Differentiation of mixtures of monovarietal olive oils by mid‐infrared spectroscopy and chemometrics

Fourier transform infrared (FT‐IR) spectroscopy in combination with chemometric techniques has become a useful tool for authenticity determination of extra‐virgin olive oils. Spectroscopic analysis of monovarietal extra‐virgin olive oils obtained from three different olive cultivars (Erkence, Ayvalik and Nizip) and mixtures (Erkence‐Nizip and Ayvalik‐Nizip) of monovarietal olive oils was performed with an FT‐IR spectrometer equipped with a ZnSe attenuated total reflection sample accessory and a deuterated tri‐glycine sulfate detector. Using spectral data, principal component analysis successfully classified each cultivar and differentiated the mixtures from pure monovarietal oils. Quantification of two different monovarietal oil mixtures (2–20%) is achieved using partial least square (PLS) regression models. Correlation coefficients (R²) of the proposed PLS regression models are 0.94 and 0.96 for the Erkence‐Nizip and Ayvalik‐Nizip mixtures, respectively. Cross‐validation was applied to check the goodness of fit for the PLS regression models, and R² of the cross‐validation was determined as 0.84 and 0.91, respectively, for the two mixtures.     

Application of Infrared Spectroscopy for Characterization of Dietary Omega‐3 Oil Supplements

Fish oil dietary supplements have been linked with health benefits, due to high omega‐3 concentration. The sources of these effects, polyunsaturated fatty acids such as eicosapentaenoic acid and docosahexaenoic acid, are almost exclusively found in seafood products. Our objectives were to characterize the composition of commercial omega‐3 dietary supplements dietary supplements and to generate partial least square regression (PLSR) models using infrared spectroscopy and chemometrics. Fatty acid (FA) composition of oils was determined by FA methyl ester gas chromatography. The supplements encompassed a wide range of FA profiles and delivery methods. Infrared spectral data were collected by portable mid‐infrared Fourier transform infrared (MID FT‐IR) equipment. Principal components analysis (PCA) separated samples based on the type of ester present in the fish oil dietary supplements, showing a strong influence of the 1038 cm^?1 band, which is typically associated with C=C and C–O stretching vibrations. In addition, PLSR was used to correlate the spectra data with GC‐FAME results. PCA using the spectroscopy data allowed for tight clustering of fish oil into distinct classes, depending on the source and processing. PLSR using MID FT‐IR spectra and FA composition generated multivariate models with high correlation coefficient (R ≥ 0.93), and SEP between 0.53 and 2.13 g of FA per 100 g of oil. Our results indicate that IR spectroscopy combined with chemometrics provides for robust screening of FA composition of fish oil supplements, and discriminate types of FAs esterification.     

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.     

Phenolic Characterization and Geographical Classification of Commercial Extra Virgin Olive Oils Produced in Turkey

The aim of this research was to characterize the extra virgin olive oil samples from different locations in the Aegean coastal area of Turkey in terms of their phenolic compositions for two consecutive years to show the classification of oil samples with respect to harvest year and geography. Forty seven commercial olive oil samples were analyzed with HPLC–DAD, and 17 phenolic compounds were quantified. Hydroxytyrosol, tyrosol, vanillic acid, p-coumaric acid, ferulic acid, cinnamic acid, luteolin and apigenin were the characteristic phenols observed in all oil samples for two harvest years. Syringic acid, vanillin and m-coumaric acid were the phenolic compounds appeared in the olive oil depending on the harvest year. Partial least square-discriminant analysis (PLS-DA) of data revealed that oils from the north Aegean and south Aegean areas had different phenolic profiles. The phenolic compounds, which played significant roles in the discrimination of the olive oils, were tyrosol, oleuropein aglycon, cinnamic acid, apigenin and hydroxytyrosol to tyrosol ratio. The Aegean coastal region is the largest olive oil producer and exporter of Turkey. This study shows that the olive oils from different parts of the region have their own defining characteristics that can be used in the authentication studies and geographical labeling of Turkish olive oils.     

