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.

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.

Specific adsorbents for the treatment of OMW phenolic compounds by activation of bio-residues from the olive oil industry.

A series of adsorbents was developed by physical (CO2) and chemical (KOH) activation of two bio-residues: olive stones (OS) and wood from olive tree pruning (OTP). The physicochemical properties of such materials were determined and correlated with their adsorptive performance in the removal of phenolic compounds of olive mill wastewater (OMW). Adsorption isotherms and kinetics of single phenolic acids, as well as the kinetics for competitive multi-compound adsorption, were fitted by applying different models, though Langmuir and pseudo-second order models fitted better the experimental results, respectively. The intraparticle diffusion model pointed out that mesoporosity reduces the influence of phenolic compounds' restrictions in the external film diffusion of the adsorbent particle-solution interphase, but adsorption capacity linearly increases with the micropore volume accessible to N2 at -196 °C (and also with BET surface area), while diffusion into ultramicropores (<0.7 nm, determined by CO2-adsorption) is slow and presents minor influence on the total adsorption capacity. After saturation, thermal regeneration of spent adsorbents allows the removal of adsorbed products, enabling the reuse of samples whilst maintaining a significant performance.

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.

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.

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.

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.

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.

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.

An overview of photocatalysis phenomena applied to NOx abatement.

This review provides a short introduction to photocatalysis technology in terms of the present environmental remediation paradigm and, in particular, NOx photoabatement. The fundamentals of photoelectrochemical devices and the photocatalysis phenomena are reviewed, highlighting the main reaction mechanisms. The critical historical developments on heterogeneous photocatalysis are briefly discussed, giving particular emphasis to the pioneer works in this field. The third part of this work focus mainly on NOx removal technology considering topics such as: TiO2 photochemistry; effect of the operating conditions on the photocatalysis process; Langmuir-Hinshelwood modeling; TiO2 photocatalytic immobilization approaches; and their applications. The last section of the paper presents the main conclusions and perspectives on the opportunities related to this technology.

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.

Use of Pd-Ag Membrane Reactors for Low-Temperature Dry Reforming of Biogas-A Simulation Study.

Biogas is a valuable renewable energy source that can help mitigate greenhouse emissions. The dry reforming of methane (DRM) offers an alternative hydrogen production route with the advantage of using two main greenhouse gases, CO2 and CH4. However, its real application is limited mainly due to catalyst deactivation by coke formation and the reverse water gas shift (RWGS) reaction that can occur in parallel. Additionally, the typical dry reforming temperature range is 700-950 °C, often leading to catalyst sintering. A low-temperature DRM process could be in principle achieved using a membrane reactor (MR) to shift the dry reforming equilibrium forward and inhibit the RWGS reaction. In this work, biogas reforming was investigated through the simulation of MRs with thin (3.4 µm) and thick (50 µm) Pd-Ag membranes. The effects of the feed temperature (from 450 to 550 °C), pressure (in the range of 2-20 bar), and biogas composition (CH4/CO2 molar ratios from 1/1 to 7/3) were studied for the thin membrane through the calculation and comparison of several process indicators, namely CH4 and CO2 conversions, H2 yield, H2/CO ratio and H2 recovery. Estimation of the CO-inhibiting effect on the H2 molar flux through the membrane was assessed for a thick membrane. Simulations for a thin Pd-Ag MR show that (i) CO2 and CH4 conversions and H2 yield increase with the feed temperature; (ii) H2 yield and average rate of coke formation increase for higher pressures; and (iii) increasing CH4/CO2 feed molar ratio leads to higher H2/CO ratios, but lower H2 yields. Moreover, simulations for a thick Pd-Ag MR showed that the average H2 molar flux decreases due to the CO inhibiting effect (ca. 15%) in the temperature range considered. In conclusion, this work showed that for the considered simulation conditions, the use of an MR leads to the inhibition of the RWGS reaction and improves H2 yield, but coke formation and CO inhibition on H2 permeation may pose limitations on its practical feasibility, for which proper strategies must be explored.

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.

Novel Adsorption-Reaction Process for Biomethane Purification/Production and Renewable Energy Storage.

