WO2010027286A1 - Method for honey type authentication - Google Patents

Method for honey type authentication Download PDF

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Publication number
WO2010027286A1
WO2010027286A1 PCT/PL2009/000006 PL2009000006W WO2010027286A1 WO 2010027286 A1 WO2010027286 A1 WO 2010027286A1 PL 2009000006 W PL2009000006 W PL 2009000006W WO 2010027286 A1 WO2010027286 A1 WO 2010027286A1
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WO
WIPO (PCT)
Prior art keywords
honey
fluorescent light
wavelength
types
specific
Prior art date
Application number
PCT/PL2009/000006
Other languages
French (fr)
Inventor
Stefan Gebala
Piotr Przybylowski
Original Assignee
Akademia Morska
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Akademia Morska filed Critical Akademia Morska
Publication of WO2010027286A1 publication Critical patent/WO2010027286A1/en

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Classifications

    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/64—Fluorescence; Phosphorescence
    • G01N21/6486—Measuring fluorescence of biological material, e.g. DNA, RNA, cells
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/02—Food

Definitions

  • the invention concerns a method for honey type authentication.
  • Honey types today are identified under the method of the melitopalynologic analysis.
  • the method consists in examining an insoluble honey component fraction composed in part of pollen, fungal spores, and green algae.
  • the mutual relations between the three elements differs from one honey type to another.
  • Determination of the specific floral honey types under the method requires preparing a microscope sample of the centrifuged honey sediment, establishing the identity of the there present pollen from nectar producing plants, finally estimating the pollen volumes.
  • the experimentally identified pollen- dusting ratios for individual nectar types are said to enable establishment of the quantitative proportions between these nectars of flowers which bees have used to produce the specific honey. Its type is identified based on the adopted criteria.
  • the melitopalyngologic method is complex, time-consuming, and requires qualified personnel. Moreover, the results are not entirely satisfying. Therefore, it is applied sporadically and tends to be viewed as a reference tool in scientific research rather than the method of identifying the types of honey as merchandise.
  • honeys by multivariant techniques based on metal content data The Analyst 125, 307-312, is the identification method based on the mineral content in honey.
  • identification attempts have been made to combine measurements for various parameters such as water or ash content, acidity, electric conduction, sugar content, or shades of colour. Building the identification method on such extensive compilations of numerous parameters carries the risk of coming across such types of honey whose identification would require introducing further new parameters which would substantially complicate the already complex method.
  • the purpose of the invention is to develop a method of honey type authentication based on a parameter closely linked to their authenticity in the consumers' perception, a parameter characteristic for the specific types of honey , which would allow an objective, reliable, readily available, cheap, and instant identification of the type of the tested honey.
  • the essence of the invention consists in making use of the phenomenon where natural floral dies, particularly carotenoids and flavonoids, concentrate on the free surface of unprocessed honey.
  • honeys differ as to the dye content and type.
  • Dye particles invariably contain pairs of two-electron ⁇ bonds frequently interacting with ⁇ electrons of aromatic rings. The composition of these compounds is responsible for the specific light absorption and emission properties.
