Performance of two color scales for virgin olive oils: Influence of ripeness,variety, and harvest season

The purpose of this investigation was to compare the performance of the bromthymol blue (BTB) method and the Uniform Oil Color Scale (UOCS) method with different sets of virgin olive oil samples from Andalusia (Spain), namely, 1213 samples from olives at three stages of ripeness, 1008 samples from eight olive varieties, and 1700 samples from olives harvested in four different crop seasons. All oils were extracted in the laboratory by the same procedure. The performance of the two color scales was compared using CIELAB color differences between the oil samples and the nearest standard from each scale. The UOCS performed at least 2.0 times better than the BTB for each of the three stages of olive ripeness, and the difference between the two color scales was statistically significant (P<0.001). The UOCS performed at least 1.3 times better than the BTB for each of the eight olive varieties studied, and the differences between the two color scales were statistically significant (P<0.02). The UOCS also performed at least 1.6 times better than the BTB for each of the four harvests analyzed, and the differences between the two color scales were statistically significant (P<0.001). Using the current oil samples, we could discern no substantial improvements to the UOCS standards.     

Reproducibility of the bromthymol blue standards used for color specification of virgin olive oil

Three replicates were prepared for each of 60 BTB (bromthymol blue) standards, which are usually employed to determine the color of virgin olive and seed oils, and their colors were measured by spectrophotometric and spectroradiometric techniques on a monthly basis over a year. Although in principle both techniques are valid, their results are weakly correlated. The major color change of the BTB standards occurred soon after sample preparation; after 5 mon, the color stabilized at approximately 3.0 Commission Internationale de l’éclairage 1976-(L^*a^*b^*) (CIELAB) units, with respect to the initial values. Therefore, after preparation, a certain waiting period would be advisable before using the BTB standards. The color of the BTB standards changes over time in the sense of becoming lighter, more saturated, and less greenish. In the monthly periods after the fifth month, the average color change of the BTB standards was negligible, being slightly lower than the average variability of the three replicates (which is around 1.5 CIELAB units).     

Reliability of the bromthymol blue method for color in virgin olive oils

The bromthymol blue (BTB) method is currently used for the assessment of color in olive and seed oils by visual comparison with standard solutions. Two BTB scales were prepared with 2 yr difference and compared, and the recent one was used to analyze 502 virgin olive oil samples, obtained by the Abencor® technique reproducing the industrial procedure. The temporal chromatic degradation of the BTB samples after 2 yr [3.93 Commission Internationale de l’Eclairage (CIE) 1976-(L*a*b*) (CIELAB) units, on the average], as well as the small percentage of virgin olive oils matching the colors of the samples provided by the BTB scales (13.1% with a suprathreshold color tolerance of 1.52 CIELAB units), indicates the limitations of the BTB method. Linear regression models are proposed in order to compute with acceptable accuracy the BTB indices from chromaticparameters. The use of CIELAB for the specification and future studies on color in virgin olive oils is recommended.     

Precision and accuracy in the color specification of virgin olive oils from the bromthymol blue method

Twenty experienced observers with nondefective color vision judged 27 virgin olive oil samples within an acceptable color range, using the bromthymol blue (BTB) method, under controlled observation conditions (daylight source with a correlated color temperature of 6500 K, and standard gray back-ground). On the average, 44.8% of the observers agreed in their selections of the BTB standard solution matching a given oil sample, and this percentage increased to 88.2% considering ±one step in the two dimensions (pH and concentration) of the BTB scale. On the average, the lowest color difference between oil samples and available BTB solutions was 6.6 Commission Internationale de l'éclairage 1976-(L^*a^*b^*) (CIELAB) units, but this color difference was approximately two times greater for the color difference between oil samples and BTB solutions selected by our observers. The colors of the BTB standard solutions in the CIELAB space are not uniformly distributed, and thus one step in pH or concentration is equivalent to CIELAB color differences varying in a wide range (1.7–13.5 and 1.7–26.3 CIELAB units, respectively). From these values, indicating low precision, accuracy, and uniformity, some suggestions are made for future improvements of the current BTB method.     

