SIST EN 16718:2016
(Main)Wood and wood based products - Dosage of the total organic carbon (TOC) in wood and wood based products
Wood and wood based products - Dosage of the total organic carbon (TOC) in wood and wood based products
This document describes a method for determining total organic carbon by calculating the difference between the results of measurements of total carbon (TC) and total inorganic carbon (TIC). The identification of the bio-based content given by the stable isotopes such as 13C is described also.
This method is applicable to all wood species, wood-based materials (panels, plywood, wood-polymer, etc.) and woods containing chemicals in general.
Holz und Holzprodukte - Bestimmung des gesamten organischen Kohlenstoffs (TOC) in Holz und Holzprodukten
Dieses Dokument beschreibt ein Verfahren zur Bestimmung des gesamten organischen Kohlenstoffs durch Berechnung der Differenz zwischen den Messergebnissen des gesamten Kohlenstoffs (TC) und des gesamten anorganischen Kohlenstoffs (TIC). Die Identifizierung des durch die stabilen Isotope, wie 13C, festgestellten biobasierten Gehalts wird ebenfalls beschrieben.
Dieses Verfahren ist für alle Holzarten, Holzprodukte (Platten, Sperrholz, Holzpolymer usw.) und die in Hölzern im Allgemeinen enthaltenen Chemikalien anwendbar.
Produits de préservation du bois et matériaux à base de bois - Dosage du carbone organique total (COT) dans les bois et matériaux à base de bois
Le présent document décrit une méthode de détermination du carbone organique total par calcul de la différence entre les résultats des mesures de carbone total (CT) et du carbone inorganique total (CI). Il décrit également l'identification du contenu biosourcé indiqué par les isotopes stables tels que 13C.
Cette méthode est applicable sur toutes les essences de bois, les matériaux à base de bois (panneaux, contre-plaqués, bois-polymères, etc.) et les bois contenant des produits chimiques en général.
Les in lesni proizvodi - Delež celotnega organskega ogljika (TOC) v lesu in lesnih proizvodih
Ta dokument opisuje metodo za ugotavljanje skupnega organskega ogljika z izračunom razlike med rezultati merjenja skupnega ogljika (TC) in skupnega anorganskega ogljika (TIC). Opisuje tudi identifikacijo biološke vsebine, ki jo podajajo stabilni izotopi, kot je 13C.
Metoda splošno velja za vse lesne vrste, materiale na osnovi lesa (plošče, vezan les, lesni polimer itd.) in les, ki vsebuje kemikalije.
General Information
Standards Content (Sample)
SLOVENSKI STANDARD
SIST EN 16718:2016
01-februar-2016
Les in lesni proizvodi - Delež celotnega organskega ogljika (TOC) v lesu in lesnih
proizvodih
Wood and wood based products - Dosage of the total organic carbon (TOC) in wood and
wood based products
Holz und Holzprodukte - Bestimmung des gesamten organischen Kohlenstoffs (TOC) in
Holz und Holzprodukten
Produits de préservation du bois et matériaux à base de bois - Dosage du carbone
organique total (COT) dans les bois et matériaux à base de bois
Ta slovenski standard je istoveten z: EN 16718:2015
ICS:
79.040 Les, hlodovina in žagan les Wood, sawlogs and sawn
timber
79.060.01 /HVQHSORãþHQDVSORãQR Wood-based panels in
general
SIST EN 16718:2016 en,fr,de
2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.
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SIST EN 16718:2016
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SIST EN 16718:2016
EN 16718
EUROPEAN STANDARD
NORME EUROPÉENNE
November 2015
EUROPÄISCHE NORM
ICS 79.060.01
English Version
Wood and wood based products - Dosage of the total
organic carbon (TOC) in wood and wood based products
Produits de préservation du bois et matériaux à base Holz und Holzprodukte - Bestimmung des gesamten
de bois - Dosage du carbone organique total (COT) organischen Kohlenstoffs (TOC) in Holz und
dans les bois et matériaux à base de bois Holzprodukten
This European Standard was approved by CEN on 12 September 2015.
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
CEN-CENELEC Management Centre: Avenue Marnix 17, B-1000 Brussels
© 2015 CEN All rights of exploitation in any form and by any means reserved Ref. No. EN 16718:2015 E
worldwide for CEN national Members.
