Environmental impact of mining activities in the Lousal area (Portugal): chemical and diatom characterization of metal-contaminated stream sediments and surface water of Corona stream

Lousal mine is a typical “abandoned mine” with all sorts of problems as consequence of the cessation of the mining activity and lack of infrastructure maintenance. The mine is closed at present, but the heavy metal enriched tailings remain at the surface in oxidizing conditions. Surface water and stream sediments revealed much higher concentrations than the local geochemical background values, which the “Contaminated Sediment Standing Team” classifies as very toxic. High concentrations of Cu, Pb, Zn, As, Cd and Hg occurred within the stream sediments downstream of the tailings sites (up to: 817 mg kg⁻¹ As, 6.7 mg kg⁻¹ Cd, 1568 mg kg⁻¹ Cu, 1059 mg kg⁻¹ Pb, 82.4 mg kg⁻¹ Sb, 4373 mg kg⁻¹ Zn). The AMD waters showed values of pH ranging from 1.9 to 2.9 and concentrations of 9249 to 20,700 mg L⁻¹ SO₄⁻², 959 to 4830 mg L⁻¹ Fe and 136 to 624 mg L⁻¹ Al. Meanwhile, the acid effluents and mixed stream waters also carried high contents of SO₄^2−, Fe, Al, Cu, Pb, Zn, Cd, and As, generally exceeding the Fresh Water Aquatic Life Acute Criteria. Negative impacts in the diatom communities growing at different sites along a strong metal pollution gradient were shown through Canonical Correspondence Analysis: in the sites influenced by Acid Mine Drainage (AMD), the dominant taxon was Achnanthidium minutissimum. However, Pinnularia acoricola was the dominant species when the environmental conditions were extremely adverse: very low pH and high metal concentrations (sites 2 and 3). Teratological forms of Achnanthidium minutissimum (Kützing) Czarnecki, Brachysira vitrea (Grunow) Ross in Hartley, Fragilaria rumpens (Kützing) G. W. F. Carlson and Nitzschia hantzschiana Rabenhorst were found. A morphometric study of B. vitrea showed that a decrease in size was evident at the most contaminated sites. These results are evidence of metal and acidic pollution.     

Experimental and numerical study of turbulent mixing in a model of a polymerization reactor

In this study the turbulent mixing in a model of a polymerization reactor is analyzed experimentally and numerically. The model corresponds to a zone of an autoclave reactor equipped with a stirrer. Two different configurations of the stirrer, with different arrangement of the paddles, have been considered. The mixing process has been monitored by following the time-evolution of injections of a passive scalar through the different inlets of the model. The time-evolution of the mixing quality in a laboratory scale model of the reactor has been measured using water and the Planar Laser Induced Fluorescence (PLIF) technique. Numerical simulations of the flow and of the mixing processes were carried out and results of the evolution of the mixing are compared successfully with measurements. The mixing processes are dominated by the flow topology generated by the rotation of the stirrer. Superimposed to the tangential flow, secondary flows divide the length of the reactor in different zones. It has been found that macro mixing in each individual zone is a relatively fast process and that the mixing rates within each zone are very similar. However, the mixing rate between different zones is a relatively slow process.     

Rational Design of Resorcylic Acid Lactone Analogues as Covalent MNK1/2 Kinase Inhibitors by Tuning the Reactivity of an Enamide Michael Acceptor

Recent biological and computational advances in drug design have led to renewed interest in targeted covalent inhibition as an efficient and practical approach for the development of new drugs. As part of our continuing efforts in the exploration of the therapeutic potential of resorcylic acid lactones (RALs), we report herein the design, synthesis, and biological evaluation of conveniently accessible RAL enamide analogues as novel covalent inhibitors of MAP kinase interacting kinases (MNKs). In this study, we have successfully demonstrated that the covalent binding ability of RAL enamides can be tuned by attaching an electron‐withdrawing motif, such as an acyl group, to enhance its reactivity toward the cysteine residues at the MNK1/2 binding sites. We have also shown that ¹H NMR spectroscopy is a convenient and effective tool for screening the covalent binding activities of enamides using cysteamine as a mimic of the key cysteine residue in the enzyme, whereas mass spectrometric analysis confirms covalent modification of the kinases. Preliminary optimization of the initial hit led to the discovery of enamides with low micromolar activity in MNK assays. Cancer cell line assays have identified RAL enamides that inhibit the growth of cancer cells with similar potency to the natural product L‐783 ,277.     

