Catalyst-free persulfate activation by UV/visible radiation for secondary urban wastewater disinfection.

This study focuses on the treatment of secondary urban wastewater (W) to improve the effluent quality aiming at the reduction of pathogenic microorganisms for the safe reuse of the treated wastewater (TW). Catalyst-free persulfate activation by radiation-based oxidation was applied as a treatment technology. A parametric study was carried out to select the best operating conditions. Total enterobacteria inactivation (quantified by the log reduction (CFU/100 mL)) was achieved when using [S2O82-] = 1 mM, pH = 8.5 (natural pH of W), T = 25 °C, and I = 500 W/m2. However, storing TW for 3 days promoted the regrowth of bacteria, risking its reutilization. Therefore, in this study, and for the first time, the potential beneficial role of inoculation of wastewater treated by the radiation-activated persulfate process with a diverse bacterial community was evaluated in order to control the regrowth of potentially harmful microorganisms through bacterial competition. For this, TW was diluted with river water (R) in the volume percentages of 5, 25, and 50 (percentages refer to R content), and enterobacteria and total heterotrophs were enumerated before and after storage for 72 h. The results showed total heterotrophs and enterobacteria regrowth for TW and R + TW diluted 5 and 25% after storage. However, for R + TW diluted 50%, only the total heterotrophs regrew. Hence, the treated wastewater generated by the oxidative process diluted with 50% river water complies with the legislated limits for reuse in urban uses or irrigation.

Degradation of p-Nitrophenol by activated persulfate with carbon-based materials.

The removal of p-nitrophenol (PNP) from wastewater was evaluated by the activated persulfate process using different materials - carbon xerogels (XG), carbon nanotubes (CNT), and activated carbon (AC) -, and also using such materials doped with nitrogen (XGM, CNTM and ACM). These carbon materials were impregnated with 2 wt.% of iron and tested in the oxidative process to assess the influence of their textural and surface chemical properties. The carbon-based materials' properties influence the efficiencies of the adsorption and oxidative processes; in adsorption, the materials with higher specific surface areas (SBET), i.e. AC (824 m2/g) and Fe/AC (807 m2/g), have shown to be the most promising (having achieved a PNP removal of about 20%); on the other hand, in the activated persulfate process the carbon or iron-containing carbon materials with the highest mesoporous areas (Smeso) were the preferential ones - XG and Fe/XG, respectively - reaching removals of 47.3% and 75.7% for PNP and 44.9 and 63.3% for TOC, respectively. Moreover, the presence of nitrogen groups on the samples' surface benefits both processes, being found that PNP degradation and mineralization increase with the nitrogen content. The stability of the best materials (XGM and Fe/XGM) was evaluated during four cycles, being noticed that while XGM lost catalytic activity, the Fe/XGM sample remained stable without leaching of iron. The quantification of intermediate compounds formed during persulfate oxidation was performed, and only oxalic acid was detected, in addition to PNP, being that their contribution to the TOC measured was higher than 99%. Experiments carried out in the presence of radical scavengers proved that only the sulfate radical is present under the acidic conditions used. Complete PNP oxidation and TOC removal of ∼96% were reached for the activated persulfate process, proving to be more attractive than the Fenton one.

Disinfection of treated urban effluents for reuse by combination of coagulation/flocculation and Fenton processes.

In this study, a combination of coagulation/flocculation and Fenton processes was studied as tertiary treatment in order to generate treated water susceptible to reuse. The combination of both processes has never been applied in disinfection of real urban wastewater. The best removals of turbidity and enterobacteria were achieved when applying a coagulant (FeCl3) dosage of 120 mg/L and the natural pH of the effluent (7.14). The following Fenton reaction presented the maximal enterobacteria inactivation after 120 min at 25 °C, when using hydrogen peroxide and added iron concentrations of 100 mg/L and 7 mg/L, respectively. The abundance of antibiotic resistant (amoxicillin and sulfamethoxazole) enterobacteria and total enterobacteria, enterococci, and heterotrophs, and antibiotic resistance genes - ARG - (sul1, blaTEM and qnrS) was evaluated before and after each step of the treatment. Values below 10 CFU/100 mL were achieved for total and resistant cultivable enterobacteria immediately after treatment and after storage for 72 h, therefore meeting the strictest limit imposed for E. coli. Physico-chemical parameters also met the established limits for water reuse. Despite harbouring a rich and diverse bacterial community, the final stored disinfected wastewater contained high relative abundance of potentially hazardous bacteria. Such results point out the need of a deep microbiological characterization of treated wastewater to evaluate the risk of its reuse in irrigation.

