Recent advancements in detecting sugar-based adulterants in honey – A challenge

Abstract Honey is a natural sweetening agent widely used in food products and as a daily diet ingredient, but it also has medicinal properties. An increase in the demand for honey has resulted in adulteration by different sugar syrups. Authentication is therefore important for consumer confidence. This comprehensive overview covers known syrup adulterants and the analytical methodologies adopted for their detection in honey. For instance, TLC is the oldest method for honey analysis. C-isotope methods such as SCIRA, which can differentiate adulterated honey from C3 plants, are explained. Common analytical techniques such as HPAEC, GC, and HPLC are discussed. Advanced techniques, including IR, NMR, and Raman spectroscopy, which enhance the analysis process for larger numbers of samples, are also presented. Finally, Q-TOF-MS is addressed as a metabolomics-based detection method, since it has recently gained momentum following the increase in different adulterants that make detection more difficult.

[1]  Ljiljana Primorac,et al.  Flavonoid profile of Robinia honeys produced in Croatia , 2007 .

[2]  Jian Wang,et al.  Analyses of macrolide antibiotic residues in eggs, raw milk, and honey using both ultra-performance liquid chromatography/quadrupole time-of-flight mass spectrometry and high-performance liquid chromatography/tandem mass spectrometry. , 2007, Rapid communications in mass spectrometry : RCM.

[3]  E. K. Kemsley,et al.  Discriminant analysis of high-dimensional data: a comparison of principal components analysis and partial least squares data reduction methods , 1996 .

[4]  A. Atanassov,et al.  A rapid differentiation between oak honeydew honey and nectar and other honeydew honeys by NMR spectroscopy. , 2012, Food chemistry.

[5]  N. A. Abu Bakar,et al.  Low temperature followed by matrix solid-phase dispersion-sonication procedure for the determination of multiclass pesticides in palm oil using LC-TOF-MS. , 2011, Journal of hazardous materials.

[6]  A. I. Ruiz-Matute,et al.  Difructose anhydrides as quality markers of honey and coffee , 2006 .

[7]  M. Grenier-loustalot,et al.  Application of carbohydrate analysis to verify honey authenticity. , 2003, Journal of chromatography. A.

[8]  M. L. Sanz,et al.  Gas chromatographic-mass spectrometric method for the qualitative and quantitative determination of disaccharides and trisaccharides in honey. , 2004, Journal of chromatography. A.

[9]  A. I. Ruiz-Matute,et al.  Carbohydrate composition of high-fructose corn syrups (HFCS) used for bee feeding: effect on honey composition. , 2010, Journal of agricultural and food chemistry.

[10]  I. Martı́n,et al.  Detection of honey adulteration with beet sugar using stable isotope methodology , 1998 .

[11]  J. Namieśnik,et al.  Challenges in preparing honey samples for chromatographic determination of contaminants and trace residues , 2008 .

[12]  H. Wahdan,et al.  Causes of the antimicrobial activity of honey , 2007, Infection.

[13]  Ni Cheng,et al.  Identification of Acacia Honey Adulteration with Rape Honey Using Liquid Chromatography–Electrochemical Detection and Chemometrics , 2014, Food Analytical Methods.

[14]  M. Zou,et al.  Rapid authentication of olive oil adulteration by Raman spectrometry. , 2009, Journal of agricultural and food chemistry.

[15]  Qiang Wang,et al.  2-acetylfuran-3-glucopyranoside as a novel marker for the detection of honey adulterated with rice syrup. , 2013, Journal of agricultural and food chemistry.

[16]  M. Youssef,et al.  Adulteration of honey with high-fructose corn syrup: Detection by different methods , 1993 .

[17]  Nieves Corzo,et al.  HPAEC-PAD oligosaccharide analysis to detect adulterations of honey with sugar syrups , 2008 .

