Speciation of organotin compounds in waters and marine sediments using purge-and-trap capillary gas chromatography with atomic emission detection

A procedure for the simultaneous determination of six organotin compounds, including methyl-, butyl- and phenyltins, in waters and marine sediments is developed. The analytes were leached from the solid samples into an acetic acid:methanol mixture by using an ultrasonic probe. The organotins were derivatized with sodium tetraethylborate (NaBEt₄) in the aqueous phase, stripped by a flow of helium, pre-concentrated in a trap and thermally desorbed. This was followed by capillary gas chromatography with microwave-induced plasma atomic emission spectrometry as the detection system (GC-AED). Each chromatographic run took 22 min, including the purge time. Calibration curves were obtained by plotting peak area versus concentration and the correlation coefficients for linear calibration were at least 0.9991. Detection limits ranged from 11 to 50 ng Sn l⁻¹ for tributyltin and tetramethyltin, respectively. The seawater samples analyzed contained variable concentrations of mono-, di- and tributyl- and monophenyltin, ranging from 0.05 to 0.48 μg Sn l⁻¹, depending on the compound. Some of the sediments analyzed contained concentrations of dibutyl- and tributyltin of between 6.0 and 13.0 ng Sn g⁻¹. Analysis of the certified reference material PACS-2, as well as of spiked water and sediment samples showed the accuracy of the method. The proposed method is selective and reproducible, and is considered suitable for monitoring organotin compounds in water and sediment samples.     

Influence of postharvest ultrasounds treatments on tomato (Solanum lycopersicum,cv. Zinac) quality and microbial load during storage

Whole tomato fruits were treated at ultrasonic power levels from 10% to 100%, and at a constant frequency of 45 kHz, for different times (1–19 min). A central composite rotatable design (CCRD) was applied to optimise ultrasonic treatments for tomato quality (colour, texture and total phenolic content (TPC)) maintenance. According to response surface analysis, the optimal treatment parameters were 55%_10 min, 80%_15 min and 100%_19 min. At these conditions, and especially at higher power levels, a maximum retention of colour and texture, as well as an increase of TPC and microbial reduction were obtained in comparison with untreated fruits during 15 storage days at 10 °C. The ultrasounds treatment was found to be effective in delaying colour development and texture losses, preserving sensorial quality of whole tomato, with increase of TPC and microbial load reduction. Moreover, this postharvest treatment can be used as an alternative for extending fresh fruits shelf-life.     

An ultrasonic method to study the interdiffusion phenomenon between two polydimethylsiloxanes

We present an original method that allows the monitoring of the interdiffusion process between two miscible polymers. This acoustical method is nondestructive, and does not need any chain marking. It is based on the variations of the angular reflection coefficient R(θ) measured at fixed frequency, caused by the ultrasonic parameters modifications in the interphase during the diffusion process. We applied it to the interdiffusion between two polydimethylsiloxanes A and B of very different molecular weights. The evolution of R(θ) was also computed using successively the slow and the fast theories of diffusion, after calculation of the concentration profiles. The adjustment of the theoretical reflection spectra given by the slow theory on the experimental spectra allowed us to find the value the interdiffusion coefficient D₀, which is characteristic of the system. This value is very near the value determined from the molecular dynamics laws (Rouse, reptation, Stokes-Einstein). But in the studied time domain, the fast theory accounts for the experimental results as well as the slow theory. Finally, we discuss the precision of the method and the means to improve it.     

