EN ISO 13833:2013

SLOVENSKI STANDARD
01-december-2013
(PLVLMHQHSUHPLþQLKYLURY'RORþHYDQMHUD]PHUMDRJOMLNRYHJDGLRNVLGD
ELRPDVQHJDLQIRVLOQHJDL]YRUD9]RUþHQMHLQGRORþHYDQMHL]RWRSRYRJOMLND,62

Stationary source emissions - Determination of the ratio of biomass (biogenic) and fossil-
derived carbon dioxide - Radiocarbon sampling and determination (ISO 13833:2013)
Emissionen aus stationären Quellen - Bestimmung des Verhältnisses von Kohlendioxid
aus Biomasse (biogen) und aus fossilen Quellen - Probenahme und Bestimmung des
radioaktiven Kohlenstoffs (ISO 13833:2013)
Émissions de sources fixes - Détermination du rapport du dioxyde de carbone de la
biomasse (biogénique) et des dérivés fossiles - Échantillonnage et détermination du
radiocarbone (ISO 13833:2013)
Ta slovenski standard je istoveten z: EN ISO 13833:2013
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 13833
NORME EUROPÉENNE
EUROPÄISCHE NORM
April 2013
ICS 13.040.40
English Version
Stationary source emissions - Determination of the ratio of
biomass (biogenic) and fossil-derived carbon dioxide -
Radiocarbon sampling and determination (ISO 13833:2013)
Émissions de sources fixes - Détermination du rapport du Emissionen aus stationären Quellen - Bestimmung des
dioxyde de carbone de la biomasse (biogénique) et des Verhältnisses von Kohlendioxid aus Biomasse (biogen) und
dérivés fossiles - Échantillonnage et détermination du aus fossilen Quellen - Probenahme und Bestimmung des
radiocarbone (ISO 13833:2013) radioaktiven Kohlenstoffs (ISO 13833:2013)
This European Standard was approved by CEN on 1 March 2013.

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

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

CEN members are the national standards bodies of Austria, Belgium, Bulgaria, Croatia, Cyprus, Czech Republic, Denmark, Estonia,
Finland, Former Yugoslav Republic of Macedonia, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania,
Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland, Turkey and United
Kingdom.
EUROPEAN COMMITTEE FOR STANDARDIZATION
COMITÉ EUROPÉEN DE NORMALISATION

EUROPÄISCHES KOMITEE FÜR NORMUNG

Management Centre: Avenue Marnix 17, B-1000 Brussels
© 2013 CEN All rights of exploitation in any form and by any means reserved Ref. No. EN ISO 13833:2013: E
worldwide for CEN national Members.

Contents Page
Foreword .3

Foreword
This document (EN ISO 13833:2013) 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 2013, and conflicting national standards shall be withdrawn at
the latest by October 2013.
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, Former Yugoslav Republic of Macedonia, France, Germany, Greece,
Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal,
Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland, Turkey and the United Kingdom.
Endorsement notice
The text of ISO 13833:2013 has been approved by CEN as EN ISO 13833:2013 without any modification.

INTERNATIONAL ISO
STANDARD 13833
First edition
2013-04-01
Stationary source emissions —
Determination of the ratio of biomass
(biogenic) and fossil-derived carbon
dioxide — Radiocarbon sampling and
determination
Émissions de sources fixes — Détermination du rapport du dioxyde
de carbone de la biomasse (biogénique) et des dérivés fossiles —
Échantillonnage et détermination du radiocarbone
Reference number
ISO 13833:2013(E)
©
ISO 2013
ISO 13833:2013(E)
© ISO 2013
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
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 2013 – All rights reserved

