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.     

High performance size-exclusion chromatography analysis of polar compounds applied to refined, mild deodorized, extra virgin olive oils and their blends: An approach to their differentiation

An investigation was carried out to evaluate the use of High Performance Size-Exclusion Chromatography (HPSEC) of polar compounds of refined, mild deodorized, extra virgin olive oils as well as of their blends, in attempting to reveal significant differences in the amounts of the substance classes constituting polar compounds among these oils. Two sets of blends were prepared by mixing an extra virgin olive oil with both refined and mild deodorized olive oils in increasing amounts. The obtained data highlighted that the triacylglycerol oligopolymers were absent or present in traces in the extra virgin olive oil, while their mean amount was equal to 0.04 g/100 g and 0.72 g/100 g in mild deodorized and refined olive oils, respectively. Oxidized triacylglycerols and diacylglycerols were more abundant in mild deodorized oil and refined oil than in extra virgin olive oil. The Factorial Discriminant Analysis of the data showed that the HPSEC analysis could reveal the presence of refined/mild deodorized oils in extra virgin olive oils. In particular, the classification functions obtained allowed designation of mixtures containing at least 30 g/100 g of mild deodorized oil and all those containing refined olive oil as deodorized oil, therefore as oils subjected to at least a mild refining treatment.     

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.     

Separation and determination of sterols in olive oil by HPLC-MS

This study presents the first liquid chromatographic method for the identification and quantification of seven phytosterols in olive oil. Sterols were identified and quantified by liquid chromatography with mass spectrometry detection in positive APCI (atmospheric pressure chemical ionisation) mode. The samples were saponified by refluxing with 2 N ethanolic KOH, and the non-saponificable fraction was extracted with diethyl ether. This fraction was subjected to thin layer chromatography (TLC) on silica gel plates and then the band of sterols was isolated and extracted with methanol. Sterols were quantified by LC-MS, on a Waters Atlantis 5 μm dC₁₈2,1 × 150 mm column with a gradient of acetonitrile/water (0.01% acetic acid) at a flow of 0.5 mL min⁻¹; column temperature 30 °C. The method presents values between 123 and 677 ng mL⁻¹ for detection limits, with relative standard deviations between 4.0% and 5.4% at a concentration of 5 mg L⁻¹ for each sterol. Sterol contents were determined in a virgin olive oil, a refined olive oil, an olive-pomace oil and a crude olive-pomace oil.     

Olive oil adulterated with hazelnut oils: simulation to identify possible risks to allergic consumers

According to European Union Regulation EC 1531/2001, olive oil labelled as “extra-virgin” should be cold-pressed and contain no refined oil or oil from other oleaginous seeds or nuts. Adulteration of extra virgin olive oil (EVOO) with hazelnut oil (HAO) is a serious concern both for oil suppliers and consumers. The high degree of similarity between the two fats complicates the detection of low percentages of HAO in EVOO. Many analytical approaches have been developed in recent years to trace HAO in EVOO, principally based on chromatographic analyses, differential scanning calorimetry or nuclear magnetic resonance. In addition adulteration of EVOO with HAO may introduce hazelnut-derived allergens. The aim of this work was to analyse the protein and allergen content of EVOO intentionally spiked with raw cold-pressed HAO or solvent-extracted HAO. SDS–PAGE analysis confirmed the presence of hazelnut proteins in solvent-extracted HAO with molecular masses ranging 10–60 kDa. In contrast, cold-pressed HAO showed no traces of protein. In spiked EVOO, solvent-extracted HAO was still detectable at a 1% contamination level. Several bands on SDS–PAGE migrated at apparent molecular masses coinciding with known allergens, such as Cor a 1 (～17 kDa), Cor a 2 (～14 kDa), Cor a 8 (～12 kDa), oleosin (～17 kDa) and Cor a 9 (～60 kDa). MALDI–TOF MS analysis confirmed the presence of two oleosin isoforms and of Cor a 9. Immunoblotting demonstrated that an allergic patient with known reactivity to Cor a 1 and Cor a 2 recognized a 17-kDa band in solvent-extracted HAO. In conclusion, we have shown that adulteration of extra virgin olive oil with solvent-extracted hazelnut oil can be traced by simple SDS–PAGE analysis, and that adulteration introduces a potential risk for hazelnut allergic patients.     

