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Mill scale is the metallurgical waste produced by the rolling mill in the steel hot rolling process. This hazardous waste is mainly composed of oxide iron, such as hematite, magnetite and wustite. It may have a different and alternative final destination by becoming a catalyst for wastewater treatment. In this work, the catalytic potential of mill scale (MS) from a steel plant was evaluated for hexavalent chromium reduction from synthetic and real matrices under slurry conditions (MS particles dispersed in the solution) or immobilized in Raschig rings. Experiments were conducted in an annular photoreactor irradiated by UVA light. Raschig rings were coated with MS by electrostatic link with polyethylene-grafted-maleic anhydride copolymer (PEGMA) film, and further packed in the annular zone of the UV photoreactor. SEM, XRD and FTIR analysis showed a homogeneous film of MS firmly attached on Raschig rings surface. In this way, the iron-rich industrial steel waste acted as both source of iron and photocatalyst, allowing the reduction of Cr(VI) to Cr(III) in the bulk solution and MS surface, respectively, in the presence of tartaric acid as hole and hydroxyl scavenger and Fe-complexing agent. The Raschig rings (248 g) coated with MS (23 g) achieved total Cr(VI) reduction (below detection limit) after 45 min of reaction (k = 2.0 × 10-2 mg L-1 min- 1) under UVA radiation, considering the following initial conditions: [Cr(VI)]0 = 10 mg L-1, [tartaric acid]0/[Cr(VI)]0 molar ratio = 6:1, pH = 3.0, T = 25 °C. The same system was tested for the treatment of a real effluent from a galvanic industry containing 6 mg L-1 of Cr(VI). Using the same tartaric acid/Cr(VI) molar ratio (6:1) and pH 3.0, the Cr(VI) present in the effluent was totally reduced (below detection limit) in 360 min (k = 1.93 × 10-2 mg L- 1 min- 1), showing similar kinetic behavior as the process with the synthetic matrix. In all experiments, the concentrations of dissolved iron (Fe(II) and Fe(total)) were below the disposal limit established by Brazilian legislation, and total chromium removal was achieved by Cr(III) precipitation after the photocatalytic reaction.

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The remediation of a real textile wastewater aiming its reuse in the textile industry was carried out by integrating two processes: (i) a chemical or electrochemical advanced oxidation process (AOP or EAOP) based on Fenton's reaction for organics degradation, and (ii) a cation exchange process using marine macroalgae for removal of the iron acting in the Fenton's reaction based processes. Four AOPs/EAOPs at acidic pH 2.8 were tested: Fenton, photo-Fenton with ultraviolet A (UVA) radiation (PF/UVA), electro-Fenton (EF) and photoelectro-Fenton with UVA radiation (PEF/UVA). These processes provided very high color removals. After a running time of 45 min, the color removals were 68-95% for the Fenton process, 76-94% for the EF process, 80-98% for the PF/UVA process and 85-100% for the PEF/UVA process. In contrast, the mineralization was negligible for all the processes, indicating the generation/presence of persistent colorless compounds. The PF process was selected as first treatment stage due to its ability for color removal and related lower costs. A set of six marine macroalgae (Gracilaria caudata, Gracilaria cervicornis, Ascophyllum nodosum, Fucus spiralis, Laminaria hyperborea and Pelvetia canaliculata) were tested for iron uptake. Laminaria hyperborea showed the highest ion exchange capacity and affinity for iron species. Its application allowed the removal of all the iron acting in the PF process (3.4 mg/L). The textile wastewater resulting from the application of PF process followed by cation exchange with Laminaria hyperborea was successfully reused in scouring, bleaching and dyeing processes.

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The aim of this work was to study the feasibility of textile sludge as a precursor to prepare catalysts for catalytic wet peroxide oxidation (CWPO) by chemical and thermal treatments. Textile sludge was characterized by physical-chemical and metal composition analyses. The chemical activation was evaluated using iron sulfate and the thermal treatment was carried out at 720 °C in a vacuum pyrolysis reactor. Two catalysts with iron contents of 1.5% and 5.6% were selected. Process parameters influence on CWPO of phenol were evaluated and a maximum removal of phenol and TOC was observed at pH 3 and 60 °C, using 3 g L-1 of the catalyst containing 5.6% of iron and 11.8 mmol L-1 of H2O2. Metal analysis indicated that the textile sludge is suitable to be employed as both iron catalyst and adsorbent. The catalysts characterization indicated a reasonable surface area with a well-developed microporosity and the presence of Hematite structures in the carbonaceous matrix. The degradation process achieved 98.2% of phenol conversion, 68.2% of mineralization and 2.11 mg L-1 of iron leaching in 150 min of reaction. The catalyst presented activity for up to 5 cycles of use, but with loss of efficiency.