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SIST EN 16718:2016
EN 16718:2015 (E)
Contents Page
European foreword . 4
Introduction . 5
1 Scope . 7
2 Normative references . 7
3 Terms and definitions . 7
4 Principle . 7
5 Reagents and products . 8
6 Apparatus . 8
7 Procedure. 8
7.1 Preparation of the sample . 8
7.2 Water content . 8
7.3 Dosage . 9
7.3.1 General . 9
7.3.2 TC dosage . 9
7.3.3 TIC dosage . 9
7.4 Calibration . 9
7.5 Control measurements . 10
7.6 Evaluation . 10
13
7.7 C measurement by IRMS (Isotope Ratio Mass Spectrometer) . 11
7.7.1 Material and methods . 11
13
7.7.2 C isotope . 12
18
7.7.3 O isotope . 12
2
7.7.4 H isotope (Deuterium) . 12
15
7.7.5 N Isotopes . 12
13 18 2
7.7.6 Multi-isotopic determinations: C, O and H in wood and tree . 12
8 Performance characteristics . 13
9 Test report . 13
Annex A (informative) Results of the validation method . 14
A.1 General . 14
A.2 Response function . 14
A.2.1 General . 14
A.2.2 Total carbon . 15
A.2.3 Inorganic carbon . 16
A.3 Trueness . 17
A.3.1 General . 17
A.3.2 Total carbon . 18
A.3.3 Inorganic carbon . 18
A.4 Precision . 18
A.4.1 General . 18
A.4.2 Total carbon . 18
A.4.3 Inorganic carbon . 20
A.5 Measurement uncertainty . 21
A.5.1 General . 21
2
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A.5.2 Total carbon. 21
A.5.3 Inorganic carbon . 22
A.6 Accuracy . 22
A.6.1 General . 22
A.6.2 Total carbon. 22
A.6.3 Inorganic carbon . 24
A.7 Linearity of results . 25
A.7.1 Total carbon. 25
A.7.2 Inorganic carbon . 26
A.8 Quantification limit and dosage interval . 27
A.8.1 Total carbon. 27
A.8.2 Inorganic carbon . 27
A.9 Conclusion . 27
Annex B (informative) Measurements on wood species and wood-based materials . 28
Bibliography . 29
3
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EN 16718:2015 (E)
European foreword
This document (EN 16718:2015) has been prepared by Technical Committee CEN/TC 38 “Durability of
wood and wood-based products”, the secretariat of which is held by AFNOR.
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 May 2016, and conflicting national standards shall be
withdrawn at the latest by May 2016.
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.
4
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Introduction
Bio-based products from forestry and agriculture have a long history of application. The last decades
have seen the emergence of new bio-based products in the market. Acknowledging the need for
common standards for bio-based products, the European Commission issued mandate M/492, resulting
in a series of standards developed by CEN/TC 411.
For business to business transactions, claims which are relevant to describe characteristics of bio-based
products in a business to business environment will be given in the near future. Data are by
consequence required to generate and transfer information in the industrial chain and/or as an input
for product specific standards and certification schemes.
The work to be done by the CEN/TC 411/WG 3 concerns the determination of the bio-based carbon in
order to determine the level of bio-based content of a product or materials. A document
(CEN/TR 16721) has been prepared by Technical Committee CEN/TC 411 “Bio-based products”, and
describes a list of methods and an “overview of methods to determine the bio-based content and related
methods” for Bio-based products.
As part of the task force of CEN/TC 175, devoted to carbon foot printing and LCA, a European Standard
was published on the simplified calculation of the amount of biomass carbon stored in wood (using
50 % of the anhydrous wood mass): EN 16449.
This standard EN 16718 describes the methods based on analytical measurements. These methods can
be considered as complementary to the radiocarbon based method and methods based on evaluation by
calculation (mass balance approaches). One of these analytical methods is a method based on
measurement of stable isotopic ratio present in biomass in order to determine the biomass content of
the product.
The development of this method described in this report is ongoing with close collaboration between
FCBA and the “Institute des Sciences Analytiques” CNRS in order to determine the bio-based content of
wood raw materials, glues and panels made with these raw materials for end use manufactured
products with this new method. The objective is to propose correlated analysis (with the TOC method
proposed by FCBA) to determine the carbon content to purpose a quick and low cost method easy to
handle.
References:
— http://www.biobasedeconomy.eu/standardisation/cen-tc411/
— http://www2.afnor.org/espace_normalisation/structure.aspx?commid=86489
The tests that have resulted in the specification of this document were performed in the context of work
conducted by the FCBA [timber certification body] Technological Institute aimed at determining a
method for supplying data on organic carbon contents that could be used to calculate carbon balances.
The storage of biomass carbon in wood-based products is the preservation of the carbon absorbed by
the tree from atmospheric CO through photosynthesis.
2
The carbon thus captured in the material is of benefit to the climate throughout the lifespan of the
product, which can be several dozen years for a construction product, for example. The French Standard
NF P01-010 (2004), which lays out the format of environmental and health statements (FDES) for
construction products, provides the option of indicating the following supplementary information, in
addition to the “Climate change” indicator, which is calculated from the flows of greenhouse gases
associated with the product life cycle: “for some construction products (e.g. plant-based products), CO2
storage during the “service life” stage can be given if measurements are taken based on standardized
test methods.”
