Virgin olive oil volatile compounds from lipoxygenase pathway and characterization of some italian cultivars.

Fruits from seven different varieties of Olea europaea L., grown in the same environmental conditions, were harvested in two succeeding years at the same ripening degree and immediately processed. The oils obtained were submitted to gas chromatographic determination of the volatile compounds extracted by dynamic headspace technique. The results demonstrated that the accumulation of the different metabolites in the oils obtained from the various cultivars were strictly connected with the varietal parameter because of the enzyme differences genetically determined. This feature made possible the differentiation of the examined cultivars on the basis of the percent of each metabolite from the enzymatic transformation of 13-hydroperoxides of linolenic acid. Oils from Picual and Koroneiki varieties cultivated in Spain and Greece, respectively, showed contents of volatiles very similar to those detected in the oils of the same varieties cultivated in Italy, proving that they were not significantly influenced by the environmental conditions.     

Quantification of phenolic compounds in olive oil mill wastewater by artificial neural network/laccase biosensor

In this paper is considered a new computerized approach to the determination of concentrations of phenolic compounds (caffeic acid and catechol). An integrated artificial neural network (ANN)/laccase biosensor is designed. The data collected (current signals) from amperometric detection of the laccase biosensor were transferred into an ANN trained computer for modeling and prediction of output. Such an integrated ANN/laccase biosensor system is capable of the prediction of caffeic acid and catechol concentrations of olive oil mill wastewater, based on the created models and patterns, without any previous knowledge of this phenomenon. The predicted results using the ANN were compared with the amperometric detection of phenolic compounds obtained at a laccase biosensor in olive oil wastewater of the 2004-2005 harvest season. The difference between the real and the predicted values was <0.5%. biosensor; olive oil mill wastewater; chemical analysis; phenolic compounds.     

Virgin olive oil normalizes the altered triacylglycerol molecular species composition of adipose tissue in spontaneously hypertensive rats

The present study was conducted in order to evaluate the influence of hypertension on the triacylglycerol (TG) molecular species composition and other lipid classes of rat adipose tissue. In addition, the effect of two dietary oils, with a similar content in oleic acid but different TG moieties, was studied. Virgin olive oil (VOO) or high-oleic sunflower oil (HOSO) was added to a baseline diet (BD) and administrated to Wistar-Kyoto and spontaneously hypertensive rats (SHR) for 12 weeks. Both VOO and HOSO normalized the altered composition of TG molecular species and phospholipid (PL) fatty acids in SHR compared to animals fed BD, although the effect exhibited by VOO was greater. Rats fed HOSO showed a greater palmitic (p < 0.05) and lower linoleic acid (p < 0.05) incorporation into PL but a greater accumulation of linoleic acid-containing TG species, particularly dioleoyl-linoleoyl-glycerol, with a concomitant displacement of trilinolein. Both oils were capable of increasing the lipoprotein lipase (LPL) activity in normotensive rats, but only VOO did so in the SHR. Therefore, it was concluded that although oleic acid-rich diets improve some of the altered parameters of SHR adipose tissue, VOO is more effective than HOSO in this regard.     

Changes in virgin olive oil quality during low-temperature fruit storage

'Frantoio' olive fruits were stored at low temperature (4 +/- 2 degrees C) for 3 weeks to investigate the effect of postharvest fruit storage on virgin olive oil quality. Volatile compounds and phenolic compounds explained the changes in sensory quality that could not be explained with quality indices (FFA, PV, K232, and K270). Increases in concentrations of ( E)-2-hexenal and hexanal corresponded to positive sensory quality, whereas increases in ( E)-2-hexenol and (+)-acetoxypinoresinol were associated with negative sensory quality. Volatile and phenolic compounds were also indicative of the period of low-temperature fruit storage. Oleuropein and ligstroside derivatives in olive oil decreased with respect to storage time, and their significant ( p < 0.05) change corresponded to changes in bitterness and pungency. ( Z)-2-Penten-1-ol increased during low-temperature fruit storage, whereas 2-pentylfuran decreased. Changes in volatile compounds, phenolic compounds, quality indices, and sensory notes indicated that virgin olive oil quality was lost within the first week of low-temperature fruit storage and regained at 2 weeks. This research suggests that low-temperature olive fruit storage may be beneficial, with a possibility of increasing oil yield and moderating the sensory quality of virgin olive oils. This study demonstrates that deeper insights into virgin olive oil quality changes during low-temperature fruit storage may be gained by studying volatile and phenolic compounds in addition to quality indices and physical appearance of the fruit.     

