Electrochemical mineralization of sodium dodecylbenzenesulfonate at boron doped diamond anodes

Results are reported of the electrochemical oxidation of sodium dodecylbenzenesulfonate (SDBS), a common surfactant, at boron-doped diamond anodes. The measured critical micelle concentration (CMC) for SDBS in water at 24 °C was almost 150 mg dm⁻³, but this decreased to almost 30 mg dm⁻³ in 0.1 M sodium sulfate. Cyclic voltammetry of a boron doped diamond (BDD) electrode in aqueous SDBS solutions exhibited oxidation current densities at very positive potentials; however, solutions of monomers at concentrations <CMC gave rise to higher current densities than in higher concentration solutions that formed micelles. Galvanostatic electrolyses, with samples analyzed for Total Organic Carbon (TOC) and Chemical Oxygen Demand (COD), were performed in an electrolytic flow cell without separator, operating in batch recycle mode, using solutions containing SDBS at initial concentrations of 25 and 250 ppm. SDBS in basic media (pH = 12) exhibited lower TOC removal rates than in acidic or neutral solutions, due to concurrent oxidation of dissolved carbonates at potentials less positive than required for water oxidation, as evident in cyclic voltammograms. Decreasing the [electrolyte]/[surfactant] ratio from 200 to 10 increased TOC removal rates. For solutions containing monomers, TOC removal rates also increased with flow rate in the second part of the electrolysis, corresponding to reaction of smaller, fragmented organic compounds. When COD removal from a solution containing SDBS micelles was mass transport controlled, current efficiencies were constant at ca. 50%, due to dimerisation of hydroxyl radical to H₂O₂ and its oxidation to dioxygen.     

Effects of differently shaped TiO<Subscript>2</Subscript>NPs (nanospheres,nanorods and nanowires) on the <Emphasis Type="Italic">in vitro</Emphasis> model (Caco-2/HT29) of the intestinal barrier

Background

The biological effects of nanoparticles depend on several characteristics such as size and shape that must be taken into account in any type of assessment. The increased use of titanium dioxide nanoparticles (TiO₂NPs) for industrial applications, and specifically as a food additive, demands a deep assessment of their potential risk for humans, including their abilities to cross biological barriers.

Methods

We have investigated the interaction of three differently shaped TiO₂NPs (nanospheres, nanorods and nanowires) in an in vitro model of the intestinal barrier, where the coculture of Caco-2/HT29 cells confers inherent intestinal epithelium characteristics to the model (i.e. mucus secretion, brush border, tight junctions, etc.).

Results

Adverse effects in the intestinal epithelium were detected by studying the barrier’s integrity (TEER), permeability (LY) and changes in the gene expression of selected specific markers. Using Laser Scanning Confocal Microscopy, we detected a different behaviour in the bio-adhesion and biodistribution of each of the TiO₂NPs. Moreover, we were able to specifically localize each type of TiO₂NPs inside the cells. Interestingly, general DNA damage, but not oxidative DNA damage effects, were detected by using the FPG version of the comet assay.

Conclusions

Results indicate different interactions and cellular responses related to differently shaped TiO₂NPs, nanowires showing the most harmful effects.

     

Ionic liquid mediated surface micropatterning of polymer blends

A polymer of intrinsic porosity (i.e., PIM‐1) has been blended with different ionic liquids (ILs) in order to evaluate the effect of the ILs on the microstructure of the polymer blend. [C₈MIM][Cl], [BMIM][DCa], [BMPyr][DCa], and [BMIM][Tf₂N] have been selected and were mixed with PIM‐1. Polymer blends containing up to 80 wt % of ILs were prepared by a casting method with chloroform as solvent. SEM images show that during the film formation a structuring of the surface appears depending on the nature and the concentration of ILs, with appearance of well‐defined microstructure in the case of [BMIM][Tf₂N] and [BMIM][DCa]. In the case of [BMIM][Tf₂N]/PIM‐1 film, the lower IL concentration induces the denser film with small micropatterns onto the surface. AFM analysis indicates that the ILs are well dispersed on the surface. X‐ray photoelectron spectroscopy, Fourier transform infrared spectroscopy, and water contact angle measurements show that a gradient of IL concentration is observed across the film thickness. It is demonstrated that ILs are versatile co‐solvents for inducing controlled micropatterns in polymer membrane surfaces. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46109.     

Total arsenic, lead, cadmium, copper, and zinc in some salt rivers in the northern Andes of Antofagasta, Chile

Lake Velenje is located in one of the most polluted regions in Slovenia, the Salek Valley. The major source of pollution in the valley is the coal-fired thermal power plant in Sostanj (STPP, capacity 775 MW). It has five separate units. All units have electrostatic precipitators for fly ash removal. Unit 4 also has installed a wet flue gas desulfurisation system (FGD system). Total mercury (THg) concentrations were measured in lignite, slag and ash samples from the STPP. In flue gas, different mercury species (THg, MeHg, Hg2+, Hg0) were determined separately for unit 4 and unit 5 which use different flue gas cleaning technology. Mercury and methyl mercury (MeHg) concentrations were also measured in lake water at different depths, in inflow water, outflow water, rain, snow and lake sediments in order to establish the influence of the power plant on the lake. Most mercury emitted from the power plant is in the elemental form. The ratio between oxidised and elemental Hg depends on the flue gas cleaning technology. Mass balance calculations have been performed for the STPP. The results show that the major sources of mercury in Lake Velenje are wet deposition and lake inflows. Total and MeHg concentrations in the water column are very low and can be compared to other non-contaminated freshwater lakes in the world.     