ISO 13833:2013(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
4.1 Symbols . 2
4.2 Abbreviations . 3
5 Principle . 4
5.1 General . 4
5.2 Principles of sampling . 4
5.3 14
C measurement techniques. 5
6 Reagent, materials and equipment . 5
7 Analysis . 9
8 Calculation of the results . 9
9 Quality assurance and quality control procedures .11
10 Test report .11
Annex A (normative) Procedure for C determination by accelerator mass spectrometry .13
Annex B (normative) Procedure for C determination by liquid scintillation counter method .16
Annex C (normative) Procedures for C determination by beta-ionization .21
Annex D (informative) Performance characteristics C methods .24
Annex E (informative) Definitions and equations of the C-based method .28
Bibliography .36
ISO 13833:2013(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.
ISO 13833 was prepared by Technical Committee ISO/TC 146, Air quality, Subcommittee SC 1, Stationary
source emissions.
iv © ISO 2013 – All rights reserved

ISO 13833:2013(E)
Introduction
Reliable data for biogenic carbon dioxide (CO ) emissions are needed for carbon emission trading and in
order to provide more accurate inventories.
When combusting mixtures of fuels from fossil and biogenic origin, it is often difficult to determine the
exact ratio of biogenic and fossil CO in the total CO that is emitted through the stack gas, because the
2 2
biogenic and fossil composition of the combusted fuels is not always known or cannot be determined
with sufficient accuracy. This is the case when solid recovered fuels (SRF) are used.
The contribution of solid, liquid, and gaseous biofuels to energy production is likely to increase. A reliable
and robust method for the determination of the ratio of fossil and biogenic CO in the total emitted CO
2 2
of stack gas will enhance the implementation of these products, as reliable data for carbon emission
trading can be generated with this approach.
Different methods exist to determine the ratio of fossil and biogenic CO in stack gas. The radiocarbon
( C isotope) method has been applied since the 1950s in a variety of sample types, like food, fuels,
polymers, and atmospheric and combustion CO to determine the ratio of biogenic and fossil carbon
(Reference [18]). Biogenic and fossil carbon can be distinguished based on the measured amount of
the C isotope in the sample. Another, relatively new applied method is the “balance method”, which
combines standard data on the chemical composition of biogenic and fossil organic matter with routinely
measured operating data of the plant (Reference [10]). Similar methods using stoichiometric methods,
for example, can also be used.
This International Standard gives sampling and analysis methods for the determination of the ratio of
biomass and fossil fuel-derived CO in the total emitted CO from exhaust gases of stationary sources,
2 2
based on the radiocarbon ( C isotope) method. Sample strategies for integrated sampling for periods
from 1 h up to 1 month are given. Radiocarbon determination procedures include accelerated mass
spectrometry (AMS), beta-ionization (BI), and liquid scintillation (LS) measurement procedures for the
determination of the radiocarbon content.
The International Organization for Standardization (ISO) draws attention to the fact that it is
claimed that compliance with this document may involve the use of patents concerning the use of the
radiocarbon isotope as biogenic marker: a) Method for determining the relationship of renewable to non-
renewable sources of energy; b) Method for determining the fossil fuel content in a fuel stream, as well as a
an incineration furnace.
ISO takes no position concerning the evidence, validity and scope of these patent rights.
The holders of these patent rights have assured ISO that they are willing to negotiate licences under
reasonable and non-discriminatory terms and conditions with applicants throughout the world. In this
respect, statements of the holders of these patent rights are registered with ISO. Information may be
obtained from:
a) European Cement Research Academy (ECRA)
Tannenstrasse 2, D-40476, DÜSSELDORF. Tel.: +49 211 23 98 38 0; E-mail: info@ecra-online.org
b) Energy Research Centre of the Netherlands
Westerduinweg 3, PO Box 1, NL-1755 ZG PETTEN. Tel.: +31 224 56 4475; E-mail: denuijl@ecn.nl
