Influence of bleaching by ultrasound on fatty acids and minor compounds of olive oil. Qualitative and quantitative analysis of volatile compounds (by SPME coupled to GC/MS)

The effects of bleaching using high power ultrasound (20 kHz) on the quality of olive oil were considered in this study, in order to verify the modifications that can occur in fatty acid composition and minor compounds. During the treatment of olive oil under ultrasonic waves, a rancid odour has been detected. Treated olive oils show no significant changes in their chemical composition but the presence of some volatile compounds, due to ultrasonic treatment. Some off-flavour compounds (hexanal, hept-2-enal and 2(E),4(E)-decadienal) resulting from the sonodegradation of olive oil have been identified. A wide variety of analytical techniques (GLC, HPLC and GC/MS) were used to follow the quality of bleached olive oils with ultrasonic waves by the determination of the amounts of certain minor compounds such as sterols and tocopherols. Steradienes, resulting from the dehydration of sterols, were detected with small quantities especially in severe conditions of sonication. Solid phase micro-extraction (SPME) coupled to gas chromatography was known to be a sensitive technique to follow changes in the oxidative state of vegetable oils by measuring the amount of volatile materials produced during the refining process.     

Deterioration of edible oils during food processing by ultrasound

During food emulsification and processing of sunflower oil (most used edible oil), a metallic and rancid odour has been detected only for insonated oil and foods. Some off-flavour compounds (hexanal and hept-2-enal) resulting from the sono-degradation of sunflower oil have been identified. A wide variety of analytical techniques (GC determination of fatty acids, UV spectroscopy, free fatty acids and GC/MS) were used to follow the quality of insonated sunflower oil and emulsion. Different edible oils (olive, sunflower, soybean, em leader ) show significant changes in their composition (chemical and flavour) due to ultrasound treatment.     

Impact of ultrasonic pretreatment under different operational conditions on the mesophilic anaerobic digestion of sunflower oil cake in batch mode

In this study ultrasonic (US) pretreatment was investigated with the aim of improving the anaerobic digestion of sunflower oil cake (SuOC), the solid waste derived from the extraction process of sunflower oil. Five ultrasonic pretreatment assays were conducted at specific energy (SE) and sonication times in a range from 24,000 kJ/kg TS and 16.6 min (assay 1: US1) to 597,600 kJ/kg TS and 331.2 min (assay 5: US5), respectively, all operating at a constant sonication frequency (20 kHz) and ultrasonic power (120 W). As regards ultrasonic pretreatment, the working conditions of the first assay (US1) using samples of SuOC at 2% (w/v) showed to be the most appropriate in terms of both lignin and hemicellulose degradation (57.7% and 66.7%, respectively) and cellulose increase (54% increase with respect to its initial concentration). The percentage of COD solubilization increased from only 14% to 21% when SE was 25 times higher. Results obtained in batch anaerobic digestion experiments (biochemical methane potential - BMP - tests) conducted at 35°C of the solid and liquid fractions released from the different ultrasonic conditions tested, indicated that for the first experiment (US1) the average ultimate methane yield obtained was 53.8% higher than that achieved for untreated SuOC. Finally, the kinetic constants of the anaerobic digestion of the solid and liquid fractions released after the ultrasonic pretreatment were virtually independent of the operation conditions assayed.     

Effect of ultrasonic power on properties of edible composite films based on rice protein hydrolysates and chitosan

Rice protein hydrolysates (RPH) are incapable of film formation by self-crosslinking due to low molecular mass. Hence, we used chitosan (CS) as a modifier and developed rice protein hydrolysates/chitosan (RPH/CS) edible composite films by means of ultrasound. Results showed that ultrasound treatment decreased the particle size and the viscosity of film-forming solutions. The value of elongation at break of composite films was increased by 125% at 400 W compared with untreated film. The peroxide value of soybean oil was significantly reduced from 16.99 ± 0.78 meq/kg to 2.23 ± 0.09 meq/kg with the increase of ultrasonic power. Ultrasound treatment was efficient in keeping smooth on surface, and the films at ultrasound treatment of 200 W had better compatibility. Moreover, hydrogen bonds and covalent interactions were probably the main forces between RPH and CS and contributed to film formation under ultrasound treatment, which supported by analyses of Fourier transform infrared spectroscopy and X-ray diffraction. These results suggested that ultrasound was an effective method to improve the properties of edible composite films.     

