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In this study, a waste-based magnetic activated carbon (MAC) was used for the first time in a continuous-flow stirred tank reactor (CSTR). The aim was to evaluate the dynamic removal of diclofenac (DCF) from water and wastewater. Firstly, the breakthrough curves corresponding to DCF adsorption from distilled water at different feed flow rates and doses of MAC were determined. After selecting the most favourable conditions, namely 0.18 h L-1 flow rate and 400 mg L-1 of MAC, the effect of different aqueous matrices was studied, with the breakthrough curves evidencing a performance decline in wastewater in comparison with distilled water. Finally, the exhausted MAC was magnetically recovered, regenerated by microwave-assisted heating and applied in two subsequent adsorption cycles. The regeneration studies pointed to a decrease of the specific surface area and an improvement of the magnetic retrievability of MAC. After the first regeneration step, just mild effects were observed in the dynamic adsorptive performance of MAC. However, after a second regeneration step, the performance declined ca. 50%. Overall, the results highlight the feasibility of producing waste-based magnetic composites that simultaneously combine high adsorption efficiency under dynamic operation in a CSTR, with easy retrievability and successful one-stage regeneration for further reutilization.

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Oxytetracycline (OTC) is one of the most used antibiotics in aquaculture. The main concern related to its use is the bacterial resistance, when ineffective treatments are applied for its removal or inactivation. OTC photo-degradation has been suggested as an efficient complementary process to conventional methods used in intensive fish production (e.g.: ozonation). Despite this, and knowing that the complete mineralization of OTC is difficult, few studies have examined the antibacterial activity of OTC photoproducts. Thus, the main aim of this work is to assess whether the OTC photoproducts retain the antibacterial activity of its parent compound (OTC) after its irradiation, using simulated sunlight. For that, three Gram-negative bacteria (Escherichia coli, Vibrio sp. and Aeromonas sp.) and different synthetic and natural aqueous matrices (phosphate buffered solutions at different salinities, 0 and 21‰, and three different samples from marine aquaculture industries) were tested. The microbiological assays were made using the well-diffusion method before and after OTC has been exposed to sunlight. The results revealed a clear effect of simulated sunlight, resulting on the decrease or elimination of the antibacterial activity for all strains and in all aqueous matrices due to OTC photo-degradation. For E. coli, it was also observed that the antibacterial activity of OTC is lower in the presence of sea-salts, as demonstrated by comparison of halos in aqueous matrices containing or not sea-salts.

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Doxorubicin (DOX) is used in pediatric cancer treatment. This study assessed the effects of 7 weeks of DOX and 10-week recovery on bone quality and biomechanical properties in sedentary and exercised Wistar rats. DOX decreases femur diaphysis radial growth and biomechanical properties. Some of these DOX effects were aggravated by exercise. INTRODUCTION: Bone growth in pre-pubertal years critically influences adult fracture risk. DOX is widely used in the treatment of pediatric cancers, but there is limited evidence on its potential negative effects on bone growth. Exercise improves bone growth in children, but there is no evidence if it protects against DOX-induced bone toxicity. This study investigates the early and intermediate effects of a 7-week course of DOX on bone histomorphometry and strength in sedentary and exercised growing animal models. METHODS: Sixty-eight male Wistar rats (8 weeks) were treated with DOX (2 mg kg-1) or vehicle for 7 weeks and afterward housed in standard cages or in cages with a running wheel and killed 2 or 10 weeks after last DOX administration. Femurs and blood were collected for assaying geometry, trabecular microarchitecture (histology), biomechanical properties (three-point bending and shearing of the femoral neck), bone calcium content and density (atomic absorption spectroscopy), and bone turnover markers (ELISA). RESULTS: DOX treatment reduced the femur diaphysis radial growth, with DOX-treated animals having a lower tissue area, cortical area, cortical thickness, and moment of inertia. DOX also decreased distal femur trabecular bone volume and trabecular number and increased trabecular separation. Femur diaphysis stiffness and maximum load were also reduced in past DOX-treated animals. Exercise was shown to worsen the effects of past DOX treatment on the femur diaphysis mechanical properties. CONCLUSION: DOX negatively affects bone geometry, trabecular microarchitecture, and femur mechanical properties in growing Wistar rats. Exercise further aggravates the detrimental effects of past DOX treatment on bone mechanical properties.