Developing FT-NIR and PLS1 Methodology for Predicting Adulteration in Representative Varieties/Blends of Extra Virgin Olive Oils

It was previously demonstrated that Fourier transform near infrared (FT‐NIR) spectroscopy and partial least squares (PLS1) were successfully used to assess whether an olive oil was extra virgin, and if adulterated, with which type of vegetable oil and by how much using previously developed PLS1 calibration models. This last prediction required an initial set of four PLS1 calibration models that were based on gravimetrically prepared mixtures of a specific variety of extra virgin olive oil (EVOO) spiked with adulterants. The current study was undertaken after obtaining a range of EVOO varieties grown in different countries. It was found that all the different types of EVOO varieties investigated belonged to four distinct groups, and each required the development of additional sets of specific PLS1 calibration models to ensure that they can be used to predict low concentrations of vegetable oils high in linoleic, oleic, or palmitic acid, and/or refined olive oil. These four distinct sets of PLS1 calibration models were required to cover the range of EVOO varieties with a linoleic acid content from 1.3 to 15.5 % of total fatty acids. An FT‐NIR library was established with 66 EVOO products obtained from California and Europe. The quality and/or purity of EVOO were assessed by determining the FT‐NIR Index, a measure of the volatile content of EVOO. The use of these PLS1 calibration models made it possible to predict the authenticity of EVOO and the identity and quantity of potential adulterant oils in minutes.     

In‐process monitoring in industrial olive mill by means of FT‐NIR

A total of 287 olive lots and 161 olive oil samples were analyzed for fat content, moisture and free acidity, using a Fourier transform near‐infrared (FT‐NIR) instrument located in an industrial mill. Samples having a wide range of both reference values and olive lot sizes (from <0.5 to >4 t) were collected at three industrial mill plants, located in the same Italian region, which utilize different technological equipment for virgin olive oil production. Olive paste spectra were acquired in diffuse reflectance, while oil samples were measured in transmission. Calibration models for oil content and moisture of olives as well as free acidity of virgin olive oils were developed using partial least squares (PLS) regression, first derivative and straight line subtraction. Results of calibration and validation of the PLS models selected were good. The PLS results indicate good similarity between data obtained from FT‐NIR and reference laboratory methods, allowing a rapid and less expensive screening analysis. Unfortunately, the correlation between the oil yield values recorded for all olive lots at the industrial mills and the oil content predicted by FT‐NIR was not satisfactory (R² = 0.605).     

Raman Spectroscopic Barcode Use for Differentiation of Vegetable Oils and Determination of Their Major Fatty Acid Composition

In this study, differentiation of vegetable oils and determination of their major fatty acid (FA) composition were performed using Raman spectral barcoding approach. Samples from seven different sources (sunflower, corn, olive, canola, mustard, soybean and palm) were analyzed using Raman spectroscopy. Second derivative of the spectral data was utilized to generate unique barcodes of oils. Chemometric analyses, namely, principal component analysis (PCA) and partial least square (PLS) methods were used for data analysis. PCA was applied for classification of the samples according to the differences in their levels arising from their barcode data. A successful differentiation based on second derivative barcodes of Raman spectra (2D‐BRS) of vegetable oils was obtained. In addition, PLS method was applied on 2D‐BRS in order to determine the major FA composition of these samples. Coefficient of determination values for palmitic, stearic, oleic, linoleic, α‐linolenic, cis‐11 eicosenoic, erucic and nervonic acids were in the range of 0.970–0.989. Limit of detection and limit of quantification values were found to be satisfactory (0.09–8.09 and 0.30–26.95 % in oil) for these fatty acids . Advantages of both chemometric analysis and spectral barcoding approach have been utilized in the present study. Taking the second derivative of the Raman spectra has minimized background variability and sensitivity to intensity fluctuations. Spectral conversion to the barcodes has further increased the quality of information obtained from Raman spectra and also made it possible to improve the visualization of the data. Converting Raman spectra of oils into barcodes enables simpler presentation of the valuable information, and still allows further analysis such as classification of vegetable oils and prediction of their major fatty acids with high accuracy.     

Novel,Rapid Identification,and Quantification of Adulterants in Extra Virgin Olive Oil Using Near‐Infrared Spectroscopy and Chemometrics

