Bio-based products- Use of stable isotope ratios of Carbon, Hydrogen, Oxygen and Nitrogen as tools for verification of the origin of bio-based feedstock and characteristics of production processes - Overview of relevant existing applications

The stable isotope ratios of carbon, hydrogen, oxygen and nitrogen can be used to obtain information about the origin of bio-based feedstock and characteristics of production processes of bio-based products. However, no or limited attention for the use of the elements nitrogen and sulphur is given in this document due to the fact that these applications are not yet available.
This Technical Report provides an overview of existing applications of isotope ratio analysis of carbon, hydrogen, oxygen and nitrogen that are relevant to the analysis of bio-based feedstocks, products and production processes

Biobasierte Produkte - Verwendung der Verhältnisse stabiler Isotope von Kohlenstoff, Wasserstoff, Sauerstoff und Stickstoff als Werkzeuge zur Überprüfung der Herkunft von biobasierten Rohstoffen und der Eigenschaften von Produktionsprozessen - Übersicht über relevante bestehende Anwendungen

Produits biosourcés - Utilisation des rapports isotopiques stables du carbone, de l’hydrogène, de l’oxygène et de l’azote comme outils de vérification de l’origine des matières premières biosourcées et des caractéristiques des procédés de production - Vue d’ensemble des applications existantes pertinentes

Bioizdelki - Uporaba stabilnih razmerij izotopov ogljika, vodika, kisika in dušika kot orodij za preverjanje izvora biosurovin in karakteristik proizvodnih procesov - Pregled ustrezne obstoječe uporabe

General Information

Status
Published
Public Enquiry End Date
16-Jun-2021
Publication Date
16-Aug-2021
Technical Committee
Current Stage
6060 - National Implementation/Publication (Adopted Project)
Start Date
05-Aug-2021
Due Date
10-Oct-2021
Completion Date
17-Aug-2021

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SLOVENSKI STANDARD
SIST-TP CEN/TR 17674:2021
01-oktober-2021

Bioizdelki - Uporaba stabilnih razmerij izotopov ogljika, vodika, kisika in dušika kot

orodij za preverjanje izvora biosurovin in karakteristik proizvodnih procesov -
Pregled ustrezne obstoječe uporabe
Bio-based products- Use of stable isotope ratios of Carbon, Hydrogen, Oxygen and

Nitrogen as tools for verification of the origin of bio-based feedstock and characteristics

of production processes - Overview of relevant existing applications

Biobasierte Produkte - Verwendung der Verhältnisse stabiler Isotope von Kohlenstoff,

Wasserstoff, Sauerstoff und Stickstoff als Werkzeuge zur Überprüfung der Herkunft von

biobasierten Rohstoffen und der Eigenschaften von Produktionsprozessen - Übersicht

über relevante bestehende Anwendungen

Produits biosourcés - Utilisation des rapports isotopiques stables du carbone, de

l’hydrogène, de l’oxygène et de l’azote comme outils de vérification de l’origine des

matières premières biosourcées et des caractéristiques des procédés de production -

Vue d’ensemble des applications existantes pertinentes
Ta slovenski standard je istoveten z: CEN/TR 17674:2021
ICS:
13.020.55 Biološki izdelki Biobased products
SIST-TP CEN/TR 17674:2021 en,fr,de

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

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SIST-TP CEN/TR 17674:2021
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SIST-TP CEN/TR 17674:2021
CEN/TR 17674
TECHNICAL REPORT
RAPPORT TECHNIQUE
July 2021
TECHNISCHER BERICHT
ICS 71.040.40; 13.020.55
English Version
Bio-based products- Use of stable isotope ratios of Carbon,
Hydrogen, Oxygen and Nitrogen as tools for verification of
the origin of bio-based feedstock and characteristics of
production processes - Overview of relevant existing
applications

Produits biosourcés - Utilisation des rapports Biobasierte Produkte - Verwendung der Verhältnisse

isotopiques stables du carbone, de l'hydrogène, de stabiler Isotope von Kohlenstoff, Wasserstoff,

l'oxygène et de l'azote comme outils de vérification de Sauerstoff und Stickstoff als Werkzeuge zur

l'origine des matières premières biosourcées et des Überprüfung der Herkunft von biobasierten Rohstoffen

caractéristiques des procédés de production - Vue und der Eigenschaften von Produktionsprozessen -

d'ensemble des applications existantes pertinentes Übersicht über relevante bestehende Anwendungen

This Technical Report was approved by CEN on 18 July 2021. It has been drawn up by the Technical Committee CEN/TC 411.

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, Republic of North Macedonia, Romania, Serbia, 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: Rue de la Science 23, B-1040 Brussels

© 2021 CEN All rights of exploitation in any form and by any means reserved Ref. No. CEN/TR 17674:2021 E

worldwide for CEN national Members.
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Contents Page

European foreword ....................................................................................................................................................... 3

Introduction .................................................................................................................................................................... 4

1 Scope .................................................................................................................................................................... 5

2 Normative references .................................................................................................................................... 5

3 Terms and definitions ................................................................................................................................... 5

4 Direct isotopic measurements ................................................................................................................... 5

5 Assessment of the authenticity of natural products ........................................................................... 6

6 Overview of feedstock isotopic fingerprint ........................................................................................... 8

6.1 C4 plant ............................................................................................................................................................... 8

6.2 Other raw materials: C3 plants .................................................................................................................. 9

7 Determination of Biobased content for feedstocks and products .............................................. 10

7.1 Bioplastics ....................................................................................................................................................... 10

7.2 Bio-rubbers .................................................................................................................................................... 13

7.3 Biofuels – Bio-solvents ............................................................................................................................... 14

7.4 Biosurfactants ............................................................................................................................................... 15

7.5 Other bio products ....................................................................................................................................... 18

7.5.1 Biocosmetics .................................................................................................................................................. 18