Effects of olive fruit quality and oil storage practices on the diacylglycerol content of virgin olive oils

The evolution of 1,3- and 1,2-isomers of diacylglycerols (DGs) in olive oils obtained from healthy olives and the influence of the olive quality was studied. Healthy olive fruits yielded oils containing almost exclusively 1,2-isomers whereas altered olives produced oils with significant amounts of 1,3-isomers. Virgin olive oils obtained from various olive cultivars and stored at different temperatures showed triacylglycerol hydrolysis and diacylglycerol isomerization depending on the acidity and temperature. The results indicated that the relationship between acidity and total diacylglycerol content has scarce utility for detecting mild refined oil in virgin olive oil. On the other hand, the 1,3-/1,2-DG isomers ratio is useful for assessing the genuineness of virgin olive oils with low acidities during the early stages of storage.     

How heating affects extra virgin olive oil quality indexes and chemical composition

Two monovarietal extra virgin olive oils from Arbequina and Picual cultivars were subjected to heating at 180 degrees C for 36 h. Oxidation progress was monitored by measuring oil quality changes (peroxide value and conjugated dienes and trienes), fatty acid composition, and minor compound content. Tocopherols and polyphenols were the most affected by the thermal treatment and showed the highest degradation rate although their behavior was different for each cultivar. Alpha-tocopherol loss was more important in Arbequina oil whereas, total phenol content loss was greater in Picual oil. The later showed an important decrease in hydroxytyrosol (3,4-DHPEA) and its secoiridoid derivatives (3,4-DHPEA-EDA and 3,4-DHPEA-EA), while lignans decrease was lesser. For Arbequina oil these compounds remained stable, and a lowering tendency was observed for tyrosol (p-HPEA) and its derivatives (p-HPEA-EDA and p-HPEA-EA). In general, flavone content showed a decrease during heating, being higher for Arbequina oil. On the other hand, oleic acid, sterols, squalene, and triterpenic alcohols (erythrodiol and uvaol) and acids (oleanolic and maslinic) were quite constant, exhibiting a high stability against oxidation. From these results, we can conclude that despite the heating conditions, VOO maintained most of its minor compounds and, therefore, most of its nutritional properties.     

Improving virgin olive oil quality by means of innovative extracting biotechnologies

Three major virgin olive oil varieties (Dritta, Leccino, and Coratina) extracted by a modern centrifugation system aided with a new plant enzyme preparation (having prevalently pectolytic activity) were characterized. These oils showed a clearly enhanced quality standard, owing to higher levels of some important minor components (phenolics, volatiles, tocopherols, carotenes, and chlorophylls) and to frequently lower concentrations of oxidized triglycerides and diglycerides. The oils were therefore characterized by lower susceptibility to oxidation and longer shelf life, and their flavor, aroma, and color features appeared to be significantly improved. The saponifiable fraction was practically not affected as the enzymatic effects involved only the membranes of the oil droplets, where the nonglyceridic compounds are essentially located.     

采用全卷积神经网络与Stacking算法的湿地分类方法

高精度湿地制图对湿地生态保护与精细管理具有重要的支撑作用。针对传统湿地分类方法的精度不高等问题,提出了一种采用全卷积神经（Fully Convolutional Neural,FCN）网络与集成学习的湿地分类方法。首先利用全卷积神经网络（SegNet、UNet及RefineNet）对GF-6影像的语义特征进行提取与融合,然后利用Stacking集成算法对融合后的特征进行判别和分类。结果表明,采用全卷积神经网络与Stacking算法能有效提取湿地信息,总体分类精度为88.16%,Kappa系数为0.85。与采用全卷积神经网络与单一机器学习的随机森林（Random Forest,RF）、支持向量机（Support Vector Machin,SVM）与k-近邻（Nearest Neighbor,kNN）算法相比,该研究提出的湿地分类方法在总体分类精度上分别提高了4.87,5.31和5.08个百分点;与采用单一全卷积神经网络（RefineNet、SegNet、UNet）与Stacking算法下的湿地分类结果,该文提出的湿地分类方法在总体分类精度上分别提高了2.78,4.48与4.91个百分点;该方法一方面能通过卷积神经网络提取遥感影像深层的语义特征,另一方面通过集成学习根据各分类器的表征性能进行合理的选择并重组,从而提高分类精度及其泛化能力。该方法能为湿地信息提取及土地覆盖分类方法的研究提供参考。     

