Transfer of aroma compounds through the lipidic-aqueous interface in a complex system

The transfer kinetics of aroma compounds from the aqueous phase to the lipidic phase (miglyol) and from miglyol to the aqueous phase have been studied in the presence or absence of a protein, beta-lactoglobulin, and at different pH values. In the presence of beta-lactoglobulin, the transfer at the interface from the aqueous to the lipidic phase decreases, with a greater effect of the presence of the protein at pH 3 than at pH 6. This barrier effect of the protein plays a role in the transfer of the aroma compounds between the different phases of the matrix.     

Two-resistance mass transport model for the adsorption of dyes of Fuller's earth

A mass transfer model has been developed to describe the rate of adsorption of dyestuffs from aqueous solutions onto adsorbents, namely, Fuller's earth, silica, activated C and fired clay. The model is based on external film mass transfer and solid phase internal diffusion. A computer program has been used to obtain the values of the two mass transfer parameters for each dye/adsorbent system.     

Environmental fate of petroleum hydrocarbons in soil: Review of multiphase transport, mass transfer, and natural attenuation processes

The increasing use of petroleum-derived fuels over the last few decades has subsequently augmented the risk of spills in the environment. Soil pollution with petroleum hydrocarbons (principally caused by leaks in pipelines and underground storage tanks) is one of the major sources of soil degradation. Once in soil, fuel hydrocarbons suffer from a wide variety of multiphase processes including transport (advection, diffusion, and dispersion) among and within phases (aqueous and non-aqueous liquid, gas, and soil solids), mass transfer among phases (volatilization, sorption, and solution), and other natural attenuation processes, such as biodegradation and plant uptake and metabolism. This review identifies and describes the major processes occurring in soil that have a significant influence on the environmental fate of petroleum hydrocarbons. The definition of the processes involved in pollutant migration and distribution in soil and the formulation of adequate equations using accurate parameters (e.g., diffusion coefficients, velocity of advective flows, and mass transfer coefficients) will allow prediction of the final fate of soil pollutants. In addition to transport and mass transfer processes, which are more widely studied, the incorporation of attenuation mechanisms driven by microorganisms and plants is essential to predict the final concentration of the pollutants in the whole multiphase scenario. This work underlines the importance of the determination of accurate parameters through the performance of laboratory and/or field-scale experiments to develop precise pollutant migration models.     

反胶束萃取大豆蛋白反萃取过程的动力学研究

该文通过系统地研究影响总传质系数的各个主要因素（水相pH值、离子强度，初始有机相中蛋白质浓度、振荡速度和反萃取温度）,探讨了以丁二酸二异辛酯磺酸钠(AOT)/异辛烷反胶束体系反萃取大豆蛋白的动力学。结果表明，大豆蛋白反萃取过程中总传质系数，随着反萃取水相的pH值和温度的升高而增大；随着离子强度的增大而先增大后减小；随着振荡速度和初始有机相中蛋白质浓度的增大而几乎不变。说明在反萃取过程中，大豆蛋白在有机相和水相两相内的扩散阻力可以忽略，界面阻力是传质过程中的主要阻力。由此推断出大豆蛋白的反萃取过程属于界面控制类型，“满胶束”在界面上的聚结过程是反萃取的速率控制步骤。通过研究，深入了解了大豆蛋白反萃取过程的机理，可有效地控制和强化萃取过程，提高萃取率，为今后的研究提供可靠的基础数据和理论依据。     

Influence of competitive adsorption on flocculation and rheology of high-pressure-treated milk protein-stabilized emulsions

The effect of high-pressure treatment (HPT) on the droplet-size distribution and small-deformation rheology of oil-in-water emulsions containing beta-lactoglobulin and a nonionic surfactant or sodium caseinate has been investigated at neutral pH. Addition of Tween 20 (polyoxyethylenesorbitan monolaurate) to a beta-lactoglobulin-stabilized emulsion results in competitive displacement of the adsorbed globular protein film and, following HPT, the formation of a less flocculated emulsion. The age of the beta-lactoglobulin-stabilized emulsion prior to addition of sodium caseinate influences the competitive adsorption behavior. The strengthening of the beta-lactoglobulin layer with time makes it more resistant to disruption by sodium caseinate. The level of pressure-induced flocculation of beta-lactoglobulin-coated oil droplets depends on the intensity of processing conditions and on the degree of interfacial displacement. In contrast, beta-lactoglobulin added after emulsification appears to show little evidence of competitive adsorption behavior at the caseinate oil-water interface. Changes in the rheological properties of these latter systems following HPT can be attributed to pressure-induced denaturation and gelation of beta-lactoglobulin in the continuous phase of the emulsion.     

