Honey authenticity: analytical techniques, state of the art and challenges

Honey is a high-value, globally consumed, food product featuring a high market price strictly related to its origin. Moreover, honey origin has to be clearly stated on the label, and quality schemes are prescribed based on its geographical and botanical origin. Therefore, to enhance food quality, it is of utmost importance to develop analytical methods able to accurately and precisely discriminate honey origin. In this study, an all-time scientometric evaluation of the field is provided for the first time using a structured keyword on the Scopus database. The bibliometric analysis pinpoints that the botanical origin discrimination was the most studied authenticity issue, and chromatographic methods were the most frequently used for its assessment. Based on these results, we comprehensively reviewed analytical techniques that have been used in honey authenticity studies. Analytical breakthroughs and bottlenecks on methodologies to assess honey quality parameters using separation, bioanalytical, spectroscopic, elemental and isotopic techniques are presented. Emphasis is given to authenticity markers, and the necessity to apply chemometric tools to reveal them. Altogether, honey authenticity is an ever-growing field, and more advances are expected that will further secure honey quality.

[1]  L. S. Chua,et al.  Molecular identification of honey entomological origin based on bee mitochondrial 16S rRNA and COI gene sequences , 2017 .

[2]  Joana Costa,et al.  Botanical authentication of lavender (Lavandula spp.) honey by a novel DNA-barcoding approach coupled to high resolution melting analysis , 2018 .

[3]  V. Vasić,et al.  Two aspects of honeydew honey authenticity: Application of advance analytical methods and chemometrics. , 2020, Food chemistry.

[4]  M. Kontominas,et al.  A decisive strategy for monofloral honey authentication using analysis of volatile compounds and pattern recognition techniques , 2020 .

[5]  M. Kontominas,et al.  Characterization and geographical discrimination of Greek pine and thyme honeys based on their mineral content, using chemometrics , 2016, European Food Research and Technology.

[6]  M. Oroian,et al.  Heavy Metals Profile in Honey as a Potential Indicator of Botanical and Geographical Origin , 2016 .

[7]  P. Kafarski,et al.  Development of a high performance thin layer chromatography method for the rapid qualification and quantification of phenolic compounds and abscisic acid in honeys. , 2019, Journal of chromatography. A.

[8]  K. Stefanova,et al.  Main honey botanical components and techniques for identification: a review , 2020 .

[9]  G. Cristea,et al.  Applications of emerging stable isotopes and elemental markers for geographical and varietal recognition of Romanian and French honeys. , 2020, Food chemistry.

[10]  Vincenzo Chiofalo,et al.  Characterization of Sicilian Honeys Pollen Profiles Using a Commercial E-Tongue and Melissopalynological Analysis for Rapid Screening: A Pilot Study , 2018, Sensors.

[11]  Sascha Rohn,et al.  Volatile-Compound Fingerprinting by Headspace-Gas-Chromatography Ion-Mobility Spectrometry (HS-GC-IMS) as a Benchtop Alternative to 1H NMR Profiling for Assessment of the Authenticity of Honey. , 2018, Analytical chemistry.

[12]  I. Jasicka-Misiak,et al.  Chromatographic fingerprint, antioxidant activity, and colour characteristic of polish goldenrod (Solidago virgaurea L.) honey and flower , 2018, European Food Research and Technology.

[13]  D. Stanković,et al.  Mineral Content as a Tool for the Assessment of Honey Authenticity. , 2017, Journal of AOAC International.

[14]  A. Galimberti,et al.  A DNA barcoding approach to identify plant species in multiflower honey. , 2015, Food chemistry.

[15]  M. Kontominas,et al.  Characterization and classification of Thymus capitatus (L.) honey according to geographical origin based on volatile compounds, physicochemical parameters and chemometrics , 2014 .

[16]  S. Squadrone,et al.  Trace and rare earth elements in monofloral and multifloral honeys from Northwestern Italy; A first attempt of characterization by a multi-elemental profile. , 2020, Journal of trace elements in medicine and biology : organ of the Society for Minerals and Trace Elements.

[17]  Evelin Kivima,et al.  Characterisation of the aroma profiles of different honeys and corresponding flowers using solid-phase microextraction and gas chromatography-mass spectrometry/olfactometry. , 2015, Food chemistry.

[18]  E. Schievano,et al.  Entomological authentication of stingless bee honey by 1H NMR-based metabolomics approach , 2017 .

[19]  Hui Chen,et al.  Chemometric determination of the botanical origin for Chinese honeys on the basis of mineral elements determined by ICP-MS. , 2014, Journal of agricultural and food chemistry.