7.5.2 Bio-Flavours-Foods ..................................................................................................................................... 20

7.5.3 Bio-pesticides ................................................................................................................................................ 21

8 Monitoring industrial process approach ............................................................................................. 22

8.1 General ............................................................................................................................................................. 22

8.2 Synthesis of Isosorbide .............................................................................................................................. 22

8.3 Synthesis of a specific plastic ................................................................................................................... 23

9 Supplementary benefits ............................................................................................................................. 25

9.1 Technical impacts ........................................................................................................................................ 25

9.1.1 Bulk Stable Isotope Analysis .................................................................................................................... 25

9.1.2 Compound Specific Isotope Analysis ..................................................................................................... 26

9.1.3 Approach multi methods ........................................................................................................................... 27

9.2 Sustainability criteria ................................................................................................................................. 28

9.2.1 General ............................................................................................................................................................. 28

9.2.2 Agricultural and social impacts .............................................................................................................. 28

9.2.3 Cosmetic issue ............................................................................................................................................... 28

9.2.4 Religious impact ........................................................................................................................................... 28

Bibliography ................................................................................................................................................................. 29

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European foreword

This document (CEN/TR 17674:2021) has been prepared by Technical Committee CEN/TC 411 “Bio-

based products”, the secretariat of which is held by NEN.

Attention is drawn to the possibility that some of the elements of this document may be the subject of

patent rights. CEN shall not be held responsible for identifying any or all such patent rights.

Any feedback and questions on this document should be directed to the users’ national standards body.

A complete listing of these bodies can be found on the CEN website.
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Introduction

Part of OPEN BIO Deliverable N°3.8 is used as starting point for the description given in this document.

Bio-based products from forestry and agriculture have a long history of application, such as paper, board

and various chemicals and materials. Over the last decades new bio-based products have emerged in the

market. Some of the reasons for the increased interest lie in the bio-based products’ benefits in relation

to the depletion of fossil resources and climate change. Bio-based products may also provide additional

product functionalities. This has triggered a wave of innovation with the development of knowledge and

technologies allowing new transformation processes and product development.

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, with a focus on bio-based

products other than food, feed and biomass for energy applications.

The standards of CEN/TC 411 “Bio-based products” provide a common basis on the following aspects:

— Common terminology
— Bio-based content determination
— Life Cycle Assessment (LCA)
— Sustainability aspects
— Declaration tools

It is important to understand what the term bio-based product covers and how it is being used. The term

‘bio-based’ means 'derived from biomass'. Bio-based products (bottles, insulation materials, wood and

wood products, paper solvents, chemical intermediates, composite materials, etc.) are products which

are wholly or partly derived from biomass. It is essential to characterize the amount of biomass contained

in the product by, for instance, its bio-based content or bio-based carbon content.

The bio-based content of a product does not provide information on its environmental impact or

sustainability, which may be assessed through LCA and sustainability criteria. In addition, transparent

and unambiguous communication within bio-based value chains is facilitated by a harmonized

framework for certification and declaration.

This document has been developed with the aim to specify the method for the determination of oxygen

content in bio-based products using an elemental analyser. This document provides the reference test

methods for laboratories, producers, suppliers and purchasers of bio-based product materials and

products. It may be also useful for authorities and inspection organizations.

Part of the research leading to this document has been performed under the European Union Seventh

Framework Programme OpenBio (see biobasedeconomy.eu)

) A mandate is a standardization task embedded in European trade laws. Mandate M/492 is addressed to the

European Standardization bodies, CEN, CENELEC and ETSI, for the development of horizontal European Standards

for bio-based products.
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1 Scope

This document provides an overview of existing applications of isotope ratio analysis of carbon,

hydrogen, oxygen and nitrogen that are relevant to the analysis of bio-based feedstocks, products and

production processes.

The stable isotope ratios of carbon, hydrogen, oxygen and nitrogen can be used to obtain information

about the origin of bio-based feedstock and characteristics of production processes of bio-based

products. However, no or limited attention for the use of the elements nitrogen and sulphur is given in

this document due to the fact that these applications are not yet available.
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 16575:2014, Bio-based products - Vocabulary
3 Terms and definitions

For the purposes of this document, the terms and definitions given in EN 16575:2014 apply

4 Direct isotopic measurements

As described previously in Direct Automation OPEN BIO Deliverable N°3.7, isotopic measurements are

performed using an Isotope Ratio Mass Spectrometer (IRMS). In order to test various samples (solids,

liquids), automatic elemental analysers (EA)are connected to isotope ratio mass spectrometer for whole

sample material for Bulk Stable Isotope Analysis (BSIA). This methodology is easy to operate, carries out

fast analyses (few minutes), and has relative low cost enabling multi isotopic determinations. EA-IRMS is

very suitable for regular authenticity controls of pure raw materials. Usually isotopic instruments are

able to give the isotopic values of all organic elements contained in the samples.

Isotopic ratio mass spectrometer can also be connected to chromatography devices (separate methods)

combustion or pyrolysis interface for Compound Specific Isotope Analysis (CSIA).Two different processes

are available(GC-C/P-IRMS or LC-co-IRMS) depending on the molecules to be investigated. This approach

is extremely appropriate for regular authenticity control of natural mixture samples (flavour, honey, fruit

juice, essential oils…) and is well used in this scheme.

Isotopic composition is reported in Delta notation (δ) (in this case the isotopic composition of carbon is

used as an example, other isotopes can be easily replaced in the formula):
13 12
 
R (/C C )sample
13 12
δ( CC/ ) −1 *1 000
 
13 12
R (/C C )standard
 

The uncertainty of measurements carried out on modern devices in continuous flow isotope analysis is

good and enough to make difference on the difference origins of targeted compounds.

The uncertainties for BSIA are close to these values (in delta notation) depending on the supplier:

δ13C: ± 0,3 ‰ / δ15N: ± 0,3 ‰ / δ2H: ± 5 ‰ / δ18O: ± 1‰.

