Electrochemical oxidation of hydrophobic compounds in aqueous micellar solutions and oil-in-water emulsions

The electrochemical oxidation of ferrocene (Fc) and tetrathiofulvalene (TTF) has been investigated in micelles and dodecane-in-water emulsions in order to compare the diffusional process involved in these systems. It is found that the diffusion coefficients of Fc and TTF, determined from the observed limiting currents at the rotating disc electrode, are governed by the solubilization equilibrium of the neutral substrates which are predominantly solubilized in the micelle or oil-droplet phase. In the emulsion, the cyclic voltammograms show that the current is controlled also by the rate constants of the substrate partition, which depend on the size of the emulsion droplets. The determination of the diffusion coefficients of Fc⁺ and TTF⁺, produced in situ by controlled potential electrolysis, showed that, except in SDS micellar solutions, the monocation radicals are solubilized mainly in the aqueous phase. As a result, the diffusion coefficients of the species involved in the redox system are different. In the case of TTF, the above results have a great influence upon the second oxidation step TTF⁺ → TTF²⁺. Indeed, the homogeneous solution reaction between TTF and the electrogenerated dication TTF²⁺ leads to the monocation TTF⁺ which diffuses more rapidly than its parent molecule TTF. The ratios of the two waves in cyclic and rotating disc electrode voltammetry show that the enhancement of the second wave depends mainly on the difference between the diffusion coefficients of TTF and TTF⁺ and that the nature of the solution or the size of the disperse phase has little influence upon the reaction rate of the homogeneous solution reaction.     

Thermal properties of new varieties of yam starches

Starches isolated from yam varieties of Dioscorea alata and Dioscorea cayenensis‐rotundata species were prepared at different time–temperature conditions and characterised by DSC, amperometric iodine titration, light microscopy and rheology and compared to native and chemical modified tapioca starches. The observation by light microscopy showed different morphologies of the granules when heated above 100°C and the tendency for disintegration decreased in the order native tapioca starch > yam starch > modified tapioca starch. Differences between yam and tapioca starches were also revealed by DSC. Yam starch enthalpy is higher than tapioca starch, but the peak temperature is low. However, the significant differences between yam and the other tested starches were found in terms of their rheological behaviour. The viscosity of yam starch was very stable at high temperatures on the viscograph. With this property, yam starch can be used as thickening and gelling agent in food.     

Extreme catalysts from low-temperature environments

Cold-loving or psychrophilic organisms are widely distributed in nature as a large part of the earth's surface is at temperatures around 0 degrees C. To maintain metabolic rates and to prosper in cold environments, these extremophilic organisms have developed a vast array of adaptations. One main adaptive strategy developed in order to cope with the reduction of chemical reaction rates induced by low temperatures is the synthesis of cold-adapted or psychrophilic enzymes. These enzymes are characterized by a high catalytic activity at low temperatures associated with a low thermal stability. A study of protein adaptation strategies suggests that the high activity of psychrophilic enzymes could be achieved by the destabilization of the active site, allowing the catalytic center to be more flexible at low temperatures, whereas other protein regions may be destabilized or as rigid as their mesophilic counterparts. Due to these particular properties, psychrophilic enzymes offer a high potential not only for fundamental research but also for biotechnological applications.     

Hydrogen isotopic enrichment: an indicator of biodegradation at a petroleum hydrocarbon contaminated field site

Compound-specific carbon and hydrogen isotope analysis was used to investigate biodegradation of benzene and ethylbenzene in contaminated groundwater at Dow Benelux BV industrial site. delta13C values for dissolved benzene and ethylbenzene in downgradient samples were enriched by up to 2+/-0.5 per thousand, in 13C, compared to the delta13C value of the source area samples. delta2H values for dissolved benzene and ethylbenzene in downgradient samples exhibited larger isotopic enrichments of up to 27+/-5 per thousand for benzene and up to 50+/-5 per thousand for ethylbenzene relative to the source area. The observed carbon and hydrogen isotopic fractionation in downgradient samples provides evidence of biodegradation of both benzene and ethylbenzene within the study area at Dow Benelux BV. The estimated extents of biodegradation of benzene derived from carbon and hydrogen isotopic compositions for each sample are in agreement, supporting the conclusion that biodegradation is the primary control on the observed differences in carbon and hydrogen isotope values. Combined carbon and hydrogen isotope analyses provides the ability to compare biodegradation in the field based on two different parameters, and hence provides a stronger basis for assessment of biodegradation of petroleum hydrocarbon contaminants.     

