Quality assessment and authentication of virgin olive oil by NMR spectroscopy: a critical review.

Nuclear Magnetic Resonance (NMR) Spectroscopy has been extensively used for the analysis of olive oil and it has been established as a valuable tool for its quality assessment and authenticity. To date, a large number of research and review articles have been published with regards to the analysis of olive oil reflecting the potential of the NMR technique in these studies. In this critical review, we cover recent results in the field and discuss deficiencies and precautions of the three NMR techniques ((1)H, (13)C, (31)P) used for the analysis of olive oil. The two methodological approaches of metabonomics, metabolic profiling and metabolic fingerprinting, and the statistical methods applied for the classification of olive oils will be discussed in critical way. Some useful information about sample preparation, the required instrumentation for an effective analysis, the experimental conditions and data processing for obtaining high quality spectra will be presented as well. Finally, a constructive criticism will be exercised on the present methodologies used for the quality control and authentication of olive oil.

[1]  M. D. Guillén,et al.  Rapid simultaneous determination by proton NMR of unsaturation and composition of acyl groups in vegetable oils , 2003 .

[2]  N. Uccella,et al.  Biophenolic components of olives , 2000 .

[3]  G. P. Blanch,et al.  Rapid Recognition of Olive Oil Adulterated with Hazelnut Oil by Direct Analysis of the Enantiomeric Composition of Filbertone , 1998 .

[4]  D. Boskou Olive Oil : Minor Constituents and Health , 2008 .

[5]  Ray Freeman,et al.  Band-selective radiofrequency pulses , 1991 .

[6]  P. Petrakis,et al.  Influence of harvest year, cultivar and geographical origin on Greek extra virgin olive oils composition: a study by NMR spectroscopy and biometric analysis. , 2012, Food chemistry.

[7]  F. Reniero,et al.  1H NMR as a tool for the analysis of mixtures of virgin olive oil with oils of different botanical origin , 2000 .

[8]  Royston Goodacre,et al.  Rapid quantitative assessment of the adulteration of virgin olive oils with hazelnut oils using Raman spectroscopy and chemometrics. , 2003, Journal of agricultural and food chemistry.

[9]  P. Dais,et al.  Detection and quantification of phenolic compounds in olive oil by high resolution 1H nuclear magnetic resonance spectroscopy. , 2009, Analytica chimica acta.

[10]  Flow techniques in NMR spectroscopy , 2007 .

[11]  S. Hollis Analysis of Method Comparison Studies , 1996, Annals of clinical biochemistry.

[12]  D. Naughton,et al.  Generation of lipid peroxidation products in culinary oils and fats during episodes of thermal stressing: A high field 1H NMR study , 1994, FEBS letters.

[13]  L. Mannina,et al.  Olive and hazelnut oils : A study by high-field 1H NMR and gas chromatography , 1999 .

[14]  P. Petrakis,et al.  A novel analytical method to detect adulteration of virgin olive oil by other oils , 2000 .

[15]  Hartmut Schäfer,et al.  Classification of olive oils according to geographical origin by using 1H NMR fingerprinting combined with multivariate analysis , 2012 .

[16]  P. Giraudeau,et al.  Improvement of the inverse-gated-decoupling sequence for a faster quantitative analysis of various samples by 13C NMR spectroscopy. , 2006, Journal of magnetic resonance.

[17]  Manfred Spraul,et al.  Cryogenically cooled probes—a leap in NMR technology , 2005 .

[18]  K. Linnet,et al.  Evaluation of regression procedures for methods comparison studies. , 1993, Clinical chemistry.

[19]  Apostolos Spyros,et al.  Geographical characterization of greek virgin olive oils (cv. Koroneiki) using 1H and 31P NMR fingerprinting with canonical discriminant analysis and classification binary trees. , 2008, Journal of agricultural and food chemistry.

[20]  María D. Guillén,et al.  1H nuclear magnetic resonance as a fast tool for determining the composition of acyl chains in acylglycerol mixtures , 2003 .