Physicochemical characterisation and oxidative stability of fish oil and fish oil–extra virgin olive oil microencapsulated by sugar beet pectin

Spray-dried microcapsules were prepared at 25% and 50% w/w oil load from sugar beet pectin-stabilised emulsions (pH 3) containing fish oil, and a blend of fish oil and with extra virgin olive oil (1:1 w/w). Microencapsulation efficiencies were high (≥90%). However, deterioration in microcapsule wall integrity and an increase in oil droplet size were observed during storage (25 °C, 0–3 months). Lipid oxidation increased with both increased oil load (P < 0.05) and storage duration (P < 0.05), but was independent of oil composition (P > 0.05). These results suggest that sugar beet pectin functions poorly as a wall material and its residual metal ions exacerbate omega-3 oxidation, despite the presence of endogenous antioxidants found in extra virgin olive oil. Interestingly, under accelerated storage conditions (OxiPres® at 80 °C, 0.5 bar oxygen pressure), microcapsules containing the oil blend showed the best oxidative stability (P < 0.05), irrespective of oil load. A possible explanation for the superior oxidative stability of the microencapsulated oil blend at high storage temperature is discussed.     

Monitoring olive oil oxidation under thermal and UV stress through synchronous fluorescence spectroscopy and classical assays

Synchronous fluorescence (SyF) spectra combined with principal component analysis (PCA) is proven to be a useful tool for monitoring olive oil deterioration under UV irradiation at 80 °C. Spectra acquired in the range 300–500 nm during 12 h accelerated oxidation stress using a surface per volume ratio of 0.95 cm² ml⁻¹ reveal five different classes after PCA. Parallel monitoring of lipid oxidation parameters peroxide value (PV), anisidine value (AV) shows that after 12 h, TOTOX value increases 10-fold, 19-fold and almost 38-fold for extra virgin olive, olive and olive-pomace oil, respectively.     

Identification of 3-MCPD esters to verify the adulteration of extra virgin olive oil

ABSTRACT

The adulteration of olive oil is an important issue around the world. This paper reports an indirect method by which to identify 3-monochloropropane-1,2-diol (3-MCPD) esters in olive oils. Following sample preparation, the samples were spiked with 1,2-bis-palmitoyl-3-chloropropanediol standard for analysis using gas chromatograph-tandem mass spectrometry. The total recovery ranged from 102.8% to 105.5%, the coefficient of variation ranged from 1.1% to 10.1%, and the limit of quantification was 0.125 mg/kg. The content of 3-MCPD esters in samples of refined olive oil (0.97–20.53 mg/kg) exceeded those of extra virgin olive oil (non-detected to 0.24 mg/kg). These results indicate that the oil refining process increased the content of 3-MCPD esters, which means that they could be used as a target compound for the differentiation of extra virgin olive oil from refined olive oil in order to prevent adulteration.     

Effect of standard phenolic compounds and olive oil phenolic extracts on acrylamide formation in an emulsion system

In this work the effect of standard phenolic compounds such as trolox, phenolic acids (ferulic, gallic, protocatechuic and caffeic acid) and secoiridoids, extracted from virgin olive oil (VOO), on acrylamide formation in an emulsion system was investigated. The emulsion system was heated in an oil bath at different temperatures and for different periods of time. At 105 and 115 °C the generated amounts of acrylamide were negligible during the monitoring time. At 125 °C addition of standard phenolic compounds reduced acrylamide formation which was more pronounced at initial time of heating (20 min) reaching up to 70%. Protocatechuic and gallic acid were more effective than trolox, caffeic and ferulic acid in acrylamide reduction at the final time intervals of heating (30–60 min). On the contrary, addition of VOO extract in the emulsion system resulted in a remarkable increase of acrylamide level, which was ascribed to secoiridoids’ structure containing aldehydic groups.     

Oxidative changes in hazelnut,olive, soybean,and sunflower oils during microwave heating

The effects of microwave heating for 3, 6, and 9 min at a frequency of 2450 MHz on fatty acid composition, tocopherols, iodine value, free fatty acids (%), peroxide value, conjugated dienes and trienes, and hexanal contents of refined hazelnut, soybean, sunflower, and virgin olive oils were investigated. A significant (p < 0.05) decrease was observed in linoleic and linolenic acids contents of soybean oil during exposure to microwave heating. Tocopherol contents of oil samples significantly decreased (p < 0.05) during microwave heating. Free fatty acids of the samples slightly increased and iodine value showed reduction throughout the process. Conjugated dienes contents of samples showed an increasing trend up to the 6 min, followed by a reduction at 9 min. Conjugated triene fatty acids of all the samples significantly increased (p < 0.05) throughout the application. While peroxide value showed increasing trend up to the 3 min and sharply decreased at 9 min, hexanal contents of refined hazelnut, virgin olive, soybean, and sunflower oils increased 63, 28, 55, and 389 fold, respectively, after 9 min exposure to microwave heating. Kinetic analysis of data showed that the reaction orders for peroxide and hexanal formation were zero and first order, respectively, and in the tested oils the reaction rate followed the order: soybean oil ? sunflower oil ? hazelnut oil ? virgin olive oil for peroxide, and sunflower oil ? soybean oil ? hazelnut oil ? virgin olive oil for hexanal formation. It was concluded that hexanal could be considered as a parameter for evaluation of the quality of oils exposed to microwave heating.     

