Food authenticity - Determination of the δ13C value of mono- (fructose and glucose), di-, and trisaccharides in honey by liquid chromatography-isotope ratio mass spectrometry (LC-IRMS)

This document specifies a method for the determination of the ratio of stable isotopes of carbon (13C/12C) of sugars contained in honey by using liquid chromatography coupled to an isotope ratio mass spectrometer (LC-IRMS) for compound separation and subsequent determination of the 13C/12C ratio of mono-, di-, and trisaccharides. These ratios can be used to assess honey authenticity by comparing them to guidance values of genuine honey, which have been previously agreed by subject matter experts, as the 13C/12C ratios of sugars of genuine honey and sugars contained in adulterants (syrups made from starch-rich plants or from sugar cane or sugar beet) differ to a certain extent.
The compliance assessment process is not part of this document.

Lebensmittelauthentizität - Bestimmung des δ13C-Wertes von Mono- (Fructose und Glucose), Di- und Trisacchariden in Honig durch Flüssigchromatographie-Isotopenverhältnis-Massenspektrometrie (LC‑IRMS)

Dieses Dokument legt ein Verfahren zur Bestimmung des Verhältnisses stabiler Kohlenstoffisotope (13C/12C) von in Honig enthaltenen Zuckern mittels Flüssigchromatographie gekoppelt mit einem Isotopenverhältnis-Massenspektrometer (LC-IRMS) zur Trennung der Verbindungen und anschließenden Bestimmung des 13C/12C-Verhältnisses von Mono-, Di- und Trisacchariden fest. Diese Verhältnisse können zur Beurteilung der Authentizität von Honig verwendet werden, indem sie mit den Leitwerten für echten Honig verglichen werden, die zuvor von Fachexperten vereinbart wurden, da sich die 13C/12C-Verhältnisse von Zuckern in echtem Honig und Zuckern in Verfälschungsmitteln (Sirupe aus stärkereichen Pflanzen oder aus Zuckerrohr oder Zuckerrüben) in gewissem Maße unterscheiden.
Der Prozess der Konformitätsbewertung ist nicht Teil dieses Dokuments.

Authenticité des aliments - Détermination de la valeur du δ13C des mono- (fructose et glucose), di-, et trisaccharides présents dans le miel par chromatographie en phase liquide spectrométrie de masse de rapports isotopiques (CL-SMRI)

Le présent document spécifie une méthode de détermination du rapport des isotopes stables du carbone (13C/12C) des sucres contenus dans le miel par chromatographie en phase liquide couplée à la spectrométrie de masse de rapports isotopiques (CL-SMRI). La méthode présente la séparation des composés et la détermination des teneurs en 13C/12C des mono-, di- et trisaccharides. Ces rapports isotopiques peuvent être utilisés pour évaluer l’authenticité du miel par comparaison avec des valeurs recommandées pour le miel authentique et convenues par des spécialistes du sujet, car les rapports 13C/12C des sucres du miel authentique, et ceux des sucres contenus dans les produits adultérants du miel (sirops fabriqués à partir de plantes riches en amidon ou à partir de sucre de canne ou de betterave) sont, dans une certaine mesure, différents les uns des autres.
Le processus d’évaluation de la conformité n’est pas traité dans le présent document.

Pristnost živil - Določanje vrednosti δ13C mono- (fruktoza in glukoza), di- in trisaharidov v medu s tekočinsko kromatografijo - z masno spektrometrijo z izotopskim razmerjem (LC-IRMS)

General Information

Status
Published
Publication Date
26-Nov-2024
Current Stage
6060 - Definitive text made available (DAV) - Publishing
Start Date
27-Nov-2024
Due Date
30-Jul-2024
Completion Date
27-Nov-2024

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SLOVENSKI STANDARD
01-januar-2025
Pristnost živil - Določanje vrednosti δ13C mono- (fruktoza in glukoza), di- in
trisaharidov v medu s tekočinsko kromatografijo - z masno spektrometrijo z
izotopskim razmerjem (LC-IRMS)
Food authenticity - Determination of the δ13C value of mono- (fructose and glucose), di-,
and trisaccharides in honey by liquid chromatography-isotope ratio mass spectrometry
(LC-IRMS)
Lebensmittelauthentizität - Bestimmung des δ13C-Wertes von Mono- (Fructose und
Glucose), Di- und Trisacchariden in Honig durch Flüssigchromatographie-
Isotopenverhältnis-Massenspektrometrie (LC-IRMS)
Authenticité des aliments - Détermination de la valeur du δ13C des mono- (fructose et
glucose), di-, et trisaccharides présents dans le miel par chromatographie en phase
liquide spectrométrie de masse de rapports isotopiques (CL-SMRI)
Ta slovenski standard je istoveten z: EN 17958:2024
ICS:
67.180.10 Sladkor in sladkorni izdelki Sugar and sugar products
2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.

