875 resultados para Photocatalysis, Titanium dioxide, Nanofiber, Matrix effect, Municipal effluent


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Aim: To evaluate the effect of photochemical activation of hydrogen peroxide (H2O2) bleaching gel with different wavelengths. Methods: In the study, 80 bovine incisors were used, which were stained in 25% soluble coffee and divided in 4 groups. The initial color was measured with the Easy Shade spectrophotometer by CIE Lab. An experimental 35% H2O2 bleaching gel was used, either with or without the presence of titanium dioxide (TiO2) pigment, associated with two light sources: G1 - Transparent Gel (TG) and no activation; G2 - Gel with TiO2 and activation with blue LED (l=470nm)\laser (Easy Bleach) appliance; G3 - Gel with TiO2 and activation with ultraviolet (l=345nm - UV); G4 - TG and activation with UV. Three applications of the gels were made for 10 min, and in each, 3 activations of 3 min, with interval of 30 s between them. The coloration was evaluated again and the variation in color perception (DE) was calculated. The data were submitted to one-way ANOVA and Tukey's test at 5% significance level. Results: There were significant differences between G1 and G4. The greatest E value was observed in G4 (13.37). There was no statistically significant difference (p>0.05) between the groups 2, 3 and 4. Conclusions: The presence of TiO2 particules in the bleaching gel did not interfere at the bleaching results.

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Low-level laser (LLL) has been used on peri-implant tissues for accelerating bone formation. However, the effect of one session of LLL in the strength of bone-implant interface during early healing process remains unclear. The present study aims to evaluate the removal torque of titanium implants irradiated with LLL during surgical preparation of implant bed, in comparison to non-irradiation. Sixty-four Wistar rats were used. Half of the animals were included in LLL group, while the other half remained as control. All animals had the tibia prepared with a 2 mm drill, and a titanium implant (2.2 × 4 mm) was inserted. Animals from LLL group were irradiated with laser (gallium aluminum arsenide), with a wavelength of 808 nm, a measured power output of 50 mW, to emit radiation in collimated beams (0.4 cm2), for 1 min and 23 s, and an energy density of 11 J/cm2. Two applications (22 J/cm 2) were performed immediately after bed preparation for implant installation. Flaps were sutured, and animals from both groups were sacrificed 7, 15, 30, and 45 days after implant installation, when load necessary for removing implant from bone was evaluated by using a torquimeter. In both groups, torque values tended to increase overtime; and at 30 and 45 days periods, values were statistically higher for LLL group in comparison to control (ANOVA test, p < 0.0001). Thus, it could be suggested that a single session of irradiation with LLL was beneficial to improve bone-implant interface strength, contributing to the osseointegration process. © 2012 Springer-Verlag London Ltd.

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Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

