Greek Virgin Olive Oil Research Articles

The Application of Chemometrics to Volatile Compound Analysis for the Recognition of Specific Markers for Cultivar Differentiation of Greek Virgin Olive Oil Samples

In the present study, volatile compound analysis of olive oil samples belonging to ten Greek cultivars was carried out. A total of 167 olive oil samples collected from two consecutive harvest years were analyzed by Head Space-Solid Phase Microextraction-Gas Chromatography/Mass Spectrometry (HS-SPME-GC/MS). Volatile compound data were combined with chemometric methods (Multivariate Analysis of Variance (MANOVA) and Linear Discriminant Analysis (LDA)) with the aim not only to differentiate olive oils but also to identify characteristic volatile compounds that would enable differentiation of botanical origin (marker compounds). The application of Stepwise LDA (SLDA) effectively reduced the large number of statistically significant volatile compounds involved in the differentiation process, and thus, led to a set of parameters, the majority of which belong to compounds that are highly dependent on variety. In addition, the use of these marker compounds resulted in an increased correct classification rate (85.6%) using the cross-validation method indicating the validity of the model developed despite the use of a large number of dependent variables (cultivars).

Competitiveness of Greek virgin olive oil in the main destination markets

PurposeThe purpose of this paper is to analyze the competitiveness of the Greek virgin olive oil in the main destination markets (German, Italian, UK and US market).Design/methodology/approachIn order to achieve the aim, in the first stage the Revealed Comparative Advantage (RCA2) Index was employed showing that Greek virgin olive oil has a comparative advantage over the other suppliers (mainly Italy and Spain) in the markets under examination. In the second stage, the estimations of an import demand system for each market were estimated.FindingsResults demonstrate clearly the competitive advantage of Greek virgin olive oil in the German market but not so clear in the rest of the markets. A strategic shift to export high-quality branded virgin olive oil instead of bulk seems necessity, in order the Greek virgin olive oil to dominate to the international markets.Originality/valueThough there are similar works, especially for Spanish olive oil, there is no analogous research work for the Greek olive oil.

Changes occurring in the volatile composition of Greek virgin olive oils during storage: Oil variety influences stability

The present paper reports on the changes in the volatile composition of virgin olive oils (VOO) stored for 18 months. VOO samples of five Greek olive varieties were stored in dark glass bottles (headspace 0.5%) in a basement without central heating. Even after 18 months of storage, the basic quality characteristics of the samples, such as free acidity, K232, K270, and peroxide values, did not exceed the upper limits set by European Community Regulations for VOO. Regarding the lipoxygenase pathway products, responsible for the positive sensory notes, it was shown that their total amount remained stable during the storage period. Even though the physicochemical characteristics did not exceed the upper limits, high rates of formation of volatile oxidation products, which are responsible for the off‐flavors, were observed. Among the volatile oxidation products, the highest rates of formation were monitored for heptanal, 2‐heptenal, and pentanal followed by hexanal and nonanal. The formation rate of volatile oxidation products was higher in VOO from Lianolia and Asprolia compared to VOO from Koroneiki, Native from Zakynthos and Thiaki varieties. Finally, stepwise linear regression analysis (SLRA) selected linoleic acid and total phenol/ortho‐diphenols ratio as having the maximum correlation with the formation rate of 2‐heptenal.Practical applications: This research reports on the changes in the quality characteristics of VOO, stored for 18 months, of the main olive varieties cultivated in the western Greece. Furthermore, it provides information on the changes in volatile composition, which is responsible for positive and negative flavor attributes. Results from this study may contribute to a better understanding of the relationships between minor and/or major components and the autoxidation process. Moreover, results could be useful to VOO packagers and marketers in order to estimate the shelf‐life of individual varieties. VOO from Koroneiki, Native from Zakynthos and Thiaki varieties, which are characterized by low linoleic acid contents, can be preserved for a longer period compared to VOO from Lianolia and Asprolia varieties, which are characterized by high linoleic acid contents.During storage of virgin olive oil (VOO) for 18 months, lipoxygenase pathway products, responsible for the positive sensory notes, remained stable. Among the volatile oxidation products, the highest rates of formation were monitored for heptanal, 2‐heptenal, and pentanal, followed by hexanal and nonanal. 2‐heptenal was correlated with VOO unsaturation and has been suggested as oxidation marker during storage.