  • Flavonoid particles are amphophilic. The flavonoid ring is on one side hydrophobic, whereas the hydroxyl groups on the other side are hydrophilic. This makes the particles cover the honey surface and, being dies, they can fluoresce.
  • the method for honey type authentication is characterised in that the free surface of a honey sample is excited with light of the wavelengths ranging between 200 and 500 nm, directed on the surface from above, and the intensity of the fluorescent light ranging in wavelength between 250 and 650 nm and emitted in the direction opposite to that of the excitation is recorded.
  • the records are arranged in ordered set and compared against the benchmark set of fluorescent light intensity values for specific honey types.
  • the difference between the wavelength of the fluorescent light ( ⁇ F ) and the wavelength of the excitation light ( ⁇ w ) is 100 nm.
  • the benchmark set of the fluorescent light intensities for specific honey types and the set of intensity values recorded for the tested sample are presented in the form of vectors in a multidimensional space and the tested honey sample is identified as representing a specific floral types of honey based on the algebraic vector analysis.
  • Measuring the fluorescence of a honey sample in accordance with the invention allows for unequivocal and easy identification of its botanic origin.
  • the new measuring geometry has enabled obtaining fluorescent spectra, each relevantly different for honeys of different types and relevantly similar for honeys of the same type.
  • individual honey types can be correlated with specific types of the spectrum of the fluorescent light emitted from the honey surface, and individual spectra of the fluorenscent light emitted therefrom can be identified as representing specific honey types.
  • the method enables identifying sub-types of the known unifloral honey types, as well as honey types not yet discovered. Sample analysis takes less than 5 minutes. The sampled honey is not processed in any way in preparation to the analysis, which eliminates the cost of purchasing chemical reagents and speeds up the analytic procedure.
  • Exemplary synchronous spectra for different honey types are illustrated on the drawing, where fig.1 shows the acacia honey spectra, fig. 2 - the spectra of rape honey, fig.3 - the buckwheat honey spectra, fig.4 - the heather honey spectra, and fig.5 - the spectra of lime-tree honey, and, respectively, figures Ia to 5 a show the benchmark average spectra for these types.
  • a beam of excitation light of the selected wavelength falling in the 200 and 500 nm range was selected in accordance with the invention and directed from the distance of 1 mm above onto the free surface of the honey sample so as to record the intensity of the fluorescent light of the wavelengths ranging between 250 and 650 nm, emitted in the direction opposite to that of the excitation light.
  • records were only taken of those fluorescent light intensities for which the difference between the wavelength of the fluorescent light ( ⁇ F ) and the wavelength of the excitation light ( ⁇ w ) was constant and preferably stood at 100 nm.
  • the set of these intensity values was ordered against the wavelength of the excitation light ( ⁇ w ) and thus the synchronous spectrum typical of each honey type was obtained.
  • the maxima characteristic of the rape honey were recorded for excitations with the wavelengths of 224 nm, 276 nm and 334 nm - fig. 2 and fig. 2a.
  • heather honeys were found to share two maxima for excitations with the wavelengths of 220 nm and 344 nm - fig.4 and fig.4a.
  • Lime-tree honey were found to have one maximum for excitation at the wavelength of 366 nm - fig. 5 and fig. 5a.
  • a detailed analysis of the similarities between the tested honey sample and the benchmark spectrum set and its identification with a specific type can be conducted based on an algebraic vector analysis of the spectra.
  • Using the computer to control the measurement reading process and digitally process the results allows for performing an immense number of tests and their instant analysis.

