Degradation of diclofenac by TiO2 photocatalysis: UV absorbance kinetics and process evaluation through a set of toxicity bioassays

In the present study the degradation kinetics and mineralization of diclofenac (DCF) by the TiO₂ photocatalysis were investigated in terms of UV absorbance and COD measurements for a wide range of initial DCF concentrations (5-80 mg L⁻¹) and photocatalyst loadings (0.2-1.6 g TiO₂ L⁻¹) in a batch reactor system. A set of bioassays (Daphnia magna, Pseudokirchneriella subcapitata and Artemia salina) was performed to evaluate the potential detoxification of DCF. A pseudo-first-order kinetic model was found to fit well most of the experimental data, while at high initial DCF concentrations (40 and 80 mg L⁻¹) and at 1.6 g TiO₂ L⁻¹ photocatalyst loading a second-order kinetic model was found to fit the data better. The toxicity of the treated DCF samples on D. magna and P. subcapitata varied during the oxidation, probably due to the formation of some intermediate products more toxic than DCF. Unicellular freshwater algae was found to be very sensitive to the treated samples as well as the results from D. magna test were consistent to those of algae tests. A. salina was not found to be sensitive under the investigated conditions. Finally, UV absorbance analysis were found to be an useful tool for a fast and easy to perform measurement to get preliminary information on the organic intermediates that are formed during oxidation and also on their disappearance rate.     

Effect of bromide on the formation of disinfection by-products during wastewater chlorination

The effect of bromide ion on the formation and speciation of trihalomethanes (THMs) and haloacetic acids (HAAs) during the chlorination of biologically treated wastewaters was investigated. The experimental results showed that the formation of total THMs and total HAAs during chlorine disinfection increased with increasing bromide levels in wastewater. The formation of CHBr₃ increased nearly linearly with increasing bromide ion levels, while CHCl₂Br and CHClBr₂ increased with increasing bromide concentration from 0 to 3.2 mg L⁻¹ and thereafter remained constant or slightly decreased. Increasing initial bromide levels up to 12.8 mg L⁻¹ resulted in sharp decrease of the concentration of CHCl₃ and chloro- HAAs. The mixed bromochloro- HAAs and bromo-only species replaced chloro- HAAs as the dominated species of HAA with increasing bromide levels. The distribution of monohalogenated, dihalogenated and trihalogenated species of HAAs in chlorinated wastewater at high concentration of bromide (>2 mg L⁻¹) is different from that of drinking/natural water. The values of the bromine incorporation factors, n (Br) and n′ (Br), increased with increasing bromide concentration and remained constant or slightly decreased with increasing contact time under the studied range of bromide ion concentrations during chlorination. Moreover, the bromine incorporation into THMs was higher than that of HAAs with bromide levels ranging from 1.0 to 12.8 mg L⁻¹, indicating the dissimilar formation mechanisms of THMs and HAAs involving bromide.     

Disinfection of Legionella pneumophila by ultrasonic treatment with TiO2

An ultrasonic treatment system, using a TiO₂ photocatalyst, was used to disinfect Legionella pneumophila. A kinetic study of the process indicates that TiO₂ significantly improves the disinfection process. The concentrations of viable cells were reduced to 6% of the initial concentrations in the presence of 0.2 g/ml TiO₂ after a 30 min of treatment period, while only an 18% reduction was observed in the absence of TiO₂. The potency of the disinfection could be enhanced, to some extent, by increasing the amount of TiO₂ used. Cell concentrations were decreased by an order of 3 within 30 min of treatment in the presence of 1.0 g/ml TiO₂. The disinfection power in the presence of TiO₂ versus Al₂O₃ was also compared and the findings showed that TiO₂ induced a higher cell killing. No significant effect of initial cell concentration on the disinfection was found in the range of 10²-10⁷ CFU/ml after a 30 min of treatment period. The mechanism of cell killing was investigated by examining the effects of OH radical scavengers such as ascorbic acid, histidine and glutathione. The disinfection power was reduced in samples that contained these radical scavengers, thus indicating the importance of OH radicals.     