5
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Furthermore, the Guide to Best Practices on environmental labelling of mass-market consumer
products (BP X30-323) includes in Annex G: “Carbon accounting integrating time lag” which also
requires knowledge of the biomass carbon contents of the products.
The purpose of this document is therefore to propose a laboratory measurement method of the amount
of biomass carbon that will provide values of carbon or CO equivalent stored in wood-based products,
2
with the aim to integrate this information in the environmental statements of these products according
to the texts referenced above.
While measurement is not systematically necessary for solid wood products, for example, given the
common knowledge on the densities of the various wood species and on the proportion of carbon
contained in wood, this experimental measurement may prove to be necessary for products made of
wood-based composite materials.
The organic carbon contained in wood and wood-based materials is found in several different forms.
Cumulative measurements, such as total organic carbon (TOC), need to be used. Isotopic ratio enables
the differentiation between synthetic and natural products. IRMS (Isotope Ratio Mass Spectrometer) is
13
a complementary method to the TOC method by an identification of the isotope C: both techniques are
necessary to give reliable data on a bio-based content on a wood based material such as panel, board,
and woods containing chemicals in general. A study is currently in progress in France on wood based
materials: the results will enable to improve this present document and to give data with multi-isotopic
13 15 2 18
determinations ( C, N, H, O).
6
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EN 16718:2015 (E)
1 Scope
This European Standard describes a method for determining total organic carbon by calculating the
difference between the results of measurements of total carbon (TC) and total inorganic carbon (TIC).
13
The identification of the bio-based content given by the stable isotopes such as C is described also.
This method is applicable to all wood species, wood-based materials (panels, plywood, wood-polymer,
etc.) and woods containing chemicals in general.
2 Normative references
The following documents, in whole or in part, are normatively referenced in this document and are
indispensable for its application. For dated references, only the edition cited applies. For undated
references, the latest edition of the referenced document (including any amendments) applies.
EN 13183-1, Moisture content of a piece of sawn timber — Part 1: Determination by oven dry method
3 Terms and definitions
For the purposes of this document, the following terms and definitions apply.
3.1
total carbon
TC
amount of carbon found in waste, in organic, inorganic and elemental-state forms
3.2
total inorganic carbon
TIC
amount of carbon released as carbon dioxide through acidification
3.3
total organic carbon
TOC
carbon that is transformed into carbon dioxide through combustion and not released through
acidification as carbon dioxide
Note 1 to entry: The definitions given above are only applicable in this document and only partly overlap the
scientific definitions of TC, TOC and TIC.
4 Principle
In this procedure, TOC is obtained by subtraction between the measurement results of TC and TIC.
The total carbon (TC) present in the undried sample is transformed into carbon dioxide through
combustion in a flow of gas that contains oxygen and is free of carbon dioxide. To ensure combustion is
total, catalysers and/or modifiers can be used. The amount of carbon dioxide released is measured
using infrared spectrometry, gravimetry, coulometry, conductometry, thermal conductivity detection or
flame ionization detection after reduction to methane, or any other appropriate technique.
The TIC is determined separately using another sub-sample, through acidification and purging of the
released carbon dioxide, which is then measured using one of the techniques mentioned above.
13
The C identification by IRMS is described in 7.7. This protocol is able also to work on other isotopes:
15 2 18
N, H and O, which could be useful for complex materials containing wood.
7
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5 Reagents and products
All the reagents used shall be of analytical grade at least and suitable for their specific uses. Hygroscopic
products shall be kept in a dessicator.
5.1 Glucose, C H O .
6 12 6
5.2 Anhydrous sodium carbonate, Na CO .
2 3
5.3 Non-oxidizing mineral acid used to release the carbon dioxide, e.g. phosphoric acid H PO ,
3 4
(m = 85 %).
5.4 Synthetic air, nitrogen, oxygen, argon, free of carbon dioxide and organic impurities,
according to the instructions supplied by the machine manufacturer.
6 Apparatus
6.1 Homogenization device, such as mixers, stirrers.
6.2 Analytical balance accurate to at least 0,5 % of test portion weight.
6.3 Apparatus for dosing carbon in solid matter, along with its accessories.
6.4 Purging device for dosing TIC.
6.5 Mixer mill.
7 Procedure
7.1 Preparation of the sample
Before the sample preparation, the sampling program shall be properly designed in accordance with the
context of the testing and objectives.
The samples to be analysed should be as homogeneous as possible and undried.
The samples of wood or wood-based materials can be directly ground (avoiding any heating) and
reduced to powder, preferably with a particle size below 500 μm. The samples are ground in their
entire thickness.
The samples that contain negligible concentrations (taking into account the accuracy of the method
used) of volatile compounds other than water can be dried at 105 °C before they are homogenized.
