Extraction of organic components from aqueous streams by vacuum membrane distillation

The removal of volatile organic compounds from aqueous streams by vacuum membrane distillation (VMD) has been analyzed. VMD is an evaporation process which takes place through microporous hydrophobic membranes; at low pressure the mass transfer through the membrane is generally dominated by the Knudsen mechanism, while the process selectivity is essentially determined by the liquid-vapor equilibrium conditions existing at the interface. Dilute aqueous mixtures containing ethanol or methylterbutyl ether have been experimentally investigated, in a wide range of operating conditions. The role of concentration-polarization phenomena on the separation factor was also investigated. A detailed model of the transport phenomena involved in the process is developed and compared with the experimental data. A VMD system is finally designed for the purification of waste waters and the related treatment costs are evaluated.     

Concentration and temperature polarization effects during osmotic membrane distillation

Pineapple juice is one of the popular fruit juice due to its pleasant aroma and flavor. Concentration of clarified pineapple juice was carried out by osmotic membrane distillation in a plate and frame membrane module. Concentration and temperature polarization effects are found to have significant role on flux reduction during osmotic membrane distillation process. The contribution of these polarization effects on reduction of the driving force (in turn the flux) at various process conditions such as osmotic agent concentration (2–10 mol/kg (1 molality = 1 mol/kg)), flow rate (25–100 ml/min) of feed and osmotic agent are studied. Concentration polarization has more significant effect on flux reduction when compared to temperature polarization. The experimental fluxes were in good agreement with theoretical fluxes when calculated by considering both concentration and temperature polarization effects. The pineapple juice was concentrated up to a total soluble solids content of 62°Brix at ambient temperature.     

Removal of 2,4-dichlorophenol from wasterwater by vacuum membrane distillation using hydrophobic PPESK hollow hiber membrane

2,4-Dichlorophenol was removed from wasterwater using a new hydrophobic poly(phthalazinone ether sulfone ketone) (PPESK) hollow fiber membrane by vacuum membrane distillation(VMD).     

Factors affecting flux and ethanol separation performance in vacuum membrane distillation (VMD)

Membrane distillation (MD) has a great potential as a concentration process for temperature labile liquids such as fruit juices, etc. Besides water, also aroma compounds will permeate through the membrane depending on their volatility and how the MD process is operated on the permeate side.In this paper, an experimental and theoretical investigation of the influence of concentration polarisation and temperature polarisation on the flux and selectivity of binary aqueous mixtures of ethanol is presented for vacuum membrane distillation (VMD) processes. Experimental results include changes of the following parameters: nature of solutions, membrane material and pore size, feed temperature, recirculation flow rate. One method was proposed in order to evaluate the concentration polarisation effects from the fit of the experimental data. General models taking into account Knudsen and viscous flows were proposed, but viscous contribution resulted to be negligible under our operating conditions. Therefore, theoretical fluxes were estimated using Knudsen model and a good agreement between them and the experimental ones was found.     

Characterization of the Key Aroma Compounds of Three Kinds of Chinese Representative Black Tea and Elucidation of the Perceptual Interactions of Methyl Salicylate and Floral Odorants

Jinjunmei (JJM), Keemun (KM), and Dianhong (DH) are the representative black teas in China, and they have always been favored by consumers. In this study, we aim to obtain the aroma characteristic information of volatile components in black tea samples through headspace solid-phase microextraction (HS-SPME), solvent-assisted flavor evaporation (SAFE), and gas chromatography-mass spectrometry combined with gas chromatography-olfactometry technology. The results showed that 70 compounds including α-methylbenzyl alcohol (isomer of β-phenylethanol) were identified as odorants. Among them, 39 compounds such as linalool and geraniol showed a high degree of aroma contribution. Furthermore, the Feller’s additive model was used to explore the perceptual interactions among the methyl salicylate and the floral compounds (10 groups): five groups of binary compounds showed masking effect after mixing, one group showed additive effect, and four groups showed synergistic effect. The ratio (R) was compared with the aroma index (n) of Steven’s law, which found a high-fitness exponential relationship. The results of this study help to provide additional and new theoretical guidance for improving the aroma quality of black tea.     