Biodegradability enhancement of a pesticide-containing bio-treated wastewater using a solar photo-Fenton treatment step followed by a biological oxidation process

This work proposes an efficient combined treatment for the decontamination of a pesticide-containing wastewater resulting from phytopharmaceutical plastic containers washing, presenting a moderate organic load (COD = 1662-1960 mg O₂ L⁻¹; DOC = 513-696 mg C L⁻¹), with a high biodegradable organic carbon fraction (81%; BOD₅ = 1350-1600 mg O₂ L⁻¹) and a remaining recalcitrant organic carbon mainly due to pesticides. Nineteen pesticides were quantified by LC-MS/MS at concentrations between 0.02 and 45 mg L⁻¹ (14-19% of DOC). The decontamination strategy involved a sequential three-step treatment: (a) biological oxidation process, leading to almost complete removal of the biodegradable organic carbon fraction; (b) solar photo-Fenton process using CPCs, enhancing the bio-treated wastewater biodegradability, mainly due to pesticides degradation into low-molecular-weight carboxylate anions; (c) and a final polishing step to remove the residual biodegradable organic carbon, using a biological oxidation process. Treatment performance was evaluated in terms of mineralization degree (DOC), pesticides content (LC-MS/MS), inorganic ions and low-molecular-weight carboxylate anions (IC) concentrations. The estimated phototreatment energy necessary to reach a biodegradable wastewater, considering pesticides and low-molecular-weight carboxylate anions concentrations, Zahn-Wellens test and BOD₅/COD ratio, was only 2.3 kJ_UV L⁻¹ (45 min of photo-Fenton at a constant solar UV power of 30 W m⁻²), consuming 16 mM of H₂O₂, which pointed to 52% mineralization and an abatement higher than 86% for 18 pesticides. The biological oxidation/solar photo-Fenton/biological oxidation treatment system achieved pesticide removals below the respective detection limits and 79% mineralization, leading to a COD value lower than 150 mg O₂ L⁻¹, which is in agreement with Portuguese discharge limits regarding water bodies.     

Degradation of fifteen emerging contaminants at μg L initial concentrations by mild solar photo-Fenton in MWTP effluents

The degradation of 15 emerging contaminants (ECs) at low concentrations in simulated and real effluent of municipal wastewater treatment plant with photo-Fenton at unchanged pH and Fe = 5 mg L⁻¹ in a pilot-scale solar CPC reactor was studied. The degradation of those 15 compounds (Acetaminophen, Antipyrine, Atrazine, Caffeine, Carbamazepine, Diclofenac, Flumequine, Hydroxybiphenyl, Ibuprofen, Isoproturon, Ketorolac, Ofloxacin, Progesterone, Sulfamethoxazole and Triclosan), each with an initial concentration of 100 μg L⁻¹, was found to depend on the presence of CO₃²⁻ and HCO₃⁻ (hydroxyl radicals scavengers) and on the type of water (simulated water, simulated effluent wastewater and real effluent wastewater), but is relatively independent of pH, the type of acid used for release of hydroxyl radicals scavengers and the initial H₂O₂ concentration used. Toxicity tests with Vibrio fisheri showed that degradation of the compounds in real effluent wastewater led to toxicity increase.     

Oxidation of 2,4-dichlorophenol and 3,4-dichlorophenol by means of Fe(III)-homogeneous photocatalysis and algal toxicity assessment of the treated solutions