Kinetic modeling of the ultrasound-assisted extraction of polyphenols from Picea abies bark

In this paper, the kinetics of polyphenols extraction from spruce bark (Picea abies) under ultrasounds action was investigated. Studies were performed in order to express the effect of some specific parameters (as: ultrasounds, surface contact between solvent and solid, extraction time and temperature) on the total phenolic content (TPC). Experiments were performed in the presence and absence of ultrasounds, using different contact surfaces between solvent and solid, for times from 5 to 75 min and temperatures of 318, 323 and 333 K. All these factors have a positive influence on the process, enhancing the extraction rate by recovering higher amounts of polyphenols. The process takes place in two stages: a fast one in the first 20–30 min (first stage), followed by a slow one approaching to an equilibrium concentration after 40 min (second stage). In these conditions, the second-order kinetic model was successfully developed for describing the mechanism of ultrasound-assisted extraction of polyphenols from P. abies bark. Based on this model, values of second-order extraction rate constant (k), initial extraction rate (h), saturation concentration (C_s) and activation energy (E_a) could be predicted. Model validation was done by plotting experimental and predicted values of TPC’s, revealing a very good correlation between the obtained data (R² > 0.98).     

Effects of ultrasonic waves on the heat transfer enhancement in subcooled boiling

This work represents an experimental basic research aimed to investigate the influence on the heat transfer rate of the ultrasounds, in free convection and in presence of liquid. In fact the ultrasonic waves induce, thanks to vibrations, turbulence on the dynamic field, and so an increase of the convection coefficient. The heater is a circular cylinder, immersed in distilled water, and warmed up by Joule effect. This study has carried on for 1 year at Energetics Department “L. Poggi”. The effect was observed since 1960s: different authors had studied the cooling effect due to the ultrasonic waves at different heat transfer regimes, especially from a thin platinum wire to water. We have chosen to investigate the subcooled boiling regime, because this one is the best condition for the heat transfer enhancement, according to the scientific literature. We have carried out a wide experimental study, varying the different water subcooling degrees, the ultrasonic generator power, the ultrasound frequency and the placement of the heater inside the ultrasonic tank, in function of the range of the values of heat flux per unit surface needed dissipating. These values were supplied us by a possible practical application of the ultrasonic streaming: the cooling of 3D highly integrated electronic components. These packaging systems should have to provide all future devices, such as electronics, actuators, sensors and antenna. In fact, for these systems the thermal problem is a critical challenge, because they do not have to overtake critical temperature, after that they could damage irreversibly. Moreover, the traditional cooling systems used in electronic do not seem to be useful for them. On the contrary, the results obtained with ultrasounds, allow heat transfer coefficient enhancement of about 50% to be reached.The purpose is to find out the set of optimal conditions, in order to apply successively all the results to a real packaging system.     

SH ultrasonic guided waves for the evaluation of interfacial adhesion

Shear-Horizontally (SH) polarized, ultrasonic, guided wave modes are considered in order to infer changes in the adhesive properties at several interfaces located within an adhesive bond joining two metallic plates. Specific aluminium lap-joint samples were produced, with different adhesive properties at up to four interfaces when a glass–epoxy film is inserted into the adhesive bond. EMAT transducers were used to generate and detect the fundamental SH₀ mode. This is launched from one plate and detected at the other plate, past the lap joint. Signals are picked up for different propagation paths along each sample, in order to check measurement reproducibility as well as the uniformity of the adhesively bonded zones. Signals measured for four samples are then compared, showing very good sensitivity of the SH₀ mode to changes in the interfacial adhesive properties. In addition, a Finite Element-based model is used to simulate the experimental measurements. The model includes adhesive viscoelasticity, as well as spatial distributions of shear springs (with shear stiffness K_T) at both metal–adhesive interfaces, and also at the adhesive–film interfaces when these are present. This model is solved in the frequency domain, but temporal excitation and inverse FFT procedure are implemented in order to simulate the measured time traces. Values of the interfacial adhesive parameters, K_T, are determined by an optimization process so that best fit is obtained between both sets of measured and numerically predicted waveforms. Such agreement was also possible by adjusting the shear modulus of the adhesive component. This work suggests a promising use of SH-like guided modes for quantifying shear properties at adhesive interfaces, and shows that such waves can be used for inferring adhesive and cohesive properties of bonds separately. Finally, the paper considers improvements that could be made to the process, and its potential for testing the interfacial adhesion of adhesively bonded composite components.     