Anthocyanin-rich black currant extract suppresses the growth of human hepatocellular carcinoma cells

Dietary antioxidants, such as anthocyanins, are helpful in the prevention and control of various diseases by counteracting the imbalance of oxidative and antioxidative factors in the living systems. Black currant (Ribes nigrum L., Grossulariaceae) is known to contain high amounts of anthocyanins (250 mg/100 g fresh fruit). Black currant fruits have been used in Asian and European traditional medicine for the treatment of a variety of diseases. Black currant extract has recently been found to be the second most effective amongst nine different berry extracts studied for their free radical scavenging activity. Constituents present in black currant juice have been found to exert a number of health-promoting effects, including immunomodulatory, antimicrobial and antiinflammatory actions, inhibition of low-density lipoprotein, and reduction of cardiovascular diseases. Although antioxidant and antiinflammatory effects of black currant juice could be of value in preventing and treating oxidative stress- and inflammation-driven cancers, no experimental evidence is available to now. The objective of the present study was to evaluate the potential antiproliferative effects of black currant fruit skin extract against HepG2 human liver cancer cells. The aqueous extract yielded an anthocyanin-rich fraction with cyanidin-3-O-rutinoside as one of the major anthocyanins. This fraction exhibited a potent cytotoxic effect on HepG2 cells and this effect was more pronounced than that of delphinidin and cyanidin, two major aglycones of anthocyanins present in black currant. Our results indicate, for the first time, that black currant skin containing an anthocyanin-rich fraction inhibits the proliferation of liver cancer cells, possibly due to additive as well as synergistic effects. This product could be useful in the prevention and treatment of human hepatocellular carcinoma.     

Concentration of noni juice by means of osmotic distillation

Osmotic distillation (OD) or osmotic evaporation (OE) is a promising membrane process generally applied to concentrate solutions under isothermal conditions. In this work, this process was applied to concentrate commercial noni juice (Morinda citrifolia). Several nutraceutical properties have been reported for noni-derived products, mainly associated to the phenolic content of the fruit.The analyzed system is an osmotic distillation system where the solutions are circulated through a hollow fiber membrane contactor operating in transient configuration with circulation rates between 0.1 and 1.0 L min⁻¹ and concentrated solutions of CaCl₂ were used as extraction brine. At isothermal conditions (30 °C), transmembrane vapor water flux was experimentally determined from 0.090 up to 0.413 kg h⁻¹ m⁻². Noni juice was concentrated from 8 to 32 °Brix after 60 min of treatment. The content of phenolic compounds was preserved after this processing.Simulation algorithms based on phenomenological equations of heat and mass transfer were developed considering a resistances-in-series model to predict the performance of the process from theoretical information. The values of transmembrane water flux obtained by simulations showed deviations between 2.35 and 16.19% with the experimental ones for the operating conditions applied in this work.     

Hydrophobic modification of poly(phthalazinone ether sulfone ketone) hollow fiber membrane for vacuum membrane distillation