Geometry dependence of coercivity in Ni nanowire arrays

Magnetic properties of arrays of nanowires produced inside the pores of anodic alumina membranes have been studied by means of vibrating sample magnetometer techniques. In these systems the length of the wires strongly influences the coercivity of the array. A simple model for the coercivity as a function of the geometry is presented which exhibits good agreement with experimental results. Magnetostatic interactions between the wires are responsible for a decrease of the coercive field.     

Comparison of Fenton and sono-Fenton bisphenol A degradation

Degradation of bisphenol A (BPA) was carried out with the Fenton reagent with and without additional sonochemical treatment. The Fenton and the sono-Fenton decomposition of BPA showed that ultrasound irradiation of wastewater improved the wet oxidation process of 25 mg l(-1) BPA solutions. The sonochemical degradation of BPA was monitored using UV absorption and large volume injection packed capillary LC measurements.     

Anaerobic fluidized bed reactor application to tropical fruit wine effluent.

The influence of the organic loading rate (OLR), the fluidization level (FL) and the particle diameter of natural zeolite used as support (D(p)), was evaluated at a laboratory scale anaerobic fluidized bed reactor (AFBR), treating tropical fruit wine effluent (vinasse). The experiment was carried out at an OLR from 2-5 kg COD/m3 d, FL of 20 and 40% and D(p) from 0.25 to 0.80 mm. It was demonstrated that OLR and FL had a slight influence on chemical oxygen demand removal and strong influence on the methane production rate. The COD removal was slightly higher for the higher particle diameter used. Additionally using the scanning electron microscope (SEM), it was observed that natural zeolites have excellent physical characteristics as a support medium in AFBR.     

Chemical affinities between the major volatile compounds present in a grape pomace distillate

BACKGROUND: The distillation of vinification by‐products to obtain alcoholic drinks is potentially an important source of income for the producing countries and avoids the environmental problem of waste management. Traditional technologies of distillation involve an important cost in terms of time and staff. Nowadays, companies install new distillation equipment, with high capacity and equipped with rectification columns, which is an important advance. Nevertheless, few studieshave been published concerning their correct management. In this study, the major volatile compounds were determined by gas chromatography in 61 samples of grape pomace distillate, corresponding to the fractions collected during seven complete distillation cycles. RESULTS: With a high degree of significance, the concentrations of 1,1‐diethoxyethane, propanol, hexanoate and ethyl acetate present positive correlations with the ethanol. However, those of benzyl alcohol, 2‐phenylethanol, furfurol, lactate, ethyl mirystate and diethyl succinate, were negative, which indicates that both groups of compounds were vented in the fractions of major or minor alcoholic degree, respectively. In addition, knowledge of the relationships between the volatile compounds contributes to improved management of an industrial distillation unit. CONCLUSION: The correlations established between the concentrations of the different volatile compounds indicate their physico‐chemical affinities or their biochemical origin. Copyright © 2009 Society of Chemical Industry     

Online automatic identification of the modal parameters of a long span arch bridge

The “Infante D. Henrique” bridge is a concrete arch bridge, with a span of 280 m that crosses the Douro River, linking the cities of Porto and Gaia located in the North of Portugal. This structure is being monitored by a recently installed dynamic monitoring system that comprises 12 acceleration channels. This paper describes the bridge structure, its dynamic parameters identified with a previously developed ambient vibration test, the installed monitoring equipment and the software that continuously processes the data received from the bridge through an Internet connection. Special emphasis is given to the algorithms that have been developed and implemented to perform the online automatic identification of the structure modal parameters from its measured responses during normal operation. The proposed methodology uses the covariance driven stochastic subspace identification method (SSI-COV), which is then complemented by a new algorithm developed for the automatic analysis of stabilization diagrams. This new tool, based on a hierarchical clustering algorithm, proved to be very efficient on the identification of the bridge first 12 modes. The results achieved during 2 months of observation, which involved the analysis of more than 2500 datasets, are presented in detail. It is demonstrated that with the combination of high-quality equipment and powerful identification algorithms, it is possible to estimate, in an automatic manner, accurate modal parameters for several modes. These can then be used as inputs for damage detection algorithms.     

Adsorption of Me(II), HEDP, and Me(II)-HEDP onto boehmite at nonstoichiometric Me(II)-HEDP concentrations

In aqueous environments, certain heavy metals are toxic even at very low concentrations. The main pathway of metal removal in the aquatic systems is via adsorption onto surfaces. These are desired processes that help decrease the dissolved fraction of metals in natural water. The presence of organic ligands as mono- and polyphosphonates may produce drastic changes in the mobility of the heavy metals. 1-Hydroxyethane-(1,1-diphosphonic acid) (HEDP) is a very strong chelating agent widely used in industrial applications. This study examines the effect of HEDP on the adsorption of Cu(II), Zn(II), and Cd(II) onto boehmite in nonstoichiometric conditions, with the HEDP concentration higher than the corresponding Me(II) cations. At high surface loading and low pH, HEDP removes Zn(II) and Cd(II) from solution to an appreciable extent. The data are modeled assuming an anionic-ternary complex formation. In the same conditions, Cu(II) adsorption is significantly suppressed at intermediate values of pH, and this behavior is linked to Cu-HEDP complex formation in solution. At low surface covering, the effects of HEDP on metal adsorption are either negligible or slight. This behavior suggests that both ligand and metal are mainly adsorbed in separate form. All experimental data indicate that no changes are observed in the pH edges for phosphonate adsorption. The surface constants to fit the experimental data were calculated by applying the 2-K model constant capacitance (CCM).