Stationary source emissions - Determination of the mass concentration of carbon monoxide, carbon dioxide and oxygen in flue gas - Performance characteristics of automated measuring systems

This document specifies the fundamental structure and the most important performance characteristics of automated measuring systems for carbon monoxide (CO), carbon dioxide (CO2) and oxygen (O2) to be used on stationary source emissions. This document describes methods and equipment for the measurement of concentrations of these gases. The method allows continuous monitoring with permanently installed measuring systems of CO, CO2 and O2 emissions. This international standard describes extractive systems and in situ (non-extractive) systems in connection with analysers that operate using, for example, the following principles:
— infrared absorption (CO and CO2);
— paramagnetism (O2);
— zirconium oxide (O2);
— electrochemical cell (O2);
— tuneable laser spectroscopy (TLS) (CO, CO2 and O2).
Other instrumental methods can be used provided they meet the minimum requirements proposed in this document. Automated measuring systems (AMS) based on the principles above have been used successfully in this application for measuring ranges which are described in Annex G.

Émissions de sources fixes - Détermination de la concentration de monoxyde de carbone, de dioxyde de carbone et d'oxygène - Caractéristiques de fonctionnement et étalonnage de systèmes automatiques de mesure

Emisije nepremičnih virov - Določevanje masne koncentracije ogljikovega monoksida, ogljikovega dioksida in kisika v odpadnih plinih - Delovne karakteristike avtomatskih merilnih sistemov

Ta dokument določa temeljno strukturo in najpomembnejše značilnosti delovanja avtomatskih sistemov za merjenje ogljikovega monoksida (CO), ogljikovega dioksida (CO2) in kisika (O2), ki se uporabljajo pri emisijah nepremičnih virov. Ta dokument opisuje metode in opremo za merjenje koncentracij teh plinov. Metoda omogoča neprekinjen nadzor s trajno vgrajenimi sistemi za merjenje emisij CO, CO2 in O2. Ta mednarodni standard opisuje ekstraktivne sisteme ter sisteme in situ (ne ekstraktivne) v povezavi z analizatorji, ki delujejo na primer z naslednjimi načeli:
– infrardeča absorpcija (CO in CO2);
– paramagnetizem (O2);
– cirkonijev oksid (O2);
– elektrokemična celica (O2);
– nastavljiva laserska spektroskopija (TLS) (CO, CO2 in O2).
Uporabiti je mogoče tudi druge instrumentalne metode, če izpolnjujejo minimalne zahteve, predlagane v tem dokumentu. V tej aplikaciji se za uporabo merilnih območij, opisanih v dodatku G, uspešno uporabljajo avtomatizirani merilni sistemi (AMS), ki temeljijo na zgornjih načelih

General Information

Status
Published
Public Enquiry End Date
04-Jan-2020
Publication Date
16-Feb-2020
Technical Committee
Current Stage
6060 - National Implementation/Publication (Adopted Project)
Start Date
17-Feb-2020
Due Date
23-Apr-2020
Completion Date
17-Feb-2020

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INTERNATIONAL ISO
STANDARD 12039
Second edition
2019-10
Stationary source emissions —
Determination of the mass
concentration of carbon monoxide,
carbon dioxide and oxygen in flue
gas — Performance characteristics of
automated measuring systems
Émissions de sources fixes — Détermination de la concentration
de monoxyde de carbone, de dioxyde de carbone et d'oxygène —
Caractéristiques de fonctionnement et étalonnage de systèmes
automatiques de mesure
Reference number
ISO 12039:2019(E)
ISO 2019
---------------------- Page: 1 ----------------------
ISO 12039:2019(E)
COPYRIGHT PROTECTED DOCUMENT
© ISO 2019

All rights reserved. Unless otherwise specified, or required in the context of its implementation, 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
CP 401 • Ch. de Blandonnet 8
CH-1214 Vernier, Geneva
Phone: +41 22 749 01 11
Fax: +41 22 749 09 47
Email: copyright@iso.org
Website: www.iso.org
Published in Switzerland
ii © ISO 2019 – All rights reserved
---------------------- Page: 2 ----------------------
ISO 12039:2019(E)
Contents Page

Foreword ........................................................................................................................................................................................................................................iv

Introduction ..................................................................................................................................................................................................................................v

1 Scope ................................................................................................................................................................................................................................. 1

2 Normative references ...................................................................................................................................................................................... 1

3 Terms and definitions ..................................................................................................................................................................................... 1

4 Symbols and abbreviated terms ........................................................................................................................................................... 4

5 Principle ........................................................................................................................................................................................................................ 5

6 Description of the automated measuring systems ............................................................................................................ 5

6.1 Sampling and sample gas conditioning systems ........................................................................................................ 5

6.2 Analyser equipment ........................................................................................................................................................................... 5

7 Performance characteristics and criteria .................................................................................................................................. 6

7.1 Performance criteria .......................................................................................................................................................................... 6

7.2 Determination of the performance characteristics ................................................................................................. 7

7.2.1 Performance test .............................................................................................................................................................. 7

7.2.2 Ongoing quality control ............................................................................................................................................. 7

8 Selection and installation procedure .............................................................................................................................................. 8

8.1 Choice of the measuring system .............................................................................................................................................. 8

8.2 Sampling ....................................................................................................................................................................................................... 8

8.2.1 Sampling location ............................................................................................................................................................ 8

8.2.2 Representative sampling .......................................................................................................................................... 8

8.3 Calculation .................................................................................................................................................................................................. 8

8.3.1 Conversion from volume to mass concentration for CO ................................................................ 8

