Rui C. Martins

Fenton's oxidation process for phenolic wastewater remediation and biodegradability enhancement

A mixture of six phenolic acids, corresponding to an initial TOC of 370 mgC/L, was studied by Fentons peroxidation aiming to improve the biodegradability of agro-industrial wastewaters. Input operating variables including the concentration of pollutants, iron and hydrogen peroxide as well as the reaction time were used to assess the mineralization degree through a factorial experimental methodology. A TOC removal in the range of 15.0-58.8% was attained within the operational conditions used. A reduced model was achieved using the statistically important independent factors and interactions to predict TOC degradation. On the hydrogen peroxide injection methodology, the results showed that the continuous introduction of small volumes is advantageous when compared with one single addition of the overall volume at the zero reaction time with a mineralization improvement of 11%. The use of FeSO(4).7H(2)O correspondent to a Fe(2+) load of 271 mg; [H(2)O(2)]=488.0 mM, injected in twelve aliquots each 30 min during 6h of reaction reached optimal efficiencies with the parent compounds (quantified by HPLC and the Folin-Ciocalteau method) quickly totally removed and TOC, COD and BOD(5) final values of 123 mgC/L, 180 mgO(2)/L and 146 mgO(2)/L, respectively. Toxicity assessment by Vibrio fischeri light inhibition revealed that Fentons process reduces the effluent ecological impact related with the decomposition of the toxic phenolic acids. Indeed, EC(50) changed from 32.2% dilution to no-dilution needed. The analysis of BOD(5)/COD ratio pointed out a high improvement of the treated wastewater biodegradability from 0.30 to 0.80 meaning that the application of Fentons oxidation as a pre-treatment enables a further application of an efficient post-biological technology which was also confirmed by respirometry.

Application of hydrophobic silica based aerogels and xerogels for removal of toxic organic compounds from aqueous solutions

This work is devoted to the application of hydrophobic silica based aerogels and xerogels for the removal of three toxic organic compounds from aqueous solutions. These materials were tested and characterized regarding their morphology, particle size distribution, surface area and porous structure. The equilibrium tests were carried out at different adsorbate concentrations and the experimental data were correlated by means of Langmuir and Freundlich isotherms. The equilibrium data were well described by Langmuir and Freundlich in most cases. The maximum adsorption capacity by Langmuir model was observed for the adsorption of benzene onto aerogel (192.31 mg/g), though the most promising results were obtained for toluene adsorption due to the greater adsorption energy involved. Comparing these results with other reported results, the hydrophobic silica based aerogels/xerogels were found to exhibit a remarkable performance for the removal of benzene and toluene. In addition, the regeneration of previously saturated aerogel/toluene was also investigated by using an ozonation process. The adsorption/regeneration tests with ozone oxidation showed that the aerogel might be regenerated, nevertheless the materials lost their hydrophobicity and thus different methods should be evaluated in forthcoming investigations.

Application of ozonation for pharmaceuticals and personal care products removal from water

Due to the shortening on natural water resources, reclaimed wastewater will be an important water supply source. However, suitable technologies must be available to guaranty its proper detoxification with special concern for the emerging pharmaceutical and personal care products that are continuously reaching municipal wastewater treatment plants. While conventional biological systems are not suitable to remove these compounds, ozone, due to its interesting features involving molecular ozone oxidation and the possibility of generating unselective hydroxyl radicals, has a wider range of action on micropollutants removal and water disinfection. This paper aims to review the studies dealing with ozone based processes for water reuse by considering municipal wastewater reclamation as well as natural and drinking water treatment. A comparison with alternative technologies is given. The main drawback of ozonation is related with the low mineralization achieved that may lead to the production of reaction intermediates with toxic features. The use of hydrogen peroxide and light aided systems enhance ozone action over pollutants. Moreover, scientific community is focused on the development of solid catalysts able to improve the mineralization level achieved by ozone. Special interest is now being given to solar light catalytic ozonation systems with interesting results both for chemical and biological contaminants abatement. Nowadays the integration between ozonation and sand biofiltration seems to be the most interesting cost effective methodology for water treatment. However, further studies must be performed to optimize this system by understanding the biofiltration mechanisms.

Advanced oxidation processes for treatment of effluents from a detergent industry

Ozonation, catalytic ozonation, Fenton’s and heterogeneous Fenton‐like processes were investigated as possible pretreatments of a low biodegradable and highly toxic wastewater produced by a detergent industry. The presence of a Mn–Ce–O catalyst in ozonation enhances the biodegradability and improves the degradation at low pH values. However, a high content of carbonyl compounds adsorbed on the recovered solid indicates some limitations for real‐scale application. A commercial Fe2O3–MnOx catalyst shows higher activity as well as higher stability concerning carbon adsorption, but the leaching of metals is larger than for Mn–Ce–O. Regarding the heterogeneous Fenton‐like route with an Fe–Ce–O catalyst, even though a high activity and stability are attained, the intermediates are less biodegradable than the original compounds, indicating that the resulting effluent cannot be conducted to an activated sludge post‐treatment. The highest enhancement of effluent biodegradability is obtained with the classic homogeneous Fenton’s process, with the BOD5/COD ratio increasing from 0.32 to 0.80. This process was scaled up and the treated effluent is now safely directed to a municipal wastewater treatment plant.