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In this work, magnetic photocatalysts were synthesized containing differents levels of TiO2 (40, 60 e 80%) supported at the supporter of C/LV, forming the photocatalysts 40, 60, 80Ti/C/LV, using tar pitch as carbon (C) source and red mud (LV) as iron source. The prepared magnetic photocatalysts and TiO2 were used to degrade the Remazol Black textile dye (PR5) and the organic material present in samples of a textile dye effluent. The characterization of photocatalysts by Raman, X-Ray Diffraction, Transmission Electron Micoscope and Scanning, Energy Dispersive X-ray Spectrometry, Termogravimetry and Elemental Analysis, confirms the presence of carbon and magnetite in support C/LV and the presence of TiO2 in prepared photocatalysts. The photocatalytic reactions with TiO2 were analyzed by different experimental conditions, such as: mass of TiO2 (30-240 mg), solution pH (2-10), light intensity (0.871 and 1.20 mWcm-2), type of radiation (UV and sunlight-1.420 mWcm-2), radiation incidence area (44.2 to 143.1 cm2) and dissolved oxygen (OD, 1.9 and 7.6 mg L- 1). Results showed that reactions with the following conditions: 220 mg of TiO2, pH 10, solar radiation, 7.6 mg L-1 of OD and an incidence area of radiation of 143.1 cm2 showed the best results for degradation of PR5 dye. Photocatalytic reactions with magnetic photocatalysts for degrading PR5 shows that efficiency increases with TiO2 content in the C/LV support, where, above 60% of TiO2, there was not significant increase in reaction velocity. In addition, solar radiation has proved to be advantageous for photocatalytic reactions. In order to verify the presence of a non-magnetic fraction in the photocatalyst 60Ti/C/LV0, magnetic separation was proceeded. The characterizations of the magnetic (FM) and nonmagnetic (NMF) fraction confirmed that about 25% of TiO2 did not fixed in 60Ti/C/LV photocatalyst. Results of photocatalytic reactions with FM and FNM showed that both phases have photocatalytic activity for degradation of PR5. The reactions executed for the degradation of organic matter present in the actual sample of textile effluent showed that TiO2 and magnetic photocatalyst 60Ti/C/ LV have better results for color removal (85 to 35%), soluble solids ( 11 and 3%), DQO (90 and 86%) and turbidity (94 and 11%) than the treatment done by the textile industry. Sedimentation kinetics tests in presence of a magnet showed that photocatalysts are separated faster from aqueous environment than pure TiO2. Obtained results showed that magnetic photocatalysts have excellent photocatalytic activity and can be separated from the reaction environment on a simple and quick way when a magnetic field is applied.

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Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

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Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

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Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

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Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

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Among the many methods developed for the synthesis of titanium dioxide, cathodic electrosynthesis has not received much attention because the resulting amorphous oxy-hydroxide matrix demands a further thermal annealing step to be transformed into crystalline titania. However, the possibility of filling deep recessed templates by the control of the solidliquid interface makes it a potentially suitable technique for the fabrication of porous scaffolds for photovoltaics and photocatalysis. Furthermore, a careful control of the crystallization process enables the growth of larger grains with lower density of grain boundaries, which act as electron traps that slow down electronic transport and promote charge recombination. In this report, well crystallized titania deposits were obtained by thermal annealing of amorphous deposits fabricated by cathodically assisted electrosynthesis on indium-tin oxide (ITO)substrates. The combined use of Raman spectroscopy and X-ray diffraction showed that the crystallization process is more intricate than previously assumed. It is shown that the amorphous matrix evolves into a rutile-free mixture of brookite and anatase at temperatures as low as 200 degrees C that persists up to 800 degrees C, when pure anatase dominates. The amount of brookite in the brookiteanatase mixture reaches a maximum at 400 degrees C. This very simple method for obtaining a brookiteanatase mixture and the ability to tune their proportions by thermal annealing is a promising alternative whose potential for solar cells and photocatalysis deserves a careful evaluation. Copyright (C) 2011 John Wiley & Sons, Ltd.