Physical and oxidative stability of fish oil-in-water emulsions stabilized with beta-lactoglobulin and pectin

The oxidation of fatty acids can be inhibited by engineering the surface of oil-in-water emulsion droplets to decrease interactions between aqueous phase prooxidants and lipids. The objective of this research was to evaluate whether emulsions stabilized by a multilayer emulsifier systems consisting of beta-lactoglobulin and citrus or sugar beet pectin could produce fish oil-in-water emulsions that had good physical and oxidative stability. Sugar beet pectin was compared to citrus pectin because the sugar beet pectin contains the known antioxidant, ferulic acid. A primary Menhaden oil-in-water emulsion was prepared with beta-lactoglobulin upon which the pectins were electrostatically deposited at pH 3.5. Emulsions prepared with 1% oil, 0.05% beta-lactoglobulin, and 0.06% pectins were physically stable for up to 16 days. As determined by monitoring lipid hydroperoxide and headspace propanal formation, emulsions prepared with the multilayer system of beta-lactoglobulin and citrus pectin were more stable than emulsions stabilized with beta-lactoglobulin alone. Emulsions prepared with the multilayer system of beta-lactoglobulin and sugar beet pectin were less stable than emulsions stabilized with beta-lactoglobulin alone despite the presence of ferulic acid in the sugar beet pectin. The lower oxidative stability of the emulsions with the sugar beet pectin could be due to its higher iron and copper concentrations which would produce oxidative stress that would overcome the antioxidant capacity of ferulic acid. These data suggest that the oxidative stability of oil-in-water emulsions containing omega-3 fatty acids could be improved by the use of multilayer emulsion systems containing pectins with low metal concentrations.     

As(III) removal from aqueous solution by adsorption

The removal of As(III) from aqueous solutions at different concentrations, pH and temperatures by haematite has been carried out successfully. The maximum removal was found to be 96 % at concentration 13.34 μmol L^?1, temperature 20 °C and pH 7.0. The process of uptake follows first-order adsorption rate expression and obeys the Langmuir's model of adsorption. The removal of As(III) by haematite is also partially diffusion controlled and mass transfer coefficients, diffusion coefficients and thermodynamic parameters have been determined to explain the results.     

Improved oil solubilization in oil/water food grade microemulsions in the presence of polyols and ethanol

Microemulsions based on five-component mixtures for food applications and improved oil solubilization have been studied. The compositions included water, oil phase [such as R(+)-limonene and medium-chain triglycerides (MCT)], short-chain alcohols (such as ethanol), polyols (propylene glycol and glycerol), and several surfactants and their corresponding mixtures (nonionic, such as ethoxylated sorbitan esters, polyglycerol esters, sugar ester, and anionic, such as phosphatidylcholine). The phase behavior of these systems is discussed with respect to the influence of polyols and short-chain alcohols on the degree of solubilization of oils in the aqueous phase. The alcohol and polyols modify the interfacial spontaneous curvature and the flexibility of the surfactant film, enhancing the oil solubilization capacity of the microemulsions. The solubilization of R(+)-limonene was dramatically improved in the presence of the alcohol and polyols, whereas the improvement of solubilization for triglycerides containing MCT was less pronounced. In some systems high oil solubilization was achieved, and some of them can be easily diluted to infinity both with the aqueous phase and with the oil phase. Viscosity measurements along selected dilution lines [characterized by a single continuous microemulsion region starting from a pseudo binary solution (surfactant/oil phase) to the microemulsion (water/polyol corner)] indicate that at a certain composition the system inverts from a W/O to an O/W microemulsion.     

Enhancement of the foaming properties of protein dried in the presence of trehalose

Surface tension, foamability, and foam stability kinetics have been measured for the pure proteins bovine serum albumin (BSA) and beta-lactoglobulin, before and after aqueous solutions of the proteins had been subjected to different drying conditions, and also for whey protein concentrate (WPC). Pure proteins were air-dried, at 78 or 88 degrees C, in the presence and absence of sucrose or trehalose, at a mass ratio of 5:1 sugar/protein. WPC was spray-dried in the presence of various sugars: trehalose, sucrose, lactose, and lactitol. Spray-drying WPC without sugars resulted in a dramatic decrease in the foam stability, whereas drying in the presence of sugars gave better retention of the original foaming properties. Trehalose in particular resulted in almost complete retention of the foam stability observed for the nondried WPC. Pure beta-lactoglobulin showed similar behavior, but trehalose did not seem to afford the same protection to BSA.     

