NMR and statistical study of olive oils from Lazio: A geographical,ecological and agronomic characterization

NMR and statistical procedures were used to analyse olive oils obtained from trees grown in different areas of Lazio, an Italian region, under different irrigation conditions. In order to obtain information on “real” commercial olive oils and to study the effects of some agronomical and ecological factors on the olive oil composition, we studied commercial multi-varietal olive oils, all produced in well-characterized areas of Lazio. ¹H and ¹³C NMR techniques, coupled to a suitable multivariate statistical procedure, were used to analyse 72 multi-varietal extra virgin and PDO (Protected Denomination of Origin) olive oils harvested in 2003, from the northern area, the centre and the southern area of Lazio. The intensity of selected ¹H and ¹³C NMR variables were submitted to three different statistical methods, namely, analysis of variance (ANOVA), principal component analysis (PCA) and linear discriminant analysis (LDA). ¹H and ¹³C NMR spectroscopy allowed us to obtain a good chemical characterization of the samples, giving information on major and minor compounds with an experimental error exactly the same and always extremely low for all the analyzed components. As a result of the statistical analysis, olive oils from the same geographical areas were well grouped. Since the amounts of some minor volatile components, such as aldehydes, terpenes and squalene, as well as, the content of β-sitosterol, the most important sterol present in olive oils, are sensitive to the pedoclimatic conditions, the intensity of the corresponding NMR signals turned out to be the most discriminating factors in the geographic classification. Moreover, the NMR and statistical protocol allowed us to investigate the roles of irrigation and altitude on the olive oil composition: the contents of oleic and saturated fatty acids turned out to be strongly influenced by the irrigation practice, whereas the content of volatile compounds was sensitive to the altitude of the olive trees. As a result of our study, olive oils were well grouped according to the irrigation practice as well as to the altitude at which olive trees were grown.     

Instrumental and multivariate statistical analyses for the characterisation of the geographical origin of Apulian virgin olive oils

In this paper, virgin olive oils (VOOs) coming from three different geographic origins of Apulia, were analysed for free acidity, peroxide value, spectrophotometric indexes, chlorophyll content, sterol, fatty acid, and triacylglycerol compositions. In order to predict the geographical origin of VOOs, different multivariate approaches were applied. By performing principal component analysis (PCA) a modest natural grouping of the VOOs was observed on the basis of their origin, and consequently three supervised techniques, i.e., general discriminant analysis (GDA), partial least squares-discriminant analysis (PLS-DA) and soft independent modelling of class analogy (SIMCA) were used and the results were compared. In particular, the best prediction ability was produced by applying GDA (average prediction ability of 82.5%), even if interesting results were obtained also by applying the other two classification techniques, i.e., 77.2% and 75.5% for PLS-DA and SIMCA, respectively.     

Pigment profile and colour of monovarietal virgin olive oils from Arbequina cultivar obtained during two consecutive crop seasons

Monovarietal virgin olive oils are labelled with the olive varieties giving them their distinctive character. There are numerous studies focussed on the characterisation and quantification of the minor fractions of virgin olive oils that have generated databases on varietal olive oils. However, few studies have focussed on the components of the pigment fraction of virgin olive oils. The aim of this work was to quantify the components of the chlorophyll and carotenoid fractions of the monovarietal virgin olive oils from the Arbequina cultivar, growing in the Spanish area of Catalonia, during two consecutive crop seasons. Additionally the pigment changes occurring during 24 months of oil storage were evaluated. The results of this study showed minor qualitative differences between monovarietal virgin olive oils from two consecutive seasons. The quantitative differences could be attributed to the harvest period in each season rather than to the year’s weather conditions. Storage of the monovarietal virgin olive oils probably caused an important loss of the chlorophyll fraction, mainly chlorophyll a, during the first 6 months of storage. On the other hand, the carotenoid fraction was very stable and the retention of provitamin A was close to 80%, even after 24 months of storage.     