EN 17958
EUROPEAN STANDARD
NORME EUROPÉENNE
November 2024
EUROPÄISCHE NORM
ICS 67.180.10; 67.180.20
English Version
Food authenticity - Determination of the δ C value of
mono- (fructose and glucose), di-, and trisaccharides in
honey by liquid chromatography-isotope ratio mass
spectrometry (LC-IRMS)
Authenticité des aliments - Détermination de la valeur Lebensmittelauthentizität - Bestimmung des δ C -
du δ C des mono- (fructose et glucose), di-, et Wertes von Mono- (Fructose und Glucose), Di- und
trisaccharides présents dans le miel par Trisacchariden in Honig durch
chromatographie en phase liquide spectrométrie de Flüssigchromatographie-Isotopenverhältnis-
masse de rapports isotopiques (CL-SMRI) Massenspektrometrie (LC-IRMS)
This European Standard was approved by CEN on 24 June 2024.

CEN members are bound to comply with the CEN/CENELEC Internal Regulations which stipulate the conditions for giving this
European Standard the status of a national standard without any alteration. Up-to-date lists and bibliographical references
concerning such national standards may be obtained on application to the CEN-CENELEC Management Centre or to any CEN
member.
This European Standard exists in three official versions (English, French, German). A version in any other language made by
translation under the responsibility of a CEN member into its own language and notified to the CEN-CENELEC Management
Centre has the same status as the official versions.

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

EUROPÄISCHES KOMITEE FÜR NORMUN G

CEN-CENELEC Management Centre: Rue de la Science 23, B-1040 Brussels
© 2024 CEN All rights of exploitation in any form and by any means reserved Ref. No. EN 17958:2024 E
worldwide for CEN national Members.

Contents Page
European foreword . 3
Introduction . 4
1 Scope . 5
2 Normative references . 5
3 Terms and definitions . 5
4 Principle . 6
5 Reagents . 6
6 Apparatus . 7
7 Procedure. 8
7.1 Preparation of the test sample . 8
7.2 Preparation of the test sample solution . 8
7.3 LC-IRMS setup and performance qualification . 8
7.3.1 LC-IRMS interface setup . 8
7.3.2 IRMS calibration . 8
7.4 Determination and analytical sequence . 8
7.5 Calculations . 8
7.5.1 General . 8
7.5.2 Calculation of compound specific δ C values using two-point linear normalization . 8
8 Precision . 9
8.1 General . 9
8.2 Repeatability . 9
8.3 Reproducibility . 9
Annex A (informative) Experimental conditions used by the participants in the
interlaboratory comparison .10
Annex B (informative) Example of a chromatogram of the expected separation of the honey
saccharides .11
Annex C (informative) Precision data .12
Bibliography .16