茶籽油油学性质的光谱分析研究

用气相色谱测定了思茅地区普洱茶果油中的脂肪酸的组成,并将其与花生油、菜籽油、油茶籽油、橄榄油中的脂肪酸组成进行了比较,发现普洱茶果油中油酸的质最分数高于花生油、菜籽油,低于油茶籽油、橄榄油,芥酸的质量分数低于花生油、菜籽油及油茶籽油,略高于橄榄油,故普洱茶果是一种理想的油料资源.用气-质联用从普洱茶果油挥发性物质中鉴定出30种化合物,其中大部分为醇、醛、酮、酯类物质,并且多数同时含有不饱和键,国内鲜见报道.     

Impact of ultrasound treatment on lipid oxidation of Cheddar cheese whey

Ultrasound (US) has been suggested for many whey processing applications. This study examined the effects of ultrasound treatment on the oxidation of lipids in Cheddar cheese whey. Freshly pasteurized whey (0.86 L) was ultrasonicated in a contained environment at the same range of frequencies and energies for 10 and 30 min at 37 °C. The US reactor used was characterized by measuring the generation of free radicals in deionized water at different frequencies (20–2000 kHz) and specific energies (8.0–390 kJ/kg). Polar lipid (PL), free and bound fatty acids and lipid oxidation derived compounds were identified and quantified before and after US processing using high performance liquid chromatography equipped with an evaporative light scattering detector (HPLC–ELSD), methylation followed by gas chromatography flame ionized detector (GC-FID) and solid phase micro-extraction gas chromatography mass spectrometry (SPME-GCMS), respectively. The highest concentration of hydroxyl radical formation in the sonicated whey was found between 400 and 1000 kHz. There were no changes in phospholipid composition after US processing at 20, 400, 1000 and 2000 kHz compared to non-sonicated samples. Lipid oxidation volatile compounds were detected in both non-sonicated and sonicated whey. Lipid oxidation was not promoted at any tested frequency or specific energy. Free fatty acid concentration was not affected by US treatment per se. Results revealed that US can be utilized in whey processing applications with no negative impact on whey lipid chemistry.     

Effect of oil extraction assisted by ultrasound on the physicochemical properties and fatty acid profile of pumpkin seed oil (Cucurbita pepo)

The effects of amplitude and time of ultrasound-assisted extraction on the physicochemical properties and the fatty acid profile of pumpkin seed oil (Cucurbita pepo) were evaluated. Ultrasound time (5–30 min) and the response variables amplitude (25–100%), extraction yield, efficiency, oxidative stability in terms of the free fatty acids (FFA) of the plant design comprising two independent experiments variables, peroxide (PV), p-anisidine (AV), totox value (TV) and the fatty acid profile were evaluated. The results were analyzed by multiple linear regression. The time and amplitude showed significant differences (P < 0.05) for all variables. The highest yield of extraction was achieved at 5 min and amplitude of 62.5% (62%). However, the optimal ultrasound-assisted extraction conditions were as follows: ultrasound time of 26.34 min and amplitude of 89.02%. All extracts showed low FFA (2.75–4.93% oleic acid), PV (1.67–4.68 meq/kg), AV (1.94–3.69) and TV (6.25–12.55) values. The main fatty acids in all the extracts were oleic and linoleic acid. Therefore, ultrasound-assisted oil extraction had increased performance and reduced extraction time without affecting the oil quality.     