8.3.2 Conversion from wet to dry conditions for CO, CO and O concentrations ................ 9

2 2

9 Quality assurance and quality control procedures .......................................................................................................... 9

9.1 General ........................................................................................................................................................................................................... 9

9.2 Frequency of checks ........................................................................................................................................................................10

9.3 Calibration, validation and measurement uncertainty .....................................................................................10

10 Test report ................................................................................................................................................................................................................11

Annex A (informative) Infrared absorption method (CO and CO ) ....................................................................................12

Annex B (informative) Extractive O measurement techniques ...........................................................................................19

Annex C (informative) In situ CO, CO and O measurement ....................................................................................................26

2 2

Annex D (normative) Operational gases .......................................................................................................................................................30

Annex E (normative) Procedures for determination of the performance characteristics ........................31

Annex F (informative) Examples of the results for the assessment of CO, CO and O AMS .....................39

2 2

Annex G (informative) Calculation of uncertainty of measurement of CO, CO and O .................................44

2 2

Bibliography .............................................................................................................................................................................................................................51

© ISO 2019 – All rights reserved iii
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ISO 12039:2019(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 voluntary nature of standards, the meaning of ISO specific terms and

expressions related to conformity assessment, as well as information about ISO's adherence to the

World Trade Organization (WTO) principles in the Technical Barriers to Trade (TBT) see the following

URL: www .iso .org/iso/foreword .html.

This document was prepared by Technical Committee ISO/TC 146, Air quality, Subcommittee SC 1,

Stationary source emissions.

This second edition cancels and replaces the first edition (ISO 12039:2001), which has been technically

revised. The main changes compared to the previous edition are as follows:

— The structure and the components are changed to be similar to the latest ISO standards; ISO 17179

(measurement of NH ), ISO 13199 (measurement of total VOC), ISO 25140 (measurement of CH ),

3 4
ISO 21258 (measurement of N O) and others.
— Addition or deletion and change in terms and definitions.

— Addition of a new analytical technique (tuneable laser spectroscopy) for in-situ measurement of CO,

CO and O
2 2

— The performance characteristics and criteria as well as QA/QC procedures are changed to harmonize

with latest ISO standards.

— Examples of performance test results and the results of uncertainty calculation are shown for CO,

CO and O measurement.
2 2

Any feedback or questions on this document should be directed to the user’s national standards body. A

complete listing of these bodies can be found at www .iso .org/members .html.
iv © ISO 2019 – All rights reserved
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ISO 12039:2019(E)
Introduction

Carbon monoxide, carbon dioxide, and oxygen are gases found in the exhaust gases of combustion

processes. Determination of the concentration of these gases is necessary to demonstrate compliance

with local regulations and can assist the operator in the optimization of the combustion process. The

determination of O and/or CO is also necessary to normalize the measured concentration of other

2 2

gases and dusts to defined conditions. There are a number of ways to measure concentrations of CO,

CO and O in stacks/ducts.
2 2
© ISO 2019 – All rights reserved v
---------------------- Page: 5 ----------------------
INTERNATIONAL STANDARD ISO 12039:2019(E)
Stationary source emissions — Determination of the
mass concentration of carbon monoxide, carbon dioxide
and oxygen in flue gas — Performance characteristics of
automated measuring systems
1 Scope

This document specifies the fundamental structure and the most important performance characteristics

of automated measuring systems for carbon monoxide (CO), carbon dioxide (CO ) and oxygen (O )

2 2

to be used on stationary source emissions. This document describes methods and equipment for the

measurement of concentrations of these gases.

The method allows continuous monitoring with permanently installed measuring systems of CO, CO

and O emissions. This international standard describes extractive systems and in situ (non-extractive)

systems in connection with analysers that operate using, for example, the following principles:

— infrared absorption (CO and CO );
— paramagnetism (O );
— zirconium oxide (O );
— electrochemical cell (O );
— tuneable laser spectroscopy (TLS) (CO, CO and O ).
2 2

Other instrumental methods can be used provided they meet the minimum requirements proposed in

this document.

Automated measuring systems (AMS) based on the principles above have been used successfully in this

application for measuring ranges which are described in Annex G.
2 Normative references

The following documents are referred to in the text in such a way that some or all of their content

constitutes requirements of this document. For dated references, only the edition cited applies. For

undated references, the latest edition of the referenced document (including any amendments) applies.

ISO 14956, Air quality — Evaluation of the suitability of a measurement procedure by comparison with a

required measurement uncertainty
3 Terms and definitions
For the purposes of this document, the following terms and definitions apply.
3.1
analyser
analytical part in an extractive or in situ AMS (3.3)
© ISO 2019 – All rights reserved 1
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ISO 12039:2019(E)
3.2
automated measuring system
AMS

measuring system interacting with the flue gas under investigation, returning an output signal

proportional to the physical unit of the measurand (3.8) in unattended operation
[SOURCE: ISO 9169:2006, 2.1.2 modified]

Note 1 to entry: In the sense of this document, an AMS is a system that can be attached to a duct or stack to

continuously or intermittently measure the mass concentration of CO, CO and O passing through the duct.

2 2
3.3
in situ AMS

non-extractive systems that measure the concentration directly in the duct or stack

Note 1 to entry: In situ systems measure either across the stack or duct or at a point within the duct or stack.

