Mechanism and kinetics of sulfamethoxazole photocatalytic ozonation in water

The photocatalytic ozonation of sulfamethoxazole (SMT) has been studied in water under different experimental conditions. The effect of gas flow rate, initial concentration of ozone, SMT and TiO₂ has been investigated to establish the importance of mass transfer and chemical reaction. Under the conditions investigated the process is chemically controlled. Both, SMT and TOC kinetics have been considered. Fast and slow kinetic regime of ozone reactions have been observed for SMT and TOC oxidation, respectively. Application of different inhibitors allows for the establishment of reaction mechanism involving direct ozonation, direct photolysis, hydroxyl radical reactions and photocatalytic reactions. Rate constants of the direct reaction between ozone and protonated, non-protonated and anionic SMT species have been determined to be 1.71 × 10⁵, 3.24 × 10⁵ and 4.18 × 10⁵ M⁻¹ s⁻¹, respectively. SMT quantum yield at 313 nm was found to be 0.012 moles per Einstein at pH 5 and 0.003 moles per Einstein at pHs 7 and 9. Main contributions to SMT removal were direct ozone reaction, positive hole oxidation and hydroxyl radical reactions. For TOC removal, main contributions were due to positive hole oxidation and hydroxyl radical reactions.     

Influence of added concrete compressive strength on adhesion to an existing concrete substrate

An experimental study was performed to evaluate the bond strength between two concrete layers of different ages, considering different mixtures of added concrete, with different strengths. The specimens first had the roughness of the substrate surface increased by sand blasting. Later, the new concrete was added. Afterwards, slant shear tests were performed to quantify the bond strength in shear. These tests indicated that increasing the compressive strength of the added concrete relative to the compressive strength of the substrate concrete improves the bond strength and changes the rupture mode from adhesive to monolithic. A finite element analysis showed that, increasing the difference between the compressive strengths of the added concrete and the substrate concrete, higher values of normal stress are present in the interface, for the same level of shear stress. The study presented in this paper reveals that the added concrete, normally with higher compressive strength than the substrate concrete, may possibly have an influence on concrete-to-concrete bond strength. Therefore, design of shear at the interface between concrete cast at different ages, according to Eurocode 2, could be improved, since here only the lowest strength concrete is considered.     

Regional characteristics and the decision to innovate in a developing country: A multilevel analysis of Ecuadorian firms

This is the first study that uses multilevel modelling to analyse regional influence on the decision to invest in innovation activities of firms in a single developing country, Ecuador. Our results indicate that the decision to invest in R&D and in other innovation activities are conditioned by the region in which the firm is located. Regional loan volume, orientation towards knowledge exploitation and intra-regional-sectorial R&D spillovers are positively associated with both types of innovation activities, while regional levels of co-operation and inter-regional R&D spillovers are only positively associated with the probability of investing in other innovation activities.     

Nonlinear response of masonry wall structures subjected to cyclic and dynamic loading

The assessment of the dynamic or seismic performance of complex structures often requires the integration in the time domain of the structural equation of motion in the frame of a nonlinear analysis. Although sophisticated methods have been developed for the nonlinear analysis of masonry wall structures, including the macro- and micro-modeling approaches, these require large computational effort still limiting the extent and complexity of the structures analyzed. This paper presents an alternative method based on the Generalized Matrix Formulation for masonry skeletal structures and load bearing wall systems, which has been proved as an efficient formulation for the analysis of the strength capacity of these kinds of structures (Roca et al. (2005) [17]). The basic formulation has been complemented with a uniaxial cyclic constitutive model for masonry and a time integration scheme. The ability of the resulting approach to predict the nonlinear dynamic response of masonry structures is shown through its application to the time domain analysis of an experimental scale masonry building with available experimental results on its dynamic response.     