[20]  D. Pavlova,et al.  Characteristics of Honey from Serpentine Area in the Eastern Rhodopes Mt., Bulgaria , 2016, Biological Trace Element Research.

[21]  L. Estevinho,et al.  Spanish honeys with quality brand: a multivariate approach to physicochemical parameters, microbiological quality, and floral origin , 2018, Journal of Apicultural Research.

[22]  I. Escriche,et al.  Quality parameters, pollen and volatile profiles of honey from North and Central Mozambique. , 2019, Food chemistry.

[23]  Stavros Kontakos,et al.  Characterisation and classification of Greek pine honeys according to their geographical origin based on volatiles, physicochemical parameters and chemometrics. , 2014, Food chemistry.

[24]  V. Vasić,et al.  Towards better quality criteria of European honeydew honey: Phenolic profile and antioxidant capacity. , 2019, Food chemistry.

[25]  S. Sulaiman,et al.  Assessment of gas chromatography time-of-flight accurate mass spectrometry for identification of volatile and semi-volatile compounds in honey. , 2014, Talanta.

[26]  A. Pulvirenti,et al.  Multivariate statistical analysis of the polyphenols content for the discrimination of honey produced in Sicily (Southern Italy) , 2019, Journal of Food Composition and Analysis.

[27]  E. Yeşilada,et al.  Importance of chromatographic and spectrophotometric methods in determining authenticity, classification and bioactivity of honey , 2020 .

[28]  M. Kontominas,et al.  Nutritional aspects and botanical origin recognition of Mediterranean honeys based on the “mineral imprint’’ with the application of supervised and non-supervised statistical techniques , 2019, European Food Research and Technology.

[29]  Sorina Ropciuc,et al.  Romanian honey authentication using voltammetric electronic tongue. Correlation of voltammetric data with physico-chemical parameters and phenolic compounds , 2019, Comput. Electron. Agric..

[30]  P. Pohl Determination of metal content in honey by atomic absorption and emission spectrometries , 2009 .

[31]  Béla Kovács,et al.  Macro-element ratios provide improved identification of the botanical origin of mono-floral honeys , 2018, European Food Research and Technology.

[32]  J. Quiles,et al.  Phenolic Compounds in Honey and Their Associated Health Benefits: A Review , 2018, Molecules.

[33]  Jânio Sousa Santos,et al.  Trends in Chemometrics: Food Authentication, Microbiology, and Effects of Processing. , 2018, Comprehensive reviews in food science and food safety.

[34]  L. S. Chua,et al.  Comparison of DNA extraction methods for entomological origin identification of honey using simple additive weighting method , 2018, International Journal of Food Science & Technology.

[35]  Zhangfeng Zhao,et al.  Fast Classification of Geographical Origins of Honey Based on Laser-Induced Breakdown Spectroscopy and Multivariate Analysis , 2020, Sensors.

[36]  M. Fletcher,et al.  Analysis of Pyrrolizidine Alkaloids in Queensland Honey: Using Low Temperature Chromatography to Resolve Stereoisomers and Identify Botanical Sources by UHPLC-MS/MS , 2019, Toxins.

[37]  C T Elliott,et al.  Discrimination of honey of different floral origins by a combination of various chemical parameters. , 2015, Food Chemistry.

[38]  L. E. B. Soledade,et al.  Phenolic profile, antioxidant activity and palynological analysis of stingless bee honey from Amazonas, Northern Brazil. , 2013, Food chemistry.

[39]  G. Cristea,et al.  Geographical origin and species differentiation of Transylvanian cheese. Comparative study of isotopic and elemental profiling vs. DNA results. , 2019, Food chemistry.

[40]  K. Loomes,et al.  Fluorescence markers in some New Zealand honeys. , 2016, Food chemistry.

[41]  R. Ionete,et al.  Evaluation of honey in terms of quality and authenticity based on the general physicochemical pattern, major sugar composition and δ13C signature , 2020 .

[42]  C. Balderas,et al.  Free amino acid determination by GC-MS combined with a chemometric approach for geographical classification of bracatinga honeydew honey (Mimosa scabrella Bentham) , 2017 .

[43]  Roberto Larcher,et al.  Isotopic and elemental composition of selected types of Italian honey , 2017 .

[44]  M. Kontominas,et al.  Floral authentication of Greek unifloral honeys based on the combination of phenolic compounds, physicochemical parameters and chemometrics , 2014 .

[45]  Manuel Vázquez,et al.  Differences between honeydew and blossom honeys: A review , 2017 .