3.4
parallel measurements

measurements taken on the same duct in the same sampling plane for the same period of time with the

AMS (3.2) under test and with the reference method (3.12) at points a short distance from each other,

providing pairs of measured values
3.5
interference
cross-sensitivity

negative or positive effect upon the response of the measuring system, due to a component of the

sample that is not the measurand (3.8)
3.6
interferent
interfering substance

substance present in the air mass under investigation, other than the measurand (3.8), that affects the

response of AMS (3.2)
3.7
lack-of-fit

systematic deviation within the range of application between the measurement results obtained

by applying the calibration function to the observed response of the measuring system, measuring

reference materials (3.11) and the corresponding accepted value of such reference materials (3.11)

Note 1 to entry: Lack-of-fit may be a function of the measurement result.

Note 2 to entry: The expression “lack-of-fit” is often replaced in everyday language for linear relations by

“linearity” or “deviation from linearity”.
[SOURCE: ISO 9169:2006, 2.2.9]
3.8
measurand
particular quantity subject to measurement
[SOURCE: ISO/IEC Guide 98 3:2008, B.2.9, modified — Example and Note removed.]
3.9
performance characteristic
one of the quantities assigned to equipment in order to define its performance

Note 1 to entry: Performance characteristics can be described by values, tolerances, or ranges.

2 © ISO 2019 – All rights reserved
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ISO 12039:2019(E)
3.10
period of unattended operation

maximum interval of time for which the performance characteristics (3.9) remain within a predefined

range without external servicing, e.g. refill, adjustment
[SOURCE: ISO 9169:2006, 2.2.11]

Note 1 to entry: The period of unattended operation is often called maintenance interval.

3.11
reference material

substance or mixture of substances with a known concentration within specified limits, or a device of

known characteristics

Note 1 to entry: Normally calibration gases, gas cells, gratings or filters are used.

[SOURCE: ISO 14385-1:2014]
3.12
reference method

measurement method taken as a reference by convention, which gives the accepted reference value of

the measurand (3.8)
3.13
transport time

time period for transportation of the sampled gas from the inlet of the probe to

the inlet of the measurement instrument
3.14
response time

time interval between the instant when a stimulus is subjected to bring about a specified abrupt change

and the instant when the response reaches and remains within specified limits around its final stable

value, determined as the sum of the lag time and the rise time in the rising mode, and the sum of the lag

time and the fall time in the falling mode
[SOURCE: ISO 9169:2006, 2.2.4]
Note 1 to entry: Lag time, rise time and fall time are defined in ISO 9169:2006.
3.15
span gas

gas or gas mixture used to adjust and check the span point on the response line of the measuring system

Note 1 to entry: This concentration is often chosen around 70 % to 90 % of full scale.

3.16
span point

value of the output quantity (measured signal) of the automated measuring system (3.2) for the purpose

of calibration, adjustment, etc. that represents a correct measured value generated by reference gas

3.17
standard uncertainty

uncertainty (3.18) of the result of a measurement expressed as a standard deviation

[SOURCE: ISO/IEC Guide 98 3:2008, 2.3.1]
3.18
uncertainty (of measurement)

parameter associated with the result of a measurement, that characterizes the dispersion of the values

that could reasonably be attributed to the measurand (3.8)
[SOURCE: ISO/IEC Guide 98 3:2008, 2.2.3, modified — Note 1,2 and 3 removed.]
© ISO 2019 – All rights reserved 3
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ISO 12039:2019(E)
3.19
validation of automated measuring system

procedure to check the statistical relationship between values of the measurand (3.8) indicated by the

automated measuring system (3.2) and the corresponding values given by parallel measurements (3.4)

implemented simultaneously at the same measuring point
3.20
zero gas

gas or gas mixture used to establish the zero point (3.21) on a calibration curve within a given

concentration range
3.21
zero point

specified value of the output quantity (measured signal) of the AMS (3.2) and which, in the absence of

the measured component, represents the zero crossing of the calibration line. In case of O monitoring

AMS (3.2), the zero point is interpreted as the lowest measurable value.
4 Symbols and abbreviated terms
e Residual (lack-of-fit) at level i
K Coverage factor
N Number of measurements
s Standard deviation of repeatability
u(γ ) Combined uncertainty of X (CO, CO or O ) mass concentration
X 2 2
U(γ ) Expanded uncertainty of X (CO, CO or O ) mass concentration
X 2 2
M Molar mass of X (CO, CO or O , g/mol)
x 2 2
V Molar volume (22,4 l/mol at standard conditions)
φ Volume fraction of X (CO, CO or O )
X 2 2
γ X (CO, CO or O ) mass concentration in mg/m
X 2 2
γ CO, CO or O mass concentration at standard conditions in mg/m (273,15 K;
s 2 2
101,325 kPa)
γ CO, CO or O mass concentration at reference conditions in mg/m (273,15 K;
R 2 2
101,325 kPa; H O corrected)
Average of the measured values x
x ith measured value
Average of the measured value at level i
Value estimated by the regression line at level i
AMS Automated measuring system
FTIR Fourier transform infrared
GFC Gas filter correlation
4 © ISO 2019 – All rights reserved
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ISO 12039:2019(E)
NDIR Non-dispersive infrared
QA Quality assurance
QC Quality control
TLS Tuneable laser spectroscopy
5 Principle

This document describes automated measurement systems for sampling, sample conditioning, and

determining CO, CO and O content in flue gas using instrumental methods (analysers).

2 2
There are two types of automated measuring systems:
— extractive systems;
— in situ systems.

With extractive systems, the representative gas sample is taken from the stack with a sampling probe

and conveyed to the analyser through the sampling line and sample gas conditioning system.

In situ systems do not require any sample processing. For the installation of these systems, a

representative place in the stack is to be chosen.

