Characterization and Classification of Extra Virgin Olive Oil from Five Less Well-Known Greek Olive Cultivars

The present study comprises the second part of an ongoing study focusing on olive oil from five less well‐known Greek cultivars for three of which there are no data available in the literature regarding their chemical composition. A total of 74 olive oil samples were collected during the harvesting periods 2012–2013 and 2013–2014. Headspace‐solid phase microextraction was applied to determine the olive oil volatile profile. Fifty‐six compounds were identified and semi‐quantified by CG–MS. Furthermore, fatty acid composition, conventional quality parameters and color parameters were determined in an effort to characterize and differentiate olive oils according to cultivar. All samples were characterized as extra virgin olive oils. Data obtained showed significant differences between the cultivars. Multi‐element analysis in combination with chemometrics resulted in a high classification rate of 86.5 % for the combination of volatiles plus color, 89.2 % for the combination of VC plus FA, and 91.9 % for the combination of FA composition plus color plus CQP.     

Influence of Vertical Centrifugation on Extra Virgin Olive Oil Quality

The qualitative effects of vertical centrifugation (VC), i.e., the last step of the extra virgin olive oil (EVOO) extraction process, were investigated on an industrial scale by sampling EVOOs before and after VC. Several parameters were determined to evaluate EVOO quality. Vertical centrifugation results in a marked loss of volatile aromatic compounds, whereas only a slightly variation was recorded in the hydrophilic phenols concentration.     

Biochemical Characterization of Arbequina Extra Virgin Olive Oil Produced in Turkey

Varieties of the olive cultivar Arbequina have recently been cultivated in Turkey. The objective of the study is to characterize and evaluate extra‐virgin olive oils (EVOO) produced from Arbequina grown in the Aegean and Mediterranean regions of Turkey. Major and minor components such as carotenoids, squalene, phenolics and tocopherols were studied to assess their effects on product quality and health benefits. The samples, identified as ArbqI and ArbqA, were from the Izmir and Adana provinces, respectively. Samples were analyzed by GC‐FID to determine fatty acid composition, sterol composition, TAG profile and squalene content. Individual phenolic fractions were analyzed by LC–MS/MS and tocopherol isomers were determined by HPLC. According to the results obtained from this study; Total phenolic content (TPC) of the samples were 454.68 and 50.86 mg Gallic acid/kg oil for ArbqI and ArbqA, respectively. Hydroxytyrosol and tyrosol were determined to be the main phenols. The major tocopherol isomer found in ArbqI and ArbqA was α‐tocopherol with levels of 179.55 and 202.5 mg/kg oil, respectively. β‐Carotene levels in both samples were similar at 0.2 mg/kg. Findings of this study were compared with the literature on Arbequina olive oil produced in different countries. It was determined that Arbequina olive oil of high quality can be produced in Turkey, especially in the Aegean region.     

Characterization of Turkish Virgin Olive Oils Produced from Early Harvest Olives

Olives were collected from various districts of Turkey (North and South Aegean sub-region, Bursa-Akhisar, South East Anatolia region) harvested over seven (2001–2007) seasons. The aim of this study was to characterize the chemical profiles of the oils derived from single variety Turkish olives including Ayvalik, Memecik, Gemlik, Erkence, Nizip Yaglik and Uslu. The olive oils were extracted by super press and three phase centrifugation from early harvest olives. Chosen quality indices included free fatty acid content (FFA), peroxide value (PV) and spectrophotometric characteristics in the ultraviolet (UV) region. According to the FFA results, 46% (11 out of 24 samples) were classified as extra virgin olive oils; whereas using the results of PV and UV, over 83% (over 19 of the 24 samples) had the extra virgin olive oil classification. Other measured parameters included oil stability (oxidative stability, chlorophyll pigment, pheophytin-α), cis–trans fatty acid composition and color index. Oxidative stability among oils differed whereas the cis–trans fatty acid values were within the national and international averages. Through the application of two multivariate statistical methods, Principal component and hierarchical analyses, early harvest virgin olive oil samples were classified according to the geographical locations categorized in terms of fatty acid profiles. Such statistical clustering gave rise to defined groups. These data provide evidence of the variation in virgin olive oil quality, especially early harvest and cis–trans isomers of fatty acid profiles from the diverse agronomic conditions in the olive growing regions of Turkey.     