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Oxytracycline (OTC) is a broad spectrum antibiotic authorized for use in European aquaculture. Its photo-degradation has been widely studied in synthetic aqueous solutions, sometimes resorting to expensive methods and without proven effectiveness in natural waters. Thus, this work studied the possibility to apply the solar photo-degradation for removal of OTC from marine aquaculture's waters. For that, water samples were collected at different locals of the water treatment circuit, from two different aquaculture companies. Water samples were firstly characterized regarding to pH, salinity, total suspended solids (TSS), organic carbon and UV-Vis spectroscopic characteristics. Then, the samples were spiked with OTC and irradiated using simulated sunlight in order to evaluate the matrix effects on OTC photo-degradation. From kinetic results, the apparent quantum yields and the outdoor half-life times, at 40°N for midsummer and midwinter days were estimated by the first time for these conditions. For a midsummer day, at sea level, the outdoor half-life time predicted for OTC in these aquaculture's waters ranged between 21 and 25 min. Additionally, the pH and salinity effects on the OTC photo-degradation were evaluated and it has been shown that high pH values and the presence of sea salt increase the OTC photo-degradation rate in aquaculture's waters, compared to results in deionised water. The results are very promising to apply this low-cost methodology using the natural sunlight in aquaculture's waters to remove OTC.

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BDE-209 is a brominated flame retardant and a priority contaminant, which has been found in several environmental matrices, namely, in water. To date, there are no quantum yield data for BDE-209 photodegradation by sunlight in water, to allow predicting half-life times in aquatic systems. In this work, the kinetics of BDE-209 photodegradation in water was studied and the influence of different fractions of aquatic humic substances (HS) was evaluated. Aqueous solutions of BDE-209 exposed for different periods of time to simulated sunlight were analyzed by HPLC-UV after being concentrated using dispersive liquid-liquid microextraction (DLLME) or solid-phase extraction (SPE). The photodegradation of BDE-209 in aqueous solution followed pseudo-first-order kinetics. The average quantum yield obtained of 0.010 ± 0.001 (about 20-fold lower than the quantum yield determined in ethanol) allow to predict an outdoor half-life time of 3.5 h. The photodegradation percentage of BDE-209 was not significantly affected by the XAD-4 fraction of HS, but it decreased substantially in the presence of humic and fulvic acids. Light screening by the humic substances could not explain this delay, which is probably the result of the association of the compound with the hydrophobic sites of the humic material.

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In order to assess the status of a North Atlantic Ocean Ecoregion (Mondego system, Portugal) after the implementation of a management programme, a study on PO4-P sorption was carried out. Considering that sorption velocity markedly determines the systems promptness to phosphorus external loading, the kinetics of the sorption of PO4-P onto estuarine sediments and the upstream agricultural soils was studied. The pseudo-second order kinetic equation gave an appropriate description of PO4-P sorption onto these soils and sediments, allowing for a quantitative comparison. For soils, the kinetic constants (k2*, µg(-1) g h(-1)) ranged between 0.007 and 0.017 µg(-1) g h(-1) while, in the case of sediments these ranged between 0.008 and 0.012 µg(-1) g h(-1). Results showed that the reduction of water residence time after the management action was relevant for the system status, affecting its reaction capacity to phosphorus loading.

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The organic acids present in beer provide important information on the product's quality and history, determining organoleptic properties and being useful indicators of fermentation performance. NMR spectroscopy may be used for rapid quantification of organic acids in beer and different NMR-based methodologies are hereby compared for the six main acids found in beer (acetic, citric, lactic, malic, pyruvic and succinic). The use of partial least squares (PLS) regression enables faster quantification, compared to traditional integration methods, and the performance of PLS models built using different reference methods (capillary electrophoresis (CE), both with direct and indirect UV detection, and enzymatic essays) was investigated. The best multivariate models were obtained using CE/indirect detection and enzymatic essays as reference and their response was compared with NMR integration, either using an internal reference or an electrical reference signal (Electronic REference To access In vivo Concentrations, ERETIC). NMR integration results generally agree with those obtained by PLS, with some overestimation for malic and pyruvic acids, probably due to peak overlap and subsequent integral errors, and an apparent relative underestimation for citric acid. Overall, these results make the PLS-NMR method an interesting choice for organic acid quantification in beer.

