EN ISO 25139:2011

SLOVENSKI STANDARD
01-december-2011
(PLVLMHQHSUHPLþQLKYLURY5RþQDPHWRGD]DGRORþHYDQMHNRQFHQWUDFLMHPHWDQDV
SOLQVNRNURPDWRJUDILMR,62
Stationary source emissions - Manual method for the determination of the methane
concentration using gas chromatography (ISO 25139:2011)
Emissionen aus stationären Quellen - Manuelles Verfahren zur Bestimmung der Methan-
Konzentration mit Gaschromatographie (ISO 25139:2011)
Émissions de sources fixes - Méthode manuelle pour la détermination de la
concentration en méthane par chromatographie en phase gazeuse (ISO 25139:2011)
Ta slovenski standard je istoveten z: EN ISO 25139:2011
ICS:
13.040.40 (PLVLMHQHSUHPLþQLKYLURY Stationary source emissions
2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.

EUROPEAN STANDARD
EN ISO 25139
NORME EUROPÉENNE
EUROPÄISCHE NORM
April 2011
ICS 13.040.40
English Version
Stationary source emissions - Manual method for the
determination of the methane concentration using gas
chromatography (ISO 25139:2011)
Émissions de sources fixes - Méthode manuelle pour la Emissionen aus stationären Quellen - Manuelles Verfahren
détermination de la concentration en méthane par zur Bestimmung der Methan-Konzentration mit
chromatographie en phase gazeuse (ISO 25139:2011) Gaschromatographie (ISO 25139:2011)
This European Standard was approved by CEN on 14 April 2011.

CEN members are bound to comply with the CEN/CENELEC Internal Regulations which stipulate the conditions for giving this European
Standard the status of a national standard without any alteration. Up-to-date lists and bibliographical references concerning such national
standards may be obtained on application to the CEN-CENELEC Management Centre or to any CEN member.

This European Standard exists in three official versions (English, French, German). A version in any other language made by translation
under the responsibility of a CEN member into its own language and notified to the CEN-CENELEC Management Centre has the same
status as the official versions.

CEN members are the national standards bodies of Austria, Belgium, Bulgaria, Croatia, Cyprus, Czech Republic, Denmark, Estonia,
Finland, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland,
Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland and United Kingdom.

EUROPEAN COMMITTEE FOR STANDARDIZATION
COMITÉ EUROPÉEN DE NORMALISATION

EUROPÄISCHES KOMITEE FÜR NORMUNG

Management Centre: Avenue Marnix 17, B-1000 Brussels
© 2011 CEN All rights of exploitation in any form and by any means reserved Ref. No. EN ISO 25139:2011: E
worldwide for CEN national Members.

Contents Page
Foreword .3

Foreword
This document (EN ISO 25139:2011) has been prepared by Technical Committee ISO/TC 146 "Air quality" in
collaboration with Technical Committee CEN/TC 264 “Air quality” the secretariat of which is held by DIN.
This European Standard shall be given the status of a national standard, either by publication of an identical
text or by endorsement, at the latest by October 2011, and conflicting national standards shall be withdrawn at
the latest by October 2011.
Attention is drawn to the possibility that some of the elements of this document may be the subject of patent
rights. CEN [and/or CENELEC] shall not be held responsible for identifying any or all such patent rights.
According to the CEN/CENELEC Internal Regulations, the national standards organizations of the following
countries are bound to implement this European Standard: Austria, Belgium, Bulgaria, Croatia, Cyprus, Czech
Republic, Denmark, Estonia, Finland, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia,
Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain,
Sweden, Switzerland and the United Kingdom.
Endorsement notice
The text of ISO 25139:2011 has been approved by CEN as a EN ISO 25139:2011 without any modification.