Characterization of the antioxidant activity of sugars and polyhydric alcohols in fish oil emulsions

Polyols have been incorporated into fish oil emulsions as a means for the inhibition of lipid oxidation and suppression of fishy flavor. However, the role of sugars and polyhydric alcohols as antioxidants has not been clearly established. Selected polyols were evaluated for their performance as antioxidants and modifiers of oxidation pathways in a model system. Oil/water (O/W) emulsions were prepared with freshly steam-deodorized menhaden oil. A layer of emulsion in aluminum pans held at 5 degrees C was exposed to 2550 lx fluorescent lights for 24 h before peroxide values and volatile flavor compounds were analyzed by GC headspace entrainment procedure. Antioxidant activity was confirmed for fructose, sucrose, raffinose, sorbitol, or mannitol when incorporated at 16% of the aqueous phase into model fish oil-in-water emulsions. Peroxide values were suppressed 10-18% in treated samples compared to control samples. Viscosity data did not exclude possible contributions from a restricted oxygen diffusion mechanism in the antioxidant activity, but revealed that emulsion viscosity did not govern fish oil oxidation rates. Combining polyols with phenolic antioxidants (alpha-tocopherol, BHT, or TBHQ) frequently diminished the antioxidant activity compared to that for individual phenolic antioxidants, which was interpreted as indicating that the H-donating activity of phenolic antioxidants was hindered by the H-bonding activity of polyols. A viscosity-based inhibition of the retroaldol conversion of (E,Z)-2,6-nonadienal to (Z)-4-heptenal with a high fructose concentration (67%) was attributed to a restriction of molecular mobility of reactants, but the conversion was only slightly inhibited by the concentration of fructose (16%) used in experimental emulsions. The data supported a hypothesis that either or both free radical scavenging and transition state metal chelation activities were provided by polyols in fish oil emulsions. Also, polyols retarded the water-requiring retroaldol decomposition of (E,Z)-2,6-nonadienal to (Z)-4-heptenal in the model systems and the reaction may be involved in some suppression of fishy flavors in emulsions.     

Investigation of the lactosylation of whey proteins by liquid chromatography-mass spectrometry

Heat treatment of milk induces a reaction between the milk proteins and lactose, resulting in lactosylated protein species. The lactosylation of the two major whey proteins alpha-lactalbumin and beta-lactoglobulin was investigated by reversed phase liquid chromatography-mass spectrometry (LC-MS). Three sample series, consisting of aqueous model solutions of each whey protein separately and in mixture and whole milk, were heated for different time periods, and the progression of the lactosylation reaction was monitored. The observed degrees of lactosylation and the reaction kinetics showed that the lactosylation of beta-lactoglobulin was not influenced by the presence of other components, whereas the lactosylation of alpha-lactalbumin was enhanced in whole milk compared to the aqueous model systems. An in-depth evaluation of the LC-MS data yielded information regarding changes of physicochemical properties of the whey proteins upon lactosylation. Whereas retention time shifts indicated changes in hydrophobicity for both alpha-lactalbumin and beta-lactoglobulin, changes in the charge state distribution denoting conformational alterations were observed only for beta-lactoglobulin. The analysis of different liquid and solid milk products showed that the lactosylation patterns of the whey proteins can be used as indicators for the extent of heat treatment.     

Desorption of Dieldrin from field aged sediments: Simulating flood events

Background, Aim and Scope

With the predicted climate change, it is expected that the chances of flooding may increase. During flood events, sediments will resuspend and when the sediments are polluted, contaminants can be transferred to the surrounding water. Mass transfer of organic compounds like Persistent Organic Pollutants (POPs) from soils and sediments to the surrounding aqueous phase are essential regarding fate and transport of these chemicals in the aqueous environment. The distribution of POPs between sorbed and aqueous phases and the time needed to obtain equilibrium are required to calculate the exposure to potential receptors. A reactor was designed in which the water flow is controlled and low POP concentrations could be measured by tenax extraction outside the reactor vessel. This reactor design named SPEED (Solid Phase Extraction with External Desorption) was used to study desorption from aged contaminated sediment in relation to sediment particle size.

Materials and Methods

In the newly developed SPEED (Solid Phase Extraction with External Desorption) reactor, the water flow rate was set and controlled, and low aqueous POP concentrations were measured by sorption to Tenax® outside the reaction vessel. The effect of particle size on desorption rate was studied using a widely used Tenax® solid phase extraction method.