Chlorophenols are used worldwide as broad-spectrum biocides and fungicides. They have half-life times in water from 0.6 to 550 h and in sediments up to 1700 h and, due to their numerous origins, they can be found in wastewaters, groundwaters or soils. Moreover, chlorophenols are not readily biodegradable.Recently, classic Advanced Oxidation Processes (AOP) have been proposed for their abatement in an aqueous solution. This paper investigates the oxidation of 2,4-dichlorophenol and 3,4-dichlorophenol, at starting concentrations of 6.1 · 10⁻⁵ mol L⁻¹, in aqueous solutions through Fe(III)/O₂ homogeneous photocatalysis under UV light (303 ÷ 366 nm). The Fe(III)/O₂ homogeneous photocatalysis is less expensive than using H₂O₂ due to the capability of Fe(III) to produce OH radicals, if irradiated with an UVA radiation, and of oxygen to re-oxidize ferrous ions to ferric ones when dissolved in solution. The results show that the best working conditions, for both compounds, are found for pH = 3.0 and initial Fe(III) concentration equal to 1.5·10⁻⁴ mol L⁻¹ although the investigated oxidizing system can be used even at pH close to 4.0 but with slower abatement kinetics. Toxicity assessment on algae indicates that treated solutions of 2,4-dichlorophenol are less toxic on algae Pseudokirchneriella subcapitata if compared to not treated solutions whereas in the case of 3,4-dichlorophenol only the samples collected during the runs at 20 and 60 min are capable of inhibiting the growth of the adopted organism.The values of the kinetic constant for the photochemical re-oxidation of iron (II) to iron (III) and for HO attack to intermediates are evaluated by a mathematical model for pH range of 2.0-3.0 and initial Fe(III) concentrations range of 1.5 · 10⁻⁵-5.2 · 10⁻⁴ mol L⁻¹.     

Photoassisted reduction of metal ions and organic dye by titanium dioxide nanoparticles in aqueous solution under anoxic conditions

The photoassisted reduction of metal ions and organic dye by metal-deposited Degussa P25 TiO₂ nanoparticles was investigated. Copper and silver ions were selected as the target metal ions to modify the surface properties of TiO₂ and to enhance the photocatalytic activity of TiO₂ towards methylene blue (MB) degradation. X-ray powder diffraction (XRPD), X-ray photoelectron spectroscopy (XPS), and transmission electron microscopy (TEM) were used to characterize the crystallinity, chemical species and morphology of metal-deposited TiO₂, respectively. Results showed that the particle size of metal-deposited TiO₂ was larger than that of Degussa P25 TiO₂. Based on XRPD patterns and XPS spectra, it was observed that the addition of formate promoted the photoreduction of metal ion by lowering its oxidation number, and subsequently enhancing the photodegradation efficiency and rate of MB. The pseudo-first-order rate constant (k_obs) for MB photodegradation by Degussa P25 TiO₂ was 3.94 × 10^− 2 min^− 1 and increased by 1.4-1.7 times in k_obs with metal-deposited TiO₂ for MB photodegradation compared to simple Degussa P25 TiO₂. The increase in mass loading of metal ions significantly enhanced the photodegradation efficiency of MB; the k_obs for MB degradation increased from 3.94 × 10^− 2 min^− 1 in the absence of metal ion to 4.64-7.28 × 10^− 2 min^− 1 for Ag/TiO₂ and to 5.14-7.61 × 10^− 2 min^− 1 for Cu/TiO₂. In addition, the electrons generated from TiO₂ can effectively reduce metal ions and MB simultaneously under anoxic conditions. However, metal ions and organic dye would compete for electrons from the illuminated TiO₂.     

Ultrasonic treatment of water contaminated with ibuprofen

The application of ultrasound (US) waves for remediation of wastewater is an area of increasing interest and promising results. The aim of this paper is to evaluate the influence of several parameters of the US process on the degradation of ibuprofen (IBP), a widely used non-steroidal anti-inflammatory recalcitrant drug found in water. Applied US power, dissolved gas, pH and initial concentration of IBP were the parameters investigated under sonication (300 kHz).Ultrasound increased the degradation of IBP from 30 to 98% in 30 min. Initial rate of IBP degradation was evaluated in the range of 1.35 and 6.1 μmol L⁻¹ min⁻¹ for initial concentrations of 2 to 21 mg L⁻¹ or 9.7 μmol L⁻¹ to 101 μmol L⁻¹, respectively. Under air and oxygen the degradation rate of IBP was 4 μmol L⁻¹ min⁻¹ being higher than that when argon was used. The most favorable degradation pH was acidic media. Complete removal of IBP was achieved but some dissolved organic carbon (DOC) remained in solution showing that long-lived intermediates were recalcitrant to the US irradiation. However, chemical and biological oxygen demands (COD and BOD₅) indicated that the process oxidize the ibuprofen compound to biodegradable substances removable in a subsequent biological step.     

