be represented on that committee. International
organizations, governmental and non-governmental, in liaison with ISO, also take part in the work.
ISO collaborates closely with the International Electrotechnical Commission (IEC) on all matters of
electrotechnical standardization.
The procedures used to develop this document and those intended for its further maintenance are
described in the ISO/IEC Directives, Part 1. In particular the different approval criteria needed for the
different types of ISO documents should be noted. This document was drafted in accordance with the
editorial rules of the ISO/IEC Directives, Part 2 (see www.iso.org/directives).
Attention is drawn to the possibility that some of the elements of this document may be the subject of
patent rights. ISO shall not be held responsible for identifying any or all such patent rights. Details of
any patent rights identified during the development of the document will be in the Introduction and/or
on the ISO list of patent declarations received (see www.iso.org/patents).
Any trade name used in this document is information given for the convenience of users and does not
constitute an endorsement.
For an explanation on the meaning of ISO specific terms and expressions related to conformity
assessment, as well as information about ISO’s adherence to the WTO principles in the Technical
Barriers to Trade (TBT) see the following URL: Foreword - Supplementary information
The committee responsible for this document is ISO/TC 146, Air quality, Subcommittee SC 1, Stationary
source emissions.
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ISO 17211:2015(E)
Introduction
Since it is estimated that selenium is exhausted from stationary sources like coal combustion plants, the
investigation of the emission amounts of selenium from the stationary source is increasingly important
for preventing a potential risk.
This International Standard describes a method for the sampling and determination of selenium
compounds in a flue gas passing through ducts or chimneys. Selenium compounds generally exist both
in vapour phase and in solid phase in flue gases, this method allows the determination of both gaseous
and particulate selenium concentrations in flue gases.
vi © ISO 2015 – All rights reserved
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INTERNATIONAL STANDARD ISO 17211:2015(E)
Stationary source emissions — Sampling and
determination of selenium compounds in flue gas
1 Scope
This International Standard describes the method for the sampling and determination of selenium
compounds in both vapour phase and solid phase that are entrained in flue gases carried in stacks or
ducts. The selenium content in flue gas is expressed as a mass concentration of elemental selenium in
the stack gas.
Particulate and gaseous selenium compounds are captured by a filter and an absorber solution,
respectively. The total concentration of selenium compounds in flue gas is expressed as the sum of both
concentrations.
The concentrations of selenium in both samples are determined using inductively coupled plasma
optical emission spectrometry (ICP-OES), inductively coupled plasma mass spectrometry (ICP-MS)
or graphite furnace atomic absorption spectrometry (GFAAS). Hydride generation (HG) techniques
coupled to atomic spectrometry can also be used such as HG-AAS, HG-AFS (atomic fluorescence
spectrometry), HG-ICP-OES and HG-ICP-MS.
3
The detection limit for gaseous selenium compounds is 0,3 μg/m using HG-ICP-MS at a sampling
3 3
volume of 0,12 m . The detection limit for particulate selenium compounds is 0,001 2 μg/m using this
3
technique at a sampling volume of 2,0 m .
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.
ISO 3696, Water for analytical laboratory use — Specification and test methods
ISO 9096, Stationary source emissions — Manual determination of mass concentration of particulate
matter
ISO 10396, Stationary source emissions — Sampling for the automated determination of gas emission
concentrations for permanently-installed monitoring systems
ISO 11885, Water quality — Determination of selected elements by inductively coupled plasma optical
emission spectrometry (ICP-OES)
ISO 12141, Stationary source emissions — Determination of mass concentration of particulate matter
(dust) at low concentrations — Manual gravimetric method
ISO 15586, Water quality — Determination of trace elements using atomic absorption spectrometry with
graphite furnace
ISO 16911-1, Stationary source emissions — Manual and automatic determination of velocity and volume
flow rate in ducts — Part 1: Manual reference method
ISO 17294-1, Water quality — Application of inductively coupled plasma mass spectrometry (ICP-MS) —
Part 1: General guidelines
ISO 17294-2, Water quality — Application of inductively coupled plasma mass spectrometry (ICP-MS) —
Part 2: Determination of 62 elements
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ISO 17211:2015(E)
ISO/TS 17379-1, Water quality — Determination of selenium — Part 1: Method using hydride generation
atomic fluorescence spectrometry (HG-AFS)
ISO/TS 17379-2, Water quality — Determination of selenium — Part 2: Method using hydride generation
atomic absorption spectrometry (HG-AAS)
ISO 20988, Air quality — Guidelines for estimating measurement uncertainty
ISO 23210:2009, Stationary source emissions — Determination of PM10/PM2,5 mass concentration in flue
gas — Measurement at low concentrations by use of impactors
ISO/IEC Guide 98-3, Uncertainty of measurement — Part 3: Guide to the expression of uncertainty in
measurement (GUM:1995)
3 Terms and definitions
For the purposes of this document, the following terms and definitions apply.
3.1
gaseous selenium compounds
selenium compounds passing through a filter having at least 99,5 % collection efficiency for 0,3 μm
diameter particles
3.2
isokinetic sampling
sampling at a flow rate such that the velocity and direction of the gas entering the sampling nozzle are
the same as those of the gas in the duct at the sampling point
3.3
particulate selenium compounds
selenium compounds contained in a solid phase particle collected by a filter having at least 99,5 %
collection efficiency for 0,3 μm diameter particles
3.4
sampling point
specific position on the sampling section at which a sample is extracted
3.5
STP
standard conditions for temperature, 273,15 K, and pressure, 101,325 kPa
4 Symbols and abbreviated terms
4.1 Symbols
C concentration of selenium in prepared sample of the first and second absorber solutions
A1,Se
(μg/ml)
C concentration of selenium in prepared sample of the third absorber solution (μg/ml)
A2,Se
C concentration of selenium in prepared sample of rinse solution that washed transfer line
R,Se
from the filter housing to the first impinger nozzle in main-stream sampling (μg/ml)
C concentration of selenium in prepared sample of rinse solution that washed transfer line
R1,Se
from the filter housing to the T-piece in side-stream sampling (μg/ml)
C concentration of selenium in prepared sample of rinse solution that washed transfer line
R2,Se
after the T-piece to the first impinger nozzle in side-stream sampling (μg/ml)
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ISO 17211:2015(E)
C concentration of selenium in prepared sample solution for particulate selenium analysis
S,Se
(μg/ml)
d density of reagent solution (g/ml)
p atmospheric pressure (kPa)
atm
p average pressure difference between the sample gas before the gas meter and the atmos-
av
phere (kPa)
q rate of mass discharge of selenium expressed as elemental selenium (mg/s)
m,Se
q volume flow rate of flue gas through the sampling plane at conditions i of temperature,
V,fg,i
3
pressure, moisture and oxygen content (m /s)
T average temperature of the sample gas before the gas meter (K)
av
3
u(y) standard uncertainty (μg/m )
3
V volume of dry flue gas sample normalized to STP (m )
d
3
V final gas meter reading at the end of sampling (m )
f
3
V volume of dry flue gas sample for gaseous selenium analysis normalized to STP (m )
G,d
3
V initial gas meter reading at the beginning of sampling (m )
i
3
V volume of air drawn through the gas meter during any intermediate leak tests (m )
l
3
V volume of dry flue gas sample (m )
m
V volume of dry flue gas sample in main stream, normalized to STP, in side-stream sampling
main,d
3
(m )
3
V volume of dry flue gas sample for particulate selenium analysis normalized to STP (m )
S,d
volume of dry flue gas sampled in side stream, normalized to STP, in side-stream sampling
V
side,d
3
(m )
v volume of recovered sample of the first and second absorber solutions (ml)
A1
v volume of recovered sample of the third absorber solution (ml)
A2
v volume of recovered sample of rinse solution that washed transfer line from the filter
R
housing to the first impinger nozzle in main-stream sampling (ml)
v volume of recovered sample of rinse solution that washed transfer line from the filter
R1
housing to the T-piece in side-stream sampling (ml)
v volume of recovered sample of rinse solution that washed transfer line after the T-piece to
R2
the first impinger nozzle in side-stream sampling (ml)
v volume of prepared sample solution for particulate selenium analysis (ml)
S
w average moisture content of the flue gas at the sampling plane during the sampling period (%)
W
3
y j th concentration value of the first measuring system (μg/m )
1,j
3
y j th concentration value of the second measuring system (μg/m )
2,j
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ISO 17211:2015(E)
ρ mass concentration of gaseous selenium expressed as elemental selenium in the flue gas
G,Se,dry
3
on a dry basis at STP (μg/m )
ρ mass concentration of particulate selenium expressed as elemental selenium in the flue
S,Se,dry
3
gas on a dry basis at STP (μg/m )
ρ mass concentration of total selenium expressed as elemental selenium in the flue gas on
Se,dry
3
a dry basis at STP (μg/m )
ρ mass concentration of selenium expressed as elemental selenium in the flue gas on a dry
Se,dry,O
3
basis at STP and reference oxygen concentration (μg/m )
ρ mass concentration of selenium expressed as elemental selenium at conditions i of tem-
Se,i
3
perature, pressure, oxygen and moisture conditions (μg/m )
ρ mass concentration of selenium expressed as elemental selenium in the flue gas on a wet
Se,wet
3
basis at STP (μg/m )
ρ mass concentration of selenium expressed as elemental selenium in the flue gas on a wet
Se,wet,O
3
basis at STP and reference oxygen concentration (μg/m )
volume fraction of the oxygen on a dry basis measured during the sampling (%)
ϕ
O,d
volume fraction of the reference oxygen for the process (%)
ϕ
O,ref
4.2 Abbreviated terms
AAS atomic absorption spectrometry
AFS atomic fluorescence spectrometry
GFAAS graphite furnace atomic absorption spectrometry
HG hydride generation
ICP-MS inductively coupled plasma mass spectrometry
ICP-OES inductively coupled plasma optical emission spectrometry
FEP hexafluoroethene propene, perfluoro(ethane-propene)
PFA perfluoroalkoxy
PTFE polytetrafluoroethylene
5 Principle
Selenium compounds generally exist both in vapour phase and in solid phase in a flue gas. Particulate
and gaseous selenium compounds are captured by a filter and an absorber solution, respectively. The
concentration of selenium in a flue gas is expressed as the sum of both concentrations.