A rapid estimation of pigment content in virgin olive oils by a solvent-free method

In this work, a fast method was proposed for estimating the virgin olive oils (VOOs) carotenoids and chlorophylls concentration using color measurement. The pigment content by conventional spectrophotometry method and CIELAB color (L*, a*, and b*) at different degree of sample thickness (from 5 to 50 mm) of one hundred VOOs were measured. Oil carotenoids and chlorophylls content were correlated with the color parameters for the different oil thickness studied to design the prediction models of the new method. The best regression coefficients (R²) were obtained for multiple linear regression model using the three independent variables (L*, a*, and b*) together measured at 5 mm of oil thickness. The R² were 0.9679, 0.9515, and 0.9644 for predicting carotenoids, chlorophylls, and total pigments, respectively. External validation of these prediction models was satisfactory (relative error < 0.1). Therefore, this new solvent-free colorimetric method is a useful method for determination of carotenoids and chlorophylls content in VOOs. Practical applications: The simple colorimetric method developed in this study offers a fast and accurate alternative to current methods published in the literature to estimate the pigment content in VOOs. It is a rapid (less than 1 min) and cheap method, with the advantage of ease of operation, no sample pretreatment and solvent-free, thus environmentally friendly. This methodology can potentially be used by trained “nonprofessional analytical skilled” people in small laboratories or olive oil mills with limited technical facilities. Therefore, the technique is highly plausible as an alternative to determine the pigment content in VOOs. Finally, future works with this methodology could be carried out to online control of VOOs pigments content in the oil extraction process.     

Chromatic evolution of virgin olive oils submitted to an accelerated oxidation test

Six samples of virgin olive oil obtained from several varieties of olive fruits (Picual, Manzanilla, Lechín, and Arbequina) were submitted to an accelerated oxidation process during a 63-h period under the conditions of the oil stability index (OSI), as measured by a Rancimat (100°C) apparatus. Spectra were measured every 3 h, and chlorophyll and carotenoid indexes and CIFLAB color ordinates were calculated. As oxidation time increased, remarkable changes in the spectral characteristics and color ordinates were observed. Oxidation provoked less vivid colors (lower values for chroma, C _* ^ab ) in all the samples; however, only some varieties became darker (lower values for lightness, L^*). The pigment loss calculated for oxidized oils was 67% for the carotenoid index and 58% for the chlorophyll index. Mathematical models are offered to predict color changes with time of storage at 20°C.     

The role of water in the oxidation process of extra virgin olive oils

Different emulsifying techniques were used to study the influence of water on the oxidative degradation of extra virgin olive oil. The emulsions of water/extra virgin olive oil, oxidized with O₂, UV radiation, and Air, were prepared by dispersing water under different conditions. Oil oxidation, monitored by measuring the PV and polyphenolic content, was greater for emulsions obtained with low dispersing power. A linear model was used to correlate the PV and the polyphenolic content with dispersing energy. An important result was that the dispersed water exerted a positive antioxidant effect on the oil.     

Simplified measurement of virgin olive oil color by application of the characteristic vector method

There are several simplified methods to measure the color of virgin olive oils. However, their reliability is questionable, as they provide errors that sometimes can be considerable. A new method to calculate color coordinates and objective chromatic parameters in the color region of these olive oils is proposed with the aim of overcoming these objections. The method is a simplification of the original method proposed by the Commission Internationale de l'Eclairage (CIE), based on the measurement of the complete visible spectrum, from 380 to 770 nm. The characteristic vector analysis provides new equations to calculate tristimulus values as functions of these transmittance values based on a reconstruction of oil transmission spectra measuring from three to six wavelengths. The results show that color differences exist between the color coordinates of the experimental samples and those obtained by means of the proposed method. For more than 90% of the samples, the difference was smaller than three CIELAB units when equations based on four or more wavelengths were used.     

Comparison of the metrics between the CIELAB and the DIN99 uniform color spaces using dental resin composite material values

The sizes for the perceptible or acceptable color difference measured with instruments vary by factors such as instrument, material, and color‐difference formula. To compensate for disagreement of the CIELAB color difference (ΔE^*_ab) with the human observer, the CIEDE2000 formula was developed. However, since this formula has no uniform color space (UCS), DIN99 UCS may be an alternative UCS at present. The purpose of this study was to determine the correlation between the CIELAB UCS and DIN99 UCS using dental resin composites. Changes and correlations in color coordinates (CIE L*,a*, and b* versus L₉₉, a₉₉, and b₉₉ from DIN99) and color differences (ΔE^*_ab and ΔE₉₉) of dental resin composites after polymerization and thermocycling were determined. After transformation into DIN99 formula, the a value (red–green parameter) shifted to higher values, and the span of distribution was maintained after transformation. However, the span of distribution of b values (yellow–blue parameter) was reduced. Although color differences with the two formulas were correlated after polymerization and thermocycling (r = 0.77 and 0.68, respectively), the color coordinates and color differences with DIN99 were significantly different from those with CIELAB. New UCS (DIN99) was different from the present CIELAB UCS with respect to color coordinates (a and b) and color difference. Adaptation of a more observer‐response relevant uniform color space should be considered after visual confirmation with dental esthetic materials. © 2006 Wiley Periodicals, Inc. Col Res Appl, 31, 168–173, 2006     

Susceptibility of water-emulsified extra virgin olive oils to oxidation

The effect of emulsion structure on the susceptibility to oxidation of emulsified olive oils was tested. Olive oil samples were emulsified by adding a certain quantity of water in different ways. The resulting water-in-oil emulsions were then oxidized with UV light. The results revealed that the emulsion structure played a significant role in the oxidation process of emulsified olive oils. A kinetic mechanism is discussed based on the PV determined experimentally. The susceptibility of water-emulsified extra virgin olive oils to oxidation was quantified by means of a dimensionless parameter that displayed a characteristic dependence on the specific surface area of the water dispersed phase.     