Stability of avocado oil during heating: Comparative study to olive oil

The stability of the saponifiable and unsaponifiable fractions of avocado oil, under a drastic heating treatment, was studied and compared to that of olive oil. Avocado and olive oil were characterised and compared at time 0 h and after different times of heating process (180 °C). PUFA/SFA (0.61 at t = 0) and ω-6/ω-3 (14.05 at t = 0) were higher in avocado oil than in olive oil during the whole experiment. Avocado oil was richer than olive oil in total phytosterols at time 0 h (339.64; 228.27 mg/100 g) and at 9 h (270.44; 210.30 mg/100 g) of heating. TBARs was higher in olive oil after 3 h, reaching the maximum values in both oils at 6 h of heating treatment. Vitamin E was higher in olive oil (35.52 vs. 24.5 mg/100 g) and it disappeared earlier in avocado oil (at 4 vs. 5 h). The stability of avocado oil was similar to that of olive oil.     

Emissions of volatile aldehydes from heated cooking oils

Emissions of volatile organic compounds, including aldehydes, formed during heating of cooking oils: coconut, safflower, canola, and extra virgin olive oils were studied at different temperatures: 180, 210, 240, and 240 °C after 6 h. Fumes were collected in Tedlar^® bags and later analysed by GC–MS. The emissions of volatiles were constant with time and increased with the oil temperature. When the temperature of the oil was above its smoke point, the emission of volatiles drastically increased, implying that oils with low smoke point, such as coconut, are not useful for deep-frying operations. Canola was the oil generating the lowest amount of potentially toxic volatile chemicals. Acrolein formation was found even at low temperatures, indicating that home cooking has to be considered as an indoor pollution problem.     

Review of the use of phytosterols as a detection tool for adulteration of olive oil with hazelnut oil

Adulteration of virgin olive oil with less expensive oils such as hazelnut oil is a serious problem for quality control of olive oil. Detection of the presence of hazelnut oil in olive oil at low percentages (<20%) is limited with current official standard methods. In this review, various classes of phytosterols in these two oils are assessed as possible markers to detect adulterated olive oil. The composition of 4-desmethyl- and 4-monomethylsterols is similar in both oils, but the 4,4′-dimethylsterols differ. Lupeol and an unknown (lupane skeleton) compound from 4,4′-dimethylsterols are exclusively present in hazelnut oil and can be used as markers via GC–MS monitoring to detect adulteration at levels as low as 2%. The phytosterol classes need to be separated and enriched by a preparative method prior to analysis by GC or GC/MS; these SPE and TLC methods are also described in this review.     

Microwave heating of different commercial categories of olive oil: Part II. Effect on thermal properties

The effect of microwave heating of commercial categories of olive oil for human consumption (extra virgin olive oil [EVOo], olive–pomace oil [Po] and olive oil [Oo]) on DSC thermal properties was evaluated at different times of microwave treatment.     

The influence of the malaxation temperature on the activity of polyphenoloxidase and peroxidase and on the phenolic composition of virgin olive oil

The effect of the malaxation temperature under sealed conditions on the qualitative and quantitative composition of the phenolic compounds in virgin olive oils produced from four Italian cultivars was assessed for two atmospheric conditions. In both cases, the results show a positive relationship between temperature and the concentration of the derivatives of the secoiridoid aglycones; the effect of the temperature on the oxidoreductases that promote oxidation (polyphenoloxidase and peroxidase) was investigated to determine their optimal temperatures and thermal stability. While olive peroxidase (POD) showed the highest activity at 37 °C and high stability in the temperature range tested, polyphenoloxidase (PPO) exhibited the optimum activity at approximately 50 °C, but showed low stability at 40 °C, with a large variation in stability according to the olive cultivar. These results may contribute to an understanding of the increase in the phenol concentration found in virgin olive oils obtained following higher temperatures of malaxation.     