基于紫外可见光谱技术和色素组成区分橄榄油与其他食用油

目的 通过紫外可见光谱技术和色素组成,探究区分橄榄油与其他食用油的方法。方法 选择市售橄榄油(特级初榨橄榄油、混合橄榄油)和其他食用油(菜籽油、玉米油、葵花籽油、大豆油、花生油、调和油)作为研究对象,分别在220~800 nm的波长范围内进行全光谱扫描以及在波长为450 nm和670 nm处进行光度测量;通过比较不同食用油的紫外可见吸收光谱并结合主成分分析(principal component analysis, PCA)和偏最小二乘法判别(partial least squares discriminant analysis, PLS-DA)对不同橄榄油和其他食用油进行比较区分。结果 通过观察比较各食用油紫外可见吸收光谱的最大吸收波长所在位置,可以对不同食用油进行初步区分。并且PCA和PLS-DA结果显示,以波长450 nm和670 nm处的吸光度A450和A670以及A450/A670为变量,可用于区分不同橄榄油和其他食用油。结论 基于紫外可见光谱技术对不同食用油中色素的检测结果可以对食用油进行分类,并且A450、A670和A450/A670可以作为区分橄榄油与其他食用油的标记。     

Analytical evaluation of two monovarietal virgin olive oils cultivated in the south of Tunisia: Jemri‐Bouchouka and Chemlali‐Tataouin cultivars

BACKGROUND: The characterisation of virgin olive oils from two Tunisian cultivars, growing in the Tataouin zone, namely Jemri‐Bouchouka, a rare olive cultivar, and Chemlali‐Tataouin, was carried out. Several analytical parameters were evaluated; these include quality index, fatty acids, phenolic, chlorophyll, carotenoid, squalene, α‐tocopherol compositions and oxidative stability. RESULTS: Jemri‐Bouchouka olive oil had the highest value of oleic acid (74.50%) while Chemlali‐Tataouin was characterised by a high percentage of palmitic acid (14.75%), which makes this oil freeze at a low temperature. On the other hand, Jemri‐Bouchouka oil was characterised by a low phenolic and α‐tocopherol content (267.72 mg GAE kg^?1 and 278.34 mg kg^?1, respectively). Ten phenolic compounds were identified. The main phenols found in the two olive oils were oleuropein aglycon and pinoresinol. All phenolic compounds showed significant correlations with oxidative stability. CONCLUSION: The analytical parameters of virgin olive oil that were determined in this study were greatly influenced by cultivar. © 2012 Society of Chemical Industry     

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.     

Detection of the adulteration of olive oils by solid phase microextraction and multidimensional gas chromatography

The presence or absence of filbertone in 21 admixtures of olive oil with virgin and refined hazelnut oils obtained using various processing techniques from different varieties and geographical origins was evaluated by solid phase microextraction and multidimensional gas chromatography (SPME–MDGC). The obtained results showed that the sensitivity achievable with the proposed procedure was enough to detect filbertone and, hence, to establish the adulteration of olive oil of different varieties with virgin hazelnut oils in percentages of up to 7%. The very low concentrations in which filbertone occurs in some refined hazelnut oils made difficult its detection in specific admixtures. In any case, the minimum adulteration level to be detected depends on the oil varieties present in the adulterated samples. In the present study, the presence of R- and S-enantiomers of filbertone could be occasionally detected in olive oils adulterated with 10–20% of refined hazelnut oil.     

Quality assessment of edible vegetable oils used as liquid medium in canned tuna

An experimental investigation was conducted to assess the quality of vegetable oils used as liquid medium in preserved fish. Sixteen tuna preserves were tested, including two in extra virgin olive oil, nine in olive oil (refined olive oil plus virgin olive oil) and five in refined seed oil. Next to the traditional routine analyses prescribed by the EEC Regulation N° 2568/91 (useful for a preliminary characterisation of oils used as liquid medium), the content of trans isomers of unsaturated fatty acids was determined and the analysis of polar compounds was performed by HPSEC (high performance size-exclusion chromatography). The acid composition showed the presence of highly unsaturated fatty acids, typical of fish lipids. Trans isomers were always absent in extra virgin olive oils, whereas they were always present in olive oils and in refined seed oils. Triglyceride oligopolymers, oxidised triglycerides and diglycerides, measured by means of the HPSEC analysis of polar compounds, ranged within 0.13-1.07%, 0.51-2.36% and 0.96-4.02%, respectively. The HPSEC analysis of polar compounds and the determination of trans isomers enabled better assessment of the quality of different types of oils used as liquid medium for canned tuna.     

