Classification of extra virgin olive oils according to their geographical origin using phenolic compound profiles obtained by capillary electrochromatography

A simple and reliable method for the evaluation of the phenolic fraction of extra virgin olive oils (EVOO) by capillary electrochromatography (CEC) with UV–Vis detection, using lauryl acrylate (LA) ester-based monolithic columns, has been developed. The percentages of the porogenic solvents in the polymerization mixture, and the mobile phase composition, were optimized. The optimum monolith was obtained with a monomers/porogens ratio of 40:60% (wt/wt) using a LA/1,3-butanediol diacrylate ratio of 70:30% (wt/wt) and a 1,4-butanediol/1-propanol ratio of 25:75% (wt/wt). A satisfactory resolution between the phenolic compounds was achieved in less than 25 min with a 15:85 (v/v) ACN–water buffer containing 5 mM formic acid at pH 3.0. The method was applied to the analysis of the phenolic fraction of EVOO samples. Using linear discriminant analysis of the CEC phenolic profiles, the EVOO samples belonging to three different geographical origins (Croatia, Italy and Spain) were correctly classified with an excellent resolution among all the categories.     

Analysis of extra virgin olive oils from stoned olives

This paper focuses on comparing the main chemical characteristics of 16 fresh commercial samples of extra virgin olive oil obtained from four harvest years (1999–2002) and derived from both stoned and whole fruits. The qualitative and quantitative contents of minor polar compounds (MPCs) together with other reference analytical parameters (acidity, peroxides, UV absorption values and Rancimat test) were evaluated. An investigation of the MPCs and oil composition obtained from only stoned olives was also carried out. The acidity values of the oils from stoned fruits were always similar to or lower than those of the corresponding oils from whole fruits. For almost all the samples from stoned olives a better resistance to oxidation was revealed in comparison with the corresponding traditional oils. Five pairs obtained from the 2000 and 2001 harvests showed higher concentrations of both MPCs and hydroxytyrosol derivatives in the oils from stoned fruits, in agreement with their higher Rancimat values. Overall, our findings with regard to acidity values, % hydrolysis, the Rancimat test and the qualitative and quantitative distribution of MPCs suggest a higher antioxidant capacity of the oils from stoned olives. Copyright © 2004 Society of Chemical Industry     

风味和功能性特级初榨橄榄油的研制

以特级初榨橄榄油为基础油,分别添加橘子、橙子、柠檬、辣椒、花椒天然风味香料进行调味,或添加植物甾醇酯、茶多酚增加其功能性。通过感官评定确定了橘子、橙子、柠檬3种水果风味香料最佳添加量均为1.3%,辣椒、花椒2种香辛料风味香料最佳添加量分别为0.5%和3.0%,植物甾醇酯、茶多酚添加量分别为1.0%和0.03%。在最佳添加量条件下,风味油和功能性油过氧化值、酸值稳定性良好;水果风味油p-茴香胺值上升比较明显,其他风味油和功能性油与特级初榨橄榄油的p-茴香胺值基本持平。     

Minor compounds in the phenolic fraction of virgin olive oils

The phenolic fraction of 34 virgin olive oils was analysed by gas chromatography–mass spectrometry (GC–MS) with the aim to identify new compounds at low level. Twenty-seven compounds previously described in olive oils were identified; several new minor compounds with phenolic structure were detected in the samples: amongst them, 4-hydroxyphenylacetaldehyde, trans-isoeugenol (trans-2-methoxy-4-(1-propenyl)-phenol), 1,4-dihydroxy-2,6-dimethoxybenzene, 3,4-dihydroxybenzyl alcohol and 3,4-dihydroxyphenylacetic acid were identified by their mass spectra and confirmed using standards. In 34 virgin olive oils (cv. Nocellara del Belice) the mean concentrations for these five substances were always below 0.2 mg kg⁻¹ and only in two samples the level of 3,4-dihydroxyphenylacetic acid reached 1.47 and 1.97 mg kg⁻¹, respectively. These compounds could be used to characterise olive oils; low concentrations of 3,4-dihydroxyphenylacetic acid may show the initial autoxidation processes of olive oils.     

Authentication of extra virgin olive oils by Fourier-transform infrared spectroscopy

Fourier-transform infrared spectroscopy (FTIR), followed by multivariate treatment of the spectral data, was used to classify vegetable oils according to their botanical origin, and also to establish the composition of binary mixtures of extra virgin olive oil (EVOO) with other low cost edible oils. Oil samples corresponding to five different botanical origins (EVOO, sunflower, corn, soybean and hazelnut) were used. The wavelength scale of the FTIR spectra of the oils was divided in 26 regions. The normalized absorbance peak areas within these regions were used as predictors. Classification of the oil samples according to their botanical origin was achieved by linear discriminant analysis (LDA). An excellent resolution among all categories was achieved using an LDA model constructed with eight predictors. In addition, multiple linear regression models were used to predict the composition of binary mixtures of EVOO with sunflower, corn, soybean and hazelnut oils. For all the binary mixtures, models capable of detecting a low cost oil content in EVOO as low as 5% were obtained.     