To determine particulate selenium contents in a flue gas, a stack sample gas is taken isokinetically and
particles are collected on a filter in accordance with ISO 9096 or ISO 12141.
To determine gaseous selenium content in a flue gas, a stack sample gas is taken through a filter. Gaseous
selenium compounds that pass through the filter are collected in an absorber solution. Since some
of gaseous selenium compounds, mostly SeO , are adsorbed and in some cases reduced to elemental
2
selenium on the inner surface of a sampling system in the presence of steam and SO , the sampling
2
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ISO 17211:2015(E)
system components such as the filter housing, heated transfer line and impinger nozzle is rinsed by an
oxidation solution to recover the stuck selenium.
If the flow rates and the total sampling volumes for the measurements of particulate and gaseous
selenium are the same, particulate and gaseous sampling shall be performed simultaneously with an
isokinetic sampling procedure.
Each sample is prepared to be analysed by either ICP-OES, ICP-MS or GFAAS. HG-AAS, HG-AFS, HG-ICP-
OES or HG-ICP-MS may be used if greater analytical sensitivity is required to determine the selenium
concentration.
6 Reagents
6.1 General. To carry out the method, the following reagents are required to be of a recognized
analytical grade.
6.2 Water, complying with grade 1 s specified in ISO 3696 for all sample preparation and dilutions.
6.3 Nitric acid, d(HNO ) = 1,4 g/ml.
3
NOTE Nitric acid is available both as d(HNO ) = 1,40 g/ml [w(HNO ) = 650 g/kg] and d(HNO ) = 1,42 g/ml
3 3 3
[w(HNO ) = 690 g/kg].
3
6.4 Hydrogen peroxide, w(H O ) = 30 %.
2 2
6.5 Sulfuric acid, d(H SO ) = 1,84 g/ml.
2 4
6.6 Potassium permanganate, KMnO .
4
6.7 Selenium stock solution, complying with selenium standard solutions as specified in
ISO/TS 17379-1 and ISO/TS 17379-2.
6.8 Absorber solution, mixture of 0,7 mol/l HNO solution and 3 mol/l H O solution.
3 2 2
Add carefully 50 ml of concentrated HNO (6.3) to a 1 000 ml volumetric flask containing approximately
3
500 ml of water, and then add 333 ml of 30 % H O (6.4) carefully. Add water with stirring to make a
2 2
volume of 1 000 ml.
6.9 Rinse solution, mixture of 0,06 mol/l KMnO solution and 1,8 mol/l H SO solution.
4 2 4
Add carefully with stirring 100 ml of concentrated H SO (6.5) to a 1 000 ml volumetric flask containing
2 4
approximately 500 ml of water, and then add 10 g of KMnO (6.6) carefully with stirring. Add water
4
with stirring to make a volume of 1 000 ml.
6.10 Sample gas drying agent, self-indicating coarse grade silica gel.
6.11 Hydrofluoric acid, w(HF) = 40 %.
6.12 Hydrochloric acid solution, c(HCl) = 6 mol/l.
Add carefully with stirring 250 ml of concentrated HCl [d(HCl) = 1,19 g/ml] to a 500 ml volumetric flask
containing approximately 150 ml of water. Add water with stirring to make a volume of 500 ml.
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ISO 17211:2015(E)
7 Apparatus
7.1 General.
Two types of absorber systems, a main-stream and a side-stream arrangement, can be employed.
Schematics of both systems are given in Figure 1. In the main-stream system all the sampled flue gas is
passed though the absorber solutions, while in the side-stream arrangement only a part of the sampled
flue gas is passed through the absorber solutions. The main-stream sampling is used if the flow rate
and total sampling volume for the measurements of gaseous and particulate selenium are the same.
The side-stream sampling is used if the flow rate or total sampling volume for the measurements of
gaseous and particulate selenium is different.
If the representative sampling is allowed, particulate selenium and gaseous selenium are sampled
separately using two main stream sampling. Determine a representative sampling point in accordance
with ISO 23210:2009, Annex G. Two sampling nozzles, for particulate selenium and gaseous selenium
respectively, are placed at neighbouring points in which the physicochemical parameters such as
selenium concentration and gas flow rate are considered to be equivalent. Particulate selenium sample
is collected by the filter isokinetically. Gaseous selenium sample is captured in an absorber solution
either isokinetically or anisokinetically after particles are removed.
The apparatus consists of a sampling probe including a nozzle and filter assembly that may be heated
if required, an impinger train containing absorber solution to capture gaseous selenium, a manometer,
a suction pump, a gas meter, and a sample gas volume flow rate measurement system. A thermometer
and manometer shall be included in the sampling train to measure the temperature and pressure of the
metered gas. A barometer shall be used to measure atmospheric pressure during the test in order that
the volume of the gas sampled can be normalized to the standard condition of 273,15 K and 101,325 kPa.
a) Main-stream sampling
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ISO 17211:2015(E)
b) Side-stream sampling
Key
1 nozzle 9 gas meter
2 filter and filter housing 10 thermometer and manometer
3 transfer line 11 rotameter
4 T-piece 12 impinger nozzle
5 HNO /H O impingers 13 cooler bath
3 2 2
6 dry impinger 14 main stream
7 drying tube or silica gel 15 side stream
8 pump
Figure 1 — Schematic diagram of a sampling train
7.2 Nozzle. The diameter shall be chosen to be compatible with the required gas sampling volume
flow rate. The choice of the nozzle shall be in accordance with ISO 9096 or ISO 12141.
The nozzle shall be capable of withstanding the temperature in the duct. It shall be resistant to chemical
attack from various pollutants in the duct. Suitable materials for selenium sampling are silica glass,
PTFE and titanium.
The nozzle shall be cleaned thoroughly before each sample run by rinsing with distilled water. The
rinse shall be repeated until the rinse water shows no evidence of particulate matter.
7.3 Filter and filter housing. The silica fibre filter is placed in the duct between the nozzle and the
transfer line (in-stack filtration). Silica fibre filters without binders are recommended. The filter holder
shall have an airtight seal against leakage. If the flue gas temperature is below the dew point or the filter
housing cannot be inserted in the duct, the filter housing shall be placed outside the duct (out-stack
filtration) in accordance with ISO 9096 or ISO 12141.
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ISO 17211:2015(E)
NOTE If the out-stack filtration is employed, separation between particulate and gaseous selenium is
difficult and only total selenium can be determined.
The filter shall be capable of withstanding prolonged exposures up to 40 K above the sampling
temperature to prevent a change in filter quality. The filter efficiency shall be better than 99,5 % on a
test aerosol with a mean particle diamete
...
SLOVENSKI STANDARD
SIST ISO 17211:2019
01-julij-2019
Emisije nepremičnih virov - Vzorčenje in določevanje selenovih spojin v odpadnih
plinih
Stationary source emissions - Sampling and determination of selenium compounds in
flue gas
Émission des sources fixes - Échantillonnage et détermination des composés de
sélénium dans les effluents gazeux
Ta slovenski standard je istoveten z: ISO 17211:2015
ICS:
13.040.40 Emisije nepremičnih virov Stationary source emissions
SIST ISO 17211:2019 en,fr
2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.
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SIST ISO 17211:2019
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SIST ISO 17211:2019
INTERNATIONAL ISO
STANDARD 17211
First edition
2015-08-15
Stationary source emissions —
Sampling and determination of
selenium compounds in flue gas
Émission des sources fixes — Échantillonnage et détermination des
composés de sélénium dans les effluents gazeux
Reference number
ISO 17211:2015(E)
©
ISO 2015
---------------------- Page: 3 ----------------------
SIST ISO 17211:2019
ISO 17211:2015(E)
COPYRIGHT PROTECTED DOCUMENT
© ISO 2015, Published in Switzerland
All rights reserved. Unless otherwise specified, no part of this publication may be reproduced or utilized otherwise in any form
or by any means, electronic or mechanical, including photocopying, or posting on the internet or an intranet, without prior
written permission. Permission can be requested from either ISO at the address below or ISO’s member body in the country of
the requester.
ISO copyright office
Ch. de Blandonnet 8 • CP 401
CH-1214 Vernier, Geneva, Switzerland
Tel. +41 22 749 01 11
Fax +41 22 749 09 47
copyright@iso.org
www.iso.org
ii © ISO 2015 – All rights reserved
---------------------- Page: 4 ----------------------
SIST ISO 17211:2019
ISO 17211:2015(E)
Contents Page
Foreword .v
Introduction .vi
1 Scope . 1
2 Normative references . 1
3 Terms and definitions . 2
4 Symbols and abbreviated terms . 2
4.1 Symbols . 2
4.2 Abbreviated terms . 4
5 Principle . 4
6 Reagents . 5
7 Apparatus . 6
8 Sampling . 9
8.1 General . 9
8.2 Sampling position and sampling point . 9
8.3 Minimum sampling duration and minimum sample volume . 9
8.4 Other measurements to be made prior to sampling . 9
8.4.1 Volumetric gas flow through duct at the sampling plane . 9
8.4.2 Moisture content of gas . 9
8.4.3 Oxygen content of gas .10
8.5 Assembly of sampling apparatus .10
8.6 Sampling .10
8.7 Checking for leaks .10
8.8 Quality assurance.10
8.9 Sample recovery .11
8.9.1 Sample recovery for gaseous selenium .11
8.9.2 Sample recovery for particulate selenium .11
8.10 Field blank .11
9 Sample preparation .12
9.1 General .12
9.2 Sample preparation for analysis with hydride generation .12
9.2.1 Sample preparation for gaseous selenium analysis .12
9.2.2 Sample preparation for particulate selenium analysis .12
9.3 Sample preparation for analysis without hydride generation .12
9.3.1 Sample preparation for gaseous selenium analysis .12
9.3.2 Sample preparation for particulate selenium analysis .12
10 Analytical procedure .13
11 Expression of results .13
11.1 Calculation of the volume of dry flue gas sampled at sampling conditions, V .13
m
11.2 Calculation of the volume of dry flue gas sample normalized to standard
temperature and pressure, V .14
d
11.3 Mass concentration of selenium expressed as elemental selenium in the flue gas
on a dry basis at STP, ρ .14
Se,dry
11.4 Mass concentration of selenium expressed as elemental selenium in the flue gas
on a dry basis at STP and reference oxygen volume fraction, ρ .16
Se,dry,O
11.5 Rate of mass discharge of selenium expressed as elemental selenium, q .17
m,Se
11.6 Mass concentration of selenium expressed as elemental selenium in the flue gas
on a wet basis at STP, ρ .17
Se,wet
11.7 Mass concentration of selenium expressed as elemental selenium in the flue gas
on a wet basis at STP and reference oxygen concentration, ρ .17
Se,wet,O
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12 Performance characteristics .18
12.1 Detection limits .18
12.2 Evaluation of measurement uncertainty .18
13 Test report .18
Annex A (informative) Results of evaluation of measurement uncertainties.20
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Foreword
ISO (the International Organization for Standardization) is a worldwide federation of national standards
bodies (ISO member bodies). The work of preparing International Standards is normally carried out
through ISO technical committees. Each member body interested in a subject for which a technical
committee has been established has the right to be represented on that committee. International
organizations, governmental and non-governmental, in liaison with ISO, also take part in the work.