A new, rapid Fourier transform near infrared (FT‐NIR) spectroscopic procedure is described to screen for the authenticity of extra virgin olive oils (EVOO) and to determine the kind and amount of an adulterant in EVOO. To screen EVOO, a partial least squares (PLS1) calibration model was developed to estimate a newly created FT‐NIR index based mainly on the relative intensities of two unique carbonyl overtone absorptions in the FT‐NIR spectra of EVOO and other mixtures attributed to volatile (5280 cm^?1) and non‐volatile (5180 cm^?1) components. Spectra were also used to predict the fatty acid (FA) composition of EVOO or samples spiked with an adulterant using previously developed PLS1 calibration models. Some adulterated mixtures could be identified provided the FA profile was sufficiently different from those of EVOO. To identify the type and determine the quantity of an adulterant, gravimetric mixtures were prepared by spiking EVOO with different concentrations of each adulterant. Based on FT‐NIR spectra, four PLS1 calibration models were developed for four specific groups of adulterants, each with a characteristic FA composition. Using these different PLS1 calibration models for prediction, plots of predicted vs. gravimetric concentrations of an adulterant in EVOO yielded linear regression functions with four unique sets of slopes, one for each group of adulterants. Four corresponding slope rules were defined that allowed for the determination of the nature and concentration of an adulterant in EVOO products by applying these four calibration models. The standard addition technique was used for confirmation.     

Classification of virgin olive oils of the two major cretan cultivars based on their fatty acid composition

Fatty acid composition was determined for 105 virgin olive oil samples of the two dominant Cretan olive cultivars, Koroneiki and Mastoides, harvested from different producing areas at different maturity stages. The oils of the Koroneiki cultivar were characterized by lower concentrations of oleic and decaheptanoic and higher concentrations of linoleic and palmitic acids. Oils obtained from high-altitude locations were rich in monounsaturated fatty acids, while oils obtained from low-altitude locations had higher content of saturated fatty acids. Palmitic and palmitoleic acids increased with increasing altitude in both cultivars examined. The statistical analysis of the compositional data showed significant potential for the classification of the samples according to cultivar and location of origin.     

Effects of Variety,Maturation and Growing Region on Chemical Properties,Fatty Acid and Sterol Compositions of Virgin Olive Oils

Chemical properties, fatty acid and sterol compositions of olive oils extracted from Gemlik and Halhal? varieties grown in Hatay and Mardin provinces in Turkey were investigated during four maturation stages. The olive oil samples were analyzed for their chemical properties such as free acidity, peroxide value, total carotenoid, total chlorophyll, total phenolic contents, antioxidant activity, fatty acid and sterol compositions. Chemical properties, fatty acids and sterol profiles of olive oil samples generally showed statistically significant differences depending on the varieties, maturation and growing areas (p < 0.05). As free fatty acid contents and total phenolic contents increased, total carotenoid and chlorophyll contents decreased throughout the maturity stages. Total carotenoid and chlorophyll contents of oil samples from Mardin were higher than those of Hatay. The total phenolic compounds of olive oil samples ranged from 20.62 in Gemlik to 525.22 mg GAE/kg oil in Halhal? from Hatay. In general, the phenolic contents and antioxidant activities of olive oil samples were positively associated. Oleic acid content was the highest 71.53 % in H1 samples in Hatay. Total sterol contents were 1194.33 mg/kg in Halhal? and 2008.66 mg/kg in Gemlik from Hatay. Stigmasterol contents of oils obtained from Hatay were lower than those of Mardin. Oleic acid, palmitic acid, β‐sitosterol, ?‐5‐avenasterol and campesterol contents fluctuated with maturation for each of variety from both growing regions. These results showed that the variety, growing area and maturation influence the chemical properties, fatty acid and sterol compositions.     

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.     

Quality and Composition of Virgin Olive Oils from Indigenous and European Cultivars Grown in China

The characteristics of eight varieties of virgin olive oil (Arbosana, Arbequina, Coratina, Cornicabra, Frantoio, Koroneiki, Picual, and Ezhi 8) obtained in two successive crops in the southwest of China (Xichang, Sichuan Province) were investigated. Significant differences (P < 0.05) were observed in physicochemical properties, fatty acid profile, minor component contents, and oxidative stability between different varieties of olive oils. The physicochemical properties of all samples met IOC standards for extra virgin olive oil, while in Koroneiki, olive oils were present the optimum oxidation stability among studied varieties. The results of hierarchical cluster analysis and principal component analysis (PCA) showed a good classification between varieties based on their qualitative characteristics. Koroneiki and Ezhi 8 olive oils were significantly different from other varieties mainly due to color, fatty acid profile, and minor components. PCA result also showed that harvest crop influences the characteristics of samples mainly due to the variance of temperature and rainfall.     