Abstract

A method of honey type authentication, characterised in that the free surface of a honey sample is excited with light of the wavelengths ranging between 200 and 500 nm, directed on the surface from above, and the intensity of the fluorescent light ranging in wavelength between 250 and 650 nm and emitted in the direction opposite to that of the excitation is recorded. The records are arranged in ordered set and compared against the benchmark set of fluorescent light intensity values for specific honey types. In order to narrow down the spectrum data, records are taken for those intensities of the fluorescent light, for which the difference between the wavelength of the fluorescent light (λF) and the wavelength of the excitation light (λW) is constant and preferably 100 nm. The benchmark set of the fluorescent light intensity values for specific honey types and the set of intensity values identified for the tested sample are preferably presented in the form of vectors in multi- dimensional space, and the tested honey sample is identified as representing a specific type based on the algebraic vector analysis.

Description

Method for honey type authentication
The invention concerns a method for honey type authentication.
Honey types today are identified under the method of the melitopalynologic analysis. The method consists in examining an insoluble honey component fraction composed in part of pollen, fungal spores, and green algae. The mutual relations between the three elements differs from one honey type to another. Determination of the specific floral honey types under the method requires preparing a microscope sample of the centrifuged honey sediment, establishing the identity of the there present pollen from nectar producing plants, finally estimating the pollen volumes. The experimentally identified pollen- dusting ratios for individual nectar types are said to enable establishment of the quantitative proportions between these nectars of flowers which bees have used to produce the specific honey. Its type is identified based on the adopted criteria.
The melitopalyngologic method is complex, time-consuming, and requires qualified personnel. Moreover, the results are not entirely satisfying. Therefore, it is applied sporadically and tends to be viewed as a reference tool in scientific research rather than the method of identifying the types of honey as merchandise. Disclosed in the publication by Popek S.: "Studium identyfikacji miodόw odmianowych i metodologii oceny wlasciwosci fizykochemicznych determinuja^cych ich jakosc" [,,The Identification of Honey Variants and a Methodology for Assessing the Physio-chemical Properties Determining their Quality: A Study" , Monografie 147, Wydawnictwo AE w Krakowie [Academy of Economy in Krakow Publications], and in the article by Krauze A, ZaIe wski R., 1999: Classification of Honeys by Principal Component Analysis on the Basis of Chemical and Physical Parameters, Zeitschrift fur LebensMittel Untersung und Forschung" 192, 19-23, are methods of identifying honey types based on analysis of a single physical and chemical parameter or on the basis of the developed mathematical functions comprising several honey properties.
Also disclosed in the article by Bogdanov S., 1989 determination of Pinocembrin in Honey Using HPLC, Journal of Apicultural Research 28 (1), 55-57, is the method of identifying honey types based on their dye content.
Disclosed in the dissertation by Giemza M 1999 ,,Znaczenie barwy w ocenie jakosci produktόw na przykladzie miodόw odmianowych" [,,The Significance of Colour in Assessing Product Quality on the Example of Unifloral Honeys"], AE in Krakow, is the method of identifying honey types based on their sensorily-assessed colour. Also disclosed in the publication by Latorre M et al. 1999: ,,Chemometric classification of honeys according to their type. II. Metal content data, Food Chemistry 66, 263-268, and 2000: „ Authentication of Galician (N. W. Spain) honeys by multivariant techniques based on metal content data, The Analyst 125, 307-312, is the identification method based on the mineral content in honey. In order to arrive at satisfying results of honey type identification attempts have been made to combine measurements for various parameters such as water or ash content, acidity, electric conduction, sugar content, or shades of colour. Building the identification method on such extensive compilations of numerous parameters carries the risk of coming across such types of honey whose identification would require introducing further new parameters which would substantially complicate the already complex method.
Such optional solutions to the problem of honey type identification are described in the overview study by: Bogdanov, Rudoff, Persano Oddo, 2004, "Physico-chemical methods for the characterisation of unifloral honeys: a review", Apidologie 35 (2004) pp 4-17 The modest number of officially recognized honey types is the consequence of the difficulties encountered in their identification.
The purpose of the invention is to develop a method of honey type authentication based on a parameter closely linked to their authenticity in the consumers' perception, a parameter characteristic for the specific types of honey , which would allow an objective, reliable, readily available, cheap, and instant identification of the type of the tested honey.