Detection of extra virgin olive oil adulteration with lampante olive oil and refined olive oil using nuclear magnetic resonance spectroscopy and multivariate statistical analysis

High-field 31P NMR (202.2 MHz) spectroscopy was applied to the analysis of 59 samples from three grades of olive oils, 34 extra virgin olive oils from various regions of Greece, and from different olive varieties, namely, 13 samples of refined olive oils and 12 samples of lampante olive oils. Classification of the three grades of olive oils was achieved by two multivariate statistical methods applied to five variables, the latter being determined upon analysis of the respective 31P NMR spectra and selected on the basis of one-way ANOVA. The hierarchical clustering statistical procedure was able to classify in a satisfactory manner the three olive oil groups. Subsequent application of discriminant analysis to the five selected variables of oils allowed the grouping of 59 samples according to their quality with no error. Different artificial mixtures of extra virgin olive oil-refined olive oil and extra virgin olive oil-lampante olive oil were prepared and analyzed by 31P NMR spectroscopy. Subsequent discriminant analysis of the data allowed detection of extra virgin olive oil adulteration as low as 5% w/w for refined and lampante olive oils. Further application of the classification/prediction model allowed the estimation of the percent concentration of refined olive oil in six commercial blended olive oils composed of refined and virgin olive oils purchased from supermarkets.     

The influence of bearing cycles on olive oil quality response to irrigation

Five rates of water application were applied in a 4 year study on olive (Olea europaea) varieties 'Barnea' and 'Souri'. Increased irrigation lead to increased tree-scale oil yields, lower polyphenol content, and, frequently, higher oil acidity. These effects were predominant in "off" years. The fatty acid profile was influenced primarily by bearing level and variety and secondarily by irrigation rate. The saturated to unsaturated fatty acid ratio was higher in "off" than in "on" years, and the monounsaturated fatty acid to polyunsaturated fatty acid ratio was higher in "on" years as a result of the fact that oleic and stearic acids were higher in "on" years, while palmitic, palmitoleic, and linoleic acids were greater in "off" years. Squalene was higher in 'Souri' than in 'Barnea' oils, was not affected by bearing cycle, and was consistently lower in oil from trees receiving the lowest irrigation level.     

Polyphenolic content in olive oil waste waters and related olive samples

The production of olive oil yields a considerable amount of waste water, which is a powerful pollutant and is currently discarded. Polyphenols and other natural antioxidants, extracted from olives during oil extraction process, partially end up in the waste waters. Experimental and commercial olive oil waste waters from four Mediterranean countries were analyzed for a possible recovering of these biologically interesting constituents. Identification and quantitation of the main polyphenols were carried out by applying HPLC-DAD and HPLC-MS methods. Representative samples of ripe olives were also analyzed at the same time to correlate, if possible, their polyphenolic profiles with those of the corresponding olive oil waste waters. The results demonstrate that Italian commercial olive oil waste waters were the richest in total polyphenolic compounds with amounts between 150 and 400 mg/100 mL of waste waters. These raw, as yet unused, matrices could represent an interesting and alternative source of biologically active polyphenols.     

