Quantitation of Metals During the Extraction of Virgin Olive Oil from Olives Using ICP-MS after Microwave-assisted Acid Digestion

Trace metals such as Cu and Fe have negative effects on the oxidative stability of olive oils, and consequently, their concentrations are used as quality criterion. Also, maximum levels are established for heavy metals (As and Pb) in olive oils due to their high toxicity. Olive fruits can be contaminated with these metals from soil and air and from the use of pesticides or fertilizers, with the potential contamination of virgin olive oil (VOO) during its extraction from the fruits. This work presents two goals: (a) to optimize an analytical method for the determination of metals in raw olive fruits using an Abencor system; (b) to carry out a preliminary study of the fate of the metals during VOO extraction. The selected metals were quantified in raw olive fruits, and in the olive pomace and VOO obtained after their processing. The metal determination was performed by inductively coupled plasma-mass spectrometry after microwave-assisted acid digestion with HNO₃/H₂O₂. The results showed that most of the metals (at least 90 %) present in the olive fruits were retained by the olive pomace, so obtaining high-quality VOO from the point of view of its metal content.     

Phenolic profiles of Turkish olives and olive oils

Phenolic compound distribution of Turkish olive cultivars and their matching olive oils together with the influence of growing region were investigated. One hundred and one samples of olives from 18 cultivars were collected during two crop years from west, south and south‐east regions of Turkey. The olives were processed to oils and both olive and olive oil samples were evaluated for their phenolic compound distribution. The results have shown that main phenolics of Turkish olives were tyrosol, oleuropein, p‐coumaric acid, verbascoside, luteolin 7‐O‐glucoside, rutin, trans cinnamic acid, luteolin, apigenin, cyanidin 3‐O‐glucoside and cyanidin 3‐O‐rutinoside. Oleuropein and trans cinnamic acid were present in higher amounts among all phenolics. Principal component analyses showed that the growing region did not have drastic effect on phenolic profile of olives. The major phenolic compounds of olive oils were tyrosol, syringic acid, p‐coumaric acid, luteolin‐7‐O‐glucoside, trans cinnamic acid, luteolin and apigenin. Luteolin is a predominant phenolic compound in almost all oil samples. Total phenol concentrations of Southeast Anatolian oils were found to be lower than those of the other regions.     

Chemiluminescent Methods in Olive Oil Analysis

The present review describes chemiluminescence applications to olive oil analysis and olive mill wastewater and covers the literature published in recent years. The article has been divided into several sections that discuss specific applications for determining phenolic compounds, antioxidant activity, radical scavenging, oxidative stability and the detection of possible adulteration by seed oils. The advantages and disadvantages of the chemiluminescence detection systems for these purposes are evaluated.     

Changes in Olive and Olive Oil Characteristics During Maturation

Changes in olive properties and oil quality, oxidative stability, phenolic and chemical composition of two common Turkish varieties (Memecik and Edremit) during maturation were investigated. Olive samples were collected in their own growing region for five different harvest dates and processed to oil with a laboratory scale mill. Metabolic behaviors of these two varieties along with the maturation were different in terms of some compositional parameters. Oleic acid, triolein, β-sitosterol, oleuropein, hydroxytyrosol, and tyrosol contents of olive or olive oils fluctuated with maturation. However, changes in average weight, flesh/pit ratio, water and oil contents of the olives were observed. Phenolics such as trans cinnamic acid contents of both olive fruits decreased whereas cyanidin 3-O-glucoside and cyanidin 3-O-rutinoside anthocyanins increased. Free fatty acids of virgin olive oils were found independent of maturity although some slight changes were determined in peroxide value, dien and trien conjugations. Some compositional parameters such as pigment concentration, tocopherols, stearic acid, linolenic acid, palmitodiolein and monounsaturated/polyunsaturated fatty acid ratio decreased while linoleic acid, dioleolinolein, palmitooleolinolein and Δ-5-avenasterol percentages increased with the maturation. A clear discrimination was observed with principal component analysis. The data obtained can also be considered useful for providing information to determine the ideal maturity stage.     