Performances and precision of the different devices must be verified using references standards.

International reference standards are supplied by different organisations (International Agency of

Atomic Energy, National Bureau of Standards...) and validated by inter-comparison assessments.

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5 Assessment of the authenticity of natural products

During the last decades the measurement of isotope ratios has acquired increasing importance in quality

control, in the authenticity assessment of natural flavours, proof of authenticity of various food products.

Although chemical methods can be used to detect contamination they are limited when looking at the

geographical origin or to bring proof of authenticity. A high precision was developed for methods used to

detect adulteration of natural products and particularly the addition of synthesis molecules. Methods

13 12

based on the determination of C/ C ratios were first applied on molecules previously isolated and

measured on offline combustion instruments.

The carbon isotopic composition of plants depends on the carbon dioxide assimilation and the fixation of

carbon. Plants can be divided in three classes according to their metabolism assimilation. For most of the

plants (so called C3 plants) the first intermediary molecule elaborated is the phosphoglycerate (molecule

with 3 carbons atoms) and δ C generally range from −20 ‰ to −33 ‰. For the second class (C4 plants)

the first intermediate molecule is a malate (molecule with 4 carbons) and δ C are generally in the range

from −10 ‰ to −12 ‰ .Two plants are mainly representatives in this class: corn and sugar cane. Finally

the third class concern plants which can process with the 2 pathway phosphoglycerate and malate (CAM

plant) and the δ C ranges from −10 ‰ to −24 ‰. In this last category we can find vanilla and pineapple.

Among food flavours, vanilla has been probably the most investigated. Vanillin is the principal flavouring

constituent of vanilla beans an orchid which operates according to the CAM pathway. δ C of vanillin

origin beans is close to −20 ‰ where the δ C of synthesized vanillin are close to −28 ‰ when derived

from wood lignin (C3 plant) and −29 ‰ when derived from guaiacol (J., 1982).

The development of a reference method about the detection of C4 plant sugars in honey by Jonathan

White was a significant progress in the struggle of adulteration (WhiteJ.W., 1992). The methodology

13 13

C of protein extracted from honey and used as internal standard with δ C of honey. A

compares δ

difference in excess of 1 permil in δ C evidences the presence of C4 additional sugar.

In 1990, the involvement of online coupling of high resolution gas chromatography (HRGC) with IRMS

through combustion interface (HRGC-C-IRMS) has provided access to the analysis of individual

constituents of complex flavouring products by meolecules. This work is important and must be

continued to ensure a steady evaluation of the database collected for authenticity validation.

Some isotopic methods have been also recognized as international methods. The list in Table 1 gives some

examples of the official methods elaborated in the naturalness authenticity assessment.

Table 1 — Examples of official methods using stable isotope ratios
Organization Method reference Title
Fruit and vegetables juices - Determination of the stable
carbon isotope ratio (13C/12C) of sugars from fruit juices-
CEN ENV 12140 method using isotope ratio mass spectrometry
Method for determination of stable oxygen isotope ratio
(18O/16O) of water from fruit juices, using isotope ratio mass
CEN ENV 12141 spectrometry
Method for determination of stable hydrogen isotope ratio
(2H/1H) of water from fruit juices, using isotope ratio mass
CEN ENV 12142 spectrometry
AOAC Method 998.12 Detection of C-4 Plant Sugars in Honey by 13C/12C analysis
Methods 981.09 and Detection of addition of beet sugars in fruit juices (13C/12C
AOAC 982.21 analysis)
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Organization Method reference Title
Carbon isotope ratio mass spectrometric method for
AOAC Method 984.23 detection of corn syrup and cane sugar in maple syrup
Determination of sugar beet derived syrups in frozen
AOAC Method 992.09 concentrated orange juice- δ18O measurements in water
Carbon stable isotope ratio of ethanol derived from fruit
AOAC Method 2004.01 juices and maple syrups
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Organization Method reference Title
Determination by isotope ratio mass spectrometry of
Resolution 13C/12C of wine ethanol or that obtained through the
OIV OENO/7/2001 fermentation of musts, concentrated must or grape sugar
Determination of the carbon isotope ratio 13C/12C of CO in
Resolution sparkling wines method using isotope ratio mass
OIV OENO/7/2005 spectrometry (IRMS)
Association of analytical communities
International Organization of vine and wine

Isotopic analysis used for the assessment of natural product are undertaken to validate (or not) the

authenticity of the target samples. In the field of biobased product, a compound could be biobased, non-

biobased or partly biobased with a known level of biobased content. If the isotopic methodology would

be used as an accepted method, it could bring this assessment of the biobased content with the higher

acceptable uncertainty.
6 Overview of feedstock isotopic fingerprint
6.1 C4 plant

Sugar cane and maize have a specific isotopic C fingerprint due to their belonging to the C4

photosynthesis pathway cycle and are among the major feedstock employed.
Sugar cane

Rodushkin et al. (Rodushkin I., 2011) present the results of an inter-laboratory program based on the

multi elements and isotopic measurements of several sugar samples with different geographical origins:

USA, Costa Rica, Argentina and Swaziland. The results obtained on these cane sugar samples were:

δ C Values range from −10,5 to −12,6 ‰ .
δ C Average −11,70 ‰ SD 0,52 ‰
Two samples have been analysed (see Table 2).
Table 2 - measurement of sugar cane samples from various geographical origins
13 2 18
references plant origin δ C (‰) δ H (‰) δ O (‰)
sugar cane Paraguay −11.71 −3 35
Reunion Island −11.66 11 37
Corn

Several samples of starch have been analysed. They originate from the fields of production feeding the

biobased industry factories (Table 3).
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CEN/TR 17674:2021 (E)
Table 3 - Measurements of corn samples from various geographical origins
13 2 18
references plant origin δ C (‰) δ H (‰) δ O
(‰)
starch corn China −11.66 −28 30
France −11.44 −16 32
Italia −11.81 −19 32
Spain −11.49 −21 32
France −11.42 −2.5 33
Brazil −10.72 −21 29
Brazil −11.02 −25 29
USA −10.82 −17 29
Turkey −11.51 −22 31
δ C Values range from −11,81 to −10,72 ‰ .
δ C Average −11,34 ‰ SD 0,35 ‰

δ C measured on C4 plant origin sample were in good agreement with data published.