New microarchitectures of (Er,Yb):Lu2O3 nanocrystals embedded in PMMA: synthesis,structural characterization,and luminescent properties

We report the formation of two-dimensional disordered arrays of poly(methyl)methacrylate (PMMA) microcolumns with embedded single size distribution of Lu_0.990Er_0.520Yb₀.₄₉₀ nanocrystals, (Er,Yb):Lu₂O₃, using a disordered porous silicon template. The cubic (Er,Yb):Lu₂O₃ nanocrystals, which crystallize into the cubic system with Ia3¯ space group, were synthesized using the modified Pechini method. Electronic microscopic techniques were used to study the distribution of the nanocrystals in the PMMA columns. Cathodoluminescence was used to observe the visible luminescence of the particles. Red emission attributed to ⁴ F_9/2 → ⁴I_15/2 erbium transition is predominant in these new composites.     

Laser induced fluorescence spectroscopy of aromatic species produced in atmospheric sooting flames using UV and visible excitation wavelengths

In this work, laser induced fluorescence (LIF) has been applied to probe PAHs in two atmospheric sooting flames: a premixed flat flame of methane and a Diesel turbulent spray one. Different laser excitation wavelengths have been used. UV excitations at 266 and 355 nm have been operated from the fourth and the third harmonic frequencies of an Nd: YAG laser while visible excitations were emitted by an OPO pumped by the third harmonic of the YAG laser.     

Effect of Al dopant concentration on structural,optical and photoconducting properties in nanostructured zinc oxide thin films

Thin films of undoped and doped ZnO, with different Al concentrations (1–5 wt%) were deposited onto glass substrates, by the sol–gel spin coating method. Grazing incidence X-ray diffraction (GIXRD) studies confirmed the nature of films as poly-crystalline, with typical hexagonal wurtzite structure. The films showed variation in crystallite size and change in relative intensities, upon different Al doping concentrations. The surface morphology of the films examined using FE-SEM, showed the grain size becoming smaller upon Al doping. The influence of Al with different concentrations, onto ZnO on the optical absorption and transmittance was studied using UV–Vis–NIR spectrophotometer in the wavelength range 300–2500 nm. The UV absorption shifted towards shorter wavelength upon Al doping. The average transmittance in the visible region increased for Al doped films up to 1–2 wt% and decreased for other concentration. The dark and photo conductivity measurements of the films indicated increase in the current values upon doping up to 1–2 wt% of Al and decreased for further concentrations. The rise and decay time measured from the photoresponse study, indicate larger values of rise time for the doped films compared to undoped ZnO. However, the film with 1–2 wt% doping of Al showed better response within the doping concentration. The thermal activation energy obtained from temperature-dependant conductivity showed decrease in the value upon Al doping up to 2 wt% and increased beyond this concentration in the temperature range 300–400 K.     

Modification of epoxy–anhydride thermosets with a hyperbranched poly(ester amide). II. Thermal,dynamic mechanical,and dielectric properties and thermal reworkability

An epoxy–anhydride formulation used for the coating electrical devices was modified with a commercially available hyperbranched poly(ester amide), Hybrane S2200, to improve the thermal degradability of the resulting thermoset and, thus, facilitate the recovery of substrate materials after the service life of the component. The thermomechanical, mechanical, and dielectric properties and thermal degradability were studied and interpreted in terms of the composition and network structure of the cured thermosets. Although the crosslinking density was significantly reduced with the incorporation of S2200, the glass transition temperature of the fully cured material (T_g∞) of the modified thermoset was hardly affected because of the enhancement of H‐bonding interactions in the presence of S2200. Despite the different network structures, the combined dielectric and dynamic mechanical analysis revealed that the relaxation dynamics of both networks were very similar. In terms of application, improvements in the dielectric and mechanical properties were observed. The incorporation of S2200 accelerated the thermal decomposition of the material and, thus, facilitated the recovery of the valuable parts from the substrate at the end of the service life of the apparatus. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