Activated sludge deflocculation under temperature upshifts from 30 to 45 degrees C

Twelve independent batch experiments (<9h) with fresh municipal activated sludge were conducted to assess the occurrence and the mechanisms of deflocculation under a temperature shift from 30 to 45 degrees C. In each experiment, a transient reactor (2 L) was subjected to the temperature shift and a control reactor was operated at a constant temperature of 30 degrees C. The occurrence of deflocculation was demonstrated by the increase in turbidity and in the concentrations of biopolymers in the sludge supernatant from the transient reactor. The maximum levels of proteins in the supernatants ranged from 53 to 81 mg/L, for DNA from 34 to 36 mg/L, for humic compounds from 20 to 40 mg/L, and for carbohydrates from 21 to 31 mg/L. All the biopolymer concentrations in the control reactor remained below 5-10 mg/L. The release of biopolymers was accompanied by an increase in sludge supernatant conductivity (16-32% increase, up to 1.20 mS/cm), soluble chemical oxygen demand (from 129 to 440 mg/L), total suspended solids (>25 mg/L up to 128 mg/L), and a decrease in the mixed liquor volatile suspended solids (up to 11%). The temperature shift was also found to inhibit microbial metabolism by reducing the sludge biomass substrate removal capacity, as measured by oxygen-uptake rates. The temperature shift had a marginal effect causing sludge lysis (as an increase in beta-galactosidase activity) and had no significant impact on sludge viability (live/dead ratio of bacterial cells). It was concluded that sludge deflocculation under a temperature shift from 30 to 45 degrees C involves the solubilisation of extracellular polymeric substances from the flocs and likely also floc fragmentation. In addition, sludge deflocculation and the inhibition of microbial metabolism explain the poor treatment performance observed in previous continuous reactors under similar temperature shifts.     

Collapse analysis of steel jacket structures for offshore oil exploitation

This work describes the formulation of finite-element based numerical methods for global nonlinear collapse analyses of three-dimensional steel framed structures. Particular emphasis is dedicated to the reassessment and determination of residual strength of steel jackets that support offshore oil exploitation platforms. Two main aspects are considered: (1) the formulation for a three-dimensional geometric and material nonlinear frame element, and (2) the implementation of specialized techniques for the solution of the nonlinear problem. The formulation of the element combines a co-rotational approach to represent geometric nonlinearities, providing an accurate treatment of finite rotations, with the plastic hinge approach to represent material nonlinearities. The stiffness reduction due to yielding is performed through a smooth degradation, following a parabolic function. Effects of strain hardening, geometric imperfections and residual stresses are modeled in an efficient manner. In order to determine the full nonlinear equilibrium path and allow the correct determination of the collapse load, the solution strategies consider specialized “continuation” techniques such as the Arc-Length and the Generalized Displacement Control methods. Case studies are presented in order to demonstrate the accuracy, efficiency, and suitability of the implemented methods and techniques.     

Field validation of specific ecotoxicological tools for aquatic systems impacted with acid mine drainage

Acid mine drainage (AMD) is characterised by very low pH and high heavy metal concentrations. Serious ecotoxicological effects, often leading to the complete disruption of the ecosystem, can be observed at the regions suffering this kind of contamination. Those effects can be caused either by low pH itself or by other contaminants that emerge with water acidification (mobilisation and increased solubility of heavy metals). The discrimination between the toxicity due to each of these two factors is not possible with the existing toxicity tests; the addition of chelating agents or serial dilution methods seriously alter the chemical and physical properties of the effluent. A toxicity test, based on the survival time of Ceriodaphnia dubia (Crustacea, Cladocera) neonates exposed to the unchanged effluent, was developed and field validated, on an AMD contaminated site.     

Genotoxic potential of aqueous extracts of Artemisia verlotorum on the cell cycle of Allium cepa

Artemisia verlotorum, popularly ‘infalivina’, is a medicinal herb used for respiratory, circulatory and digestive treatments. Antiproliferative and genotoxic effects of A. verlotorum aqueous extracts in three different concentrations (6, 32 and 48 g/L) were evaluated on the Allium cepa cell cycle. Results clearly showed a significant difference using the χ² test (p = 0.05) among treatments with a decrease in the mitotic index as the concentration of the extract increased. Extracts of A. verlotorum proved to be genotoxic and showed antiproliferative potential on the A. cepa cell cycle. This study suggests the use of infusions of A. verloturum for medicinal purposes only after selecting suitable concentrations.