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.     

Malaxing temperature affects volatile and phenol composition as well as other analytical features of virgin olive oil

Three Italian olive varieties (Caroleo, Leccino and Dritta) were processed by centrifugation in the oil mill. The olive paste was kneaded at 20, 25, 30 and 35 °C. The results achieved revealed that the oil content in green volatiles from lipoxygenase pathway (including C₅ and C₆ compounds and especially unsaturated C₆ aldehydes) decreased progressively as the kneading temperature increased, dropping markedly at 35 °C. The content of phenols, o‐diphenols and secoiridoids showed an opposite trend, but the temperature of 35 °C was critical also for them, as it was for the majority of the other components, analytical parameters and indices related to quality, typicality and genuineness. In general, an increasing kneading temperatures increased the release of oil constituents from the vegetable tissue. This factor also affected the oil extraction yields. The best overall results were achieved by malaxing the olive paste at 30 °C. In fact, this temperature level led to achieving both pleasant green virgin olive oils and satisfactory oil extraction outputs.     

High-performance liquid chromatography evaluation of phenols in virgin olive oil during extraction at laboratory and industrial scale

Phenolic compounds are of fundamental importance to the quality and nutritional properties of virgin olive oils. In this paper, the high-performance liquid chromatographic analysis of simple and complex olive oil phenols in the streams generated in the two-phase extraction system was carried out using Arbequina and Picual olives. The malaxation stage reduced the concentration of orthodiphenols in oil ca 50–70%, while the concentration of the nonorthodiphenols remained constant, particularly the recently identified lignans 1-acetoxypinoresinol and pinoresinol. Oxidation of orthodiphenols at laboratory scale was avoided by malaxing the paste under a nitrogen atmosphere. Phenolic compounds in the wash water used in the vertical centrifuge were also identified. Hydroxytyrosol, tyrosol, the dialdehydic form of elenolic acid linked to hydroxytyrosol were the most representative phenols in these waters. Hence, phenolic compounds in the wash waters came from both the aqueous and the lipid phases of the decanter oily must.     

Antioxidant activity of tocopherols and phenolic compounds of virgin olive oil

The antioxidant effects of hydrophilic phenols and tocopherols on the oxidative stability in virgin olive oils and in purified olive oil have been evaluated. Total hydrophilic phenols and the oleosidic forms of 3,4-dihydroxyphenolethanol (3,4-DHPEA) were correlated (r=0.97) with the oxidative stability of virgin olive oil. On the contrary, tocopherols showed low correlation (r=0.05). Purified olive oil with the dialdehydic form of elenolic acid linked to 3,4-DHPEA, an isomer of oleuropeine aglycon, and 3,4-DHPEA had good oxidative stability. A synergistic effect was observed in the mixture of 3,4-DHPEA and its oleosidic forms with α-tocopherol in purified olive oil by the Rancimat method at 120°C.     

Malaxation of Olive Paste Under Sealed Conditions

Virgin olive oils from pilot-scale malaxation under hermetically sealed conditions were compared with olive oils from industrial conventional open-to-air malaxation (control). Under sealed conditions, large CO₂ emissions coupled with O₂ depletion occur. Oil samples produced under sealed conditions were less oxidized and contained greater concentrations of antioxidant compounds (especially secoiridoids phenols) than the control. These results were attributed to the reduced O₂ concentration in the hermetically sealed pilot-scale malaxer. The amounts and types of volatile compounds present in the oil were only slightly affected by the treatment.     

The influence of stabilizers on mechanochemical processes in SBR rubbers

Mechanochemical processes in commercial and model SBR rubbers containing different stabilizers were investigated. The influence of chemical structure and concentration of stabilizers in the temperature range from 20–170°C and in the presence of air, i.e., under conditions similar to that in industrial processes, were studied. Stabilizers used were diaryl‐p‐phenylene‐diamine, alkyl‐aryl‐p‐phenylene diamine, polynuclear phenol, aryl‐alkyl phenol, and alkyl‐alkyl phenol. It was found that mechanochemical processes in SBR rubbers are less developed in the temperature region from 70–130°C, so the influence of stabilizer is less expressive. During increasing temperature (130–170°C) structure and concentration of stabilizers both show a strong influence on type and intensity of mechanochemical processes in SBR rubbers: p‐phenylene‐diamines favor processes of linear degradation, while phenol stabilizers direct them toward branching and crosslinking, which is more expressed in the presence of aryl‐substituted phenols than alkyl‐substituted phenols. This fact is based on the differences in stability of free stable radicals of p‐phenylene‐diamines, alkyl‐substituted phenols and aryl‐substituted phenols. The fact that phenol stabilizers are involved in chain degradation as well as in branching and crosslinking processes during rubber processing, can be of high practical importance. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 835–847, 1999     