New hydrophobic poly(phthalazinone ether sulfone ketone) (PPESK) hollow fiber composite membranes coated with silicone rubber and with sol–gel polytrifluoropropylsiloxane were obtained by surface-coated modification method. The effects of coating time, coating temperature and the concentration of silicone rubber solution on the vacuum membrane distillation (VMD) properties of silicone rubber coated membranes were investigated. It was found that high water permeate flux could be gotten in low temperature and low concentration of silicone rubber solution. When the coating temperature is 60 °C, the coating time is 9 h and the concentration of silicone rubber solution is 5 g L⁻¹ the water permeate flux of the silicone rubber coated membrane is 3.5 L m⁻² h⁻¹. The prepolymerization time influence the performance of polytrifluoropropylsiloxane coated membranes, and higher prepolymerization time decrease the water permeate flux of the membrane. The water permeate flux and the salt rejection was 3.7 L m⁻² h⁻¹ and 94.6%, respectively in 30 min prepolymerization period. The VMD performances of two composite membranes during long-term operation were studied, and the results indicated that the VMD performances of two composite membranes are quite stable. The salt rejection of silicone rubber coated membrane decreased from 99 to 95% and the water permeate flux fluctuated between 2.0 and 2.5 L m⁻² h⁻¹. The salt rejection of polytrifluoropropylsiloxane coated membrane decreased from 98 to 94% and the water permeate flux fluctuated in 1 L m⁻² h⁻¹ range.     

Effect of Ultrasound and Enzymatic Mash Treatment on Bioactive Compounds and Antioxidant Capacity of Black,Red and White Currant Juices

Ultrasound treatment is recognized as a potential technique for improvement in the nutritional values of fruit juices. This study was initiated with the objective of evaluating bioactive compounds and some important quality parameters of black (BC), red (RC) and white (WC) currant juices obtained from fruit mash preliminarily treated by enzymes combined with ultrasound. Individual and total phenolic content (TPC), anthocyanins, color parameters, ascorbic acid, antioxidant capacity (TEAC), juice yield, pH, titratable acidity, and soluble solids were investigated. Significant increases in the levels of TPC and antioxidant capacity of sonicated samples were observed. However, ultrasound treatment had no effect on individual phenolic compounds of juices. Sonication of mash before juice pressing did not cause any noticeable changes in ascorbic acid content. Only in the case of WC was an increase in content of vitamin C noticed. The color of juices obtained after treatment was similar to the control sample. It was demonstrated that enzymatic combined with ultrasound treatment of mash for different colored currant fruit did not have any dismissive effect and could even improve some parameters of the juice obtained.     

运用气相色谱检测数据定量评价加工果蔬汁的香气协调性变化

为了建立加工果蔬汁香气协调性变化程度的定量评价模式,运用数学方法归纳果蔬汁样品的气相色谱(GC)检测数据,以原果蔬汁为基准,计算经浓缩或其他加工处理后样品中含有的各挥发性组分的百分含量相对于原果蔬汁的整体变化值(即样品偏差值),用以定量描述果蔬汁处理前后香气组分的整体变化程度。当需要比较不同加工方法或工艺对果蔬汁香气协调性的影响时,可对其进行相同条件的GC检测获取数据并计算比较样品偏差值。用此方法将冷冻浓缩柠檬汁、真空蒸发浓缩柠檬汁与原汁进行了比较,结果显示冷冻浓缩柠檬汁不仅能够很好地保持柠檬汁香气成分的绝对含量,同时也很好地保持了天然柠檬汁原有的香气协调性。     

Coupled membrane process applied to fruit juice concentration

A coupled membrane process of membrane distillation and osmotic evaporation, where the solutions were thermostated separately at different temperatures, was developed. Enhanced water flux was obtained since the total driving force of the coupled process was higher than the sum of the driving forces of single processes. Apple, raspberry, sour cherry, red, and black currant juices were concentrated by the novel, mild technique. Presented at the 33rd International Conference of the Slovak Society of Chemical Engineering, Tatranské Matliare, 22–26 May 2006.     