[46]  Georgios P Danezis,et al.  Rare earth elements minimal harvest year variation facilitates robust geographical origin discrimination: The case of PDO "Fava Santorinis". , 2016, Food chemistry.

[47]  Douglas N Rutledge,et al.  Fast and global authenticity screening of honey using ¹H-NMR profiling. , 2015, Food chemistry.

[48]  S. Castiglioni,et al.  Geographical characterisation of multifloral honeys from the Marche region (Italy) according to their antioxidant activity and colour using a chemometric approach , 2018 .

[49]  Minghui Zhu,et al.  Using sensor and spectral analysis to classify botanical origin and determine adulteration of raw honey , 2016 .

[50]  J. Ruíz-Ruíz,et al.  Electrophoresis characterisation of protein as a method to establish the entomological origin of stingless bee honeys. , 2015, Food chemistry.

[51]  H. Kawashima,et al.  Stable carbon isotope ratios for organic acids in commercial honey samples. , 2019, Food chemistry.

[52]  L. Estevinho,et al.  Practical procedure for discriminating monofloral honey with a broad pollen profile variability using an electronic tongue. , 2014, Talanta.

[53]  M. Stocchero,et al.  NMR assessment of European acacia honey origin and composition of EU-blend based on geographical floral markers. , 2019, Food chemistry.

[54]  Sib Krishna Ghoshal,et al.  Detection techniques for adulterants in honey: Challenges and recent trends , 2019, Journal of Food Composition and Analysis.

[55]  Bin Wang,et al.  Molecular Tracing of the Origin of Six Different Plant Species in Bee Honey Using Real-Time PCR. , 2017, Journal of AOAC International.

[56]  M. Halagarda,et al.  A new model to identify botanical origin of Polish honeys based on the physicochemical parameters and chemometric analysis , 2017 .

[57]  Syed Ghulam Musharraf,et al.  Application of analytical methods in authentication and adulteration of honey. , 2017, Food chemistry.

[58]  P. Pohl,et al.  Determination and Fractionation of Metals in Honey , 2009 .

[59]  H. Kawashima,et al.  Heart-cutting two-dimensional liquid chromatography combined with isotope ratio mass spectrometry for the determination of stable carbon isotope ratios of gluconic acid in honey. , 2019, Journal of chromatography. A.

[60]  Verónica Berriel Carbon Stable-Isotope and Physicochemical Data as a Possible Tool to Differentiate between Honey-Production Environments in Uruguay , 2018, Foods.

[61]  Mircea Oroian,et al.  Honey authentication based on physicochemical parameters and phenolic compounds , 2017, Comput. Electron. Agric..

[62]  P. Pohl,et al.  Recent achievements in element analysis of bee honeys by atomic and mass spectrometry methods , 2017 .

[63]  E. Haubruge,et al.  Volatile Profile and Physico-Chemical Analysis of Acacia Honey for Geographical Origin and Nutritional Value Determination , 2019, Foods.

[64]  S. Ražić,et al.  Comparative study of the chemical composition and biological potential of honey from different regions of Serbia , 2020 .

[65]  Andrew Cannavan,et al.  An investigative study on discrimination of honey of various floral and geographical origins using UPLC-QToF MS and multivariate data analysis , 2017 .

[66]  Z. Zakaria,et al.  Honey and its nutritional and anti-inflammatory value , 2021, BMC Complementary Medicine and Therapies.

[67]  S. Mammi,et al.  Objective Definition of Monofloral and Polyfloral Honeys Based on NMR Metabolomic Profiling. , 2016, Journal of agricultural and food chemistry.

[68]  G. Radu,et al.  Geographical and Botanical Origin Discrimination of Romanian Honey Using Complex Stable Isotope Data and Chemometrics , 2015, Food Analytical Methods.

[69]  Luana Bontempo,et al.  Multielement stable isotope ratios (H, C, N, S) of honey from different European regions , 2010 .

[70]  M. Yohda,et al.  Identification and classification of honey’s authenticity by attenuated total reflectance Fourier-transform infrared spectroscopy and chemometric method , 2019, Veterinary world.

[71]  Hongbo Song,et al.  Discrimination of geographical origins of Chinese acacia honey using complex 13C/12C, oligosaccharides and polyphenols. , 2019, Food chemistry.

[72]  Anton du Plessis,et al.  Verification of authenticity and fraud detection in South African honey using NIR spectroscopy , 2017 .

[73]  I. Jerković,et al.  Color evaluation of seventeen European unifloral honey types by means of spectrophotometrically determined CIE L*Cab*h(ab)° chromaticity coordinates. , 2014, Food chemistry.