ISO collaborates closely with the International Electrotechnical Commission (IEC) on all matters of
electrotechnical standardization.
The procedures used to develop this document and those intended for its further maintenance are
described in the ISO/IEC Directives, Part 1. In particular the different approval criteria needed for the
different types of ISO documents should be noted. This document was drafted in accordance with the
editorial rules of the ISO/IEC Directives, Part 2 (see www.iso.org/directives).
Attention is drawn to the possibility that some of the elements of this document may be the subject of
patent rights. ISO shall not be held responsible for identifying any or all such patent rights. Details of
any patent rights identified during the development of the document will be in the Introduction and/or
on the ISO list of patent declarations received (see www.iso.org/patents).
Any trade name used in this document is information given for the convenience of users and does not
constitute an endorsement.
For an explanation on the meaning of ISO specific terms and expressions related to conformity
assessment, as well as information about ISO’s adherence to the WTO principles in the Technical
Barriers to Trade (TBT) see the following URL: Foreword - Supplementary information
The committee responsible for this document is ISO/TC 146, Air quality, Subcommittee SC 1, Stationary
source emissions.
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Introduction
Since it is estimated that selenium is exhausted from stationary sources like coal combustion plants, the
investigation of the emission amounts of selenium from the stationary source is increasingly important
for preventing a potential risk.
This International Standard describes a method for the sampling and determination of selenium
compounds in a flue gas passing through ducts or chimneys. Selenium compounds generally exist both
in vapour phase and in solid phase in flue gases, this method allows the determination of both gaseous
and particulate selenium concentrations in flue gases.
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INTERNATIONAL STANDARD ISO 17211:2015(E)
Stationary source emissions — Sampling and
determination of selenium compounds in flue gas
1 Scope
This International Standard describes the method for the sampling and determination of selenium
compounds in both vapour phase and solid phase that are entrained in flue gases carried in stacks or
ducts. The selenium content in flue gas is expressed as a mass concentration of elemental selenium in
the stack gas.
Particulate and gaseous selenium compounds are captured by a filter and an absorber solution,
respectively. The total concentration of selenium compounds in flue gas is expressed as the sum of both
concentrations.
The concentrations of selenium in both samples are determined using inductively coupled plasma
optical emission spectrometry (ICP-OES), inductively coupled plasma mass spectrometry (ICP-MS)
or graphite furnace atomic absorption spectrometry (GFAAS). Hydride generation (HG) techniques
coupled to atomic spectrometry can also be used such as HG-AAS, HG-AFS (atomic fluorescence
spectrometry), HG-ICP-OES and HG-ICP-MS.
3
The detection limit for gaseous selenium compounds is 0,3 μg/m using HG-ICP-MS at a sampling
3 3
volume of 0,12 m . The detection limit for particulate selenium compounds is 0,001 2 μg/m using this
3
technique at a sampling volume of 2,0 m .
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.
ISO 3696, Water for analytical laboratory use — Specification and test methods
ISO 9096, Stationary source emissions — Manual determination of mass concentration of particulate
matter
ISO 10396, Stationary source emissions — Sampling for the automated determination of gas emission
concentrations for permanently-installed monitoring systems
ISO 11885, Water quality — Determination of selected elements by inductively coupled plasma optical
emission spectrometry (ICP-OES)
ISO 12141, Stationary source emissions — Determination of mass concentration of particulate matter
(dust) at low concentrations — Manual gravimetric method
ISO 15586, Water quality — Determination of trace elements using atomic absorption spectrometry with
graphite furnace
ISO 16911-1, Stationary source emissions — Manual and automatic determination of velocity and volume
flow rate in ducts — Part 1: Manual reference method
ISO 17294-1, Water quality — Application of inductively coupled plasma mass spectrometry (ICP-MS) —
Part 1: General guidelines
ISO 17294-2, Water quality — Application of inductively coupled plasma mass spectrometry (ICP-MS) —
Part 2: Determination of 62 elements
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ISO/TS 17379-1, Water quality — Determination of selenium — Part 1: Method using hydride generation
atomic fluorescence spectrometry (HG-AFS)
ISO/TS 17379-2, Water quality — Determination of selenium — Part 2: Method using hydride generation
atomic absorption spectrometry (HG-AAS)
ISO 20988, Air quality — Guidelines for estimating measurement uncertainty
ISO 23210:2009, Stationary source emissions — Determination of PM10/PM2,5 mass concentration in flue
gas — Measurement at low concentrations by use of impactors
ISO/IEC Guide 98-3, Uncertainty of measurement — Part 3: Guide to the expression of uncertainty in
measurement (GUM:1995)
3 Terms and definitions
For the purposes of this document, the following terms and definitions apply.
3.1
gaseous selenium compounds
selenium compounds passing through a filter having at least 99,5 % collection efficiency for 0,3 μm
diameter particles
3.2
isokinetic sampling
sampling at a flow rate such that the velocity and direction of the gas entering the sampling nozzle are
the same as those of the gas in the duct at the sampling point
3.3
particulate selenium compounds
selenium compounds contained in a solid phase particle collected by a filter having at least 99,5 %
collection efficiency for 0,3 μm diameter particles
3.4
sampling point
specific position on the sampling section at which a sample is extracted
3.5
STP
standard conditions for temperature, 273,15 K, and pressure, 101,325 kPa
4 Symbols and abbreviated terms
4.1 Symbols
C concentration of selenium in prepared sample of the first and second absorber solutions
A1,Se
(μg/ml)
C concentration of selenium in prepared sample of the third absorber solution (μg/ml)
A2,Se
C concentration of selenium in prepared sample of rinse solution that washed transfer line
R,Se
from the filter housing to the first impinger nozzle in main-stream sampling (μg/ml)
C concentration of selenium in prepared sample of rinse solution that washed transfer line
R1,Se
from the filter housing to the T-piece in side-stream sampling (μg/ml)
C concentration of selenium in prepared sample of rinse solution that washed transfer line
R2,Se
after the T-piece to the first impinger nozzle in side-stream sampling (μg/ml)
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C concentration of selenium in prepared sample solution for particulate selenium analysis
S,Se
(μg/ml)
d density of reagent solution (g/ml)
p atmospheric pressure (kPa)
atm
p average pressure difference between the sample gas before the gas meter and the atmos-
av
phere (kPa)
q rate of mass discharge of selenium expressed as elemental selenium (mg/s)
m,Se
q volume flow rate of flue gas through the sampling plane at conditions i of temperature,
V,fg,i
3
pressure, moisture and oxygen content (m /s)
T average temperature of the sample gas before the gas meter (K)
av
3
u(y) standard uncertainty (μg/m )
3
V volume of dry flue gas sample normalized to STP (m )
d
3
V final gas meter reading at the end of sampling (m )
f
3
V volume of dry flue gas sample for gaseous selenium analysis normalized to STP (m )
G,d
3
V initial gas meter reading at the beginning of sampling (m )
i
3
V volume of air drawn through the gas meter during any intermediate leak tests (m )
l
3
V volume of dry flue gas sample (m )
m
V volume of dry flue gas sample in main stream, normalized to STP, in side-stream sampling
main,d
3
(m )
3
V volume of dry flue gas sample for particulate selenium analysis normalized to STP (m )
S,d
volume of dry flue gas sampled in side stream, normalized to STP, in side-stream sampling
V
side,d
3
(m )
v volume of recovered sample of the first and second absorber solutions (ml)
A1
v volume of recovered sample of the third absorber solution (ml)
A2
v volume of recovered sample of rinse solution that washed transfer line from the filter
R
housing to the first impinger nozzle in main-stream sampling (ml)
v volume of recovered sample of rinse solution that washed transfer line from the filter
R1
housing to the T-piece in side-stream sampling (ml)
v volume of recovered sample of rinse solution that washed transfer line after the T-piece to
R2
the first impinger nozzle in side-stream sampling (ml)
v volume of prepared sample solution for particulate selenium analysis (ml)
S
w average moisture content of the flue gas at the sampling plane during the sampling period (%)
W
3
y j th concentration value of the first measuring system (μg/m )
1,j
3
y j th concentration value of the second measuring system (μg/m )
2,j
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ρ mass concentration of gaseous selenium expressed as elemental selenium in the flue gas
G,Se,dry
3
on a dry basis at STP (μg/m )
ρ mass concentration of particulate selenium expressed as elemental selenium in the flue
S,Se,dry
3
gas on a dry basis at STP (μg/m )
ρ mass concentration of total selenium expressed as elemental selenium in the flue gas on
Se,dry
3
a dry basis at STP (μg/m )
ρ mass concentration of selenium expressed as elemental selenium in the flue gas on a dry
Se,dry,O
3
basis at STP and reference oxygen concentration (μg/m )
ρ mass concentration of selenium expressed as elemental selenium at conditions i of tem-
Se,i
3
perature, pressure, oxygen and moisture conditions (μg/m )
ρ mass concentration of selenium expressed as elemental selenium in the flue gas on a wet
Se,wet
3
basis at STP (μg/m )
ρ mass concentration of selenium expressed as elemental selenium in the flue gas on a wet
Se,wet,O
3
basis at STP and reference oxygen concentration (μg/m )
volume fraction of the oxygen on a dry basis measured during the sampling (%)
ϕ
O,d
volume fraction of the reference oxygen for the process (%)
ϕ
O,ref
4.2 Abbreviated terms
AAS atomic absorption spectrometry
AFS atomic fluorescence spectrometry
GFAAS graphite furnace atomic absorption spectrometry
HG hydride generation
ICP-MS inductively coupled plasma mass spectrometry
ICP-OES inductively coupled plasma optical emission spectrometry
FEP hexafluoroethene propene, perfluoro(ethane-propene)
PFA perfluoroalkoxy
PTFE polytetrafluoroethylene
5 Principle
Selenium compounds generally exist both in vapour phase and in solid phase in a flue gas. Particulate
and gaseous selenium compounds are captured by a filter and an absorber solution, respectively. The
concentration of selenium in a flue gas is expressed as the sum of both concentrations.