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This thesis wad aimed at the study and application of titanium dioxide photocatalytic activity on ceramic materials. As a matter of fact, photocatalysis is a very promising method to face most of the problems connected with the increasing environmental pollution. Furthermore, titanium dioxide, in its anatase crystallographic phase, is one of the most investigated photocatalytic material and results to be perfectly compatible with silicate body mixes. That goal was pursued by two different strategies: 1. the addition to a body mix used for heavy clay products of several titania powders, with different mean crystallite size, surface area, morphology and anatase/rutile ratio and a titania nanosuspension as well. The titania addition followed two procedures: bulk and spray addition over the ceramic samples surface. Titania was added in two different percentages: 2.5 and 7.5 wt.% in both of the methods. The ceramic samples were then fired at three maximum temperatures: 900, 950 and 1000 °C. Afterwards, the photocatalytic activity of the prepared ceramic samples was evaluated by following the degradation of an organic compound in aqueous medium, under UV radiation. The influence of titania morphological characteristics on the photoactivity of the fired materials was studied by means of XRD and SEM observations. The ceramic samples, sprayed with a slip containing 7.5 wt.% of titania powder and fired at 900 °C, have the best photoactivity, with a complete photo-decomposition of the organic compound. At 1000 °C no sample acted as a photocatalyst due to the anatase-to-rutile phase transformation and to the reaction between titania and calcium and iron oxides in the raw materials. 2. The second one foresaw the synthesis of TiO2-SiO2 solid solutions, using the following stoichiometry: Ti1-xSixO2 where x = 0, 0.1, 0.3 and 0.5 atoms per formula unit (apfu). The mixtures were then fired following two thermal cycles, each with three maximum temperatures. The effect of SiO2 addition into the TiO2 crystal structure and, consequently, on its photocatalytic activity when fired at high temperature, was thoroughly investigated by means of XRD, XPS, FE-SEM, TEM and BET analysis. The photoactivity of the prepared powders was assessed both in gas and liquid phase. Subsequently, the TiO2-SiO2 solid solutions, previously fired at 900 °C, were sprayed over the ceramic samples surface in the percentage of 7.5 wt.%. The prepared ceramic samples were fired at 900 and 1000 °C. The photocatalytic activity of the ceramic samples was evaluated in liquid phase. Unfortunately, that samples did not show any appreciable photoactivity. In fact, samples fired at 900 °C showed a pretty low photoactivity, while the one fired at 1000 °C showed no photoactivity at all. This was explained by the excessive coarsening of titania particles. To summarise, titania particle size, more than its crystalline phase, seems to have a relevant role in the photocatalytic activity of the ceramic samples.