7.2 Water content
The determination of moisture content shall be carried out using a different test portion. It can be
calculated from the dry matter mass, determined according to EN 13183-1.
NOTE Any other determination method (e.g. with a desiccator’s balance) can be used if it has been previously
validated.
8
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7.3 Dosage
7.3.1 General
This document does not give any recommendations for the apparatus and its mode of operation. The
operating conditions should be selected and verified according to the instructions supplied by the
manufacturer.
It is advisable to select a test portion with the greatest mass possible, making sure that the amount of
carbon dioxide released is within the apparatus measurement range and the calibration range.
7.3.2 TC dosage
The sample, prepared according to 7.1, is weighed in an appropriate container, i.e. inert and not liable to
interact during the carbon content analysis reaction or to contain carbon in any form whatsoever
(scoop or crucible made of e.g. ceramic, silica glass, platinum or tin). The container can be previously
conditioned by heating (in a muffle furnace or in the analyser itself) to minimize blank carbon values.
The sample is burned or broken down in a carrier gas current that contains oxygen.
The combustion temperature shall be sufficiently high to transform all the carbon into carbon dioxide.
For samples containing carbonates that are difficult to break down, such as barium carbonate, carbon
dioxide release can be improved by increasing the temperature or using modifiers (e.g. tin, copper).
The temperature range of commercially available devices is between 900 °C and 1 500 °C.
During combustion of the reactive samples, any detonation or production of smoke can be avoided by
covering the sample with an inert material (e.g. siliceous sand).
The carbon dioxide released while gas is being discharged is measured using the detection method
described in chapter 4, and expressed as carbon.
7.3.3 TIC dosage
The sample prepared according to 7.1 is weighed in the purging device.
The system is closed so as to be impermeable to gases and purged using the carrier gas until the carbon
dioxide from the ambient air is eliminated. Then, acid is added and the carbon dioxide is carried out
through purging or stirring and/or heating. The carbon dioxide released is transferred to the detector
by means of the carrier gas.
The carbon dioxide released while gas is being discharged is measured using the detection method
described in Clause 4, and expressed as carbon.
7.4 Calibration
If detection is carried out using a relative method, e.g. infrared detection, calibration is necessary.
Glucose is an example of a standard substance that is appropriate for TC dosage.
Sodium carbonate or calcium carbonate can be used for TIC calibration.
Other standard substances can be used, provided their suitability has been verified.
During calibration, the procedure below should be followed:
— set the preliminary measurement range;
— analyse a series of four calibration samples minimum at least twice, at three different times. The
concentration of these master samples shall be regularly distributed over the entire measurement
range;
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— calculate the mean values for each concentration;
— perform a linear regression analysis using the mean values.
This function should be linear. If this is not the case, the measurement range needs to be reduced to the
linear range.
This calibration should not be implemented for initial validation purposes or when major modifications
of the apparatus are carried out.
7.5 Control measurements
Control measurements shall be taken to make sure the apparatus is functioning properly. They should
be taken every working day. It is deemed sufficient to perform the dosage three times from a point
located in the middle of the respective measurement ranges. For TC and TIC, the mean recovery rate
shall be between 90 % and 110 % with a variation coefficient ≤ 5 %.
7.6 Evaluation
The TC and TIC masses contained in the samples prepared according to 7.1 are calculated using:
— The calibration function and the sample mass where relative detection methods are used;
— Specific constants and the sample mass where absolute detection methods are used.
TC and TIC contents are the means of at least two measurements each. The respective differences
between the two values should be less than or equal to 10 % of the mean value. If this is not the case, at
least one other additional dosage needs to be carried out; in such a case, the variation coefficient should
be less than or equal to 10 %. If this is not the case, the coefficient shall be recorded along with the
result obtained.
The TOC content is calculated using the difference between the mean TC and TIC values with the
following formula:
ω ωω− (1)
TOC TC TIC
where
ω is the TOC content in carbon dioxide form in the original sample, in grams per kilogram (g/kg);
TOC
ω is the mean value of the TC content in carbon dioxide form in the sample, in grams per kilogram
TC
(g/kg);
ω is the mean value of the TIC content in carbon dioxide form in the sample, in grams per kilogram
TIC
(g/kg).
The TOC content yielded by Formula (1) is correlated to the dry matter using Formula (2). To do so, the
water content, determined separately, is used:
100
ω =ω (2)
TOCdm TOC
100−w
where
ω is the TOC content in carbon dioxide form, correlated to the dry matter base, in grams per kilogram
TOCdm
(g/kg);
is the TOC content in carbon dioxide form in the original sample, in grams per kilogram (g/kg);
ω
TOC
w is the water content of the original sample, expressed as a mass fraction in percentage (%).