Antioxidants in Greek Virgin Olive Oils.

Greece is ranked third after Spain and Italy in virgin olive oil production. The number of Greek olive cultivars—excluding clonal selections—is greater than 40; however, more than 90% of the acreage is cultivated with 20 cultivars, adapted to a wide range of environmental conditions. Greek virgin olive oils, produced mainly with traditional, non-intensive cultivation practices, are mostly of exceptional quality. The benefits of consuming virgin olive oil, originally attributed to its high oleic acid content, are now considered to be the combined result of several nutrient and non-nutrient phytochemicals. The present work summarizes available data regarding natural antioxidants in Greek virgin olive oils (VOO) namely, polar phenolic compounds, tocopherols, squalene, and triterpenic acids. The literature survey indicated gaps in information, which should be filled in the near future so that the intrinsic properties of this major agricultural product of Greece will be substantiated on a solid scientific basis.

Classification of Western Greek virgin olive oils according to geographical origin based on chromatographic, spectroscopic, conventional and chemometric analyses

Forty seven monovarietal olive oils were collected from four Western Greek islands during the 2007–2008 harvesting period. Samples were subjected to physicochemical parameter analysis including determination of acidity, peroxide value, K232, K270, ΔK indices, chlorophyll and carotenoid content, trace elements, fatty acids and δ18O and δ13C isotope ratios in an effort to classify olive oil samples according to geographical origin. Chemometric analysis including MANOVA and Linear Discriminant Analysis (LDA) showed that when all above (14 different physicochemical parameters) were combined, a correct classification rate of 94.5% and 82.6% was achieved using the original and cross validation method respectively.

Characterisation of the geographical origin of Western Greek virgin olive oils based on instrumental and multivariate statistical analysis

In this work, measurements of free acidity, peroxide content, spectrophotometric parameters, chlorophyll content, phenol, sterol, fatty acid and triacylglycerol composition, were carried out on samples of virgin olive oils (VOOs) coming from four different Greek Ionian islands, i.e. Zakynthos, Kefalonia, Lefkada and Kerkyra. An analysis of variance (ANOVA) highlighted statistically significant differences (p<0.01) in the values of 26 analytical parameters amongst the VOOs produced in the four different geographical regions but a post-hoc test showed that no variable was able to distinguish all four origins. Analogously, a Principal Component Analysis (PCA) showed a modest grouping of VOOs according to geographical origin except for Kerkyra samples which were more distinct from others. Applying discriminant function analysis (DFA) a good separation of the four geographical groups was achieved with classification and prediction abilities equal to 97.7% and 95.3%, respectively. Moreover, the analysis of the standardised coefficients showed that the fatty acids and triacylglycerols were the most discriminant variables. This last outcome was confirmed by comparison of the prediction performances obtained applying DFA on four subdatasets containing fatty acids (69.8%), triacylglycerols (76.7%), sterols (62.8%), and remaining parameters (65.1%) together, respectively. As the results showed, the multidisciplinary approach that combines different types of analytical determinations improved the discrimination of geographical origin for Greek virgin olive oils.

Pesticide residue assessment of Organically Cultivated Greek Virgin Olive Oil, during 2009

Pesticide residue assessment of Organically Cultivated Greek Virgin Olive Oil, during 2009

Comparison of different tests used in mapping the Greek virgin olive oil production for the determination of its total antioxidant capacity