Attention is drawn to the possibility that some of the elements of this document may be the subject of
patent rights other than those identified above. ISO shall not be held responsible for identifying any or
all such patent rights.
ISO (www.iso.org/patents) maintains on-line databases of patents relevant to its documents. Users are
encouraged to consult the databases for the most up to date information concerning patents.
INTERNATIONAL STANDARD ISO 13833:2013(E)
Stationary source emissions — Determination of the ratio
of biomass (biogenic) and fossil-derived carbon dioxide —
Radiocarbon sampling and determination
1 Scope
This International Standard specifies sampling methods and analysis methods for the determination of
the ratio of biomass- and fossil-derived carbon dioxide (CO ) in the CO from exhaust gases of stationary
2 2
sources, based on the radiocarbon ( C isotope) method. The lower limit of application is a biogenic to
total CO fraction of 0,02. The working range is a biogenic to total CO fraction of 0,02 to 1,0.
2 2
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 7934, Stationary source emissions — Determination of the mass concentration of sulfur dioxide —
Hydrogen peroxide/barium perchlorate/Thorin method
ISO 10396, Stationary source emissions — Sampling for the automated determination of gas emission
concentrations for permanently-installed monitoring systems
ISO 15713, Stationary source emissions — Sampling and determination of gaseous fluoride content
3 Terms and definitions
For the purposes of this document, the following terms and definitions apply.
3.1
biogenic
produced in natural processes by living organisms but not fossilized or derived from fossil resources
3.2
biomass
material of biological origin excluding material embedded in geological formation or transformed to fossil
3.3
isotope abundance
fraction of atoms of a particular isotope of an element
3.4
organic carbon
amount of carbon bound in an organic material
3.5
percentage modern carbon
pmC
normalized and standardized value for the amount of the C isotope in a sample, calculated relative to the
1)
standardized and normalized C isotope amount of oxalic acid standard reference material, SRM 4990c
Note 1 to entry: In 2009, the value of 100 % bio-based carbon was set at 105 pmC.
1) SRM 4990c is the trade name of a product supplied by the US National Institute of Standards and Technology.
ISO 13833:2013(E)
3.6
proportional sampling
flow proportional sampling
technique for obtaining a sample from flowing stack gas in which the wet or dry sample flow rate is
directly proportional to the mass flow rate, volume flow rate or velocity in the stack
3.7
radiocarbon
radioactive isotope of the element carbon, C, having 8 neutrons, 6 protons, and 6 electrons
−10 14
Note 1 to entry: Of the total carbon on Earth, 1 × 10 % mass fraction is C. It decays exponentially with a half-
life of 5 730 years and as such it is not measurable in fossil materials derived from petroleum, coal, natural gas or
any other source older than about 50 000 years.
3.8
sample
quantity of material, representative of a larger quantity for which the property is to be determined
3.9
sample preparation
all the actions taken to obtain representative analyses, samples or test portions from the original sample
3.10
test portion
quantity of material drawn from the test sample (or from the laboratory sample if both are the same)
and on which the test or observation is actually carried out
3.11
beta-particle
electron or positron which has been emitted by an atomic nucleus or neutron in a nuclear transformation
[1]
[ISO 921:1997, definition 81]
4 Symbols and abbreviated terms
4.1 Symbols
A disintegrations per second
b default C content (in pmC) of 100 % biomass, produced and harvested in 2011
E counting rate
C coefficient of variation
V
E(R ) counting rate of blank
E(R ) lower limit of detection
n,LLD
i increment number
k + k coverage factor (typical value: 1,645)
1 − α 1 − β
m measured C content of the sample
m mass of CO
CO
This information is given for the convenience of users of this document and does not constitute an endorsement by
ISO of the product named. Equivalent products may be used if they can be shown to lead to the same results.
2 © ISO 2013 – All rights reserved