The systems described in this document measure CO, CO and O concentrations using instrumental

2 2
methods that shall meet the minimum performance specifications given.
This document specifies performance characteristics and criteria for AMS.
6 Description of the automated measuring systems
6.1 Sampling and sample gas conditioning systems

Sampling and sample gas conditioning systems for extractive and in situ methods shall conform to

ISO 10396.

In extractive sampling, these gases are conditioned to remove aerosols, particulate matter and other

interfering substances before being conveyed to the instruments. Three kinds of extractive systems:

a) Cold-dry,
b) Hot-wet, and
c) Dilution,

as well as non-extractive systems, are described in ISO 10396. In non-extractive sampling, the

measurements are made in situ; therefore, no sample conditioning other than filtering of filterable

materials at the probe tip is required.

The details of the extractive sampling and sample gas conditioning systems as well as analyser

equipment are described in Annex A and Annex B. In Annex C, two kinds of in situ systems are

illustrated.
6.2 Analyser equipment

Examples of the typical analytical methods available are described in the Annex A, Annex B and

Annex C.
AMS shall meet the performance characteristics described in Clause 7.
© ISO 2019 – All rights reserved 5
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ISO 12039:2019(E)
7 Performance characteristics and criteria
7.1 Performance criteria

Table 1 gives the performance characteristics and performance criteria of the analyser and measurement

system to be evaluated during performance tests, by means of ongoing QA/QC in the laboratory and

during field operation. Test procedures for the performance test are specified in Annex E.

Table 1 — Performance characteristics and criteria of AMS for measurement of CO, CO and O

2 2
Performance characteristic Performance criterion Test procedure
CO and CO O
2 2
Response time ≤200 s ≤200 s E.2

Standard deviation of repeatability ≤2,0 % of the upper ≤0,2 % for O volume E.3.2

at zero point limit of the lowest concentration
measuring range
used

Standard deviation of repeatability ≤2,0 % of the upper ≤0,2 % for O volume E.3.3

at span point limit of the lowest concentration
measuring range
used
Lack-of-fit (linearity) ≤2,0 % of the upper ≤0,2 % for O volume E.4
limit of the lowest concentration
measuring range
used
Zero drift within 24 h ≤2,0 % of the upper ≤0,2 % for O volume E.8
limit of the lowest concentration
measuring range
used
Span drift within 24 h ≤2,0 % of the upper ≤0,2 % for O volume E.8
limit of the lowest concentration
measuring range
used
Zero drift within the period of ≤3,0 % of the upper ≤0,2 % for O volume E.9
unattended operation limit of the lowest concentration
measuring range
used
Span drift within the period of ≤3,0 % of the upper ≤0,2 % for O volume E.9
unattended operation limit of the lowest concentration
measuring range
used
Sensitivity to sample gas pressure, ≤3,0 % of the upper ≤0,2 % for O volume E.11
for a pressure change of 2 kPa limit of the lowest concentration
measuring range
used
Sensitivity to sample gas flow for ≤2,0 % of the upper ≤0,2 % for O volume E.12
extractive AMS limit of the lowest concentration
measuring range
used
Sensitivity to ambient temperature, ≤3,0 % of the upper ≤0,3 % for O volume E.13
for a change of 10 K in the limit of the lowest concentration
temperature range specified by the measuring range
manufacturer used

Percentage value as percentage of the upper limit of the lowest measuring range used.

Percentage value as oxygen volume concentration (volume fraction).
6 © ISO 2019 – All rights reserved
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ISO 12039:2019(E)
Table 1 (continued)
Performance characteristic Performance criterion Test procedure
CO and CO O
2 2

Sensitivity to electric voltage in the ≤2,0 % of the upper ≤0,2% for O volume E.14

voltage range specified by the limit of the lowest concentration
manufacturer measuring range
used per 10V
Cross-sensitivity ≤4,0 % of the upper ≤0,4 % for O volume E.5
limit of the lowest concentration
measuring range
used
Losses and leakage in the sampling ≤2,0 % of the E.6 for loss and E.7
line and conditioning system measured value for leakage
Excursion of the measurement beam ≤2,0 % of the E.10
of cross-stack in situ AMS measured value of
the lowest
measuring range
used

Percentage value as percentage of the upper limit of the lowest measuring range used.

Percentage value as oxygen volume concentration (volume fraction).

The measuring range is defined by two values of the measurand, or quantity to be supplied, within

which the limits of uncertainty of the measuring instrument are specified. The upper limit of the lowest

measuring range used should be set suitable to the application such that the measurement values lie

within 20 % to 80 % of the measuring range.
7.2 Determination of the performance characteristics
7.2.1 Performance test

The performance characteristics of the AMS shall be determined during the performance tests

described in Annex E. The values of the performance characteristics determined shall meet the

performance criteria specified in Table 1.
The ambient conditions applied during the performance tests shall be documented.

The measurement uncertainty of the AMS measured values shall be calculated in accordance with

ISO 14956 on the basis of the performance characteristics determined during the performance test

and shall meet the level of uncertainty appropriate for the intended use. These characteristics may be

determined either by the manufacturer or by the user.
7.2.2 Ongoing quality control

The user shall check specific performance characteristics during ongoing operation of the measuring

system with a periodicity specified in Table 2.

The measurement uncertainty during field application shall be determined by the user of the measuring

system in accordance with applicable international or national standards. For process monitoring (non-

regulatory application), the level of uncertainty shall be appropriate for the intended use. It can be

determined by a direct or an indirect approach for uncertainty estimation as described in ISO 20988.