[21]  M. Dobarganes,et al.  Oil fractionation as a preliminary step in the characterization of vegetable oils by high-resolution 13C NMR spectroscopy , 2002 .

[22]  S. Simova,et al.  Alternative NMR method for quantitative determination of acyl positional distribution in triacylglycerols and related compounds. , 2003, Chemistry and physics of lipids.

[23]  Apostolos Spyros,et al.  Classification of edible oils by employing 31P and 1H NMR spectroscopy in combination with multivariate statistical analysis. A proposal for the detection of seed oil adulteration in virgin olive oils. , 2003, Journal of agricultural and food chemistry.

[24]  L. Mannina,et al.  Geographical characterization of italian extra virgin olive oils using high-field (1)H NMR spectroscopy. , 2001, Journal of agricultural and food chemistry.

[25]  G. Vlahov Regiospecific analysis of natural mixtures of triglycerides using quantitative 13C nuclear magnetic resonance of acyl chain carbonyl carbons , 1998 .

[26]  Luisa Ciobanu,et al.  Reduced data acquisition time in multi-dimensional NMR spectroscopy using multiple-coil probes. , 2005, Journal of magnetic resonance.

[27]  Carmen García-Ruiz,et al.  Traceability markers to the botanical origin in olive oils. , 2010, Journal of agricultural and food chemistry.

[28]  M. Tsimidou,et al.  Loss of stability of “veiled” (cloudy) virgin olive oils in storage , 2005 .

[29]  K. Karaghiosoff Phosphorus‐31 NMR , 2007 .

[30]  Károly Héberger,et al.  Classification of olive oils using high throughput flow 1H NMR fingerprinting with principal component analysis, linear discriminant analysis and probabilistic neural networks , 2005 .

[31]  Ramón Aparicio,et al.  The detection of the presence of hazelnut oil in olive oil by free and esterified sterols , 2006 .

[32]  K. Albert On-line LC-NMR and related techniques , 2002 .

[33]  L. Tseng,et al.  Separation and identification of phenolic compounds in olive oil by coupling high-performance liquid chromatography with postcolumn solid-phase extraction to nuclear magnetic resonance spectroscopy (LC-SPE-NMR). , 2005, Journal of agricultural and food chemistry.

[34]  D. L. García-González,et al.  Detection of the presence of refined hazelnut oil in refined olive oil by fluorescence spectroscopy. , 2007, Journal of agricultural and food chemistry.

[35]  Innocenzo Muzzalupo,et al.  Multivariate Analysis of 1H-NMR Spectra of Genetically Characterized Extra Virgin Olive Oils and Growth Soil Correlations , 2011 .

[36]  Randall D. Tobias,et al.  Chemometrics: A Practical Guide , 1998, Technometrics.

[37]  Francesco Addeo,et al.  1H and 13C NMR of virgin olive oil. An overview , 1997 .

[38]  E. Goicoechea,et al.  Detection of primary and secondary oxidation products by Fourier transform infrared spectroscopy (FTIR) and 1H nuclear magnetic resonance (NMR) in sunflower oil during storage. , 2007, Journal of agricultural and food chemistry.

[39]  C. Schiavone,et al.  Quantitative 13C NMR method using the DEPT pulse sequence for the determination of the geographical origin (DOP) of olive oils , 2001 .

[40]  Luisa Mannina,et al.  Liquid state 1H high field NMR in food analysis. , 2012, Progress in nuclear magnetic resonance spectroscopy.

[41]  H. Bartsch,et al.  Identification of lignans as major components in the phenolic fraction of olive oil. , 2000, Clinical chemistry.

[42]  E. Frankel,et al.  Chemistry of extra virgin olive oil: adulteration, oxidative stability, and antioxidants. , 2010, Journal of agricultural and food chemistry.

[43]  F. Reniero,et al.  Characterization of italian olive oils based on analytical and nuclear magnetic resonance determinations , 2000 .