Degradation of Toluene from Gas Streams by Heterogeneous Fenton Oxidation in a Slurry Bubble Reactor with Activated Carbon-Based Catalysts.

A novel approach for the treatment of volatile organic compounds from gaseous streams was developed. In order to accomplish this, a semi-batch bubble reactor was used, aiming to assess the toluene (selected as model compound) degradation from gaseous streams via heterogeneous Fenton oxidation. Activated carbon-based catalysts-metal-free or iron-impregnated-with different textural and chemical surface properties were used for the first time as catalysts, in order to degrade gaseous toluene using such technology. Complementary characterization techniques, such as nitrogen adsorption at -196 °C, elemental analysis, pH at the point of zero charge (pHPZC), inductively coupled plasma optical emission spectrometry (ICP-OES) and transmission electron microscopy (TEM), were used. The materials' chemical surface properties, particularly the presence of N-surface groups, were herein found to play an important role in toluene adsorption and catalytic performance. The maximum amount of toluene transferred, 6.39 × 10-3 mol, was achieved using melamine-doped activated carbon (N-doped material) that was impregnated with iron (sample herein called ACM-Fe). This iron-based catalyst was found to be quite stable during three reutilization cycles.

Gaseous toluene abatement by the heterogeneous Fenton-like process using iron/carbon-coated monolith as catalyst: Proof of concept.

The degradation of toluene from a gas stream by the heterogeneous Fenton process was evaluated over a carbon-coated monolith impregnated or not with iron as catalyst in a bubble column reactor (BCR). The carbon-coated monolith support (CM) was prepared by chemical vapor deposition and the catalyst (CM impregnated with iron - herein called CM-Fe) by adsorption. In the screening of processes (absorption, adsorption and reaction), it was shown that the heterogeneous Fenton process catalyzed by CM-Fe presents the best efficiency (toluene transfer (η) = 10 × 10-3 mol, for 300 mL of liquid solution and 0.69 g of catalyst). Finally, the stability of CM and CM-Fe was evaluated, wherein ten consecutive runs were carried out, the results showing a considerable deactivation of CM during the first five cycles. In contrast, the CM-Fe sample only slightly decreases its activity from the 1st to 2nd cycle (due to a small amount of iron leached from the monolith, 0.7%), remaining stable after that, which is important for applying this technology at the industrial level. This work showed for the first time that the treatment of gaseous effluents containing organic compounds by the Fenton process (which takes place in the liquid phase) using a carbon-coated monolith impregnated with iron is plausible, so the proof of concept was successfully accomplished.

Application of iron-activated persulfate for municipal wastewater disinfection.

To address the increasing contamination of aquatic environments and incidence of waterborne diseases, advanced oxidation processes with activated persulfate have emerged as tools to inactivate wastewater microorganisms and contaminants. In this work, the disinfection of a secondary effluent from a wastewater treatment plant by iron-based persulfate activation was studied. Experiments in a batch stirred tank reactor were carried out to evaluate the performance along reaction time and the effect of operational parameters in the oxidative process efficiency (oxidant and iron concentration, pH and temperature). After 60 min of reaction, persulfate and iron concentrations of 3 mM and 0.75 mM, respectively, combined with a neutral initial pH (7.5) and a temperature of 40 °C, allowed to reach values below the detection limit (<10 CFU/100 mL) of enterococci and enterobacteria with and without ciprofloxacin resistance, as well as a 91% inactivation of total heterotrophic organisms and a 70% removal of total organic carbon. Regrowth of microorganisms was evaluated 72 h after treatment and it was only noticed a slight increase in total heterotrophs. Evaluation of physico-chemical characteristics of the treated water showed that it meets the requirements imposed by European and Portuguese legislation for its reuse in irrigation and most urban utilities.