Nanofiltration for the recovery of caustic cleaning-in-place solutions: robustness towards large variations of composition

In the dairy industry re-use and multi-use cleaning-in-place (CIP) systems are operated by circulating chemicals and water without taking the equipment apart. The solutions, which become polluted due to the removal of fouling compounds, are drained periodically when they are considered to be too polluted. This work shows the large variations in composition (pollution, surface tension, etc) of the industrial caustic solutions coming from milk standardization and pasteurization plant CIP throughout their life time (7 days) and from 1 week to another. The work is also intended to show how nanofiltration (1 kg mol(-1) molecular weight cut-off) was robust and performed well, with good recovery of caustic solutions, even when faced with large variations of solutions composition: high caustic yield, permeation flux (J) in the range 42-110 l h(-1) m(-2), average chemical oxygen demand (COD) reduction equal to 0.58 and low surface tension change. Equations have been established for the prediction of J as a function of initial membrane hydraulic resistance (Rm) caustic concentration, volume reduction ratio (VRR) and initial soluble COD. When VRR increased, both J and pollution retention decreased despite the increase in irreversible fouling induced by the increase of soluble pollution concentration in retentate. The higher the initial soluble COD, the sharper the decrease in J vs. VRR. Since irreversible fouling was usually small (0.1-3.4 x 10(13) m(-1), that is to say of the same order of magnitude as Rm), the membrane cleaning could be efficiently performed by using single phase sodium hypochlorite alternately with a more expensive acid-base cleaning sequence. The obtained permeate was a clear regenerated cleaning solution with low soluble COD (0.2-3.5 g/l) and surface tension (56-30 mJ m(-2)) which could be successfully exploited owing to its cleaning potential.     

A parametric investigation on seat/occupant contact forces and their relationship with initially perceived discomfort using a configurable seat

The present work investigates the contact forces between sitters and seat as well as their correlations with perceived discomfort. Twelve different economy class aeroplane seat configurations were simulated using a multi-adjustable experimental seat by varying seat pan and backrest angles, as well as seat pan compressed surface. Eighteen males and 18 females, selected by their body mass index and stature, tested these configurations for two sitting postures. Perceived discomfort was significantly affected by seat parameters and posture and correlated both with normal force distribution on the seat-pan surface and with normal forces at the lumbar and head supports. Lower discomfort ratings were obtained for more evenly distributed normal forces on the seat pan. Shear force at the seat pan surface was at its lowest when sitters were allowed to self-select their seat-pan angle, supporting that a shear force should be reduced but not zeroed to improve seating comfort.

Practitioner Summary: The effects of seat-pan and backrest angle, anthropometric dimensions and sitting posture on contact forces and perceived discomfort were investigated using a multi-adjustable experimental seat. In addition to preferred seat profile parameters, the present work provides quantitative guidelines on contact force requirement for improving seating comfort.     

Values of the mass transfer coefficient of the linear driving force model for VOC adsorption on activated carbons

Modelling of activated carbon cartridges is essential in personal protective equipments against toxic gases in order to know the duration of protection. The linear driving force model seems to be more adapted than the actual Wheeler–Jonas model because it has more physical significance. The difficulty is that the mass transfer coefficient can not be calculated a priori. Values of the LDF mass transfer coefficient are disseminated in the literature and thus there is no overview of the range and variations with different adsorbents, adsorbates and concentrations. The object of this paper is thus twofold: obtaining values of the mass transfer coefficient at different concentrations and adsorbates in order to have a comprehensive view of variations and appreciating the validity of the LDF constant pattern model.     