ISO 13833:2013(E)
M 44,01 kg/kmole
CO
n number of increments
r biogenic CO to total CO ratio derived from the measured pmC value
2 2
t operating time
t counting time of sample
b
t counting time of blank
V total amount of stack gas emitted
V volume of CO
CO

V actual stack gas flow at moment i
i
V 22,41 m /kmol (at 273 K and 1 013 hPa)
m
−
β beta-particle (electron emitted during radioactive decay)
ϕ average concentration of CO
CO
ϕ actual concentration of CO
CO ,i
η counting efficiency of the apparatus (0 < η < 1)
4.2 Abbreviations
AMS accelerator mass spectrometer; accelerator mass spectrometry
BI beta-ionization measurement, gas proportional counter, proportional gas counter
cpm counts per minute
cps counts per second
dpm disintegrations per minute
dps disintegrations per second, equivalent to becquerel
GM Geiger–Müller
LLD lower limit of detection
LSC liquid scintillation counter; liquid scintillation counting
pmC percentage modern carbon
SRF solid recovered fuel
ISO 13833:2013(E)
5 Principle
5.1 General
The measurement of the presence of the C isotope in flue gas or stack gas enables the determination
of the biogenic and fossil fractions of the CO that is emitted. The determination of the biogenic CO
2 2
fraction in flue gas or stack gas consists of:
— representative sampling of CO ;
— measurement of the sampled C;
— calculation of the biogenic CO fraction in the stack gas emitted during the sampling period.
Procedures for collection of whole gas samples and absorption of CO in liquid and solid alkaline media
are given. Three C determination procedures that can be used are described. The biogenic fraction
is determined using the measured C value. From the calculated biogenic CO fraction, the emitted
amount of biogenic and fossil CO can be calculated. Examples are given.
5.2 Principles of sampling
5.2.1 General
Sampling of CO in stack gas is in principle not different from sampling of other acid gaseous substances
like sulfur dioxide (SO ) or hydrogen chloride (HCl). The CO present in a representative stack gas sample
2 2
is absorbed in an alkaline medium or transferred to a gas bag or lecture bottle and after sampling the
collected CO is prepared for C analysis.
Standard equipment as used for other gaseous components may be utilized. As CO is present in relatively
high concentrations compared to other acidic gaseous substances, the capacity of the absorption media
used requires consideration, an excess of alkaline media shall be used to ensure complete absorption
during the sampling period.
Sampling shall be carried out in accordance with applicable standards.
NOTE Sampling and sampling strategies for continuous and intermittent measurements of stationary source
[4]
emissions are specified, for example, in ISO 10396 and EN 15259. Unlike other species where a concentration is
determined, for biogenic CO a ratio of biogenic CO to the total is determined. Many uncertainties that occur if a
2 2
concentration is actually measured can be excluded if an amount of a component with exactly the same chemical
behaviour as the various CO isotopes is determined instead. Some uncertainties specific for spectroscopic
measurement can, however, affect the preferred CO analyser for flow proportional sampling.
5.2.2 Grab gas samples
If applicable, use accepted procedures for the collection of gas in gas bags, canisters or gas bottles.
Only gas bags impenetrable to CO shall be used. Most aluminium-lined gas bags are suitable.
5.2.3 Absorption samples
When liquid or solid absorbers are used, the CO is collected in a medium containing alkaline reagents.
For sampling with liquids, alkaline solutions of, for example, 2 mol/l to 4 mol/l potassium hydroxide
(KOH) or equivalent (sodium hydroxide, NaOH) are suitable. For solid CO absorbers, commercial
products are suitable.
After collection of the samples, close the absorbers and ensure that they are gastight, in order to prevent
the ingress of atmospheric CO .
4 © ISO 2013 – All rights reserved