Industrial wastewater treatment using a bubble photo-Fenton reactor with continuous gas supply.

The present study assesses the treatability of a real industrial wastewater (WW) with a high organic load (chemical oxygen demand (COD) above 5800 mgO2 L-1) by photo-Fenton's oxidation with the goal of improving the organic matter degradation reached previously, in another work, where the Fenton process was applied in a bubbling reactor. Thus, the process was carried out in a bubble photo reactor (BPR) wherein continuous air supply ensures an efficient mixing of the liquid phase. The effect of the main operatory parameters that influence the WW treatment (i.e., H2O2 and Fe2+ concentrations, initial pH, and UV-Vis radiation intensity) were evaluated, being found that in the best conditions tested (pH0 = 4.6, [Fe2+] = 0.1 g L-1, [H2O2] = 18 g L-1, Qair = 1.0 L min-1-measured at room temperature and atmospheric pressure-and irradiance of 500 W m-2), removals of 95% and 97% for total organic carbon (TOC) and COD, respectively, were achieved. Still, a high reduction of the concentration of the main constituents of this WW was reached, being total for aniline and 86% for sulfanilic acid. The continuous air supply reactor configuration was compared with magnetic stirring; similar mineralization was achieved. However, the air bubbling promotes a good heat transfer within the reactor, minimizing temperature gradients, which is quite advantageous due to the strong exothermicity of the oxidation process during the treatment of such highly loaded real effluents.

Simultaneous treatment of toluene-containing gas waste and industrial wastewater by the Fenton process.

This study reports a new perspective for the simultaneous oxidation of a volatile organic compound (VOC) - a toluene gas stream - and a real industrial liquid effluent by the Fenton's process; for that, a lab-scale bubbling reactor, operating in semi-continuous mode, was used. A parametric study was carried out to evaluate the effect of the aqueous matrix (water vs. real effluent), catalyst species nature (Fe2+ vs. Fe3+), concentration of organic matter in the liquid, and inlet toluene concentration in the gas phase. Their effects in the simultaneous gas-liquid treatment were assessed in terms of the toluene removal (from the gas stream) and wastewater mineralization (removal of dissolved organic carbon - DOC). The presence of organic matter in the liquid phase decreased toluene absorption. However, the simultaneous oxidation in the liquid phase extended the period of absorption until its saturation (and inherently the amount of toluene transferred) while still oxidizing 25% of the organic matter present in the industrial effluent. The application of the Fenton-like (H2O2 + Fe3+) process yielded a slightly reduced toluene transfer as compared to the Fenton one (H2O2 + Fe2+) - ca. 10%, although the overall mineralization has been similar. As expected, increasing the inlet toluene concentration reduces the process duration until liquid saturation, at the same time that a higher accumulation of by-products in the liquid due to oxidation was observed. Finally, a sequential treatment approach was performed, wherein liquid oxidation follows the previous simultaneous gas-liquid treatment, representing a strategy for long term operation, providing an opportunity for further VOC abatement in subsequent cycles. The main compounds resulting from oxidation remaining in the liquid phase after each stage were identified, allowing to close the carbon balance by ca. 80%.

Insights into real industrial wastewater treatment by Fenton's oxidation in gas bubbling reactors.