Evidences of non-reactive mercury-selenium compounds generated from cultures of Pseudomonas fluorescens

This work was designed to determine chemically inert mercury-selenium (Hg-Se) compounds formed in a culture of Pseudomonas fluorescens exposed to Hg²⁺ and Se^IV (selenite). To isolate these compounds, different digestion methods were studied and sodium dodecyl sulfate (SDS) lysis was selected. The Hg⁰ and non-reactive Hg were determined in two series of cultures containing 0.0-6.00 μg L⁻¹ Se^IV (0.0-76.0 μmol L⁻¹) in combination with low 5.00 μg L⁻¹ (0.025 μmol L⁻¹) or high 100 μg L⁻¹ (0.500 μmol L⁻¹) Hg²⁺. It was found that Hg⁰ formed in the culture decreased with the increase of initial Se^IV, while the non-reactive Hg increased with the Se^IV. In cultures with low initial [Hg²⁺], a median Se^IV (2.0 μg L⁻¹ or 25.3 μmol L⁻¹) resulted in about 70% of the added Hg²⁺ sequestered as non-reactive Hg, and in culture with high initial Hg²⁺, about 40% was sequestered. P. fluorescens was proved to be indispensible for the formation of the non-reactive Hg-Se compounds. The Hg:Se molar ratio in the non-reactive Hg-Se compounds was close to 1, suggesting the existence of mercuric selenide in cells. Mechanisms for the formation of the non-reactive Hg-Se compounds are proposed.     

Degradation of the antibiotic oxolinic acid by photocatalysis with TiO2 in suspension

In the work presented here, a photocatalytic system using titanium Degussa P-25 in suspension was used to evaluate the degradation of 20 mg L⁻¹ of antibiotic oxolinic acid (OA). The effects of catalyst load (0.2-1.5 g L⁻¹) and pH (7.5-11) were evaluated and optimized using the surface response methodology and the Pareto diagram. In the range of variables studied, low pH values and 1.0 g L⁻¹ of TiO₂ favoured the efficiency of the process. Under optimal conditions the evolution of the substrate, chemical oxygen demand, dissolved organic carbon, toxicity and antimicrobial activity on Escherichia coli cultures were evaluated. The results indicate that, under optimal conditions, after 30 min, the TiO₂ photocatalytic system is able to eliminate both the substrate and the antimicrobial activity, and to reduce the toxicity of the solution by 60%. However, at the same time, ∼53% of both initial DOC and COD remain in solution. Thus, the photocatalytical system is able to transform the target compound into more oxidized by-products without antimicrobial activity and with a low toxicity. The study of OA by-products using liquid chromatography coupled with mass spectrometry, as well as the evaluation of OA degradation in acetonitrile media as solvent or in the presence of isopropanol and iodide suggest that the reaction is initiated by the photo-Kolbe reaction. Adsorption isotherm experiments in the dark indicated that under pH 7.5, adsorption corresponded to the Langmuir adsorption model, indicating the dependence of the reaction on an initial adsorption step.     

Occurrence and fate of organophosphorus flame retardants and plasticizers in urban and remote surface waters in Germany

Within this study, concentration levels and distribution of the organophosphates tris(2-chloroethyl) phosphate (TCEP), tris(2-chloro-1-methylethyl) phosphate (TCPP), tris(2-butoxyethyl) phosphate (TBEP), tri-iso-butyl phosphate (TiBP), and tri-n-butyl phosphate (TnBP) were investigated at nine lentic surface waters under different anthropogenic impact between June 2007 and October 2009. Furthermore, the possibility of in-lake photochemical degradation of the analytes was studied in laboratory experiments using spiked ultrapure water and lake water samples incubated in Teflon bottles (which transmit sunlight). TBEP, TiBP, and TnBP were photochemically degraded in spiked lake water samples upon exposure to sunlight. Organophosphate concentrations in the more remote lakes were often below or close to the limits of quantification (LOQ). TCPP was the substance with the highest median concentration in rural volcanic lakes (7-18 ng L⁻¹) indicating an atmospheric transport of the compound. At urban lakes their median concentrations were in the range of 23-61 ng L⁻¹ (TCEP), 85-126 ng L⁻¹ (TCPP), <LOQ-53 ng L⁻¹ (TBEP), 8-10 ng L⁻¹ (TiBP), and 17-32 ng L⁻¹ (TnBP). High variability but no significant seasonal trends were observed for all five organophosphates in urban lake water samples.     