Changes in Phenols,Polysaccharides and Volatile Profiles of Noni (Morinda citrifolia L.) Juice during Fermentation

The change in phenols, polysaccharides and volatile profiles of noni juice from laboratory- and factory-scale fermentation was analyzed during a 63-day fermentation process. The phenol and polysaccharide contents and aroma characteristics clearly changed according to fermentation scale and time conditions. The flavonoid content in noni juice gradually increased with fermentation. Seventy-three volatile compounds were identified by solid-phase microextraction coupled with gas chromatography–mass spectrometry (SPME-GC-MS). Methyl hexanoate, 3-methyl-3-buten-1-ol, octanoic acid, hexanoic acid and 2-heptanone were found to be the main aroma components of fresh and fermented noni juice. A decrease in octanoic acid and hexanoic acid contents resulted in the less pungent aroma in noni juice from factory-scale fermentation. The results of principal component analysis of the electronic nose suggested that the difference in nitrogen oxide, alkanes, alcohols, and aromatic and sulfur compounds, contributed to the discrimination of noni juice from different fermentation times and scales.     

The Effects of Berry Extracts on Oxidative Stress in Cultured Cardiomyocytes and Microglial Cells: A Potential Cardioprotective and Neuroprotective Mechanism

Oxidative stress is a key underlying factor in cognitive decline and atherosclerosis. Oxidative stress occurs at the cellular level with an imbalance between reactive oxygen species and reactive nitrogen species and a deficiency in antioxidants. Mounting evidence suggests that berry flavonoids may promote cellular health by exerting antioxidant properties. Black currant and various berry extracts were tested in microglia (BV-2) and cardiomyocyte (HL-1) cell lines to study their biological effects. The principal ingredients in black currant and cranberry extract–delphinidin 3-rutinoside (D3R) and cyanidin 3-glucoside (C3G), were also assessed. A menadione-induced oxidative stressor was used, and its output was quantified to detect oxidative stress (CellROX^TM). Black currant extract had similar antioxidant effects as N-acetylcysteine (NAC) in HL-1 cells with regard to cellular protection, whereas cranberry extract was ineffective. In contrast, cranberry extract was comparable in effectiveness to black currant extract in BV-2 cells. D3R and C3G also reduced oxidative stress similarly to whole berry extracts, which indicates that these ingredients may confer the antioxidant effects of berries. Black currant and cranberry extracts inhibit oxidative stress in microglial and cardiomyocyte cell lines. Black currant extract was more effective in reducing oxidative stress in the HL-1 cells, whereas cranberry extract was comparable in reducing oxidative stress in the BV-2 cells. The results suggest that berry flavonoids exert neuro- and cardioprotective effects.     

Multicomponent pervaporation process for volatile aroma compounds recovery from pomegranate juice

The present work describes the possibility of using pervaporation process to recover the pomegranate aroma compounds from an actual pomegranate juice and a model aroma solution. Four different chemicals representing four major kinds of aroma compounds, namely, 3-methyl butanal, isopentyl acetate, n-hexanol and α-ionone, were utilized in this work. Three POMS membranes and two PDMS membranes were tested for pervaporation and compared for their separation performance. The influence of various operating parameters such as feed flow rate, feed temperature and permeate pressure on the permeation flux and aroma compounds enrichment factor was investigated. Feed flow rate was shown to have no significant effect on both total flux and aroma enrichment factor, whereas feed temperature and permeate pressure had highly significant effects. An increase in feed temperature led to higher flux and enrichment factor. As permeate pressure increased, the flux and enrichment factor of some aroma compounds decreased. Some of the aroma compounds showed higher enrichment factor at higher permeate pressures. Finally, the activation energy of permeation and the membrane permeability for each aroma compound were determined.     

Permeation of gases through microporous silica hollow-fiber membranes: Application of the transition-site model