ISO 13833:2013(E)
5.3 14
C measurement techniques
The C content of the collected samples can be determined using:
— accelerator mass spectrometry (AMS);
— beta-ionization (BI) measurement (gas proportional counter);
— the liquid scintillation counting technique (LSC).
All sampling methods mentioned in 5.2 are suitable for the collection of CO .
Depending on the C analysis technique different amounts of sampled CO are required. For AMS
measurements the minimum volume of CO is 4 ml. For BI measurements, 2 l to 10 l CO are required.
2 2
For LSC measurements, the required amount of CO depends on the way the sample is prepared for
measurement, but at least a few grams are necessary.
6 Reagent, materials and equipment
During the analysis, unless otherwise stated, use only reagents of recognized analytical grade and
distilled or demineralized water or water of equivalent purity containing negligible amounts of
carbonate, i.e. at concentrations that do not contribute significantly to the determinations.
6.1 Reagent. A setup consisting of:
— glass bottle (standard glass sample bottle with plastic screw cap resistant to the alkaline medium used);
— alkaline absorption medium;
2)
— solid absorber suitable for the collection of CO .
Mixing of water and NaOH or KOH should be done under the addition of inert gas, in order to reduce
absorption of CO from ambient air and exhalation.
For the preparation of a carbonate-free absorption liquid, preparation using freshly opened NaOH or
KOH pellet containers is sufficient. Dissolve the NaOH or KOH pellets in a small amount of water (the
heat produced enhances dissolution). Small amounts of precipitation are an indication of the presence
of sodium carbonate (Na CO ). By decanting the clear phase, the almost carbonate-free solution can be
2 3
diluted to the desired volume. As NaOH dissolution is an exothermic process, take extra care as boiling
of the concentrated solution during dilution can occur.
6.2 Materials and equipment. The components in the sampling device are listed in the following.
— Stack gas flow measurement device (typically based on S-type, P-type or L-type Pitot tube) according
[2]
to ISO 10780.
NOTE 1 Under “steady-state” conditions, the stack gas flow can be calculated from the fuel consumption. If this
is done, no instrumentation for stack gas flow determination is needed.
— Standard equipment for sampling stack gas for main component analysis.
NOTE 2 If a conditioning system for gas analysis is already present, this needs to be taken into consideration in
the sampling plan and part of the conditioned gas used, e.g. using a T-piece somewhere in the sampling line. In these
standard gas conditioning devices, usually a typical gas flow of 60 l/h to 100 l/h is available after conditioning,
— Mass flow controller, externally adjustable. An external adjustable mass flow controller is needed
only for proportional sampling as it is necessary to use the signal obtained from the measurement
of the total flow in the duct to adjust the sampling flow linearly proportionally to it. Use mass flow
2) Ascarite II is an example of a suitable product available commercially. This information is given for the
convenience of users of this document and does not constitute an endorsement by ISO of this product.
ISO 13833:2013(E)
controllers in the range of e.g. 0,1 ml/min . 1 ml/min or 10 ml/min . 100 ml/min, tuned for stack
gas composition.
— Sample containers.
— Gas sampling: use air tight vessels, compatible with the system design, which includes flexible
bags, evacuated canisters, lecture gas bottles.
— Liquid sampling: use accepted gas wash bottles (e.g. 250 ml glass wash bottles).
— Solid sampling: use air tight container (e.g. glass tube, length by diameter: 200 mm × 18 mm,
with standard fitting).
— Gas analysis system for CO and O measurement.
2 2
[3]
Perform any CO , CO, or O measurements required according to ISO 12039.
2 2
Before measurement, the homogeneity of the stack gas shall be tested. Perform homogeneity testing
in accordance with ISO 10396. Use the CO concentration as measurand. If homogeneity testing is
successful, sampling can be done on a single point.
Comprehensive measurement planning shall be performed before sampling, taking into consideration
the specific measurement task.
If stack gas pre-sample and analysis equipment is already present, part of this gas sampling stream can
be used to collect the sample. If that is not the case, a probe suitable for gas sampling, equipped with an
in-stack or out of stack filter for removal of particulate matter shall be used, and provisions shall be made
for excess water removal. To ensure representative sampling and to ensure the equivalence between the
measured total CO concentration and the CO sampled for the C analysis, accepted standards for the
2 2
[4]
measurement of bulk components in stack gas, namely ISO 10396 or EN 15259, shall be used.
There are several methods for intermediate storage of the collected CO . The simplest solution is the
use of a gasbag. If long storage periods are expected, the use of aluminium-lined gas bags is preferred
to prevent the ingress of CO from ambient air. Proper blank procedures shall ensure that suitable gas
bags were used.
When more CO has to be collected, a gas cylinder can be used for storage. Standard canisters can be
used for this purpose. Provisions shall be made for controlled intake of stack gas independent of pressure
build-up during the sampling process.
As CO in stack gas can be trapped with 100 % efficiency using alkaline media, collection of the emitted
CO can be done using a wash bottle filled with alkaline solution or a suitable solid alkaline scrubber, as
long as excess absorption capacity is present and the sample flow does not exceed the flow that is typical
for the type of scrubber used.
Typical values for liquid sampling are: 250 ml wash bottle filled with 200 ml 2 mol/l KOH solution,
sampling flow 1 ml/min to 50 ml/min, corresponding to sampling periods in the range of 1 day
(50 ml/min) to 1 month (1 ml/min) for flue gas with ~10 % volume fraction CO .
2)
Typical values for solid sampling are: glass tube (200 × 18 mm) packed with 40 g Ascarite II® absorbent
(~8 mesh to ~20 mesh), sampling flow 1 ml/min to 50 ml/min, corresponding to sampling periods in the
range of 1 day (50 ml/min) to 1 month (1 ml/min) for flue gas with ~10 % volume fraction CO .
If standard gas analysis probes and pre-sample systems are present, part of the conditioned gas can be
used for CO sampling. The standard gas analysis can be combined with simultaneous sampling of CO
2 2
as long as this sampling does not affect the standard gas analysis (consider the required sample flow
and the risk of leakage).
If the required measurements concern a steady-state situation, a sampling setup as shown in Figure 1
or equivalent may be used.
6 © ISO 2013 – All rights reserved

