Effect of extraction conditions on sensory quality of virgin olive oil

The extraction conditions of virgin olive oil have a great influence on its sensory quality. During the centrifugation process, temperature and time of malaxing can be altered to potentially affect quality. Malaxing times (15, 30, 45, 60, and 90 min) and temperatures (25 and 35°C) were studied in an experimental oil mill. Volatile compounds, produced through the lipoxygenase pathway (hexanal, Z-3-hexenal, E-2-hexenal, hexyl acetate, Z-3-hexenyl acetate, hexan-1-ol, E-3-hexen-1-ol, Z-3-hexen-1-ol, and E-2-hexen-1-ol), were analyzed by dynamic headspace gas chromatography, gas chromatographymass spectrometry, and gas chromatography-olfactometry. Different amounts of volatiles responsible for positive attributes of green aroma and negative attributes of astringent mouthfeel of virgin olive oil were determined. The results, after applying mathematical procedures, showed that a temperature of 25°C and a malaxing time between 30 and 45 min produced volatile compounds that contribute to the best sensory quality. High temperature (T≥35°C) with minimum values of time (t<30 min) could also be useful as an alternative way to obtain pleasant green virgin olive oils.     

Effect of extraction system, stage of ripeness, and kneading temperature on the sterol composition of virgin olive oils

Comparative extraction trials were carried out among a classical pressing, a dual-, and a three-phase centrifugation system using olive crops of Koroneiki variety. Two different kneading temperatures, 30 and 45°C, were tested at three stages of ripeness for two consecutive years of harvest, 1995–1996 and 1996–1997. Composition of the sterol fraction was determined in the resulting olive oil samples (n=72). Stigmasterol was found to be affected by the extraction system; it was obtained in the highest amount in the pressing system. The ratio campesterol/stigmasterol was significantly higher in oils extracted by dual- and three-phase centrifugation. Sterols were significantly affected by the ripening stage of the fruit. During December, the ratio campesterol/stigmasterol reached the maximal and β-sitosterol the minimal values; this appears to be the optimal period for harvesting the olives. Comparison of the different kneading temperatures showed that at 30°C, Δ⁵-avenasterol and campesterol/stigmasterol ratio reached higher values than at 45°C.     

Deacidification of olive oils by supercritical carbon dioxide

An investigation of the application of supercritical carbon dioxide (SC-CO₂) extraction to the deacidification of olive oils has been made to verify that the nutritional properties of the oil remain unchanged when this technique is applied. Preliminary runs at 20 and 30 MPa in the temperature range of 35–60°C were performed on fatty acids and triglycerides as pure compounds or mixtures, to determine their solubility in SC-CO₂. The solubility data obtained show that CO₂ extracts fatty acids more selectively than triglycerides under specific conditions of temperature and pressure (60°C and 20 MPa). It has been noted that the physical state of the solutes plays an important role in determining the solubility trends as a function of temperature and pressure. Extraction of free fatty acids from olive oil was performed on samples with different free fatty acid (FFA) contents at 20 and 30 MPa and at 40 and 60°C. Experimental data suggest that the selectivity factor for fatty acids is higher than 5 and increases significantly as the fatty acid concentration of the oil decreases. For a FFA content of 2.62%, the selectivity reaches a value of 16. In order to evaluate any variations in the composition, several SC-CO₂ extractions of husk oil with high FFA content (29.3%) were made. The results show that selectivity is still significant (≈5) and the composition in the minor component of the deacidified oil has not changed. On the basis of the experimental results and preliminary process evaluations, the authors conclude that SC-CO₂ extraction could be a suitable technique for the deacidification of olive oils, especially for oils with relatively high FFA (<10%).     

Modelling lipase‐catalysed transesterification of fats containing n‐3 fatty acids monitored by their solid fat content

Transesterification of fat blends rich in n‐3 polyunsaturated fatty acids (n‐3 PUFA), catalysed by a commercial immobilised thermostable lipase from Thermomyces lanuginosa, was carried out batch‐wise. Experiments were performed, following central composite rotatable designs (CCRDs) as a function of reaction time, temperature and media formulation. Mixtures of palm stearin, palm kernel oil and a commercial concentrate of triacylglycerols rich in n‐3 PUFA (“EPAX 2050TG” in CCRD‐1 and “EPAX 4510TG” in CCRD‐2) were used. The time‐course of transesterification was indirectly followed by the solid fat content (SFC) values of the blend at 10 °C, 20 °C, 30 °C and 35 °C. A decrease in all SFC values of the blends at 10 °C, 20 °C, 30 °C and 35°C was observed upon transesterification. The SFC_{10 °C} and SFC_{20 °C} of transesterified blends varied between 18 and 48 and SFC_{35 °C} between 6 and 24. These values fulfil the technological requirements for the production of margarines. Under our conditions, lipid oxidation may be neglected. However, the accumulation up to 8.3% free fatty acids in reaction media is a problem to overcome. The development of response surface models, describing both the final SFC value and the SFC decrease, will allow predicting results for novel proportions of fats and oils and/or a novel combination time‐temperature.     