Fatty acids,volatiles, sterols and triterpenic alcohols of six monovarietal Tunisian virgin olive oils

Fatty acids, volatiles, sterols, aliphatic and triterpenic alcohols of six monovarietal Tunisian virgin olive oils were analyzed. The results suggested that the compositional data concerning the above analytical fractions were effective in discriminating between varieties. The oils were found to contain high levels of oleic acid (up to 71.70% in the Oueslati variety). β‐Sitosterol (up to 85.46% in the Jdallou variety) and Δ5‐avenasterol (up to 30.97% in the El Hor variety) were the principal sterols in all samples; campesterol and stigmasterol were found at low levels. (E)‐2‐Hexenal was the main compound that characterizes the olive oil headspace of all samples. The other compounds identified were mainly C₆ aliphatic components.     

Impact of Microwave Assisted Infusion on the Quality and Volatile Composition of Olive Oil Aromatized with Rosemary Leaves

Olive oil with rosemary leaves by microwave assisted infusion (MAI) as an alternative to conventional infusion (CI) was evaluated. Microwave heating was applied to the mixture in order to accelerate diffusion of the rosemary volatile compounds into the olive oil. The volatile components of the aromatized oils were quantified by HS‐SPME/GC–MS, as well as several quality indexes such as free fatty acids (FFA), peroxide value (PV), specific coefficients of extinction, chlorophyll and carotenoid content, and color assessment. Fatty acid profiles of the oils aromatized by MAI were compared to those produced by CI. Results showed that the infusion time is reduced from 12 h to 10 min when utilizing MAI in place of CI. MAI treatment caused a slight increase in FFA levels, and specific extinction coefficient indices (K₂₃₂ and K₂₇₀). PV during MAI remained unchanged for the first 3 min, after which there was an observable increase. All physico‐chemical values were found to be well below the maximum permitted limits. The MAI treatment reduced chlorophyll and carotenoid levels during the final step of aromatization, thus affecting final color. The MAI aromatized oil was characterized by its clear green color (L*, a*, b* parameters). Fatty acid analysis showed that MAI slightly changed the fatty acid composition of the olive oil. This study indicates that MAI appears to be a viable and rapid method to flavor olive oil with rosemary leaves.     

Handheld Near‐Infrared Spectroscopy for Distinction of Extra Virgin Olive Oil from Other Olive Oil Grades Substantiated by Compositional Data

Miniaturization of analytical technology has paved the way for in‐situ screening of foods. In the current study, the spectral features of olive oils are examined by handheld near‐infrared spectroscopy to explore the technology's capabilities to distinguish extra virgin olive oil (EVOO) from lower grade oils. Eighty EVOO, forty refined olive oil (ROO), and ten pomace olive oil (POO) samples are analysed for their spectral and compositional features. The latter included analysis of the fatty acids (FAs), the chlorophylls and carotenoids, chromatic coordinates and moisture contents. The 1350–1570 nm wavelength range appeared most suitable for distinction of the oils. One‐class classification models with three different classifiers are subsequently estimated using this range, and their quantitative performance is assessed from probabilistic data. Soft independent modeling of class analogies models appears to predict the identity of the oils with a high success rate. Compared to the other oils, POO comprises a significantly higher and lower proportion of polyunsaturated and monounsaturated FAs, respectively. Higher contents of chlorophylls, carotenoids, and moisture are noted for EVOO. The relevant spectral information for distinction of the oils correlates strongly with the degree of unsaturation of the oils as well as their levels of chlorophylls, carotenoids, and moisture. Practical Applications: The findings of this study demonstrate that the handheld NIRS technique is promising for future rapid screening of olive oil grades. The statistical methods used and the robust validation procedure will help potential users to select the optimal strategy for multivariate data analysis. In addition, the exploration of correlations with compositional characteristics provides insight into the handheld NIRS working mechanism in regard to EVOO authentication.     

Classification of Turkish Extra Virgin Olive Oils by a SAW Detector Electronic Nose

An electronic nose (e-nose), in combination with chemometrics, has been used to classify the cultivar, harvest year, and geographical origin of economically important Turkish extra virgin olive oils. The aroma fingerprints of the eight different olive oil samples [Memecik (M), Erkence (E), Gemlik (G), Ayvalık (A), Domat (D), Nizip (N), Gemlik–Edremit (GE), Ayvalık–Edremit (AE)] were obtained using an e-nose consisting a surface acoustic wave detector. Data were analyzed by principal component analysis (PCA) and discriminant function analysis (DFA). Classification of cultivars using PCA revealed that A class model was correctly discriminated from N in two harvest years. The DFA classified 100 and 97% of the samples correctly according to the cultivar in the 1st and 2nd harvest years, respectively. Successful separation among the harvest years and geographical origins were obtained. Sensory analyses were performed for determining the differences in the geographical origin of the olive oils and the preferences of the panelists. The panelists could not detect the differences among olive oils from two different regions. The cultivar, harvest year, and geographical origin of extra virgin olive oils could be discriminated successfully by the e-nose.     