ISO 13833:2013(E)
Key
1 flue gas 9 sampling pump
2 probe 10 bypass valve
3 heater 11 to analyser(s)
4 primary filter 12 manifold
5 heated sample line 13 flow meter (optional)
6 dehumidifier unit 14 exhaust
7 water discharge 15 mass flow controller
8 secondary filter 16 CO
absorber (LS)
Figure 1 — Example of sampling train for steady-state measurements
If the stack gas flow rate of the installation is expected to be fluctuating, then an assessment of that
influence will have to be made and if a significant contribution from fluctuation is foreseen, a sampling
setup as shown in Figure 2 or equivalent may be used. Guidelines of how to prepare a sampling plan are
[4]
available (see EN 15259 ).
In practice, overall changes in stack gas flow rates not exceeding a coefficient of variation (2C ) of 55 % can
V
be considered as a condition for constant sampling, assuming continuous operation in the sampling period.
Use the readings from the flow rate indicator (e.g. pressure differential, steam rate, fuel rate) to calculate
the mean (μ) and standard deviation (s).
[7]
NOTE The 55 % (2C ) specification is in accordance with ASTM 7459.
v
ISO 13833:2013(E)
Key
1 flue gas 10 bypass valve
2 probe 11 to analyser(s)
3 heater 12 manifold
4 primary filter 13 flow meter (optional)
5 heated sample line 14 exhaust
6 dehumidifier unit 15 mass flow controller
7 water discharge 16 CO absorber (LS)
8 secondary filter 17 velocity measurement
9 sampling pump 18 flow rate meter
Figure 2 — Example of sampling train for proportional sampling
If proportional sampling is required, the flow rate of the mass flow controller shall be proportional to
the measured flue gas velocity, volume flow or mass flow.
In the sampling plan, an assessment of the minimum number of increments (sampling rate) needed for
effective proportional sampling shall be made.
6.3 Minimum requirements for sampling equipment
In order to be able to obtain the performance characteristics as given in this International Standard, the
following requirements shall be met:
— external adjustable mass flow controller: accuracy at least 5 % of reading;
— solid adsorber: containing more than 90 % mass fraction NaOH;
— liquid adsorber: concentration more than 1 mol/l NaOH;
— capacity left after sampling: more than 25 % of the total capacity of the adsorber.
NOTE Instead of NaOH, other strong bases like KOH can be used.
8 © ISO 2013 – All rights reserved

