Thermal Antioxidative Kinetics of Hydroxytyrosol in Selected Lipid Systems of Different Unsaturation Degree

The oxidation kinetics of the purified triacylglycerols of olive, canola, and fish oils as affected by different concentrations of hydroxytyrosol were studied at 60–100 °C. On average, hydroxytyrosol improved the temperature susceptibility (temperature coefficient, T_C, and Q₁₀ number) of olive oil, whereas opposite results were observed for canola and fish oils. Despite the results observed in canola and fish oils, hydroxytyrosol caused much greater changes in the Arrhenius equation parameters (activation energy, E_a, and frequency factor, A) for the oxidation of olive oil. On the whole, the highest increase in the Gibbs free energy, ΔG⁺⁺, of the activated complex formation as affected by the antioxidant was for olive (9.7%), canola (8.9%), and fish (5.7%) oils, respectively.     

Evolution of Oxidative Values during Kinetic Studies on Olive Oil Oxidation in the Rancimat Test

A comparative study was carried out in order to evaluate the kinetics of the formation of a number of primary and secondary oxidation products during oxidation of olive oil in the Rancimat test at 100–130 °C. There were good correlations between the Rancimat index (OSI) and stability indices (IP) measured in the Rancimat test with no significant differences in kinetic parameters calculated from them. Mean values of the temperature coefficient, Q₁₀ number, activation energy (E_a), frequency factor (A), and free energy of activation (ΔG⁺⁺) for olive oil oxidation were calculated to be ?3.44 × 10^?2°C^?1, 2.21, 98.91 kJ/mol, 12.17 × 10¹² h^?1, and 128.25 kJ/mol, respectively. Each unit change in E_a was accompanied by an average 1.43 × 10¹² change in A, indicating a higher contribution for factor A than for E_a to the olive oil stability. The E_a and A correlated well with the values of enthalpy and entropy, respectively. The values of OSI or IP could be described well by the ΔG⁺⁺ values. Kinetic data indicated that olive oil stability is more affected by the indigenous antioxidants than by the fatty acid composition.     

Kinetic parameter determination of vegetable oil oxidation under Rancimat test conditions

In this research, five different vegetable oils were oxidized at four different temperatures (373, 383, 393, and 403 K) under Rancimat test conditions. An increasing rate of oxidation could be observed as temperature increased. The natural logarithms of the kinetic rate constant (k value) varied linearly with respect to temperature, with the temperature coefficients (T_Coeff) ranging from 6.95×10^–2 to 7.40× 10^–2 K^–1 for the vegetable oils. On the basis of the Arrhenius equation and the activated complex theory, frequency factors (A), activation energies (E_a), Q₁₀ numbers, activation enthalpies (ΔH⁺⁺), and activation entropies (ΔS⁺⁺) for oxidative stability of the vegetable oils were calculated. The A, E_a, Q₁₀, ΔH⁺⁺, and ΔS⁺⁺ values for the vegetable oils ranged from 6.38×10³ to 28.03×10³ h^–1, from 86.86 to 92.42 kJ/mol, from 2.08 to 2.18, from 83.64 to 89.20 kJ/mol, and from –116.66 to –104.35 J/mol K, respectively.     

The Role of Oil Phase in the Stability and Physicochemical Properties of Oil-in-Water Emulsions in the Presence of Gum Tragacanth

Different emulsions based on six types of vegetable oils (sunflower, canola, sesame, olive, coconut, and palm olein) were studied to investigate the role of the oil phase in the stability and physicochemical characteristics of oil-in-water emulsions prepared with gum tragacanth. The results indicated that the stability, rheological parameters, and size distribution of emulsions were dependent on the oil type. Based on the interfacial tension value, the type of oil did not have a significant effect on the gum tragacanth-emulsifying properties. The formulation based on sunflower and coconut oil led to producing more stable emulsion and a sample containing palm olein resulted in an unstable emulsion. Rheological analysis revealed that the sample based on palm olein showed the lowest consistency coefficient (2.10 ± 0.05 Pas ⁿ), elastic modulus (3.90 ± 0.21 Pa), and energy of cohesion (80.87 ± 1.1 J m⁻³). This study revealed that using oils with lower viscosity and higher density led to the higher stability of the emulsion samples.     