[74]  G. Pastore,et al.  Volatile profile of monofloral honeys produced in Brazilian semiarid region by stingless bees and key volatile compounds , 2018, LWT.

[75]  N. Mahat,et al.  Provenance Establishment of Stingless Bee Honey Using Multi‐element Analysis in Combination with Chemometrics Techniques , 2018, Journal of forensic sciences.

[76]  A. Conchado,et al.  Volatile profile in the accurate labelling of monofloral honey. The case of lavender and thyme honey. , 2017, Food chemistry.

[77]  J. Grúz,et al.  Content of metals and metabolites in honey originated from the vicinity of industrial town Košice (eastern Slovakia) , 2016, Environmental Science and Pollution Research.

[78]  C. Perdomo,et al.  Differentiating pasture honey from eucalyptus honey based on carbon isotopic data in Uruguay , 2019, Heliyon.

[79]  Stavros Kontakos,et al.  Botanical discrimination of Greek unifloral honeys with physico-chemical and chemometric analyses. , 2014, Food chemistry.

[80]  M. Biesaga,et al.  Solid-phase extraction procedure for determination of phenolic acids and some flavonols in honey. , 2008, Journal of chromatography. A.

[81]  G. Piva,et al.  Sensory analysis integrated by palynological and physicochemical determinations plays a key role in differentiating unifloral honeys of similar botanical origins (Myrtaceae honeys from southern Spain) , 2015 .

[82]  D. Cozzolino,et al.  Fraud in Animal Origin Food Products: Advances in Emerging Spectroscopic Detection Methods over the Past Five Years , 2020, Foods.

[83]  L. V. Gonzaga,et al.  Development and validation of a LC-ESI-MS/MS method for the determination of phenolic compounds in honeydew honeys with the diluted-and-shoot approach. , 2016, Food research international.

[84]  Søren Balling Engelsen,et al.  TRENDS IN THE APPLICATION OF CHEMOMETRICS TO FOODOMICS STUDIES , 2015 .

[85]  Robert S Plumb,et al.  Current practice of liquid chromatography-mass spectrometry in metabolomics and metabonomics. , 2014, Journal of pharmaceutical and biomedical analysis.

[86]  E. Baranyai,et al.  Elemental analysis of Hungarian honey samples and bee products by MP-AES method , 2019, Microchemical Journal.

[87]  Du Bing,et al.  Recent advancements in detecting sugar-based adulterants in honey – A challenge , 2017 .

[88]  L. V. Gonzaga,et al.  Differentiation of honeydew honeys and blossom honeys: a new model based on colour parameters , 2019, Journal of Food Science and Technology.

[89]  Joana Costa,et al.  Novel diagnostic tools for Asian (Apis cerana) and European (Apis mellifera) honey authentication. , 2018, Food research international.

[90]  A. Segura‐Carretero,et al.  Characterisation of phenolic compounds in Algerian honeys by RP-HPLC coupled to electrospray time-of-flight mass spectrometry , 2017 .

[91]  L. V. Gonzaga,et al.  Physicochemical characteristics of bracatinga honeydew honey and blossom honey produced in the state of Santa Catarina: An approach to honey differentiation. , 2019, Food research international.

[92]  F. Longobardi,et al.  Investigating the impact of botanical origin and harvesting period on carbon stable isotope ratio values (13C/12C) and different parameter analysis of Greek unifloral honeys: A chemometric approach for correct botanical discrimination , 2016 .

[93]  L. V. Gonzaga,et al.  Honey: Chemical composition, stability and authenticity. , 2016, Food chemistry.

[94]  M. Kontominas,et al.  Differentiation of Greek Thyme Honeys According to Geographical Origin Based on the Combination of Phenolic Compounds and Conventional Quality Parameters Using Chemometrics , 2014, Food Analytical Methods.

[95]  Rasmus Bro,et al.  Determination of the Botanical Origin of Honey by Front-Face Synchronous Fluorescence Spectroscopy , 2014, Applied spectroscopy.

[96]  A. Verzera,et al.  Chiral volatile compounds for the determination of orange honey authenticity , 2014 .

[97]  Federica Camin,et al.  Food authentication: Techniques, trends & emerging approaches , 2016 .

[98]  J. Simal-Gándara,et al.  Phenolic compounds from Mediterranean foods as nutraceutical tools for the prevention of cancer: The effect of honey polyphenols on colorectal cancer stem-like cells from spheroids. , 2020, Food chemistry.

[99]  L. Mannina,et al.  Advances in Nuclear Magnetic Resonance Spectroscopy for Food Authenticity Testing , 2016 .