Results

The experiments, by specific measurement of the aqueous dieldrin concentration at different HRT, show that desorption of dieldrin in time is faster when short HRTs were applied. However, the mass of dieldrin desorbed per liter refreshed water is higher for longer HRTs. Therefore, the mass transfer of dieldrin within the sediment particles is the rate determining process in contaminant desorption. This observation was confirmed by Tenax® solid phase extractions which were applied for different particle size fractions. Desorption rates of POPs from the sediment fraction with small particles were faster than desorption rates from the sediment fraction with large particles. Organic matter was present as separate particles in the sediment sample. All experiments demonstrated biphasic desorption. The fluxes calculated for both phases are supportive of non-stationary diffusion as the main process of mass transfer.

Discussion

In the literature, the relation between particle size and desorption of organic contaminants from soils and sediments is contradictory. Most often this seems to be due to overlooking the spatial configuration of organic matter in the soils and sediments. In several papers the presence of organic matter as a thin coating around mineral particles has been overlooked. There-fore, milling had no effect on desorption behavior of contaminants, as the diffusion length will not be affected. In our opinion, both the particle size and spatial configuration of organic matter are rate determining parameters of the desorption process.

Conclusions

Flood events will result in an increase of desorption rate of POPs from sediments to the surrounding water. HRT and particle size determine the concentration gradient and, thereby, the desorption rate. Furthermore, the diffusion length will be smaller when sediment particles are suspended and more water is present to decrease the aqueous concentration. We conclude that non-stationary diffusion within organic matter is the main process of mass transfer. The combination of simulated in-situ measurements of desorption from sediments with generic measurable parameters like flow rate and particle size distribution results in a quantitative measurable flux of contaminants, which resembles the in-situ (bio)availability as the result of dynamic processes in the sediment/water system.

Recommendations and Perspectives

The results obtained provided a sound basis for mechanistic modeling of POP mass transfer from sediment to water. The modeling results will be presented in a separate paper. Besides the HRT, also mixing conditions can be changed to assess the desorption from sediment layers. The possibility to combine flow rate and mixing intensity enables the study of the effect of hydraulically different river systems on desorption of contaminants. In a long term perspective we foresee a link with hydrology and sediment transport with desorption in water bodies.     

Retronasal transport of aroma compounds

A comparison was made between the amounts of volatiles in the headspace above a solution and the breath volatile content (exhaled from the nose or mouth) after consumption of the same solution. The amounts of volatiles in the breath were lower than those in the headspace, with breath exhaled via the mouth containing, on average, 8-fold more volatiles than breath exhaled via the nose. Dilution of the sample by saliva in-mouth did not appear to be a major factor affecting volatile delivery. Instead, the rate of in vivo equilibration (mass transfer) appeared to be the most significant factor, principally affecting volatile delivery from the solution to the gas phase. Thereafter, gas-phase dilution of the volatile as it passed through the upper airway resulted in a further decrease in volatile concentration. The final factor affecting the volatile concentration exhaled from the nose was absorption of volatiles to the nasal epithelia, which was greatest for those compounds with the lowest air/water partition coefficients.     

Spectrofluorometric characterization of beta-lactoglobulin B covalently labeled with 2-(4'-maleimidylanilino)naphthalene-6-sulfonate.

Bovine beta-lactoglobulin, genetic variant B, has been labeled with 2-(4'-maleimidylanilino)naphthalene-6-sulfonic acid through covalent attachment through the Cys-121 thiol group for the study of stepwise pressure denaturation of this whey protein by fluorescence spectroscopy. The labeling was performed under nondenaturing conditions with a factor of 5 excess of the fluorophore in dimethylformamide/water (1:10) to yield the whey protein highly labeled after chromatographic separation. MALDI-TOF mass spectroscopy confirmed labeling. The emission from the fluorophore, which is sensitive to the microenvironment, has been characterized for the labeled protein (aqueous pH 7.4 solution, 25 degrees C) and has a lambda(em,max) = 410 nm (lambda(ex,max) = 318 nm) with a fluorescence lifetime of 6.1 +/- 0.2 ns. Fluorescence anisotropy increases and fluorescence quantum yield (Phi(f) = 0.103 at 320 nm) decreases with increasing excitation wavelength. For increasing hydrostatic pressure, fluorescence quantum yield showed a minimum at approximately 50 MPa, corresponding to the pre-denatured "pressure-melted" state in which thiol reactivity previously was found to increase prior to reversible protein unfolding.     