6.2 Other raw materials: C3 plants

Rodushkin et al. have reported the results of an inter-laboratory program based on the multi elements

and isotopic measurements of several sugar samples with different geographical origins: Moldavia,

Poland, France, Netherlands, Germany, Hungary and USA. The results obtained on various cane sugar

samples were:
δ C Values range from −23,8 to −26,5 ‰ .
δ C Average −24,98 ‰ SD 0,75 ‰

Starch which is a significant raw-material could be originated from various origins. Table 4 presents the

δ C of starch samples from C3 plants.
Table 4 - Measurements of starches from various origins
13 2 18
references plant origin δ C (‰) δ H (‰) δ O (‰)
wheat France −26.91 −47 31
Corby −27.00 −43 32
France −27.21 −43 32
pea France −27.38 −40.5 33
potatoes Denmark −28.44 −102 27
France −26.51 −79 35
tapioca Brazil −26.11 −82 29
13 18

δ C measured of C3 starch samples range from −26 to −28 ‰. δ O obtained on C3 and C4 starch plant

origins seem to be in the same isotopic area.
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7 Determination of Biobased content for feedstocks and products
7.1 Bioplastics

Current plastics products are composed of biobased synthetic polymers, fossil-based synthetic polymers,

natural polymers and additives that can include biobased materials. “Biobased plastic” refers to plastic

that contains materials wholly or partly of biogenic origin (Plastics - Biobased Content Part 5: declaration

of biobased carbon content, biobased synthetic polymer content and biobased mass content).

Polyethylene Terephthalate (PET)

In 2009 the Coca-Cola Company presented their Plant Bottle® PET packaging innovation made from up

to 30 % biobased, sugar cane renewable materials. The new product encompasses a part of MEG (mono

ethylene glycol) biobased origin in the PET final product.

In response, the Coca-Cola Analytical Science Team has developed a novel patent (pending) using an

analytical method to quantify the amount of biobased material in Plant Bottle® PET resin. This new

approach has shown good reproducibility and accuracy, with excellent correlation to the conventional

ASTM 6866 method using radiocarbon analysis. The new method is performed using an elemental

analyser TOC (total organic carbon) connected to a cavity ring-down spectroscopy (CRDS) detector (TOC-

CRDS). This equipment allows the determination of the delta C value from a sample after combustion.

13 14

The correlation between the delta C values and the C measurements connected to the biobased carbon

content were in good accordance allowing the C method to be an efficient alternative method in this

particular industrial process. Rapidity and relatively inexpensive test are also significant advantages of

the alternative stable isotopic approach (Brevet n° WO 2012/174104 Al, 2012).

Suzuki et al. presented the ability of δ C method to discriminate between plant and petroleum derived

plastics (Suzuki Y., 2010). The δ C values of the plastics investigated range from −17,3 ‰ to −10,0 ‰

for corn derived plastics PLA (Poly-Lactic acid), from −28,6 ‰ to −25,8 ‰ for sugar cane-derived plastics

PE (polyethylene) from −28,6 ‰ to −25,8 ‰ for rice-derived plastics PLA and from −32,1 ‰ to −25,4

‰ for petroleum derived plastics PE. The δ C results obtained suggest that plastics derived from C4

plants are clearly significant higher than the fossil origins.

In addition, several PET mineral water bottles have been collected from the French market for a multi-

isotopic approach. PET is made by an esterification reaction between terephthalic acid and ethylene

glycol. Only ethylene glycol was biobased since it was made from cane sugar. The plastic elaborated has

31 % of biobased content, and if recycled PET is added (35 %), this biobased content part decreases to

20 %.

Sample preparation has been directly carried out by cutting out small parts of the plastic bottles.

Determination was done according to EA-IRMS method.
The results in Table 5 present different types of origins of the samples:

— Sample M1 and M2 called “green bottle” are partly biobased and the % of biobased content is the

statement given by the manufacturer.
— Samples from M3 to M6 are fossil originated bottles
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Table 5 - Measurements of PET mineral water bottles
2 18
References % Biobased δ C (‰) δ H (‰) δ O (‰)
Sugar cane 100 −11,7
M1 30 −23,83 −89 9,6
M1 30 −23,54 −90 9,1
M2 20 −24,96 −99 8,7
M2 20 −25,00 −101 8,5
M3 0 −27,63 −70 21,6
M3 0 −27,79 −68 21,9
M4 0 −28,73 −58 12,9
M4 0 −28,69 −55 13,8
M5 0 −28,06 −80 21,1
M5 0 −27,86 −70 21,1
M6 0 −28,93 −56 15,5
M6 0 −28,91 −50 15,2
Figure 1 — Representation of δ C vs % biobased content on PET plastic samples

A linear regression between δ C and biobased content % (Figure 1) is clearly shown, allowing a

measurement with an uncertainty lower than 5 %. these results indicate the ability to use the regression

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line to obtain biobased content values from δ C analyses. These results are in good agreement with

previous data provided by Coca Cola Company about the biobased sugar cane PET bottles.

Yellow data points correspond to synthetic origin plastic whereas blue and pink data points are the

representation of 30 % and 20 % Biobased plastics, respectively.
2 18

Figure 2 — Representation of δ H vs δ O for PET Biobased and non-bio-based plastic samples.