[100]  Joana S. Amaral,et al.  A Comprehensive Review on the Main Honey Authentication Issues: Production and Origin. , 2017, Comprehensive reviews in food science and food safety.

[101]  R. Consonni,et al.  NMR-based metabolomic approach to differentiate organic and conventional Italian honey , 2019, Food Control.

[102]  S. M. Osés,et al.  Sugar composition and sugar-related parameters of honeys from the northern Iberian Plateau , 2018, Journal of Food Composition and Analysis.

[103]  K. Rogers,et al.  Untargeted and Targeted Discrimination of Honey Collected by Apis cerana and Apis mellifera Based on Volatiles Using HS-GC-IMS and HS-SPME-GC-MS. , 2019, Journal of agricultural and food chemistry.

[104]  Darija Vukić Lušić,et al.  Chemical markers for the authentication of unifloral Salvia officinalis L. honey , 2015 .

[105]  Zhenbin Wu,et al.  Investigation on the adsorption of phosphorus in all fractions from sediment by modified maifanite , 2018, Scientific Reports.

[106]  Yongxin Zhang,et al.  Strategy for comparative untargeted metabolomics reveals honey markers of different floral and geographic origins using ultrahigh-performance liquid chromatography-hybrid quadrupole-orbitrap mass spectrometry. , 2017, Journal of chromatography. A.

[107]  N. L. García The Current Situation on the International Honey Market , 2018, Bee World.

[108]  M. Loghavi,et al.  Physicochemical properties of Iranian ziziphus honey and emerging approach for predicting them using electronic nose , 2019 .

[109]  E. Geană,et al.  Establishing authenticity of honey via comprehensive Romanian honey analysis. , 2020, Food chemistry.

[110]  Jing Zhao,et al.  Floral classification of honey using liquid chromatography-diode array detection-tandem mass spectrometry and chemometric analysis. , 2014, Food chemistry.

[111]  U. Gašić,et al.  Phenolic profile and antioxidant activity of Serbian polyfloral honeys. , 2014, Food chemistry.

[112]  G. Cristea,et al.  REEs – a possible tool for geographical origin assessment? , 2020 .

[113]  M. Yang,et al.  Broadband Dielectric Properties of Honey: Effect of Water Content , 2018 .

[114]  R. Perestrelo,et al.  Establishment of authenticity and typicality of sugarcane honey based on volatile profile and multivariate analysis , 2017 .

[115]  M. Glória,et al.  Synephrine - A potential biomarker for orange honey authenticity. , 2017, Food chemistry.

[116]  G. Eppe,et al.  Headspace Solid Phase Microextraction Coupled to GC/MS for the Analysis of Volatiles of Honeys from Arid and Mediterranean Areas of Algeria , 2019, Chemistry & biodiversity.

[117]  L. Fontanesi,et al.  Authentication of honey based on a DNA method to differentiate Apis mellifera subspecies: Application to Sicilian honey bee ( A. m. siciliana ) and Iberian honey bee ( A. m. iberiensis ) honeys , 2018, Food Control.

[118]  Y. R. Torres,et al.  Comparative analysis of the volatile composition of honeys from Brazilian stingless bees by static headspace GC-MS. , 2017, Food research international.

[119]  M. Tessari,et al.  NMR carbohydrate profile in tracing acacia honey authenticity. , 2019, Food chemistry.

[120]  Roberto G. Pellerano,et al.  Multivariate classification of honeys from Corrientes (Argentina) according to geographical origin based on physicochemical properties , 2016 .

[121]  M. Antunes,et al.  Honey as a Complementary Medicine , 2017, Integrative medicine insights.

[122]  E. Doménech,et al.  Effect of country origin on physicochemical, sugar and volatile composition of acacia, sunflower and tilia honeys , 2014 .

[123]  M. Battino,et al.  Therapeutic and preventive properties of honey and its bioactive compounds in cancer: an evidence-based review , 2019, Nutrition Research Reviews.

[124]  I. Mafra,et al.  Improving DNA isolation from honey for the botanical origin identification , 2015 .

[125]  A. Seiman,et al.  Characterization of Estonian honeys by botanical origin , 2014 .

[126]  Rommel M. Barbosa,et al.  Predicting the botanical and geographical origin of honey with multivariate data analysis and machine learning techniques: A review , 2019, Comput. Electron. Agric..

[127]  D. Barałkiewicz,et al.  Characterization of Polish rape and honeydew honey according to their mineral contents using ICP-MS and F-AAS/AES. , 2008, Analytica chimica acta.