A Kinetic-Thermodynamic Study of the Effect of the Cultivar/Total Phenols on the Oxidative Stability of Olive Oils

Physicochemical parameters, total phenols contents (TPC), and oxidative stabilities at 120–160 °C were evaluated for two monovarietal (Arbequina and Cobrançosa cultivars, cvs.) and one blend extra-virgin olive oil, confirming the label quality grade and allowing grouping them according to the different TPC (TPC = 88 ± 7, 112 ± 6 and 144 ± 4 mg CAE/kg, for cv. Arbequina, blend and cv. Cobrançosa oils, respectively). The lipid oxidation rate increased with the decrease of the TPC, being Cobrançosa oils (higher TPC) more thermally stable. Kinetic-thermodynamic parameters were determined using the activated complex/transition-state theory and the values did not significantly differ for Cobrançosa and blend oils, which had the highest TPC, suggesting a hypothetically threshold saturation of the beneficial effect. Cobrançosa oils had a significant more negative temperature coefficient, higher temperature acceleration factor, greater activation energy and frequency factor, higher positive enthalpy of activation, lower negative entropy of activation, and greater positive Gibbs free energy of activation, probably due to the higher TPC. The results confirmed that lipid oxidation was a nonspontaneous, endothermic, and endergonic process with activated formed complexes structurally more ordered than the reactants. A negative deviation from the Arrhenius behavior was observed for all oils being the super-Arrhenius behavior more marked for Arbequina oils that had the lowest TPC. Finally, the kinetic-thermodynamic parameters allowed classifying oils according to the binomial olive cultivar/total phenols level, being the temperature acceleration factor and the Gibbs free energy of activation at 160 °C the most powerful discriminating parameters.     

Improving olive oil quality using CO2 evolved from olive pastes during processing

The effect of blanketing with CO₂, naturally evolved during malaxation of olive pastes, on the quality of virgin olive oil was investigated at lab‐scale. The O₂ depletion was monitored along with CO₂ emission to confirm the previously hypothesized accelerated respiration. Malaxation experiments were conducted for 180 min both in sealed (SC) and in the traditional open‐to‐air conditions to ascertain whether the oil quality was affected by O₂ concentration as afforded by CO₂ blanketing. The quality of olive oils obtained at different time intervals was monitored by total acidity, peroxide value (PV), specific extinction coefficients K₂₃₂ and K₂₇₀, total chlorophyll and total hydrophilic phenols, and HPLC hydrophilic phenols profile. A rapid decrease in oxygen concentration and a simultaneous increase in CO₂ concentration were recorded, confirming the accelerated respiration. The oil produced in SC showed a lower PV and K₂₃₂ coefficient and a higher chlorophyll (10–17 mg/kg) and hydrophilic phenols (110 mg/kg) concentration. No differences in total acidity and K₂₇₀ coefficient were observed. The hydrophilic phenols profile indicated that, at least for the Frantoio cultivar and an advanced ripeness state, the maximal extraction is generally achieved already after 20 min. Most of the individual hydrophilic phenols have higher concentrations (up to 50%) in SC.     