To determine particulate selenium contents in a flue gas, a stack sample gas is taken isokinetically and
particles are collected on a filter in accordance with ISO 9096 or ISO 12141.
To determine gaseous selenium content in a flue gas, a stack sample gas is taken through a filter. Gaseous
selenium compounds that pass through the filter are collected in an absorber solution. Since some
of gaseous selenium compounds, mostly SeO , are adsorbed and in some cases reduced to elemental
2
selenium on the inner surface of a sampling system in the presence of steam and SO , the sampling
2
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system components such as the filter housing, heated transfer line and impinger nozzle is rinsed by an
oxidation solution to recover the stuck selenium.
If the flow rates and the total sampling volumes for the measurements of particulate and gaseous
selenium are the same, particulate and gaseous sampling shall be performed simultaneously with an
isokinetic sampling procedure.
Each sample is prepared to be analysed by either ICP-OES, ICP-MS or GFAAS. HG-AAS, HG-AFS, HG-ICP-
OES or HG-ICP-MS may be used if greater analytical sensitivity is required to determine the selenium
concentration.
6 Reagents
6.1 General. To carry out the method, the following reagents are required to be of a recognized
analytical grade.
6.2 Water, complying with grade 1 s specified in ISO 3696 for all sample preparation and dilutions.
6.3 Nitric acid, d(HNO ) = 1,4 g/ml.
3
NOTE Nitric acid is available both as d(HNO ) = 1,40 g/ml [w(HNO ) = 650 g/kg] and d(HNO ) = 1,42 g/ml
3 3 3
[w(HNO ) = 690 g/kg].
3
6.4 Hydrogen peroxide, w(H O ) = 30 %.
2 2
6.5 Sulfuric acid, d(H SO ) = 1,84 g/ml.
2 4
6.6 Potassium permanganate, KMnO .
4
6.7 Selenium stock solution, complying with selenium standard solutions as specified in
ISO/TS 17379-1 and ISO/TS 17379-2.
6.8 Absorber solution, mixture of 0,7 mol/l HNO solution and 3 mol/l H O solution.
3 2 2
Add carefully 50 ml of concentrated HNO (6.3) to a 1 000 ml volumetric flask containing approximately
3
500 ml of water, and then add 333 ml of 30 % H O (6.4) carefully. Add water with stirring to make a
2 2
volume of 1 000 ml.
6.9 Rinse solution, mixture of 0,06 mol/l KMnO solution and 1,8 mol/l H SO solution.
4 2 4
Add carefully with stirring 100 ml of concentrated H SO (6.5) to a 1 000 ml volumetric flask containing
2 4
approximately 500 ml of water, and then add 10 g of KMnO (6.6) carefully with stirring. Add water
4
with stirring to make a volume of 1 000 ml.
6.10 Sample gas drying agent, self-indicating coarse grade silica gel.
6.11 Hydrofluoric acid, w(HF) = 40 %.
6.12 Hydrochloric acid solution, c(HCl) = 6 mol/l.
Add carefully with stirring 250 ml of concentrated HCl [d(HCl) = 1,19 g/ml] to a 500 ml volumetric flask
containing approximately 150 ml of water. Add water with stirring to make a volume of 500 ml.
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7 Apparatus
7.1 General.
Two types of absorber systems, a main-stream and a side-stream arrangement, can be employed.
Schematics of both systems are given in Figure 1. In the main-stream system all the sampled flue gas is
passed though the absorber solutions, while in the side-stream arrangement only a part of the sampled
flue gas is passed through the absorber solutions. The main-stream sampling is used if the flow rate
and total sampling volume for the measurements of gaseous and particulate selenium are the same.
The side-stream sampling is used if the flow rate or total sampling volume for the measurements of
gaseous and particulate selenium is different.
If the representative sampling is allowed, particulate selenium and gaseous selenium are sampled
separately using two main stream sampling. Determine a representative sampling point in accordance
with ISO 23210:2009, Annex G. Two sampling nozzles, for particulate selenium and gaseous selenium
respectively, are placed at neighbouring points in which the physicochemical parameters such as
selenium concentration and gas flow rate are considered to be equivalent. Particulate selenium sample
is collected by the filter isokinetically. Gaseous selenium sample is captured in an absorber solution
either isokinetically or anisokinetically after particles are removed.
The apparatus consists of a sampling probe including a nozzle and filter assembly that may be heated
if required, an impinger train containing absorber solution to capture gaseous selenium, a manometer,
a suction pump, a gas meter, and a sample gas volume flow rate measurement system. A thermometer
and manometer shall be included in the sampling train to measure the temperature and pressure of the
metered gas. A barometer shall be used to measure atmospheric pressure during the test in order that
the volume of the gas sampled can be normalized to the standard condition of 273,15 K and 101,325 kPa.
a) Main-stream sampling
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b) Side-stream sampling
Key
1 nozzle 9 gas meter
2 filter and filter housing 10 thermometer and manometer
3 transfer line 11 rotameter
4 T-piece 12 impinger nozzle
5 HNO /H O impingers 13 cooler bath
3 2 2
6 dry impinger 14 main stream
7 drying tube or silica gel 15 side stream
8 pump
Figure 1 — Schematic diagram of a sampling train
7.2 Nozzle. The diameter shall be chosen to be compatible with the required gas sampling volume
flow rate. The choice of the nozzle shall be in accordance with ISO 9096 or ISO 12141.
The nozzle shall be capable of withstanding the temperature in the duct. It shall be resistant to chemical
attack from various pollutants in the duct. Suitable materials for selenium sampling are silica glass,
PTFE and titanium.
The nozzle shall be cleaned thoroughly before each sample run by rinsing with distilled water. The
rinse shall be repeated until the rinse water shows n
...
NORME ISO
INTERNATIONALE 17211
Première édition
2015-08-15
Émission des sources fixes —
Échantillonnage et détermination
des composés de sélénium dans les
effluents gazeux
Stationary source emissions — Sampling and determination of
selenium compounds in flue gas
Numéro de référence
ISO 17211:2015(F)
©
ISO 2015
---------------------- Page: 1 ----------------------
ISO 17211:2015(F)
DOCUMENT PROTÉGÉ PAR COPYRIGHT
© ISO 2015, Publié en Suisse
Droits de reproduction réservés. Sauf indication contraire, aucune partie de cette publication ne peut être reproduite ni utilisée
sous quelque forme que ce soit et par aucun procédé, électronique ou mécanique, y compris la photocopie, l’affichage sur
l’internet ou sur un Intranet, sans autorisation écrite préalable. Les demandes d’autorisation peuvent être adressées à l’ISO à
l’adresse ci-après ou au comité membre de l’ISO dans le pays du demandeur.
ISO copyright office
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Tel. +41 22 749 01 11
Fax +41 22 749 09 47
copyright@iso.org
www.iso.org
ii © ISO 2015 – Tous droits réservés
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ISO 17211:2015(F)
Sommaire Page
Avant-propos .v
Introduction .vi
1 Domaine d’application . 1
2 Références normatives . 1
3 Termes et définitions . 2
4 Symboles et abréviations . 2
4.1 Symboles . 2
4.2 Abréviations . 4
5 Principe . 5
6 Réactifs . 5
7 Appareillage . 6
8 Prélèvement .10
8.1 Généralités .10
8.2 Position de prélèvement et point de prélèvement .10
8.3 Durée minimale de prélèvement et volume minimal d’échantillon .10
8.4 Autres mesurages à effectuer avant le prélèvement.11
8.4.1 Débit volumique du gaz dans le conduit au niveau du plan de prélèvement .11
8.4.2 Teneur en humidité du gaz .11
8.4.3 Teneur en oxygène du gaz .11
8.5 Montage de l’appareillage de prélèvement .11
8.6 Prélèvement . .11
8.7 Vérification des fuites .11
8.8 Assurance de la qualité .12
8.9 Récupération des échantillons .12
8.9.1 Récupération des échantillons de sélénium gazeux .12
8.9.2 Récupération des échantillons de sélénium particulaire .13
8.10 Blanc de site .13
9 Préparation de l’échantillon .13
9.1 Généralités .13
9.2 Préparation de l’échantillon pour l’analyse avec génération d’hydrures .13
9.2.1 Préparation de l’échantillon pour l’analyse du sélénium gazeux .13
9.2.2 Préparation de l’échantillon pour l’analyse du sélénium particulaire .13
9.3 Préparation de l’échantillon pour l’analyse sans génération d’hydrures .14
9.3.1 Préparation de l’échantillon pour l’analyse du sélénium gazeux .14
9.3.2 Préparation de l’échantillon pour l’analyse du sélénium particulaire .14
10 Mode opératoire d’analyse .14
11 Expression des résultats.15
11.1 Calcul du volume de l’échantillon d’effluent gazeux sec prélevé dans les conditions
de prélèvement, V .
m 15
11.2 Calcul du volume de l’échantillon d’effluent gazeux sec ramené aux conditions
normales de température et de pression, V .
d 15
11.3 Concentration en masse du sélénium, exprimée en sélénium élémentaire dans
l’effluent gazeux, sur sec dans les conditions normales NTP, ρ .
Se,sec 15
11.4 Concentration en masse du sélénium, exprimée en sélénium élémentaire dans
l’effluent gazeux, sur sec dans les conditions normales NTP et à la teneur en
volume d’oxygène de référence, ρ .
Se,sec,O 17
11.5 Débit massique de sélénium exprimé en sélénium élémentaire, q .
m,Se 18
11.6 Concentration en masse du sélénium, exprimée en sélénium élémentaire dans
l’effluent gazeux, sur humide dans les conditions normales NTP, ρ .
Se,hum 18
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ISO 17211:2015(F)
11.7 Concentration en masse du sélénium, exprimée en sélénium élémentaire
dans l’effluent gazeux, sur humide dans les conditions normales NTP et à la
concentration en oxygène de référence, ρ .