Characteristics of flaxseed hull oil

Oils from two commercial flaxseed hulls extracted by six procedures were evaluated for physicochemical characteristics. Oil yield ranged from 9% to 28% depending on solvent and extraction. Lipid fractionation of crude flaxseed hull oil yielded 92.5% neutral lipids, 3.1% phospholipids, 2.4% acidic lipids and 2.1% free fatty acids. Flaxseed hull oil exhibited three thermal transitions between −35 and −13 °C with solvent dependent polymorphism. Thermal oxidation by differential scanning calorimetry (DSC) revealed three step oxidation of flaxseed hull oil with mean onset and oxidation temperatures at 121 and 150–253 °C, respectively depending on the extraction procedure. Flaxseed hull oil exhibited two-fold difference (0.6–1.2 μm Trolox equivalent/g) in antioxidant activity measured by a photochemiluminescence (PCL) assay. Supercritical CO₂ extracted the most oil with the highest antioxidant capacity of all evaluated procedures resulting in a defatted flaxseed hull containing the highest (53 mg/g) secoisolariciresinol diglucoside (SDG) level.     

Characteristics of Prunus serotina seed oil

Oils from Prunus serotina raw and toasted seeds extracted with hexane and supercritical CO₂ were evaluated for their physicochemical characteristics. Supercritical CO₂ extracted the least oil (21.3%), with high absorbing carotenoid pigments. P. serotina oil had characteristically high refractive index and density with three typical absorbance peaks in the UVC (100–290 nm) range centred at 260, 270 and 280 nm. The oil was highly polyunsaturated and abundant in oleic (35%), α-elostearic (27%), linoleic (27%), palmitic (4%), stearic (4%) and β-elostearic (1%) acids. P. serotina seed oil exhibited at least three distinct thermal structural transitions between −35 and −13 °C with two reversing transitions between −19 and −12 °C. Thermal oxidation by differential scanning calorimetry (DSC) revealed a three step oxidation of P. serotina seed oil with the mean onset and oxidation temperatures at 121 and 130–273 °C, respectively, depending on processing. Supercritical CO₂ extraction and toasting significantly affected the thermal and oxidation characteristics, fluorescence, and fatty acids of oils.     

Volatile aldehyde emissions from heated cooking oils

Low molecular weight aldehydes (LMWAs) formed during the heating of frying media (triglycerides) were adsorbed onto tenax and analyzed by GC‐MS after thermal desorption. Six alkanals (C₅ to C₁₀), seven 2‐alkenals (C₅ to C₁₁) and 3 alkadienals (C₇, C₉ and C₁₀) were found in the fumes of canola oil (control), extra virgin olive oil, and refined olive oil, heated at 180 and 240 °C. The emission rates of these aldehydes depended on the heating temperature. Frying in any type of olive oil, independently of its commercial category, will effectively decrease the emission of volatile aldehydes at temperatures below the smoking point. Thus, using the cheaper olive oil for deep‐frying purposes will not affect aldehyde emissions. This is important since olive oil is usually used for deep‐frying operations while extra virgin olive oil is used as salad dressing in Spain. The mixture of refined olive oil with some virgin olive oil is the most acceptable type of olive oil in non‐Mediterranean countries due to its milder flavor. However, if higher temperatures are needed the use of canola oil is more advisable due to its higher smoke point. Copyright © 2004 Society of Chemical Industry     

Melatonin is a phytochemical in olive oil

Given the numerous observations regarding the positive effects of olive oil consumption and the presence of melatonin in edible plants, we addressed for the first time the question of melatonin determination in virgin olive oil. All the extra virgin olive oil registered designation of origins from Spain and commercial samples of refined olive and sunflower oil were used. Immunoprecipitation and ELISA were combined for melatonin determination. Melatonin is present in olive oil at higher levels in extra virgin olive oil than in refined olive or sunflower oil samples. We concluded that melatonin is part of the phytochemical profile of the olive oil. Particularly, extra virgin olive oil had almost double the melatonin contents of the other refined oils analysed. Thus, melatonin may account for the healthy effects of the Mediterranean diet in which olive oil is the main source of fat.     

Influence of olive paste preparation conditions on virgin olive oil triterpenic compounds at laboratory-scale

The influence of olive paste preparation conditions on the triterpenic content of virgin olive oils from Arbequina and Picual cultivars was investigated. For this purpose, three sieve diameters of the hammer mill (4, 5, and 6 mm), two malaxation temperatures (20 and 30 °C), and two malaxation times (20 and 40 min) were tested. Results obtained showed that for Arbequina oils, a finer crushing level resulted in higher maslinic acid and erythrodiol content. Increasing malaxing temperature and time lead to a rise in both oleanolic and maslinic acid concentration, whereas erythrodiol content increased only for the longer malaxation time. For Picual oils, higher concentrations of oleanolic acid, maslinic acid, and uvaol were obtained by prolonging the paste malaxation time. A finer crushing level resulted also in an increase of maslinic acid content. These findings suggest that virgin olive oil triterpenic composition can be improved by regulating olive paste preparation conditions.