These results (Figure 2) emphasize that multi isotope methodology could be discriminant for the

assessment of Biobased content regarding PET biobased sugar cane plastics. The figure presents 2 groups

of synthetic components.

But PET bio-plastic is currently withdrawn from the drinking water commercial market and no more

investigation could be performed on this type of plastic.

It must be realized that this method only works with biobased plastic originating from C4 plants. When

biobased plastic originating from C3 plants are used, the amount of biobased percentage is

underestimated. Until now the correlation between this method and the original biobased content is very

good, but one should be aware of this limitation.
Polyethylene furanoate (PEF)

Another plastic elaborated from sugar and interesting for it physical property is PEF (Poly-Ethylene

Furanoate). The results of isotopic measurements are given in Table 6.
Table 6 — Measurements of a sugar cane PEF sample
13 2 18
composition Biobased δ C (‰) δ H δ O
(‰) (‰)
PEF sample 100 −11,57 −114 12

In this case δ C of the PEF sample analysed is clearly in good correlation with the footprint of C4 plant.

But if PEF was made from sugar either beet or cane,
...

SLOVENSKI STANDARD
kSIST-TP FprCEN/TR 17674:2021
01-junij-2021

Bioizdelki - Uporaba stabilnih razmerij izotopov ogljika, vodika, kisika in dušika kot

orodij za preverjanje izvora biosurovin in karakteristik proizvodnih procesov -
Pregled ustrezne obstoječe uporabe
Bio-based products- Use of stable isotope ratios of Carbon, Hydrogen, Oxygen and

Nitrogen as tools for verification of the origin of bio-based feedstock and characteristics

of production processes - overview of relevant existing applications

Biobasierte Produkte - Verwendung der Verhältnisse stabiler Isotope von Kohlenstoff,

Wasserstoff, Sauerstoff und Stickstoff als Werkzeuge zur Überprüfung der Herkunft von

biobasierten Rohstoffen und der Eigenschaften von Produktionsprozessen - Übersicht

über relevante bestehende Anwendungen

Produits biosourcés - Utilisation des rapports isotopiques stables du carbone, de

l’hydrogène, de l’oxygène et de l’azote comme outils de vérification de l’origine des

matières premières biosourcées et des caractéristiques des procédés de production -

Vue d’ensemble des applications existantes pertinentes
Ta slovenski standard je istoveten z: FprCEN/TR 17674
ICS:
13.020.55 Biološki izdelki Biobased products
kSIST-TP FprCEN/TR 17674:2021 en,fr,de

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

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kSIST-TP FprCEN/TR 17674:2021
FINAL DRAFT
TECHNICAL REPORT
FprCEN/TR 17674
RAPPORT TECHNIQUE
TECHNISCHER BERICHT
March 2021
ICS
English Version
Bio-based products- Use of stable isotope ratios of Carbon,
Hydrogen, Oxygen and Nitrogen as tools for verification of
the origin of bio-based feedstock and characteristics of
production processes - overview of relevant existing
applications

Produits biosourcés - Utilisation des rapports Biobasierte Produkte - Verwendung der Verhältnisse

isotopiques stables du carbone, de l'hydrogène, de stabiler Isotope von Kohlenstoff, Wasserstoff,

l'oxygène et de l'azote comme outils de vérification de Sauerstoff und Stickstoff als Werkzeuge zur

l'origine des matières premières biosourcées et des Überprüfung der Herkunft von biobasierten Rohstoffen

caractéristiques des procédés de production - Vue und der Eigenschaften von Produktionsprozessen -

d'ensemble des applications existantes pertinentes Übersicht über relevante bestehende Anwendungen

This draft Technical Report is submitted to CEN members for Vote. It has been drawn up by the Technical Committee CEN/TC

411.

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, Republic of North Macedonia, Romania, Serbia, 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 Technical Report. It is distributed for review and comments. It is subject to change without

notice and shall not be referred to as a Technical Report.
EUROPEAN COMMITTEE FOR STANDARDIZATION
COMITÉ EUROPÉEN DE NORMALISATION
EUROPÄISCHES KOMITEE FÜR NORMUNG
CEN-CENELEC Management Centre: Rue de la Science 23, B-1040 Brussels

© 2021 CEN All rights of exploitation in any form and by any means reserved Ref. No. FprCEN/TR 17674:2021 E

worldwide for CEN national Members.
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Contents Page

European foreword ....................................................................................................................................................... 3

Introduction .................................................................................................................................................................... 4

1 Scope .................................................................................................................................................................... 5

2 Normative references .................................................................................................................................... 5

3 Terms and definitions ................................................................................................................................... 5

4 Direct isotopic measurements ................................................................................................................... 5

5 Assessment of the authenticity of natural products ........................................................................... 6

6 Overview of feedstock isotopic fingerprint ........................................................................................... 8

6.1 C4 plant ............................................................................................................................................................... 8

6.2 Other raw materials: C3 plants .................................................................................................................. 9

7 Determination of Biobased content for feedstocks and products .............................................. 10

7.1 Bioplastics ....................................................................................................................................................... 10

7.2 Bio-rubbers .................................................................................................................................................... 13

7.3 Biofuels – Bio-solvents ............................................................................................................................... 14

7.4 Biosurfactants ............................................................................................................................................... 15

7.5 Other bio products ....................................................................................................................................... 18

7.5.1 Biocosmetics .................................................................................................................................................. 18

7.5.2 Bio-Flavours-Foods ..................................................................................................................................... 21

7.5.3 Bio-pesticides ................................................................................................................................................ 21

8 Monitoring industrial process approach ............................................................................................. 22

8.1 General ............................................................................................................................................................. 22

8.2 Synthesis of Isosorbide .............................................................................................................................. 22

8.3 Synthesis of a specific plastic ................................................................................................................... 23

9 Supplementary benefits ............................................................................................................................. 25