Se,hum,O 18
12 Caractéristiques de performance .19
12.1 Limites de détection .19
12.2 Évaluation de l’incertitude de mesure .19
13 Rapport d’essai .19
Annex A (informative) Résultats de l’évaluation des incertitudes de mesure .21
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ISO 17211:2015(F)
Avant-propos
L’ISO (Organisation internationale de normalisation) est une fédération mondiale d’organismes
nationaux de normalisation (comités membres de l’ISO). L’élaboration des Normes internationales est
en général confiée aux comités techniques de l’ISO. Chaque comité membre intéressé par une étude
a le droit de faire partie du comité technique créé à cet effet. Les organisations internationales,
gouvernementales et non gouvernementales, en liaison avec l’ISO participent également aux travaux.
L’ISO collabore étroitement avec la Commission électrotechnique internationale (IEC) en ce qui
concerne la normalisation électrotechnique.
Les procédures utilisées pour élaborer le présent document et celles destinées à sa mise à jour sont
décrites dans les Directives ISO/IEC, Partie 1. Il convient, en particulier de prendre note des différents
critères d’approbation requis pour les différents types de documents ISO. Le présent document a été
rédigé conformément aux règles de rédaction données dans les Directives ISO/IEC, Partie 2 (voir www.
iso.org/directives).
L’attention est appelée sur le fait que certains des éléments du présent document peuvent faire l’objet de
droits de propriété intellectuelle ou de droits analogues. L’ISO ne saurait être tenue pour responsable
de ne pas avoir identifié de tels droits de propriété et averti de leur existence. Les détails concernant
les références aux droits de propriété intellectuelle ou autres droits analogues identifiés lors de
l’élaboration du document sont indiqués dans l’Introduction et/ou dans la liste des déclarations de
brevets reçues par l’ISO (voir www.iso.org/brevets).
Les appellations commerciales éventuellement mentionnées dans le présent document sont données
pour information, par souci de commodité, à l’intention des utilisateurs et ne sauraient constituer
un engagement.
Pour une explication de la signification des termes et expressions spécifiques de l’ISO liés à
l’évaluation de la conformité, ou pour toute information au sujet de l’adhésion de l’ISO aux principes
de l’OMC concernant les obstacles techniques au commerce (OTC), voir le lien suivant: Avant-propos —
Informations supplémentaires.
Le comité chargé de l’élaboration du présent document est l’ISO/TC 146, Qualité de l’air, sous–comité
SC 1, Émissions de sources fixes.
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ISO 17211:2015(F)
Introduction
Du fait que l’on estime que du sélénium est émis par les sources fixes telles que les centrales thermiques
alimentées au charbon, il devient de plus en plus important de déterminer les quantités de sélénium
émises par les sources fixes pour prévenir un risque potentiel.
La présente Norme internationale décrit une méthode pour le prélèvement et la détermination des
composés de sélénium dans des effluents gazeux s’échappant de conduits ou de cheminées. En général,
les composés de sélénium existent à la fois en phase gazeuse et en phase solide dans les effluents gazeux.
La présente méthode permet de déterminer les concentrations en sélénium gazeux et particulaire dans
les effluents gazeux.
vi © ISO 2015 – Tous droits réservés
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NORME INTERNATIONALE ISO 17211:2015(F)
Émission des sources fixes — Échantillonnage et
détermination des composés de sélénium dans les
effluents gazeux
1 Domaine d’application
La présente Norme internationale décrit la méthode de prélèvement et de détermination des composés
de sélénium, en phase vapeur et en phase solide, qui sont entraînées dans les effluents gazeux circulant
dans les cheminées ou les conduits. La teneur en sélénium dans un effluent gazeux est exprimée sous
forme de masse de sélénium élémentaire dans le gaz du conduit.
Les composés gazeux et particulaires du sélénium sont respectivement capturés par une solution
d’absorption et un filtre. La concentration totale des composés de sélénium dans l’effluent gazeux est
exprimée comme la somme des deux concentrations.
Les concentrations en sélénium dans les deux échantillons sont déterminées par spectroscopie d’émission
optique avec plasma induit par haute fréquence (ICP-OES), spectrométrie de masse avec plasma à couplage
inductif (ICP-MS) ou spectrométrie d’absorption atomique en four graphite (GFAAS). Les techniques de
génération d’hydrures (HG) couplées à la spectrométrie atomique peuvent également être utilisées, telles
que HG-AAS, HG-AFS (spectrométrie de fluorescence atomique), HG-ICP-OES et HG-ICP-MS.
3
La limite de détection pour les composés de sélénium gazeux sera de 0,3 μg/m en utilisant la technique
3
HG-ICP-MS pour un volume de prélèvement de 0,12 m . La limite de détection pour les composés de
3
sélénium particulaires sera de 0,001 2 μg/m en utilisant la même technique HG-ICP-MS pour un volume
3
de prélèvement de 2,0 m .
2 Références normatives
Les documents ci-après, dans leur intégralité ou non, sont des références normatives indispensables à
l’application du présent document. Pour les références datées, seule l’édition citée s’applique. Pour les
références non datées, la dernière édition du document de référence s’applique (y compris les éventuels
amendements).
ISO 3696, Eau pour laboratoire à usage analytique — Spécification et méthodes d’essai
ISO 9096, Émissions de sources fixes — Détermination manuelle de la concentration en masse de poussières
ISO 10396, Émissions de sources fixes — Échantillonnage pour la détermination automatisée des
concentrations d’émission de gaz pour des systèmes fixes de surveillance
ISO 11885, Qualité de l’eau — Dosage d’éléments choisis par spectroscopie d’émission optique avec plasma
induit par haute fréquence (ICP-OES)
ISO 12141, Émissions de sources fixes — Détermination d’une faible concentration en masse de matières
particulaires (poussières) — Méthode gravimétrique manuelle
ISO 15586, Qualité de l’eau — Dosage des éléments traces par spectrométrie d’absorption atomique en
four graphite
ISO 16911-1, Émissions de sources fixes — Détermination manuelle et automatique de la vitesse et du débit-
volume d’écoulement dans les conduits — Partie 1: Méthode de référence manuelle
ISO 17294-1, Qualité de l’eau — Application de la spectrométrie de masse avec plasma à couplage inductif
(ICP-MS) — Partie 1: Lignes directrices générales
© ISO 2015 – Tous droits réservés 1
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ISO 17211:2015(F)
ISO 17294-2, Qualité de l’eau — Application de la spectrométrie de masse avec plasma à couplage inductif
(ICP-MS) — Partie 2: Dosage de 62 éléments
ISO/TS 17379-1, Qualité de l’eau — Dosage du sélénium — Partie 1: Méthode par spectrométrie de
fluorescence atomique à génération d’hydrures (HG-AFS)
ISO/TS 17379-2, Qualité de l’eau — Dosage du sélénium — Partie 2: Méthode par spectrométrie
d’absorption atomique à génération d’hydrures (HG-AAS)
ISO 20988, Qualité de l’air — Lignes directrices pour estimer l’incertitude de mesure
ISO 23210:2009, Émissions de sources fixes — Détermination de la concentration en masse de PM10/PM2,5
dans les effluents gazeux — Mesurage à des faibles concentrations au moyen d’impacteurs
Guide ISO/IEC 98-3, Incertitude de mesure — Partie 3: Guide pour l’expression de l’incertitude de
mesure (GUM:1995)
3 Termes et définitions
Pour les besoins du présent document, les termes et définitions suivants s’appliquent.