Distribution and retention of phytosterols in frying oils and fried potatoes during repeated deep and pan frying

The retention and distribution of phytosterols in fried oils and French-fries during eight successive pan- and deep-frying sessions of pre-fried potatoes in sunflower oil, palm oil, cottonseed oil, virgin olive oil and a vegetable shortening were evaluated. Phytosterols (β-sitosterol, campesterol, stigmasterol, Δ⁵-avenasterol) were determined in the unsaponifiable fraction of frying oils and lipids extracted from French-fries by GC/FID after derivatization to trimethylsilyl ethers. French-fries were enriched with phytosterols due to the absorption of frying oil, with β-sitosterol predominating in both fried oils and potatoes. The amount of phytosterols decreased during frying, their overall retentions reaching 9.5–22.8% and 29.4–51.2% after eight successive pan- and deep-frying sessions, respectively, while their deterioration was found to be affected by frying time, frying technique, being more prolonged during pan-frying, and by the oils’ unsaturation, being more extended in polyunsaturated oils. Phytosterols were more or less uniformly distributed between the fried oil and the fried potatoes. The phytosterols dietary intake by consuming potatoes fried in the oils tested is discussed.     

FTIR Spectroscopy and PLS-DA Classification and Prediction of Four Commercial Grade Virgin Olive Oils from Morocco

Fourier transform infrared (FTIR) coupled to chemometrics was shown to be a useful method to classify and predict the quality of four commercial grade virgin olive oils (VOO). FTIR and physicochemical data were collected using a set of 70 samples representing extra virgin (EV), virgin (V), ordinary virgin (OV), and lampante (L) commercial grade olive oils collected in Beni Mellal region (central Morocco). Two partial least squares discriminant analysis (PLS-DA) models using physicochemical data and FTIR data were established and compared. The PLS-DA model using only physicochemical data was not accurate enough to distinguish satisfactorily among OV, V, and EV olive oil grades. On the contrary, the PLS-DA model on FTIR data was better in the calibration, able to describe 98 % of the spectral information and predicting 93 % of the VOO grades. In the external validation, this PLS-DA model accurately classified VOO commercial grades with prediction accuracy of 100 %. The proposed procedure is fast, nondestructive, simple, and easy to operate, and it is recommended for the quick monitoring of olive oil’s quality.     

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.     

Estimation of the intake of phenol compounds from virgin olive oil of a population from southern Spain

The objective of the study was to determine the mean polyphenol composition of different varieties of virgin olive oil (VOO) habitually consumed in the region of southern Spain and to estimate the dietary exposure to olive oil polyphenols in that population. There were statistically significant differences in total polyphenols among varieties, with the Picual variety containing the largest amount with a mean value of 591.8 mg kg^–1. The main phenolic compounds found in the VOOs under study were tyrosol and hydroxytyrosol. The highest amounts of both substances were found in Picual olive oils with concentrations of 2.3–6.6 mg kg^?1. The total intake of polyphenols from VOO ranged between 8.2 mg day^–1 (SD = 4.14) for the under 19 year olds and 21.3 mg day^–1 (SD = 3) for the over 50 year olds. Some polyphenols, including tyrosol and hydroxytyrosol, were consumed principally as olive oil. The intake of these compounds in the studied population was in the range of 88.5–237.4 μg day^–1. This has particular importance as recent studies have demonstrated that hydroxytyrosol helps to improve plasma lipids levels and repair oxidative damage related to cardiovascular disease. There was a greater dietary consumption of polyphenols in olive oil among the participants who more closely followed the Mediterranean diet pattern. A higher consumption of olive oil and therefore a greater exposure to polyphenols was observed in females versus males and in participants of normal weight versus those who were overweight. The total intake of polyphenols from VOO significantly increased with higher age, reflecting the greater intake of this oil by older people, who also show a closer adherence to the Mediterranean diet. The over 50-year-old age group showed the greatest consumption of this olive oil and therefore of phenolic compounds, which are healthy protectors in the human diet that contribute to the acknowledged benefits of the Mediterranean diet.     

Migrated phthalate levels into edible oils

The determination of phthalates in edible oils (virgin olive oil, olive oil, canola oil, hazelnut oil, sunflower oil, corn oil) sold in Turkish markets was carried out using gas chromatography–mass spectrometry. Mean phthalate concentrations were between 0.102 and 3.863 mg L^?1 in virgin olive oil; 0.172 and 6.486 mg L^?1 in olive oil; 0.501 and 3.651 mg L^?1 in hazelnut oil; 0.457 and 3.415 mg L^?1 in canola oil; 2.227 and 6.673 mg L^?1 in sunflower oil; and 1.585 and 6.248 mg L^?1 in corn oil. Furthermore, the influence of the types of oil and container to the phthalate migration was investigated. The highest phthalate levels were measured in sunflower oil. The lowest phthalate levels were determined in virgin olive oil and hazelnut oil. The highest phthalate levels were determined in oil samples contained in polyethylene terephthalate.     

