Implementing Dynamic Headspace With SPME Sampling of Virgin Olive Oil Volatiles: Optimization, Quality Analytical Study, and Performance Testing.

Competition and interaction phenomena among volatiles during their adsorption process by solid phase microextraction (SPME) fibers in static headspace sampling procedure (SHS) cast doubt on its ability to quantify virgin olive oil volatiles. SPME fibers being excellent traps, their use was analyzed with a new device allowing the concentration of volatiles in a dynamic headspace sampling procedure (DHS). A central composite experimental design optimized the main variables of the device (4 g sample weight, 40 °C temperature, 150 mL/min flow rate, 50 min adsorption time), while values of the analytical quality control parameters of the method (repeatability, limits of detection and quantification, working range, sensitivity, and resolution) were compared with those ones from static headspace. DHS shows better precision results for aldehydes and alcohols than SHS and allowed analyzing higher concentrations with no problem of saturation. In 19 of 28 compounds analyzed in 50 samples the chromatographic areas were higher when running DHS. The concentration values of volatile compounds in these samples after applying SHS and DHS are discussed together with the ability of the new method for distinguishing virgin olive oil by their categories (extra virgin, virgin, and lampante) by the volatiles quantified in commercial oils.

PhotooxidationEffect in Liquid Lipid Matrices: Answers from an Innovative FTIR Spectroscopy Strategy with "Mesh Cell" Incubation.

Developing new approaches to evaluate the stability of edible oils under moderate conditions is highly demanded today to avoid accelerated experiments that are not well correlated with actual shelf life. In particular, low intensity of visible light (photooxidation) needs to be integrated in stability studies, together with mild temperature. Thus, in this work, a strategy based on a "mesh cell"-FTIR to monitor chemical changes in lipid matrices using a combination of light and mild heating was applied. The results were compared with those obtained for the stability of triolein used as a molecular model. The study showed that the moderate light intensity (400 lx) at a low temperature (23 °C) has an early effect on the degradation of lipid matrices that is not observed when they are stored at 35 °C in the absence of light. Thus, the results proved that the exposure to light (400 lx) was more relevant than mild heating (35 °C) in monounsaturated lipid matrices, while polyunsaturated lipid matrices were more sensitive to mild heating.

Virgin olive oil stability study by mesh cell-FTIR spectroscopy.

Mesh cell is a rapid tool designed to monitor chemical changes that occurs as a consequence of oxidation at moderate conditions. In this study this accessory has been proposed for assessing virgin olive oil (VOO) stability by Fourier transform infrared (FTIR) spectroscopy. Monocultivar VOOs have been stored in mesh cells under different temperatures (at 23, 35, 65°C) simulating the real conditions during storage and transport (<60°C). In addition to temperature, the samples have been also stored in mesh cells at different light intensities (400, 1000, 7000lx) to evaluate the resistance of the samples to photooxidation. The oil stability of the samples determined by using this accessory has been compared with the oil stability determined with the common methods used for this purpose (e.g. Rancimat). Despite the moderate conditions applied, mesh cell-FTIR spectra have revealed the formation of hydroperoxides and the subsequent formation of alcohols and aldehydes. Unlike other methods that require high temperature to accelerate the oxidation rate, mesh cell-FTIR has allowed differentiate the oil stability of the samples from a multi-factor perspective that includes several properties (temperature and light) and chemical species (primary and secondary oxidation products). The information obtained with this method can be relevant for optimizing handling (e.g. packaging and storage temperature) of VOO samples during their shelf life.

Soft-deodorization of virgin olive oil: Study of the changes of quality and chemical composition.