3.1
composés gazeux du sélénium
composés de sélénium passant à travers un filtre ayant une efficacité de rétention de 99,5 % pour des
particules de 0,3 µm de diamètre
3.2
prélèvement isocinétique
prélèvement réalisé à un débit tel que la vitesse et la direction du gaz entrant dans la buse de prélèvement
sont les mêmes que celles du gaz dans le conduit au point de prélèvement
3.3
composés particulaires du sélénium
composés de sélénium contenus dans la phase solide particulaire recueillie par un filtre ayant une
efficacité de rétention de 99,5 % pour des particules de 0,3 µm de diamètre
3.4
point de prélèvement
sur la ligne de prélèvement, position spécifique à laquelle un échantillon est prélevé
3.5
NTP
conditions normales de température (273,15 K) et de pression (101,325 kPa)
4 Symboles et abréviations
4.1 Symboles
C concentration en sélénium dans un échantillon issu des solutions des premier et deuxième
A1,Se
absorbeurs (μg/ml)
C concentration en sélénium dans un échantillon issu de la solution du troisième absorbeur(μg/
A2,Se
ml)
C concentration en sélénium dans un échantillon issu de la solution de rinçage qui a servi au
R,Se
lavage de la ligne de transfert, depuis le support-filtre jusqu’à la buse du premier impacteur,
lors d’un prélèvement dans la ligne sans dérivation (μg/ml)
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ISO 17211:2015(F)
C concentration en sélénium dans un échantillon issu de la solution de rinçage qui a servi
R1,Se
au lavage de la ligne de transfert, depuis le support-filtre jusqu’à l’élément en T lors d’un
prélèvement dans la ligne avec dérivation (μg/ml)
C concentration en sélénium dans un échantillon issu de la solution de rinçage qui a servi au
R2,Se
lavage de la ligne de transfert, après l’élément en T jusqu’à la buse du premier impacteur,
lors d’un prélèvement dans la ligne avec dérivation (μg/ml)
C concentration en sélénium dans une solution d’échantillon préparée pour l’analyse du
S,Se
sélénium particulaire (μg/ml)
d masse volumique de la solution de réactif (g/ml)
p pression atmosphérique (kPa)
atm
P différence de pression moyenne entre l’échantillon de gaz avant le compteur de gaz et
moy
l’atmosphère (kPa)
q débit massique de sélénium exprimé en sélénium élémentaire (mg/s)
m,Se
q débit-volume d’écoulement de l’effluent gazeux à travers le plan de prélèvement dans les
V,fg,i
3
conditions i de température, de pression, d’humidité et de teneur en oxygène (m /s)
T température moyenne de l’échantillon de gaz avant le compteur de gaz (K)
moy
3
u(y) incertitude-type (μg/m )
3
V volume d’un échantillon d’effluent gazeux sec, ramené aux conditions NTP (m )
d
3
V valeur finale relevée sur le compteur de gaz à la fin du prélèvement (m )
f
V volume d’un échantillon d’effluent gazeux sec pour l’analyse du sélénium gazeux, ramené
G,sec
3
aux conditions NTP (m )
3
V valeur initiale relevée sur le compteur de gaz au début du prélèvement (m )
i
V volume d’air soutiré à travers le compteur de gaz lors d’essais d’étanchéité intermédiaires
l
3
(m )
3
V volume d’un échantillon d’effluent gazeux sec (m )
m
V volume d’un échantillon d’effluent gazeux sec dans la ligne principale, ramené aux condi-
princ,sec
3
tions NTP, lors d’un prélèvement avec ligne en dérivation (m )
V volume d’un échantillon d’effluent gazeux sec pour l’analyse du sélénium particulaire,
S,sec
3
ramené aux conditions NTP (m )
V volume d’un échantillon d’effluent gazeux sec prélevé dans la ligne dérivée, ramené aux
dérivé,sec
3
conditions NTP, lors d’un prélèvement avec ligne en dérivation (m )
v volume d’un échantillon récupéré des solutions issues des premier et deuxième absorbeurs
A1
(ml)
v volume d’un échantillon récupéré de la solution issue du troisième absorbeur (ml)
A2
v volume d’un échantillon récupéré de la solution de rinçage qui a servi au lavage de la ligne
R
de transfert, depuis le support-filtre jusqu’à la buse du premier impacteur, de la ligne
principale (ml)
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ISO 17211:2015(F)
v volume d’un échantillon récupéré de la solution de rinçage qui a servi au lavage de la ligne
R1
de transfert, depuis le support-filtre jusqu’à l’élément en T, de la ligne dérivée (ml)
v volume d’un échantillon récupéré de la solution de rinçage qui a servi au lavage de la ligne de
R2
transfert après l’élément en T jusqu’à la buse du premier impacteur de la ligne dérivée (ml)
v volume d’une solution d’échantillon préparée pour l’analyse du sélénium particulaire (ml)
S
W teneur moyenne en humidité de l’effluent gazeux au niveau du plan de prélèvement durant
hum
la période de prélèvement (%)
ème 3
y j valeur de concentration du premier système de mesurage (μg/m )
1,j
ème 3
y j valeur de concentration du deuxième système de mesurage (μg/m )
2,j
ρ concentration en masse du sélénium gazeux, exprimée en sélénium élémentaire dans
G,Se,sec
3
l’effluent gazeux, sur sec dans les conditions normales NTP (μg/m )
ρ concentration en masse du sélénium particulaire, exprimée en sélénium élémentaire dans
S,Se,sec
3
l’effluent gazeux, sur sec dans les conditions normales NTP (μg/m )
ρ concentration en masse du sélénium total, exprimée en sélénium élémentaire dans l’effluent
Se,sec
3
gazeux, sur sec dans les conditions normales NTP (μg/m )
ρ concentration en masse du sélénium, exprimée en sélénium élémentaire dans l’effluent
Se,sec,O
gazeux, sur sec dans les conditions normales NTP et à la concentration en oxygène de
3
référence (μg/m )
ρ concentration en masse du sélénium, exprimée en sélénium élémentaire dans les condi-
Se,i
3
tions i de température, de pression, d’oxygène et d’humidité (μg/m )
ρ concentration en masse du sélénium, exprimée en sélénium élémentaire dans l’effluent
Se,hum
3
gazeux, sur humide dans les conditions normales NTP (μg/m )
ρ concentration en masse du sélénium, exprimée en sélénium élémentaire dans l’effluent
Se,hum,O
gazeux, sur humide dans les conditions normales NTP et à la concentration en oxygène de
3
référence (μg/m )
teneur en volume de l’oxygène, sur sec, mesurée au cours du prélèvement (%)
ϕ
O,d
teneur en volume de l’oxygène de référence pour le procédé (%)
ϕ
O,ref
4.2 Abréviations
AAS spectrométrie d’absorption atomique
AFS spectrométrie de fluorescence atomique
GFAAS spectrométrie d’absorption atomique en four graphite
HG génération d’hydrures
ICP-MS spectrométrie de masse avec plasma à couplage inductif
ICP-OES spectroscopie d’émission optique avec plasma induit par haute fréquence
FEP hexafluoroéthène propène, perfluoro(éthane-propène)
4 © ISO 2015 – Tous droits réservés
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ISO 17211:2015(F)
PFA alkoxyde perfluoré
PTFE polytétrafluoroéthylène
5 Principe
En général, les composés de sélénium existent à la fois sous forme gazeuse et sous forme solide dans
un effluent gazeux. Les composés gazeux et particulaires du sélénium sont respectivement capturés
par une solution d’absorption et un filtre. La concentration en sélénium dans un effluent gazeux est
exprimée comme la somme des deux concentrations.
Pour déterminer la teneur en sélénium particulaire dans un effluent gazeux, un échantillon de
gaz est prélevé de façon isocinétique dans un conduit et les particules sont recueillies sur un filtre
conformément à l’ISO 9096 ou à l’ISO 12141.
Pour déterminer la teneur en sélénium gazeux dans un effluent gazeux, un échantillon de gaz est prélevé
dans un conduit et passe à travers un filtre. Les composés gazeux du sélénium qui passent à travers le
filtre sont recueillis dans une solution d’absorption. Dans la mesure où certains composés gazeux du
sélénium, en particulier le dioxyde de sélénium (SeO ), sont adsorbés et, dans la plupart des cas, réduits
2
en sélénium élémentaire sur la surface interne d’un système de prélèvement en présence de vapeur et
de dioxyde de soufre (SO ), les composants du système de prélèvement, c’est-à-dire le support-filtre, la
2
ligne de transfert chauffée et la buse d’impacteur, sont rincés par une solution oxydante pour récupérer
le sélénium qui a adhéré à la surface.
Si les débits et les volumes totaux de prélèvement pour les mesurages du sélénium particulaire et du
sélénium gazeux sont égaux, les deux prélèvements doivent être effectués simultanément selon une
procédure de prélèvement isocinétique.
Chaque échantillon est préparé en vue d’être analysé par ICP-OES, ICP-MS ou GFAAS. Les techniques
HG-AAS, HG-AFS, HG-ICP-OES ou HG-ICP-MS peuvent être utilisées si une sensibilité analytique plus
grande est requise pour déterminer la concentration en sélénium.
6 Réactifs
6.1 Généralités. Pour appliquer la méthode, il est nécessaire d’utiliser les réactifs de qualité analytique
reconnue suivants.
6.2 Water, conforme à la qualité 1 telle que spécifiée dans l’ISO 3696 pour toutes les préparations et
dilutions d’échantillons.
6.3 Acide nitrique, ρ(HNO ) = 1,4 g/ml.
3
NOTE L’acide nitrique est disponible à la fois sous forme de ρ(HNO ) = 1,40 g/ml [w(HNO ) = 650 g/kg] et
3 3
d(HNO ) = 1,42 g/ml [w(HNO ) = 690 g/kg].
3 3
6.4 Peroxyde d’hydrogène, w(H O ) = 30 %.
2 2
6.5 Acide sulfurique, ρ(H SO ) = 1,84 g/ml.
2 4
6.6 Permanganate de potassium, KMnO .
4
6.7 Solution mère de sélénium, conforme aux solutions étalons de sélénium telles que spécifiées
dans l’ISO/TS 17379-1 et l’ISO/TS 17379-2.
© ISO 2015 – Tous droits réservés 5
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ISO 17211:2015(F)
6.8 Solution d’absorption, mélange de solution de HNO à 0,7 mol/l et de solution de H O à 3 mol/l.
3 2 2
Dans une fiole jaugée de 1 000 ml contenant environ 500 ml d’eau, ajouter avec précaution 50 ml de
HNO concentré (6.3), puis 333 ml de H O à 30 % (6.4). Tout en agitant, ajouter de l’eau pour compléter
3 2 2
à un volume de 1 000 ml.
6.9 Solution de rinçage, mélange de solution de KMnO à 0,06 mol/l et de solution de H SO à 1,8 mol/l.
4 2 4
Dans une fiole jaugée de 1 000 ml contenant environ 500 ml d’eau, tout en agitant, ajouter avec
précaution 100 ml de H SO concentré (6.5), puis 10 g de KMnO (6.6). Tout en agitant, ajouter de l’eau
2 4 4
pour compléter à un volume de 1 000 ml.
6.10 Agent déshydratant pour échantillon de gaz, gel de silice à gros grains avec indicateur.
6.11 Acide fluorhydrique, w(HF) = 40 %.
6.12 Solution d’acide chlorhydrique, ρ(HCl) = 6 mol/l.
Dans une fiole jaugée de 500 ml contenant environ 150 ml d’eau, tout en agitant, introduire avec
précaution 250 ml de HCl concentré [ρ(HCl) = 1,19 g/ml]. Tout en agitant, ajouter de l’eau pour compléter
à un volume de 500 ml.
7 Appareillage
7.1 Généralités
Deux types de systèmes d’absorption peuvent être employés: un montage avec une ligne sans dérivation
et un montage avec une ligne avec dérivation. Des schémas des deux systèmes sont illustrés à la Figure 1.
Dans le montage sans dérivation, la totalité de l’effluent gazeux prélevé passe dans les solutions
d’absorption, alors que dans le montage avec dérivation, seule une partie de l’effluent gazeux prélevé
passe dans les solutions d’absorption. Le prélèvement dans la ligne sans dérivation est utilisé si le débit
et le volume total de prélèvement pour le mesurage du sélénium gazeux et du sélénium particulaire
sont identiques. Le prélèvement dans la ligne avec dérivation est utilisé si le débit ou le volume total de
prélèvement pour le mesurage du sélénium gazeux et du sélénium particulaire est identique.
Si le prélèvement d’un échantillon représentatif est autorisé, le sélénium particulaire et le sélénium
gazeux sont prélevés séparément en utilisant deux lignes sans dérivation. Déterminer le point de
prélèvement d’un échantillon représentatif conformément à l’ISO 23210:2009, Annexe G. Deux buses de
prélèvement, une pour le sélénium particulaire et l’autre pour le sélénium gazeux, sont placées en des
points voisins où les paramètres physicochimiques,
...