Prediction of the genetic variety of Spanish extra virgin olive oils using fatty acid and phenolic compound profiles established by direct infusion mass spectrometry

The genetic varieties of Spanish extra virgin olive oils (Arbequina, Hojiblanca and Picual) were predicted by direct infusion of the samples in the electrospray ionization source of a mass spectrometer, followed by linear discriminant analysis of the spectral data. The samples were 1:50 diluted (v/v) with an 85:15 propanol/methanol (v/v) mixture containing 40 mM KOH and infused. The abundances of the [M–H]⁻ peaks of the free fatty acids (7 peaks) and 28 phenolic compounds (20 peaks) were measured. Ratios of pairs of peak abundances were used as predictors in the construction of the linear discriminant analysis models. An excellent resolution between the three genetic varieties was achieved.     

Chemical changes in extra virgin olive oils from Slovenian Istra after thermal treatment

Changes in the physico-chemical parameters of extra virgin olive oils after heating for 142 h at 100 °C with an air flow 10 L/h were investigated. The experimental study was carried out on the two predominant olive cultivars in Slovenian Istra – cv. Istrska belica and cv. Leccino. The data obtained showed that oils from Istrska belica were more stable than those from Leccino. Peroxide values and spectrophotometric data showed higher amounts of oxidation products in oils from Leccino than in those from Istrska belica. After thermal treatment fatty acid composition was changed more in Leccino oils; particularly the amounts of polyunsaturated fatty acids dropped significantly, while α-tocopherol was completely depleted in all samples. The content of total biophenols decreased from 598 mg/kg to 241 mg/kg in Istrska belica oils and from 391 mg/kg to 176 mg/kg in Leccino oils. HPLC data showed that transformation of secoiridoid biophenols to the simple biophenols, tyrosol and hydroxytyrosol took place.     

Pigment profiles of Spanish extra virgin olive oils by ultra-high-performance liquid chromatography coupled to high-resolution mass spectrometry

ABSTRACT

This work studies the natural pigment profiles (chlorophylls and carotenoids) of Spanish Extra Virgin Olive Oils (EVOO) produced in different Spanish regions. The simultaneous qualitative and quantitative analysis of EVOO natural pigments has been performed by ultra-high-performance liquid chromatography coupled to high-resolution mass spectrometry (UHPLC-HRMS) using atmospheric pressure chemical ionisation (APCI). The results showed a similar natural pigment pattern for all the analysed EVOOs, although the total pigments content differed significantly. Moreover, the chlorophyll/carotenoid ratio was close to 1, while the lutein/β-carotene ratio was higher than 1, showing that lutein is the most abundant carotenoid in the studied Spanish EVOOs. Data from multivariate statistical approach demonstrated that the olive variety does not discriminate between EVOO samples. However, they were classified based on their origin allowing good differentiation of samples from the Basque Country and Canary Islands from the rest of regions. The results of this study show the differences of the nature and pigments concentration of Spanish EVOO samples, parameters that are of significance for reliable characterisation.     

Evaluating two kinds of centrifuged virgin oils arising from continuous olive processing

Oils extracted from olive pastes by the direct centrifugation mode were compared with the homologous oils produced by the indirect centrifugation (after percolation) mode. The former were characterised by: (i) higher contents of total phenols, o‐diphenols, hydroxytyrosol, hydroxytyrosol‐aglycons, total volatiles, trans‐2‐hexanal and other pleasant volatiles, total tocopherols, total sterols and waxes; (ii) lower contents of triterpene dialcohols, aliphatic and triterpene alcohols, chlorophylls and pheophytins; (iii) lower values of integral colour index; (iv) higher values of turbidity, campesterol/stigmasterol ratio, 1,2‐diglycerides/1,3‐diglycerides ratio, oxidative stability and overall quality indices; and (v) higher sensory score. Stigmastadienes and trans‐isomer C₁₈ fatty acids were always not detected. The average oil outputs of the two centrifugation extraction procedures were comparable, as confirmed by similar overall oil amounts found in the by‐products. © 2000 Society of Chemical Industry     