In the present study, bubbling reactors (BRs) were chosen to design a new procedure for real industrial wastewater (WW) treatment by Fenton's oxidation. The process was carried out in BRs under batch mode for the treatment of a WW with a high organic load (chemical oxygen demand (COD) above 7000 mgO2/L), being the efficient mixing of the liquid phase ensured by the gas bubbling. The parameters that influenced the WW treatment (i.e., H2O2 and Fe2+ concentration, and initial pH) were optimized in a smaller BR (0.5 L volumetric capacity); the maximum oxidation efficiency (dissolved organic carbon (DOC) removal = 52% and COD removal = 83% after 60 min) was reached under the following conditions: Qair = 1.0 L/min (measured at room temperature and atmospheric pressure), [H2O2] = 22.5 g/L, [Fe2+] = 0.75 g/L, and pH = 4.6 - original WW pH. It was not detected any significant effect in the process efficiency of the air flow rate and gas phase composition (i.e., N2, and air), but when the process was performed with continuous O2 bubbling an increase in the DOC removal (from 43% to 53%) was observed after 5 min of oxidation. Even so, the high costs discourage the use of pure oxygen streams in real WWTPs. To understand the dynamics of the process, the continuous air bubbling was compared to another mixing mode (mechanical stirring), and similar mineralization was achieved, proving the feasibility of Fenton's process in a BR. In addition, the gas bubbling proved to be more efficient in terms of heat dissipation during the treatment, decreasing temperature profiles along the oxidation of heavily charged real effluents. An effective scale-up with a bubble column reactor with a higher volumetric capacity by a factor of almost one order of magnitude was also proved, providing similar mineralization. The final effluent was non-toxic and more biodegradable.

Treatment of biodigested coffee processing wastewater using Fenton's oxidation and coagulation/flocculation.

Biodigested coffee processing wastewater (CPW) presents a high organic load and does not meet the limits imposed by legislation (namely in Brazil) for discharge into water bodies. Anaerobic digestion generally cannot provide a satisfactory organic matter reduction in CPW as a significant fraction of recalcitrant compounds still persists in the treated effluent. So, this study aims to find alternative ways to remove refractory organic compounds from this wastewater in order to improve the biodegradability and reduce the toxicity, which will allow its recirculation back into the anaerobic digester. Three treatment approaches (Fenton's oxidation - Approach 1, Coagulation/flocculation (C/F) - Approach 2, and the combination of C/F with Fenton's process - Approach 3) were selected to be applied to the biodigested CPW in order to achieve that objective. The application of the Fenton process under the optimal operating conditions (initial pH = 5.0; T = 55 °C, [Fe3+] = 1.8 g L-1 and [H2O2] = 9.0 g L-1) increased the biodegradability (the BOD5:COD ratio raised from 0.34 ± 0.02 in biodigested CPW to 0.44 ± 0.01 after treatment) and eliminated the toxicity (0.0% of Vibrio fischeri inhibition) along with moderate removals of organic matter (51.3%, 55.7% and 39.7% for total organic carbon - TOC, chemical oxygen demand - COD and biochemical oxygen demand - BOD5, respectively). The implementation of a coagulation/flocculation process upstream from Fenton's oxidation, under the best operating conditions (pH 10-11 and [Fe3+] = 250 mg L-1), also allowed to slightly increase the biodegradability (from 0.34 to 0.47) and reduce the toxicity, whereas providing a higher removal of organic matter (TOC = 76.2%, COD = 76.5 and BOD5 = 66.3% for both processes together). Approach 1 and Approach 3 showed to be the best ones, implying similar operating costs (∼74 R$ m-3/∼17 € m-3) and constitute an attractive option for managing biodigested CPW.

Application of the Fenton's process in a bubble column reactor for hydroquinone degradation.