[18]  Daniel Cabrol-Bass,et al.  Detection and quantification of honey adulteration via direct incorporation of sugar syrups or bee-feeding: preliminary study using high-performance anion exchange chromatography with pulsed amperometric detection (HPAEC-PAD) and chemometrics , 2005 .

[19]  A. I. Ruiz-Matute,et al.  Detection of adulterations of honey with high fructose syrups from inulin by GC analysis. , 2010 .

[20]  Gerard Downey,et al.  Potential of near Infrared Transflectance Spectroscopy to Detect Adulteration of Irish Honey by Beet Invert Syrup and High Fructose Corn Syrup , 2006 .

[21]  L. Croft Stable isotope mass spectrometry in honey analysis , 1987 .

[22]  Johan A. K. Suykens,et al.  Least Squares Support Vector Machine Classifiers , 1999, Neural Processing Letters.

[23]  K. Rogers,et al.  Investigating C-4 sugar contamination of manuka honey and other New Zealand honey varieties using carbon isotopes. , 2014, Journal of agricultural and food chemistry.

[24]  Arnaud Salvador,et al.  Polysaccharides as a marker for detection of corn sugar syrup addition in honey. , 2009, Journal of agricultural and food chemistry.

[25]  S. Mammi,et al.  1H nuclear magnetic resonance spectra of chloroform extracts of honey for chemometric determination of its botanical origin. , 2010, Journal of agricultural and food chemistry.

[26]  M. E. Conti Lazio region (central Italy) honeys: a survey of mineral content and typical quality parameters. , 2000 .

[27]  Robert G. Dambergs,et al.  Preliminary study on the application of visible–near infrared spectroscopy and chemometrics to classify Riesling wines from different countries , 2008 .

[28]  David De Jong,et al.  Detection of adulteration of commercial honey samples by the 13C/12C isotopic ratio , 2003 .

[29]  Ludovic Duponchel,et al.  Comparison of supervised pattern recognition methods with McNemar’s statistical test: Application to qualitative analysis of sugar beet by near-infrared spectroscopy , 2003 .

[30]  I Kushnir Sensitive thin layer chromatographic detection of high fructose corn sirup and other adulterants in honey. , 1979, Journal - Association of Official Analytical Chemists.

[31]  R. Dasari,et al.  Ultrasensitive chemical analysis by Raman spectroscopy. , 1999, Chemical reviews.

[32]  Jiewen Zhao,et al.  Determination of rice syrup adulterant concentration in honey using three-dimensional fluorescence spectra and multivariate calibrations. , 2014, Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy.

[33]  Qilei Guo,et al.  Detection of honey adulteration with starch syrup by high performance liquid chromatography. , 2015, Food chemistry.

[34]  Marcelo Blanco,et al.  NIR spectroscopy: a rapid-response analytical tool , 2002 .

[35]  C. Kumaravelu,et al.  Detection and Quantification of Adulteration in Honey through Near Infrared Spectroscopy , 2015 .

[36]  Fang Chen,et al.  Determination of Chinese honey adulterated with high fructose corn syrup by near infrared spectroscopy , 2011 .

[37]  A. Laere,et al.  Inulin metabolism in dicots: chicory as a model system , 2002 .

[38]  Ana I Cabañero,et al.  Liquid chromatography coupled to isotope ratio mass spectrometry: a new perspective on honey adulteration detection. , 2006, Journal of agricultural and food chemistry.

[39]  C. Corradini,et al.  High-Performance Anion-Exchange Chromatography Coupled with Pulsed Electrochemical Detection as a Powerful Tool to Evaluate Carbohydrates of Food Interest: Principles and Applications , 2012 .

[40]  Hongyuan Chen,et al.  Rapid and reliable method for analysis of raw and honey-processed astragalus by UPLC/ESI-Q-TOF-MS using HSS T3 columns , 2014 .

[41]  M. Grenier-loustalot,et al.  Characterization of honey amino acid profiles using high-pressure liquid chromatography to control authenticity , 2004, Analytical and bioanalytical chemistry.