Effect of hydrogen bond formation on dynamic mechanical properties of amorphous cellulose

The temperature dependence of the dynamic modulus (E′) and the mechanical loss tangent (tanδ) of amorphous cellulose prepared from cellulose triacetate by saponification was measured and compared with that of cellophane, recrystallized cellulose obtained by immersing amorphous cellulose in water, and cellulose triacetate. The E′ of amorphous cellulose decreased initially with increasing temperature and then began to increase at about 70°C with a maximum at 80°C, decreasing again at about 100°C. Another decrease in E′ was observed at 220°C accompanied by a discontinuity at 155°C. In the tan δ-versus-temperature curve, a medium peak at 60°C a shoulder peak at 146°C, and a broad peak at 200°C were observed. It was found that the transition at about 60°C was related to hydrogen bond formation by free OH groups. The transition at about 150°C was attributed to a recrystallization process by heating, and the relaxation at 200°C, to the glass transition of the polymer. The decrement in E′ observed at about 100°C was attributed to the cooperative motion of an individual pyranose ring in amorphous cellulose, juding from the E′ and tan δ assignment of other cellulose materials. The change in E′ was also measured isothermally as a function of time in the temperature range between 40°C and 80°C, where a maximum in tan δ and an increment in E′ were observed as the temperature dependence of the dynamic viscoelasticity. The change in E′ with elapsed time was analyzed kinetically, and an activation energy of 2.6 kcal/mole was calculated. This value is the expected activation energy of hydrogen bond formation.     

Effect of Lipase Activity and Specificity on the DAG Content of Olive Oil from the Shodoshima-Produced Olive Fruits

Olive oils have a higher relative diacylglycerol (DAG) content than other plant oils. The lipase in olive fruits is involved in DAG production and is directly related to the acidity of the olive oil. However, the lipase activity and positional selectivity have not been clarified. To investigate the properties of olive fruit lipase, olive fruits of the Mission variety harvested during mid-December of 2005 on Shodoshima Island (Japan) were stored at 20, 30 or 40 °C for 4 weeks. Changes in the acidity and acylglycerol content of the oils extracted from the stored fruits were analyzed. The acidity and DAG content of the olive oils increased due to triacylglycerol (TAG) hydrolysis during storage. sn-1,2-DAGs preferentially increased during the early stages of storage, indicating that the olive fruit lipase is enantioselective for the sn-3 position, while non-enzymatic isomerization of sn-1,2-DAGs was observed throughout the entire duration of storage. Kinetic analysis revealed that the enantioselectivity of olive fruit lipase for the sn-3 position was approximately four times greater than for the sn-1 position. The lipase was gradually inactivated at temperatures of 30 °C or higher, and the ratios of the rate constant for inactivation to TAG hydrolysis at the sn-3 position was 0.2, 13, and 23 at 20, 30, and 40 °C, respectively.     

Hydrophilic antioxidants of virgin olive oil. Part 2: Biosynthesis and biotransformation of phenolic compounds in virgin olive oil as affected by agronomic and processing factors

The biosynthesis of the phenolic fraction of olive fruits during ripening and the transformations occurring in this moiety during virgin olive oil (VOO) extraction are discussed in this paper. The influence of agronomical factors that can significantly affect the phenolic profile of VOO is also discussed. Particularly, it is worth emphasizing the role of genetic factors, cultivation and climatic conditions such as water availability, atmospheric temperature, altitude, health status of the fruits, alternate bearing in the olive, and some processing factors such as crushing, malaxation time and temperature or volume of water added during milling. Among these parameters, special attention has been paid to genetic factors due to the high variability observed among Olea europaea genotypes for all recorded traits. In this context, interesting experimental results have been obtained with cultivated and wild olive trees, and also with segregating populations resulting from olive breeding programs. To the authors' knowledge, reviews evaluating the influence of the main factors that contribute to the profile of hydrophilic phenols have not been previously published. The discussion concerning olive breeding programs is a major and novel aspect to be emphasized considering recent trends to obtain new olive cultivars that confer better organoleptic properties and better quality to VOO.     