Geographical Differentiation of Greek Extra Virgin Olive Oil from Late-Harvested Koroneiki Cultivar Fruits

Seventy‐four monovarietal olive oil samples belonging to the Koroneiki cultivar were collected from four selected olive oil‐producing regions of Greece (Messinia, Lakonia, Irakleio and Etoloakarnania), during two harvesting periods (2012/2013 and 2013/2014) at the stage of full maturation (maturation index 5–6). Determination of volatile compounds (VC), fatty acid (FA) composition, total phenolic content (TPC) and color parameters was carried out in an effort to classify Koroneiki olive oil samples according to geographical origin, while conventional quality parameters (CQP) were used to characterize the samples. The analytical data were then subjected to statistical analysis using multivariate analysis of variance (MANOVA) and linear discriminant analysis (LDA). The results showed a correct classification rate of 79.7% based on VC analysis, 81.1% based on the combination of VC analysis and FA composition, and 87.8% based on the combination of VC analysis and color parameters.     

Effects of Olive Trees Age on the Minor Components of Oueslati Virgin Olive Oils Produced from Olives Harvested at Different Ripening Degrees

Phenolics, volatiles, squalene, tocopherols, and fatty acids of virgin olive oils (VOO) from adult and young olive trees of the Oueslati variety, typically cultivated in the Center of Tunisia, were analyzed at three different harvesting periods. Significant differences in contents of saturated fatty acids (p < 0.05), squalene (p < 0.05), alpha-tocopherol and total tocopherol (p < 0.02) and oxidized form of decarboxymethyl oleuropein aglycon (p < 0.05) were seen between VOO from adult and young trees during maturation. Moreover, the volatile profiles of VOO from adult and young trees showed significant differences in the amounts of hexanal, 1-penten-3-ol (p < 0.05), (Z)-3-hexenal and (Z)-2-penten-1-ol (p < 0.01). Principal component analysis showed that olives from adult trees should be harvested at the cherry stage of maturation to obtain a satisfactory level of oil quality, while olives from young trees should be harvested at the black maturation stage.     

Authentication of Commercial Extra Virgin Olive Oils

The goal of the current contribution is to determine the geographical origins of olive oil samples obtained from eight different countries during the harvest seasons of 2013 and 2014. First, the contents of olive oil samples were quantified by integrating the peaks of ¹H‐NMR spectra and using linear mathematical equations. The results were analyzed by analysis of variance (ANOVA), a statistical method examining whether there is a significant difference between the groups mean. The origins of the majority of the olive oil samples were discriminated by ANOVA and the minor constituents of the olive oils. Tocopherol and cycloartenol were the most discriminative minor constituents of the olive oil samples.     

Quantitation of Metals During the Extraction of Virgin Olive Oil from Olives Using ICP-MS after Microwave-assisted Acid Digestion

Trace metals such as Cu and Fe have negative effects on the oxidative stability of olive oils, and consequently, their concentrations are used as quality criterion. Also, maximum levels are established for heavy metals (As and Pb) in olive oils due to their high toxicity. Olive fruits can be contaminated with these metals from soil and air and from the use of pesticides or fertilizers, with the potential contamination of virgin olive oil (VOO) during its extraction from the fruits. This work presents two goals: (a) to optimize an analytical method for the determination of metals in raw olive fruits using an Abencor system; (b) to carry out a preliminary study of the fate of the metals during VOO extraction. The selected metals were quantified in raw olive fruits, and in the olive pomace and VOO obtained after their processing. The metal determination was performed by inductively coupled plasma-mass spectrometry after microwave-assisted acid digestion with HNO₃/H₂O₂. The results showed that most of the metals (at least 90 %) present in the olive fruits were retained by the olive pomace, so obtaining high-quality VOO from the point of view of its metal content.     

Synthesis of Infant Formula Fat Analogs Enriched with DHA from Extra Virgin Olive Oil and Tripalmitin

Structured lipids (SLs) containing palmitic, oleic, and docosahexaenoic acids for possible use in infant formulas were synthesized by enzymatic acidolysis reactions. The substrates used were tripalmitin, extra virgin olive oil free fatty acids (EVOOFFA), and docosahexaenoic acid single cell oil free fatty acids (DHASCOFFA) in 1:1:1, 1:2:1, 1:3:2, 1:4:2, and 1:5:1 molar ratios. Reactions were carried out at 65 °C for 24 h using Lipozyme^® TL IM lipase. The products were analyzed for total and positional fatty acids by GC-FID, triacylglycerol (TAG) molecular species by HPLC-ELSD, and thermal behavior by DSC. The SLs, SL132, SL142, and SL151 had desirable fatty acid distribution for infant formula use with nearly 60 mol% palmitic acid at the sn-2 position and oleic acid predominantly at the sn-1,3 positions. The total DHA content of SL132, SL142, and SL151 were 7.54, 6.72, and 5.89 mol%, respectively. The major TAG molecular species in the SLs were PPP, OPO, and PPO. The melting completion temperature of SL132 was 37.1, 35.2 °C in SL142, and 32.9 °C in SL151. The SLs synthesized in this study have potential use in infant formulas.     