The potential adulteration of extra virgin olive oil (EVOO) with soft-deodorized virgin olive oil (VOO) has raised the interest of researchers in investigating this fraud in recent years. The objective of this study was to determine chemical changes occurring after a soft-deodorization process in terms of volatiles, fatty acid ethyl esters (FAEEs) and pyropheophytins (PPPs) concentrations in VOOs. After testing several conditions (80, 100 and 130°C, for 30 and 60min), the parameters of 100°C and 60min were considered as the optima. These conditions allowed removing volatiles responsible for sensory defects with low losses of total phenols (14%-32%), and values of PPPs (11.83%) and FAEEs (34.53mg/kg) lower than the limits of standard regulations. The experiments show that soft-deodorized VOOs could be added up to 50% to EVOOs and current standard methods would not detect this kind of adulteration.

Characterization of Virgin Olive Oils with Two Kinds of 'Frostbitten Olives' Sensory Defect.

The frost of olives on the tree due to drops of temperature can produce sensory defects in virgin olive oil (VOO). Temperature changes can be abrupt with freeze-thaw cycles or gradual, and they produce sensory and chemical variations in the oil. This study has analyzed the quality parameters (free fatty acids, peroxide value, UV absorption, and fatty acid ethyl esters) and phenols of VOOs described with the 'frostbitten olives' sensory defect. The phenol profiles allowed grouping these VOOs into two types. One of them, characterized with "soapy" and "strawberry-like" aroma descriptors, had higher values of 1-acetoxypinoresinol, pinoresinol, and aldehydic form of the ligstroside aglycon. The other one, characterized with "wood" and "humidity" descriptors, had higher concentrations of luteolin and apigenin. Most VOOs (75%) from the first group, associated with abrupt drops of temperature, have concentration of phenols higher than the value established by the health claim on olive oil polyphenols approved by the European Commission.

Influence of agroclimatic parameters on phenolic and volatile compounds of Chilean virgin olive oils and characterization based on geographical origin, cultivar and ripening stage.

BACKGROUND: This study involved two commercial orchards located in Limarí Valley and Molina from two important Chilean production zones of extra virgin olive oil (EVOO). The investigation evaluated the effects of climate, soil composition, agricultural practices (fertilization and irrigation) and variety (considering two harvests) on the compounds responsible for the flavor of EVOO (volatiles and phenols) and how these compounds can explain the differences in chemical profiles by geographical origin, cultivar and fruit ripeness stage. RESULTS: Varieties from the Limarí Valley presented the highest content of phenolic compounds. A significant relationship (P < 0.05) between volatile compounds and climate indicated that the compounds produced via the lipoxygenase cascade were affected by the maximum temperature and, to a lesser extent, by evapo-transpiration and irrigation. The selection of different individual phenolic and volatile compounds independently allowed the significant differentiation of EVOOs, principally by geographical origin, crop season, fruit ripeness stage and, in a few cases, by cultivar. CONCLUSION: Soil and climate of the Chilean regions have much more influence than cultivars on the concentration of sensory quality compounds. Difference in latitude between orchards increases the importance of the geographical origin on the virgin olive oil chemical composition while full irrigation decreases the impact of the cultivar.

In-depth assessment of analytical methods for olive oil purity, safety, and quality characterization.

This paper evaluates the performance of the current analytical methods (standard and widely used otherwise) that are used in olive oil for determining fatty acids, triacylglycerols, mono- and diacylglycerols, waxes, sterols, alkyl esters, erythrodiol and uvaol, tocopherols, pigments, volatiles, and phenols. Other indices that are commonly used, such as free acidity and peroxide value, are also discussed in relation to their actual utility in assessing quality and safety and their possible alternatives. The methods have been grouped on the basis of their applications: (i) purity and authenticity; (ii) sensory quality control; and (iii) unifying methods for different applications. The speed of the analysis, advantages and disadvantages, and multiple quality parameters are assessed. Sample pretreatment, physicochemical and data analysis, and evaluation of the results have been taken into consideration. Solutions based on new chromatographic methods or spectroscopic analysis and their analytical characteristics are also presented.

Geographical traceability of virgin olive oils from south-western Spain by their multi-elemental composition.