The uncertainty of the measured values under field operation is not only influenced by the performance

characteristics of the analyser itself but also by uncertainty contributions due to:

— the sampling line and conditioning system,
— the site-specific conditions, and
— the calibration gases used.
© ISO 2019 – All rights reserved 7
---------------------- Page: 12 ----------------------
ISO 12039:2019(E)
8 Selection and installation procedure
8.1 Choice of the measuring system

To choose an appropriate analyser, sampling line and conditioning unit, the following characteristics of

flue gases should be known before the field operation:
— ambient temperature range;
— temperature range of the flue gas;
— water vapour content of the flue gas;
— dust loading of the gases;
— expected concentration range of CO, CO and O ;
2 2
— expected concentration of potentially interfering substances;

To avoid long response time and memory effects, the sampling line should be as short as possible. If

necessary, a bypass pump should be used. If there is a high dust loading in the sample gas, an appropriate

heated filter shall be used.

Before monitoring emissions, the user shall verify that the necessary QA/QC procedures have been

performed.
NOTE Information on QA/QC procedures is provided in ISO 14385-1 and ISO 14385-2.
8.2 Sampling
8.2.1 Sampling location

The sampling site shall be in an accessible location where a representative measurement can be made.

In addition, the sampling location shall be chosen with regard to safety of the personnel.

8.2.2 Representative sampling

It is necessary to ensure that the gas concentrations measured are representative of the average

conditions inside the flue gas duct.

NOTE The selection of sampling points for representative sampling is described e.g. in ISO 10396, where gas

stratification, fluctuations in gas velocity, temperature and others are mentioned.

8.3 Calculation
8.3.1 Conversion from volume to mass concentration for CO

Results of the measurement for CO shall be expressed as mass concentrations at reference conditions.

If the CO concentration is provided as a volume fraction, Formula (1) shall be used to convert volume

fraction of CO (10 ), ϕ , to CO mass concentrations, γ :
CO CO
γϕ=⋅MV/ (1)
CO CO CO M
where
8 © ISO 2019 – All rights reserved
---------------------- Page: 13 ----------------------
ISO 12039:2019(E)
γ is the CO mass concentration in mg/m ;
φ is the volume fraction of CO (by volume, 10 );
M is the molar mass of CO (=28,010 g/mol);
V is the molar vol
...

SLOVENSKI STANDARD
SIST ISO 12039:2020
01-marec-2020
Nadomešča:
SIST ISO 12039:2002
Emisije nepremičnih virov - Določevanje masne koncentracije ogljikovega
monoksida, ogljikovega dioksida in kisika v odpadnih plinih - Delovne
karakteristike avtomatskih merilnih sistemov
Stationary source emissions - Determination of the mass concentration of carbon
monoxide, carbon dioxide and oxygen in flue gas - Performance characteristics of
automated measuring systems
Émissions de sources fixes - Détermination de la concentration de monoxyde de

carbone, de dioxyde de carbone et d'oxygène - Caractéristiques de fonctionnement et

étalonnage de systèmes automatiques de mesure
Ta slovenski standard je istoveten z: ISO 12039:2019
ICS:
13.040.40 Emisije nepremičnih virov Stationary source emissions
SIST ISO 12039:2020 en

2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.

---------------------- Page: 1 ----------------------
SIST ISO 12039:2020
---------------------- Page: 2 ----------------------
SIST ISO 12039:2020
INTERNATIONAL ISO
STANDARD 12039
Second edition
2019-10
Stationary source emissions —
Determination of the mass
concentration of carbon monoxide,
carbon dioxide and oxygen in flue
gas — Performance characteristics of
automated measuring systems
Émissions de sources fixes — Détermination de la concentration
de monoxyde de carbone, de dioxyde de carbone et d'oxygène —
Caractéristiques de fonctionnement et étalonnage de systèmes
automatiques de mesure
Reference number
ISO 12039:2019(E)
ISO 2019
---------------------- Page: 3 ----------------------
SIST ISO 12039:2020
ISO 12039:2019(E)
COPYRIGHT PROTECTED DOCUMENT
© ISO 2019

All rights reserved. Unless otherwise specified, or required in the context of its implementation, 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.
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ii © ISO 2019 – All rights reserved
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SIST ISO 12039:2020
ISO 12039:2019(E)
Contents Page

Foreword ........................................................................................................................................................................................................................................iv

Introduction ..................................................................................................................................................................................................................................v

1 Scope ................................................................................................................................................................................................................................. 1

2 Normative references ...................................................................................................................................................................................... 1

3 Terms and definitions ..................................................................................................................................................................................... 1

4 Symbols and abbreviated terms ........................................................................................................................................................... 4

5 Principle ........................................................................................................................................................................................................................ 5

6 Description of the automated measuring systems ............................................................................................................ 5

6.1 Sampling and sample gas conditioning systems ........................................................................................................ 5

6.2 Analyser equipment ........................................................................................................................................................................... 5

7 Performance characteristics and criteria .................................................................................................................................. 6

7.1 Performance criteria .......................................................................................................................................................................... 6

7.2 Determination of the performance characteristics ................................................................................................. 7

7.2.1 Performance test .............................................................................................................................................................. 7

7.2.2 Ongoing quality control ............................................................................................................................................. 7

8 Selection and installation procedure .............................................................................................................................................. 8

8.1 Choice of the measuring system .............................................................................................................................................. 8

8.2 Sampling ....................................................................................................................................................................................................... 8

8.2.1 Sampling location ............................................................................................................................................................ 8

8.2.2 Representative sampling .......................................................................................................................................... 8

8.3 Calculation .................................................................................................................................................................................................. 8

8.3.1 Conversion from volume to mass concentration for CO ................................................................ 8

8.3.2 Conversion from wet to dry conditions for CO, CO and O concentrations ................ 9

2 2

9 Quality assurance and quality control procedures .......................................................................................................... 9