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El gran desarrollo industrial y demográfico de las últimas décadas ha dado lugar a un consumo crecientemente insostenible de energía y materias primas, que influye negativamente en el ambiente por la gran cantidad de contaminantes generados. Entre las emisiones tienen gran importancia los compuestos orgánicos volátiles (COV), y entre ellos los compuestos halogenados como el tricloroetileno, debido a su elevada toxicidad y resistencia a la degradación. Las tecnologías generalmente empleadas para la degradación de estos compuestos presentan inconvenientes derivados de la generación de productos tóxicos intermedios o su elevado coste. Dentro de los procesos avanzados de oxidación (Advanced Oxidation Processes AOP), la fotocatálisis resulta una técnica atractiva e innovadora de interés creciente en su aplicación para la eliminación de multitud de compuestos orgánicos e inorgánicos, y se ha revelado como una tecnología efectiva en la eliminación de compuestos orgánicos volátiles clorados como el tricloroetileno. Además, al poder aprovechar la luz solar como fuente de radiación UV permite una reducción significativa de costes energéticos y de operación. Los semiconductores más adecuados para su empleo como fotocatalizadores con aprovechamiento de la luz solar son aquellos que tienen una banda de energía comparable a la de los fotones de luz visible o, en su defecto, de luz ultravioleta A (Eg < 3,5 eV), siendo el más empleado el dióxido de titanio (TiO2). El objetivo principal de este trabajo es el estudio de polímeros orgánicos comerciales como soporte para el TiO2 en fotocatálisis heterogénea y su ensayo para la eliminación de tricloroetileno en aire. Para ello, se han evaluado sus propiedades ópticas y su resistencia a la fotodegradación, y se ha optimizado la fijación del fotocatalizador para conseguir un recubrimiento homogéneo, duradero y con elevada actividad fotocatalítica en diversas condiciones de operación. Los materiales plásticos ensayados fueron el polietileno (PE), copolímero de etil vinil acetato con distintos aditivos (EVA, EVA-H y EVA-SH), polipropileno (PP), polimetil (metacrilato) fabricado en colada y extrusión (PMMA-C y PMMA-E), policarbonato compacto y celular (PC-C y PC-Ce), polivinilo rígido y flexible (PVC-R y PVC-F), poliestireno (PS) y poliésteres (PET y PETG). En base a sus propiedades ópticas se seleccionaron el PP, PS, PMMA-C, EVA-SH y PVC-R, los cuales mostraron un valor de transmitancia superior al 80% en el entorno de la región estudiada (λ=365nm). Para la síntesis del fotocatalizador se empleó la tecnología sol-gel y la impregnación multicapa de los polímeros seleccionados por el método de dip-coating con secado intermedio a temperaturas moderadas. Con el fin de evaluar el envejecimiento de los polímeros bajo la radiación UV, y el efecto sobre éste del recubrimiento fotoactivo, se realizó un estudio en una cámara de exposición a la luz solar durante 150 días, evaluándose la resistencia química y la resistencia mecánica. Los resultados de espectroscopía infrarroja y del test de tracción tras el envejecimiento revelaron una mayor resistencia del PMMA y una degradación mayor en el PS, PVC-R y EVA SH, con una apreciable pérdida del recubrimiento en todos los polímeros. Los fotocatalizadores preparados sobre soportes sin tratamiento y con tres capas de óxido de titanio mostraron mejores resultados de actividad con PMMA-C, PET y PS, con buenos resultados de mineralización. Para conseguir una mayor y mejor fijación de la película al soporte se realizaron tratamientos químicos abrasivos con H2SO4 y NaOH y tratamientos de funcionalización superficial por tecnología de plasma a presión atmosférica (APP) y a baja presión (LPP). Con los tratamientos de plasma se consiguió una excelente mojabilidad de los soportes, que dio lugar a una distribución uniforme y más abundante del fotocatalizador, mientras que con los tratamientos químicos no se obtuvo una mejora significativa. Asimismo, se prepararon fotocatalizadores con una capa previa de dióxido de silicio con la intervención de surfactantes (PDDA-SiO2-3TiO2 y SiO2FC-3TiO2), consiguiéndose buenas propiedades de la película en todos los casos. Los mejores resultados de actividad con tratamiento LPP y tres capas de TiO2 se lograron con PMMA-C (91% de conversión a 30 ppm de TCE y caudal 200 ml·min-1) mejorando significativamente también la actividad fotocatalítica en PVC-R y PS. Sin embargo, el material más activo de todos los ensayados fue el PMMA-C con el recubrimiento SiO2FC-3TiO2, logrando el mejor grado de mineralización, del 45%, y una velocidad de 1,89 x 10-6 mol· m-2 · s-1, que dio lugar a la eliminación del 100 % del tricloroetileno en las condiciones anteriormente descritas. A modo comparativo se realizaron ensayos de actividad con otro contaminante orgánico tipo, el formaldehído, cuya degradación fotocatalítica fue también excelente (100% de conversión y 80% de mineralización con 24 ppm de HCHO en un caudal de aire seco de 200 ml·min-1). Los buenos resultados de actividad