9.1 Technical impacts ........................................................................................................................................ 25

9.1.1 Bulk Stable Isotope Analysis .................................................................................................................... 25

9.1.2 Compound Specific Isotope Analysis ..................................................................................................... 25

9.1.3 Approach multi methods ........................................................................................................................... 26

9.2 Sustainability criteria ................................................................................................................................. 27

9.2.1 General ............................................................................................................................................................. 27

9.2.2 Agricultural and social impacts .............................................................................................................. 27

9.2.3 Cosmetic issue ............................................................................................................................................... 27

9.2.4 Religious impact ........................................................................................................................................... 27

Bibliography ................................................................................................................................................................. 28

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European foreword

This document (FprCEN/TR 17674:2021) has been prepared by Technical Committee CEN/TC 411 “Bio-

based products”, the secretariat of which is held by NEN.
This document is currently submitted to the Vote on TR.
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Introduction

Part of OPEN BIO Deliverable N°3.8 is used as starting point for the description given in this document.

Bio-based products from forestry and agriculture have a long history of application, such as paper, board

and various chemicals and materials. Over the last decades new bio-based products have emerged in the

market. Some of the reasons for the increased interest lie in the bio-based products’ benefits in relation

to the depletion of fossil resources and climate change. Bio-based products may also provide additional

product functionalities. This has triggered a wave of innovation with the development of knowledge and

technologies allowing new transformation processes and product development.

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, with a focus on bio-based

products other than food, feed and biomass for energy applications.

The standards of CEN/TC 411 “Bio-based products” provide a common basis on the following aspects:

— Common terminology
— Bio-based content determination
— Life Cycle Assessment (LCA)
— Sustainability aspects
— Declaration tools

It is important to understand what the term bio-based product covers and how it is being used. The term

‘bio-based’ means 'derived from biomass'. Bio-based products (bottles, insulation materials, wood and

wood products, paper solvents, chemical intermediates, composite materials, etc.) are products which

are wholly or partly derived from biomass. It is essential to characterize the amount of biomass contained

in the product by, for instance, its bio-based content or bio-based carbon content.

The bio-based content of a product does not provide information on its environmental impact or

sustainability, which may be assessed through LCA and sustainability criteria. In addition, transparent

and unambiguous communication within bio-based value chains is facilitated by a harmonized

framework for certification and declaration.

This European Standard has been developed with the aim to specify the method for the determination of

oxygen content in bio-based products using an elemental analyser. This European Standard provides the

reference test methods for laboratories, producers, suppliers and purchasers of bio-based product

materials and products. It may be also useful for authorities and inspection organizations.

Part of the research leading to this document has been performed under the European Union Seventh

Framework Programme OpenBio (see biobasedeconomy.eu)

) A mandate is a standardization task embedded in European trade laws. Mandate M/492 is addressed to the

European Standardization bodies, CEN, CENELEC and ETSI, for the development of horizontal European Standards

for bio-based products.
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1 Scope

This document provides an overview of existing applications of isotope ratio analysis of carbon,

hydrogen, oxygen and nitrogen that are relevant to the analysis of bio-based feedstocks, products and

production processes.

The stable isotope ratios of carbon, hydrogen, oxygen and nitrogen can be used to obtain information

about the origin of bio-based feedstock and characteristics of production processes of bio-based

products. However, no or limited attention for the use of the elements nitrogen and sulphur is given in

this document due to the fact that these applications are not yet available.
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 16575:2014, Bio-based products - Vocabulary
3 Terms and definitions

For the purposes of this document, the terms and definitions given in EN 16575:2014 apply.

4 Direct isotopic measurements

As described previously in Direct Automation OPEN BIO Deliverable N°3.7, isotopic measurements are

performed using an Isotope Ratio Mass Spectrometer (IRMS). In order to test various samples (solids,

liquids), automatic elemental analysers (EA)are connected to isotope ratio mass spectrometer for whole

sample material for Bulk Stable Isotope Analysis (BSIA). This methodology is easy to operate, carries out

fast analyses (few minutes), and has relative low cost enabling multi isotopic determinations. EA-IRMS is

very suitable for regular authenticity controls of pure raw materials. Usually isotopic instruments are

able to give the isotopic values of all organic elements contained in the samples.

Isotopic ratio mass spectrometer can also be connected to chromatography devices (separate methods)

combustion or pyrolysis interface for Compound Specific Isotope Analysis (CSIA).Two different processes

are available(GC-C/P-IRMS or LC-co-IRMS) depending on the molecules to be investigated. This approach

is extremely appropriate for regular authenticity control of natural mixture samples (flavour, honey, fruit

juice, essential oils…) and is well used in this scheme.

Isotopic composition is reported in Delta notation (δ) (in this case the isotopic composition of carbon is

used as an example, other isotopes can be easily replaced in the formula):
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 
R (/C C )sample
13 12
δ( CC/ ) −1 *1 000
 
13 12
R (/C C )standard
 

The uncertainty of measurements carried out on modern devices in continuous flow isotope analysis is

good and enough to make difference on the difference origins of targeted compounds.

The uncertainties for BSIA are close to these values (in delta notation) depending on the supplier:

δ13C: ± 0.3 ‰ / δ15N: ± 0.3 ‰ / δ2H: ± 5 ‰ / δ18O: ± 1‰.

Performances and precision of the different devices must be verified using references standards.

International reference standards are supplied by different organisations (International Agency of

Atomic Energy, National Bureau of Standards...) and validated by inter-comparison assessments.

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5 Assessment of the authenticity of natural products

During the last decades the measurement of isotope ratios has acquired increasing importance in quality

control, in the authenticity assessment of natural flavours, proof of authenticity of various food products.

Although chemical methods can be used to detect contamination they are limited when looking at the

geographical origin or to bring proof of authenticity. A high precision was developed for methods used to

detect adulteration of natural products and particularly the addition of synthesis molecules. Methods

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based on the determination of C/ C ratios were first applied on molecules previously isolated and

measured on offline combustion instruments.