9.1 General ........................................................................................................................................................................................................... 9

9.2 Frequency of checks ........................................................................................................................................................................10

9.3 Calibration, validation and measurement uncertainty .....................................................................................10

10 Test report ................................................................................................................................................................................................................11

Annex A (informative) Infrared absorption method (CO and CO ) ....................................................................................12

Annex B (informative) Extractive O measurement techniques ...........................................................................................19

Annex C (informative) In situ CO, CO and O measurement ....................................................................................................26

2 2

Annex D (normative) Operational gases .......................................................................................................................................................30

Annex E (normative) Procedures for determination of the performance characteristics ........................31

Annex F (informative) Examples of the results for the assessment of CO, CO and O AMS .....................39

2 2

Annex G (informative) Calculation of uncertainty of measurement of CO, CO and O .................................44

2 2

Bibliography .............................................................................................................................................................................................................................51

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SIST ISO 12039:2020
ISO 12039:2019(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 voluntary nature of standards, the meaning of ISO specific terms and

expressions related to conformity assessment, as well as information about ISO's adherence to the

World Trade Organization (WTO) principles in the Technical Barriers to Trade (TBT) see the following

URL: www .iso .org/iso/foreword .html.

This document was prepared by Technical Committee ISO/TC 146, Air quality, Subcommittee SC 1,

Stationary source emissions.

This second edition cancels and replaces the first edition (ISO 12039:2001), which has been technically

revised. The main changes compared to the previous edition are as follows:

— The structure and the components are changed to be similar to the latest ISO standards; ISO 17179

(measurement of NH ), ISO 13199 (measurement of total VOC), ISO 25140 (measurement of CH ),

3 4
ISO 21258 (measurement of N O) and others.
— Addition or deletion and change in terms and definitions.

— Addition of a new analytical technique (tuneable laser spectroscopy) for in-situ measurement of CO,

CO and O
2 2

— The performance characteristics and criteria as well as QA/QC procedures are changed to harmonize

with latest ISO standards.

— Examples of performance test results and the results of uncertainty calculation are shown for CO,

CO and O measurement.
2 2

Any feedback or questions on this document should be directed to the user’s national standards body. A

complete listing of these bodies can be found at www .iso .org/members .html.
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ISO 12039:2019(E)
Introduction

Carbon monoxide, carbon dioxide, and oxygen are gases found in the exhaust gases of combustion

processes. Determination of the concentration of these gases is necessary to demonstrate compliance

with local regulations and can assist the operator in the optimization of the combustion process. The

determination of O and/or CO is also necessary to normalize the measured concentration of other

2 2

gases and dusts to defined conditions. There are a number of ways to measure concentrations of CO,

CO and O in stacks/ducts.
2 2
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SIST ISO 12039:2020
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SIST ISO 12039:2020
INTERNATIONAL STANDARD ISO 12039:2019(E)
Stationary source emissions — Determination of the
mass concentration of carbon monoxide, carbon dioxide
and oxygen in flue gas — Performance characteristics of
automated measuring systems
1 Scope

This document specifies the fundamental structure and the most important performance characteristics

of automated measuring systems for carbon monoxide (CO), carbon dioxide (CO ) and oxygen (O )

2 2

to be used on stationary source emissions. This document describes methods and equipment for the

measurement of concentrations of these gases.

The method allows continuous monitoring with permanently installed measuring systems of CO, CO

and O emissions. This international standard describes extractive systems and in situ (non-extractive)

systems in connection with analysers that operate using, for example, the following principles:

— infrared absorption (CO and CO );
— paramagnetism (O );
— zirconium oxide (O );
— electrochemical cell (O );
— tuneable laser spectroscopy (TLS) (CO, CO and O ).
2 2

Other instrumental methods can be used provided they meet the minimum requirements proposed in

this document.

Automated measuring systems (AMS) based on the principles above have been used successfully in this

application for measuring ranges which are described in Annex G.
2 Normative references

The following documents are referred to in the text in such a way that some or all of their content

constitutes requirements of this document. For dated references, only the edition cited applies. For

undated references, the latest edition of the referenced document (including any amendments) applies.

ISO 14956, Air quality — Evaluation of the suitability of a measurement procedure by comparison with a

required measurement uncertainty
3 Terms and definitions
For the purposes of this document, the following terms and definitions apply.
3.1
analyser
analytical part in an extractive or in situ AMS (3.3)
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3.2
automated measuring system
AMS

measuring system interacting with the flue gas under investigation, returning an output signal

proportional to the physical unit of the measurand (3.8) in unattended operation
[SOURCE: ISO 9169:2006, 2.1.2 modified]

Note 1 to entry: In the sense of this document, an AMS is a system that can be attached to a duct or stack to

continuously or intermittently measure the mass concentration of CO, CO and O passing through the duct.

2 2
3.3
in situ AMS

non-extractive systems that measure the concentration directly in the duct or stack

Note 1 to entry: In situ systems measure either across the stack or duct or at a point within the duct or stack.

3.4
parallel measurements

measurements taken on the same duct in the same sampling plane for the same period of time with the

AMS (3.2) under test and with the reference method (3.12) at points a short distance from each other,

providing pairs of measured values
3.5
interference
cross-sensitivity

negative or positive effect upon the response of the measuring system, due to a component of the

sample that is not the measurand (3.8)
3.6
interferent
interfering substance

substance present in the air mass under investigation, other than the measurand (3.8), that affects the

response of AMS (3.2)
3.7
lack-of-fit

systematic deviation within the range of application between the measurement results obtained

by applying the calibration function to the observed response of the measuring system, measuring

reference materials (3.11) and the corresponding accepted value of such reference materials (3.11)

Note 1 to entry: Lack-of-fit may be a function of the measurement result.