obtenidos confirman las enormes posibilidades que ofrecen los polímeros transparentes en el UV-A como soportes del dióxido de titanio para la eliminación fotocatalítica de contaminantes en aire. ABSTRACT The great industrial and demographic development of recent decades has led to an unsustainable increase of energy and raw materials consumption that negatively affects the environment due to the large amount of waste and pollutants generated. Between emissions generated organic compounds (VOCs), specially the halogenated ones such as trichloroethylene, are particularly important due to its high toxicity and resistance to degradation. The technologies generally used for the degradation of these compounds have serious inconveniences due to the generation of toxic intermediates turn creating the problem of disposal besides the high cost. Among the advanced oxidation processes (AOP), photocatalysis is an attractive and innovative technique with growing interest in its application for the removal of many organic and inorganic compounds, and has emerged as an effective technology in eliminating chlorinated organic compounds such as trichloroethylene. In addition, as it allows the use of sunlight as a source of UV radiation there is a significant reduction of energy costs and operation. Semiconductors suitable to be used as photocatalyst activated by sunlight are those having an energy band comparable to that of the visible or UV-A light (Eg <3,5 eV), being titanium dioxide (TiO2), the most widely used. The main objective of this study is the test of commercial organic polymers as supports for TiO2 to be applied in heterogeneous photocatalysis and its assay for removing trichloroethylene in air. To accomplish that, its optical properties and resistance to photooxidation have been evaluated, and different operating conditions have been tested in order to optimize the fixation of the photocatalyst to obtain a homogeneous coating, with durable and high photocatalytic activity. The plastic materials tested were: polyethylene (PE), ethyl vinyl acetace copolymers with different additives (EVA, EVA-H and EVA -SH), polypropylene (PP), poly methyl (methacrylate) manufactured by sheet moulding and extrusion (PMMA-C and PMMA-E), compact and cellular polycarbonates (PC-C PC-Ce), rigid and flexible polyvinyl chloride (PVC-R and PVC-F), polystyrene (PS) and polyesters (PET and PETG). On the basis of their optical properties PP, PS, PMMA-C, EVA-SH and PVC-R were selected, as they showed a transmittance value greater than 80% in the range of the studied region (λ = 365nm). For the synthesis of the photocatalyst sol-gel technology was employed with multilayers impregnation of the polymers selected by dip-coating, with intermediate TiO2 drying at moderate temperatures. To evaluate the polymers aging due to UV radiation, and the effect of photoactive coating thereon, a study in an sunlight exposure chamber for 150 days was performed, evaluating the chemical resistance and the mechanical strength. The results of infrared spectroscopy and tensile stress test after aging showed the PMMA is the most resistant sample, but a greater degradation in PS, PVC-R and EVA SH, with a visible loss of the coating in all the polymers tested. The photocatalysts prepared on the untreated substrates with three layers of TiO2 showed better activity results when PMMA-C, PET and PS where used. To achieve greater and better fixation of the film to the support, chemical abrasive treatments, with H2SO4 and NaOH, as well as surface functionalization treatments with atmospheric pressure plasma (APP) and low pressure plasma (LPP) technologies were performed. The plasma treatment showed the best results, with an excellent wettability of the substrates that lead to a better and uniform distribution of the photocatalyst compared to the chemical treatments tested, in which no significant improvement was obtained. Also photocatalysts were prepared with the a silicon dioxide previous layer with the help of surfactants (SiO2- 3TiO2 PDDA-and-3TiO2 SiO2FC), obtaining good properties of the film in all cases. The best activity results for LPP-treated samples with three layers of TiO2 were achieved with PMMA-C (91% conversion, in conditions of 30 ppm of TCE and 200 ml·min-1 air flow rate), with a significant improvement of the photocatalytic activity in PVC-R and PS samples too. However, among all the materials assayed, PMMA-C with SiO2FC-3TiO2 coating was the most active one, achieving the highest mineralization grade (45%) and a reaction rate of 1,89 x 10-6 mol· m-2 · s-1, with total trichloroethylene elimination in the same conditions. As a comparative assay, an activity test was also performed with another typical organic contaminant, formaldehyde, also with good results (100% conversion with 24 ppm of HCHO and 200 ml·min-1 gas flow rate). The good activity results obtained in this study confirm the great potential of organic polymers which are transparent in the UV-A as supports for titanium dioxide for photocatalytic removal of air organic pollutants.