New chemically reworkable epoxy coatings obtained by the addition of polyesters with star topologies to diglycidyl ether of bisphenol A resins

A new multiarm star with hyperbranched aromatic–aliphatic polyester core and poly(?-caprolactone) arms (HBPCL) was synthesized and characterized. Mixtures of diglycidyl ether of bisphenol A (DGEBA) resin and different proportions of this star type modifier were cured using a thermal cationic curing agent, Yb(OTf)₃. The HBPCL prepared has hydroxyl groups as chain ends, which are capable of chemically incorporating to the epoxy matrix by means of the monomer activated mechanism. This, together with the chemical structure of the modifier, allowed the preparation of new homogeneous thermosets for coating applications. The curing mixtures were investigated by differential scanning calorimetry (DSC) to study the curing process and evaluate the kinetic parameters of the formulations. These studies demonstrated that HBPCL decreased the curing rate and affected the gelation process. The thermosets obtained showed an improvement in impact strength with a discrete reduction of the T_g. The modified coatings showed an increased reworkability in alkaline solution with the maintenance of thermal stability.     

Multi-scale individual-based model of microbial and bioconversion dynamics in aerobic granular sludge

Aerobic granular sludge is a novel compact biological wastewater treatment technology for integrated removal of COD (chemical oxygen demand), nitrogen, and phosphate charges. We present here a multiscale model of aerobic granular sludge sequencing batch reactors (GSBR) describing the complex dynamics of populations and nutrient removal. The macro scale describes bulk concentrations and effluent composition in six solutes (oxygen, acetate, ammonium, nitrite, nitrate, and phosphate). A finer scale, the scale of one granule (1.1 mm of diameter), describes the two-dimensional spatial arrangement of four bacterial groups--heterotrophs, ammonium oxidizers, nitrite oxidizers, and phosphate accumulating organisms (PAO)--using individual based modeling (IbM) with species-specific kinetic models. The model for PAO includes three internal storage compounds: polyhydroxyalkanoates (PHA), poly phosphate, and glycogen. Simulations of long-term reactor operation show how the microbial population and activity depends on the operating conditions. Short-term dynamics of solute bulk concentrations are also generated with results comparable to experimental data from lab scale reactors. Our results suggest that N-removal in GSBR occurs mostly via alternating nitrification/denitrification rather than simultaneous nitrification/denitrification, supporting an alternative strategy to improve N-removal in this promising wastewater treatment process.     

Biodiversity and characterization of Staphylococcus species isolated from a small manufacturing dairy plant in Portugal

The level and the diversity of the staphylococcal community occurring in the environment and dairy products of a small manufacturing dairy plant were investigated. Species identification was performed using different molecular methods, viz. Multiplex-PCR, amplified ribosomal DNA restriction analysis (ARDRA), and sodA gene sequencing. The main species encountered corresponded to Staphylococcus equorum (41 isolates, 39.0%), S. saprophyticus (28 isolates, 26.7%) and S. epidermidis (15 isolates, 14.3%). Additionally, low incidence of enterotoxin genes was obtained, with only 9 strains (8.6%) being positive for one or more toxin genes. With regard to antimicrobial resistance, 57.1% of the isolates showed at least resistance against one antibiotic, and 28.6% were multi-resistant, which might accomplish resistance for up to 6 antibiotics simultaneously. These results provided evidence that the presence of Staphylococcus species in dairy environment are mostly represented by S. equorum and S. saprophyticus, and illustrate that carrying antimicrobial resistance genes has become reasonably widespread in cheese and dairy environment.