Evolution of phenols and pigments in extra virgin olive oil from irrigated super‐intensive orchard

Phenolic compounds have a high importance in olive oil because of their effect on shelf life and sensory properties. This study reports on the HPLC profiles of the phenolic compounds of virgin olive oils obtained from Arbequina olives from the harvesting in a super‐intensive orchard under a linear irrigation system. In addition, phenolic content, carotenoid and chlorophyllic pigments, and oxidative stability were analyzed. Total phenol content and 3,4‐DHPEA‐EDA increased up to a maximum throughout the ripening process. The simple phenols tyrosol and hydroxytyrosol acetate increased throughout the ripening process, however, there was not found a clear trend in hydroxytyrosol content. Minor constituents such as vanillic acid and p‐coumaric acid increased up to a maximum and then decreased, since vanillin decreased progressively throughout the time of harvest. 3,4‐DHPEA‐EDA and lignans were present in considerable amounts in the studied samples, while oleuropein aglycone was present in a low amount. Total phenol content and oil stability followed the same trend throughout the study, so a very good correlation was established between them. Total secoiridoids and, specifically, 3,4‐DHPEA‐EDA seemed to be responsible for oil stability. The pigment content decreased during ripening, and not a positive correlation was found between pigments and oil stability. Practical applications : The results can be used to determine the best time for harvesting in order to obtain olive oils with different phenols and pigment contents. This is important for sensory characteristics of the olive oils and also for olive oil stability.     

Chemical Profiling of Bosana Virgin Olive Oils Produced in Different Areas of Sardinia

In a 3-year study, the chemical compositions of extra virgin olive oils (EVOO) of Bosana variety deriving from three different growing areas in Northern Sardinia were characterized, together with the pedo-climatic conditions of the three different growing areas, to gauge any differences at the chemical level. The main chemical differences in the oils from the three-studied areas were recorded in the fatty acid profiles [palmitic, oleic, and linoleic acid; sum of saturated (SFA), monounsaturated (MUFA), and polyunsaturated (PUFA) fatty acids]: these dissimilarities were ascribable to the environmental characteristics of the Alghero area, while others analytical parameters such as tocopherols, pigments, phenolic, and volatile compounds were not affected by production area. Fatty acids profile revealed a clear relation with temperature at a mesoclimate level, allowing a clusterization of the production areas. Our study provided evidences that pedo-climatic factors affect the quality of EVOO; in particular, in the case of Bosana cultivar the acidic fraction resulted one of the main traits differentiating the olive growing areas.     

Volatile compounds and triacylglycerol composition of original Indian fatty plant oils

Some typical original Indian edible and non‐edible fatty plant oils were subject of our investigations. Fundamental research was done on analyzing volatile compounds using HS‐SPME‐GC‐MS. In addition, a sensorial evaluation was applied to receive data on the smell of the samples. Furthermore, the typical and prevailing triacylglycerols (TAG) were investigated by MALDI‐TOF‐MS. Mass spectra reflect the TAG profiles of the whole oil samples based on the detection of [M+Na]⁺ ions. Oil samples exhibit quite unique TAG profiles, which are suitable for rapid characterization of the original plant oils. The fatty acid composition of the corresponding TAG structures was calculated using lipid analysis software based on the known fatty acid composition. Relative quantification of TAG components was in good agreement with the literature, in case appropriate data are available so far.     

Detection of olive oil adulteration with canola oil from triacylglycerol analysis by reversed-phase high-performance liquid chromatography

The objective of this study was to explore the use of reversed-phase high-performance liquid chromatography (RP-HPLC) as a means to detect adulteration of olive oil with less expensive canola oil. Previously this method has been shown to be useful in the detection of some other added seed oils; however, the detection of adulteration with canola oil might be more difficult due to similarities in fatty acid composition between canola oil and olive oil. Various mixtures of canola oil with olive oils were prepared, and RP-HPLC profiles were obtained. Adulteration of olive oil samples with less than 7.5% (w/w) canola oil could not be detected.