10
=
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The TOC content is generally determined using the undried sample, but it is always recorded as carbon
correlated to dry matter. With Formula (2), the results are obtained in g/kg. They can be converted to
other units by using the app
...
SLOVENSKI STANDARD
kSIST FprEN 16718:2015
01-september-2015
Les in lesni proizvodi - Delež celotnega organskega ogljika (TOC) v lesu in lesnih
proizvodih
Wood and wood based products - Dosage of the total organic carbon (TOC) in wood and
wood based products
Holz und Holzprodukte - Bestimmung des gesamten organischen Kohlenstoffs (TOC) in
Holz und Holzprodukten
Produits de préservation du bois et matériaux à base de bois - Dosage du carbone
organique total (COT) dans les bois et matériaux à base de bois
Ta slovenski standard je istoveten z: FprEN 16718
ICS:
79.040 Les, hlodovina in žagan les Wood, sawlogs and sawn
timber
79.060.01 /HVQHSORãþHQDVSORãQR Wood-based panels in
general
kSIST FprEN 16718:2015 en,fr,de
2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.
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kSIST FprEN 16718:2015
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kSIST FprEN 16718:2015
EUROPEAN STANDARD
FINAL DRAFT
FprEN 16718
NORME EUROPÉENNE
EUROPÄISCHE NORM
June 2015
ICS 79.060.01
English Version
Wood and wood based products - Dosage of the total organic
carbon (TOC) in wood and wood based products
Produits de préservation du bois et matériaux à base de Holz und Holzprodukte - Bestimmung des gesamten
bois - Dosage du carbone organique total (COT) dans les organischen Kohlenstoffs (TOC) in Holz und Holzprodukten
bois et matériaux à base de bois
This draft European Standard is submitted to CEN members for formal vote. It has been drawn up by the Technical Committee CEN/TC 38.
If this draft becomes a European Standard, CEN members are bound to comply with the CEN/CENELEC Internal Regulations which
stipulate the conditions for giving this European Standard the status of a national standard without any alteration.
This draft European Standard was established by CEN in three official versions (English, French, German). A version in any other language
made by translation under the responsibility of a CEN member into its own language and notified to the CEN-CENELEC Management
Centre has the same status as the official versions.
CEN members are the national standards bodies of Austria, Belgium, Bulgaria, Croatia, Cyprus, Czech Republic, Denmark, Estonia,
Finland, Former Yugoslav Republic of Macedonia, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania,
Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland, Turkey and United
Kingdom.
Recipients of this draft are invited to submit, with their comments, notification of any relevant patent rights of which they are aware and to
provide supporting documentation.
Warning : This document is not a European Standard. It is distributed for review and comments. It is subject to change without notice and
shall not be referred to as a European Standard.
EUROPEAN COMMITTEE FOR STANDARDIZATION
COMITÉ EUROPÉEN DE NORMALISATION
EUROPÄISCHES KOMITEE FÜR NORMUNG
CEN-CENELEC Management Centre: Avenue Marnix 17, B-1000 Brussels
© 2015 CEN All rights of exploitation in any form and by any means reserved Ref. No. FprEN 16718:2015 E
worldwide for CEN national Members.
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kSIST FprEN 16718:2015
FprEN 16718:2015 (E)
Contents Page
Foreword .4
Introduction .5
1 Scope .7
2 Normative references .7
3 Terms and definitions .7
4 Principle .7
5 Reagents and products .8
6 Apparatus .8
7 Procedure .8
7.1 Preparation of the sample .8
7.2 Water content .8
7.3 Dosage .9
7.3.1 General .9
7.3.2 TC dosage .9
7.3.3 TIC dosage .9
7.4 Calibration .9
7.5 Control measurements . 10
7.6 Evaluation . 10
13
7.7 C measurement by IRMS (Isotope Ratio Mass Spectrometer) . 11
7.7.1 Material and methods . 11
13
7.7.2 C isotope . 12
18
7.7.3 O isotope . 12
2
7.7.4 H isotope (Deuterium) . 12
15
7.7.5 N Isotopes . 12
13 18 2
7.7.6 Multi-isotopic determinations: C, O and H in wood and tree. 12
8 Performance characteristics . 13
9 Test report . 13
Annex A (informative) Results of the validation method . 14
A.1 General . 14
A.2 Response function. 14
A.2.1 General . 14
A.2.2 Total carbon . 15
A.2.3 Inorganic carbon . 16
A.3 Trueness . 17
A.3.1 General . 17
A.3.2 Total carbon . 18
A.3.3 Inorganic carbon . 18
A.4 Precision . 18
A.4.1 General . 18
A.4.2 Total carbon . 18
A.4.3 Inorganic carbon . 20
A.5 Measurement uncertainty . 21
A.5.1 General . 21
A.5.2 Total carbon . 21
A.5.3 Inorganic carbon . 22
A.6 Accuracy . 22
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A.6.1 General . 22
A.6.2 Total carbon . 22
A.6.3 Inorganic carbon . 24
A.7 Linearity of results . 25
A.7.1 Total carbon . 25
A.7.2 Inorganic carbon . 26
A.8 Quantification limit and dosage interval . 27
A.8.1 Total carbon . 27
A.8.2 Inorganic carbon . 27
A.9 Conclusion . 27
Annex B (informative) Measurements on wood species and wood-based materials . 28
Bibliography . 29
3
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kSIST FprEN 16718:2015
FprEN 16718:2015 (E)
Foreword
This document (FprEN 16718:2015) has been prepared by Technical Committee CEN/TC 38 “Durability of
wood and wood-based products”, the secretariat of which is held by AFNOR.