Effect of filtration on virgin olive oil stability during storage

The effect of filtration and dehydration on the stability and quality of virgin olive oil during storage at room temperature (25 °C) and under accelerated conditions (40 °C) was studied. Different types of monovarietal olive oil, namely unfiltered (UF), filtered (F) and filtered‐dehydrated (FD), were obtained from Arbequina, Colombaia, Cornicabra, Picual and Taggiasca cultivars. Results showed that filtration and dehydration decreased the rate of hydrolysis of the triacylglycerol matrix, especially at the higher temperature and in oils with a higher initial free acidity (e.g. free acidity of 0.82% and 0.63% in UF and FD Colombaia samples, respectively, after 8 months of storage), and delayed the appearance of rancid defects (e.g. UF and FD Arbequina samples lost extra‐virgin grade after 10 and 12 months of storage, respectively). The formation of simple phenols due to the hydrolysis rate of their secoiridoid derivatives was also greater in unfiltered olive oils (e.g. 174 μmol/kg and 137 μmol/kg in UF and FD Picual samples, respectively, after 8 months of storage). Thus, filtration and especially dehydration could help to prolong the shelf life of high‐quality and less stable olive oils like those obtained from the Arbequina and Colombaia varieties.     

Media Optimization for Poly(β-hydroxybutyrate) Production Using Azotobacter Beijerinckii

In the present study, efforts were made to optimize the growth of Azotobacter beijerinckii in the media with essential nutrients for production of PHB. The effects of temperature, agitation rate, carbon and nitrogen source concentrations on microbial grows and PHB production were investigated. Glucose and ammonium chloride were used as carbon and nitrogen source, respectively. The optimal temperature for the growth and PHB synthesis appeared to be 30°C. However, over the range of 25–38°C, the effect of temperature was not very significant. Fermentation under controlled conditions such as agitation rate of 250 rpm, incubated inoculums for 15 h, fermentation temperature at 30°C, and fermentation time of 72 h was performed. Glucose concentration of 30 to 60 g/l with increment of 10 g/l and ammonium chloride in the range of 0.5 to 2 g/l with increment of 0.5 g/l were utilized as carbon and nitrogen sources, respectively. The PHB production was maximized at the desired concentration of glucose (50 g/l) and ammonium chloride (1.5) for carbon and nitrogen sources, respectively. A. beijerinckii exhibited maximum biomass of 17.31 g/l with a PHB concentration of 5.84 g/l. Under the best conditions, PHB constituted up to 34% of dry cell mass after 64 h of culture. The average biomass yield coefficient on glucose was about 0.57 kg/kg.     

Efficiency of EDTA,SDS, and NaOH Solutions to Clean RO Membranes Processing Swine Wastewater

The increasing use of membranes to treat a broad range of wastewaters requires the development of efficient cleaning strategies. The objective of this study was to optimize the efficiency of EDTA-SDS-NaOH solutions to recover flux and remove proteins and bacteria from RO membranes filtering swine wastewater. At 60-min cleaning time, flux recovery (FR) increased with SDS concentrations up to 18 mM, but decreased at 36 mM. Adding up to 20 mM EDTA to the SDS solutions did not improve FR. The SDS-NaOH solutions yielded higher FRs at pH 11/40°C and pH 12/33°C than pH 10/45°C, indicating that increasing pH had a greater impact on cleaning efficiency than increasing temperature. At pH 11/40°C and pH 10/45°C, increasing cleaning time from 60 to 120 min decreased FR at all SDS concentrations, probably because of surfactant adsorption on membrane surface, as opposed to inadequate foulant removal, since residual protein concentration was lower on membranes cleaned for 120 than 60 or 30 min. At pH 12/33°C, however, increasing cleaning time to 120 min improved FR at all SDS levels. The lower temperature or higher pH may have prevented surfactant attachment to the membrane. At pH 12/33°C and 120 min, a solution containing NaOH only yielded similar FRs than an 18-mM SDS solution after up to four consecutive fouling-cleaning cycles. Increasing cleaning time and pH would thus eliminate the need to add a surfactant to the cleaning solution.     

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.     

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.     

Mechanical Properties of Plateau Burn Azide Composite Propellants

The effects of cure ratio, crosslinking density, ammonium perchlorate (AP) particle size, and other additives on the mechanical properties of azide polymer composite propellants were characterized. The equivalence ratio of 1.0 and IPDI/TPA=7/3 were effective on low temperature mechanical properties. Relatively high amount of plasticizer was required in BAMO/NMMO binder and preferred the equivalence ratio of 1.0 to retain itself in the three-dimensional binder matrix. Excellent elasticity was obtained at a temperature range between −20°C and 2°C and normal strain rate dependency was obtained at from 54°C to −20°C. Glass transition occurred at −30°C to −35°C in Sample 17. The increase in contact area between AP particle and binder and in bonding strength played an important role on the prevention of the propagation of crack around a boundary and, therefore, ϵ_m was increased with decrease of particle size. Almost exactly the same σ_m, however, was observed in whole temperature range with increment of 5% to 10% in ϵ_m.     