Note 2 to entry: The expression “lack-of-fit” is often replaced in everyday language for linear relations by

“linearity” or “deviation from linearity”.
[SOURCE: ISO 9169:2006, 2.2.9]
3.8
measurand
particular quantity subject to measurement
[SOURCE: ISO/IEC Guide 98 3:2008, B.2.9, modified — Example and Note removed.]
3.9
performance characteristic
one of the quantities assigned to equipment in order to define its performance

Note 1 to entry: Performance characteristics can be described by values, tolerances, or ranges.

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3.10
period of unattended operation

maximum interval of time for which the performance characteristics (3.9) remain within a predefined

range without external servicing, e.g. refill, adjustment
[SOURCE: ISO 9169:2006, 2.2.11]

Note 1 to entry: The period of unattended operation is often called maintenance interval.

3.11
reference material

substance or mixture of substances with a known concentration within specified limits, or a device of

known characteristics

Note 1 to entry: Normally calibration gases, gas cells, gratings or filters are used.

[SOURCE: ISO 14385-1:2014]
3.12
reference method

measurement method taken as a reference by convention, which gives the accepted reference value of

the measurand (3.8)
3.13
transport time

time period for transportation of the sampled gas from the inlet of the probe to

the inlet of the measurement instrument
3.14
response time

time interval between the instant when a stimulus is subjected to bring about a specified abrupt change

and the instant when the response reaches and remains within specified limits around its final stable

value, determined as the sum of the lag time and the rise time in the rising mode, and the sum of the lag

time and the fall time in the falling mode
[SOURCE: ISO 9169:2006, 2.2.4]
Note 1 to entry: Lag time, rise time and fall time are defined in ISO 9169:2006.
3.15
span gas

gas or gas mixture used to adjust and check the span point on the response line of the measuring system

Note 1 to entry: This concentration is often chosen around 70 % to 90 % of full scale.

3.16
span point

value of the output quantity (measured signal) of the automated measuring system (3.2) for the purpose

of calibration, adjustment, etc. that represents a correct measured value generated by reference gas

3.17
standard uncertainty

uncertainty (3.18) of the result of a measurement expressed as a standard deviation

[SOURCE: ISO/IEC Guide 98 3:2008, 2.3.1]
3.18
uncertainty (of measurement)

parameter associated with the result of a measurement, that characterizes the dispersion of the values

that could reasonably be attributed to the measurand (3.8)
[SOURCE: ISO/IEC Guide 98 3:2008, 2.2.3, modified — Note 1,2 and 3 removed.]
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3.19
validation of automated measuring system

procedure to check the statistical relationship between values of the measurand (3.8) indicated by the

automated measuring system (3.2) and the corresponding values given by parallel measurements (3.4)

implemented simultaneously at the same measuring point
3.20
zero gas

gas or gas mixture used to establish the zero point (3.21) on a calibration curve within a given

concentration range
3.21
zero point

specified value of the output quantity (measured signal) of the AMS (3.2) and which, in the absence of

the measured component, represents the zero crossing of the calibration line. In case of O monitoring

AMS (3.2), the zero point is interpreted as the lowest measurable value.
4 Symbols and abbreviated terms
e Residual (lack-of-fit) at level i
K Coverage factor
N Number of measurements
s Standard deviation of repeatability
u(γ ) Combined uncertainty of X (CO, CO or O ) mass concentration
X 2 2
U(γ ) Expanded uncertainty of X (CO, CO or O ) mass concentration
X 2 2
M Molar mass of X (CO, CO or O , g/mol)
x 2 2
V Molar volume (22,4 l/mol at standard conditions)
φ Volume fraction of X (CO, CO or O )
X 2 2
γ X (CO, CO or O ) mass concentration in mg/m
X 2 2
γ CO, CO or O mass concentration at standard conditions in mg/m (273,15 K;
s 2 2
101,325 kPa)
γ CO, CO or O mass concentration at reference conditions in mg/m (273,15 K;
R 2 2
101,325 kPa; H O corrected)
Average of the measured values x
x ith measured value
Average of the measured value at level i
Value estimated by the regression line at level i
AMS Automated measuring system
FTIR Fourier transform infrared
GFC Gas filter correlation
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NDIR Non-dispersive infrared
QA Quality assurance
QC Quality control
TLS Tuneable laser spectroscopy
5 Principle

This document describes automated measurement systems for sampling, sample conditioning, and

determining CO, CO and O content in flue gas using instrumental methods (analysers).

2 2
There are two types of automated measuring systems:
— extractive systems;
— in situ systems.

With extractive systems, the representative gas sample is taken from the stack with a sampling probe

and conveyed to the analyser through the sampling line and sample gas conditioning system.

In situ systems do not require any sample processing. For the installation of these systems, a

representative place in the stack is to be chosen.

The systems described in this document measure CO, CO and O concentrations using instrumental

2 2
methods that shall meet the minimum performance specifications given.
This document specifies performance characteristics and criteria for AMS.
6 Description of the automated measuring systems
6.1 Sampling and sample gas conditioning systems

Sampling and sample gas conditioning systems for extractive and in situ methods shall conform to

ISO 10396.

In extractive sampling, these gases are conditioned to remove aerosols, particulate matter and other

interfering substances before being conveyed to the instruments. Three kinds of extractive systems:

a) Cold-dry,
b) Hot-wet, and
c) Dilution,

as well as non-extractive systems, are described in ISO 10396. In non-extractive sampling, the

measurements are made in situ; therefore, no sample conditioning other than filtering of filterable

materials at the probe tip is required.