The carbon isotopic composition of plants depends on the carbon dioxide assimilation and the fixation of

carbon. Plants can be divided in three classes according to their metabolism assimilation. For most of the

plants (so called C3 plants) the first intermediary molecule elaborated is the phosphoglycerate (molecule

with 3 carbons atoms) and δ C generally range from −20 ‰ to −33 ‰. For the second class (C4 plants)

the first intermediate molecule is a malate (molecule with 4 carbons) and δ C are generally in the range

from −10 ‰ to −12 ‰ .Two plants are mainly representatives in this class: corn and sugar cane. Finally

the third class concern plants which can process with the 2 pathway phosphoglycerate and malate (CAM

plant) and the δ C ranges from −10 ‰ to −24 ‰. In this last category we can find vanilla and pineapple.

Among food flavours, vanilla has been probably the most investigated. Vanillin is the principal flavouring

constituent of vanilla beans an orchid which operates according to the CAM pathway. δ C of vanillin

origin beans is close to −20 ‰ where the δ C of synthesized vanillin are close to −28 ‰ when derived

from wood lignin (C3 plant) and −29 ‰ when derived from guaiacol (J., 1982).

The development of a reference method about the detection of C4 plant sugars in honey by Jonathan

White was a significant progress in the struggle of adulteration (WhiteJ.W., 1992). The methodology

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C of protein extracted from honey and used as internal standard with δ C of honey. A

compares δ

difference in excess of 1 permil in δ C evidences the presence of C4 additional sugar.

In 1990, the involvement of online coupling of high resolution gas chromatography (HRGC) with IRMS

through combustion interface (HRGC-C-IRMS) has provided access to the analysis of individual

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constituents of complex flavouring products by measuring in particularly C/ C ratios (Gleixner, 1998).

For food authenticity assessment, removal of the required extraction steps to isolate pure molecules was

a significant time saving. Several applied methods based on GC-C-IRMS have been developed:

Authenticity of essential oils such as Coriandrum (Franck C., 1995) mandarin oils (Faulhaber S., 1997)

beverages such as whisky (ParkerI.G., 1998) oils such as olive oil (Angerosa F., 1997).

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Plant water is always enriched in the heavy isotopes O and H related to the precipitation or

groundwater, and this enrichment depends on plant transpiration as a function of assimilation type (C3,

C4 or CAM plant). It can be assumed that the plant water O enrichment relative to precipitation water

decreases with increasing North latitude (Schmidt H.L., 2001).

The development of the online gas chromatography pyrolysis isotope ratio mass spectrometry (HRGC–

2 1

P-IRMS) technique used for the quantification of the ratio H/ H allows to acquire new data in the

authenticity of natural flavours assessment of natural origin of the main flavour compounds: Decanal,

2 1

linalool, linalyl acetate (Hör K. R. C., 2001). All of these evidences results to the large variations in H/ H

ratios in nature and the wide gap between natural and synthesis origins.
2 13

Furthermore the combination of H and C investigation using HRGC-C/P–IRMS has been a significant

improvement in the knowledge of the assessment of natural molecules: citral (Hör K. R. C., 2001) (Trang

T.T.N, 2006) ά and β ionone (Sewenig S., 2005) (Caja M.del M., 2007) Ϫ and β decalactone (Tamura H.,

2005).
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The last step has been to associate the pyrolysis interface for the determination of O/ O isotope ratios

2 1 13 12

in complement to the others isotope ( H/ H and C/ C) with the aim to deliver a three-dimensional plot.

New applications were demonstrated for the authenticity of natural compounds: linalyl acetate and

linalool in lavender essential oil (Jung J., 2005).
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In 2004, the development of Liquid Chromatography coupled to stable carbon Isotope Ratio Mass

Spectrometry via a Chemical Oxidation interface LC-Co-IRMS allowed new applications and perspectives

in the authentication of origin. Twenty two amino acids were separated and the C values determined.

The results were similar to those extracted with chemical process and evaluated using an EA-IRMS

approach (Godin J.P., 2005). Cabanero et al. (Cabanero A.I., 2010) showed a method allowing the

determination of glycerol and ethanol. The results obtained were in good agreement with those

performed using EA-IRMS. Guyon et al. (Guyon F., 2011) improved this method leading the determination

of δ C of glucose, fructose, glycerol and ethanol in the same run for wine authentication check.

The development of laser spectroscopy permits to determine the organic isotope ratios in gases with an

inherent compound–specific. Analytes do not necessarily need to be isolated, separated or trapped.

Keppler et al. (KepplerF., 2010) showed the interest of the determination of C in methane from

anaerobic digesters. A large part of these isotopic methods are regularly undertaken to check the

authenticity of flavours, essential oils and natural products in trading process. For industries involved in

the fields of food, perfumes, essentials oils and cosmetics, stable isotopic approaches are definitely useful

tools in the aim of validating the authenticity of natural products regarding synthesis adulteration, even

if they know that the uncertainty could be quite important due to the variation of plants origins.

During the last decade, stable isotope laboratories involved in authenticity assessment collected lots of

isotopic data related to the different origins of molecules. This work is important and must be continued

to ensure a steady evaluation of the database collected for authenticity validation.

Some isotopic methods have been also recognized as international methods. The list in Table 1 gives some

examples of the official methods elaborated in the naturalness authenticity assessment.

