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The Water Company of the North Alentejo (Águas do Norte Alentejano) (Portugal) has decided to implement a treatment plant to treat an urban wastewater with a significant influence of tannery effluents. The design of the wastewater treatment plant was attributed to a consortium coordinated by Sisaqua Company. Since the levels of the biodegradability and toxicity of the wastewater to be treated were unknown, Sisaqua Company asked the New University of Lisboa to develop and execute a monitoring plan to define the chemical composition and the levels of the biodegradability and toxicity of the wastewater.
A composite sampling procedure of the wastewater was performed during a daily working cycle of the tanneries. The composite sample was characterized for 19 chemical parameters. Five of these parameters were total Cr, Cr (VI), Zn, Cu and Al, which were determined in the dissolved and suspended fractions. The composite sample was also submitted to a biological test to assess its biodegradability degree. This assay was performed according to the methodology indicated in the test 301E of OECD [1], taking into account the amendment of 1992. A respirometric assay was carried out, to assess the toxic effect of the composite sample on the biological populations involved in the biological stabilization of organic compounds. This assay followed the “Sapromat” methodology developed by Brabander and Vandeputte [2]. Finally, the composite sample was submitted to a coagulation-flocculation process according to the methodologies proposed by Eckenfelder [3, 4] and Pereira [5]. The supernatants were characterized for the same chemical and biological parameters as it was described for the composite sample.
It was possible to conclude that the high levels of Cr present in the composite wastewater were mainly in the trivalent oxidation state. Since this oxidation state is less toxic for biological populations than the Cr (VI) and this metal was mainly in the suspended fraction, it was possible to obtain a biodegradability of the organic compounds quite similar to those observed for domestic wastewaters. The toxicity determined by the “Sapromat” method was slightly higher than those determined for domestic wastewaters. Nevertheless, this toxicity did not affect significantly the wastewater biodegradability. The Cr (III) was easily removed by a chemical coagulation-flocculation process.

In this paper, the author proves that the set of all integrable functions whose sequences of negative (resp. nonnegative) Fourier coefficients belong to \(\ell^1\cap\ell^\Phi_{\varphi,w}\) (resp. to \(\ell^1\cap\ell^\Psi_{\psi,\varrho}\)), where \(\ell^\Phi_{\varphi,w}\) and \(\ell^\Psi_{\psi,\varrho}\) are two-weighted Orlicz sequence spaces, forms an algebra under pointwise multiplication whenever the weight sequences
\[
\varphi=\{\varphi_n\},\quad
\psi=\{\psi_n\},\quad
w=\{w_n\},\quad
\varrho=\{\varrho_n\}
\]
increase and satisfy the \(\Delta_2\)-condition.

Transparent and conductive high preferential c-axis oriented ZnO thin films doped with Al have been prepared by sol-gel method using zinc acetate and aluminium chloride as cations source, 2-methoxiethanol as solvent and monoethanolamine as sol stabilizer. Film deposition was performed by dip-coating technique at a withdrawal rate of 1.5 cm min-1 on Corning 1737 glass substrate. The effect of dopant concentration, heating treatment and annealing in reducing atmosphere on the microstructure as well as on the electrical and optical properties of the thin films is discussed. The optical transmittance spectra of the films showed a very good transmittance, between 85 and 95%, within the visible wavelength region. The minimum resistivity of 1.3 × 10-3 Ω cm was obtained for the film doped with 2 wt.% Al, preheated at 400 °C and post-heated at 600 °C, after annealing under a reduced atmosphere of forming gas. © 2003 Elsevier B.V. All rights reserved.

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This paper presents preliminary results on Al doped ZnO thin films prepared by the solgel method. The thin films were produced by a dip-coater technique on glass substrate, using zinc acetate dihydrate, aluminium chloride hexahydrate, 2-methoxyethanol and monoethanolamine as raw materials. The ZnO thin films were analysed by XRD, Hall effect and SEM measurements. In order to determine the influence of the thermal treatments on the film properties, a set of four different heat treatments (atmosphere and temperature) were studied. All the films are polycrystalline presenting a crystallographic c-axis orientation (002) perpendicular to the substrate. The best results were obtained for films pre-heated at 400°C and post-heated for 1 hour in air at 600°C, after annealing under a reduced atmosphere of forming gas, where a resistivity of 3.9×10-3 Ωcm, a Hall mobility of 34.1 cm2/Vs, a carrier concentration of 4.7×1019 cm-3 and an optical transmittance of 90% were achieved.

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Cytochrome c peroxidase (CCP) catalyses the reduction of H2O2 to H2O, an important step in the cellular detoxification process. The crystal structure of the di-heme CCP from Pseudomonas nautica 617 was obtained in two different conformations in a redox state with the electron transfer heme reduced. Form IN, obtained at pH 4.0, does not contain Ca2+ and was refined at 2.2 Angstrom resolution. This inactive form presents a closed conformation where the peroxidatic heme adopts a six-ligand coordination, hindering the peroxidatic reaction from taking place. Form OUT is Ca2+ dependent and was crystallized at pH 5.3 and refined at 2.4 Angstrom resolution. This active form shows an open conformation, with release of the distal histidine (His71) ligand, providing peroxide access to the active site. This is the first time that the active and inactive states are reported for a di-heme peroxidase.