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The discharge of inadequately treated or untreated industrial wastewaters has greatly contributed to the release of contaminants into the environment, including toxic metals. Toxic metals are persistent and bioaccumulative, being their removal from wastewaters prior to release into water bodies of great concern. Literature reports the use of brown marine macroalgae for toxic metals removal from aqueous solutions as an economic and eco-friendly technique, even when applied to diluted solutions. Minor attention has been given to the application of this technique in the treatment of real wastewaters, which present a complex composition that can compromise the biosorption performance. Therefore, the main goal of this comprehensive review is to critically outline studies that: (i) applied brown marine macroalgae as natural cation exchanger for toxic metals removal from real and complex matrices; (ii) optimised the biosorption process in a fixed-bed column, which was further scaled-up to pilot plants. An overview of toxic metals sources, chemistry and toxicity, which are relevant aspects to understand and develop treatment techniques, is initially presented. The problem of water resources pollution by toxic metals and more specifically the participation of metal finishing industries in the environmental contamination are issues also covered. The current and potential decontamination methods are presented including a discussion of their advantages and drawbacks. The literature on biosorption was reviewed in detail, considering especially the ion exchange properties of cell wall constituents, such as alginate and fucoidan, and their role in metal sequestration. Besides that, a detailed description of biosorption process design, especially in continuous mode, and the application of mechanistic models is addressed.

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The aim of this work was to remove the dyes Reactive Blue 221 (RB 221) and Reactive Blue 198 (RB 198) of synthetic effluent using the immobilized enzyme horseradish peroxidase (HRP) in Ca-alginate beads. Experimental parameters affecting the dye removal process such as the effect of pH, temperature, hydrogen peroxide concentration, mass capsules, and reuse were evaluated, and a numerical model of mass transfer was developed. A maximum removal of 93 and 75%, respectively, for the dyes RB 221 and RB 198, at pH 5.5 and temperature of 30 °C, concentration of hydrogen peroxide of 43.75 µM for dye RB 221 and 37.5 µM for the dye of RB 198 was obtained. A removal reaction of 180 min for RB 221 and 240 min for RB 198 was observed. Three reuse cycles of use of immobilized enzyme were achieved for both dyes. The numerical model proposed led to a good fit compared to experimental data. The HRP enzyme immobilized in Ca-alginate capsules showed a great potential for biotechnological applications, especially for the removal of reactive dyes.

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Sludge from the textile industry was used as a low-cost adsorbent to remove the dye Reactive Red 2 from an aqueous solution. Adsorbents were prepared through the thermal and chemical treatment of sludge originating from physical-chemical (PC) and biological (BIO) effluent treatment processes. The adsorbent characterization was carried out through physical-chemical analysis, X-ray fluorescence (XRF) spectroscopy, Fourier transform infrared (FTIR) spectroscopy, pHPZC determination, Boehm titration method, Brunauer-Emmett-Teller (BET) surface area analysis and scanning electron microscopy (SEM). Batch kinetic experiments and adsorption isotherm modeling were conducted under different pH and temperature conditions. The results for the kinetic studies indicate that the adsorption processes associated with these systems can be described by a pseudo-second-order model and for the equilibrium data the Langmuir model provided the best fit. The adsorption was strongly dependent on the pH but not on the temperature within the ranges studied. The maxima adsorption capacities were 159.3 mg g(-1) for the BIO adsorbent and 213.9 mg g(-1) for PC adsorbent at pH of 2 and 25 °C.