[44]  M. Brenes,et al.  Comparison of analytical methodologies based on 1h and 31p NMR spectroscopy with conventional methods of analysis for the determination of some olive oil constituents. , 2007, Journal of agricultural and food chemistry.

[45]  P. Barone,et al.  A high-field1H nuclear magnetic resonance study of the minor components in virgin olive oils , 1996 .

[46]  D. Boskou,et al.  Determination of phospholipids in olive oil by 31P NMR spectroscopy. , 2008, Journal of agricultural and food chemistry.

[47]  H. Bartsch,et al.  Isolation, structure elucidation and antioxidant potential of the major phenolic and flavonoid compounds in brined olive drupes. , 2003, Food and chemical toxicology : an international journal published for the British Industrial Biological Research Association.

[48]  G. Vlahov,et al.  Determination of geographical origin of olive oils using 13C nuclear magnetic resonance spectroscopy. I - Classification of olive oils of the Puglia region with denomination of protected origin. , 2003, Journal of agricultural and food chemistry.

[49]  F. Schena,et al.  1H Nuclear Magnetic Resonance Study of Olive Oils Commercially Available as Italian Products in the United States of America , 2012, Nutrients.

[50]  R. Komoroski,et al.  Resolution of phospholipid molecular species by 31P NMR , 1993, Magnetic resonance in medicine.

[51]  Maria Luisa Ruiz del Castillo,et al.  Detection of the adulteration of olive oils by solid phase microextraction and multidimensional gas chromatography , 2006 .

[52]  D. Kell,et al.  Use of 13C nuclear magnetic resonance distortionless enhancement by polarization transfer pulse sequence and multivariate analysis to discriminate olive oil cultivars , 1999 .

[53]  L. Mannina,et al.  P.D.O. (Protected Designation of Origin) : Geographical characterization of tuscan extra virgin olive oils using high-field 1H NMR spectroscopy , 2001 .

[54]  A. Sacco,et al.  Chemometric classification of olive cultivars based on compositional data of oils , 2003 .

[55]  N. Frega,et al.  “Veiled” extra-virgin olive oils: Dispersion response related to oil quality , 1994 .

[56]  Antonio Sacco,et al.  Compositional and structural investigations of ripening of table olives, Bella della Daunia, by means of traditional and magnetic resonance imaging analyses , 2007 .

[57]  Emmanuel Hatzakis,et al.  Determination of water content in olive oil by 31P NMR spectroscopy. , 2008, Journal of agricultural and food chemistry.

[58]  P. Dais,et al.  Kinetics of diglyceride formation and isomerization in virgin olive oils by employing 31P NMR spectroscopy. Formulation of a quantitative measure to assess olive oil storage history. , 2004, Journal of agricultural and food chemistry.

[59]  Yukihiro Ozaki,et al.  The Detection and Quantification of Adulteration in Olive Oil by Near-Infrared Spectroscopy and Chemometrics , 2004, Analytical sciences : the international journal of the Japan Society for Analytical Chemistry.

[60]  T. Claridge High-Resolution NMR Techniques in Organic Chemistry , 1999 .

[61]  M. K. Alam,et al.  Chemometric Analysis of NMR Spectroscopy Data: A Review , 2004 .

[62]  P. Petrakis,et al.  Detection of refined olive oil adulteration with refined hazelnut oil by employing NMR spectroscopy and multivariate statistical analysis. , 2010, Talanta.

[63]  Victor R. Preedy,et al.  Olives and Olive Oil in Health and Disease Prevention , 2010 .

[64]  D. Argyropoulos,et al.  31P NMR Spectroscopy in Wood Chemistry. I. Model Compounds , 1991 .

[65]  L. Mannina,et al.  High resolution nuclear magnetic resonance: from chemical structure to food authenticity , 2002 .