The aim of this study was to assess the degradation and mineralization of hydroquinone (HQ) by the Fenton's process in a bubble column reactor (BCR). The effect of the main operating variables, namely, air flow rate, effluent volume, hydrogen peroxide (H2O2) concentration, catalyst (Fe2+) dose, initial pH, and temperature, were assessed. For all air flow rates tested, no concentration gradients along the column were noticed, evidencing that a good mixing was reached in the BCR. For the best conditions tested ([H2O2] = 500 mg/L, [Fe2+] = 45 mg/L, T = 24 °C, Q air = 2.5 mL/min, pH = 3.0, and V = 5 L), complete HQ degradation was reached, with ~ 39% of total organic carbon (TOC) removal, and an efficiency of the oxidant use-η H2O2-of 0.39 (ratio between TOC removed per H2O2 consumed normalized by the theoretical stoichiometric value); moreover, a non-toxic effluent was generated. Under these conditions, the intermediates and final oxidation compounds identified and quantified were a few carboxylic acids, namely, maleic, pyruvic, and oxalic. As a strategy to improve the TOC removal, a gradual dosage of the optimal H2O2 concentration was implemented, being obtained ~ 55% of mineralization (with complete HQ degradation). Finally, the matrix effect was evaluated, for which a real wastewater was spiked with 100 mg/L of HQ; no reduction in terms of HQ degradation and mineralization was observed compared to the solution in distilled water.

p-Nitrophenol degradation by Fenton's oxidation in a bubble column reactor.

This paper reports on a study of the oxidation of p-nitrophenol (PNP) in a bubble column reactor (BCR). The use of the air stream aimed to provide perfect mixing in the liquid phase, which was successfully achieved and checked experimentally; there were no concentration gradients along the column, even at the lowest air flow rate used (Q = 1 mL/min at room temperature and atmospheric pressure). The effect of the operating variables was assessed, and a total reduction of PNP was reached, as well as mineralization of 49.2%, oxidant consumption of 90.3%, and with an efficiency of use - ηH2O2 - of 0.09 mg C/mg H2O2, under the best operating conditions found - Q = 1 mL/min, [H2O2] = 1.6 g/L, [Fe2+] = 80 mg/L, pH = 3.0 and T = 22-24 °C - (after 120 min of reaction). Following this, various strategies were developed for improving the mineralization rate; it was found that the addition of H2O2 every 5 min and readjusting the pH after 30 min of reaction allow the attainment of a much higher TOC removal (75.1%) and efficiency of oxidant use (ηH2O2 = 0.17 mg C/mg H2O2) with less oxidant. A reaction mechanism was proposed, based on intermediates identified that include p-nitrocatechol - PNC, p-benzoquinone - PB, hydroquinone - HQ - and carboxylic acids (oxalic, maleic and fumaric). Since the performance achieved in the BCR was good, and very similar to that obtained in a conventional batch reactor, it was possible to verify the efficacy of carrying out the Fenton process in this reactor configuration, which in our future work will focus on the treatability of industrial effluents.

Synthetic olive mill wastewater treatment by Fenton's process in batch and continuous reactors operation.

Degradation of total phenol (TPh) and organic matter, (expressed as total organic carbon TOC), of a simulated olive mill wastewater was evaluated by the Fenton oxidation process under batch and continuous mode conditions. A mixture of six phenolic acids usually found in these agro-industrial wastewaters was used for this purpose. The study focused on the optimization of key operational parameters of the Fenton process in a batch reactor, namely Fe2+ dosage, hydrogen peroxide concentration, pH, and reaction temperature. On the assessment of the process efficiency, > 99% of TPh and > 56% of TOC removal were attained when [Fe2+] = 100 ppm, [H2O2] = 2.0 g/L, T = 30 °C, and initial pH = 5.0, after 300 min of reaction. Under those operational conditions, experiments on a continuous stirred-tank reactor (CSTR) were performed for different space-time values (τ). TOC and TPh removals of 47.5 and 96.9%, respectively, were reached at steady-state (for τ = 120 min). High removal of COD (> 75%) and BOD5 (> 70%) was achieved for both batch and CSTR optimum conditions; analysis of the BOD5/COD ratio also revealed an increase in the effluent's biodegradability. Despite the high removal of lumped parameters, the treated effluent did not met the Portuguese legal limits for direct discharge of wastewaters into water bodies, which indicates that coupled chemical-biological process may be the best solution for real olive mill wastewater treatment.

Treatment of sugarcane vinasse by combination of coagulation/flocculation and Fenton's oxidation.