Influence of milling conditions on the α‐tocopherol content of Picual olive oil

The aim of this study was to estimate the α‐tocopherol content in Picual extra‐virgin olive oils obtained from the 2004/2005 harvesting season and to evaluate the influence that different extraction processes and sample handling had on the final vitamin E content in the oils. A new experimental oil extraction carried out at 9 °C enabled us to obtain encouragingly high quantities of α‐tocopherol with an average quantity reaching 341.34 ± 50.17 mg/L (n = 13), with significant differences among the same oil types produced from the traditional two‐phase system at low (9 °C, p <0.01) and moderate (21.5 °C, p <0.001; 33 °C, p <0.0001) temperatures. The temperature at which extraction was carried out should be considered as a major factor to be taken into account. Additionally, we also developed a precise method for the extraction of α‐tocopherol from olive oil samples, which enables high recovery (96 ± 2%) for use in subsequent HPLC/DAD/fluorescence quantification.     

Effect of olive paste kneading process time on the overall quality of virgin olive oil

The influence of the olive paste malaxation time on the composition and the industrial output of oil was investigated. To this purpose, three Italian olive varieties (Leccino, Dritta, Caroleo) were processed with a centrifugal system for six malaxation periods (0, 15, 30, 45, 60 and 75 min). The concentrations of the majority of the oil constituents changed during the malaxation. However, these changes were not significant for all of them: the contents of β‐carotene, the major xanthophylls, chlorophylls a and b, pheophytins a and b in the oils increased progressively with increasing malaxing times, whereas the contents of simple and hydrolysable phenols (secoiridoid derivatives), o‐diphenols and total phenols decreased. A significant increase in total volatiles and green volatiles of the lipoxygenase cascade (C₆ aldehydes, C₆ alcohols, C₅ alcohols and C₅ carbonyls) was detected. An opposite trend was observed for the green C₆ esters. As a result, the global analytical quality, flavour, aroma and shelf‐life of the oils were negatively affected. The oil yield increased substantially up to 45 min of paste malaxation times. Beyond 60 min, the yields tended to decrease.     

Ethanol-Modified Supercritical Carbon Dioxide Extraction of the Bioactive Lipid Components of <Emphasis Type="Italic">Camelina sativa</Emphasis> Seed

Camelina sativa seed is an underutilized oil source that attracts a growing interest, but it requires more research on its composition and processing. Its high omega‐3 content and growing demand for clean food processing technologies make conventional oil extraction less attractive. In this study, the effect of extraction methods on the bioactive lipid composition of the camelina seed lipid was investigated, and its bioactive lipid composition was modified at the extraction stage using ethanol‐modified supercritical carbon dioxide (SC‐CO₂). Ethanol‐modified SC‐CO₂ extractions were carried out at varying temperatures (50 and 70 °C), pressures (35 and 45 MPa), and ethanol concentrations (0–10%, w/w), and were compared to SC‐CO₂, cold press, and hexane extraction. The highest total lipid yield (37.6%) was at 45 MPa/70 °C/10% (w/w) ethanol. Phospholipids and phenolic content increased significantly with ethanol‐modified SC‐CO₂ (p < 0.05). SC‐CO₂ with 10% (w/w) ethanol concentration selectively increased phosphatidylcholine (PC) content. Apparent solubility of camelina seed lipids in SC‐CO₂, determined using the Chrastil model, ranged from 0.0065 kg oil/kg CO₂ (35 MPa/50 °C) to 0.0133 kg oil/kg CO₂ (45 MPa/70 °C). Ethanol‐modified SC‐CO₂ extraction allowed modification of the lipid composition that was not possible with the conventional extraction methods. This is a promising green method for extraction and fractionation of camelina seed lipids to separate and enrich its bioactives.     