Study of phenolic compounds in virgin olive oils of the Picual variety

Monovarietal Picual olive oils possibly represent 25% of the world's olive oil production. HPLC was used to analyse phenolic compounds and tocopherols in Picual olive oils obtained during two successive crop seasons (1999/2000 and 2000/2001) and from different geographic areas of the Jaén province, which is located in the south of Spain. Oils obtained at the beginning of each season had a higher content of each phenolic compound than those obtained at the end, although this effect was more pronounced for orthodiphenols than for non-orthodiphenols. The main phenolic compound detected in this monovarietal oil was the aglycon of oleuropein followed by the other secoiridoid aglycons. Lignan concentration in oil showed low variability with season and harvesting time, and pinoresinol in particular was present at a concentration of about 40 ppm. Therefore, the total polyphenol content of this monovarietal oil ranged from 300 to 700 ppm. Similarly, significant differences in these compounds were not detected between geographic areas. This monovarietal oil is very stable due to its high content of oleic acid and for this reason, the storage of oils for 2 years in amber glass bottles caused only a 30% decrease in phenolic compounds. An increase was found in simple phenols such as hydroxytyrosol and tyrosol liberated from the acid hydrolysis of the secoiridoid aglycons, and minor losses in tocopherols were also observed. These data provide a basis for the evaluation of polyphenol intake from virgin olive oil consumption, particularly from the monovarietal olive oil most consumed in the world.     

特级初榨橄榄油中酚类化合物不同提取方法对比研究

采用液液萃取法(LLE)、固相萃取法(SPE)和液液微萃取法(LLME)分别对特级初榨橄榄油中酚类成分进行提取,应用超高效液相色谱-高分辨质谱法(UPLC-HRMS)及Folin-Ciocalteus比色法分别进行酚类化合物组成研究和总酚含量测定,比较3种方法的提取效率。结果表明:特级初榨橄榄油中共检测到40种酚类化合物,其中液液萃取样品检出33种,固相萃取样品检出20种,液液微萃取样品检出15种,液液萃取法提取酚类化合物种类显著多于其他两种方法;液液萃取法提取的总酚含量分别为固相萃取法及液液微萃取法的2. 9倍和3. 7倍,液液萃取法对酚类化合物的提取效率明显优于其他两种方法;但从实验过程角度考量,液液微萃取法具有操作简单、省时省力、有机溶剂用量少、对实验人员伤害小、环境污染小等优点,具有进一步优化的潜力。     

Classification of extra virgin olive oils according to their genetic variety using linear discriminant analysis of sterol profiles established by ultra-performance liquid chromatography with mass spectrometry detection

A method to classify extra virgin olive oils (EVOOs) according to their genetic variety using sterol profiles obtained by ultra-performance liquid chromatography (UPLC) with atmospheric pressure chemical ionization mass spectrometry (APCI-MS) detection has been developed. The optimal separation conditions were obtained using a gradient acetonitrile/water (0.01% acetic acid) at a flow rate of 0.8 mL min^− 1 and 10 °C. Linear discriminant analysis (LDA) models were constructed with the 11 UPLC-APCI-MS sterol peaks taken from the selective ion recording mode chromatograms. Ratios of the peak areas selected by pairs were used as predictors. With the sequential application of two LDA models and using a 95% probability, the EVOO samples belonging to seven genetic varieties mainly produced at La Comunitat Valenciana, Spain, were correctly classified with a prediction capability higher than 97%.     

A modified sorting task to investigate consumer perceptions of extra virgin olive oils

A two-stage sorting task was used to probe Californian consumers’ opinions of twenty-five extra virgin olive oils based on visual assessments of the bottles. The modification of the simple sorting task aimed to encourage consumers to further discriminate products through sub-groupings of products within the groups they had already made. Sorting data were analyzed using a 3-way extension of classical multidimensional scaling called DISTATIS which explores the level of consumer agreement as well as the structure of the extra virgin olive oil products. Consumer agreements were explained by 46% of the variances found in the ways consumers sorted the bottles. Decreased amount of explained variance from the first stage to the second stage of the sorting task was observed in the olive oil product structures. Consumers were asked to describe the characteristics defining each group formed. Consumer comments were analyzed qualitatively prior to statistical analysis and were later used to understand the sorting results. Despite background differences in the usage of olive oil products, the majority of the consumers perceived the product set similarly. The two-stage sorting task allowed subjects to provide more criteria or multidimensional views of their perception of the products.     

Distribution of simple phenols,phenolic acids and flavonoids in Turkish monovarietal extra virgin olive oils for two harvest years

Monovarietal extra virgin olive oils extracted from six dominant and economically important Turkish olive cultivars (memecik, erkence, domat, nizip-yaglik, gemlik, ayvalik) were examined for their simple phenolics, phenolic acids and flavonoid compounds over 2005 and 2006 harvest years. Total phenol contents, oxidative stabilities and chromatic ordinates as colour parameters were also measured. The most typical phenolic compounds that were identified in both years are hydroxytyrosol, tyrosol, vanillic acid, p-coumaric acid, cinnamic acid, luteolin, and apigenin. Multivariate data were analysed by principal component and partial least square-discriminant analyses. It was observed that phenolic profiles of olive oils depended highly on harvest season. In addition, oils of different olive cultivars have different distribution of phenols. No significant correlation was observed between oxidative stability and phenolic compounds. Increase in peroxide value over an accelerated oxidation period of 11 days showed weak correlations with total phenol content, vanillin, syringic acid and colour parameter a^∗, as 0.56, 0.55, −0.42, and 0.51, respectively, in terms of correlation coefficient r.     