INTERNATIONAL ISO
STANDARD 25139
First edition
2011-04-15
Stationary source emissions — Manual
method for the determination of the
methane concentration using gas
chromatography
Émissions de sources fixes — Méthode manuelle pour la détermination
de la concentration en méthane par chromatographie en phase
gazeuse
Reference number
ISO 25139:2011(E)
©
ISO 2011
ISO 25139:2011(E)
©  ISO 2011
All rights reserved. Unless otherwise specified, no part of this publication may be reproduced or utilized in any form or by any means,
electronic or mechanical, including photocopying and microfilm, without permission in writing from either ISO at the address below or
ISO's member body in the country of the requester.
ISO copyright office
Case postale 56  CH-1211 Geneva 20
Tel. + 41 22 749 01 11
Fax + 41 22 749 09 47
E-mail copyright@iso.org
Web www.iso.org
Published in Switzerland
ii © ISO 2011 – All rights reserved

ISO 25139:2011(E)
Contents Page
Foreword . iv
Introduction . v
1 Scope . 1
2 Normative references . 1
3 Terms and definitions . 1
4 Symbols and abbreviated terms . 2
5 Principle . 3
6 Equipment . 4
6.1 Sampling system . 4
6.2 Analytical apparatus . 6
7 Measurement procedure . 6
7.1 General . 6
7.2 Sampling . 6
7.3 Analytical determination . 8
7.4 Interferents . 8
8 Calculation of the results . 8
9 Quality assurance and quality control procedures . 10
9.1 General . 10
9.2 Criteria and frequency of checks . 10
9.3 Performing the checks . 11
9.4 Check of the measurement system . 12
10 Performance characteristics . 12
11 Test report . 12
Annex A (normative) Operational gases . 13
Annex B (normative) Quality assurance and quality control procedures . 14
Annex C (informative) Typical performance characteristics . 16
Bibliography . 18

ISO 25139:2011(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.
International Standards are drafted in accordance with the rules given in the ISO/IEC Directives, Part 2.
The main task of technical committees is to prepare International Standards. Draft International Standards
adopted by the technical committees are circulated to the member bodies for voting. Publication as an
International Standard requires approval by at least 75 % of the member bodies casting a vote.
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.
ISO 25139 was prepared by Technical Committee ISO/TC 146, Air quality, Subcommittee SC 1, Stationary
source emissions.
iv © ISO 2011 – All rights reserved

ISO 25139:2011(E)
Introduction
Methane (CH ) is a gas of relevance to the climate (“greenhouse gas”) and contributes directly to the
atmospheric greenhouse effect. The emissions of methane originate from natural sources and those due to
human activity. Significant sources are, for example, cattle breeding, cultivation of rice, extraction and
transport of natural gas, and landfills. Other important sources contributing to emissions of methane are, for
example, composting plants, the use of biogas and natural gas, and biomass firings. This International
Standard specifies a method of measurement for the determination of methane emissions from stationary
sources.
INTERNATIONAL STANDARD ISO 25139:2011(E)

Stationary source emissions — Manual method for the
determination of the methane concentration using gas
chromatography
1 Scope
This International Standard specifies a manual method for the determination of the concentration of methane
emissions from stationary sources.
This International Standard specifies an independent method of measurement, which is validated for mass
concentrations up to 1 500 mg/m .
NOTE 1 An independent method of measurement is used for such purposes as calibration or validation of permanently
installed measuring systems.
[5]
NOTE 2 An “independent method of measurement” is termed “standard reference method (SRM)” in EN 14181 .
2 Normative references
The following referenced documents are indispensable for the application 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 9169, Air quality — Definition and determination of performance characteristics of an automatic
measuring system
EN 15267-3, Air quality — Certification of automated measuring systems — Part 3: Performance criteria and
test procedures for automated measuring systems for monitoring emissions from stationary sources
3 Terms and definitions
For the purposes of this document, the following terms and definitions apply.
3.1
reference gas
air quality gas of known, reliable and stable composition
NOTE In the context of this International Standard, a reference gas is used to calibrate the gas chromatograph.
3.2
interferent
interfering substance
air quality substance present in the air mass under investigation, other than the measurand, that affects the
response
[ISO 9169:2006, 2.1.12]
ISO 25139:2011(E)
3.3
mass concentration
stationary source emissions concentration of a substance in an emitted waste gas expressed as mass per
volume
NOTE Mass concentration is often expressed in milligrams per cubic metre.
[3]
[ISO 25140:2010 , 3.14]
3.4
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
[4]
[ISO/IEC Guide 98-3:2008 , 2.2.3]
3.5
standard uncertainty
uncertainty of the result of a measurement expressed as a standard deviation
[4]
[ISO/IEC Guide 98-3:2008 , 2.3.1]
4 Symbols and abbreviated terms
AMS automatic measuring system
FID flame ionization detector
FKM fluoro rubber
GC gas chromatograph
PE polyethylene
PET poly(ethylene terephthalate)
PLOT porous layer open tubular
PTFE polytetrafluoroethylene
QA/QC quality assurance and quality control