Application of FTIR spectroscopy in determining sesamol in sesame seed oil

A new analytical method was developed for determining sesamol in sesame seed oil by FTIR spectroscopy. Sesamol was also spiked at 0 to 1000 mg/kg in freshly refined, bleached, and deodorized palm olein (RBDPOo) and groundnut (peanut) oil. FTIR spectra were recorded using a transmission (NaCl) cell accessory at room temperature, and the partial least squares regression statistical method was used to derive calibration models for each oil. The standard errors of calibration were 6.07, 5.88, and 4.24 mg/100 g for sesame, RBDPOo, and groundnut oils, with coefficients of determination (R ²) of 0.9947, 0.9940, and 0.9662, respectively. The calibration models were validated by the “leave-one-out” cross-validation method, and the R ² of validation, the standard errors of prediction, and SD of the differences for repeatability and accuracy were computed. Our results support the premise that FTIR spectroscopy is an efficient and accurate method for determining minor components such as sesamol in edible oils.     

Design and Characteristics of Novel Sensory and Nutritionally Oriented Olive,Seed, and Nut Virgin Oils’ Blendings

Virgin olive oil is considered a key component of the Mediterranean Diet, while nut and seed “cold-pressed” oils stand out as an interesting ingredient due to the growing consumer demand toward so-called gourmet and healthy oils. The main objective of this work is the development and characterization of novel virgin vegetal oils based on blendings of virgin olive oil with virgin oils obtained from seeds (sesame and flaxseed) and nuts (hazelnut and pistachio) of interest due to their peculiar nutritional and organoleptic characteristics. Oil formulations elaborated with 5% of sesame oils achieve a high content in vitamin E (842 mg kg⁻¹, 11.8 mg per standard 14 g oil dose, corresponding to an 80% of the recommended daily intake) and with 10% of flaxseed a high level in essential α-linolenic acid (6.4%, 0.90 mg per dose corresponding to a 66% of the recommended daily intake). In addition, sensory analysis shows that blends enriched with both 50% hazelnut oil and 75% pistachio oil not only maintain the typical aroma of virgin olive oil, but incorporate the characteristic nutty, roasty, seed-like, and sweet sensory attributes of nuts, providing an added value to the consumers.     

Detection of Adulteration in Iranian Olive Oils Using Instrumental (GC,NMR, DSC) Methods

This paper describes an investigation into the usefulness of some instrumental methods (GC, NMR, and DSC) in the detection of adulteration of olive oil with soybean, sunflower, and canola oils (that are relatively cheap oils mixed as adulterants with olive oil). These seed oils were compared with genuine and commercial olive oils, two of which appeared to have been adulterated. It was observed that from among physical and chemical indices, the iodine value and the refractive index in the two olive oil samples (named A and B) were significantly higher (P < 0.01) than in the reference (genuine) olive oil, both values being above standard limits established for olive oil. On the other hand, fatty acid (FA) profiles in these two samples exhibited higher amounts of linolenic and linoleic acids (5.34 and 39.92%, 6.38 and 54.42%, 0.79 and 12.88% for A, B and genuine olive oils respectively) but significantly lower amounts of oleic acid (30.07, 21.72 and 67.86%, respectively). The number and intensity of signals observed using ¹H NMR indicated that the peaks numbered 2 and 7 were useful in the determination of olive oil purity. Because of higher linolenic and linoleic acid contents in samples A and B, the intensity and integrated areas for these two signals were higher than those for other olive oil samples in which signal 2 was not observed and signal 7 had a very low intensity. Satisfactory results were achieved from quantitation of DSC parameters. The results show that due to increased unsaturated FAs in samples A and B and the consequent changes in triacylglycerol profiles, offset crystallization temperature and onset melting temperature in these two olive oils differed from those of the reference and clearly shifted to lower values. Crystallization and melting curves were similar to the corresponding curves observed for soybean and sunflower oils in terms of shape and number of peaks.     

Ultrasonic attenuation of edible oils

The frequency dependence (1–60 MHz) of the ultrasonic attenuation coefficient of canola oil, corn oil, olive oil, peanut oil, safflower oil, soybean oil, and sunflower oil was measured at 25°C. The attenuation coefficient of all the oils could be described by the relation: α ∼ Af ⁿ(with A between 6 and 40 × 10⁻¹², and n between 1.74 and 1.86).     