Comparative study of virgin olive oil quality from single varieties cultivated in Chile and Spain

Olive tree varieties that were cultivated only in the Mediterranean basin a few decades ago are now planted in the Southern Hemisphere as well. The chemical composition of the oils produced in countries as far distant as Spain and Chile are affected by differences in latitude and climate. In this work, seven monovarietal virgin olive oils from Chile (Arbequina, Barnea, Frantoio, Koroneiki, Leccino, Manzanilla and Picual) have been characterized by the chemical compounds responsible for taste (phenols) and aroma (volatiles). The oils were produced in five regions of Chile, and the concentration values of some chemical compounds were related to the geographical location of the olive tree orchards. Virgin olive oils from the major cultivars, Arbequina and Picual, were characterized in comparison with the same monovarietal oils produced in Spain. The concentration values of fourteen volatile compounds showed significant differences (p < 0.05) between the oils produced in Spain and Chile. Concerning the phenol composition, main differences were found on the secoiridoids derivatives of oleuropein and ligstroside, apigenin and luteolin.     

Relation of acidity and sensory quality with sterol content of olive oil from stored fruit

Composition of the sterol fraction, fatty acid, acidity, and the sensorial evaluation of virgin olive oils were studied in two eastern Spanish varieties grown and processed under the same conditions. Fruits were stored at 5 degrees C and ambient temperature for different times. During fruit storage, there was no significant variation (P = 0.05) in fatty acid composition. However, the sterol composition of the oil varied markedly (in particular, there was an increase in stigmasterol), acidity increased, and there was a very significant decrease in sensorial quality. The stigmasterol content presented a high correlation with the acidity and sensory evaluation (P < 10(-)(6)). The total sterol content increased gradually with olive storage time. Oils with stigmasterol greater than campesterol are graded to a low level (lampant). It is of interest that sensorial quality is revealed by stigmasterol content, a fact unknown until now.     

Polycyclic aromatic hydrocarbons and olive pomace oil

The occurrence of polycyclic aromatic hydrocarbons (PAHs) in five samples of olive pomace oil has been studied to determine the contamination degree of this type of oil and to evaluate if specific purification steps must be introduced during its manufacture. The PAHs present have been determined by gas chromatography-mass spectrometry. A high number of PAHs, with a wide range of molecular weights and in very high concentrations, have been found in four of the samples studied. A very high number of alkyl derivatives and, in many cases, in higher concentrations than their respective parent PAHs, have also been identified. One of the samples, however, presents a more reduced number of PAHs and in significantly lower concentrations than the others. These findings reveal that it is necessary to introduce adequate cleanup steps in the manufacturing process of olive pomace oil, which can give rise to oils with a relatively low content of PAHs. Some carcinogenic PAHs have also been identified, both unalkylated and alkylated.     

Partitioning of olive oil antioxidants between oil and water phases.

The partition coefficient (K(p)) of the natural phenolic antioxidant compounds in the olive fruit between aqueous and olive oil phases was determined. The antioxidants of olive oil are either present in the olive fruit or formed during the olive oil extraction process. The antioxidants impart stability to and determine properties of the oil and are valuable from the nutritional point of view. The olive oil antioxidants are amphiphilic in nature and are more soluble in the water than in the oil phase. Consequently, a large amount of the antioxidants is lost with the wastewater during processing. The determination of antioxidants was performed using HPLC, and the K(p) was estimated to be from as low as 0.0006 for oleuropein to a maximum of 1.5 for 3,4-DHPEA-EA (di-hydroxy-phenyl-ethanol-elenolic acid, oleuropein aglycon). Henry's law fitted very well to the experimental data. The partition coefficients were also estimated by applying the activity coefficients of the antioxidants in the two phases using a predictive group contribution method, the UNIFAC equation. The K(p) values estimated with UNIFAC method were of the same order of magnitude but varied from the experimental values. Nevertheless, this method may be a rough predictive tool for process optimization or design. Because the K(p) values were very low, some changes in the process are recommended in order to achieve a higher concentration of antioxidants in the oil. A temperature increase may lead to increasing the partition coefficient. Also, limiting the quantity of water during oil extraction could be a basis for designing alternative processes for increasing the antioxidant concentration in the olive oil.     

Rotenone residues on olives and in olive oil

The disappearance of rotenone on olives under field conditions was studied. The field data showed that rotenone residues on olives decreased with a half-life (t(1/2)) of 4.0 days. After pre-harvest time (10 days) the residues were higher than the maximum residue level fixed in Italy (0.04 mg/kg). Experiments with model systems showed that the mechanism of disappearance of rotenone is not related to evaporation, thermodegradation, or co-distillation, but only to photodegradation. When the olives were processed for oil, the residues in the oil were higher than the residues on the olives by a factor of 2.4-4.8.     