In a previous paper [P. Molyneux, “Transition-site” model for the permeation of gases and vapors through compact films of polymers, J. Appl. Polym. Sci. 79 (2001) 981–1024] a transition-site model (TSM) for the activated permeation of gases through compact amorphous solids was developed and applied to organic polymers; the present paper examines the applicability of the TSM to permeation through microporous silica. The basis of the TSM theory for amorphous solids in general is outlined; the present extension to inorganic glasses has revealed that the transition sites (TS) of this theory, which are the three-dimensional saddle-points critical in the molecular sieving action, equate to the doorways long recognized in permeation through amorphous silica and other inorganic glasses. The TSM, which views permeation as a primary process, is contrasted with the conventional sorption–diffusion model (SDM) for permeation. It is pointed out that in the SDM, the widely accepted analysis into two apparently distinct factors – sorption (equilibrium) and diffusion (kinetic) – has the fundamental flaw that these factors are not independent, since both involve the sorbed state. By contrast, the TSM focuses on the permeant molecule in only two states: as the free gas, and as inserted in a doorway D; hence the characteristics of these doorways – (unperturbed) diameter σ_D, spacing λ, and the thermodynamic parameters θ (force constant) and ν (entropy increment) for the insertion process – can be evaluated. The theory is applied to literature data [J.D. Way, D.L. Roberts, Hollow fiber inorganic membranes for gas separations, Sep. Sci. Technol. 27 (1992) 29–41; J.D. Way, A mechanistic study of molecular sieving inorganic membranes for gas separations, Final Report submitted to U.S. Department of Energy under contract DE-FG06-92-ER14290, Colorado School of Mines, Golden, CO, 1993, www.osti.gov/bridge/servlets/purl/10118702-ZAx4Au/native/1011872.pdf; M.H. Hassan, J.D. Way, P.M. Thoen, A.C. Dillon, Single component and mixed gas transport in silica hollow fiber membrane, J. Membr. Sci. 104 (1995) 27–42] on the permeation through microporous silica hollow-fiber membranes (developed by PPG Industries Inc.) of the nine gases: Ar, He, H₂, N₂, O₂, CO, CO₂, CH₄ and C₂H₄, over the temperature range 25–200 °C. The derived Arrhenius parameters for the permeation of these gases (excepting He) lead to estimates of the four doorway-parameters: σ_D, 125 pm; λ, ca. 30 nm; θ, 0.43 nN; ν, 1.7 pN K⁻¹; these values lie within the ranges of those obtained with the glassy organic polymers. Some “secondary effects”, shown particularly by CO and CO₂, are interpreted as host–guest interactions at the doorway. The behavior of He is anomalous, the permeation rising linearly with temperature. This study confirms that the TSM may be applied to gas permeation by activated molecular sieving for this type of inorganic membrane.     

The Impact of Type of Brandy on the Volatile Aroma Compounds and Sensory Properties of Grape Brandy in Montenegro

This paper presents the results of a study that examined the impact of grape variety on the volatile aroma compounds and sensory properties of standard and Muscat grape brandy produced in the Podgorica sub-region (Montenegro) in vintages 2011, 2012, and 2013. The brandies were prepared by the distillation of crushed grapes, from the autochthonous varieties of Vranac and Kratošija, and Muscat grapes, in a traditional copper alembic, under the same conditions. The gas chromatographic-mass spectrometric (GC/MS) method of 82 volatile aroma compounds that belong to the group (alcohols, volatile acids, volatile esters, terpenes, volatile aldehydes, acetals, ethers, ketones, and alkanes) and an evaluation of the sensory properties of brandies were carried out to determine the typical characteristics of the examined brandies. Alcohols, fatty acid esters, and terpene compound contents were significantly more abundant in all Muscat grape brandies compared to the brandies from the Vranac and Kratošija wine varieties (Standard brandy). Research results revealed that variety had a significant impact on the volatile aroma compound and sensory properties of brandy. The varietal effect was also confirmed, by multivariate analysis, based on the aroma volatile composition, which showed a grouping by type of grape brandy (varietal origin). Sensory analyses showed that all the brandies belonged to the category of high-quality brandies.     