Oxidative stability of oils containing olive leaf extracts obtained by pressure,supercritical and solvent‐extraction

The effect of the addition of olive leaf (Olea europaea, cv. Arbequina) extracts, i.e. hydroalcoholic (ethanol–water 1:1; OHE), juice (OJ) and supercritical fluid‐CO₂ (OSFE) on the oxidative stability of vegetable oils with different unsaturation, such as soybean oil (SBO), canola oil (CO) and high oleic sunflower oil (HOSO), were studied at two concentrations (250 and 630 mg/kg oil, expressed as caffeic acid equivalent (CAE)). The extracts were characterized by the total phenolic content (Folin–Ciocalteau method), phenol chromatographic profiles (LC‐MS) and antioxidant activity (DPPH). OHE showed the highest phenol content (7.7 mg CAE/mL) while OJ and OSFE showed values of 5.4 and 2.2 mg CAE/mL, respectively. Oleuropein and its derivatives were the major phenolic compounds identified in OHE. The addition of 630 mg CAE/kg oil of OHE and OSFE to HOSO, SBO and CO showed an antioxidant effect, increasing significantly the induction time (IT) (p<0.05). That effect was highest when the system was more monounsaturated. In contrast, OJ showed a pro‐oxidant effect for all oils systems for both concentration studied. This behaviour could be attributed to the diphenol oxidase (PPO) activity.     

Modelling the temperature dependence of kinematic viscosity for refined canola oil

Viscosities of refined, bleached, deodorized (RBD) and refined, bleached, winterized (RBW) canola oils were measured at temperatures from 4 to 100°C. The viscosities of these refined canola oils were exponentially related to the oil temperature. Viscosity of the RBW oil was slightly greater than that of the RBD oil when the temperature was below 15°C. Compared to refined soybean oil, the canola oils were substantially more viscous. The viscosity of canola oil was modelled asv = exp(C₀ + C₁T + C₂T²). The maximum predicted error was less than 1.6% over the tested temperature range.     

Partial separation of polyunsaturated fatty acid esters from FAMEs mixtures by adsorption on silver nitrate-impregnated silica gel

Mixtures of FAMEs derived from soybean and canola oils were fractionated by contacting their hexane solutions with AgNO₃/SiO₂ adsorbents. Methyl linolenate (18∶3) adsorbed most strongly, followed by methyl linoleate (18∶2), on the AgNO₃/SiO₂. Conditions of the extractions (AgNO₃ loading, amount of adsorbent, methyl soyate/hexane solution concentration, use of successive extractions, and methods of adsorbent regeneration) were varied. Under optimal conditions, the 7.0% of 18∶3 in methyl soyate could be reduced to 0.1%. The described process is a simple method for separating a FAMEs mixture into a fraction that is depleted in polyunsaturated FAMEs and one that is enriched.     

Fatty Acids Composition of Vegetable Oils and Its Contribution to Dietary Energy Intake and Dependence of Cardiovascular Mortality on Dietary Intake of Fatty Acids

Characterizations of fatty acids composition in % of total methylester of fatty acids (FAMEs) of fourteen vegetable oils—safflower, grape, silybum marianum, hemp, sunflower, wheat germ, pumpkin seed, sesame, rice bran, almond, rapeseed, peanut, olive, and coconut oil—were obtained by using gas chromatography (GC). Saturated (SFA), monounsaturated (MUFA) and polyunsaturated fatty acids (PUFA), palmitic acid (C16:0; 4.6%–20.0%), oleic acid (C18:1; 6.2%–71.1%) and linoleic acid (C18:2; 1.6%–79%), respectively, were found predominant. The nutritional aspect of analyzed oils was evaluated by determination of the energy contribution of SFAs (19.4%–695.7% E_RDI), PUFAs (10.6%–786.8% E_RDI), n-3 FAs (4.4%–117.1% E_RDI) and n-6 FAs (1.8%–959.2% E_RDI), expressed in % E_RDI of 1 g oil to energy recommended dietary intakes (E_RDI) for total fat (E_RDI—37.7 kJ/g). The significant relationship between the reported data of total fat, SFAs, MUFAs and PUFAs intakes (% E_RDI) for adults and mortality caused by coronary heart diseases (CHD) and cardiovascular diseases (CVD) in twelve countries has not been confirmed by Spearman’s correlations.     

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

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

Accelerated oxidation: Comparative study of a new reactor with oxidation stability instrument

Accelerated oxidation tests, such as the determination of the induction period, increase the lipid oxidation rate by exposing a food to elevated temperatures, in the presence of excess quantities of air or oxygen. In addition to the well‐founded oxidative stability index (OSI) method, an innovative and promising technique is the oxidation test (OXITEST) reactor. A new analytical method was developed with OXITEST to oxidize vegetable oils. At a preliminary stage of the investigation, the induction periods of sunflower and extra‐virgin olive oil obtained by the OXITEST reactor were plotted against temperature, on the basis of the Arrhenius law; the activation energy and the frequency factor of lipid oxidation were calculated and resulted in 98.61 kJ/mol and 2.33×10¹⁰ s^–1, respectively, for sunflower oil and 106.48 kJ/mol and 6.27×10¹⁰ s^–1, respectively for extra‐virgin olive oil. The new oxidative technique was employed to determine the induction periods of vegetable oils; the results obtained were well correlated with those achieved with OSI technology, with a Pearson correlation coefficient r = 0.9785 (p <0.05) for oilseeds and palm oil and r = 0.9501 (p <0.05) for extra‐virgin olive oils.     