[42]  H. Förstel The natural fingerprint of stable isotopes—use of IRMS to test food authenticity , 2007, Analytical and bioanalytical chemistry.

[43]  Hasan Kocaokutgen,et al.  Detection of adulterated honey produced by honeybee (Apis mellifera L.) colonies fed with different levels of commercial industrial sugar (C₃ and C₄ plants) syrups by the carbon isotope ratio analysis. , 2014, Food chemistry.

[44]  M. Pérez-Coello,et al.  Wine science in the metabolomics era , 2015 .

[45]  A. Sabatini,et al.  Use of quinoline alkaloids as markers of the floral origin of chestnut honey. , 2009, Journal of agricultural and food chemistry.

[46]  A. Hosu,et al.  Application of a newly developed and validated high-performance thin-layer chromatographic method to control honey adulteration. , 2013, Journal of chromatography. A.

[47]  J. Irudayaraj,et al.  Comparison of FTIR, FT‐Raman, and NIR Spectroscopy in a Maple Syrup Adulteration Study , 2002 .

[48]  A. Guler,et al.  Verification test of sensory analyses of comb and strained honeys produced as pure and feeding intensively with sucrose (Saccharum officinarum L.) syrup. , 2008, Food chemistry.

[49]  Ammar Zakaria,et al.  A Hybrid Sensing Approach for Pure and Adulterated Honey Classification , 2012, Sensors.

[50]  Stefan Bogdanov,et al.  Physico-chemical and bioactive properties of different floral origin honeys from Romania , 2009 .

[51]  An NMR-based metabolomic approach to identify the botanical origin of honey , 2012, Metabolomics.

[52]  A. Sabatini,et al.  Classification of Italian honeys by 2D HR-NMR. , 2008, Journal of agricultural and food chemistry.

[53]  P. Sivaperumal,et al.  Rapid determination of pesticide residues in fruits and vegetables, using ultra-high-performance liquid chromatography/time-of-flight mass spectrometry. , 2015, Food chemistry.

[54]  Harpreet Kaur,et al.  Detection of jaggery syrup in honey using near-infrared spectroscopy , 2010, International journal of food sciences and nutrition.

[55]  G. Osorio-Revilla,et al.  Application of FTIR-HATR spectroscopy and multivariate analysis to the quantification of adulterants in Mexican honeys. , 2009 .

[56]  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 .

[57]  Ali Topcu,et al.  Rapid analysis of sugars in honey by processing Raman spectrum using chemometric methods and artificial neural networks. , 2013, Food chemistry.

[58]  Gerard Downey,et al.  Detection and Quantification of Apple Adulteration in Strawberry and Raspberry Purées Using Visible and near Infrared Spectroscopy , 2002 .

[59]  Joseph Maria Kumar Irudayaraj,et al.  Detection of inverted beet sugar adulteration of honey by FTIR spectroscopy , 2001 .

[60]  Joseph Maria Kumar Irudayaraj,et al.  Determination of Sugars in Aqueous Mixtures Using Mid-infrared Spectroscopy , 2000 .

[61]  Yang Shan,et al.  Detection of honey adulteration by high fructose corn syrup and maltose syrup using Raman spectroscopy , 2012 .

[62]  Gerard Downey,et al.  Initial study of honey adulteration by sugar solutions using midinfrared (MIR) spectroscopy and chemometrics. , 2004, Journal of agricultural and food chemistry.

[63]  M. A. Rios-Corripio,et al.  Analysis of adulteration in honey with standard sugar solutions and syrups using attenuated total reflectance-Fourier transform infrared spectroscopy and multivariate methods , 2012 .

[64]  Ricard Boqué,et al.  Data fusion methodologies for food and beverage authentication and quality assessment - a review. , 2015, Analytica chimica acta.