The effect of malaxation temperature on the virgin olive oil phenolic profile under laboratory‐scale conditions

The relationship between olive paste malaxation temperature and the concentration of olive oil hydrophilic phenols (HP), i.e. simple phenols, secoiridoids and lignans, was investigated. Malaxation experiments were performed at laboratory scale for 45 min at 21, 24, 27, 30, 33 and 36 °C. A significant (p <0.05) increment of total phenols concentration was found with a maximum at 27 °C, whereas for higher temperatures (30–36 °C) a progressive decrement was observed. A similar pattern was recorded approximately for all the secoiridoid compounds, i.e. a quasi‐linear increment of concentrations with increasing temperature until 30 °C, followed by a marked decrease in correspondence with the higher malaxation temperature (33 and 36 °C). The amount of simple phenols increased linearly with increasing temperature and no decrements were observed up to the maximal temperature investigated (36 °C), while no significant differences were found for lignans. A small increment of peroxide values and total chlorophyll was recorded as a function of the increasing malaxation temperature, whereas no differences were observed in the free acidity. The results highlight that there is not a univocal relationship between HP concentration and malaxation temperature. An equilibrium between degradation (chemical and biochemical oxidation and hydrolysis) and transfer (partitioning) phenomena was hypothesized.     

Antioxidant Activity and Total Polyphenols Content of Camellia Oil Extracted by Optimized Supercritical Carbon Dioxide

In this study, Camellia oil is co-extracted from Camellia oleifera seeds and green tea scraps by supercritical carbon dioxide (SC-CO₂), which is optimized on the extraction yield, ABTS-scavenging activity, and total polyphenols content (TPC) of oil by single-factor experiments combined with response surface methodology (RSM). The extraction temperature, pressure, dynamic time, carbon dioxide (CO₂) flow rate, and seed mass ratio were investigated with single-factor experiments. The results indicated the optimum CO₂ flow rate and dynamic extraction time were 15 L hour⁻¹ and 60 min (i.e., 2.382 kg CO₂/100 g sample). Furthermore, the complicated effects of extraction temperature (40–50 °C), pressure (20–30 MPa), and seed mass ratio (0.25–0.75) were optimized by RSM based on the Box–Behnken design (BBD). The models with high R-squared values were obtained and used to predict the optimum operating conditions of the process. Under the optimum operating conditions (i.e., temperature of 46 °C, pressure of 30 MPa, and seed mass ratio of 0.35), the extraction yield, ABTS-scavenging activity, and TPC of oil were 14.43 ± 0.17 g/100 g sample, 73.70 ± 0.34%, and 2.18 ± 0.05 mg GAE/g oil, which were in good agreement with the predicted values. In addition, the experiments indicated that the Camellia oil obtained was rich in polyphenols, resulting in better oxidation stability and antioxidant activity than the original oil.     

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.     

Solubility of red pepper (C<Emphasis Type="Italic">apsicum annum</Emphasis>) oil in near- and supercritical carbon dioxide and quantification of capsaicin

Red pepper oil was extracted using near- and supercritical carbon dioxide. Extraction was carried out at pressures ranging from 10 to 35 MPa and temperatures from 30 to 60 °C, with a CO₂ flow rate of 24.01 g/min using a semi-continuous high-pressure extraction apparatus. The duration for extraction was 2 h. The highest oil yield was found at high pressure and temperature. The highest solubility of oil (1.18 mg/g of CO₂) was found at 35 MPa and 60 °C. The solubility data of red pepper oil in near- and supercritical CO₂ were fitted in Chrastil model. The fatty acid composition of red pepper oil was analyzed by gas chromatography (GC). Linoleic acid was found to be the major fatty acid in the oil. Capsaicin was quantified in different extracts by high performance liquid chromatography (HPLC). The highest capsaicin yield was found at 35 MPa and 60 °C.     

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.     

Extraction of rice brain oil using supercritical carbon dioxide and propane

Extraction of rice bran lipids was performed using supercritical carbon dioxide (SC−CO₂) and liquid propane. To provide a basis for extraction efficiency, accelerated solvent extraction with hexane was performed at 100°C and 10.34 MPa. Extraction pressure was varied for propane and SC−CO₂ extractions. Also, the role of temperature in SC−CO₂ extraction efficiency was investigated at 45,65, and 85°C. For the SC−CO₂ experiments, extraction efficiencies were proportional to pressure and inversely proportional to temperature, and the maximal yield of oil achieved using SC−CO₂ was 0.222±0.013 kg of oil extracted per kg of rice bran for conditions of 45°C and 35 MPa. The maximal yield achieved with propane was 0.224±0.016 kg of oil per kg of rice bran at 0.76 MPa and ambient temperature. The maximum extraction efficiencies of both SC−CO₂ and propane were found to be significantly different from the hexane extraction baseline yield, which was 0.261±0.005 kg oil extracted per kg of rice bran. A simulated economic analysis was performed on the possibility of using SC−CO₂ and propane extraction technologies to remove oil from rice bran generated in Mississippi. Although the economic analysis was based on the maximal extraction efficiency for each technology, neither process resulted in a positive rate of return on investment.     