This study aims to map the total antioxidant capacity (TAC) of 50 Greek olive oil samples from the 2005-2006 season according to production region and cultivar and to compare the 2, 2’-azino-bis (3-ethylbenzo-thiazoline-6- sulfonic acid (ABTS), 2, 2-diphenyl-1-picrylhydrazyl radical (DPPH) and Folin-Ciocalteu tests for use with olive oil. Antioxidant capacities determined in the hydrophilic fraction range between 5.42 - 22.5 mM gallic acid Kg -1 olive oil for the ABTS method and 1.29 - 9.95 mM Kg -1 for the DPPH method while in total, olive oil TAC ranges between 77 - 177 mM Kg -1 as assessed by the DPPH method. The results of total phenol content range between 3.8 and 29.4 mM Kg -1 olive oil. Total phenol content correlates with total antioxidant capacity assessed in the hydrophilic fraction through the DPPH (r = 0.89) and the ABTS (r = 0.69) assays. The hydrophilic fraction DPPH values correlate significantly with the ABTS values (r = 0.81). However, the DPPH values for total olive oil correlate poorly with the ABTS assay, the Folin-Ciocalteu method and the DPPH assay in hydrophilic fraction. Although total phenolic content shows good correlation with ABTS and DPPH values and could serve as a useful indicator for olive oil antioxidant capacity, the use of a battery of tests contributes to better characterization of the antioxidant capacity of olive oil.

Organophosphorus pesticide residues in Greek virgin olive oil: levels, dietary intake and risk assessment

The occurrence of organophosphorus pesticide (OPs) and their metabolite residues was investigated in 167 samples of Greek virgin olive oil during a 2-year (2004–2005) sampling campaign. A total of 30.5% of samples contained detectable residues, although only one sample contained dimethoate residues above the maximum residue limit. Among the seven detected OPs, fenthion and fenthion sulfoxide residues were detected in 10.8 and 14.4% of the samples, respectively, at levels of 0.003–0.61 mg kg−1. Dimethoate was detected in 10.2% of the samples at 0.003–0.057 mg kg−1. The acute dietary risk assessment was undertaken by determining the national estimated short-term intake (NESTI); for chronic dietary risk assessment, the national theoretical maximum daily intake (NTMDI) and national estimated daily intake (NEDI) were calculated. The estimated intakes (NESTI and NEDI) of each pesticide were <7 and <0.86% of the corresponding acute reference doses (ARfDs) and acceptable daily intakes (ADIs), respectively. A cumulative risk assessment was performed using the hazard index (HI) and toxicity equivalence factor (TEF), taking into account that OPs share the same toxicological mechanism. The determined HI and TEF values were found to represent only a small portion of the respective ADIs or ARfDs. These results indicate that there is neither acute nor chronic risk for the Greek population through olive oil consumption.

Geographical Characterization of Greek Virgin Olive Oils (Cv. Koroneiki) Using 1H and 31P NMR Fingerprinting with Canonical Discriminant Analysis and Classification Binary Trees

This work deals with the prediction of the geographical origin of monovarietal virgin olive oil (cv. Koroneiki) samples from three regions of southern Greece, namely, Peloponnesus, Crete, and Zakynthos, and collected in five harvesting years (2001-2006). All samples were chemically analyzed by means of 1H and 31P NMR spectroscopy and characterized according to their content in fatty acids, phenolics, diacylglycerols, total free sterols, free acidity, and iodine number. Biostatistical analysis showed that the fruiting pattern of the olive tree complicates the geographical separation of oil samples and the selection of significant chemical compounds. In this way the inclusion of the harvesting year improved the classification of samples, but increased the dimensionality of the data. Discriminant analysis showed that the geographical prediction at the level of three regions is very high (87%) and becomes (74%) when we pass to the thinner level of six sites (Chania, Sitia, and Heraklion in Crete; Lakonia and Messinia in Peloponnesus; Zakynthos). The use of classification and binary trees made possible the construction of a geographical prediction algorithm for unknown samples in a self-improvement fashion, which can be readily extended to other varieties and areas.

On the importance of total polar phenols to monitor the stability of Greek virgin olive oil

A large number of virgin olive oil samples obtained from different areas in Greece were analyzed for various quality parameters. The work focuses on the colorimetric determination of total phenols with the Folin-Ciocalteu reagent and its importance in predicting shelf life of virgin olive oil. The results indicate a good correlation of total polar phenol content with the stability of the oil. Colorimetric determination of ortho-diphenol content does not seem to be a better means for predicting virgin olive oil stability. RP-HPLC quantification of hydroxytyrosol and tyrosol in their free form gives poor results in the case of freshly extracted oils. It is concluded that until an easy-to-manage HPLC method will be available, which will quantify accurately both free and bound forms of hydroxytyrosol and other phenolics, the colorimetric method for the determination of total polar phenols remains a good practical means to evaluate the stability of virgin olive oil.