This document is currently submitted to the Formal Vote.
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Introduction
Bio-based products from forestry and agriculture have a long history of application. The last decades have
seen the emergence of new bio-based products in the market. Acknowledging the need for common
standards for bio-based products, the European Commission issued mandate M/492, resulting in a series of
standards developed by CEN/TC 411.
For business to business transactions, claims which are relevant to describe characteristics of bio-based
products in a business to business environment will be given in the near future. Data are by consequence
required to generate and transfer information in the industrial chain and/or as an input for product specific
standards and certification schemes.
The work to be done by the CEN/TC 411/WG 3 concerns the determination of the bio-based carbon in order
to determine the level of bio-based content of a product or materials. A document (CEN/TR 16721) has been
prepared by Technical Committee CEN/TC 411 “Bio-based products”, and describes a list of methods and an
“overview of methods to determine the bio-based content and related methods” for Bio-based products.
This standard FprEN 16718 describes the methods based on analytical measurements. These methods can
be considered as complementary to the radiocarbon based method and methods based on evaluation by
calculation (mass balance approaches). One of these analytical methods is a method based on measurement
of stable isotopic ratio present in biomass in order to determine the biomass content of the product.
The development of this method described in this report is ongoing with close collaboration between FCBA
and the “Institute des Sciences Analytiques” CNRS in order to determine the bio-based content of wood raw
materials, glues and panels made with these raw materials for end use manufactured products with this new
method. The objective is to propose correlated analysis (with the TOC method proposed by FCBA) to
determine the carbon content to purpose a quick and low cost method easy to handle.
References:
— http://www.biobasedeconomy.eu/standardisation/cen-tc411/
— http://www2.afnor.org/espace_normalisation/structure.aspx?commid=86489
The tests that have resulted in the specification of this document were performed in the context of work
conducted by the FCBA [timber certification body] Technological Institute aimed at determining a method for
supplying data on organic carbon contents that could be used to calculate carbon balances.
The storage of biomass carbon in wood-based products is the preservation of the carbon absorbed by the tree
from atmospheric CO through photosynthesis.
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The carbon thus captured in the material is of benefit to the climate throughout the lifespan of the product,
which can be several dozen years for a construction product, for example. The French Standard NF P01-010
(2004), which lays out the format of environmental and health statements (FDES) for construction products,
provides the option of indicating the following supplementary information, in addition to the “Climate change”
indicator, which is calculated from the flows of greenhouse gases associated with the product life cycle: “for
some construction products (e.g. plant-based products), CO2 storage during the “service life” stage can be
given if measurements are taken based on standardized test methods.”
Furthermore, the Guide to Best Practices on environmental labelling of mass-market consumer products
(BP X30-323) includes in Annex G: “Carbon accounting integrating time lag” which also requires knowledge of
the biomass carbon contents of the products.
As part of the task force of CEN/TC 175, devoted to carbon foot printing and LCA, a European standard was
published on the simplified calculation of the amount of biomass carbon stored in wood (using 50 % of the
anhydrous wood mass): EN 16449.
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The purpose of this document is therefore to propose a laboratory measurement method of the amount of
biomass carbon that will provide values of carbon or CO equivalent stored in wood-based products, with the
2
aim to integrate this information in the environmental statements of these products according to the texts
referenced above.
While measurement is not systematically necessary for solid wood products, for example, given the common
knowledge on the densities of the various wood species and on the proportion of carbon contained in wood,
this experimental measurement may prove to be necessary for products made of wood-based composite
materials.
The organic carbon contained in wood and wood-based materials is found in several different forms.
Cumulative measurements, such as total organic carbon (TOC), need to be used. Isotopic ratio enables the
differentiation between synthetic and natural products. IRMS (Isotope Ratio Mass Spectrometer) is a
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complementary method to the TOC method by an identification of the isotope C: both technics are
necessary to give reliable data on a bio-based content on a wood based material such as panel, board, and
woods containing chemicals in general. A study is currently in progress in France on wood based materials:
the results will enable to improve this present document and to give data with multi-isotopic determinations
13 15 2 18
( C, N, H, O).