Utilization of high-melting palm stearin in lipase-catalyzed interesterification with liquid oils

Palm stearin with a melting point (m.p.) of 49.8°C was fractionated from acetone to produce a low-melting palm stearin (m.p.=35°C) and a higher-melting palm stearin (HMPS, m.p.=58°C) fraction. HMPS was modified by interesterification with 60% (by weight) of individual liquid oils from sunflower, soybean, and rice bran by means of Mucor miehei lipase. The interesterified products were evaluated for m.p., solid fat content, and carbon number glyceride composition. When HMPS was interesterified individually with sunflower, soybean or rice bran at the 60% level, the m.p. of the interesterified products were 37.5, 38.9, and 39.6°C, respectively. The solid fat content of the interesterified products were 30–35 at 10°C, 17–19 at 20°C, and 6–10 at 30°C, respectively. The carbon number glyceride compositions also changed significantly. C₄₈ and C₅₄ glycerides decreased remarkably with a corresponding increase of the C₅₀ and C₅₂ glycerides. All these interesterified products were suitable for use as trans acid-free and polyunsaturated fatty acid-rich shortening and margarine fat bases.     

Characterization of oil including astaxanthin extracted from krill (Euphausia superba) using supercritical carbon dioxide and organic solvent as comparative method

Krill oil including astaxanthin was extracted using supercritical CO₂ and hexane. The effects of different parameters such as pressure (15 to 25MPa), temperature (35 to 45 °C), and extraction time, were investigated. The flow rate of CO₂ (22 gmin⁻¹) was constant for the entire extraction period of 2.5 h. The maximum oil yield was found at higher extraction temperature and pressure. The oil obtained by SC-CO₂ extraction contained a high percentage of polyunsaturated fatty acids, especially EPA and DHA. The acidity and peroxide value of krill oil obtained by SC-CO₂ extraction were lower than that of the oil obtained by hexane. The SC-CO₂ extracted oil showed more stability than the oil obtained by hexane extraction. The amount of astaxanthin in krill oil was determined by HPLC and compared at different extraction conditions. The maximum yield of astaxanthin was found in krill oil extracted at 25 MPa and 45 °C.     

Performance of a Cocoa Butter-Like Fat Enzymatically Produced from Olive Pomace Oil as a Partial Cocoa Butter Replacer

Olive pomace oil is a by-product of olive oil processing and it is considered a low-quality oil. Considering its suitable triacylglycerol (TAG) composition, this work aimed to convert refined olive pomace oil (ROPO) to a cocoa butter (CB)-like fat using sn-1,3 specific lipase, and to investigate its performance as a partial CB replacer. CB-like fat was produced from olive pomace oil by sn-1,3-specific lipase-catalyzed acidolysis in a packed bed reactor. Binary blends of CB and CB-like fat (CB:CB-like fat) were prepared in different proportions, and their physicochemical characteristics [TAG content, melting profile, solid fat content (SFC) and microstructure] were investigated. The contents of 1,3-dipalmitoyl-2-oleoyl-glycerol (POP), 1(3)-palmitoyl-3(1)stearoyl-2-oleoyl-glycerol (POS) and 1,3-distearoyl-2-oleoyl-glycerol (SOS) in the 100:0 blend were 18.9, 33.1 and 24.7%, respectively. These contents decreased to 11.0, 20.0 and 11.7%, respectively, in the 0:100 blend. Although the melting point (28.5 °C) did not change significantly above 30% CB-like fat addition, the shape of the melting peak became wider and irregular. An isothermal solid diagram of SFC showed that better compatibility was observed at temperatures above 35 °C for all blends. Addition of over 30% CB-like fat caused significant difference in the microstructure.     