This work proposes an innovative method for the simultaneous upgrading of biogas streams and valorization of the separated CO2, through its conversion to renewable methane. To this end, two sorptive reactors were filled with a layered bed containing a CO2 sorbent (K-promoted hydrotalcite) and a methanation catalyst (Ru/Al2O3). The continuous cyclic operation of the parallel sorptive reactors was carried out by alternately feeding a biogas stream (CO2/CH4 mixture) or H2. The CO2/CH4 mixture is fed to the sorptive reactor during the sorption stage, with CO2 being captured by the sorbent and CH4 exiting as a purified stream (i.e., as biomethane). During the reactive regeneration stage, the inlet stream is switched to pure H2, which reacts with the previously captured CO2 at the methanation catalyst active sites thus producing additional methane. For continuous operation, the two sorptive reactors were operated 180° out of phase and cyclic steady-state could be reached after ca. five cycles. The performance of the cyclic sorptive-reactive unit was assessed through a parametric study to evaluate the influence of different operating conditions, namely, the inlet flow rate and CO2 content during the sorption stage, the hydrogen inlet flow rate during the reactive regeneration stage, the stage duration, and temperature. The inclusion of an inert purge after the reactive regeneration stage was also tested. The performance of the unit was compared to the case of direct hydrogenation of biogas, and conclusions were drawn regarding future optimization, with special attention being given to CH4 productivity and purity. During the parametric study, a compromise between these process indicators, i.e., a productivity of 1.63 molCH4 kgcat -1 h-1 with 70.3% of CH4 purity, was obtained at 350 °C. However, biomethane purities above 80% were easily achieved, though at the expense of methane productivities.

Assessment of the Potential of Using Nanofiltration Polymeric and Ceramic Membranes to Treat Refinery Spent Caustic Effluents.

Spent caustic effluents are very challenging due to their very hazardous nature in terms of toxicity as well as their extreme pH (approximately 12-14). Spent caustic has presented a challenge for wastewater treatment in refineries, due to its composition rich in mercaptans, sulfides and other aromatic compounds. To address such problems, membrane filtration was studied using real effluents from Sines Refinery, in Portugal. The present study attempts to assess the potential for spent caustic treatment with nanofiltration (NF) polymeric and ceramic membranes, assessing membrane life expectancy. For that, membrane aging studies in static mode were performed with the polymeric membrane before attempting NF treatment (dynamic studies). A ceramic membrane was also tested for the first time with this type of effluents, though only in dynamic mode. Although the polymeric membrane performance was very good and in accordance with previous studies, its lifespan was very reduced after 6 weeks of contact with spent caustic, compromising its use in an industrial unit. Contrarily to expectations, the ceramic membrane tested was not chemically more resistant than the polymeric one upon direct contact with spent caustic (loss of retention capacity in less than 1 h in contact with the spent caustic). The results obtained suggest that a pH of 13.9 is very aggressive, even for ceramic membranes.

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.

Intensification strategies for cytostatics degradation by ozone-based processes in aqueous phase.

Over the past decade there has been an increasing concern on the presence of cytostatics (also known as anticancer drugs) in natural waterbodies. The conventional wastewater treatments seem not to be effective enough to remove them, and therefore new processes must be considered. This work investigates the performance of ozonation (O3), catalytic ozonation (O3/Fe2+) and peroxone (O3/H2O2) processes, under dark or UV radiation conditions, for the degradation of cytostatics of worldwide concern. The degradation of bicalutamide (a representative of recalcitrant cytostatics) was firstly assessed in batch and then in a tubular column reactor (continuous flow mode runs) using a wastewater treatment plant (WWTP) secondary effluent. Bicalutamide removal ranged between 66 % (O3) and 98 % (O3/H2O2/UV) in continuous flow mode runs, the peroxone process being the most effective. The performance of these processes was then assessed against a mixture of twelve cytostatics of worldwide concern spiked in the WWTP effluent (25-350 ng/L). After treatment, seven cytostatics were completely removed, whereas the five most recalcitrant ones were eliminated to an extent of 8-92 % in O3/H2O2, and 44-95 % in O3/H2O2/UV. Phytotoxicity tests revealed a noticeable reduction in the effluent toxicity, demonstrating the feasibility of these processes in realistic conditions as tertiary treatment.

Photo-oxidation of NO using an exterior paint--screening of various commercial titania in powder pressed and paint films.

The present work aims to evaluate the photocatalytic activity of photo-TiO(2) from various producers (Evonik, Kemira, Kronos, Millennium, Sachtleben and Tayca), in the form of powder pressed films and upon incorporation in a water-based paint, for outdoor NO abatement. The photocatalytic activity of the different samples was evaluated in terms of NO conversion and selectivity towards nitrite and nitrate ions following approximately the ISO 22197-1:2007(E) standard. The highest yields obtained for powder pressed films were achieved with VLP7000 (0.70), followed by VLP7101 (0.55) and UVLP7500 (0.55), all from Kronos. On the other hand, when incorporated in paint films, the highest yields were obtained with PC500 and PC105 from Millennium and UV100 from Sachtleben (ca. 0.15). The paint matrix plays an important role on the photocatalytic activity. In particular, the time for steady state is one or two orders of magnitude higher when the photocatalysts are incorporated in paint films in relation to the powder pressed films. The paint films were activated following the procedure recommended by the above-mentioned standard. However, the photocatalytic activity of films incorporating P25 (Evonik) was displayed only when higher power radiation and higher humidity conditions were used. This allowed for similar levels of photocatalytic activity as the other paint films.

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.