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1 Scope
This European Standard describes a method for determining total organic carbon by calculating the difference
between the results of measurements of total carbon (TC) and total inorganic carbon (TIC). The identification
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of the bio-based content given by the stable isotopes such as C is described also.
This method is applicable to all wood species, wood-based materials (panels, plywood, wood-polymer, etc.)
and woods containing chemicals in general.
2 Normative references
The following documents, in whole or in part, are normatively referenced in this document and are
indispensable for its application. For dated references, only the edition cited applies. For undated references,
the latest edition of the referenced document (including any amendments) applies.
EN 13183-1, Moisture content of a piece of sawn timber — Part 1: Determination by oven dry method
3 Terms and definitions
For the purposes of this document, the following terms and definitions apply.
3.1
total carbon
TC
amount of carbon found in waste, in organic, inorganic and elemental-state forms
3.2
total inorganic carbon
TIC
amount of carbon released as carbon dioxide through acidification
3.3
total organic carbon
TOC
carbon that is transformed into carbon dioxide through combustion and not released through acidification as
carbon dioxide
Note 1 to entry: The definitions given above are only applicable in this document and only partly overlap the scientific
definitions of TC, TOC and TIC.
4 Principle
In this procedure, TOC is obtained by subtraction between the measurement results of TC and TIC.
The total carbon (TC) present in the undried sample is transformed into carbon dioxide through combustion in
a flow of gas that contains oxygen and is free of carbon dioxide. To ensure combustion is total, catalysers
and/or modifiers can be used. The amount of carbon dioxide released is measured using infrared
spectrometry, gravimetry, coulometry, conductometry, thermal conductivity detection or flame ionization
detection after reduction to methane, or any other appropriate technique.
The TIC is determined separately using another sub-sample, through acidification and purging of the released
carbon dioxide, which is then measured using one of the techniques mentioned above.
13 15 2
The C identification by IRMS is described in 7.7. This protocol is able also to work on other isotopes: N, H
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and O, which could be useful for complex materials containing wood.
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5 Reagents and products
All the reagents used shall be of analytical grade at least and suitable for their specific uses. Hygroscopic
products shall be kept in a dessicator.
H O .
5.1 Glucose, C
6 12 6
CO .
5.2 Anhydrous sodium carbonate, Na
2 3
PO ,
5.3 Non-oxidizing mineral acid used to release the carbon dioxide, e.g. phosphoric acid H
3 4
(m = 85 %).
5.7 Synthetic air, nitrogen, oxygen, argon, free of carbon dioxide and organic impurities, according
to the instructions supplied by the machine manufacturer.
6 Apparatus
6.1 Homogenization device, such as mixers, stirrers.
6.2 Analytical balance accurate to at least 0,5 % of test portion weight.
6.3 Apparatus for dosing carbon in solid matter, along with its accessories.
6.4 Purging device for dosing TIC.
6.5 Mixer mill.
7 Procedure
7.1 Preparation of the sample
Before the sample preparation, the sampling program shall be properly designed in accordance with the
context of the testing and objectives.
The samples to be analysed should be as homogeneous as possible and undried.
The samples of wood or wood-based materials can be directly ground (avoiding any heating) and reduced to
powder, preferably with a particle size below 500 μm. The samples are ground in their entire thickness.
The samples that contain negligible concentrations (taking into account the accuracy of the method used) of
volatile compounds other than water can be dried at 105 °C before they are homogenized.
7.2 Water content
The determination of moisture content shall be carried out using a different test portion. It can be calculated
from the dry matter mass, determined according to EN 13183-1.
NOTE Any other determination method (e.g. with a desiccator’s balance) can be used if it has been previously
validated.
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7.3 Dosage
7.3.1 General
This document does not give any recommendations for the apparatus and its mode of operation. The
operating conditions should be selected and verified according to the instructions supplied by the
manufacturer.
It is advisable to select a test portion with the greatest mass possible, making sure that the amount of carbon
dioxide released is within the apparatus measurement range and the calibration range.
7.3.2 TC dosage
The sample, prepared according to 7.1, is weighed in an appropriate container, i.e. inert and not liable to
interact during the carbon content analysis reaction or to contain carbon in any form whatsoever (scoop or
crucible made of e.g. ceramic, silica glass, platinum or tin). The container can be previously conditioned by
heating (in a muffle furnace or in the analyser itself) to minimize blank carbon values.
The sample is burned or broken down in a carrier gas current that contains oxygen.
The combustion temperature shall be sufficiently high to transform all the carbon into carbon dioxide. For
samples containing carbonates that are difficult to break down, such as barium carbonate, carbon dioxide
release can be improved by increasing the temperature or using modifiers (e.g. tin, copper).