[66]  A. Ferreira,et al.  A simple methodology for the determination of fatty acid composition in edible oils through 1H NMR spectroscopy , 2010, Magnetic resonance in chemistry : MRC.

[67]  P. Koehler,et al.  Comparison of methods for the quantitative determination of phospholipids in lecithins and flour improvers. , 2003, Journal of agricultural and food chemistry.

[68]  A Spyros,et al.  Application of (31)P NMR spectroscopy in food analysis. 1. Quantitative determination of the mono- and diglyceride composition of olive oils. , 2000, Journal of agricultural and food chemistry.

[69]  Apostolos Spyros,et al.  Detection of extra virgin olive oil adulteration with lampante olive oil and refined olive oil using nuclear magnetic resonance spectroscopy and multivariate statistical analysis. , 2005, Journal of agricultural and food chemistry.

[70]  Erin E. Carlson,et al.  Targeted profiling: quantitative analysis of 1H NMR metabolomics data. , 2006, Analytical chemistry.

[71]  R. Burger,et al.  DEPTQ: distorsionless enhancement by polarization transfer including the detection of quaternary nuclei. , 1998, Journal of magnetic resonance.

[72]  Ray Freeman,et al.  Shaped radiofrequency pulses in high resolution NMR , 1998 .

[73]  Ramón Aparicio,et al.  Characterisation of monovarietal virgin olive oils , 2002 .

[74]  A. Carelli,et al.  Characterization of Monovarietal Argentinian Olive Oils from New Productive Zones , 2007 .

[75]  J. A. Menéndez,et al.  Olive oil and health: summary of the II international conference on olive oil and health consensus report, Jaén and Córdoba (Spain) 2008. , 2010, Nutrition, metabolism, and cardiovascular diseases : NMCD.

[76]  P. Dais,et al.  31P NMR spectroscopy in the quality control and authentication of extra‐virgin olive oil: A review of recent progress , 2007, Magnetic resonance in chemistry : MRC.

[77]  F. Hidalgo,et al.  Classification of vegetable oils by high-resolution 13C NMR spectroscopy using chromatographically obtained oil fractions , 2002 .

[78]  Károly Héberger,et al.  Multivariate analysis of NMR fingerprint of the unsaponifiable fraction of virgin olive oils for authentication purposes , 2010 .

[79]  R. Sacchi,et al.  Proton nuclear magnetic resonance rapid and structure-specific determination ofω-3 polyunsaturated fatty acids in fish lipids , 1993 .

[80]  Y. Miyake,et al.  Rapid determination of iodine value by 1H nuclear magnetic resonance spectroscopy , 1998 .

[81]  Giacomo Dugo,et al.  Study of the cultivar-composition relationship in Sicilian olive oils by GC, NMR, and statistical methods. , 2003, Journal of agricultural and food chemistry.

[82]  Margaret V. Holland,et al.  1H-NMR fingerprinting to evaluate the stability of olive oil , 2011 .

[83]  A. Perlin,et al.  Proton spin-lattice relaxation rates in the structural analysis of carbohydrate molecules in solution. , 1987, Advances in carbohydrate chemistry and biochemistry.

[84]  Martin T. Hagan,et al.  Neural network design , 1995 .

[85]  Palmira Villa,et al.  Descriptive review of current NMR-based metabolomic data analysis packages. , 2011, Progress in nuclear magnetic resonance spectroscopy.

[86]  A. Ruiz,et al.  Monitoring the oxidation of unsaturated oils and formation of oxygenated aldehydes by proton NMR , 2005 .

[87]  G. C. Levy Topics in carbon-13 NMR spectroscopy , 1974 .

[88]  P. Barone,et al.  Characterization of Italian extra virgin olive oils using 1H-NMR spectroscopy , 1998 .

[89]  D. L. García-González,et al.  Using 1H and 13C NMR techniques and artificial neural networks to detect the adulteration of olive oil with hazelnut oil , 2004 .