Effect of COD/SO4ratio and Fe(II) under the variable hydraulic retention time (HRT) on fermentative hydrogen production

The effect of chemical oxygen demand/sulfate (COD/SO₄²⁻) ratio on fermentative hydrogen production using enriched mixed microflora has been studied. The chemostat system maintained with a substrate (glucose) concentration of 15 g COD L⁻¹ exhibited stable H₂ production at inlet sulfate concentrations of 0-20 g L⁻¹ during 282 days. The tested COD/SO₄²⁻ ratios ranged from 150 to 0.75 (with control) at pH 5.5 with hydraulic retention time (HRT) of 24, 12 and 6 h. The hydrogen production at HRT 6 h and pH 5.5 was not influenced by decreasing the COD/SO₄²⁻ ratio from 150 to 15 (with control) followed by noticeable increase at COD/SO₄²⁻ ratios of 5 and 3, but it was slightly decreased when the COD/SO₄²⁻ ratio further decreased to 1.5 and 0.75. These results indicate that high sulfate concentrations (up to 20,000 mg L⁻¹) would not interfere with hydrogen production under the investigated experimental conditions. Maximum hydrogen production was 2.95, 4.60 and 9.40 L day⁻¹ with hydrogen yields of 2.0, 1.8 and 1.6 mol H₂ mol⁻¹ glucose at HRTs of 24, 12 and 6 h, respectively. The volatile fatty acid (VFA) fraction produced during the reaction was in the order of butyrate > acetate > ethanol > propionate in all experiments. Fluorescence In Situ Hybridization (FISH) analysis indicated the presence of Clostridium spp., Clostridium butyricum, Clostridium perfringens and Ruminococcus flavefaciens as hydrogen producing bacteria (HPB) and absence of sulfate reducing bacteria (SRB) in our study.     

Heterogenous photocatalytic degradation kinetics and detoxification of an urban wastewater treatment plant effluent contaminated with pharmaceuticals

Degradation kinetics and mineralization of an urban wastewater treatment plant effluent contaminated with a mixture of pharmaceutical compounds composed of amoxicillin (10 mg L⁻¹), carbamazepine (5 mg L⁻¹) and diclofenac (2.5 mg L⁻¹) by TiO₂ photocatalysis were investigated. The photocatalytic effect was investigated using both spiked distilled water and actual wastewater solutions. The process efficiency was evaluated through UV absorbance and TOC measurements. A set of bioassays (Daphnia magna, Pseudokirchneriella subcapitata and Lepidium sativum) was performed to evaluate the potential toxicity of the oxidation intermediates. A pseudo-first order kinetic model was found to fit well the experimental data. The mineralization rate (TOC) of the wastewater contaminated with the pharmaceuticals was found to be really slow (t_1/2 = 86.6 min) compared to that of the same pharmaceuticals spiked in distilled water (t_1/2 = 46.5 min). The results from the toxicity tests of single pharmaceuticals, their mixture and the wastewater matrix spiked with the pharmaceuticals displayed a general accordance between the responses of the freshwater aquatic species (P. subscapitata > D. magna). In general the photocatalytic treatment did not completely reduce the toxicity under the investigated conditions (maximum catalyst loading and irradiation time 0.8 g TiO₂ L⁻¹ and 120 min respectively).     