Natural antioxidants and volatile compounds of virgin olive oils obtained by two or three‐phases centrifugal decanters

Research has been carried out to ascertain the influence of different centrifugal decanters employed in olive process on oil yields and qualitative characteristics and composition of volatile compounds of virgin olive oil. Tests were performed in an olive oil mill equipped with centrifugal decanters at two or three‐phases. Results show that oil yields were similar and oils extracted from good‐quality olives do not differ in free fatty acids, peroxide value, UV absorptions and organoleptic assessment. Total phenols and o‐diphenols content as well as induction time values are higher in oils obtained by the centrifugal decanter at two‐phases, because it requires less quantity of water added to olive paste in comparison to the three‐phases centrifugal decanter. The amount of water added determines the dilution of the aqueous phase and lowers the concentration of the phenolic substances more soluble in vegetable waste water. Due to the partition equilibrium law the concentration of the same substances consequently diminishes in the oil. In this research, the coefficient of the partition equilibrium of total phenols between oil and vegetable water has been calculated and discussed. No significant difference occurred, due to the different decanters employed, in the average values of the volatile components of the head‐space of oils.     

Analytical evaluation of six monovarietal virgin olive oils from Northern Tunisia

The characterization of virgin olive oils from six Tunisian cultivars, namely Chétoui, Ain Jarboua, Jarboui, Regregui, Rekhami and Neb Jmel, grown in Nebeur (a region of the Kef) was carried out. These cultivars dominate their natural habitats, but with the exception of the Chétoui cultivar they are only scattered throughout the nation. Several analytical parameters were evaluated; these include quality index, fatty acid composition, chlorophylls, carotenoids, sterols, α‐tocopherol and phenolic compounds. Their relationship with oxidative stability was also tested. The main phenols found were tyrosol, hydroxytyrosol, the dialdehydic form of elenolic acid linked to tyrosol and hydroxytyrosol, oleuropein aglycon and pinoresinol. These phenolic compounds, the colorimetric total phenol content and o‐diphenols showed significant correlations with oxidative stability. Furthermore, most of the analytical parameters of the oils that were determined in this study were greatly influenced by genetic factors (cultivar).     

Stability to oxidation of virgin olive oils as related to olive conditions: Study of polar compounds by chemometric methods

Polar compounds of virgin olive oils were analyzed. They influence oil flavor and aroma and improve the shelf-life of the oil. The orthodiphenolic fraction is particularly significant for oil stability because of its antioxidative activity. A relationship between the composition of the whole fraction of polar compounds and the state of health of the olives was established. For this purpose, oil samples were obtained from olives that had reached different degrees of ripeness and that had been affected by Dacus oleae infestation differently. The polar compounds were then analyzed by high-performance liquid chromatography. The data set was studied by means of chemometric methods. Partial least squares regression was used to obtain models that show a significant correlation between composition of the oil’s polar compounds and conditions of the olives sampled. In particular, compounds with antioxidative activity were directly linked with the state of health of the olives. The models obtained allow tracing of the state of health of the olives sampled through analysis of the polar fraction of virgin olive oil with a high degree of accuracy, and thus prediction of the oil’s expected shelf life.     

A high-field1H nuclear magnetic resonance study of the minor components in virgin olive oils

High-field (600 MHz) nuclear magnetic resonance (NMR) spectroscopy was applied to the direct analysis of virgin olive oil. Minor components were studied to assess oil quality and genuineness. Unsaturated and saturated aldehyde resonances, as well as those related to other volatile compounds, were identified in the low-field region of the spectrum by two-dimensional techniques. Unsaturated aldehydes can be related to the sensory quality of oils. Other unidentified peaks are due to volatile components, because they disappear after nitrogen fluxing. The statistical analysis performed on the intensity of these peaks in several oil samples, obtained from different olive varieties, allows clustering and identification of oils arising from the same olive variety. Diacylglycerols, linolenic acid, other volatile components, water, acetic acid, phenols, and sterols can be detected simulteneously, suggesting a useful application of high-field NMR in the authentication and quality assessment of virgin olive oil.     