ISO 13833:2013(E)
6.4 Interferents
Consider the possible interferents listed in the following.
— Several acidic substances (e.g NO , SO , HCl, RCOOH) may be present in the flue gas and may be
x x
captured by alkaline samplers. Care shall be taken to avoid potential interference from such
substances; see description of the particular analysis methods (in Annex B and C).
— CO concentrations well above 0,1 % volume fraction in the stack gas (e.g. pyrolysis plants), might
contribute to the measured pmC value in CO .
— Take into account the presence of CO in the combustion air (0,04 % volume fraction if ambient air
[4] 14
is used as combustion air) when the biogenic CO fraction is <0,1 (see EN 15259 ). The C value
(in pmC) of the ambient air depends on the location of the sampling site and on the time of sampling
(specific year and time of year).
7 Analysis
The methods for the determination of the carbon dioxide content derived from biomass specified in this
International Standard are based on the determination of the C content.
The measurement of the C content of the sample shall be done according to one of the methods in
Annexes A, B or C. The performance characteristics of the three techniques are different, the typical
analytical error (expressed as standard deviation) for AMS and proportional gas counting is 0,1 pmC to
0,5 pmC, the typical analytical error for LSC with benzene synthesis is 0,3 pmC to 2 pmC and the typical
analytical error for LSC with CO absorption is 20 pmC, which can be improved to 2 pmC to 4 pmC under
strict laboratory controlled conditions and using high-precision LSC instrumentation.
The results of the measurements shall be expressed as the percentage modern carbon (pmC).
When the collected samples are sent to specialized laboratories, the samples should be stored in a way
that no CO from ambient air can enter the absorption solution. A check on the ingress of CO from air
2 2
shall be performed by preparing laboratory and field blanks during the sampling stage.
8 Calculation of the results
Calculate the ratio of biogenic CO in the total CO of a sample from the measured C content and a
2 2
reference C value for 100 % biogenic CO using Formula (1):
m
r= (1)
b
where
r is the biogenic CO to total CO ratio derived from the measured pmC value;
2 2
m is the measured C content of the sample (in pmC) (as determined according to Annex A, B or
C);
b is the default C content (in pmC) of 100 % biomass, produced and harvested in 2011.
NOTE 1 In 2011, a consensus outdoor air CO value of 104 was used by radiocarbon laboratories. Therefore the
pmC value for 100 % biomass, grown and harvested in 2011 is set at 104 pmC. An annual decrease of 0,3 % can be
taken into account.
NOTE 2 For municipal waste or other mixed fuel streams, typical regional values are reported in studies on local
reference pmC values. These values can be used as local reference value if generally accepted evidence is provided.
ISO 13833:2013(E)
NOTE 3 See Annex E for detailed information about the definition of pmC and discussion on the used
reference value.
EXAMPLE A C value of 40 pmC is measured in the CO sample. Then the percentage biogenic CO in the CO
2 2 2
sample is (40/104) × 100 = 38 % and the fossil CO fraction is 100 % − 38 % = 62 %
The total amount of biogenic CO emitted in the sampling period can be derived from the measured total
CO concentration, the total stack gas amount emitted and the calculated biogenic CO fraction.
2 2
For steady-state sampling conditions, use Formula (2)
ϕ
CO
V = Vr (2)
CO
where
is the total amount of biogenic CO emitted in m ;
V 2
CO
ϕ is the average concentration of CO expressed as a % volume fraction;
CO
V is the total amount of stack gas emitted in m ;
r is the biogenic CO to total CO ratio derived from the measured pmC value.
2 2
If no CO measurements are available, the total amount of emitted CO can be derived from the amount
2 2
of fuel that was combusted during the sampling period taking in account the carbon content of that fuel.
For proportional sampling conditions use Formula (3).
n
 
 
r

 
VV=  ϕ  100×n ××t (3)
CO CO ,ii
∑
 
 
 i 
 
where
is the total amount of biogenic CO emitted in m ;
V
CO
ϕ is the actual CO concentration at moment i expressed as a % volume fraction;
CO ,i

V is the actual stack gas flow at moment i in m /h;
i
r is the calculated biogenic CO fraction of the sample CO expressed as a %;
2 2
n is the number of increments;
i is the increment number;
t is the operating time in hours.
10 © ISO 2013 – All rights reserved