A peak area
e residual at mass concentration level 
j j
f GC calibration factor
GC
k slope of the calibration line
L limit of detection
m mass of water vapour
HO,v
M molecular mass of methane (16 g/mol)
CH
2 © ISO 2011 – All rights reserved

ISO 25139:2011(E)
M molecular mass of water (18 g/mol)
HO
n number of measurements
s repeatability standard deviation
r
S GC signal
GC
S GC signal in response to the reference gas applied
GC,cal
V volume of the dry gas sampled
V standard molar volume (22,4 l/mol)
m
x ith measured value
i
x average of the measured values x
i
x average of the measured values at mass concentration level 
j j
 methane mass concentration at standard conditions of temperature and pressure
CH ,s
 methane mass concentration at reference conditions of water vapour (dry gas)
CH ,(H O)
42 0
 methane mass concentration at reference conditions of oxygen
CH ,O
 jth mass concentration level
j
 density of water vapour
HO,v
 methane content, as a volume fraction, of the reference gas applied during calibration
CH ,cal
 methane content, as a volume fraction, at operating conditions
CH ,o
 water vapour content, as a volume fraction, in the waste gas
HO
 measured oxygen content, as a volume fraction, in the waste gas
O,m
 reference oxygen content, as a volume fraction
O,ref
5 Principle
The sample gas is extracted from the waste gas duct via a sampling system and pumped into a gas-sampling
bag or canister. A portion of the sample is taken off from the gas-sampling bag or canister and introduced into
a gas chromatographic system. After separation on a packed or capillary column, methane is determined by
means of a flame ionization detector.
ISO 25139:2011(E)
6 Equipment
6.1 Sampling system
The sampling system shall allow for the extraction of the sample gas from the waste gas duct. It consists in
principle of:
 sampling probe;
 particle filter;
 sample gas cooler;
 sample gas flow meter;
 sample gas pump;
 vacuum pump, if necessary;
 gas-sampling vessel (bag, glass tube or canister), or direct sampling loop to the GC.
Several sampling techniques are suitable such as:
 use of gas-sampling bags with upstream pump (see Figure 1);
 use of evacuated gas-sampling vessels made of glass or canisters made of corrosion-resistant materials
(e.g. stainless steel) with upstream pump (see Figure 2);
 use of the “lung principle” with the gas-sampling bag placed in an evacuated container;
 use of a sampling system as shown in Figure 1 but with the gas-sampling bag replaced by a sampling line
directly connected to the loop sampling system of the GC.
7 9
Key
1 sampling probe, heated (if necessary) 6 flow meter
2 valve for introducing test gases 7 bypass valve for purging the sampling system
3 particle filter, heated 8 sampling bag valve
4 sample gas cooler or permeation dryer 9 gas-sampling bag
5 sample gas pump
Figure 1 — Example of a sampling system with gas-sampling bag