PRELIMINARY EVALUATION OF THE APPLICATION OF THE FTIR SPECTROSCOPY TO CONTROL THE GEOGRAPHIC ORIGIN AND QUALITY OF VIRGIN OLIVE OILS

ABSTRACT

A rapid Fourier transform infrared (FTIR) attenuated total reflectance spectroscopic method was applied to determine qualitative parameters such as free fatty acid (FFA) content and the peroxide value (POV) in virgin olive oils. Calibration models were constructed using partial least squares regression on a large number of virgin olive oil samples. The best results (R² = 0.955, root mean square error in cross validation [RMSECV] = 0.15) to evaluate FFA content expressed in oleic acid % (w/w) were obtained considering a calibration range from 0.2 to 9.2% of FFA relative to 190 samples. For POV determination, the result obtained, built on 80 olive oil samples with a calibration range from 11.1 to 49.7 meq O₂/kg of oil, was not satisfactory (R² = 0.855, RMSECV = 3.96). We also investigated the capability of FTIR spectroscopy, in combination with multivariate analysis, to distinguish virgin olive oils based on geographic origin. The spectra of 84 monovarietal virgin olive oil samples from eight Italian regions were collected and elaborated by principal component analysis (PCA), considering the fingerprint region. The results were satisfactory and could successfully discriminate the majority of samples coming from the Emilia Romagna, Sardinian and Sicilian regions. Moreover, the explained variance from this PCA was higher than 96%.

PRACTICAL APPLICATIONS

The verification of the declared origin or the determination of the origin of an unidentified virgin olive oil is a challenging problem. In this work, we have studied the applicability of Fourier transform infrared coupled with multivariate statistical analysis to discriminate the geographic origin of virgin olive oil samples from different Italian regions.

     

Influence of the different oils used in dough formulation on the lipid fraction of taralli

Abstract: An experimental investigation was carried out to evaluate the quality of taralli as a function of the type of oil used in their dough formulation. To this end, 4 types of oil (extra virgin olive oil, olive oil, olive‐pomace oil, and refined palm oil) were utilized to prepare taralli to investigate on the lipid fraction degradation and evaluate the taralli acceptability by consumers. The data obtained pointed out that taralli manufactured with extra virgin olive oil were significantly more appreciated than those made with refined oils due to their visual appearance and odor. Moreover, with respect to the other kinds of oil, the use of extra virgin olive oil led to significantly lower values (P < 0.05) of specific absorption at 232 and 270 nm (K₂₃₂ and K₂₇₀, respectively) and of triacylglycerol oligopolymers. It also proved to present a much lower content in oxidized triacylglycerols and diacylglycerols than olive‐pomace oil and refined palm oil, respectively. Furthermore, trans fatty acid isomers were absent in taralli made with extra virgin olive oil but were constantly present in those produced with refined oils.     

Waxy fraction containing long-chain aliphatic aldehydes in virgin olive oils

Long-chain aliphatic aldehydes are natural minor components occurring in the cuticle of numerous plant species and also evidenced in virgin olive oils. The fraction containing these compounds can be isolated from the oil samples by using a solid-phase extraction silica-gel cartridge and then directly analysed by GC on a 5% diphenyl-95% dimethylsiloxane capillary column, using an on column-injection system. The proposed methodology showed that extra virgin olive oils contain long-chain aliphatic aldehydes, with even carbon-atom numbers from C₂₂ to C₃₀. Quantitative results, using the synthesised aldehyde C₂₁ as internal standard, give concentrations of total long-chain aliphatic aldehydes in a variable range below 116 mg kg⁻¹, being hexacosanal (C₂₆-al) the most abundant aldehyde. The different experimental conditions utilised during olive oil extraction processes influence the total aldehydes concentration. Besides contribution to the knowledge of the minor-component composition present in olive oil, their interest and relationship with wax esters, aliphatic alcohols and n-alkanes are discussed.     