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In the field of energy saving, finding composite materials with the ability of coloring upon both illumination and change of the applied electrode potential keeps on being an important goal. In this context, chemical bath deposition of Ni(OH)2 into nanoporous TiO2 thin films supported on conducting glass leads to electrodes showing both conventional electrochromic behavior (from colorless to dark brown and vice versa) together with photochromism at constant applied potential. The latter phenomenon, reported here for the first time, is characterized by fast and reversible coloration upon UV illumination. The bleaching kinetics shows first order behavior with respect to the NiIII centers in the film, and an order 1.2 with respect to electrons in the TiO2 film. From a more applied point of view, this study opens up the possibility of having two-mode smart windows showing not only conventional electrochromism but also reversible darkening upon illumination.

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Atualmente assiste-se a um grave problema de salubridade visual das cidades, designadamente no espaço edificado/ construído. A sujidade é uma ameaça que, junto com os graffitis, tem contribuído para a degradação precoce dos espaços urbanos. A fim de se enfrentar este problema, que tem vindo a proliferar nas cidades, um pouco por todo o mundo, a presente dissertação de mestrado ambiciona contribuir para a sistematização da informação existente sobre a produção e caracterização de argamassas de auto-limpeza. As argamassas de auto-limpeza são produzidas por uma de duas formas: com a adição de nanopartículas de dióxido de titânio (TiO2) na sua matriz ou com a aplicação de um filme fino à base de TiO2 na sua superfície. Esta segunda é apontada como a técnica mais eficaz e económica. Salienta-se o facto do TiO2 ser um dos nanomateriais mais utilizados na construção pelas suas propriedades fotocatalíticas que o capacitam como um dos mais exímios fotocatalisadores, aquando da fotocatálise heterogénea. É graças ao processo de fotodegradação química da fotocatálise, que na presença de luz solar e da ação da água, que o TiO2 é ativado, desencadeando reações químicas que aumentam a eficácia e eficiência fotocatalítica. Analisou-se um conjunto de trabalhos de investigação recentes que comprovam que o uso das argamassas de auto-limpeza é adequado e benéfico em intervenções em edifícios novos como em obras de conservação e reabilitação de edifícios antigos. Além de reduzirem os investimentos em obras de limpeza, manutenção/conservação e reabilitação, prolongam a conservação das fachadas e melhoram os níveis da qualidade do ar. Apesar do crescente número de patentes pedidas e concedidas nesta área, as normas aplicáveis ainda não se encontram uniformizadas. Nesse sentido, a experiência do Japão deve ser tida como exemplo para que os restantes países desenvolvam de forma consensual as suas próprias normas e patentes, permitindo, futuramente, conferir maior credibilidade, segurança no uso dos nanomateriais e uma maior permeabilidade no setor da construção. Elencam-se alguns nano-produtos à base de nano TiO2 comercializados que têm vindo a ser aplicados sobretudo na China, Japão e na Alemanha.

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Mode of access: Internet.

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In this work, the oxidation and mineralization of paracetamol, based in an advanced oxidative process promoted by heterogeneous photocatalysis, was evaluated. The action of two photocatalysts (titanium dioxide, and a composite based on the association between titanium dioxide and zinc phthalocyanine dye) was studied. First of all, experiments in laboratory scale were performed using as radiation font a 400 W high pressure mercury lamp. The mineralization of paracetamol, promoted by both photocatalysts, was evaluated working with 4L of solution containing 10 mg L-1 of paracetamol and 100 mg L-1 of photocatalyst. To find the best experimental conditions, the influence of hydrogen peroxide concentration and pH was evaluated for the reactions. The best results for the reactions in laboratory scale was obtained using 33,00 mg L-1 of hydrogen peroxide in natural pH (6,80). Under these conditions, 100% oxidation was reached in just 40 minutes of reaction using TiO2 P25, while the mineralization was 78%. Using the composite, the mineralization was 63% in 2 hours of reaction and a oxidation of almost 100% was reached after 60 minutes. A CPC reactor (compound parabolic concentrator) was employed in the expanded work scale, using the sun as irradiation source. In this case the experiments were performed using 50 L of aqueous solution containing 10 mg L-1 of paracetamol and 100 mg L-1 of photocatalyst. The assays were done at pH 3,00 and natural pH (6,80). The used concentration of hydrogen peroxide was 33,00 mg L-1, adopted after laboratory scale studies. The reaction at pH 3,00 shows to be more advantageous, since under natural pH (6,80), the use of deionized water was necessary to prepare the solutions, probably because the deleterious action of carbonate ions, known hydroxyl radical scavengers. Using solar irradiation, the reaction mediated by the composite was more efficient when compared with the assays under laboratory scale since the composite presents the advantage of promoting a better use of visible radiation. Under these conditions, the mineralization increased from 40% to 56% under pH 3,00. At natural pH the oxidation occurred more slowly and the mineralization decreased from 56% to 50%. Thus, the use of pH 3,00 will be more interesting in real scale applications, even if it is necessary the pH correction before the discard of the treated effluent to the environment.