SLOVENSKI STANDARD
oSIST ISO 17211:2018
01-september-2018
(PLVLMHQHSUHPLþQLKYLURY9]RUþHQMHLQGRORþHYDQMHVHOHQRYLKVSRMLQYRGSDGQLK
SOLQLK
Stationary source emissions - Sampling and determination of selenium compounds in
flue gas
Émission des sources fixes - Échantillonnage et détermination des composés de
sélénium dans les effluents gazeux
Ta slovenski standard je istoveten z: ISO 17211:2015
ICS:
13.040.40 (PLVLMHQHSUHPLþQLKYLURY Stationary source emissions
oSIST ISO 17211:2018 en,fr
2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.
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oSIST ISO 17211:2018
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oSIST ISO 17211:2018
INTERNATIONAL ISO
STANDARD 17211
First edition
2015-08-15
Stationary source emissions —
Sampling and determination of
selenium compounds in flue gas
Émission des sources fixes — Échantillonnage et détermination des
composés de sélénium dans les effluents gazeux
Reference number
ISO 17211:2015(E)
©
ISO 2015
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oSIST ISO 17211:2018
ISO 17211:2015(E)
COPYRIGHT PROTECTED DOCUMENT
© ISO 2015, Published in Switzerland
All rights reserved. Unless otherwise specified, no part of this publication may be reproduced or utilized otherwise in any form
or by any means, electronic or mechanical, including photocopying, or posting on the internet or an intranet, without prior
written permission. Permission can be requested from either ISO at the address below or ISO’s member body in the country of
the requester.
ISO copyright office
Ch. de Blandonnet 8 • CP 401
CH-1214 Vernier, Geneva, Switzerland
Tel. +41 22 749 01 11
Fax +41 22 749 09 47
copyright@iso.org
www.iso.org
ii © ISO 2015 – All rights reserved
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oSIST ISO 17211:2018
ISO 17211:2015(E)
Contents Page
Foreword .v
Introduction .vi
1 Scope . 1
2 Normative references . 1
3 Terms and definitions . 2
4 Symbols and abbreviated terms . 2
4.1 Symbols . 2
4.2 Abbreviated terms . 4
5 Principle . 4
6 Reagents . 5
7 Apparatus . 6
8 Sampling . 9
8.1 General . 9
8.2 Sampling position and sampling point . 9
8.3 Minimum sampling duration and minimum sample volume . 9
8.4 Other measurements to be made prior to sampling . 9
8.4.1 Volumetric gas flow through duct at the sampling plane . 9
8.4.2 Moisture content of gas . 9
8.4.3 Oxygen content of gas .10
8.5 Assembly of sampling apparatus .10
8.6 Sampling .10
8.7 Checking for leaks .10
8.8 Quality assurance.10
8.9 Sample recovery .11
8.9.1 Sample recovery for gaseous selenium .11
8.9.2 Sample recovery for particulate selenium .11
8.10 Field blank .11
9 Sample preparation .12
9.1 General .12
9.2 Sample preparation for analysis with hydride generation .12
9.2.1 Sample preparation for gaseous selenium analysis .12
9.2.2 Sample preparation for particulate selenium analysis .12
9.3 Sample preparation for analysis without hydride generation .12
9.3.1 Sample preparation for gaseous selenium analysis .12
9.3.2 Sample preparation for particulate selenium analysis .12
10 Analytical procedure .13
11 Expression of results .13
11.1 Calculation of the volume of dry flue gas sampled at sampling conditions, V .13
m
11.2 Calculation of the volume of dry flue gas sample normalized to standard
temperature and pressure, V .14
d
11.3 Mass concentration of selenium expressed as elemental selenium in the flue gas
on a dry basis at STP, ρ .14
Se,dry
11.4 Mass concentration of selenium expressed as elemental selenium in the flue gas
on a dry basis at STP and reference oxygen volume fraction, ρ .16
Se,dry,O
11.5 Rate of mass discharge of selenium expressed as elemental selenium, q .17
m,Se
11.6 Mass concentration of selenium expressed as elemental selenium in the flue gas
on a wet basis at STP, ρ .17
Se,wet
11.7 Mass concentration of selenium expressed as elemental selenium in the flue gas
on a wet basis at STP and reference oxygen concentration, ρ .17
Se,wet,O
© ISO 2015 – All rights reserved iii
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oSIST ISO 17211:2018
ISO 17211:2015(E)
12 Performance characteristics .18
12.1 Detection limits .18
12.2 Evaluation of measurement uncertainty .18
13 Test report .18
Annex A (informative) Results of evaluation of measurement uncertainties.20
iv © ISO 2015 – All rights reserved
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oSIST ISO 17211:2018
ISO 17211:2015(E)
Foreword
ISO (the International Organization for Standardization) is a worldwide federation of national standards
bodies (ISO member bodies). The work of preparing International Standards is normally carried out
through ISO technical committees. Each member body interested in a subject for which a technical
committee has been established has the right to be represented on that committee. International
organizations, governmental and non-governmental, in liaison with ISO, also take part in the work.
ISO collaborates closely with the International Electrotechnical Commission (IEC) on all matters of
electrotechnical standardization.
The procedures used to develop this document and those intended for its further maintenance are
described in the ISO/IEC Directives, Part 1. In particular the different approval criteria needed for the
different types of ISO documents should be noted. This document was drafted in accordance with the
editorial rules of the ISO/IEC Directives, Part 2 (see www.iso.org/directives).
Attention is drawn to the possibility that some of the elements of this document may be the subject of
patent rights. ISO shall not be held responsible for identifying any or all such patent rights. Details of
any patent rights identified during the development of the document will be in the Introduction and/or
on the ISO list of patent declarations received (see www.iso.org/patents).
Any trade name used in this document is information given for the convenience of users and does not
constitute an endorsement.
For an explanation on the meaning of ISO specific terms and expressions related to conformity
assessment, as well as information about ISO’s adherence to the WTO principles in the Technical
Barriers to Trade (TBT) see the following URL: Foreword - Supplementary information
The committee responsible for this document is ISO/TC 146, Air quality, Subcommittee SC 1, Stationary
source emissions.
© ISO 2015 – All rights reserved v
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oSIST ISO 17211:2018
ISO 17211:2015(E)
Introduction
Since it is estimated that selenium is exhausted from stationary sources like coal combustion plants, the
investigation of the emission amounts of selenium from the stationary source is increasingly important
for preventing a potential risk.
This International Standard describes a method for the sampling and determination of selenium
compounds in a flue gas passing through ducts or chimneys. Selenium compounds generally exist both
in vapour phase and in solid phase in flue gases, this method allows the determination of both gaseous
and particulate selenium concentrations in flue gases.
vi © ISO 2015 – All rights reserved
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oSIST ISO 17211:2018
INTERNATIONAL STANDARD ISO 17211:2015(E)
Stationary source emissions — Sampling and
determination of selenium compounds in flue gas
1 Scope
This International Standard describes the method for the sampling and determination of selenium
compounds in both vapour phase and solid phase that are entrained in flue gases carried in stacks or
ducts. The selenium content in flue gas is expressed as a mass concentration of elemental selenium in
the stack gas.
Particulate and gaseous selenium compounds are captured by a filter and an absorber solution,
respectively. The total concentration of selenium compounds in flue gas is expressed as the sum of both
concentrations.
The concentrations of selenium in both samples are determined using inductively coupled plasma
optical emission spectrometry (ICP-OES), inductively coupled plasma mass spectrometry (ICP-MS)
or graphite furnace atomic absorption spectrometry (GFAAS). Hydride generation (HG) techniques
coupled to atomic spectrometry can also be used such as HG-AAS, HG-AFS (atomic fluorescence
spectrometry), HG-ICP-OES and HG-ICP-MS.
3
The detection limit for gaseous selenium compounds is 0,3 μg/m using HG-ICP-MS at a sampling
3 3
volume of 0,12 m . The detection limit for particulate selenium compounds is 0,001 2 μg/m using this
3
technique at a sampling volume of 2,0 m .
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.
ISO 3696, Water for analytical laboratory use — Specification and test methods
ISO 9096, Stationary source emissions — Manual determination of mass concentration of particulate
matter
ISO 10396, Stationary source emissions — Sampling for the automated determination of gas emission
concentrations for permanently-installed monitoring systems
ISO 11885, Water quality — Determination of selected elements by inductively coupled plasma optical
emission spectrometry (ICP-OES)
ISO 12141, Stationary source emissions — Determination of mass concentration of particulate matter
(dust) at low concentrations — Manual gravimetric method
ISO 15586, Water quality — Determination of trace elements using atomic absorption spectrometry with
graphite furnace
ISO 16911-1, Stationary source emissions — Manual and automatic determination of velocity and volume
flow rate in ducts — Part 1: Manual reference method
ISO 17294-1, Water quality — Application of inductively coupled plasma mass spectrometry (ICP-MS) —
Part 1: General guidelines
ISO 17294-2, Water quality — Application of inductively coupled plasma mass spectrometry (ICP-MS) —
Part 2: Determination of 62 elements
© ISO 2015 – All rights reserved 1
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oSIST ISO 17211:2018
ISO 17211:2015(E)
ISO/TS 17379-1, Water quality — Determination of selenium — Part 1: Method using hydride generation
atomic fluorescence spectrometry (HG-AFS)
ISO/TS 17379-2, Water quality — Determination of selenium — Part 2: Method using hydride generation
atomic absorption spectrometry (HG-AAS)
ISO 20988, Air quality — Guidelines for estimating measurement uncertainty
ISO 23210:2009, Stationary source emissions — Determination of PM10/PM2,5 mass concentration in flue
gas — Measurement at low concentrations by use of impactors
ISO/IEC Guide 98-3, Uncertainty of measurement — Part 3: Guide to the expression of uncertainty in
measurement (GUM:1995)
3 Terms and definitions
For the purposes of this document, the following terms and definitions apply.