Impact of ultrasonic treatment process on pour point of vegetable oils based liquid insulation

This study presents an application of ultrasonic technology in the high voltage liquid insulation domain towards the reduction of pour point of vegetable oil samples for the utilization of vegetable oils as liquid insulation in cold climate areas on power transformers. Pour point reduction has been achieved by processing the vegetable oil samples by using ultrasonic treatment process with 100 W and 30 kHz ultrasonic waves for various exposure times of 15, 30, 45 and 60 min. Edible vegetable oils such as sunflower oil, palm oil, sesame oil and non edible vegetable oils such as honge oil, neem oil and punna oil are considered as two categories of vegetable oils for this experimental investigation. Ultrasonic treatment process results in the reduction of pour point of vegetable oils to meet out the standard value of pour point for liquid insulation as per IEEE Standard C57.147, 2018. A significant reduction in pour point temperature of vegetable oil samples have been obtained with an increased exposure time. The obtained variations in pour point after exposure with ultrasonic waves may be due to the possible changes in crystallization kinetics of fatty acids components of vegetable oil samples due to energy input of ultrasonic waves. The experimental results have given a way towards the positive encouragement and development with ultrasonic treatment for achieving low pour point vegetable oils as liquid insulation in power transformers for applications on cold climatic areas.     

酯交换生物柴油的柱层析分离纯化与分析

以文冠果油通过酯交换法制备的粗生物柴油为原料,采用柱层析进行精制纯化,然后利用气相色谱、GC-MS、红外光谱和1 H核磁共振等分析产物的成分。粗油经柱层析分离出两个馏分:石油醚洗脱馏分(A1),主要是由文冠果油经酯交换反应得到的生物柴油,包括亚油酸甲酯、油酸甲酯等;甲醇洗脱馏分(A2)主要是甘油馏分,是油脂酯交换反应的副产物。结果表明:由柱层析进行分离纯化后,生物柴油的纯度由原来的77.51%提高到93.87%,生物柴油的回收率也高达91.04%;红外光谱和1 H核磁共振的分析结果进一步表明柱层析能够有效地提高生物柴油的纯度,为工业化纯化生物柴油提供了依据。     

A study of chemical transformations of organic compounds under the action of cavitation

The action of ultrasonic and hydrodynamic cavitation on the cracking of organic compounds of various natures (linear alkanes (octane, undecane, and hexadecane), carboxylic acids (decanoic and oleic acids), alcohols (decanol), and esters (ethyl caprate)) and transesterification of rapeseed oil and methanol and ethanol was studied. An analysis of hydrocarbon transformation products by gas chromatography, high-performance liquid chromatography, NMR, and chromato-mass spectrometry showed that cavitation treatment of any class of organic compounds of those mentioned above resulted in transformations no more than 1.1% deep. In experiments with transesterification of rapeseed oil and methanol and ethanol without a catalyst under the action of cavitation, the yield of fatty acid esters did not exceed 2.1 mol %. The energy efficiency of the cavitation apparatus was estimated at 0.002% for endothermic cracking of alkanes. The data obtained led us to conclude that the use of cavitation directly for performing cracking of various organic compounds and noncatalytic transesterification of vegetable oils was ineffective.     

Influence of particles on sonochemical reactions in aqueous solutions

Numerous publications deal with the possible application of ultrasound for elimination of organic pollutants as a tool for water pollution abatement. Most of the experiments were performed in pure water under laboratory conditions. For developing technologies that hold promise it is necessary to investigate the effect of ultrasound in natural systems or waste water where particulate matter could play an important role. In this paper the influence of quartz particles (2-25 microm) on the chemical effects of ultrasound in aqueous system using a high power ultrasound generator (68-1028 kHz, 100 W, reactor volume 500 ml) is reported. In pure water in dependence on particle size, concentration and frequency the formation rate of hydrogen peroxide under Ar/O2 (4:1) shows a maximum using 206 kHz in presence of 3-5 microm quartz particles (4-8 g/l). Under these conditions the yield of peroxide is higher than without quartz. Additionally under N2/O2 (4:1) besides hydrogen peroxide the formation of nitrite/nitrate was measured. Compared to pure water quartz particle depressed the formation of nitrite/nitrate up to 10-fold but not the formation of H2O2. According to the results of H2O2 formation the elimination of organic compounds by sonolysis (206 kHz) and the influence of quartz particles were investigated. As organic compounds salicylic acid, 2-chlorobenzoic acid and p-toluenesulfonic acid were used. The influence of quartz on the oxidation of organic compounds (206 kHz) is similar to that on the formation of H2O2.     