The temperature range of commercially available devices is between 900 °C and 1 500 °C.
During combustion of the reactive samples, any detonation or production of smoke can be avoided by
covering the sample with an inert material (e.g. siliceous sand).
The carbon dioxide released while gas is being discharged is measured using the detection method described
in chapter 4, and expressed as carbon.
7.3.3 TIC dosage
The sample prepared according to 7.1 is weighed in the purging device.
The system is closed so as to be impermeable to gases and purged using the carrier gas until the carbon
dioxide from the ambient air is eliminated. Then, acid is added and the carbon dioxide is carried out through
purging or stirring and/or heating. The carbon dioxide released is transferred to the detector by means of the
carrier gas.
The carbon dioxide released while gas is being discharged is measured using the detection method described
in Clause 4, and expressed as carbon.
7.4 Calibration
If detection is carried out using a relative method, e.g. infrared detection, calibration is necessary.
Glucose is an example of a standard substance that is appropriate for TC dosage.
Sodium carbonate or calcium carbonate can be used for TIC calibration.
Other standard substances can be used, provided their suitability has been verified.
During calibration, the procedure below should be followed:
— set the preliminary measurement range;
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— analyse a series of four calibration samples minimum at least twice, at three different times. The
concentration of these master samples shall be regularly distributed over the entire measurement range;
— calculate the mean values for each concentration;
— perform a linear regression analysis using the mean values.
This function should be linear. If this is not the case, the measurement range needs to be reduced to the linear
range.
This calibration should not be implemented for initial validation purposes or when major modifications of the
apparatus are carried out.
7.5 Control measurements
Control measurements shall be taken to make sure the apparatus is functioning properly. They should be
taken every working day. It is deemed sufficient to perform the dosage three times from a point located in the
middle of the respective measurement ranges. For TC and TIC, the mean recovery rate shall be
between 90 % and 110 % with a variation coefficient ≤ 5 %.
7.6 Evaluation
The TC and TIC masses contained in the samples prepared according to 7.1 are calculated using:
— The calibration function and the sample mass where relative detection methods are used;
— Specific constants and the sample mass where absolute detection methods are used.
TC and TIC contents are the means of at least two measurements each. The respective differences between
the two values should be less than or equal to 10 % of the mean value. If this is not the case, at least one
other additional dosage needs to be carried out; in such a case, the variation coefficient should be less than or
equal to 10 %. If this is not the case, the coefficient shall be recorded along with the result obtained.
The TOC content is calculated using the difference between the mean TC and TIC values with the following
formula:
ω ωω− (1)
TOC TC TIC
where
ω is the TOC content in carbon dioxide form in the original sample, in grams per kilogram (g/kg);
TOC
ω
is the mean value of the TC content in carbon dioxide form in the sample, in grams per kilogram
TC
(g/kg);
ω
is the mean value of the TIC content in carbon dioxide form in the sample, in grams per kilogram
TIC
(g/kg).
The TOC content yielded by Formula (1) is correlated to the dry matter using Formula (2). To do so, the water
content, determined separately, is used:
100
ω =ω (2)
TOCdm TOC
100− w
where
ω is the TOC content in carbon dioxide form, correlated to the dry matter base, in grams per
TOCdm
10
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kilogram (g/kg);
is the TOC content in carbon dioxide form in the original sample, in grams per kilogram (g/kg);
ω
TOC
w
is the water content of the original sample, expressed as a mass fraction in percentage (%).
The TOC content is generally determined using the undried sample, but it is always recorded as carbon
correlated to dry matter. With Formula (2), the results are obtained in g/kg. They can be converted to other
units by using the appropriate factors.
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7.7 C measurement by IRMS (Isotope Ratio Mass Spectrometer)
7.7.1 Material and methods
Isotopic analyses are performed using an elemental analyser (carbon nitrogen analyser or oxygen hydrogen
analyser) linked to an isotope ratio mass spectrometer (IRMS). At first the samples are mineralized into gas:
carbon and nitrogen are transformed into CO and N by combustion and reduction of nitrogen oxides, and
2 2
hydrogen and oxygen are converted into H and CO by a pyrolysis reaction.
2
The determination of the isotopic ratios is carried out by using the different atomic masses of gas as follows:
— CO : atomic mass 44, 45 and 46;
2
— N : atomic mass 28, 29 and 30;
2
— H : atomic mass 2, 3;
2
— CO: atomic mass 28, 30.
As the isotopic variations are very small, a relative scale (value δ) is used to express the isotopic ratio.
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The isotopic ratios of samples for carbon, nitrogen, hydrogen and oxygen are expressed as values δ C,
15 2 18
δ N, δ H and δ O respectively.
The STD ratio is given by the isotopic ratio of an international reference defi
...
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