3.1
gaseous selenium compounds
selenium compounds passing through a filter having at least 99,5 % collection efficiency for 0,3 μm
diameter particles
3.2
isokinetic sampling
sampling at a flow rate such that the velocity and direction of the gas entering the sampling nozzle are
the same as those of the gas in the duct at the sampling point
3.3
particulate selenium compounds
selenium compounds contained in a solid phase particle collected by a filter having at least 99,5 %
collection efficiency for 0,3 μm diameter particles
3.4
sampling point
specific position on the sampling section at which a sample is extracted
3.5
STP
standard conditions for temperature, 273,15 K, and pressure, 101,325 kPa
4 Symbols and abbreviated terms
4.1 Symbols
C concentration of selenium in prepared sample of the first and second absorber solutions
A1,Se
(μg/ml)
C concentration of selenium in prepared sample of the third absorber solution (μg/ml)
A2,Se
C concentration of selenium in prepared sample of rinse solution that washed transfer line
R,Se
from the filter housing to the first impinger nozzle in main-stream sampling (μg/ml)
C concentration of selenium in prepared sample of rinse solution that washed transfer line
R1,Se
from the filter housing to the T-piece in side-stream sampling (μg/ml)
C concentration of selenium in prepared sample of rinse solution that washed transfer line
R2,Se
after the T-piece to the first impinger nozzle in side-stream sampling (μg/ml)
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C concentration of selenium in prepared sample solution for particulate selenium analysis
S,Se
(μg/ml)
d density of reagent solution (g/ml)
p atmospheric pressure (kPa)
atm
p average pressure difference between the sample gas before the gas meter and the atmos-
av
phere (kPa)
q rate of mass discharge of selenium expressed as elemental selenium (mg/s)
m,Se
q volume flow rate of flue gas through the sampling plane at conditions i of temperature,
V,fg,i
3
pressure, moisture and oxygen content (m /s)
T average temperature of the sample gas before the gas meter (K)
av
3
u(y) standard uncertainty (μg/m )
3
V volume of dry flue gas sample normalized to STP (m )
d
3
V final gas meter reading at the end of sampling (m )
f
3
V volume of dry flue gas sample for gaseous selenium analysis normalized to STP (m )
G,d
3
V initial gas meter reading at the beginning of sampling (m )
i
3
V volume of air drawn through the gas meter during any intermediate leak tests (m )
l
3
V volume of dry flue gas sample (m )
m
V volume of dry flue gas sample in main stream, normalized to STP, in side-stream sampling
main,d
3
(m )
3
V volume of dry flue gas sample for particulate selenium analysis normalized to STP (m )
S,d
volume of dry flue gas sampled in side stream, normalized to STP, in side-stream sampling
V
side,d
3
(m )
v volume of recovered sample of the first and second absorber solutions (ml)
A1
v volume of recovered sample of the third absorber solution (ml)
A2
v volume of recovered sample of rinse solution that washed transfer line from the filter
R
housing to the first impinger nozzle in main-stream sampling (ml)
v volume of recovered sample of rinse solution that washed transfer line from the filter
R1
housing to the T-piece in side-stream sampling (ml)
v volume of recovered sample of rinse solution that washed transfer line after the T-piece to
R2
the first impinger nozzle in side-stream sampling (ml)
v volume of prepared sample solution for particulate selenium analysis (ml)
S
w average moisture content of the flue gas at the sampling plane during the sampling period (%)
W
3
y j th concentration value of the first measuring system (μg/m )
1,j
3
y j th concentration value of the second measuring system (μg/m )
2,j
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ρ mass concentration of gaseous selenium expressed as elemental selenium in the flue gas
G,Se,dry
3
on a dry basis at STP (μg/m )
ρ mass concentration of particulate selenium expressed as elemental selenium in the flue
S,Se,dry
3
gas on a dry basis at STP (μg/m )
ρ mass concentration of total selenium expressed as elemental selenium in the flue gas on
Se,dry
3
a dry basis at STP (μg/m )
ρ mass concentration of selenium expressed as elemental selenium in the flue gas on a dry
Se,dry,O
3
basis at STP and reference oxygen concentration (μg/m )
ρ mass concentration of selenium expressed as elemental selenium at conditions i of tem-
Se,i
3
perature, pressure, oxygen and moisture conditions (μg/m )
ρ mass concentration of selenium expressed as elemental selenium in the flue gas on a wet
Se,wet
3
basis at STP (μg/m )
ρ mass concentration of selenium expressed as elemental selenium in the flue gas on a wet
Se,wet,O
3
basis at STP and reference oxygen concentration (μg/m )
volume fraction of the oxygen on a dry basis measured during the sampling (%)
ϕ
O,d
volume fraction of the reference oxygen for the process (%)
ϕ
O,ref
4.2 Abbreviated terms
AAS atomic absorption spectrometry
AFS atomic fluorescence spectrometry
GFAAS graphite furnace atomic absorption spectrometry
HG hydride generation
ICP-MS inductively coupled plasma mass spectrometry
ICP-OES inductively coupled plasma optical emission spectrometry
FEP hexafluoroethene propene, perfluoro(ethane-propene)
PFA perfluoroalkoxy
PTFE polytetrafluoroethylene
5 Principle
Selenium compounds generally exist both in vapour phase and in solid phase in a flue gas. Particulate
and gaseous selenium compounds are captured by a filter and an absorber solution, respectively. The
concentration of selenium in a flue gas is expressed as the sum of both concentrations.
To determine particulate selenium contents in a flue gas, a stack sample gas is taken isokinetically and
particles are collected on a filter in accordance with ISO 9096 or ISO 12141.
To determine gaseous selenium content in a flue gas, a stack sample gas is taken through a filter. Gaseous
selenium compounds that pass through the filter are collected in an absorber solution. Since some
of gaseous selenium compounds, mostly SeO , are adsorbed and in some cases reduced to elemental
2
selenium on the inner surface of a sampling system in the presence of steam and SO , the sampling
2
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system components such as the filter housing, heated transfer line and impinger nozzle is rinsed by an
oxidation solution to recover the stuck selenium.
If the flow rates and the total sampling volumes for the measurements of particulate and gaseous
selenium are the same, particulate and gaseous sampling shall be performed simultaneously with an
isokinetic sampling procedure.
Each sample is prepared to be analysed by either ICP-OES, ICP-MS or GFAAS. HG-AAS, HG-AFS, HG-ICP-
OES or HG-ICP-MS may be used if greater analytical sensitivity is required to determine the selenium
concentration.
6 Reagents
6.1 General. To carry out the method, the following reagents are required to be of a recognized
analytical grade.
6.2 Water, complying with grade 1 s specified in ISO 3696 for all sample preparation and dilutions.
6.3 Nitric acid, d(HNO ) = 1,4 g/ml.
3
NOTE Nitric acid is available both as d(HNO ) = 1,40 g/ml [w(HNO ) = 650 g/kg] and d(HNO ) = 1,42 g/ml
3 3 3
[w(HNO ) = 690 g/kg].
3
6.4 Hydrogen peroxide, w(H O ) = 30 %.
2 2
6.5 Sulfuric acid, d(H SO ) = 1,84 g/ml.
2 4
6.6 Potassium permanganate, KMnO .
4
6.7 Selenium stock solution, complying with selenium standard solutions as specified in
ISO/TS 17379-1 and ISO/TS 17379-2.
6.8 Absorber solution, mixture of 0,7 mol/l HNO solution and 3 mol/l H O solution.
3 2 2
Add carefully 50 ml of concentrated HNO (6.3) to a 1 000 ml volumetric flask containing approximately
3
500 ml of water, and then add 333 ml of 30 % H O (6.4) carefully. Add water with stirring to make a
2 2
volume of 1 000 ml.
6.9 Rinse solution, mixture of 0,06 mol/l KMnO solution and 1,8 mol/l H SO solution.
4 2 4
Add carefully with stirring 100 ml of concentrated H SO (6.5) to a 1 000 ml volumetric flask containing
2 4
approximately 500 ml of water, and then add 10 g of KMnO (6.6) carefully with stirring. Add water
4
with stirring to make a volume of 1 000 ml.
6.10 Sample gas drying agent, self-indicating coarse grade silica gel.
6.11 Hydrofluoric acid, w(HF) = 40 %.
6.12 Hydrochloric acid solution, c(HCl) = 6 mol/l.
Add carefully with stirring 250 ml of concentrated HCl [d(HCl) = 1,19 g/ml] to a 500 ml volumetric flask
containing approximately 150 ml of water. Add water with stirring to make a volume of 500 ml.
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7 Apparatus
7.1 General.
Two types of absorber systems, a main-stream and a side-stream arrangement, can be employed.
Schematics of both systems are given in Figure 1. In the main-stream system all the sampled flue gas is
passed though the absorber solutions, while in the side-stream arrangement only a part of the sampled
flue gas is passed through the absorber solutions. The main-stream sampling is used if the flow rate
and total sampling volume for the measurements of gaseous and particulate selenium are the same.
The side-stream sampling is used if the flow rate or total sampling volume for the measurements of
gaseous and particulate selenium is different.
If the representative sampling is allowed, particulate selenium and gaseous selenium are sampled
separately using two main stream sampling. Determine a representative sampling point in accordance
with ISO 23210:2009, Annex G. Two sampling nozzles, for particulate selenium and gaseous selenium
respectively, are placed at neighbouring points in which the physicochemical parameters such as
selenium concentration and gas flow rate are considered to be equivalent. Particulate selenium sample
is collected by the filter isokinetically. Gaseous selenium sample is captured in an absorber solution
either isokinetically or anisokinetically after particles are removed.
The apparatus consists of a sampling probe including a nozzle and filter assembly that may be heated
if required, an impinger train containing absorber solution to capture gaseous selenium, a manometer,
a suction pump, a gas meter, and a sample gas volume flow rate measurement system. A thermometer
and manometer shall be included in the sampling train to measure the temperature and pressure of the
metered gas. A barometer shall be used to measure atmospheric pressure during the test in order that
the volume of the gas sampled can be normalized to the standard condition of 273,15 K and 101,325 kPa.
a) Main-stream sampling
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b) Side-stream sampling
Key
1 nozzle 9 gas meter
2 filter and filter housing 10 thermometer and manometer
3 transfer line 11 rotameter
4 T-piece 12 impinger nozzle
5 HNO /H O impingers 13 cooler bath
3 2 2
6 dry impinger 14 main stream
7 drying tube or silica gel 15 side stream
8 pump
Figure 1 — Schematic diagram of a sampling train
7.2 Nozzle. The diameter shall be chosen to be compatible with the required gas sampling volume
flow rate. The choice of the nozzle shall be in accordance with ISO 9096 or ISO 12141.
The nozzle shall be capable of withstanding the temperature in the duct. It shall be resistant to chemical
attack from various pollutants in the duct. Suitable materials for selenium sampling are silica glass,
PTFE and titanium.
The nozzle shall be cleaned thoroughly before each sample run by rinsing with distilled water. The
rinse shall be repeated until the rinse water shows no evidence
...
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