Ultrasound induced aqueous polycyclic aromatic hydrocarbon reactivity

An investigation to determine the ability of ultrasonic radiation to chemically alter polycyclic aromatic hydrocarbons (PAHs) in aqueous solution has been conducted. The data indicate that chemical alteration of PAHs can be induced under intense ultrasonic treatment. The extent and outcome of reaction is a function of irridation time and aqueous solution parameters. Reaction products were analysed by gas chromatography (GC) and gas chromatography/mass spectrometry (GC/MS). Reaction products from ultrasonic treatment of aqueous solutions of biphenyl include ortho, meta, and para-1,1 biphenols. The principal product from ultrasonic treatment of aqueous phenanthrene solutions appears to be a phenanthrene-diol. The number and composition of reaction products for both PAHs tested suggest that a free radical mechanism is likely during aqueous high intensity ultrasonic treatment. The use of ultrasound to treat PAH contaminated aqueous solutions in tandem with other methodologies appears promising. However, the toxicity of reaction products produced by treatment remains to be determined.     

Sonochemical degradation of phenol in water: a comparison of classical equipment with a new cylindrical reactor

Cavitation due to ultrasonic waves produces highly reactive oxidising species in water. As a result, it can be used to oxidise organic pollutants such as aromatic compounds in dilute aqueous solutions. Recent studies have demonstrated that reactors operating in the high frequency range (e.g. 500 kHz) are more efficient than reactors working at lower frequency (20 kHz) for the destruction of these kinds of contaminants. Our study describes the degradation of phenol with the help of a cylindrical ultrasonic apparatus that operates at 35 kHz (Sonitube-SODEVA). To date, the use of this type of reactor has not been reported. The reaction rates thus obtained were compared to those obtained at the same ultrasonic power (50 W) with more classical devices operating at 20 and 500 kHz. The general result is that in aqueous solution, the rate of phenol destruction is higher at 500 kHz than at 35 or 20 kHz. Addition of hydrogen peroxide and copper sulphate to the medium provides a different oxidative system that proceeds more efficiently at 35 kHz; the time of destruction was about one-third of the time needed at 500 kHz. It was also observed that the intermediate organic compounds are eliminated much faster at 35 kHz in comparison with the two frequencies. The observation of such different behaviour is not necessarily a pure frequency effect, but can be due to a response to other parameters such as the acoustic field and intensity.     

High-intensity ultrasound-based process strategies for obtaining edible sunflower (Helianthus annuus L.) flour with low-phenolic and high-protein content

The sunflower Helianthus annuus L. represents the 4th largest oilseed cultivated area worldwide. Its balanced amino acid content and low content of antinutrient factors give sunflower protein a good nutritional value. However, it is underexploited as a supplement to human nutrition due to the high content of phenolic compounds that reduce the sensory quality of the product. Thus, this study aimed at obtaining a high protein and low phenolic compound sunflower flour for use in the food industry by designing separation processes with high intensity ultrasound technology. First, sunflower meal, a residue of cold-press oil extraction processing, was defatted using supercritical CO₂ technology. Subsequently, sunflower meal was subjected to different conditions for ultrasound-assisted extraction of phenolic compounds. The effects of solvent composition (water: ethanol) and pH (4 to 12) were investigated using different acoustic energies and continuous and pulsed process approaches. The employed process strategies reduced the oil content of sunflower meal by up to 90% and reduced 83% of the phenolic content. Furthermore, the protein content of sunflower flour was increased up to approximately 72% with respect to sunflower meal. The acoustic cavitation-based processes using the optimized solvent composition were efficient in breaking down the cellular structure of the plant matrix and facilitated the separation of proteins and phenolic compounds, while preserving the functional groups of the product. Therefore, a new ingredient with high protein content and potential application for human food was obtained from the residue of sunflower oil processing using green technologies.     