The Chemical Properties and Volatile Compounds of Virgin Olive Oil from Oueslati Variety: Influence of Maturity Stages in Olives

The aim of the present work was to investigate the influence of fruit ripening on oil quality and volatile compounds in an attempt to establish an optimum harvesting time for Oueslati olives, the minor olive variety cultivated in Tunisia. Our results showed that many analytical parameters, i.e., peroxide value, UV absorbance at 232–270 nm, chlorophyll pigments, carotenoids and oleic acid contents decreased during ripening, whilst linolenic acid increased. Free acidity remained practically stable with a very slight rise at the highest maturity index. The volatile compounds emitted by the Oueslati olive oil were characterized and quantified by HS‐SPME‐GC‐EIMS. Twenty‐three volatile compounds were identified, mainly aldehydes, sesquiterpenes and esters. The results show variations in the volatile fractions and quality parameters of Oueslati extra virgin olive oil obtained at different olive‐ripening stages. Fifteen sesquiterpenes were identified for the first time in this cultivar, mainly hydrocarbon derivatives, but also oxygenated ones. On the basis of the quality parameters and volatile fractions studied, the best stage of Oueslati olive fruits for oil processing seems to be at ripeness index about 3.0. Indeed, these results suggested the possibility of using sesquiterpenes for olive authenticity and traceability and demonstrated that the volatile fractions can be used as indicators of the degree of ripening of the olives used to obtain the corresponding virgin olive oils.     

Authenticity Assessment of Extra Virgin Olive Oil: Evaluation of Desmethylsterols and Triterpene Dialcohols

Extra virgin olive oil (EVOO) has a long history of economic adulteration, the detection of which presents significant challenges due to the diverse composition of cultivars grown around the world and the limitations of existing methods for detecting adulteration. In this study, using Method COI/T.20/Doc. No. 30/Rev. 1 of the International Olive Council, the authenticity of 88 market samples of EVOO was evaluated by comparing total sterol contents, desmethylsterol composition, and contents of triterpene dialcohols (erythrodiol and uvaol) with purity criteria specified in the United States Standards for grades of olive oil and olive‐pomace oil. Three of the 88 samples labeled as EVOO failed to meet purity criteria, indicating possible adulteration with commodity oil and/or solvent‐extracted olive oil. Detection of adulteration was also evaluated by spiking an EVOO sample with commodity oil at the 10 % level. As expected, eight of the spiked samples (canola, corn, hazelnut, peanut, safflower, soybean, and sunflower oils, and palm olein) failed to meet purity criteria. Two of the three samples spiked with 10 % hazelnut oil went undetected for adulteration. Overall, a low occurrence rate of adulteration (<5 %), based on purity criteria for desmethylsterols and triterpene dialcohols, was detected for the 88 products labeled as EVOO.     

The Use of FTIR Spectroscopy and Chemometrics for Rapid Authentication of Extra Virgin Olive Oil

The authenticity of high value edible fats and oils including extra virgin olive oil (EVOO) is an emerging issue, currently. The potential employment of Fourier transform infrared (FTIR) spectroscopy in combination with chemometrics of multivariate calibration and discriminant analysis has been exploited for rapid authentication of EVOO from canola oil (Ca‐O). The optimization of two calibration models of partial least square (PLS) and principle component regression was performed in order to quantify the level of Ca‐O in EVOO. The chemometrics of discriminant analysis (DA) was used for making the classification between pure EVOO and EVOO adulterated with Ca‐O. The individual oils and their blends were scanned on good contact with ZnSe crystals in horizontal attenuated total reflectance, as a sampling technique. The wavenumbers of 3,028–2,985 and 1,200–987 cm^?1 were used for quantification and classification of EVOO adulterated with Ca‐O. The results showed that PLS with normal FTIR spectra was well suited for quantitative analysis of Ca‐O with a value of the coefficient of determination (R²) > 0.99. The error, expressed as root mean square error of calibration obtained was relatively low, i.e. 0.108 % (v/v). DA can make the classification between pure EVOO and that adulterated with Ca‐O with one misclassified reported.     