Biological removal of 17α-ethinylestradiol by a nitrifier enrichment culture in a membrane bioreactor

Increasing concern about the fate of 17α-ethinylestradiol (EE2) in the environment stimulates the search for alternative methods for wastewater treatment plant (WWTP) effluent polishing. The aim of this study was to establish an innovative and effective biological removal technique for EE2 by means of a nitrifier enrichment culture (NEC) applied in a membrane bioreactor (MBR). In batch incubation tests, the microbial consortium was able to remove EE2 from both a synthetic minimal medium and WWTP effluent. A maximum EE2 removal rate of 9.0 μg EE2 g⁻¹ biomass-VSS h⁻¹ was achieved (>94% removal efficiency). Incubation of the heterotrophic bacteria isolated from the NEC did not result in a significant EE2 removal, indicating the importance of nitrification as driving force in the mechanism. Application of the NEC in a MBR to treat a synthetic influent with an EE2 concentration of 83 ng EE2 L⁻¹ resulted in a removal efficiency of 99% (loading rates up to 208 ng EE2 L⁻¹ d⁻¹; membrane flux rate: 6.9 L m⁻² h⁻¹). Simultaneously, complete nitrification was achieved at an optimal ammonium influent concentration of 1.0 mg NH₄⁺-N L⁻¹. This minimal NH₄⁺-N input is very advantageous for effluent polishing since the concomitant effluent nitrate concentrations will be low as well and it offers opportunities for the nitrifying MBR as a promising add-on technology for WWTP effluent polishing.     

Drugs degrading photocatalytically: Kinetics and mechanisms of ofloxacin and atenolol removal on titania suspensions

The conversion of the antibiotic ofloxacin and the β-blocker atenolol by means of TiO₂ photocatalysis was investigated. Irradiation was provided by a UVA lamp at 3.37 × 10⁻⁶ einstein/s photon flux, while emphasis was given on the effect of catalyst type and loading (50-1500 mg/L), initial substrate concentration (5-20 mg/L), initial pH (3-10) and the effect of H₂O₂ (0.07-1.4 mM) as an additional oxidant on substrate conversion and mineralization in various matrices (i.e. pure water, groundwater and treated municipal effluent). Conversion was assessed measuring sample absorbance at 288 and 224 nm for ofloxacin and atenolol, respectively, while mineralization measuring the dissolved organic carbon. Degussa P25 TiO₂ was found to be more active than other TiO₂ samples for either substrate degradation, with ofloxacin being more reactive than atenolol. Conversion generally increased with increasing catalyst loading, decreasing initial substrate concentration and adding H₂O₂, while the effect of solution pH was substrate-specific. Reaction rates, following a Langmuir-Hinshelwood kinetic expression, were maximized at a catalyst to substrate concentration ratio (w/w) of 50 and 15 for ofloxacin and atenolol, respectively, while higher ratios led to reduced efficiency. Likewise, high concentrations of H₂O₂ had an adverse effect on reaction, presumably due to excessive oxidant scavenging radicals and other reactive species. The ecotoxicity of ofloxacin and atenolol to freshwater species Daphnia magna was found to increase with increasing substrate concentration (1-10 mg/L) and exposure time (24-48 h), with atenolol being more toxic than ofloxacin. Photocatalytic treatment eliminated nearly completely toxicity and this was more pronounced for atenolol.     

Phosphate removal in agro-industry: Pilot- and full-scale operational considerations of struvite crystallization

Pilot-scale struvite crystallization tests using anaerobic effluent from potato processing industries were performed at three different plants. Two plants (P1 & P2) showed high phosphate removal efficiencies, 89 ± 3% and 75 ± 8%, resulting in final effluent levels of 12 ± 3 mg PO₄³⁻-P L⁻¹ and 11 ± 3 mg PO₄³⁻-P L⁻¹, respectively. In contrast, poor phosphate removal (19 ± 8%) was obtained at the third location (P3). Further investigations at P3 showed the negative effect of high Ca²⁺/PO₄³⁻-P molar ratio (ca. 1.25 ± 0.11) on struvite formation. A full-scale struvite plant treating anaerobic effluent from a dairy industry showed the same Ca²⁺ interference. A shift in the influent Ca²⁺/PO₄³⁻-P molar ratio from 2.69 to 1.36 resulted in average total phosphorus removal of 78 ± 7%, corresponding with effluent levels of 14 ± 4 mg P_total L⁻¹ (9 ± 3 mg PO₄³⁻-P L⁻¹). Under these conditions high quality spherical struvite crystals of 2-6 mm were produced.     