Table 1 — Examples of official methods using stable isotope ratios
Organization Method reference Title
Fruit and vegetables juices - Determination of the stable
carbon isotope ratio (13C/12C) of sugars from fruit juices-
CEN ENV 12140 method using isotope ratio mass spectrometry
Method for determination of stable oxygen isotope ratio
(18O/16O) of water from fruit juices, using isotope ratio mass
CEN ENV 12141 spectrometry
Method for determination of stable hydrogen isotope ratio
(2H/1H) of water from fruit juices, using isotope ratio mass
CEN ENV 12142 spectrometry
AOAC Method 998.12 Detection of C-4 Plant Sugars in Honey by 13C/12C analysis
Methods 981.09 and Detection of addition of beet sugars in fruit juices (13C/12C
AOAC 982.21 analysis)
Carbon isotope ratio mass spectrometric method for
AOAC Method 984.23 detection of corn syrup and cane sugar in maple syrup
Determination of sugar beet derived syrups in frozen
AOAC Method 992.09 concentrated orange juice- δ18O measurements in water
Carbon stable isotope ratio of ethanol derived from fruit
AOAC Method 2004.01 juices and maple syrups
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Organization Method reference Title
Determination by isotope ratio mass spectrometry of
Resolution 13C/12C of wine ethanol or that obtained through the
OIV OENO/7/2001 fermentation of musts, concentrated must or grape sugar
Determination of the carbon isotope ratio 13C/12C of CO in
Resolution sparkling wines method using isotope ratio mass
OIV OENO/7/2005 spectrometry (IRMS)
Association of analytical communities
International Organization of vine and wine

Isotopic analysis used for the assessment of natural product are undertaken to validate (or not) the

authenticity of the target samples. In the field of biobased product, a compound could be biobased, non-

biobased or partly biobased with a known level of biobased content. If the isotopic methodology would

be used as an accepted method, it could bring this assessment of the biobased content with the higher

acceptable uncertainty.
6 Overview of feedstock isotopic fingerprint
6.1 C4 plant

Sugar cane and maize have a specific isotopic C fingerprint due to their belonging to the C4

photosynthesis pathway cycle and are among the major feedstock employed.
Sugar cane

Rodushkin et al. (Rodushkin I., 2011) present the results of an inter-laboratory program based on the

multi elements and isotopic measurements of several sugar samples with different geographical origins:

USA, Costa Rica, Argentina and Swaziland. The results obtained on these cane sugar samples were:

δ C Values range from −10.5 to −12.6 ‰ .
δ C Average −11.70 ‰ SD 0.52 ‰
Two samples have been analysed (see Table 2).
Table 2 - measurement of sugar cane samples from various geographical origins
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references plant origin δ C (‰) δ H (‰) δ O (‰)
sugar cane Paraguay −11.71 −3 35
Reunion Island −11.66 11 37
Corn

Several samples of starch have been analysed. They originate from the fields of production feeding the

biobased industry factories (Table 3).
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Table 3 - Measurements of corn samples from various geographical origins
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references plant origin δ C (‰) δ H δ O (‰)
(‰)
starch corn China −11.66 −28 30
France −11.44 −16 32
Italia −11.81 −19 32
Spain −11.49 −21 32
France −11.42 −2.5 33
Brazil −10.72 −21 29
Brazil −11.02 −25 29
USA −10.82 −17 29
Turkey −11.51 −22 31
δ C Values range from −11.81 to −10.72 ‰ .
δ C Average −11.34 ‰ SD 0.35 ‰

δ C measured on C4 plant origin sample were in good agreement with data published.

6.2 Other raw materials: C3 plants

Rodushkin et al. (Rodushkin I., 2011) have reported the results of an inter-laboratory program based on

the multi elements and isotopic measurements of several sugar samples with different geographical

origins: Moldavia, Poland, France, Netherlands, Germany, Hungary and USA. The results obtained on

various cane sugar samples were:
δ C Values range from −23.8 to −26.5 ‰ .
δ C Average −24.98 ‰ SD 0.75 ‰

Starch which is a significant raw-material could be originated from various origins. Table 4 presents the

δ C of starch samples from C3 plants.
Table 4 - Measurements of starches from various origins
13 2 18
references plant origin δ C (‰) δ H (‰) δ O (‰)
wheat France −26.91 −47 31
Corby −27.00 −43 32
France −27.21 −43 32
pea France −27.38 −40.5 33
potatoes Denmark −28.44 −102 27
France −26.51 −79 35
tapioca Brazil −26.11 −82 29
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δ C measured of C3 starch samples range from −26 to −28 ‰. δ O obtained on C3 and C4 starch plant

origins seem to be in the same isotopic area.
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7 Determination of Biobased content for feedstocks and products
7.1 Bioplastics

Current plastics products are composed of biobased synthetic polymers, fossil-based synthetic polymers,

natural polymers and additives that can include biobased materials. “Biobased plastic” refers to plastic

that contains materials wholly or partly of biogenic origin (Plastics - Biobased Content Part 5: declaration

of biobased carbon content, biobased synthetic polymer content and biobased mass content).

Polyethylene Terephthalate (PET)

In 2009 the Coca-Cola Company presented their Plant Bottle® PET packaging innovation made from up

to 30 % biobased, sugar cane renewable materials. The new product encompasses a part of MEG (mono

ethylene glycol) biobased origin in the PET final product.

In response, the Coca-Cola Analytical Science Team has developed a novel patent (pending) using an

analytical method to quantify the amount of biobased material in Plant Bottle® PET resin. This new

approach has shown good reproducibility and accuracy, with excellent correlation to the conventional

ASTM 6866 method using radiocarbon analysis. The new method is performed using an elemental

analyser TOC (total organic carbon) connected to a cavity ring-down spectroscopy (CRDS) detector (TOC-

CRDS). This equipment allows the determination of the delta C value from a sample after combustion.

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The correlation between the delta C values and the C measurements connected to the biobased carbon

content were in good accordance allowing the C method to be an efficient alternative method in this

particular industrial process. Rapidity and relatively inexpensive test are also significant advantages of

the alternative stable isotopic approach (Brevet n° WO 2012/174104 Al, 2012).
Suzuki et al. presented the ability of δ C method to discriminate between plant
...

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