The details of the extractive sampling and sample gas conditioning systems as well as analyser

equipment are described in Annex A and Annex B. In Annex C, two kinds of in situ systems are

illustrated.
6.2 Analyser equipment

Examples of the typical analytical methods available are described in the Annex A, Annex B and

Annex C.
AMS shall meet the performance characteristics described in Clause 7.
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ISO 12039:2019(E)
7 Performance characteristics and criteria
7.1 Performance criteria

Table 1 gives the performance characteristics and performance criteria of the analyser and measurement

system to be evaluated during performance tests, by means of ongoing QA/QC in the laboratory and

during field operation. Test procedures for the performance test are specified in Annex E.

Table 1 — Performance characteristics and criteria of AMS for measurement of CO, CO and O

2 2
Performance characteristic Performance criterion Test procedure
CO and CO O
2 2
Response time ≤200 s ≤200 s E.2

Standard deviation of repeatability ≤2,0 % of the upper ≤0,2 % for O volume E.3.2

at zero point limit of the lowest concentration
measuring range
used

Standard deviation of repeatability ≤2,0 % of the upper ≤0,2 % for O volume E.3.3

at span point limit of the lowest concentration
measuring range
used
Lack-of-fit (linearity) ≤2,0 % of the upper ≤0,2 % for O volume E.4
limit of the lowest concentration
measuring range
used
Zero drift within 24 h ≤2,0 % of the upper ≤0,2 % for O volume E.8
limit of the lowest concentration
measuring range
used
Span drift within 24 h ≤2,0 % of the upper ≤0,2 % for O volume E.8
limit of the lowest concentration
measuring range
used
Zero drift within the period of ≤3,0 % of the upper ≤0,2 % for O volume E.9
unattended operation limit of the lowest concentration
measuring range
used
Span drift within the period of ≤3,0 % of the upper ≤0,2 % for O volume E.9
unattended operation limit of the lowest concentration
measuring range
used
Sensitivity to sample gas pressure, ≤3,0 % of the upper ≤0,2 % for O volume E.11
for a pressure change of 2 kPa limit of the lowest concentration
measuring range
used
Sensitivity to sample gas flow for ≤2,0 % of the upper ≤0,2 % for O volume E.12
extractive AMS limit of the lowest concentration
measuring range
used
Sensitivity to ambient temperature, ≤3,0 % of the upper ≤0,3 % for O volume E.13
for a change of 10 K in the limit of the lowest concentration
temperature range specified by the measuring range
manufacturer used

Percentage value as percentage of the upper limit of the lowest measuring range used.

Percentage value as oxygen volume concentration (volume fraction).
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Table 1 (continued)
Performance characteristic Performance criterion Test procedure
CO and CO O
2 2

Sensitivity to electric voltage in the ≤2,0 % of the upper ≤0,2% for O volume E.14

voltage range specified by the limit of the lowest concentration
manufacturer measuring range
used per 10V
Cross-sensitivity ≤4,0 % of the upper ≤0,4 % for O volume E.5
limit of the lowest concentration
measuring range
used
Losses and leakage in the sampling ≤2,0 % of the E.6 for loss and E.7
line and conditioning system measured value for leakage
Excursion of the measurement beam ≤2,0 % of the E.10
of cross-stack in situ AMS measured value of
the lowest
measuring range
used

Percentage value as percentage of the upper limit of the lowest measuring range used.

Percentage value as oxygen volume concentration (volume fraction).

The measuring range is defined by two values of the measurand, or quantity to be supplied, within

which the limits of uncertainty of the measuring instrument are specified. The upper limit of the lowest

measuring range used should be set suitable to the application such that the measurement values lie

within 20 % to 80 % of the measuring range.
7.2 Determination of the performance characteristics
7.2.1 Performance test

The performance characteristics of the AMS shall be determined during the performance tests

described in Annex E. The values of the performance characteristics determined shall meet the

performance criteria specified in Table 1.
The ambient conditions applied during the performance tests shall be documented.

The measurement uncertainty of the AMS measured values shall be calculated in accordance with

ISO 14956 on the basis of the performance characteristics determined during the performance test

and shall meet the level of uncertainty appropriate for the intended use. These characteristics may be

determined either by the manufacturer or by the user.
7.2.2 Ongoing quality control

The user shall check specific performance characteristics during ongoing operation of the measuring

system with a periodicity specified in Table 2.

The measurement uncertainty during field application shall be determined by the user of the measuring

system in accordance with applicable international or national standards. For process monitoring (non-

regulatory application), the level of uncertainty shall be appropriate for the intended use. It can be

determined by a direct or an indirect approach for uncertainty estimation as described in ISO 20988.

The uncertainty of the measured values under field operation is not only influenced by the performance

characteristics of the analyser itself but also by uncertainty contributions due to:

— the sampling line and conditioning system,
— the site-specific conditions, and
— the calibration gases used.
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8 Selection and installation procedure
8.1 Choice of the measuring system

To choose an appropriate analyser, sampling line and conditioning unit, the following characteristics of

flue gases should be known before the field operation:
— ambient temperature range;
— temperature range of the flue gas;
— water vapour content of the flue gas;
— dust loading of the gases;
— expected concentration range of CO, CO and O ;
2 2
— expected concentration of potentially interfering substances;

To avoid long response time and memory effects, the sampling line should be as short as possible. If

necessary, a bypass pump should be used. If there is a high dust loading in the sample gas, an appropriate

heated filter shall be used.
Before monitoring emissions, t
...

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