[65]  Wei Cao,et al.  Rapid Screening of Multiclass Syrup Adulterants in Honey by Ultrahigh-Performance Liquid Chromatography/Quadrupole Time of Flight Mass Spectrometry. , 2015, Journal of agricultural and food chemistry.

[66]  K. Saito,et al.  Difructose Anhydrides: Their Mass-Production and Physiological Functions , 2000, Bioscience, biotechnology, and biochemistry.

[67]  Giulia Papotti,et al.  Detection of honey adulteration by sugar syrups using one-dimensional and two-dimensional high-resolution nuclear magnetic resonance. , 2010, Journal of agricultural and food chemistry.

[68]  J. Phillips,et al.  Gas-liquid chromatographic test for honey adulteration by high fructose corn sirup. , 1979, Journal - Association of Official Analytical Chemists.

[69]  Eliane Teixeira Mársico,et al.  Detection of honey adulteration of high fructose corn syrup by Low Field Nuclear Magnetic Resonance (LF 1H NMR) , 2014 .

[70]  A. Ariño,et al.  Quality evaluation of Spanish rosemary (Rosmarinus officinalis) honey , 1994 .

[71]  Gerard Downey,et al.  Application of Fourier transform midinfrared spectroscopy to the discrimination between Irish artisanal honey and such honey adulterated with various sugar syrups. , 2006, Journal of agricultural and food chemistry.

[72]  Lutz Elflein,et al.  Improved detection of honey adulteration by measuring differences between 13C/12C stable carbon isotope ratios of protein and sugar compounds with a combination of elemental analyzer — isotope ratio mass spectrometry and liquid chromatography — isotope ratio mass spectrometry (δ13C-EA/LC-IRMS) , 2008, Apidologie.

[73]  D. Krueger,et al.  Modification of AOAC Official MethodSM 998.12 to Add Filtration and/or Centrifugation: Interlaboratory Comparison Exercise , 2013 .

[74]  Yukihiro Ozaki,et al.  Potential of Near-Infrared Fourier Transform Raman Spectroscopy in Food Analysis , 1992 .

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

[76]  Z. Lou,et al.  Analysis and pharmacokinetic study of curdione in Rhizoma Curcumae by UPLC/QTOF/MS. , 2014, Biomedical chromatography : BMC.

[77]  E. Maltini,et al.  Crystallization in “Tarassaco” Italian honey studied by DSC , 2010 .

[78]  A. Soria,et al.  A new methodology based on GC-MS to detect honey adulteration with commercial syrups. , 2007, Journal of agricultural and food chemistry.

[79]  M. Tosun,et al.  Detection of adulteration in honey samples added various sugar syrups with 13C/12C isotope ratio analysis method. , 2013, Food chemistry.

[80]  D. Cabrol-Bass,et al.  Honey characterization and adulteration detection by pattern recognition applied on HPAEC-PAD profiles. 1. Honey floral species characterization. , 2003, Journal of agricultural and food chemistry.

[81]  G. Downey,et al.  Detecting and quantifying sunflower oil adulteration in extra virgin olive oils from the eastern mediterranean by visible and near-infrared spectroscopy. , 2002, Journal of agricultural and food chemistry.

[82]  J. Irudayaraj,et al.  Rapid Determination of Invert Cane Sugar Adulteration in Honey Using FTIR Spectroscopy and Multivariate Analysis , 2003 .

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

[84]  A. Moing,et al.  Sucrose, glucose, and fructose extraction in aqueous carrot root extracts prepared at different temperatures by means of direct NMR measurements. , 2006, Journal of agricultural and food chemistry.

[85]  A. Soria,et al.  Characterization of traditional Spanish edible plant syrups based on carbohydrate GC–MS analysis , 2010 .

[86]  A. Gören,et al.  13C/12C pattern of honey from Turkey and determination of adulteration in commercially available honey samples using EA-IRMS , 2012 .

[87]  J. Friedman Regularized Discriminant Analysis , 1989 .