The efficiency of individual and integrated processes applied to organic matter reduction and biodegradability improvement of a biodigested sugarcane vinasse wastewater was assessed. Strategies considered were Fenton's oxidation (Strategy 1), coagulation/flocculation (Strategy 2) and the combination of both processes (coagulation/flocculation followed by Fenton's reaction) - Strategy 3. It was found that Fenton's oxidation per se allowed reducing the organic matter, increasing the wastewater biodegradability and a non-toxic effluent was generated; however the cost of treatment was very high (86.6 R$/m(3) - 21.2 €/m(3)). Under optimized conditions, coagulation/flocculation provided a slight increase in effluent's biodegradability, toxicity towards Vibrio fischeri was also eliminated and moderate removals of total organic carbon - TOC - (30.5%), biological oxygen demand - BOD5 - (27.9%) and chemical oxygen demand - COD - (43.6%) were achieved; however, the operating costs are much smaller. The use of dissolved iron resulting from coagulation/flocculation (270 mg/L) as catalyst in the second stage - Fenton's oxidation - was shown to be an innovative and economically attractive strategy. Under optimal conditions overall removals of 51.6% for TOC, 45.7% for BOD5 and 69.2% for COD were achieved, and a biodegradable (BOD5:COD ratio = 0.54) and non-toxic effluent was obtained. In order to increase the efficiency of the process but using less hydrogen peroxide, the Fenton's oxidation was performed by gradually adding the oxidant. This procedure allowed to obtain the highest organic matter removal efficiency (as compared with the addition of all hydrogen peroxide at the beginning of the reaction). This way it was possible to minimize the reagent consumption and, consequently, reduce the treatment cost.

Coupling of acrylic dyeing wastewater treatment by heterogeneous Fenton oxidation in a continuous stirred tank reactor with biological degradation in a sequential batch reactor.

This work deals with the treatment of a recalcitrant effluent, from the dyeing stage of acrylic fibres, by combination of the heterogeneous Fenton's process in a continuous stirred tank reactor (CSTR) with biological degradation in a sequential batch reactor (SBR). Three different catalysts (a commercial Fe/ZSM-5 zeolite and two distinct Fe-containing activated carbons - ACs - prepared by wet impregnation of iron acetate and iron nitrate) were employed on the Fenton's process, and afterwards a parametric study was carried out to determine the effect of the main operating conditions, namely the hydrogen peroxide feed concentration, temperature and contact time. Under the best operating conditions found, using the activated carbon impregnated with iron nitrate, 62.7% of discolouration and 39.9% of total organic carbon (TOC) reduction were achieved, at steady-state. Furthermore, a considerable increase in the effluent's biodegradability was attained (BOD5:COD ratio increased from <0.001 to 0.27 and SOUR - specific oxygen uptake rate - from <0.2 to 11.1 mg O2/(gVSS·h)), alongside a major decrease in its toxicity (from 92.1 to 94.0% of Vibrio fischeri inhibition down to 6.9-9.9%). This allowed the application of the subsequent biological degradation stage. The combination of the two processes provided a treated effluent that clearly complies with the legislated discharge limits. It was also found that the iron leaching from the three catalysts tested was very small in all runs, a crucial factor for the stability and long-term use of such materials.

Technical and economic feasibility of polyester dyeing wastewater treatment by coagulation/flocculation and Fenton's oxidation.