The essence of the invention consists in making use of the phenomenon where natural floral dies, particularly carotenoids and flavonoids, concentrate on the free surface of unprocessed honey. Depending on their botanical origin honeys differ as to the dye content and type. Dye particles invariably contain pairs of two-electron π bonds frequently interacting with π electrons of aromatic rings. The composition of these compounds is responsible for the specific light absorption and emission properties. Flavonoid particles are amphophilic. The flavonoid ring is on one side hydrophobic, whereas the hydroxyl groups on the other side are hydrophilic. This makes the particles cover the honey surface and, being dies, they can fluoresce. According to the invention, the method for honey type authentication is characterised in that the free surface of a honey sample is excited with light of the wavelengths ranging between 200 and 500 nm, directed on the surface from above, and the intensity of the fluorescent light ranging in wavelength between 250 and 650 nm and emitted in the direction opposite to that of the excitation is recorded. The records are arranged in ordered set and compared against the benchmark set of fluorescent light intensity values for specific honey types.
In order to narrow down the spectrum data, records are taken for those intensities of the fluorescent light, for which the difference between the wavelength of the fluorescent light (γF) and the wavelength of the excitation light (γw) is constant.
Preferably, the difference between the wavelength of the fluorescent light (γF) and the wavelength of the excitation light (γw) is 100 nm. Preferably, the benchmark set of the fluorescent light intensities for specific honey types and the set of intensity values recorded for the tested sample, are presented in the form of vectors in a multidimensional space and the tested honey sample is identified as representing a specific floral types of honey based on the algebraic vector analysis.
Measuring the fluorescence of a honey sample in accordance with the invention allows for unequivocal and easy identification of its botanic origin.
Application of the new measuring geometry has enabled obtaining fluorescent spectra, each relevantly different for honeys of different types and relevantly similar for honeys of the same type. Hence, individual honey types can be correlated with specific types of the spectrum of the fluorescent light emitted from the honey surface, and individual spectra of the fluorenscent light emitted therefrom can be identified as representing specific honey types. According to the invention, the method enables identifying sub-types of the known unifloral honey types, as well as honey types not yet discovered. Sample analysis takes less than 5 minutes. The sampled honey is not processed in any way in preparation to the analysis, which eliminates the cost of purchasing chemical reagents and speeds up the analytic procedure.
Exemplary synchronous spectra for different honey types, obtained under the method according to the invention, are illustrated on the drawing, where fig.1 shows the acacia honey spectra, fig. 2 - the spectra of rape honey, fig.3 - the buckwheat honey spectra, fig.4 - the heather honey spectra, and fig.5 - the spectra of lime-tree honey, and, respectively, figures Ia to 5 a show the benchmark average spectra for these types.
Many times, a beam of excitation light of the selected wavelength falling in the 200 and 500 nm range was selected in accordance with the invention and directed from the distance of 1 mm above onto the free surface of the honey sample so as to record the intensity of the fluorescent light of the wavelengths ranging between 250 and 650 nm, emitted in the direction opposite to that of the excitation light. In order to narrow down the spectrum data, records were only taken of those fluorescent light intensities for which the difference between the wavelength of the fluorescent light (γF) and the wavelength of the excitation light (γw) was constant and preferably stood at 100 nm. The set of these intensity values was ordered against the wavelength of the excitation light (γw) and thus the synchronous spectrum typical of each honey type was obtained.
The above procedure was followed to analyse an odd dozen samples of the same type and a set of synchronous spectra was obtained. By averaging the results obtained for specific honey types the benchmark spectra were arrived at.
In case of the acacia honey we find characteristic maxima for excitations with the wavelengths of 220 nm, 280 nm and 335 mn, - fig.
1 and fig 1 a.
The maxima characteristic of the rape honey were recorded for excitations with the wavelengths of 224 nm, 276 nm and 334 nm - fig. 2 and fig. 2a.
In case of buckwheat honey two maxima were identified for excitations with the wavelengths of 219 nm and 350 nm - fig.3 and fig.3a.
Also heather honeys were found to share two maxima for excitations with the wavelengths of 220 nm and 344 nm - fig.4 and fig.4a.
Lime-tree honey were found to have one maximum for excitation at the wavelength of 366 nm - fig. 5 and fig. 5a.
Following the same procedure for an unidentified honey type its synchronous spectrum is obtained ready to be compared against the benchmark spectra. Its similarity in shape to a benchmark spectrum forms the basis for identifying the tested honey sample as representing the specific honey type.
A detailed analysis of the similarities between the tested honey sample and the benchmark spectrum set and its identification with a specific type can be conducted based on an algebraic vector analysis of the spectra. Using the computer to control the measurement reading process and digitally process the results allows for performing an immense number of tests and their instant analysis.