European foreword
This document (EN 17958:2024) has been prepared by Technical Committee CEN/TC 460 “Food
Authenticity”, the secretariat of which is held by DIN.
This European Standard shall be given the status of a national standard, either by publication of an
identical text or by endorsement, at the latest by May 2025, and conflicting national standards shall be
withdrawn at the latest by May 2025.
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.
According to the CEN-CENELEC Internal Regulations, the national standards organisations of the
following countries are bound to implement this European Standard: Austria, Belgium, Bulgaria, Croatia,
Cyprus, Czech Republic, Denmark, Estonia, Finland, France, Germany, Greece, Hungary, Iceland, Ireland,
Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Republic of North
Macedonia, Romania, Serbia, Slovakia, Slovenia, Spain, Sweden, Switzerland, Türkiye and the United
Kingdom.
Introduction
Honey is a natural sweet substance produced by honey bees having attractive sensory properties.
Demand has increased over the years, partially due to population increase, but also due to the preference
of consumers for natural and unprocessed food. It is a globally traded commodity following complex trade
routes, which makes quality and authenticity control difficult. Honey is among the commodities most
[1]
vulnerable to fraud . The EU Honey Directive lays down the composition and authenticity criteria for
[2] [3]
honey . A set of analytical methods have been harmonized by the International Honey Commission ,
which allows enforcement of the provisions of the Directive. Those methods are widely used but are not
always appropriate for assessing the authenticity of the product: specifically, adulteration of honey by
non-declared dilution with foreign sugars/sweeteners, which is among the most frequently encountered
cases.
Syrups that mimic the composition of honey that are produced by chemical and/or enzymatic
[4]
modification of starch or sucrose are difficult to detect . If the starting product is obtained from a plant
using the Hatch–Slack pathway for carbon fixation (C4 plant), such as maize or sugar cane, stable carbon
isotope ratio analysis (SCIRA) using a combination of an elemental analyser and an isotope ratio mass
[5]
spectrometer (EA-IRMS) offers a possibility to detect additions down to a level of 7 % . Sugars
originating from C3 plants, which use the Calvin–Benson cycle, such as beet root or sugars generated from
rice or wheat starch escape detection by SCIRA. Combining liquid chromatography (LC) with IRMS (LC-
IRMS) offers new possibilities for detecting honey adulteration with sugars derived from C3 plants as
[6][7]
well as increasing the sensitivity for detecting C4 sugars . The method has gained popularity but has
never been subjected to multi-laboratory validation, which is a prerequisite for further developing it into
a standard by a Standards Developing Organization.
13 12
An LC-IRMS method for the determination of the C/ C isotope delta values of glucose, fructose,
glycerol and ethanol in products of viti-vinicultural origin was collaboratively studied by the
International Organization of Vine and Wine (OIV) and endorsed for inclusion in the Compendium of
International Methods of Analysis of Wines and Musts (OIV-OENO resolution 479-2017).
This document provides the basis for the analytical method. The setup of the required apparatus depends
to a large extent on its design principles, and the specific recommendations of the manufacturers should
be followed. It is intended to serve as a frame in which the analyst can define their own analytical work
in accordance with the standard procedure.
1 Scope
13 12
This document specifies a method for the determination of the ratio of stable isotopes of carbon ( C/ C)
of sugars contained in honey by using liquid chromatography coupled to an isotope ratio mass
13 12
spectrometer (LC-IRMS) for compound separation and subsequent determination of the C/ C ratio of
mono-, di-, and trisaccharides. These ratios can be used to assess honey authenticity by comparing them
to guidance values of genuine honey, which have been previously agreed by subject matter experts, as
13 12
the C/ C ratios of sugars of genuine honey and sugars contained in adulterants (syrups made from
starch-rich plants or from sugar cane or sugar beet) differ to a certain extent.
The compliance assessment process is not part of this document.
2 Normative references
There are no normative references in this document.
3 Terms and definitions
For the purposes of this document, the following terms and definitions apply.
ISO and IEC maintain terminology databases for use in standardization at the following addresses:
— IEC Electropedia: available at https://www.electropedia.org/
— ISO Online browsing platform: available at https://www.iso.org/obp
3.1
isotope delta
δ
stable isotope ratio of a sample expressed relative to a reference
Note 1 to entry: For carbon, this expression is given in Formula (1):
13 12
R C/ C
)
sample(
13 12
(1)
δ C/ C − 1
)
ref(
13 12
R C/ C
)
reference(
13 12 13
Note 2 to entry: The term 𝛿𝛿 ( C/ C) is often changed from the IUPAC format to 𝛿𝛿 C ; this document uses the
ref ref
IUPAC format for familiarity.
Note 3 to entry: To ensure international comparability of isotope delta values, a common reference is used; this
reference is an international measurement standard assigned by convention with isotope delta value exactly equal
to zero.
Note 4 to entry: Carbon isotope delta values for natural isotopic abundance in food materials are small and
expressed in permille (‰) rather than in their native form.
3.2
Vienna Peedee Belemnite
VPDB
international measurement standard for 𝛿𝛿 C
Note 1 to entry: VPDB is a virtual carbonate.
=
Note 2 to entry: The carbon isotopic composition of VPDB is defined by the exact isotope delta value assigned to the
calcium carbonate reference material NBS 19 of d13CVPDB = +1,95‰.
3.3
mass-to-charge ratio
m/z
dimensionless quantity formed by dividing the mass number of an ion by its charge number
3.4
working gas
gas consisting of the same molecule as the analyte gas (i.e. CO ) but introduced directly into the mass
spectrometer from a high-pressure cylinder rather than being created from the sample
3.5
sequence
continuous set of analyses including reference mate
...

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