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Literature describes a kinetic mineralization profile for most of acrylic-textile dyeing wastewaters using a photo-Fenton reaction characterized by a slow degradation process and high reactants consumption. This work tries to elucidate that the slow decay on DOC concentration is associated with the formation of stable complexes between Fe(3+) and textile auxiliary products, limiting the photoreduction of Fe(3+). This work also evaluates the enhancement of a solar photo-Fenton reaction through the use of different ferric-organic ligands applied to the treatment of a simulated acrylic-textile dyeing wastewater, as a pre-oxidation step to enhance its biodegradability. The photo-Fenton reaction was negatively affected by two dyeing auxiliary products: i) Sera(®) Tard A-AS, a surfactant mainly composed of alkyl dimethyl benzyl ammonium chloride and ii) Sera(®) Sperse M-IW, a dispersing agent composed of polyglycol solvents. The catalytic activity of the organic ligands toward the ferrous-catalysed system followed this order: Fe(III)-Oxalate > Fe(III)-Citrate > Fe(III)-EDDS, and all were better than the traditional photo-Fenton reaction. Different design parameters such as iron concentration, pH, temperature, flow conditions, UV irradiance and H2O2 addition strategy and dose were evaluated. The ferrioxalate induced photo-Fenton process presented the best results, achieving 87% mineralization after 9.3 kJUV L(-1) and allowing to work until near neutral pH values. As expected, the biodegradability of the textile wastewater was significantly enhanced during the photo-Fenton treatment, achieving a value of 73%, consuming 32.4 mM of H2O2 and 5.7 kJUV L(-1).

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The burning of fossil fuels has released a large quantity of pollutants into the atmosphere. In this context, sulfur dioxide is one of the most noxious gas which, on reacting with moist air, is transformed into sulfuric acid, causing the acid rain. In response, many countries have reformulated their legislation in order to enforce the commercialization of fuels with very low sulfur levels. The existing desulfurization processes cannot remove such low levels of sulfur and thus a biodesulfurization has been developed, where the degradation of sulfur occurs through the action of microorganisms. Rhodococcus erythropolis has been identified as one of the most promising bacteria for use in the biodesulfurization. In this study, the effectiveness of the strain R. erythropolis ATCC 4277 in the desulfurization of dibenzothiophene (DBT) was evaluated in a batch reactor using an organic phase (n-dodecane or diesel) concentrations of 20, 80, and 100 % (v/v). This strain was able to degrade 93.3, 98.0, and 95.5 % of the DBT in the presence of 20, 80, and 100 % (v/v) of dodecane, respectively. The highest value for the specific DBT degradation rate was 44 mmol DBT · kg DCW(-1) · h(-1), attained in the reactor containing 80 % (v/v) of n-dodecane as the organic phase.

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A adsorção é uma das técnicas empregadas com sucesso para remoção efetiva da cor presente em efluentes têxteis. Com o objetivo de avaliar os diferentes parâmetros adsortivos, bem como determinar a eficiência de um adsorvente alternativo desenvolvido a partir de lodo residual têxtil na remoção de corantes, foram determinadas curvas de cinética de adsorção e isotermas. Por meio dos dados cinéticos e de equilíbrio obtidos, verificou-se que a 25ºC a adsorção foi favorável para todos os corantes, sendo esta a melhor condição para os corantes RO16 e RR2 na ausência de sais. Para o corante RR141, a adição de NaCl aumentou a capacidade de adsorção do adsorvente no equilíbrio e a adição de Na2SO4 favoreceu a adsorção para o corante RO16, ao contrário do que se observou para os outros dois corantes. A quantidade máxima de corante adsorvida por unidade de massa de adsorvente (q max) nas melhores condições adsortivas para os corantes RO16, RR2 e RR141 foi de 81,30, 53,48 e 78,74 mg.g-1, respectivamente.

The adsorption is one of the techniques that have been successfully used for effective removal of the dyes present in textile effluents. With the objective to evaluate the different adsorptive parameters, as well as determining the efficiency of one alternative adsorbent in the removal of dyes, kinetics and equilibrium data of adsorption were determined. By the kinetic data and of equilibrium, it was verified that the adsorption was favorable for all the dyes in 25ºC, being the best condition for the dye RO16 and RR2 in the total absence of salt. For the dye RR141, the addition of NaCl increased the adsorption capacity of adsorbent in the equilibrium and the addition of Na2SO4 favored the adsorption for the dye RO16, in contrast to what was observed for the two other dyes. The maximum quantity of dye adsorbed per unit mass of adsorbent (q max) in the best adsorptive conditions for the dyes RO16, RR2 and RR141 was of 81.30, 53.48 and 78.74 mg.g-1 respectively.