Antioxidant activity of olive pulp and olive oil phenolic compounds of the arbequina cultivar

The aim of this study was to characterize antioxidant activities of phenolic compounds that appear in olive pulp and olive oils using both radical scavenging and antioxidant activity tests. Antiradical and antioxidant activities of olive pulp and olive oil phenolic compounds were due mainly to the presence of a 3,4-dihydroxy moiety linked to an aromatic ring, and the effect depended on the polarity of the phenolic compound. Glucosides and more complex phenolics exhibited higher antioxidant activities toward oxidation of liposomes, whereas in bulk lipids aglycons were more potent antioxidants with the exception of oleuropein. Lignans acted as antioxidants only in liposomes, which could partly be due to their chelating activity, because liposome oxidation was initiated by cupric acetate. The antioxidant activity of virgin olive oil is principally due to the dialdehydic form of elenolic acid linked to hydroxytyrosol (3,4-DHPEA-EDA), a secoiridoid derivative (peak RT 36, structure unidentified), and luteolin.     

Effect of olive stoning on the volatile and phenolic composition of virgin olive oil

Olive stoning during the virgin olive oil (VOO) mechanical extraction process was studied to show the effect on the phenolic and volatile composition of the oil. To study the impact of the constitutive parts of the fruit in the composition of olive pastes during processing, the phenolic compounds and several enzymatic activities such as polyphenoloxidase (PPO), peroxidase (POD), and lipoxygenase (LPO) of the olive pulp, stone, and seed were also studied. The olive pulp showed large amounts of oleuropein, demethyloleuropein, and lignans, while the contribution of the stone and the seed in the overall phenolic composition of the fruit was very low. The occurrence of crushed stone in the pastes, during malaxation, increased the peroxidase activity in the pastes, reducing the phenolic concentration in VOO and, at the same time, modifying the composition of volatile compounds produced by the lipoxygenase pathway. The oil obtained from stoned olive pastes contained higher amounts of secoiridoid derivatives such as the dialdehydic forms of elenolic acid linked to (3,4-dihydroxyphenyl)ethanol and (p-hydroxyphenyl)ethanol (3,4-DHPEA-EDA and p-HPEA-EDA, respectively) and the isomer of the oleuropein aglycon (3,4-DHPEA-EA) and, at the same time, did not show significant variations of lignans. The stoning process modified the volatile profile of VOO by increasing the C6 unsaturated aldehydes that are strictly related to the cut-grass sensory notes of the oil.     

Multiclass pesticide determination in olives and their processing factors in olive oil: comparison of different olive oil extraction systems

The processing factors (pesticide concentration found in olive oil/pesticide concentration found in olives) of azinphos methyl, chlorpyrifos, lambda-cyhalothrin, deltamethrin, diazinon, dimethoate, endosulfan, and fenthion were determined in olive oil production process in various laboratory-scale olive oil extractions based on three- or two-phase centrifugation systems in comparison with samples collected during olive oil extractions in conventional olive mills located at different olive oil production areas in Greece. Pesticide analyses were performed using a multiresidue method developed in our laboratory for the determination of different insecticides and herbicides in olive oil by solid-phase extraction techniques coupled to gas chromatography detection (electron capture detection and nitrogen phosphorus detection), optimized, and validated for olive fruits sample preparation. Processing factors were found to vary among the different pesticides studied. Water addition in the oil extraction procedure (as in a three-phase centrifugation system) was found to decrease the processing factors of dimethoate, alpha-endosulfan, diazinon, and chlorpyrifos, whereas those of fenthion, azinphos methyl, beta-endosulfan, lambda-cyhalothrin, and deltamethrin residues were not affected. The water content of olives processed was found to proportionally affect pesticide processing factors. Fenthion sulfoxide and endosulfan sulfate were the major metabolites of fenthion and endosulfan, respectively, that were detected in laboratory-produced olive oils, but only the concentration of fenthion sulfoxide was found to increase with the increase of water addition in the olive oil extraction process.