Determination of the diglyceride content in greek virgin olive oils and some commercial olive oils by employing (31)P NMR spectroscopy.

In this study, the diglyceride contents of 96 samples of virgin olive oils from the regions of Crete, Lesvos, Messinia, Pilion, Zakynthos, Halkidiki, and Ilia, 15 samples of commercial extra virgin and pure olive oils, and 3 samples each of refined olive oils and pomace oils were determined by a facile method introduced in a previous publication. This method is based on the phosphitylation of the free hydroxyls of the diglycerides with 2-chloro-4,4,5,5-tetramethyldioxaphospholane and the integration of the appropriate peaks in the (31)P NMR spectra. This preliminary study showed interesting trends in the diglyceride content of the virgin olive oils from the various regions of Greece that can be used as simple criteria to assess the olive oil characteristics. Analysis of variance has been carried out for the diglyceride content of each region in an attempt to detect possible differences in the diglyceride levels among the various regions. Finally, the relationship between the ratio of 1,2-diglycerides to the total amount of diglycerides and the total amount of diglycerides has been used to monitor the quality of virgin olive oils, commercial olive oils, refined olive oils, and pomace oils.

Pigments in Greek virgin olive oils: occurrence and levels

AbstractFifty‐two samples of virgin olive oil from various regions of Greece were examined for the presence and levels of chlorophyll and carotenoid pigments using normal phase liquid chromatography and spectrometry. Pheophytin α (Pheo α) was the main pigment in all the oils examined (&gt;10 mg kg−1 in more than 70% of samples). Two pheophytin α derivatives (peaks A and B), eluted close to Pheo α, may potentially be used to examine handling conditions and length of storage of oil until analysis. Analysis of 25 Greek commercial oils obtained from retail stores verified the above observations. Chlorophyll α may be present in a virgin olive oil just after production. Its absence should not be exclusively attributed to cultivar characteristics or extraction conditions, since pheophytinisation occurs rapidly. Lutein content varied between 0.2 and 3.9 mg kg−1 and β‐carotene content from 0.4 to 5.1 mg kg−1. The lutein/β‐carotene ratio was characteristic (&lt;1) for samples from Koroneiki, the major Greek cultivar for oil production. The total Pheo α (Pheo α + peak A + peak B)/total carotenoid (lutein + β‐carotene) ratio ranged between 2 and 11 owing to prevailing green hues. This ratio may be used as an indicator of oil typicality along with other analytical parameters.© 2001 Society of Chemical Industry

Alpha-tocopherol content of Greek virgin olive oils.

alpha-Tocopherol, the main tocopherol homologue found in olive oil, was determined using normal phase HPLC. Ninety Greek virgin olive oils, selected according to a designed sampling protocol from different cultivars and regions all over Greece for three successive crop years, were analyzed. For a specific olive cultivar, which is widely used for the production of olive oil in Greece, additional measurements were made to study the effect of milling conditions on alpha-tocopherol concentration. Finally, a significant number of commercial olive oil samples (25) obtained from the retail market were analyzed. High concentrations of alpha-tocopherol were observed in most of the samples selected from various regions. Values ranging between 98 and 370 mg/kg were found (>200 mg/kg in 60% of samples). Extraction conditions were not found to influence alpha-tocopherol level. alpha-Tocopherol content of retail market samples was high, ranging from 120 to 250 mg/kg of oil (>180 mg/kg in 60% of samples). Storage of samples under domestic conditions for two years showed that good handling is quite important for retaining high alpha-tocopherol levels and for increasing, thus, the storage life and nutritional value of this exquisite oil.