Claims

Claims
1. A Method for honey type authentication characterised in that the free surface of a honey sample is excited with light of the wavelengths ranging between 200 and 500 nm, directed on the surface from above, and the intensity of the fluorescent light ranging in wavelength between 250 and 650 nm and emitted in the direction opposite to that of the excitation is recorded, whereupon the records are arranged into an ordered set and compared against the benchmark set of fluorescent light intensity values for specific honey types.
2. The method as claimed in Claim 1, characterised in that the records are taken of the fluorescent light intensities for which the difference between the florescent light wavelength (γF) and the excitation light wavelength (γw) is constant.
3. The method as claimed in Claim 2, characterised in that the difference between the fluorescent light wavelength (γF) and the excitation light wavelength (γw) is 100 nm.
4. The method as claimed in Claims 1 to 3, characterised in that the benchmark set of the fluorescent light intensity values for specific honey types and the set of intensity values identified for the tested sample are presented in the form of vectors in multi-dimensional space, and the tested honey sample is identified as representing a specific type based on the algebraic vector analysis.
PCT/PL2009/000006 2008-09-05 2009-01-22 Method for honey type authentication WO2010027286A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
PL386031A PL214784B1 (en) 2008-09-05 2008-09-05 Method of identification of honey variety
PLP-386031 2008-09-05

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WO2010027286A1 true WO2010027286A1 (en) 2010-03-11

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012074413A1 (en) 2010-11-29 2012-06-07 Comvita New Zealand Limited A method and apparatus that utilises fluorescence to determine plant or botanical origin characteristics of honey
RU2506813C2 (en) * 2012-03-12 2014-02-20 Сергей Викторович Афанасьев Method for production of water honey solution and its authenticity control method
CN108645829A (en) * 2018-05-15 2018-10-12 中国农业科学院蜜蜂研究所 A kind of method of quick identification honey types and adulterated honey
CN111024637A (en) * 2019-11-04 2020-04-17 李�杰 Method for rapidly identifying true and false honey by ultraviolet spectrum scanning

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
GHOSH N. ET AL: "A Fluorescence Spectroscopic Study of Honey and Cane Sugar Syrup", FOOD SCIENCE AND TECHNOLOGY RESEARCH, vol. 11, no. 1, 2005, pages 59 - 62, XP002536760, ISSN: 1344-6606 *
KAROUI ET AL: "The use of front face fluorescence spectroscopy to classify the botanical origin of honey samples produced in Switzerland", FOOD CHEMISTRY, ELSEVIER SCIENCE PUBLISHERS LTD, GB, vol. 101, no. 1, 12 August 2006 (2006-08-12), pages 314 - 323, XP005754183, ISSN: 0308-8146 *

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012074413A1 (en) 2010-11-29 2012-06-07 Comvita New Zealand Limited A method and apparatus that utilises fluorescence to determine plant or botanical origin characteristics of honey
US8759774B2 (en) 2010-11-29 2014-06-24 Comvita New Zealand Limited Method and apparatus that utilises fluorescence to determine plant or botanical origin characteristics of honey
AU2011337271B2 (en) * 2010-11-29 2014-07-24 Comvita New Zealand Limited A method and apparatus that utilises fluorescence to determine plant or botanical origin characteristics of honey
RU2506813C2 (en) * 2012-03-12 2014-02-20 Сергей Викторович Афанасьев Method for production of water honey solution and its authenticity control method
CN108645829A (en) * 2018-05-15 2018-10-12 中国农业科学院蜜蜂研究所 A kind of method of quick identification honey types and adulterated honey
CN108645829B (en) * 2018-05-15 2021-01-15 中国农业科学院蜜蜂研究所 Method for rapidly identifying honey varieties and adulterated honey
CN111024637A (en) * 2019-11-04 2020-04-17 李�杰 Method for rapidly identifying true and false honey by ultraviolet spectrum scanning
CN111024637B (en) * 2019-11-04 2022-03-08 营口市食品药品检验检测中心 Method for rapidly identifying true and false honey by ultraviolet spectrum scanning

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Publication number Publication date
PL214784B1 (en) 2013-09-30
PL386031A1 (en) 2010-03-15

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