Distinctive arsenic(V) trapping modes by magnetite nanoparticles induced by different sorption processes

Arsenic sorption onto iron oxide spinels such as magnetite may contribute to arsenic immobilization at redox fronts in soils, sediments, and aquifers, as well as in putative remediation and water treatment technologies. We have investigated As(V) speciation resulting from different sorption processes on magnetite nanoparticles, including both adsorption and precipitation, using X-ray absorption fine structure (XAFS) spectroscopy and transmission electron microscopy (TEM). XAFS results suggest that AsO(4) tetrahedra form predominantly inner-sphere bidentate corner-sharing ((2)C) complexes and outer-sphere complexes on magnetite in the adsorption experiments. In the precipitation experiments, an increasing fraction of AsO(4) tetrahedra appears to be incorporated in clusters having a magnetite-like local structure with increasing As loading, the remaining fraction of As being adsorbed at the surface of magnetite particles. In the sample with the highest As loading (15.7 μmol/m(2)) XAFS data indicate that As(V) is fully incorporated in such clusters. Such processes help to explain the significantly higher arsenic uptake in precipitation samples compared to those generated in adsorption experiments. In addition, for the precipitation samples, TEM observations indicate the formation of amorphous coatings and small (~3 nm) nanoparticles associated with larger (~20-40 nm) magnetite nanoparticles, which are absent in the adsorption samples. These results suggest that As(V) could form complexes at the surfaces of the small nanoparticles and could be progressively incorporated in their structure with increasing As loading. These results provide some of the fundamental knowledge about As(V)-magnetite interactions that is essential for developing effective water treatment technologies for arsenic.     

Effect of B2O3 addition on structure and properties of Yb3+/Al3+/B3+-co-doped silica glasses

The homogeneous Yb³⁺/Al³⁺/B³⁺-co-doped silica glasses were prepared via a sol-gel method. The impact of B₂O₃ addition on the physical and optical properties and network structure was systematically studied. The network structure was investigated by the Fourier Transform Infrared (FT-IR), Raman spectra, and Solid State Nuclear Magnetic Resonance (SSNMR). Herein, B₂O₃ addition can continuously decrease the refractive index and density. When B₂O₃ is lower than 2 mol%, B₂O₃ addition can obviously decrease the scalar crystal field parameters, Yb³⁺ asymmetry degree, Yb³⁺ cross-sections, due to the generation of Yb–O–B bonds at the cost of partial Yb–O–Al/Si ones. When B₂O₃ is more than 2 mol%, FT-IR, Raman spectra, and SSNMR results indicate that further increased B atoms prefer to connect with Si and Al rather than Yb. Consequently, the above parameters are basically unchanged. Based on the results, an intuitive model of structure and properties evolution during the substitution of SiO₂ by B₂O₃ has been established.     

Ripening conditions: A tool for the control of Listeria monocytogenes in uncooked pressed type cheese

The effect of ripening conditions (two temperatures, 9 °C and 13 °C, and two relative humidities 93% and 97%) on the growth of Listeria monocytogenes and other microbial populations was evaluated in the cores and rinds of uncooked pressed type cheeses prepared with pasteurised milk and inoculated either with Streptococcus thermophilus only or with an anti-listerial consortium. Regardless of temperature and relative humidity (RH), inhibition by the anti-listerial consortium was stronger in the cheese cores than in the rinds. Temperature had no significant effect on L. monocytogenes counts in cores or rinds. However, at the beginning of ripening in the consortium cheese, L. monocytogenes growth was more strongly inhibited at 13 °C than at 9 °C. Regardless of inoculation type and ripening temperature, counts of L. monocytogenes were significantly lower in the cores and rinds of cheeses ripened at 93% than at 97% RH. Lactobacilli counts were higher at 13 °C than at 9 °C and at 93% than at 97% RH. Lactobacilli can help to inhibit L. monocytogenes by catabolising galactose and producing lactate. Further investigations will be needed to evaluate the effect of ripening at 13 °C and 93% RH on the sensorial properties of cheese.