Effect of the Addition of Membrane Processed Olive Mill Waste Water (OMWW) to Extra Virgin Olive Oil

Modern membrane technologies are useful for enhancing the concentration of phenolic antioxidants in olive mill waste water (OMWW) to produce concentrates with valuable applications in functional foods. Three types of OMWW concentrates, each with different levels of solute concentration and purity, were obtained from a single OMWW batch and dissolved in two extra virgin olive oils to achieve saturated solutions. Three addition levels were considered. Accelerated aging testing of the oils was performed at 60 °C and the samples were analyzed after two, four, and 6 weeks of aging. D-optimal design was used to select the 26 experiments that allowed the evaluation of the influence of the different variables on oil stability. The addition of OMWW concentrates resulted in a significant increase in the Radical Scavenging Activity (RSA) of the olive oils. Under these mild experimental conditions, the moderate formation of fatty acid hydroperoxides was probably masked by interfering compounds.     

The Effect of Different Cold Storage Conditions on the Compositions of Extra Virgin Olive Oil

Storage conditions can affect the stability and quality of extra virgin olive oil (EVOO). While many studies have reported the influence of high temperature and light exposure during storage, little is known on the influence of the cold storage. The aim of this study was to evaluate the effect of different storage conditions (25, 4.5 and ?27 °C) on the various compositions of EVOO and to determine if cold storage will prolong shelf‐life by retarding hydrolysis and oxidation. The changes of quality indices (FFA, PV, and UV) and natural antioxidants such as α‐tocopherol and phenolic compounds were evaluated periodically during storage. The characterization and quantification of phenolics were achieved by ultra‐performance liquid chromatography—diode array detector (UPLC‐DAD). In addition, 1, 2‐diacylglycerols (DAGs), pyropheophytin A (PPP) were measured to indicate thermal degradation during storage.     

Quantitation and Distribution of Polar Compounds in an Extra Virgin Olive Oil Used in Fryings with Turnover of Fresh Oil

The alteration of an extra virgin olive oil used in 75 repeated and intermittent deep-fat fryings of potatoes (with a frequent turnover of fresh oil) was measured by column and high-performance size-exclusion chromatography (HPSEC). Total polar content increased slightly but continuously in the fryer's oil during the first 30 fryings from 2.76 ± 0.01 mg/100 mg oil (mean ± SD) to 6.60 ± 0.00 mg/100 mg used oil, followed by a tendency to reach a near steady state after a large number of fryings. Compounds related to thermoxidative alteration also increased significantly in the oil used 75 times to fry potatoes. Triglyceride dimers increased from 0.03 ± 0.01 mg/100 mg unused oil to 1.65 ± 0.05 mg/100 mg oil at the thirtieth fryings while triglyceride polymers and oxidized triglycerides did so during the first 60 fryings (0.07 ± 0.01 mg/100 mg oil and 0.56 ± 0.03 mg/100 mg oil in the unused oil respectively to 0.38 ± 0.01 mg/100 mg oil or 2.95 ± 0.15 mg/100 mg oil in the used oil, respectively). Both of these changes were followed by a tendency of these polar compounds to reach a near steady state in later successive fryings. Nevertheless, diglycerides and free fatty acids related to hydrolytic alteration remained quite stable throughout the frying process. Data from this study indicate that repeated fryings of potatoes in extra virgin olive oil with a frequent turnover of fresh oil throughout the frying slightly increased the level of polar material in the fryer oil during the first fryings followed by minor changes and by a tendency to reach a near steady state in successive fryings.     

Adulteration and Presence of Polycyclic Aromatic Hydrocarbons in Extra Virgin Olive Oil Sold on the Brazilian Market

Seventy samples sold in the Brazilian market as extra virgin olive oil (EVOO) were evaluated for the presence of the 13 polycyclic aromatic hydrocarbons (PAH) classified as carcinogenic and genotoxic by the Joint FAO/WHO Expert Committee on Food Additives (JECFA), to verify if the products were adulterated and to evaluate if there is a correlation between PAH presence and adulteration. PAH were detected in 93% of the samples, with summed levels varying from not detected to 41.10 μg/kg. Five samples showed BaP concentration above acceptable levels set by European legislation and by Brazilian regulation (2.0 μg/kg) and 7 presented PAH4 levels above the limit set by European legislation (10.0 µg/kg). The levels of fatty acid composition, sterols content, stigmastadiene and specific extinction did not comply with both Brazilian and International Olive Council (IOC) standards in 18, 31, 30 and 21% of the samples, respectively. The tolerance levels for these analyses in the Brazilian standards are 55.0–83.0 g/100 g (oleic acid), 3.5–21.0 g/100 g (linoleic acid), ≤0.05 g/100 g (trans-oleic acid), ≤0.05 g/100 g (trans-linoleic + trans-linolenic acid), ≤0.15 mg/kg (stigmastadiene), ≤2.50 (K232), ≤0.22 (K270), ≤0.01 (?K), 1000–1600 mg/kg (Σ sterols). Results indicate that 19 samples were adulterated. According to principal component analysis, samples were distinguished as: (1) EVOO with addition of vegetable oil from another source, (2) EVOO with addition of refined oil and (3) samples possibly not adulterated. The variable ΣPAH was related mainly to samples of EVOO with addition of vegetable oil from another source.     