[90]  P. Dais Rotational dynamics of flexible‐chain molecules. 13C NMR relaxation study of hydrocarbon chains attached to a heavy anchor , 1989 .

[91]  F. Hidalgo,et al.  Use of high-resolution 13C nuclear magnetic resonance spectroscopy for the screening of virgin olive oils , 2001 .

[92]  F Savorani,et al.  icoshift: A versatile tool for the rapid alignment of 1D NMR spectra. , 2010, Journal of magnetic resonance.

[93]  Károly Héberger,et al.  Virgin olive oil authentication by multivariate analyses of 1H NMR fingerprints and delta13C and delta2H data. , 2010, Journal of agricultural and food chemistry.

[94]  C. Luchinat,et al.  Concentration dependence of 13C NMR spectra of triglycerides: implications for the NMR analysis of olive oils , 2000 .

[95]  T. Mavromoustakos,et al.  13C NMR analysis of the triacylglycerol composition of Greek virgin olive oils , 1997 .

[96]  F. Hidalgo,et al.  Edible oil analysis by high-resolution nuclear magnetic resonance spectroscopy: recent advances and future perspectives , 2003 .

[97]  A. Ruiz,et al.  High resolution 1H nuclear magnetic resonance in the study of edible oils and fats , 2001 .

[98]  C. Luchinat,et al.  Acyl positional distribution of glycerol tri-esters in vegetable oils: a 13C NMR study , 1999 .

[99]  G. Knothe,et al.  Determination of the fatty acid profile by 1H‐NMR spectroscopy , 2004 .

[100]  R. Aparicio,et al.  A comprehensive study of hazelnut oil composition with comparisons to other vegetable oils, particularly olive oil. , 2003 .

[101]  Julie Wilson,et al.  Analysis of complex mixtures using high-resolution nuclear magnetic resonance spectroscopy and chemometrics. , 2011, Progress in nuclear magnetic resonance spectroscopy.

[102]  W. Bermel,et al.  Multiplicity editing including quaternary carbons: improved performance for the 13C‐DEPTQ pulse sequence , 2007, Magnetic resonance in chemistry : MRC.

[103]  D. L. García-González,et al.  Determining nutritional labeling data for fats and oils by 1H NMR , 2010 .

[104]  P. Dais Carbon-13 nuclear magnetic relaxation and motional behavior of carbohydrate molecules in solution. , 1995, Advances in carbohydrate chemistry and biochemistry.

[105]  S. Mammi,et al.  Caratterizzazione NMR e analisi statistica di oli di oliva DOP veneti , 2005 .

[106]  H. Todt,et al.  Quality control with time‐domain NMR , 2001 .

[107]  R. Aparicio,et al.  Authentication of vegetable oils by chromatographic techniques. , 2000, Journal of chromatography. A.

[108]  Alessandro Piccolo,et al.  High-power gradient diffusion NMR spectroscopy for the rapid assessment of extra-virgin olive oil adulteration , 2010 .

[109]  Y. Miyake,et al.  Determination of unsaturated fatty acid composition by high-resolution nuclear magnetic resonance spectroscopy , 1998 .

[110]  L. Mannina,et al.  High resolution NMR characterization of olive oils in terms of quality, authenticity and geographical origin , 2011, Magnetic resonance in chemistry : MRC.

[111]  A. Webb,et al.  Microcoil nuclear magnetic resonance spectroscopy. , 2005, Journal of pharmaceutical and biomedical analysis.

[112]  D. Altman,et al.  STATISTICAL METHODS FOR ASSESSING AGREEMENT BETWEEN TWO METHODS OF CLINICAL MEASUREMENT , 1986, The Lancet.

[113]  M. Servili,et al.  Simple and hydrolyzable compounds in virgin olive oil. 3. Spectroscopic characterizations of the secoiridoid derivatives. , 1993 .

[114]  C. Guillou,et al.  1H NMR-based protocol for the detection of adulterations of refined olive oil with refined hazelnut oil. , 2009, Journal of agricultural and food chemistry.