ISO 13833:2013(E)
Calculate m from V using Formula (4):
CO CO
2 2
VM
CO CO
2 2
m =× (4)
CO
1000 V
m
where
is the mass of CO in tonnes;
m
CO
V is the volume of CO in m ;
CO
M is the molar mass of CO , i.e. 44,01 kg/kmol;
CO
V is the molar volume of a gas at 273 K and 1 013 hPa, i.e. 22,41 m /kmol.
m
Water can be removed before collection in the bag or container using a condensation unit, in which case
consider the necessity of corrections to Formulae (1) to (4) for concentration changes resulting from
this water removal.
9 Quality assurance and quality control procedures
The collection of the carbonate from the stack gas is in principle in line with the collection of other
gases like HF, SO , and NH using wash bottles, therefore the quality assurance and control procedures
2 3
specified in ISO 7934 and ISO 15713 shall be used.
When liquid or solid CO absorbers are used, blank samples shall be measured to confirm the absence of
ingress of CO from ambient air.
For proportional sampling, the total amount of CO collected shall be verified by standard chemical
analysis (e.g. titration) of a test portion.
The values obtained can be compared with values calculated from the fuel composition (if available).
Performance characteristics are given in Annex D.
10 Test report
The test report shall be in accordance with international or national regulations. If not specified
otherwise, the test report shall include at least the following information:
a) reference to this International Standard (ISO 13833:2013);
b) description of the purpose of tests;
c) principle of gas sampling;
d) information about the sampling and conditioning line;
e) identification of the analysis technique used;
f) description of plant and process;
g) identification the sampling plane;
h) actions taken to achieve representative samples;
i) description of the location of the sampling point(s) in the sampling plane;
ISO 13833:2013(E)
j) description of the operating conditions of the plant process;
k) changes in the plant operations during sampling;
l) sampling date, time and duration;
m) time averaging on relevant periods;
n) measurement uncertainty;
o) any deviations from this International Standard.
12 © ISO 2013 – All rights reserved

ISO 13833:2013(E)
Annex A
(normative)
Procedure for C determination by accelerator mass spectrometry
A.1 General
This annex specifies the procedure for the determination of the C content by accelerator mass
spectrometry (AMS) in the CO and exhaust gas samples collected at stationary sources.
A.2 Principle
The AMS method determines the presence of the C isotope directly. The atoms in the sample are converted
into a beam of ions. The ions formed are accelerated in an electric field, deflected in a magnetic field, and
detected in ion detectors, resulting in the determination of the relative isotope abundances of these ions.
AMS uses a high potential electrostatic field, which serves not only to accelerate but also to specifically
n+
form only C ions (n = 1 . 4) that are allowed into the spectrometer, excluding all other ionic species.
This greatly enhances sensitivity without compromising selectivity. In most AMS systems, the C is
currently determined from graphite (carbon) sample targets. To obtain graphite sample targets, it is
necessary to convert the CO in each sample into graphite before analysing.
With AMS the amount of C atoms is measured relative to the amount of (one of) the more abundant
12 13 14 12 14 13
carbon isotopes C and/or C. This measured C/ C or C/ C ratio is calculated relative to the
measured isotope ratio in a reference material with standardized C amount, to obtain standardized
and normalized C content (in pmC) for each sample.
A.3 Reagents and materials
Use only reagents of recognized analytical grade.
A.3.1 Catalyst (iron, copper).
A.3.2 Reducing reagents, hydrogen or Zn powder.
1)
A.3.3 Oxalic acid primary standard, e.g. SRM 4990c.
A.3.4 Acid solution, extra pure; containing no carbon.
A.3.5 Liquid nitrogen.
A.4 Apparatus
Usual laboratory equipment and in particular the following.
A.4.1 Sample preparation equipment.
A.4.2 Liquid nitrogen trap.
A.4.3 Accelerator mass spectrometer.
ISO 13833:2013(E)
A.5 Procedure
A.5.1 Transfer the carbonate solution to the extraction bottle.
A.5.2 Attach the acid solution dosing device.
A.5.3 Evacuate the bottle and dosing device (degassing, removal of dissolved N and O from air).
2 2
A.5.4 Add acid solution to the carbonate solution.
A.5.5 Remove water vapour by using a trap filled with acetone and dry ice.
A.5.6 Collect the CO formed in a trap that is submersed in liquid N (A.4.2).
2 2
A.5.7 Transfer the CO to the graphitizing rig system.
A.5.8 When the samples are collected in gas bags, follow the same procedure
...