Effect of location on virgin olive oils of the two main Tunisian olive cultivars

The olive oil content in phenolic compounds depends on the variety of the fruit used for its extraction as well as on the predominant climate conditions in the tree cultivation area. Here, we report on the characterization of virgin olive oil samples obtained from fruits of the main Tunisian olive cultivars Chemlali and Chétoui, grown in three different Tunisian locations, Zaghouan (North), Sousse (Center) and Sfax (South). Chétoui olive oil samples obtained from fruits of olive trees cultivated in Zaghouan and Chemlali olive oil samples obtained from fruits of olive trees cultivated in Sousse were found to have a higher mean total phenol content (1004 and 330 mg/kg, respectively). Olive oil samples obtained from fruits of both cultivars had different phenolic profiles and a higher content in 3,4‐DHPEA‐EDA when the olive trees were cultivated in Zaghouan. Both olive cultivars were found to have different responses to environmental conditions. Chétoui olive oil showed decreased oxidative stability when the fruits were obtained from olive trees cultivated in the center of Tunisia (34.8 h) and in Sfax (16.17 h). Furthermore, statistical data showed that the phenolic composition and oxidative stability of Chétoui olive oil varied more by location than those of Chemlali olive oils.     

Use of high-resolution 13C nuclear magnetic resonance spectroscopy for the screening of virgin olive oils

¹³C Nuclear magnetic resonance (NMR) spectra of 104 oil samples were obtained and analyzed in order to study the use of this technique for routine screening of virgin olive oils. The oils studied included the following: virgin olive oils from different cultivars and regions of Europe and north Africa, and refined olive, “lampante” olive, refined olive pomace, high-oleic sunflower, hazelnut, sunflower, corn, soybean, rapeseed, grapeseed, and peanut oils, as well as mixtures of virgin olive oils from different geographical origins and mixtures of 5–50% hazelnut oil in virgin olive oil. The analysis of the spectra allowed us to distinguish among virgin olive oils, oils with a high content of oleic acid, and oils with a high content of linoleic acid, by using stepwise discriminant analysis. This parametric method gave 97.1% correct validated classifications for the oils. In addition, it classified correctly all the hazelnut oil samples and the mixtures of hazelnut oil in virgin olive oil assayed. All of these results suggested that ¹³C NMR may be used satisfactorily for discriminating some specific groups of oils, but to obtain 100% correct classifications for the different oils and mixtures, more information than that obtained from the direct spectra of the oils is needed.     

Contribution of chemical components of cornicabra virgin olive oils to oxidative stability. A study of three successive crop seasons

Oxidation is the primary cause of virgin olive oil quality deterioration. This paper presents a correlation between oxidative stability, as determined by the Rancimat method, and some chemical components involved in the oxidation process of a set of 74 Cornicabra virgin olive oils obtained from three successive crop seasons (94/95 to 96/97). Results showed a clear influence of total polyphenols on virgin olive oil stability, with linear regression coefficients which were similar for the three seasons studied, and a much lower contribution of α-tocopherol and unsaturated fatty acids, mainly linoleic acid. A significant effect dependent on the crop season was also observed.     

Effect of degree of ripening on the quality of virgin olive oils produced in Longnan,China

The main purpose of this work was to study the effect of different ripening degree (0–7) on quality of two monovarietal olive oils (Arbequina and Arbosana) produced in Longnan region, located in the northwest of China, Gansu province. The qualitative characteristics of oils are evaluated by analysis of the principal quality parameters and chemical composition, such as: free acidity, peroxide value, K_232, K_270, oxidative stability, fatty acid composition, total phenols, flavonoids content and flavor profile. The maximum oil yields were obtained for both varieties at a ripening degree of 7 (13.26% and 23.59%). The Arbequina and Arbosana oils contained oleic acid (ranged 53.16%–58.92% and 66.30%–74.30%, respectively) and linoleic acid (ranged 15.51%–18.77% and 7.25%–9.45%), respectively. The ratio of MUFA/PUFA ranged from 2.93 to 3.77 and 6.73 to 9.84, respectively. The ratio of 18:1/18:2 presented ranges of 2.84–3.79 and 7.02–9.94, respectively. A significant relationship was observed between the total polyphenols (83.48–140.53 and 118.32–230.00 mg GAE⋅kg⁻¹), flavonoids (0.43–9.00 and 10.20–5.51 mg RE⋅kg⁻¹) and the oxidative stability. E–Nose could effectively identify and distinguish between different varieties and ripening degree of olive oil, especially that change in the W1W (sulfur-organic) sensor. A principal component analysis showed that the particular effect of ripening degree in the cultivars olive oils.