[115]  F. Marini,et al.  NMR and chemometrics in tracing European olive oils: the case study of Ligurian samples. , 2010, Talanta.

[116]  Francesco M. Bucarelli,et al.  NMR and statistical study of olive oils from Lazio: A geographical, ecological and agronomic characterization , 2007 .

[117]  P. Dais,et al.  Determination of the diglyceride content in greek virgin olive oils and some commercial olive oils by employing (31)P NMR spectroscopy. , 2002, Journal of agricultural and food chemistry.

[118]  G. P. Blanch,et al.  Study of the adulteration of olive oil with hazelnut oil by on-line coupled high performance liquid chromatographic and gas chromatographic analysis of filbertone. , 2006 .

[119]  S. Kostidis,et al.  High-Resolution NMR Spectroscopy: An Alternative Fast Tool for Qualitative and Quantitative Analysis of Diacylglycerol (DAG) Oil , 2011 .

[120]  S. Mammi,et al.  Olio di oliva DOP del lago di Garda : Uno studio NMR e analisi statistica multivariata , 2006 .

[121]  Douglas B. Kell,et al.  Discrimination of the variety and region of origin of extra virgin olive oils using 13C NMR and multivariate calibration with variable reduction , 1997 .

[122]  J. Sedman,et al.  Cis and trans components of lipids: Analysis by 1H NMR and silver shift reagents , 2012 .

[123]  G. Vlahov,et al.  Application of NMR to the study of olive oils , 1999 .

[124]  A. Ruiz,et al.  Formation of hydroperoxy‐ and hydroxyalkenals during thermal oxidative degradation of sesame oil monitored by proton NMR , 2004 .

[125]  George A. Mousdis,et al.  Rapid synchronous fluorescence method for virgin olive oil adulteration assessment , 2007 .

[126]  A. Ruiz,et al.  Study by means of 1H nuclear magnetic resonance of the oxidation process undergone by edible oils of different natures submitted to microwave action , 2006 .

[127]  K. Wollenberg Quantitative high resolution13C nuclear magnetic resonance of the olefinic and carbonyl carbons of edible vegetable oils , 1990 .

[128]  J. Navarro,et al.  Oil stability prediction by high-resolution (13)C nuclear magnetic resonance spectroscopy. , 2002, Journal of agricultural and food chemistry.

[129]  E. Hatzakis,et al.  Detection and Quantification of Free Glycerol in Virgin Olive Oil by 31P-NMR Spectroscopy , 2010 .

[130]  B. Nikolova-Damyanova Retention of lipids in silver ion high-performance liquid chromatography: facts and assumptions. , 2009, Journal of chromatography. A.

[131]  Maurizio Servili,et al.  Simple and hydrolyzable phenolic compounds in virgin olive oil. 1. Their extraction, separation, and quantitative and semiquantitative evaluation by HPLC , 1992 .

[132]  Nerea Cabo,et al.  Infrared spectroscopy in the study of edible oils and fats , 1997 .

[133]  Johan Trygg,et al.  Chemometrics in metabonomics. , 2007, Journal of proteome research.

[134]  K. Héberger,et al.  Supervised pattern recognition in food analysis. , 2007, Journal of chromatography. A.

[135]  G. Vlahov Quantitative 13C NMR method using the DEPT pulse sequence for the detection of olive oil adulteration with soybean oil , 1997 .

[136]  S. Berger,et al.  200 and More NMR Experiments: A Practical Course , 2004 .

[137]  E. Hatzakis,et al.  A facile NMR method for the quantification of total, free and esterified sterols in virgin olive oil. , 2010 .

[138]  M. L. Ruiz del Castillo,et al.  Off-line coupling of high-performance liquid chromatography and 1H nuclear magnetic resonance for the identification of filbertone in hazelnut oil , 2001 .

[139]  M A Pollock,et al.  Method Comparison—A Different Approach , 1992, Annals of clinical biochemistry.