On the quality control of ‘olive paste’, a specialty based on olives and olive oil

‘Olive paste’ is a preserved food gaining popularity as a gourmet product. Its quality depends on that of the major ingredients, table olives (green or black) and virgin olive oil, as well as on the changes occurring to the constituents of the latter during preparation and storage. In this view, our attention was focused on the characteristics of the lipid fraction (l.f.) of a great number of commercial products after a careful search in retail markets and the web. Ultraviolet absorbance values (K₂₃₂, K₂₇₀) of the l.f., a criterion set for edible and non‐edible olive oil oxidative status due to paste heat treatment during pasteurization, could not support the label information regarding the quality of the oil used. On the contrary, the content of α‐tocopherol (?250 mg/kg l.f. or ?50 mg/kg paste) was a strong indication of good‐quality major ingredients. Within each brand, consistency with labeling was checked through squalene (higher content in products containing higher amounts of olive oil) or β‐carotene determination (higher levels in preparations containing red pepper). For green olive paste samples, the values of the ratio pheophytin a/pyropheophytin a may be used to monitor the shelf life of the product. The findings support routine quality control of the new product.     

Deacidification of black cumin seed oil by selective supercritical carbon dioxide extraction

The deacidification of high-acidity oils from Black cumin seeds (Nigella sativa) was investigated with supercritical carbon dioxide at two temperatures (40 and 60°C), pressures (15 and 20 MPa) and polarities (pure CO₂ and CO₂/10% MeOH). For pure CO₂ at a relatively low pressure (15 MPa) and relatively high temperature (60°C), the deacidification of a highacidity (37.7 wt% free fatty acid) oil to a low-acidity (7.8 wt% free fatty acid) oil was achieved. The free fatty acids were quantitatively (90 wt%) extracted from the oil and left the majority (77 wt%) of the valuable neutral oils in the seed to be recovered at a later stage by using a higher extraction pressure. By reducing the extraction temperature to 40°C, increasing the extraction pressure to 20 MPa, or increasing the polarity of the supercritical fluid via the addition of a methanol modifier, the selectivity of the extraction was significantly reduced; the amount of neutral oil that co-extracted with the free fatty acids was increased from 23 to 94 wt%.     

Oxidative stability of olive oil flavoured by Capsicum frutescens supercritical fluid extracts

The effect of red pepper supercritical fluid extracts (SFE) on the oxidative stability of extra‐virgin olive oil was evaluated using accelerated stability tests [Rancimat and differential scanning calorimetry (DSC) methods] and by measuring the changes in the levels of polyunsaturated fatty acid primary and secondary oxidation products during storage under ambient conditions. SFE were produced according to a central composite rotatable design, at a constant temperature (40 °C), different pressures (15–23 MPa) and superficial velocities (0.04–0.08 cm/s). The results showed that the red pepper extracts produced at low extraction pressure and superficial velocity (e.g. 16.2 MPa and 0.046 cm/s) containing low/intermediate capsaicinoid levels did not affect olive oil stability. The extracts produced at higher pressure showed a slight pro‐oxidant activity. The K₂₃₂ and K₂₇₀ values always fell within the limit set by the European legislation for the quality characteristics of olive oil containing no additives. Evaluation of oxidative stability using DSC was found to be a useful methodology, which demands smaller oil samples and shorter times in comparison with the methodology using the Rancimat apparatus. Red pepper SFE obtained at low extraction pressures can be used in order to produce stable flavoured olive oils.     

Time Fractionation of Minor Lipids from Cold-Pressed Rapeseed Cake Using Supercritical CO<Subscript>2</Subscript>

This work explored the possibility of using supercritical carbon dioxide (SC-CO₂) to achieve fractionation of pre-pressed rapeseed (Brassica napus) cake oil at 30–50 MPa, at 40 or 80 °C, and increase the concentration of minor lipids (sterols, tocopherols, carotenoids) in the oil. Minor lipids are partially responsible for desirable antioxidant effects that protect against degradation and impart functional value to the oil. The weight and concentration of minor lipids in oil fractions collected during the first 60 min were analyzed. Cumulative oil yield increased with pressure, and with temperature at ≥40 MPa, but was lower at 80 °C than at 40 °C when working at pressure ≤35 MPa. Differences in solubility between the oil and minor lipids explained fractionation effects that were small for tocopherols. Unlike tocopherols, which are more soluble in SC-CO₂ than the oil, sterols and carotenoids are less soluble than the oil, and their concentration increased in the later stages of extraction, particularly at ≥40 MPa, when there was not enough oil to saturate the CO₂ phase. Because of the fractionating effects on rapeseed oil composition, there was an increase in the antioxidant activity of the oil in the second half as compared to the first half of the extraction. Consequently, this study suggests that SC-CO₂ extraction could be used to isolate vegetable oil fractions with increased functional value.