Kinetic Study of the Scavenging Reaction of the Aroxyl Radical by Eight Kinds of Vegetable Oils in Solution

A detailed kinetic study was performed for the reaction of the aroxyl radical (ArO?) with eight vegetable oils 1–8, which contain different concentrations of α‐, β‐, γ‐, and δ‐tocopherols and ‐tocotrienols (‐Tocs and ‐Toc‐3s). The second‐order rate constants (k_s) and aroxyl radical absorption capacity (ARAC) values for the reaction of ArO? with vegetable oils 1–8 (rice bran 1, perilla 2, rapeseed 3, safflower 4, grape seed 5, sesame 6, extra virgin olive 7, and olive oils 8) were measured in ethanol/chloroform/D₂O (50:50:1, v/v/v) solution at 25 °C using stopped‐flow spectrophotometry. The k_s value (16.1 × 10^?3 L g^?1 s^?1) of rice bran oil 1 with the highest activity was 8.0 times larger than that (2.02 × 10^?3) of olive oil 8 with the lowest activity. The concentrations (in mg 100 g^?1) of α‐, β‐, γ‐, and δ‐Tocs and ‐Toc‐3s contained in the vegetable oils 1–8 were determined using high performance liquid chromatography‐mass spectrometry/mass spectrometry (HPLC‐MS/MS). From these results, it was clarified that the ArO?‐scavenging rates (k_s) (i.e., the relative ARAC value) obtained for the vegetable oils 1–8 may be well explained as the sum of the product of the rate constant () and the concentration ([AOH‐i]/10⁵) of AOH‐i (Tocs and Toc‐3s) included in vegetable oils. The results suggest that the ARAC assay method might be used in the evaluation of antioxidant activity of general food extracts.     

Effect of growing area on pigment and phenolic fractions of virgin olive oils of the arbequina variety in Spain

The purpose of this investigation was to study differences in the chlorophyll, carotenoid, and phenolic fractions of virgin olive oils from the Arbequina variety cultivated in different olive growing areas of Spain. Virgin olive oil from Lleida was less heavily pigmented, and these oils showed more negative values for the ordinate a^* (of the CIELAB colorimetric system). Pheophytin a was the major chlorophyll pigment, and lutein was the major component of the carotenoid fraction in all oils analyzed. The chlorophyll a concentration in virgin olive oils from Lleida was 700 μg kg⁻¹, but was 175 μg kg⁻¹ in oils from Jaén, and 200 μg kg⁻¹ in oils from Tarragona. Finally, the chlorophyll a/chlorophyll b ratio was 9 in oils from Lleida and around 0.6 in the other two Arbequina olive oils. In relation to the phenolic fraction, the hydroxytyrosol and tyrosol contents were significantly higher in olive oils from Jaén (grown at higher altitude and precipitation rates). The secoiridoid derivatives showed a significantly higher concentration in olive oils from Tarragona, probably due to the low altitude where they grow, and finally the ratio of (dialdehydic form of elenolic acid linked to tyrosol)/lignans had a value of 1.4 in olive oils from Lleida, whereas this value was around 0.7 in the other Arbequina olive oils.     

The Effect of Harvesting Time on Olive Fruits and Oils Quality Parameters of Tortiglione and Dritta Olive Cultivars

Despite the fact that Italy holds the most important olives heritage in the world, with about 800 cultivars, most of them are still underestimated, in particular those from Abruzzo, a region located in the center of the peninsula. The aim of this work is to study the changes in quality parameters of olive fruits and related oils of two autochthonous Abruzzo olive cultivars, Tortiglione and Dritta during ripening (from September to November 2017). Both cultivar and ripening time affect the chemical parameters of olive fruits. Results highlight an increasing trend of the oil content with final values, based on fresh matter, of 38.7 ± 0.3% and 38.1 ± 0.9% for Tortiglione and Dritta, respectively. Olive oils chemical composition is also affected by ripening time and cultivar, with Tortiglione oils resulting generally richer than Dritta oils; on the first sampling time (30th of October) values for total phenolic content, antioxidant activity, and chlorophylls are 803.8 ± 68.2 mg gallic acid equivalent kg⁻¹, 2.7 ± 0.5 mmol trolox equivalent kg⁻¹, and 30.8 ± 1.6 mg pheophytin a kg⁻¹, respectively. Tocopherols seem to be more affected by ripening time than by cultivar, in particular for Dritta. Practical Application : The results on Abruzzo minor olive cultivars indicate that olive fruits and olive oil composition are strongly influenced by both cultivar and ripening time, giving rational indications about the optimal cultivar specific harvesting time and opening interesting opportunities for olive oil producers in a perspective of sustainable production to obtain high quality fruits and oils. The research provides detailed information about Tortiglione and Dritta olive cultivar, useful in the global context of revaluation of Italian minor olive varieties.     