Titanium aluminides are arising as a valuable alternative to superalloys in applications where the ratio resistance/density is important. Together with excellent mechanical and corrosion properties at high temperatures, such characteristics are very attractive for applications in the aeronautical, aerospace and automotive industries. However, the current high selling price, due to high costs of production and raw materials and the need of very specific equipment, are limitative factors for further applications. With the end of the cold war, and the decrease of traditional markets of TiAl, the strategy to develop other applications, strongly depends on the decrease of production costs. An alternative to the present production routes might be the use of traditional casting techniques, by induction melting of the alloy in a ceramic crucible and pouring into ceramic moulds, made by the investment casting process. However, due to the high reactivity of Ti alloys, the use of traditional ceramic materials cannot be used, as they lead to oxide formation and oxygen pick up both from the crucible and the moulding materials. In this work, the relative oxygen concentration of Ti-48Al castings was measured by SIMS ó Secondary Ion Mass Spectrometry. This technique provides a direct measurement of the isotopic composition with high sensitivity. The cylindrical samples were specially prepared to allow the analysis of the area close to the border. Oxygen profiles were acquired for samples obtained with different mould materials. The comparison of such profiles with hardness ones gives insight in the role of the oxygen concentration in the properties of the alloy and in the choice of the most suitable materials for TiAl production

Titanium aluminides are a valuable alternative to superalloys in applications where the ratio resistance/density is important. Since the ordinary production routes lead to high final costs, an alternative might be the use of traditional casting techniques by induction melting of the alloy in a ceramic crucible and pouring into ceramic moulds, made by the investment casting process. However, due to the high reactivity of Ti alloys, the use of traditional ceramic materials cannot be used, as they lead to oxide formation and oxygen pick up from both the crucible and the moulding materials. In this work, the effect of low level contamination was studied by SIMS. Special attention was given to the oxygen concentration for samples obtained with different mould materials. The comparison of SIMS in-depth profiles with hardness profiles, gives insight concerning the significance of the oxygen concentration in the properties of the alloy and regarding the choice of the most suitable materials for TiAl production.

Ion scattering spectroscopy (ISS) is normally considered a non-destructive technique for surface analysis, while secondary ion mass spectrometry (SIMS) is intrinsically destructive. However, both SIMS and ISS use similar primary beams in the kilo-electron-volt region to perform surface analysis. Although energies and projectile mass are chosen in order to minimize or maximize sputtering for each technique, care should be taken when ISS is performed. Indeed, while sputtering is essential for SIMS, it is unwelcome in ISS. In this paper, we discuss how sputtering may become possible by light ions in the energy range of some 100 eV to some keV. We describe the mechanisms and threshold energies, what is preferential sputtering and how large the absolute value of the sputtering yields should be. We also give details about the emission anisotropy of the sputtered particles for single crystals. Finally, we suggest a way to evaluate the erosion rate under typical ISS conditions and we present examples of Heþ and Ar+ on a Ba target.

The production of cytochrome c peroxidase (CCP) from Pseudomonas ( Ps.) stutzeri (ATCC 11607) was optimized by adjusting the composition of the growth medium and aeration of the culture. The protein was isolated and characterized biochemically and spectroscopically in the oxidized and mixed valence forms. The activity of Ps. stutzeri CCP was studied using two different ferrocytochromes as electron donors: Ps. stutzeri cytochrome c(551) (the physiological electron donor) and horse heart cytochrome c. These electron donors interact differently with Ps. stutzeri CCP, exhibiting different ionic strength dependence. The CCP from Paracoccus ( Pa.) denitrificans was proposed to have two different Ca(2+) binding sites: one usually occupied (site I) and the other either empty or partially occupied in the oxidized enzyme (site II). The Ps. stutzeri enzyme was purified in a form with tightly bound Ca(2+). The affinity for Ca(2+) in the mixed valence enzyme is so high that Ca(2+) returns to it from the EGTA which was added to empty the site in the oxidized enzyme. Molecular mass determination by ultracentrifugation and behavior on gel filtration chromatography have revealed that this CCP is isolated as an active dimer, in contrast to the Pa. denitrificans CCP which requires added Ca(2+) for formation of the dimer and also for activation of the enzyme. This is consistent with the proposal that Ca(2+) in the bacterial peroxidases influences the monomer/dimer equilibrium and the transition to the active form of the enzyme. Additional Ca(2+)does affect both the kinetics of oxidation of horse heart cytochrome c (but not cytochrome c(551)) and higher aggregation states of the enzyme. This suggests the presence of a superficial Ca(2+)binding site of low affinity.

Crystals of cytochrome c peroxidase from Pseudomonas stutzeri were obtained using sodium citrate and PEG 8000 as precipitants. A complete data set was collected to a resolution of 1.6 A under cryogenic conditions using synchrotron radiation at the ESRF. The crystals belong to space group P2(1), with unit-cell parameters a = 69.29, b = 143.31, c = 76.83 A, beta = 100.78 degrees. Four CCP molecules were found in the asymmetric unit, corresponding to a pair of dimers related by local dyads. The crystal packing in the structure shows that the functional dimers can dimerize, as suggested by previous biochemical studies.

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Superoxide reductases catalyze the monovalent reduction of superoxide anion to hydrogen peroxide. Spectroscopic evidence for the formation of a dinuclear cyano-bridged adduct after K(3)Fe(CN)(6) oxidation of the superoxide reductases neelaredoxin from Treponema pallidum and desulfoferrodoxin from Desulfovibrio vulgaris was reported. Oxidation with K(3)Fe(CN)(6) reveals a band in the near-IR with lambda(max) at 1020 nm, coupled with an increase of the iron content by almost 2-fold. Fourier transform infrared spectroscopy provided additional evidence with CN-stretching vibrations at 2095, 2025-2030, and 2047 cm(-)(1), assigned to a ferrocyanide adduct of the enzyme. Interestingly, the low-temperature electronic paramagnetic resonance (EPR) spectra of oxidized TpNlr reveal at least three different species indicating structural heterogeneity in the coordination environment of the active site Fe ion. Given the likely 6-coordinate geometry of the active site Fe(3+) ion in the ferrocyanide adduct, we propose that the rhombic EPR species can serve as a model of a hexacoordinate form of the active site.

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