The geographical traceability of virgin olive oil can be controlled by chemical species that are linked to the production area. Trace elements are among these species. The hypothesis is that the transfer of elements from the soil to the oil is subjected to minor variations and therefore this chemical information can be used for geographical traceability. In order to confirm this hypothesis, the trace elements of virgin olive oils from south-western Spain were analysed, and the same elements were determined in the corresponding olive-pomaces and soils. The differences in the concentration were studied according to cultivars and locations. Results show some coincidences in the selection of elements in soils (W, Fe, Na), olive-pomace (W, Fe, Na, Mg, Mn, Ca, Ba, Li) and olive oils (W, Fe, Mg, Mn, Ca, Ba, Li, Bi), which supports their utility in traceability. In the case of olive oils, 93% of the samples were correctly classified in their geographical origins (96% for Beas, 77% for Gibraleón, 91% for Niebla, and 100% for Sanlúcar de Guadiana).

Does "best before" date embody extra-virgin olive oil freshness?

Virgin olive oil (VOO) decays in quality properties during aging, so aged VOOs may have detectable undesirable sensory descriptors in comparison with oils recently extracted. For that reason, freshness has become a parameter of paramount importance to maintain the highest standard levels within the period indicated in the "best before" date. However, it is important to note that freshness of VOOs is not necessarily related to its sensory quality. Pigments have been suggested for tracing aging of VOO, and pyropheophytin a (PPP) seems to be the most promising molecule for this task. A predictive model has been used to estimate %PPP in VOO stored at different worldwide locations characterized with different temperatures. The recorded average temperatures, on a monthly basis, were inputs of the predictive model. The results show the influence of temperature in %PPP and how this molecule could serve as a better monitor of the storage period of VOOs. The initial value of %PPP in the oil could help to carry out the storage traceability. This information would be of interest for producers, sellers, and inspection agencies.

Sensor responses to fat food aroma: a comprehensive study of dry-cured ham typicality.

The physicochemical phenomena that explain the sensing mechanisms of gas sensors have been extensively investigated. Nevertheless, it is arduous to interpret the sensor signals in a practical approach when they response to complex mixtures of compounds responsible for food aroma. Thus, the concomitant interactions between the volatiles and the sensor give up a single response affected by synergic and masking effects between compounds. An experimental procedure is proposed to determine the individual contribution of volatile compounds in the sensor response, illustrated with the examples of aroma of dry-cured hams and metal oxide sensors. The results from mathematical correlations and the analyses of pure standards are previously analyzed to describe the behavior of sensors when interacting with individual compounds. A sensor based olfactory detector (SBOD) entailing the use of a capillary column connected to a sensor array as non-destructive detector in parallel with the flame detector served to provide definitive information about the individual contribution of volatile compounds to sensor responses. The sensor responses in this system, which is referred to as sensorgram, were interpreted by taking into account the volatile composition of the samples determined by GC.

Volatile and amino acid profiling of dry cured hams from different swine breeds and processing methods.

The flavor of dry cured ham explains the high appreciation of this product and it determines consumer acceptance. Volatile compounds provide valuable information about the odor and sensory quality of dry cured hams. Since amino acids are the origin of some volatile compounds of dry cured ham, the volatile and amino acid compositions of forty-one dry cured hams from Spain and France were determined to establish associations between them. The samples included different pig breeds (non Iberian vs. Iberian), which were additionally affected by different maturation times and feeding types (acorn vs. fodder). Results showed that 20 volatile compounds were able to distinguish Iberian and non Iberian hams, and 16 of those had relevant sensory impact according to their odor activity values. 3-Methylbutanol, 2-heptanol and hexanal were among the most concentrated volatile compounds. In the case of non-volatile compounds, the concentrations of amino acids were generally higher in Iberian hams, and all the amino acids were able to distinguish Iberian from non Iberian hams with the exception of tryptophan and asparagine. A strong correlation of some amino acids with volatile compounds was found in the particular case of alcohols and aldehydes when only Iberian hams were considered. The high correlation values found in some cases proved that proteolysis plays an important role in aroma generation.

Mapping brain activity induced by olfaction of virgin olive oil aroma.