Quality characteristics of olive leaf‐olive oil preparations

Olive leaf‐olive oil preparations were obtained by vigorous mixing at various levels of addition (5, 10, 15%w/w) of new or mature leaves. After removal of the plant material via centrifugation, quality and sensory characteristics of the preparations were determined. Oxidative stability (120°C, 20 L/h) and DPPH radical scavenging were increased ～2–7 fold depending on the level of leaves used due to enrichment with polar phenols, mainly oleuropein, and a‐tocopherol. The extraction process affected the chlorophyll content and organoleptic traits as indicated by acceptability and preference tests (n = 50). Forty‐four % of the panelists identified a strong pungency in preparations with 15% w/w new leaves. Fifty‐four % of them identified a bitter taste in those with 15% w/w mature leaves, which was attributed to high levels of oleuropein (～200 mg/kg oil). Olive leaf‐olive oil preparations had interesting properties regarding antioxidants present that can attract the interest of a functional product market. Practical applications: The wider use of olive oil and derived products is highly desirable. In this sense, the current study presents data that support introduction to the market of a new specialty olive oil based solely on olive tree products (olive oil and leaves). Thus, in addition to olive oil and olive paste, a new product, that is an olive oil enriched with olive leaf antioxidants, especially oleuropein produced via a “green” technique (mechanical means instead of extraction with organic solvent) can be made available for consumers.     

Olive Oil from “Sikitita” under Super-High-Density Planting System in California: Impact of Harvest Time and Crop Season

“Sikitita” is a relatively new olive cultivar obtained from crossbreeding between “Picual” and “Arbequina” that can be trained into the super-high-density orchard system. The impact of harvest time and crop season (2017 and 2018) on fruit parameters, oil quality, and minor compounds was assessed for super-high-density “Sikitita” in California, USA. Maximum olive fruit oil content (~49% on a dry basis) was reached between the first and second weeks of November. Quality parameters were within limits for extra virgin classification for all harvest times during both crop seasons. While total phenols were affected by harvest time, crop year, and their interaction, total volatile content was mainly influenced by harvest time. Both phenolic and volatile compounds reached a maximum concentration by the first week of October, suggesting that harvesting at the beginning of October would lead to a richer oil in terms of minor components. However, oil yield can be maximized if the harvest takes place in November. Our results demonstrated fruit parameters, oil quality, and minor compounds of super-high-density “Sikitita” followed a similar pattern and reached comparable values in both years, despite an earlier maturation in 2018. “Sikitita” has potential as a viable cultivar for growers and processors who are looking to expand on the traditional super-high-density cultivars.     

Two stages catalytic pyrolysis of olive oil waste

A study of the pyrolysis of a waste from the extraction of olive oil has been carried out. The work objective was to characterize the char, tar and gaseous phases generated in the process for their possible utilization in energy generation. On the other hand, the influence of a set of variables has been studied, including the efficacy of the dolomite as catalyst. Finally, as previous step to the design of industrial installations, a kinetic study of the process (catalyzed and uncatalyzed), based in the generation of the principal gases, has been carried out. In the uncatalyzed process only the influence of temperature (400–900 °C) was studied. In the catalytic process, the influence of temperature (500–800 °C) and mass of catalyst (0–100 g) was studied. Also, the dolomite effectiveness as catalyst was evaluated. For this motive, consecutive experiments, without reactivating dolomite, were carried out (0–6 runs), and the yields of solids, liquids and gases were determined. An increase in reaction temperature leads to a decrease in char and tar yield and to an increase in the gas phase yield. When the catalyst is present and when the mass of the same is increased, an important decrease in the tar yield and a high increase in the gas phase yield are produced. This increment in the yield of gases is very significant in the case of hydrogen. In addition, the catalyst is very stable. Your activity remains constant during six consecutive pyrolysis experiments, without need to carry out the reactivation of the same. In the kinetic study carried out, it has been considered that the gases are formed through parallel independent first-order reactions, with different activation energy. For uncatalyzed experiments, the experimental data, once adjusted to the model, provided activation energies of 77.8, 38.6, 70.5 and 16.9 kJ mol^− 1 and the Arrhenius pre-exponential factors of 210.1, 9.9, 775.3 and 0.43 min^− 1 for H₂, CO, CH₄, and CO₂, respectively. For catalyzed experiments (following the same sequence) the activation energies were 15.6, 16.5, 12.7 and 23.3 kJ mol^− 1 and the Arrhenius pre-exponential factors 3.8, 1.4, 4.3 and 3.5 min^− 1.     