The potential of coupling information using three analytical techniques for identifying the geographical origin of Liguria extra virgin olive oil

The combined use of data obtained from different analytical instruments is a complex problem.     

DNA diversity in olive (Olea europaea L.) and its relationships with fatty acid,biophenol and sensory profiles of extra virgin olive oils

Olive (Olea europaea L.) is gaining importance worldwide primarily for the production of virgin olive oil (VOO), the main lipid source of the Mediterranean diet.We evaluated the genetic diversity of 20 traditional varieties of Southern Italy using 10 SSR markers. We also produced 382 monovarietal extra virgin olive oils (EVOOs) from the same varieties and studied their chemical profiles by analysing 13 fatty acids (FAs) and 6 olive biophenols (OBPs). In addition, the sensory profile of EVOOs was also assessed.Significant differences among the 20 varieties were found in terms of DNA polymorphism, chemical composition and sensory profile of the EVOOs, highlighting that the genetic variability in olive is detected also in different EVOO features. The chemical variation of EVOOs throughout different years suggested a genotype-specific level of environmental stability and adaptation. The comparison of pairwise distances between varieties obtained by genetic, chemical and sensory data indicated a significant correlation of sensory attributes with the other parameters.The genetic and EVOO composition data underlined the significant diversity present in the varieties under investigation, suggesting that traditional varieties specialized to particular environmental conditions have distinctive, unexplored features. Our work also shows the efficacy of establishing integrated compositional databases as a means to make evident differences among VOOs from traditional varieties. This multidisciplinary information is highly useful to differentiate origin-linked products from others of the same category.     

Radical scavenging-linked antioxidant activity of ethanolic extracts of diverse types of extra virgin olive oils

The present study evaluated the radical scavenging-linked antioxidant activity of hexane/80% ethanol extracts from several types of extra virgin olive oils (EVOOs) derived from varieties arbequina, hojiblanca, picual, their blends, and pure olive oil (POO). The antioxidant potential of the olive oil extracts was assessed by radical scavenging assays using DPPH (2, 2-diphenyl-1-picrylhydrazyl), ABTS (2, 2'-azino-bis (3-ethylbenzthiazoline-6-sulfonic acid), and hydroxyl radical, as well as hydrogen peroxide and superoxide anion inhibitory activities. Electron donating ability (EDA) using DPPH assay of 80% ethanol extracts from EVOOs, except arbequina oil, was significantly higher than POO. EDA was markedly higher in blended and picual EVOOs than the extracts from arbequina and hojiblanca EVOOs (P < 0.05). Similarly, ABTS radical scavenging activity of the extracts from the EVOOs was in order of picual EVOO > blended EVOO > hojiblanca EVOO >or= POO >or= arbequina EVOO. Further, the superoxide anion scavenging activity of blended, picual, and arbequina EVOOs was significantly higher than that of hojiblanca EVOO and POO, which were barely detectable. Hydroxyl radical scavenging activity of arbequina and hojiblanca was higher than that of blended, picual EVOOs, and POO. In addition, hydrogen peroxide scavenging activity of the extracts from blended, arbequina, hojiblanca, picual EVOOs, and POO was 63.1 +/- 3.1%, 44.4 +/- 10.2%, 52.0 +/- 2.7%, 71.8 +/- 2.5%, and 35.7 +/- 10.0%, respectively. Our results indicate that ethanol extracts of several EVOOs contained higher radical scavenging and antioxidant activity than the POO. This antioxidant potential is partly due to the phenolic compounds present in different olive oil grade and is influenced by cultivar type.     

Influence of the malaxation time and olive ripening stage on oil quality and phenolic compounds of virgin olive oils

The main objective of this study was to evaluate the influence of the malaxation time (Mt) and ripening stage on oil quality and phenolic compounds of Hojiblanca and Picual virgin olive oils. In both varieties of oil, phenolic content and oxidative stability decreased as ripening progressed. The total level of tocopherols diminished by up to 40% as fruit ripened. The compositions of palmitic, stearic, lignoceric, oleic, linoleic and linolenic acids were significantly influenced by the ripening process. The present work shows that an increased Mt promoted the increase of free acidity (up to 13.3%) and tocopherols (up to 11.6%) and negatively affected the oxidative stability and the concentration of phenols. Further research is required to determine ripening stages and malaxation conditions for all olive oil varieties to achieve a satisfactory balance between the improvement of both oil yield and oil quality and composition.