Rapid Determination of Free Fatty Acid in Extra Virgin Olive Oil by Raman Spectroscopy and Multivariate Analysis

We introduce a visible Raman spectroscopic method for determining the free fatty acid (FFA) content of extra virgin olive oil with the aid of multivariate analysis. Oleic acid was used to increase the FFA content in extra virgin olive oil up to 0.80% in order to extend the calibration span. For calibration purposes, titration was carried out to determine the concentration of FFA for the investigated oil samples. As calibration model for the FFA content (FFA%), a partial least squares (PLS) regression was applied. The accuracy of the Raman calibration model was estimated using the root mean square error (RMSE) of calibration and validation and the correlation coefficient (R ²) between actual and predicted values. The calibration curve of actual FFA% obtained by titration versus predicted values based on Raman spectra was established for different spectral regions. The spectral window (945–1600 cm⁻¹), which includes carotenoid bands, was found to be a useful fingerprint region being statistically significant for the prediction of the FFA%. High R ² and small RMSE values for calibration and validation could be obtained, respectively.     

Oxidative Stability and Changes in Chemical Composition of Extra Virgin Olive Oils After Short‐Term Deep‐Frying of French Fries

We aimed at investigating oxidative stability and changes in fatty acid and tocopherol composition of extra virgin olive oil (EVOO) in comparison with refined seed oils during short‐term deep‐frying of French fries, and changes in the composition of the French fries deep‐fried in EVOO. EVOO samples from Spain, Brazil, and Portugal, and refined seed oils of soybean and sunflower were studied. Oil samples were used for deep‐frying of French fries at 180 °C, for up to 75 min of successive frying. Tocopherol and fatty acid composition were determined in fresh and spent vegetable oils. Tocopherol, fatty acid, and volatile composition (by SPME–GC–MS) were also determined in French fries deep‐fried in EVOO. Oil oxidation was monitored by peroxide, acid, and p‐anisidine values, and by Rancimat after deep‐frying. Differential scanning calorimetry (DSC) analysis was used as a proxy of the quality of the spent oils. EVOOs presented the lowest degree of oleic and linoleic acids losses, low formation of free fatty acids and carbonyl compounds, and were highly stable after deep‐frying. In addition, oleic acid, tocopherols, and flavor compounds were transferred from EVOO into the French fries. In conclusion, EVOOs were more stable than refined seed oils during short‐term deep‐frying of French fries and also contributed to enhance the nutritional value, and possibly improve the flavor, of the fries prepared in EVOO.     

Biochemical Characterization of Turkish Extra Virgin Olive Oils from Six Different Olive Varieties of Identical Growing Conditions

Extra virgin olive oils were extracted from six different major olive cultivars (Gemlik, Ayvalik, Domat, Akhisar, Memecik, Arbequina) cultivated in the Aegean region of Turkey. Fatty acid, sterol and tocopherol compositions were analyzed and the results were compared by multivariate statistical analysis. Olive samples were collected from the same orchard in order to limit the contribution of parameters such as climate, soil quality and agricultural practices to the total variance of chemical composition of olive oils. Principal component analysis (PCA) showed that cultivars can be clearly distinguished on the basis of fatty acid and sterol composition. It is of interest to note that palmitoleic acid content of Arbequina, a Spanish cultivar, is significantly (p < 0.05) higher than the local Turkish cultivars in question and it is the only olive sample whose palmitoleic acid concentration is higher than that of the stearic acid concentration, exhibiting a divergent composition from the local Turkish cultivars. β‐Sitosterol and Δ5‐avenasterol contents of the oils are significantly correlated (r = ?0.989, p < 0.05) and this results in a discriminative axis on the PCA loading plot. Tocopherol composition was relatively insufficient in discriminating the olive varieties. Regarding tocopherol compositions Gemlik cultivar is distinguished from other cultivars with its γ‐tocopherol content, which is in average two times higher than that of other cultivars. The result of the present compositional study provides important data which can be used for olive oil authenticity studies in Turkey.