Effect of ultrasound on the structural characteristics and oxidative stability of walnut oil oleogel coated with soy protein isolate-phosphatidylserine

In this study, the three-dimensional network system formed by rice bran wax (RBW) was used as the internal structure, and the external structure formed by soybean protein isolate (SPI) and phosphatidylserine (PS) was added on the basis of the internal structure to prepare walnut oil oleogel (SPI-PS-WOG). Ultrasonic treatment was applied to the mixed solution to make SPI-PS-WOG, on the basis, the effects of ultrasonic treatment on SPI-PS-WOG were investigated. The results showed that both β and β’ crystalline forms were present in all SPI-PS-WOG samples. When the ultrasonic power was 450 W, the first weight loss peak in the thermogravimetric (TGA) curve appeared at 326 °C, which was shifted to the right compared to the peak that occurred when the ultrasonic power was 0 W, indicating that the thermal stability of the SPI-PS-WOG was improved by the ultrasonic treatment. Moreover, when the ultrasonic power was 450 W, the oil holding capacity (OHC) reached 95.3 %, which was the best compared with other groups. Both confocal laser scanning microscopy (CLSM) and scanning electron microscopy (SEM) showed that the ultrasonic treatment of appropriate power succeeded in making the SPI-PS-WOG samples more evenly dispersed in the internal structure and denser in the external structure. In terms of oxidative stability, it was found that the peroxide value of SPI-PS-WOG remained at 9.8 mmol/kg oil for 50 days under 450 W ultrasonic power treatment, which was significantly improved compared with liquid walnut oil (WO). These results provide a new idea for the preparation of oleogels, and also lay a theoretical foundation for the application of ultrasonic treatment in oleogels.     

Effects of multi-frequency ultrasound on physicochemical properties,structural characteristics of gluten protein and the quality of noodle

In this study, the influence of multi-frequency ultrasound irradiation on the functional properties and structural characteristics of gluten, as well as the textural and cooking characteristics of the noodles were investigated. Results showed that the textural and cooking characteristics of noodles that contain less gluten pretreated by multi-frequency ultrasonic were ultrasonic frequency dependent. Moreover, the noodles that contain a smaller amount of sonicated gluten could achieve the textural and cooking quality of commercial noodles. There was no significant difference in the cooking and texture characteristics between commercial noodles and noodles with 12%, 11%, and 10% gluten pretreated by single-frequency (40 kHz), dual-frequency (28/40 kHz), and triple-frequency sonication (28/40/80 kHz), respectively. Furthermore, the cavitation efficiency of triple-frequency ultrasound was greater than that of dual-frequency and single-frequency. As the number of ultrasonic frequencies increased, the solubility, water holding capacity and oil holding capacity of gluten increased significantly (p < 0.05), and the particle size was reduced from 197.93 ± 5.28 nm to 110.15 ± 2.61 nm. Furthermore, compared to the control group (untreated), the UV absorption and fluorescence intensity of the gluten treated by multi-frequency ultrasonication increased. The surface hydrophobicity of gluten increased from 8159.1 ± 195.87 (untreated) to 11621.5 ± 379.72 (28/40/80 kHz). Raman spectroscopy showed that the α-helix content of all sonicated gluten protein samples decreased after sonication, while the β-sheet and β-turn content increased, and tryptophan and tyrosine residues were exposed. Through scanning electron microscope (SEM) analysis, the gluten protein network structure after ultrasonic treatment was loose, and the pore size of the gluten protein network increased from about 10 μm (untreated) to about 26 μm (28/40/80 kHz). This work elucidated the effect of ultrasonic frequency on the performance of gluten, indicating that with increasing frequency combination increases, the ultrasound effect became more pronounced and protein unfolding increased, thereby impacting the functional properties and the quality of the final product. This study provided a theoretical basis for the application of multi-frequency ultrasound technology in the modification of gluten protein and noodle processing.     