The desorption of ethane–butane mixtures from polyethylene

The desorption of mixtures of ethane and butane at atmospheric pressure from low-density polyethylene was investigated over the temperature range from 20 to 60°C. Desorbed penetrants were continuously trapped in glass tubes immersed in liquid nitrogen, and composition was determined as a function of time by means of gas chromatography. The ratio of the quantity of desorbed gas at any time t, q_t, to the quantity at complete desorption, q_∞, was used to determine diffusion coefficients and solubility constants. The diffusion coefficients for both ethane and butane increase with increasing butane concentration in the temperature interval investigated. The solubility of both penetrants can be correlated by Henry's law at 40, 50, and 60°C. However, at 20 and 30°C. the solubility constant for both penetrants increases with increasing butane concentration. This trend is consistent with experimental observations for single-component diffusion and solubility of several hydrocarbons in polyethylene, where increasing concentration of penetrant plasticizes the polymer, resulting in increasing diffusion coefficients and solubility constants.     

An FTIR solid-state analysis of the diffusion of hindered phenols in low-density polyethylene (LDPE): The effect of molecular size on the diffusion coefficient

Low-density polyethylene (LDPE) has been investigated with respect to the diffusion of hindered phenol antioxidants added to the polymer matrix. In the study, a simple method was used to measure the diffusion coeficient, with the aid of FTIR spectroscopy without any extraction or refining steps in the analysis. The diffusion coefficient, D, of five phenols containing the same 3(3,5-di-tert-butyl-4-hydroxyphenyl) structure but with different lengths of the hydrocarbon tail were obtained in the temperature range 30–60°C. The number of carbon atoms in the tail varied between 1 and 18. It was found that the logarithm of D decreased linearly with increasing molecular size. The temperature-dependence of the phenols could be described by an Arrhenius-type relationship. It was found that the activation energy, E_d, incresed linearly with increasing molecular size. © 1994 John Wiley & Sons, Inc.     

Influence of the Atmosphere Composition during Malaxation and Storage on the Shelf Life of an Unfiltered Extra Virgin Olive Oil: Preliminary Results

The nutraceutical and organoleptic quality of the extra virgin olive oil (EVOO) depends on a process that begins with the olive ripening and ends with the packaging and storage. As the EVOO quality decay is mainly induced by the oxidation process, the gaseous composition of the atmosphere during both malaxation and storage can play a key role. Because of that, the aim of this research work is to determine the influence of the gaseous composition of the atmosphere used during malaxation and storage on an unfiltered EVOO shelf life, and to individuate the best “malaxation atmosphere × storage atmosphere” combination to adopt to more effectively slow down the oil quality decay rate during storage. The combined experimental conditions used during malaxation and storage significantly affect the quality decay rate of the EVOO over one year of storage for all the evaluated parameters. In conclusion, the gaseous composition of the atmosphere used during both malaxation and storage deeply affects the shelf life of the unfiltered EVOO as regards its chemical and sensory features, especially when air is used. On the contrary, the best results are obtained when an inert gas (nitrogen or argon) is used during both phases. Practical Applications : The regular consumption of EVOO represents one of the main cornerstones of the Mediterranean diet. According to the FDA (Food and Drug Administration), this product can be considered as a healthy food because of its extraordinary nutraceutical and organoleptic properties, so that if consumers consume half a tablespoon of olive oil per day—without increasing their daily calorie intake—they can significantly reduce the incidence of several degenerative diseases as well as the risks associated with them. The knowledge of the impact of different “malaxation atmosphere × storage atmosphere” combinations on the quality decay rate during storage of an unfiltered EVOO can allow to identify the best operating conditions to be used during its production and storage, in order to preserve the nutraceutical and organoleptic properties of this product over time, thus extending its commercial life in terms of both quality parameters and healthy properties.