A statistical approach to the biosynthetic route of fatty acids in olive oil: cross-sectional and time series analyses

A study of the biosynthetic route of the fatty acids in Greek virgin olive oil is presented. The investigation of the behaviour of the fatty acids is based on the statistical analysis of data of percentage composition in fatty acids of Greek olive oil during the ripening period of the olive. The existence of time series observations within several cross-sections provides the opportunity to assess the cross-sectional effects along the time series effects. The increased availability of cross-sectional information over time provides opportunities for a more complete statistical methodology in chemometrics. The methodology of pooling time series and cross-sectional data is proposed in this study. Pooling allows us to test the homogeneity hypothesis that the slopes and intercepts for the same variables are equal for different periods. It is demonstrated here that pooling is not appropriate and the results obtained are no better than separate time series or cross-sectional estimates. However, it is important that the method be introduced. The results obtained in this paper are useful in studying a synthesis of time series and cross-sectional effects for the fatty acids of olive oil.

The presence of oxidizing enzyme activities in virgin olive oil

AbstractSamples of Greek virgin olive oils were examined for the presence of proteins and oxidative enzyme activities. All oil samples tested contained detectable amounts of protein, as well as lipoxygenase and polyphenol oxidase activities. Sodium dodecyl sulfate‐polyacrylamide gel electrophoresis and size‐exclusion chromatography of olive oil extracts revealed the presence of low‐molecular‐mass (10–40 kDa) silver‐staining and ultraviolet‐absorbing components, respectively. Both lipoxygenase and polyphenol oxidase catalytic activities were heat‐ and protease‐sensitive, and they expressed Michaelis‐Menten kinetics.

Determination of Organophosphorus Pesticide Residues in Greek Virgin Olive Oil by Capillary Gas Chromatography.

In this study, the occurrence of 15 organophosphorus pesticide residues in Greek virgin olive oil was investigated. Analysis was carried out using capillary gas chromatography with specific detectors (FPD and NPD), after sample extraction with n-hexane and cleanup by partitioning between n-hexane and acetonitrile. Sixty-two samples of virgin olive oil were taken from the major production areas and packing companies of Greece during 1992-1994. In 46 samples, 9 organophosphorus pesticides, namely dimethoate, fenthion, omethoate, chlorpyrifos, methamidophos, parathion-methyl, parathion, methidathion, and malathion, were found, in concentrations ranging from 0.0005 to 0.1800 mg/kg. Diazinon, pirimiphos-methyl, paraoxon-methyl, malaoxon, carbophenothion, and azinphos-ethyl were not detected in any sample. In most samples pesticide residues were below the detection limits (0.0001 and 0.001 mg/kg), and most of the positive findings were a fraction (i.e., <0.09-18%) of the FAO/WHO Codex Alimentarius maximum residue limits (MRLs) except for dimethoate, which was ranged between 1 and 45%. Only one sample contained dimethoate residue that exceeded the Codex MRL for refined olive oil.

13C NMR analysis of the triacylglycerol composition of Greek virgin olive oils

High-resolution 13C NMR spectroscopy was used to study the potential of the method for the quantitative analysis of the most abundant fatty acids in the triacylglycerols of virgin olive oil samples harvested at different geographic areas of Greece. The analysis of the results was compared with data obtained with gas chromatography. Both methods showed results that differed only by 1–2 mol% of the fatty acids. NMR data provided the α/β ratio of oleic and linoleic acids. The results showed a preference for the β-position in these unsaturated acids. © 1997 John Wiley & Sons, Ltd.

Geographical classification of Greek virgin olive oil by non‐parametric multivariate evaluation of fatty acid composition

AbstractFatty acid compositional data for Greek virgin olive oils from 24 years of harvest and various regions and cultivars were evaluated using chemometric methods. Non‐parametric discriminant analysis after proper transformation of the data seems to be a suitable approach to characterise the oils according to the geographical origin and may produce a scientific basis for the assignment of an ‘appellation d'origine’ trade mark.

Phenolic compounds and stability of virgin olive oil—Part I

The stability of 24 samples of Greek virgin olive oil was examined in relation to total polyphenol content, and individual phenols were determined by reversed-phase HPLC. Tyrosol, the major olive-oil phenol, is not correlated with the shelf-life of the oil. Total polyphenol content and hydroxytyrosol-to-tyrosol ratio have a significant linear correlation with the resistance of the oil to autoxidation.