Characterization of aroma active compounds in fruit juice and peel oil of Jinchen sweet orange fruit (Citrus sinensis (L.) Osbeck) by GC-MS and GC-O

Gas chromatography-mass spectrometry (GC-MS) and gas chromatography-olfactometry (GC-O) were used to determine the aromatic composition and aroma active compounds of fruit juice and peel oil of Jinchen sweet orange fruit. Totals of 49 and 32 compounds were identified in fruit juice and peel oil, respectively. GC-O was performed to study the aromatic profile of Jinchen fruit juice and peel oil. A total of 41 components appeared to contribute to the aroma of fruit juice and peel oil. Twelve components were the odorants perceived in both samples. The aromatic compositions of fruit juice were more complex than that of peel oil. Ethyl butanoate, beta-myrcene, octanal, linalool, alpha-pinene, and decanal were found to be responsible for the aromatic notes in fruit juice and peel oil. Nineteen components have been perceived only in the juice and ten compounds were described as aromatic components of only the peel oil by the panelists. These differences lead to the different overall aroma between fruit juice and peel oil.     

Physicochemical and Quality Properties of Dried Courgette Slices: Impact of Vacuum Impregnation and Drying Methods

The aim of this study was to determine the effects that the type of impregnating solution and drying method (freeze drying (FD) and vacuum drying (VD) at 45 °C and convective drying (CD) at 50, 60, and 70 °C) had on the physicochemical and quality properties of courgettes. Courgette slices were vacuum-impregnated (6 kPa) in freshly squeezed onion, kale, and onion and kale (50:50) juices with 3% NaCl solution (N). The application of vacuum impregnation (VI) with impregnating solutions from freshly squeezed onions and kale had a beneficial effect on the bioactive values of courgette. The highest contents of quercetin (41.84 μg/g d.m.) and carotenoids (276.04 μg/g d.m.) were found in courgette impregnated with onion juice after freeze drying. The highest values of lutein and zeaxanthin (216.42 μg/g d.m.) were recorded for courgette impregnated with kale juice and convective dried. By analysing the kinetics of convective drying, the best matching of the logistic model was found. Increasing the drying process temperature from 50 to 70 °C reduced the drying time from 15% to 36%, depending on the type of impregnating solution used. Water activity < 0.6 was recorded for courgette dried by freezing, vacuum, and convection at 60 and 70 °C. Conclusions: The vacuum impregnation process and the impregnation solutions from freshly squeezed vegetables can be used to develop new snacks with high levels of bioactive compounds. The FD method is the most appropriate considering both the bioactive compounds content and the obtained colour and water activity.     

The effects of pH and calcium on the diffusion coefficient of humic acid

Humic acid is a major component of natural organic matter in surface water and can cause serious fouling problems in membrane filtration processes for drinking water treatment. The transport of humic acid to the membrane surface and within membrane pores is related to its diffusivity. Thus, the diffusion coefficient of humic acid is an important mass transport parameter. Clark and Lucas [J. Membr. Sci. 143 (1998) 13–25] studied the diffusion and partitioning of humic acid into a porous ultrafiltration membrane and developed a model to predict how humic acid diffusivity changes under different pH and calcium concentration conditions. In this work, the diffusion coefficient of humic acid was directly measured and compared to the predictions of the Clark and Lucas model. The experiments were conducted in a two-chamber diffusion cell separated by a track-etched membrane. The results show that the diffusivity of humic acid increases with decreasing pH and increasing calcium concentration, which can be explained by the compaction of humic acid molecules at low pH and high ionic strength. The experimental measurements strongly support the predictions of the Clark and Lucas model.     

Isolation methods for the volatile components of grapefruit juice. Distillation and solvent extraction methods

Summary Five different methods including solvent extraction, distillation and simultaneous distillation-solvent extraction (SDE) have been compared for the isolation of the volatile components of grapefruit juice. The search for an adequare procedure was directed to obtaining aroma concentrates with an odour resembling that of the original grapefruit juice. The methods have also been compared in terms of some experimental parameters. The concentrates have been analyzed by fused-silica, capillary gas chromatography and the GC patterns have been compared in terms of the recovery efficiencies for high-, medium-, and low-volatility components. The SDE methods gave the best results, particularly when using the apparatus proposed by Godefrootet al.