The difficulty of explaining sensory descriptors of virgin olive oil aroma by the analysis of volatile compounds is partially due to the subjective opinions of panelists and the lack of information of the neural mechanisms that ultimately produce a sensory perception. In this study the technique of functional magnetic resonance imaging (fMRI) has been applied to study brain activity during the smelling of virgin olive oil of different qualities. The volatile compounds of the samples were analyzed by solid-phase microextraction gas chromatography to explain the differences in the aromas presented to the subjects during the fMRI experiments. Comparing the pleasant and unpleasant aromas, the most evident differences in brain activity were found at the anterior cingulate gyrus (Brodmann area 32) and at the temporal lobe (Brodmann area 38). The activations were also observed when subjects smelled dilutions of heptanal and hexanoic acid, both compounds being responsible for off-flavors. Other areas were inherent to the olfaction task (e.g., Brodmann area 10) and to the intensity of the aroma (Brodmann area 6).

Research in olive oil: challenges for the near future.

Olive oil, a traditional food product with thousands of years of history, is continually evolving toward a more competitive global market. Being one of the most studied foods across different disciplines, olive oil still needs intensive research activity to face some vulnerabilities and challenges. This perspective describes some of them and shows a vision of research on olive oil for the near future, bringing together those aspects that are more relevant for better understanding and protection of this edible oil. To accomplish the most urgent challenges, some possible strategies are outlined, taking advantage of the latest analytical advances, considering six areas: (i) olive growing; (ii) processing, byproduct, and environmental issues; (iii) virgin olive oil sensory quality; (iv) purity, authentication, and traceability; (v) health and nutrition; (vi) consumers. The coming research, besides achieving those challenges, would increase the understanding of some aspects that are still the subject of debate and controversy among scientists focused on olive oil.

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.

Quality characterization of the new virgin olive oil var. Sikitita by phenols and volatile compounds.

New cultivars with greater adaptability to modern irrigated (super-) high-density orchards and producing good sensory quality oils are highly demanded by an olive oil industry in continuous change. This work analyzes olive oil sensory quality, in terms of phenols and volatiles that are responsible for virgin olive oil flavor, for three cultivars: Picual, which is used for >15% of world olive oil production; Arbequina, which is cultivated worldwide; and the new progeny Sikitita, which is derived from the other two. The availability of data at three different levels of ripeness allowed quantifying the genetic and olive maturity effects on the oil composition by means of the analysis of variance (ANOVA) and principal component analysis (PCA). Phenols and volatiles varied greatly both with genotype and, to a lesser extent, with olive maturity. With regard to the phenol profile, the crossbred cultivar Sikitita showed a higher degree of similarity with the Arbequina variety. The volatile composition of var. Sikitita, however, varies significantly from that of Arbequina, in the first stages of the olive ripeness, and becomes more similar to that of Picual as the level of ripeness increases.

Evaluation of virgin olive oil thermal deterioration by fluorescence spectroscopy.

The evolution of the fluorescent compounds during the thermal deterioration of virgin olive oil is not yet well-known. Samples of heated virgin olive oils collected from a fryer every 2 h up to 94 h were analyzed to study their fluorescence spectra as well as the evolution of the concentrations of alpha-tocopherol and individual phenols by high-performance liquid chromatography (HPLC). The regions of the fluorescence spectra of the heated oils, diluted in hexane at 1%, were explained by the content of these compounds with regression coefficients higher than 0.90 (R2 adjusted). The fluorescence intensity recorded at 350 nm and the wavelength of the spectrum maximum in the range of 390-630 nm also allowed for the explanation of the increase of the percentage of polar compounds during the experiment. On the other hand, the spectra of the undiluted heated oils indicated that the maximum of the spectrum of any undiluted oil at 490 nm or beyond is related to a percentage of the polar compounds higher than 25%, which is the maximum percentage accepted for edible oils used in frying processes.

1H NMR-based protocol for the detection of adulterations of refined olive oil with refined hazelnut oil.