[88]  A. Gómez-Caravaca,et al.  Distribution of phenolic compounds and other polar compounds in the tuber of Solanum tuberosum L. by HPLC-DAD-q-TOF and study of their antioxidant activity , 2014 .

[89]  J. Marchini,et al.  Presence of C4 Sugars in Honey Samples Detected by The Carbon Isotope Ratio Measured by IRMS , 2007 .

[90]  Joseph Maria Kumar Irudayaraj,et al.  Discrimination and classification of beet and cane inverts in honey by FT-Raman spectroscopy , 2002 .

[91]  Jacek Namieśnik,et al.  Determination of antibiotic residues in honey , 2011 .

[92]  B. Senge,et al.  Analytical and rheological investigations into selected unifloral German honey , 2009 .

[93]  Serap B Çinar,et al.  Carbon isotope ratio (13C/12C) of pine honey and detection of HFCS adulteration. , 2014, Food chemistry.

[94]  N. Low,et al.  Analysis and quantitation of the carbohydrates in honey using high-performance liquid chromatography , 1990 .

[95]  K. Rogers,et al.  Eliminating false positive C4 sugar tests on New Zealand Manuka honey. , 2010, Rapid communications in mass spectrometry : RCM.

[96]  M. Grenier-loustalot,et al.  Study and validity of 13C stable carbon isotopic ratio analysis by mass spectrometry and 2H site-specific natural isotopic fractionation by nuclear magnetic resonance isotopic measurements to characterize and control the authenticity of honey. , 2007, Analytica chimica acta.

[97]  D. Lachenmeier,et al.  Qualitative and Quantitative Control of Honeys Using NMR Spectroscopy and Chemometrics , 2013 .

[98]  Ramón Aparicio,et al.  Detection of virgin olive oil adulteration by Fourier transform Raman spectroscopy , 1996 .

[99]  M. Biesaga,et al.  Analysis of phenolic acids and flavonoids in honey , 2009 .

[100]  S. Karaman,et al.  Steady, dynamic and creep rheological analysis as a novel approach to detect honey adulteration by fructose and saccharose syrups: Correlations with HPLC-RID results. , 2014, Food research international.

[101]  M. Helal,et al.  Mineral contents and physicochemical properties of natural honey produced in Al-Qassim region, Saudi Arabia , 2007 .

[102]  Roberto Maffei Facino,et al.  Standardization of antioxidant properties of honey by a combination of spectrophotometric/fluorimetric assays and chemometrics , 2005 .

[103]  M. Durak,et al.  In-house validation for the determination of honey adulteration with plant sugars (C4) by Isotope Ratio Mass Spectrometry (IR-MS) , 2014 .

[104]  Claude Deroanne,et al.  Isolation and identification of inulooligosaccharides resulting from inulin hydrolysis. , 2007, Analytica chimica acta.

[105]  Jay P. Gore,et al.  Authentication of Olive Oil Adulterated with Vegetable Oils Using Fourier Transform Infrared Spectroscopy , 2002 .

[106]  Elke Anklam,et al.  A review of the analytical methods to determine the geographical and botanical origin of honey , 1998 .

[107]  J. Irudayaraj,et al.  Prediction of Inverted Cane Sugar Adulteration of Honey by Fourier Transform Infrared Spectroscopy , 2001 .

[108]  J. White,et al.  Detection of honey adulteration by carbohydrage analysis. , 1980, Journal - Association of Official Analytical Chemists.

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

[110]  P. Molan,et al.  A Survey of the Antibacterial Activity of Some New Zealand Honeys , 1991, The Journal of pharmacy and pharmacology.

[111]  Zhuoyong Zhang,et al.  Detection of adulterants such as sweeteners materials in honey using near-infrared spectroscopy and chemometrics , 2010 .

[112]  Yidan Bao,et al.  Visible and near infrared spectroscopy for rapid detection of citric and tartaric acids in orange juice , 2007 .