On Morphometric Properties of DNAPL Sources: Relating Architecture to Mass Reduction

The fundamental step in the identification of the most appropriate strategy for the remediation of sites contaminated with dense nonaqueous phase liquids (DNAPLs) is a comprehensive characterization of the contaminated source region as the morphology of DNAPL strongly governs the mass transfer processes. The influence of DNAPL distribution geometry and groundwater flow velocity on mass reduction was explored through the evaluation of a series of laboratory studies conducted in a two-dimensional tank under different hydrodynamic conditions. An image analysis procedure was used to determine the distribution of DNAPL saturation and the morphology of the contaminated region. Experimental observations revealed a dependence of mass transfer rate on the aqueous phase velocity under high flow regimes, whereas the mass transfer rate was controlled mainly by morphometric indexes under low velocity flow conditions. Experimental results indicate that higher mass reduction and contaminant fluxes are obtained at low saturation values. The mass flux emanating from an elongated source aligned perpendicularly to the direction of water flow is greater due to a higher DNAPL?Cwater contact surface in comparison to a lower mass flux from horizontal pools with high saturation. These aspects should be considered in an inverse modeling technique for locating the source zone and also in all remediation approaches based on an increase in water circulation through a contaminated zone (i.e., pump and treat).     

乙醇水溶液提取玉米胚芽油的工艺优化

为了解决水酶法提取玉米胚芽油生产成本高、提取时间长的缺点,该文采用乙醇水溶液作为提取剂提取玉米胚芽油。通过对粒径、料液比、温度、乙醇体积分数、p H值和时间等条件对油在油相、水相和渣相中分布的研究发现,物料粒径和乙醇体积分数对提高清油得率具有显著(P0.05)的影响,而提取时间对清油得率的影响最小(P0.05)。在单因素试验的基础上通过正交试验,得出乙醇水溶液提取玉米胚芽油的最佳工艺参数为:物料细粉4次(此时粒径为49.18μm)、料液比1∶7 g/m L、温度70℃、乙醇体积分数30%、p H值9.0、提取时间2 h。在该条件下,清油的得率为94.05%±0.32%,水相含油量为3.49%±0.77%,渣相含油量为2.55%±0.82%。分析乙醇水溶液提取的玉米胚芽毛油酸价、过氧化值和含水率等指标发现,该毛油的质量优于国标规定的玉米原油,并且和压榨一级成品油指标接近,只需要经过简单精炼就可以达到食用油要求。研究结果为乙醇水溶液工业化生产玉米胚芽油提供参考。     

Influence of the addition of rosemary essential oil on the volatiles pattern of porcine frankfurters

The effect of the addition of increasing levels of rosemary essential oil (150, 300, and 600 mg/kg) on the generation of volatile compounds in frankfurters from Iberian and white pigs was analyzed using solid-phase microextraction coupled to gas chromatography and mass spectrometry (SPME-GC-MS). Lipid-derived volatiles such as aldehydes (hexanal, octanal, nonanal) and alcohols (pentan-1-ol, hexan-1-ol, oct-1-en-3-ol) were the most abundant compounds in the headspace (HS) of porcine frankfurters. Frankfurters from different pig breeds presented different volatile profiles due to their different oxidation susceptibilities as a likely result of their fatty acid composition and vitamin E content. Rosemary essential oil showed a different effect on the generation of volatiles depending on the type of frankfurter in which they were added. In frankfurters from Iberian pigs, the antioxidant effect of the essential oil improved with increasing levels, showing the highest activity at 600 mg/kg. In contrast, 150 mg/kg of the essential oil improved the oxidative stability of frankfurters from white pigs, whereas higher levels led to no effect or a prooxidant effect. The activity of the essential oil could have been affected by the different fatty acid compositions and vitamin E contents between types of frankfurters. SPME successfully allowed the isolation and analysis of volatile terpenes from frankfurters with added rosemary essential oil including alpha-pinene, beta-myrcene, l-limonene, (E)-caryophyllene, linalool, camphor, and 1,8-cineole, which might contribute to the aroma characteristics of frankfurters.     

Monoterpene composition of essential oil from peppermint (Mentha x piperita L.) with regard to leaf position using solid-phase microextraction and gas chromatography/mass spectrometry analysis.

Monoterpene compounds of leaf pairs and flowers of Mentha x piperita have been studied by direct headspace sampling using solid-phase microextraction coupled with gas chromatography/mass spectrometry (SPME-GC/MS). The content of peppermint-characteristic compounds such as menthol, menthyl acetate, and neomenthol increased in a basipetal direction (older plant parts), whereas menthone and isomenthone showed higher levels in the acropetal direction (younger plant parts). Higher levels of menthofuran were found in peppermint flowers in contrast to the leaves. SPME sampling resulted in relatively higher amounts of high-volatile monoterpenes and lower detection of less volatile compounds such as menthol and menthone, compared to solvent-based samples from essential oil distillation.