Use of capillary electrophoresis with UV detection to compare the phenolic profiles of extra‐virgin olive oils belonging to Spanish and Italian PDOs and their relation to sensorial properties

BACKGROUND: There is much interest in foods that belong to Protected Designations of Origin (PDO) because the quality and other essential and exclusive characteristics are guaranteed because of a particular geographical environment. We have used a capillary electrophoretic method for the simple, rapid and simultaneous characterization and quantification of the polyphenolic fraction of extra‐virgin olive oil from different PDOs (18 compounds in less than 7 min). To demonstrate the usefulness of this method, we have analyzed 16 samples of a Spanish PDO and nine other samples belonging to an Italian PDO (n = 5). RESULTS: In this way, it was possible to compare the phenolic profiles of the oils of different zones of the same PDO, as well as the phenolic profiles of Spanish and Italian extra‐virgin olive oils. Univariate statistics were used for differentiating the oils produced in each PDO. Furthermore, the correlations among several of the phenolic compounds present in the extracts of olive oil and its sensorial properties were checked. decarboxylated oleuropein aglycon (DOA) (b) (peak 6) was the compound more related to the bitterness of the oils, Ac Pin (peak number 4) and the unidentified peak with t_mig 4.025 min played an important role in the pungent taste of the oils, and these two latter compounds and the peak 13 seemed to be related to the fruitiness of the oils. CONCLUSIONS: The electrophoretic method described in the current work has the ability to detect and quantify simultaneously 18 phenolic compounds (belonging to five different families) in less than 7 min. This technique could improve the characterization of this polar fraction and determine the geographical origin of olive oils or detect possible ‘PDO markers’. In fact, capillary electrophoresis coupled to statistical analysis enabled discrimination among olive oils belonging to two different PDOs considering eight phenolic compounds present in the extracts, and also identification of the phenolic compounds which could have more influence on several sensory attributes such as bitterness, pungency and fruitiness. Copyright © 2009 Society of Chemical Industry     

Classification of different quality virgin olive oils by metal-oxide sensors

The European Union classifies virgin olive oils into three categories, extra virgin, virgin and lampante; lampante being the only oil that cannot be consumed before undergoing a refining process. A mathematical model based on two metal-oxide sensors has been designed and checked in order to detect on-line lampante oils inside the production systems. The model was developed using 114 samples and was successfully tested with an external test set of 55 samples taken from different single varietal olive oils and geographical origins. The model was able to detect 100% of non-lampante virgin olive oils and 89.5% of lampante virgin olive oils.     

Detection of hazelnut oil in virgin olive oil by a spectrofluorimetric method

The possibilities of a spectrofluorimetric method joined to multivariate analysis to assess the genuineness of olive oil in admixtures with hazelnut oils were studied. Virgin olive, virgin hazelnut and refined hazelnut oil samples and admixtures between them at 5, 10, 15, 20, 25 and 30% adulteration were analysed at _ex=350 nm. The precision of the method, in terms of repeatability and internal reproducibility, was established by means of the analysis of a virgin olive oil sample under different conditions, the RSD showing values less than 10%. Raw data of the spectra were subjected to mathematical treatment by calculation of the first derivative, selection of the maximum values and application of one-way ANOVA, to assess the most prominent variables in the discrimination process. The response to the addition of adulterant was linear, adjusted-R²=0.99 for virgin olive and refined hazelnut oil mixtures, and 0.98 for virgin olive and virgin hazelnut oil mixtures. Stepwise linear discriminant analysis applied to each admixture separately and to the whole set of samples allowed 100% correct classifications.     

Microwave heating effects on the chemical composition and the antioxidant capacity of tataouine virgin olive oils from Tunisia

Four Tunisian virgin olive oils (VOOs), derived from varieties (Chemlali Tataouine, Zarrazi Douirat, Fakhari Douirat, and Dhokar Douirat) grown in the harsh pedoclimatic conditions of the region of Tataouine, were evaluated for their responses to microwave heating. Aside from fatty acid composition, all other evaluated parameters were affected by microwave heating, and their variations depend on the genetic factor. Chemlali Tataouine VOO exhibited the slowest biophenol degradation rate and the least diminution in oxidative stability and consequently, its total fraction and both lipidic and methanolic fractions remained unchanged with an exceptional antioxidant potential. In the remaining studied VOOs, the biophenol contents, the oxidative stability, and the antioxidant potential underwent gradual decreases; nevertheless, their levels at the longer treatment time are close to some fresh VOOs. These results should be taken into consideration when Tataouine VOOs are recommended for microwave heating.