Formation, structure, and rheological properties of ricinelaidic acid-vegetable oil organogels

Vegetable oil-based organogels were formed using ricinelaidic acid (12-hydroxy-9-trans-octadecenoic acid, REA). Gelation kinetics, gel structure, and stability were studied. Gelation occurred with as little as 0.5% (w/w) REA, depending on temperature and oil composition. Phase diagrams were constructed using canola, sesame, and DAG oils. Lower gelation tendencies were correlated with the presence of potential hydrogen-bonding moieties in the oils. REA concentration had a significant influence on gelation kinetics and gel rheology. At 5°C, the 0.5% canola oil gel behaved like a weak, viscoelastic network composed of entangled strands. Between 1.0 and 5.0% REA, solid-like, viscoelastic gels were formed. The 24-hour G′ _LVR (storage modulus in the linear viscoelastic region) was highly dependent on concentration and less so on temperature. Values for gelation time indicated a change in behavior below 2% REA and above 20°C. Polarized light microscopy revealed that the gels were formed through the interactions of long, thin, and birefringent fibers. Structural analysis using X-ray diffractometry (XRD) indicated the presence of repeating REA dimers and increasing order with concentration and gel storage time. Increases in gel opacity, birefringence, XRD scattering, and fiber clustering were observed during storage.     

Influence of Turbidity Grade on Color and Appearance of Virgin Olive Oil

The appearance of most of the commercialized olive oils involves both their color and turbidity depending on the different technologies used for their elaboration. This research has been carried out to study the filtration impact on the colorimetric changes of virgin olive oils. Naturally turbid olive oils were blended at different proportions (100, 80, 60, 40, 20 and 0%) with their corresponding filtered replicates to obtain a scale of six levels of turbidity and simulating different turbidity grades. Tristimulus colorimetry, particularly the CIELAB uniform color, was used to follow color changes. As turbidity of the oil increased in the blend, yellowish oils, darker, and less saturated were obtained. Univariate correlations between the colorimetric parameters and turbid content were achieved with second degree polynomial equations, being chroma ( C_\textab ^* C_{{_{\text{ab}} }}^{ *} ) and hue (h _ab) the best correlated parameters. The color differences ( \Updelta E_\textab ^* \Updelta E_{{_{\text{ab}} }}^{ *} ) calculated between turbid oils (100%) and the consecutively decreasing turbid oils blends ranged from 3.18 to 18.72 CIELAB units, revealing differences in color visually perceptible to the human eye.     

Use of 13C nuclear magnetic resonance distortionless enhancement by polarization transfer pulse sequence and multivariate analysis to discriminate olive oil cultivars

Distortionless enhancement by polarization transfer (DEPT) pulse sequence was used to set up a quantitative high-resolution ¹³C nuclear magnetic resonance (NMR) method to discriminate olive oils by cultivars and geographical origin. DEPT pulse sequence enhances the intensity of NMR signals from nuclei of low magnetogyric ratio. The nuclear spin polarization is transferred from spins with large Boltzmann population differences (usually protons) to nuclear species characterized by low Boltzmann factors, e.g., ¹³C. The signal enhancement of ¹³C spectra ensures the accuracy of resonance integration, which is a major task when the resonance intensities of different spectra must be compared. The resonances of triglyceride acyl chains C _n:0, C_18:1, C_18:2, and C_18:3, were also assigned. Multivariate analysis was carried out on the 35 carbon signals obtained. By using variable reduction techniques, coupled with standard statistical methods—partial least squares and principal components analysis—it was largely possible to separate the samples according to their variety and region of origin. With one problem variety removed, 100% prediction of the three remaining varieties was achieved. Similarly, by using the three regions with greatest representation in the data, all but one of a test set of 34 samples were correctly predicted. Thus, the composition of olive oils from different cultivars and of different geographical origin were compared and successfully studied by multivariate analysis. These considerations in conjunction with the structural elucidations of triglyceride molecules demonstrated that ¹³C NMR is among the most powerful techniques yet described for analysis of olive oils.