Photocatalytic ozonation using doped TiO2 catalysts for the removal of parabens in water

Conventional wastewater treatments are inefficient for the removal of parabens. The aim of this study was finding a suitable solution using ozone and UVA irradiation combined with TiO2 catalysts doped with different noble metals (Ag, Pt, Pd, Au). Photocatalytic ozonation required lower amounts of ozone for higher efficiency on the removal of parabens, chemical oxygen demand (COD) and total organic carbon (TOC). The best catalyst for the initial contaminants degradation was 0.5% Ag-TiO2 leading to total parabens removal using 46mgO3/L. Due to the relative low mineralization achieved, the toxicity of the treated solutions was still compared with the initial one over several species (Vibrio fischeri, Lepidium sativum and Corbicula fluminea). All the treatments applied led to a clear decrease on the toxicity compared with initial mixture of parabens. From an economical point of view, it was concluded that the presence of UVA irradiation increased the energy consumption compared with catalytic ozonation with these catalysts but it can decrease the time of reaction. From the by-products analysis, it was concluded that hydroxylation appears to be the most significant reaction pathway and the main responsible for parabens degradation.

Algorithm Versus Physicians Variability Evaluation in the Cardiac Chambers Extraction

Congenital heart diseases are present in eight of every 1000 newborns. The diagnosis of those pathologies usually depends on the available imaging methods. A correct diagnosis requires a detailed observation of the heart chambers, wall motions, valves function, and quantitative evaluation of the cavity volumes. For that goal numerous automatic algorithms have been proposed to segment the echocardiographic images. In this paper, the authors evaluate the performance of a level set algorithm based on the phase symmetry approach and on a new logarithmic-based stopping function to extract the heart cavity contours simultaneously, and in a fully automatic way. The extracted cardiac borders are then statistically compared with the ones manually sketched by four physicians on a set of 240 cavities. Nonparametric statistical tests are conducted on the data using several figures of merit, in order to study the inter- and intraobserver variabilities among the four physicians and the level set algorithm, concerning to the extracted contours. The results show there is a great concordance about all the used similarity indexes. A higher interobserver variability was found among the physicians than the variability obtained when the algorithm versus physician performance is compared. The statistical analysis suggests the proposed algorithm produces results similar to the ones provided by the physicians.

Adopting strategies to improve the efficiency of ozonation in the real‐scale treatment of olive oil mill wastewaters

In this experimental work the ozone action on the depuration of olive oil mill wastewater is studied for different operational conditions based on an actual industrial treatment plant. It was verified that the application of a Mn–Ce–O catalyst prepared at the laboratory, with a Mn/Ce molar proportion of 70/30, enhances the depuration efficiency and the effluent biodegradability. Ozonation operation at the natural pH of the effluent is recommended. Moreover, the integration of the Fenton process as a pretreatment improves the final chemical oxygen demand removal and enables a totally biodegradable effluent to be obtained, as confirmed by respirometric techniques.

Final Remediation of Post-Biological Treated Milk Whey Wastewater by Ozone

This work deals with a real environmental problem related with milk whey wastewater. Even if a high depuration degree can be achieved using aerobic biological processes, the final effluent does not accomplish the legal regulation for disposal. In this context, we studied the application of ozone oxidation after an activated sludge treatment in order to obtain an effluent suitable to be discharged into the natural water courses. Even if the pH increase improved single ozonation efficiency, the treated wastewater was not yet able to be disposed of. The introduction of hydrogen peroxide at low concentrations enhanced the ozone action over the pollutants, and this combination led to residual water within the environmental law conditions to be released on the surroundings. Furthermore, heterogeneous catalytic ozonation over Mn-Ce-O 70/30 (prepared in our laboratory) and the commercial N-150 catalyst (Fe2O3-MnOx) was very efficient on the wastewater depuration. Nevertheless, the high amount of carbon adsorbed on the recovered catalysts disable the industrial implementation of this technology.

Manganese-Based Catalysts for the Catalytic Remediation of Phenolic Acids by Ozone

Manganese-based catalysts supported on Al2O3, TiO2, ZrO2 and CeO2 were tested for the catalytic ozonation of a simulated wastewater involving phenolic acids. Comparing the Mn-Ce catalysts preparation method, wetness impregnation and co-precipitation, the last one showed to be more active. Moreover, the increase of Mn/Ce molar proportion from 22/78 to 70/30 increased the ozonation efficiency. The catalysts stability in terms of Mn leaching, carbon adsorption and effluent biodegradability was evaluated. Mn-Ce-O (70/30) CP shows to be the most suitable catalyst to improve phenolic wastewaters catalytic remediation by ozone.

A Review on the Applications of Ozonation for the Treatment of Real Agro-Industrial Wastewaters

Regarding agro-wastewaters, the strong loads in bio-refractory substances and seasonality reduce the efficiency of biological treatments and ozonation can play an important role, so that this article reviews its application for such streams. Indeed, biodegradability and toxicity removal was assessed for a wide range of agro-effluents such as olive mill, wineries and distilleries, pulp and paper, cork and cheese production. Solid catalysts reveal promising potential, even though literature is still scarce reporting their use to actual streams. Thus, forthcoming research must embrace catalytic ozonation and continuous pilot-scale reactors behavior on the depuration of real agro-wastewaters to ensure future industrial application.