4 © ISO 2011 – All rights reserved

ISO 25139:2011(E)
4 9
3 11
Key
1 sampling probe, heated (if necessary) 7 throttle element
2 valve for introducing test gases 8 shut-off valve
3 particle filter, heated 9 gas-sampling vessel or canister
4 sample gas cooler or permeation dryer 10 temperature and pressure measuring device
5 control valve 11 shut-off valve
6 sample gas pump 12 vacuum pump (if necessary)
Figure 2 — Example of a sampling system with evacuated gas-sampling vessel
The sampling line shall be as short as possible. The sampling line shall be installed so as to descend to the
cooler. Condensation shall be avoided at any point of the sampling system.
The sampling system shall meet the following requirements:
 the sampling probe shall be a tube made of stainless steel or glass, which can be heated to 150 °C, if
necessary, equipped with a device (e.g. a valve) for introducing test gases;
 the dust filter shall be a quartz fibre or ceramic filter in a filter housing and shall be heatable to 150 °C, if
necessary;
 the sampling line shall be made of stainless steel or polytetrafluoroethylene (PTFE) and shall be heatable
to 150 °C, if necessary;
 the sample gas cooler or permeation dryer shall be suitable for a flow rate up to 1 l/min;
 the sample gas pump shall be gas-tight with adjustable flow rate (up to 1 l/min), and shall be heatable, if
necessary;
 vacuum pump for evacuating the gas-sampling vessel down to a residual pressure of 10 hPa to 20 hPa;
 connecting pieces for components of the sampling apparatus shall be made of an inert tubing material,
e.g. PTFE or fluoro rubber (FKM);
 the flow meter with control valve shall be suitable for measuring the sampling flow rate;
 the gas-sampling vessel shall be gas-tight (e.g. a plastic bag with closable filler nozzle or canister of
corrosion-resistant materials equipped with valves) with a volume of 5 l to 30 l;
 all components of the sampling system shall be made of corrosion-resistant material;
 all components upstream the cooler shall withstand a temperature of 150 °C, if necessary.
Suitable materials for the storage of methane samples are aluminium-coated polyethylene (PE) and poly(vinyl
fluoride). Sample storage in gas-sampling bags made from these materials for at most 10 days is possible
without significant methane losses, in aluminium-coated PE bags even longer.
ISO 25139:2011(E)
When using poly(ethylene terephthalate) (PET) bags, which are usually taken for odour sampling, storage
should not exceed 2 days. Longer storage results in significant losses of methane (Reference [6]).
CAUTION — The use of gas-sampling bags which are made from pure polyethylene is not
recommended as methane diffuses out and ambient air diffuses in.
The gas-sampling vessel should be equipped with a septum or a valve depending on the GC injection
technique (gas-tight syringe or sample loop).
6.2 Analytical apparatus
The analytical apparatus consists of the following components, which shall meet the specified requirements:
 gas chromatograph (GC) with flame ionization detector (FID), which shall be equipped with a sample
injection with gas sample loop or split injector;
 separation column, which shall be a packed column or capillary column;
 injection syringe, if necessary, which shall be gas-tight and should be suitable for a volume, for example,
of 1 ml;
 GC signal output, which can be equipped with a data evaluation unit.
7 Measurement procedure
7.1 General
Comprehensive measurement planning shall be performed before the measurement, taking into consideration
the specific measurement task.
7.2 Sampling
7.2.1 Preparation
The sampling equipment shall be cleaned, prepared, and analytically checked before transporting to the site.
The gas-sampling bags are used, they shall be cleaned before sampling by purging with nitrogen followed by
a complete removal of the purging gas. The purge and removal of the sampling bag with nitrogen shall be
repeated at least three times to ensure the cleanliness of the bag. After the last purging, the gas removed and
analysed shall give a signal below the limit of detection.
7.2.2 Sampling procedure
7.2.2.1 General
The sampling equipment shall be assembled and checked for possible leaks by sealing the entry nozzle and
starting the suction device. The leak flow, for example measured by pressure variation after evacuation of the
train at the maximal low-pressure reached during sampling, shall be below 2 % of the sampling flow rate.
Sampling shall be performed according to the sampling technique selected from 7.2.2.2 to 7.2.2.5.
6 © ISO 2011 – All rights reserved

ISO 25139:2011(E)
7.2.2.2 Bag sampling according to Figure 1
The sampling probe shall be inserted into the waste gas duct and the sampling system purged with waste gas
through the sampling probe, the particle filter and the sample gas cooler by starting the pump and by use of
the bypass for a sufficient time period.
Afterwards, a partial flow of the waste gas is pumped into the gas-sampling bag by opening the sampling bag
valve.
7.2.2.3 Evacuated vessel or canister according to Figure 2
The sampling probe shall be inserted into the waste gas duct and the sampling system purged with waste gas
through the sampling probe, the particle filter and the sample gas cooler by
...