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The objective of this work was to assess the influence of soil organic amendments on the sorption properties of the fungicide thiram. The organic amendments studied were organic household compost (COM), sewage sludge from municipal water treatment facilities (SLU) and farmyard manure (FYM), which were compared to mineral fertilizer application (MIN). Sorption-desorption experiments were performed using the batch method and the results indicated that the adsorption isotherms were non-linear and were found to conform to the Brunauer-Emmett-Teller (BET) model, suggesting multilayer adsorption and adsorbate-adsorbate interactions after the saturation of the surface layer. In general, distribution coefficient values, K(D), are dependent on, but not proportional to, the initial concentration of thiram. For a fixed thiram initial concentration, a significant correlation (r(2)>0.851; p<0.001) between K(D) values and the soil organic carbon content (OC) was observed. The highest value of K(D) was observed for the soil amended with compost, which is the one with the highest organic carbon content. K(D) values were divided by the soil organic carbon contents in order to obtain organic carbon partition coefficients K(OC). Comparing K(OC) means from 3 (initial concentrations) x 4 (soil organic matter compositions) x 3 (replicates) factorial ANOVA allow us to conclude that there is a significant but not proportional influence of the initial concentration of thiram on those values, but changes in the soil organic matter composition, associated to different soil amendments, have no significant influence on adsorption of thiram. To evaluate the reversibility of thiram adsorption, two consecutive desorption cycles were performed with CaCl(2) 0.01 mol L(-1). The desorption K(D) values were consistently higher (approximately twice) than those for adsorption at the same equilibrium concentrations for all soil samples supporting the existence of hysteresis in the adsorption-desorption behavior of thiram. Despite the fact that the adsorption K(D) values were proportionally increased with increasing total organic carbon content, this was not the case for the desorption K(D) values.

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The influence of the colonization of salt marsh sediments with Halimione portulacoides was evaluated by analysing the fluorescent dissolved organic matter (FDOM) in sediment pore waters from a salt marsh at different depths. Cores of sediments at colonized and non-colonized sites were collected from a coastal lagoon (Ria de Aveiro, Portugal). The DOC content of extracted pore waters was determined and characterized by synchronous molecular fluorescence (Deltalambda=60nm) and UV-visible spectroscopies. The common practice of freezing sediment cores for further and later chemical investigation was shown not to be an appropriate methodology of sample preservation. On the contrary, freezing of extracted and filtered pore water seemed not to affect either the DOC content or the fluorescence properties of pore waters. Two types of fluorescent substances were found in the pore waters spectra; one corresponding to humic-like substances and another one resembling proteins. However, major differences were found in the spectra of pore waters depending on both depth and the presence/absence of vegetation colonization.

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In order to provide support for the discussion of the fate of organic matter in estuaries, a laboratory simulation was performed by changing freshwater ionic strength, pH and organic matter content. The change in spectroscopic characteristics caused by variations in salinity, pH and organic matter concentration in the filtered samples was observed by UV-Vis and fluorescence spectroscopy. The increase in emission fluorescence intensity of dissolved organic matter (DOM) due to increasing salinity (in the range 0 to 5 g l-1) is affected by the pH of the samples. The emission fluorescence intensity at the three maxima observed in the fluorescence spectra, is linearly correlated with dissolved organic carbon (DOC) concentration at several salinity values in the same sample. The increase in organic matter concentration caused a shift in the emission peak wavelength at 410 nm for several salinity values. We concluded that it is necessary to take into account the influence of salinity and pH on emission fluorescence of dissolved organic matter if it is to be used as a tracer in estuarine or near shore areas.

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