Analysis of coherent surface wave dispersion and attenuation for non-destructive testing of concrete

Rayleigh waves measurements are used to characterise cover concrete and mortar in the frequency range 60–180 kHz. At these frequencies, the wavelength is comparable to the size of the aggregates, and waves propagate in a multiple scattering regime. Acquired signals are then difficult to interpret due to an important incoherent part. The method proposed here is the study of the coherent waves, obtained by averaging signals over several configurations of disorder. Coherent waves give information on an equivalent homogeneous medium. To acquire a large amount of measurements with accuracy, an optimised piezoelectric source is used with a laser interferometer for reception. Adapted signal processing technique are presented to evaluate the coherent phase and group velocities and also the coherent attenuation parameter. The sensitivity of these three parameters with the properties of concrete is discussed, as well as the necessity to use coherent waves to obtain accurate results.     

Insight into the synthesis procedure of Fe3+/TiO2-based photocatalyst applied in the selective photo-oxidation of benzyl alcohol under sun-imitating lamp

Fe³⁺/TiO₂/zeolite Y photocatalyst synthesized by using sonophotodeposition method was compared with photocatalysts prepared by simple photodeposition and sonodeposition methods in order to clarify the role of light irradiation and ultrasounds while they are used simultaneously. To gain an insight into the mechanism of this method a detailed characterization of the photocatalysts was carried out by means of the following techniques: UV–vis diffuse reflectance spectroscopy, X-ray photoelectron spectroscopy, transmission electron microscopy, Mössbauer measurements and photocatalytic test reaction. Basing on the results from these techniques the chemical role of light and mainly mechanical role of ultrasound were observed. The selective photocatalytic oxidation of benzyl alcohol into benzaldehyde in liquid phase was a test reaction verifying the utility of the prepared materials. The best photocatalytic efficiency in this reaction was performed by photocatalyst synthesized using compilation of ultrasound energy with photoexcitation.     

Effect of ultrasound and green solvents addition on the oil extraction efficiency from rapeseed flakes

The current procedure of rapeseed oil extraction is based on a first extraction step by pressing followed by a second extraction step with hexane. This solvent being toxic for the users, the consumers and the environment, its use could be forbidden within the coming years. Stimulated by a stringent regulation, the research activity for the replacement of toxic solvents shows a significant development. The aim of this study was to select alternative solvent to hexane such as ethanol or isopropanol, and, to adjust the oil extraction process by developing an ultrasound assisted method. The objective was to reach a comparable efficiency but also to enhance the oil quality. When applied to isopropanol, the ultrasound assisted extraction method has shown promising results, and comparable to those obtained with hexane (oil yield of 80% for hexane and 79% for isopropanol at optimum extraction conditions (20 min of ultrasound pretreatment followed by 2 h of additional solid/liquid extraction)). Conversely, in studied conditions, ethanol did not seem to be an appropriate alternative solvent to hexane as the extraction yields obtained by using this solvent were quite low.     

Cleaning efficiency enhancement by ultrasounds for membranes used in dairy industries

Membrane cleaning is a key point for the implementation of membrane technologies in the dairy industry for proteins concentration. In this study, four ultrafiltration (UF) membranes with different molecular weight cut-offs (MWCOs) (5, 15, 30 and 50 kDa) and materials (polyethersulfone and ceramics) were fouled with three different whey model solutions: bovine serum albumin (BSA), BSA plus CaCl₂ and whey protein concentrate solution (Renylat 45). The purpose of the study was to evaluate the effect of ultrasounds (US) on the membrane cleaning efficiency. The influence of ultrasonic frequency and the US application modes (submerging the membrane module inside the US bath or applying US to the cleaning solution) were also evaluated. The experiments were performed in a laboratory plant which included the US equipment and the possibility of using two membrane modules (flat sheet and tubular). The fouling solution that caused the highest fouling degree for all the membranes was Renylat 45. Results demonstrated that membrane cleaning with US was effective and this effectiveness increased at lower frequencies. Although no significant differences were observed between the two different US applications modes tested, slightly higher cleaning efficiencies values placing the membrane module at the bottom of the tank were achieved.