Influence of Water Deficit in Bioactive Compounds of Olive Paste and Oil Content

The main objective of this study was to evaluate the effect of different deficit irrigation treatments (control, regulated deficit irrigation [RDI]‐1, RDI‐2, and RDI‐3) on the phenolic profile of the olive paste and oil content. Irrigation treatments with more stress water led to a considerable increase in the phenolic compounds of olive paste, especially in oleuropein (60.24%), hydroxytyrosol (82%), tyrosol (195%), and verbascoside (223%) compared to control. A significant increase in the content of total flavonoids and phenolic acids was also observed for these samples. In virgin olive oils (VOO) elaborated from the most stressed olive trees (RDI‐2 and RDI‐3), a noticeable increase in phenolic substances with antioxidant properties (oleuropein, hydroxytyrosol, tyrosol, secoiridoid derivatives, and o‐vanillin) was observed. Consequently, water stress conditions improved antioxidant activity of VOO.     

On the application of supercritical fluid extraction to the deacidification of olive oils

A recent suggestion on the applicability of supercritical fluid extraction to the deacidification of olive oils of high acid content was based on solubility data in clear disagreement with the results of other authors. In this work, we measured the solubilities of substances chosen for their importance in that extraction process, namely pure glycerol trioleate, the most abundant triglyceride in olive oil, and of a husk oil with a high acid content. Our results agree well with some of the previous reports on this subject. These seem to be a trustworthy data base, but more results are needed for a definite conclusion about the technical feasibility of the process.     

Effects of Filtration on the Quality Properties of Extra Virgin Olive Oils during Storage

In this study, the effects of filtration on quality parameters, chemical characteristics, antioxidant activity, and oxidative stability (OS) of Turkish olive oils during the storage period of 12 months were investigated. The olive oil free acidity (% oleic acid per 100 g of olive oil) (free fatty acidity, FFA), peroxide values (PV) (meq O₂ kg⁻¹ oil), and UV spectrophotometric indices (K₂₃₂ and K₂₇₀ measurements) were used for evaluating the quality parameters of olive oils. α-tocopherol analysis, total phenolic content (TPC), total chlorophyll and carotenoid analyses, and 2,2-diphenyl-1-picrylhydrazyl (DPPH•) radical-scavenging activity (RSA) assays were carried out. Chromatographic methods were applied to determine the fatty-acid and triacylglycerol (TAG) composition, the content of methyl and ethyl esters (FAEE and FAME), and the content of fatty acids of olive oils. Univariate and multivariate statistical methods were performed to evaluate results. Univariate data analysis results showed that filtration of Ayvalık, Memecik, and Domat olive oils had no considerable influence on quality parameters, antioxidant compounds, FAEE and FAME, antioxidant activity, and OS, except TPC (P < 0.05). A significant difference between the samples was determined regarding storage times of the olive oils. Principal component analysis (PCA) analysis revealed that olive oils were grouped according to storage periods of the olive oils regarding fatty-acid and triacylglycerol (TAG) composition while there was no clear separation among the samples according to the filtration process. However, qualitative and quantitative changes took place on minor and major components of olive oils during the storage period.     

Differentiation of mixtures of monovarietal olive oils by mid‐infrared spectroscopy and chemometrics

Fourier transform infrared (FT‐IR) spectroscopy in combination with chemometric techniques has become a useful tool for authenticity determination of extra‐virgin olive oils. Spectroscopic analysis of monovarietal extra‐virgin olive oils obtained from three different olive cultivars (Erkence, Ayvalik and Nizip) and mixtures (Erkence‐Nizip and Ayvalik‐Nizip) of monovarietal olive oils was performed with an FT‐IR spectrometer equipped with a ZnSe attenuated total reflection sample accessory and a deuterated tri‐glycine sulfate detector. Using spectral data, principal component analysis successfully classified each cultivar and differentiated the mixtures from pure monovarietal oils. Quantification of two different monovarietal oil mixtures (2–20%) is achieved using partial least square (PLS) regression models. Correlation coefficients (R²) of the proposed PLS regression models are 0.94 and 0.96 for the Erkence‐Nizip and Ayvalik‐Nizip mixtures, respectively. Cross‐validation was applied to check the goodness of fit for the PLS regression models, and R² of the cross‐validation was determined as 0.84 and 0.91, respectively, for the two mixtures.     

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.