A (1)H NMR analytical protocol for the detection of refined hazelnut oils in admixtures with refined olive oils is reported according to ISO format. The main purpose of this research activity is to suggest a novel analytical methodology easily usable by operators with a basic knowledge of NMR spectroscopy. The protocol, developed on 92 oil samples of different origins within the European MEDEO project, is based on (1)H NMR measurements combined with a suitable statistical analysis. It was developed using a 600 MHz instrument and was tested by two independent laboratories on 600 MHz spectrometers, allowing detection down to 10% adulteration of olive oils with refined hazelnut oils. Finally, the potential and limitations of the protocol applied on spectrometers operating at different magnetic fields, that is, at the proton frequencies of 500 and 400 MHz, were investigated.

Thermal deterioration of virgin olive oil monitored by ATR-FTIR analysis of trans content.

The monitoring of frying oils by an effective and rapid method is one of the demands of food companies and small food retailers. In this work, a method based on ATR-FTIR has been developed for monitoring the oil degradation in frying procedures. The IR bands changing during frying in sunflower, soybean, and virgin olive oils have been examined in their linear relationship with the content of total polar compounds, which is a preferred parameter for frying control. The bands assigned to conjugated and isolated trans double bonds that are commonly used for the determination of trans content provided the best relationships. Then, the area covering 978-960 cm(-1) was chosen to build a model for predicting polar material content for the particular case of virgin olive oil. A virgin olive oil was heated up to 94 h, and samples collected every 2 h constituted the training set. These samples were analyzed to obtain their FTIR spectra and to determine the composition of fatty acids and the content of total polar compounds. The excellent results predicting the polar material content (adjusted R(2) 0.997) was successfully validated with an external set of samples. The analysis of the fatty acid composition confirmed the relationship between the trans content and the content of total polar compounds.

Validation of a method based on triglycerides for the detection of low percentages of hazelnut oil in olive oil by column liquid chromatography.

The difference between theoretical and empirical triglyceride content is a powerful tool to detect the presence of any vegetable oil in olive oil. The current drawback of the method is the separation between equivalent carbon number ECN42 compounds, which affects the reliability of the method and, hence, its cutoff limit. The determination of the triglyceride profile by liquid chromatography using propionitrile as the mobile phase has recently been proposed to improve their quantification, together with a mathematical algorithm whose binary response determines the presence or absence of hazelnut oil. Twenty-one laboratories from 9 countries participated in an interlaboratory study to evaluate the performance characteristics of the whole analytical method. Participants analyzed 12 samples in duplicate, split into 3 intercomparison studies. Statistically significant differences due to the experimental conditions were found in some laboratories, which were detected as outliers by use of Cochran's and Grubbs' tests. The relative standard deviations (RSD) for repeatability and reproducibility were determined following the AOAC Guidelines for Collaborative Studies. The analytical properties of the method were determined by means of the sensitivity (0.86), selectivity (0.94), and reliability (72%) for a cutoff limit of 8% (probability 94%).

Volatile compound biosynthesis by green leaves from an Arabidopsis thaliana hydroperoxide lyase knockout mutant.

The degradation of polyunsaturated fatty acids through the lipoxygenase pathway is responsible for the production of volatile compounds that confer green sensory notes to the aroma of fruits and vegetables. The peroxidation of free linoleic or linolenic acid by action of lipoxygenase and then the lysis of the resulting hydroperoxides, through a reaction catalyzed by the hydroperoxide lyase, are the most determinant steps of this pathway. This work analyzes the impact of the hydroperoxide lyase depletion on the volatile composition of leaves from Arabidopsis thaliana that is used as model system. The work involves the characterization of the volatile profiles of the Arabidopsis plants followed by a study of the metabolism of radio-labeled linoleic acid and determinations of lipoxygenase activity. Hydroperoxide lyase-knockout plants show similar levels of C6 compounds, but the total amount of C5 compounds is 4-fold higher in mutant plants. The perspectives of production of vegetable products with a modified aroma by genetically engineering the lipoxygenase pathway were discussed with respect to the statistical results.