This study aims to investigate the efficiency of individual and integrated processes applied to organic matter abatement and biodegradability improvement of a polyester dyeing wastewater, namely coagulation/flocculation combined with Fenton's reagent (Approach 1), Fenton oxidation alone (Approach 2) and its integration with coagulation/flocculation (Approach 3). The effects of Fe2+ dose, initial concentration of the oxidant (H202) and temperature during Fenton's oxidation were evaluated in Approaches 1 and 2, whereas in Approach 3 the influence ofpH and flocculant dose was also assessed, during the coagulation/flocculation stage. Toxicity and biodegradability of the final effluent were also evaluated. After oxidation, a slight increase in the specific oxygen uptake rate of the effluent was observed (from 27.0 up to 28.5-30.0mg O2/(gVSSh)) and the inhibition to Vibrio fischeri was eliminated. An effluent that complies with discharge standards was obtained in all cases; however, Approach 3 revealed to be a promising solution for treating this effluent as it leads to smaller operating costs. Therefore, the use of dissolved iron resulting from Fenton's oxidation as coagulant in the second stage was shown to be an innovative, efficient and economically attractive strategy for treating these effluents.

Treatment of textile dye wastewaters using ferrous sulphate in a chemical coagulation/flocculation process.

The coagulation/flocculation treatment using FeSO4 x 7H2O as a coagulant is evaluated in this work for the removal of organic compounds and colour from synthetic effluents simulating the cotton, acrylic and polyester dyeing wastewaters. The coagulant dose, temperature, pH, stirring speed and stirring time that maximized the removal of dissolved organic carbon (DOC) and colour for each effluent are determined for the coagulation process. The effect of the stirring speed, stirring time and the dose of flocculant (Magnafloc 155 or Superfloc C-573) on the flocculation stage is also evaluated for effluents pretreated by coagulation at the optimal conditions previously determined. The obtained results showed that the optimal operating conditions are different for each effluent, and the process (coagulation/flocculation) as a whole was efficient in terms of colour removal (-91% for cotton, -94% for acrylic effluents; polyester effluent is practically colourless). However, the DOC removal observed is not significant (33% for polyester, -45% for cotton and -28% for acrylic effluents). On the other hand, the remaining dissolved iron content is appropriate for further integrating the treatment with an iron-catalysed Fenton process, thus reducing the consumption of chemicals in the overall treatment.

Treatment of textile effluent by chemical (Fenton's Reagent) and biological (sequencing batch reactor) oxidation.

The removal of organic compounds and colour from a synthetic effluent simulating a cotton dyeing wastewater was evaluated by using a combined process of Fenton's Reagent oxidation and biological degradation in a sequencing batch reactor (SBR). The experimental design methodology was first applied to the chemical oxidation process in order to determine the values of temperature, ferrous ion concentration and hydrogen peroxide concentration that maximize dissolved organic carbon (DOC) and colour removals and increase the effluent's biodegradability. Additional studies on the biological oxidation (SBR) of the raw and previously submitted to Fenton's oxidation effluent had been performed during 15 cycles (i.e., up to steady-state conditions), each one with the duration of 11.5h; Fenton's oxidation was performed either in conditions that maximize the colour removal or the increase in the biodegradability. The obtained results allowed concluding that the combination of the two treatment processes provides much better removals of DOC, BOD(5) and colour than the biological or chemical treatment alone. Moreover, the removal of organic matter in the integrated process is particularly effective when Fenton's pre-oxidation is carried out under conditions that promote the maximum increase in wastewater biodegradability.

Optimization of the azo dye Procion Red H-EXL degradation by Fenton's reagent using experimental design.

Chemical oxidation by Fenton's reagent of a reactive azo dye (Procion Deep Red H-EXL gran) solution has been optimized making use of the experimental design methodology. The variables considered for the oxidative process optimization were the temperature and the initial concentrations of hydrogen peroxide and ferrous ion, for a dye concentration of 100mg/L at pH 3.5, the latter being fixed after some preliminary runs. Experiments were carried out according to a central composite design approach. The methodology employed allowed to evaluate and identify the effects and interactions of the considered variables with statistical meaning in the process response, i.e., in the total organic carbon (TOC) reduction after 120 min of reaction. A quadratic model with good adherence to the experimental data in the domain analysed was developed, which was used to plot the response surface curves and to perform process optimization. It was concluded that temperature and ferrous ion concentration are the only variables that affect TOC removal, and due to the cross-interactions, the effect of each variable depends on the value of the other one, thus affecting positively or negatively the process response.