Ultrasonic waste-water treatment: incidence of ultrasonic frequency on the rate of phenol and carbon tetrachloride degradation

Organic compounds in aqueous solution submitted to an ultrasonic irradiation behave differently according to their physical and chemical properties. In this work, hydrogen peroxide formation and the degradation rate of phenol and carbon tetrachloride have been studied at different frequencies: 20, 200, 500 and 800 kHz. Whatever the frequency, it is easier to decompose CCl₄ than phenol by means of ultrasonic wave. It is shown that the rates of reactions involving hydroxyl radicals (hydrogen peroxide formation and phenol degradation) have a maximum value at 200 kHz. The best yield observed at 200 kHz for the phenol degradation may be the result of better HO radicals availability outside of the bubble of cavitation. The degradation rate for carbon tetrachloride which decomposes into the bubble of cavitation increases with frequency. Calculating the reaction rate for one ultrasonic period shows that the efficiency of one ultrasonic cycle decreases as frequency increases.     

Study on ultrasound-assisted oxidative desulfurization for crude oil

The existence of sulfur compounds in crude oil will bring many problems such as corrosion, catalyst poisoning and pollution to the petroleum processing process. Therefore, how to reduce the sulfur content as much as possible in the process of crude oil processing has become an important research topic in the petroleum processing industry. In this paper, ultrasonic-oxidative desulfurization is studied. The effects of reaction temperature, reaction time, amount of oxidant and demulsifier on desulfurization rate are investigated. And the effect of oxidative desulfurization and single oxidative desulfurization under ultrasonic treatment are compared. It is found that the addition of ultrasonic treatment can enhance the desulfurization effect of desulfurizer, the desulfurization efficiency can be increased by about 10% under ultrasonic treatment (100 W, 70 kHz); ultrasonic wave plays an auxiliary role in the system, it can promote heterogeneous reactions, improve the activity of oxidants, and promote the degradation of macromolecular compounds. Finally, physical desulfurization, chemical desulfurization and biological desulfurization technologies are compared.     

The ultrasound application does not affect to the thermal properties and chemical composition of virgin olive oils

In this work, the effects of high power ultrasound treatment (40 kHz) on virgin olive oil (VOO) for different times (0, 15, 30 min) were studied, in order to verify if extent modifications in their chemical composition and thermal properties. The effects of the different ultrasound treatments on VOOs were determined considering the following parameters: quality index (free acidity, K₂₃₂ and K₂₇₀), lipid profile (fatty acids and triglycerides composition) minor components (phenols, tocopherols, pigments and volatiles) and thermal properties (crystallization and melting) by Differential Scanning Calorimetry (DSC).During the ultrasound treatments, bubbles growth was present in the VOO due to the phenomenon of cavitation and a slight increase of the temperature was observed. In general, the ultrasound treatments did not cause alterations on VOO parameters evaluated (oxidation state, lipid profile, minor components and thermal profiles). However, a slight decrease was observed in some volatile compounds.     

Modification of polyethylene powder with an organic precursor in a spiral conveyor by hollow cathode glow discharge

Hexamethyldisiloxane (HMDSO) films were deposited on polyethylene (PE, (C₂H₄)_n) powder by hollow cathode glow discharge. The reactive species in different HMDSO/Ar plasmas were studied by optical emission spectroscopy (OES). Increasing the HMDSO fraction in the gas mixture additional compounds like CH_x, OH, SiC and SiO can be identified. After deposition the formed silicon and carbon containing groups (C–O, C=O, SiC and SiO) on the PE powder surface have been analyzed by X-ray photoemission spectroscopy (XPS). Changes in wettability depending on the HMDSO fraction were investigated by contact angle measurements (CAM). The free surface energy of the PE powder decreases with increasing HMDSO fraction in the process gas and encapsulation of the powder particles occurs. An aging effect of the plasma treated PE surface was observed depending on the process gas composition. The higher the HMDSO fraction the less is the aging effect of the plasma treated PE surface.