Application of high rate nitrifying trickling filters for potable water treatment

The interference of ammonia with chlorination is a prevalent problem encountered by water treatment plants located throughout South East Asia. The efficacy of high rate, plastic-packed trickling filters as a pre-treatment process to remove low concentrations of ammonia from polluted surface water was investigated. This paper presents the findings from a series of pilot experiments, which were designed to investigate the effect of specific conditions—namely low ammonia feed concentrations (0.5-5.0 mg NH₄-N L⁻¹), variations in hydraulic surface load (72.5-145 m³ m⁻² d⁻¹) and high suspended solid loads (51 ± 25 mg L⁻¹)—on filter nitrifying capacity. The distribution of nitrification activity throughout a trickling filter bed was also characterised. Results confirmed that high hydraulic rate trickling filters were able to operate successfully, under ammonia-N concentrations some 10- to 50-fold lower and at hydraulic loading rates 30-100 times greater than those of conventional wastewater applications. Mass transport limitations posed by low ammonia-N concentrations on overall filter performance were insignificant, where apparent nitrification rates (0.4-1.6 g NH₄-N m⁻² d⁻¹), equivalent to that of wastewater filters were recorded. High inert suspended solid loadings had no adverse effect on nitrification. Results imply that implementation of high rate trickling filters at the front-end of a water treatment train would reduce the ammonia-related chlorine demand, thereby offering significant cost savings.     

Performance of a Sequencing Batch Biofilm Reactor for the treatment of pre-oxidized Sulfamethoxazole solutions

A combined strategy of a photo-Fenton pretreatment followed by a Sequencing Batch Biofilm Reactor (SBBR) was evaluated for total C and N removal from a synthetic wastewater containing exclusively 200 mg L⁻¹ of the antibiotic Sulfamethoxazole (SMX). Photo-Fenton reaction was optimized at the minimum reagent doses in order to improve the biocompatibility of effluents with the subsequent biological reactor. Consequently, the pretreatment was performed with two different initial H₂O₂ concentrations (300 and 400 mg L⁻¹) and 10 mg L⁻¹ of Fe²⁺. The pre-treated effluents with the antibiotic intermediates as sole carbon source were used as feed for the biological reactor. The SBBR was operated under aerobic conditions to mineralize the organic carbon, and the Hydraulic Retention Time (HRT) was optimized down to 8 h reaching a removal of 75.7% of the initial Total Organic Carbon (TOC). The total denitrification of the NO₃⁻ generated along the chemical-biological treatment was achieved by means of the inclusion of a 24-h anoxic stage in the SBBR strategy. In addition, the Activated Sludge Model No. 1 (ASM1) was successfully used to complete the N balance determining the N fate in the SBBR.The characterization and the good performance of the SBBR allow presenting the assessed combination as an efficient way for the treatment of wastewaters contaminated with biorecalcitrant pharmaceuticals as the SMX.     

Oxidation of organics in retentates from reverse osmosis wastewater reuse facilities

The use of membrane processes for wastewater treatment and reuse is rapidly expanding. Organic, inorganic, and biological constituents are effectively removed by reverse osmosis (RO) membrane processes, but concentrate in membrane retentates Disposal of membrane concentrates is a growing concern. Applying advanced oxidation processes (AOPs) to RO retentate is logical because extensive treatment and energy inputs were expended to concentrate the organics, and it is cheaper to treat smaller flowstreams. AOPs (e.g., UV irradiation in the presence of titanium dioxide; UV/TiO₂) can remove a high percentage of organic matter from RO retentates. The combination of AOPs and a simple biological system (e.g., sand filter) can remove higher levels of organic matter at lower UV dosages because AOPs produce biologically degradable material (e.g., organic acids) that have low hydroxyl radical rate constants, meaning that their oxidation, rather than that of the primary organic matter in the RO retentate, dictates the required UV energy inputs. At the highest applied UV dose (10 kWh m⁻3), the dissolved organic carbon (DOC) in the RO retentate decreased from ∼40 to 8 mg L⁻1, of which approximately 6 mg L⁻1 were readily biologically degradable. Therefore, after combined UV treatment and biodegradation, the final DOC concentration was 2 mg L⁻1, representing a 91% removal. These results suggest that UV/TiO₂ plus biodegradation of RO retentates is feasible and would significantly reduce the organic pollutant loading into the environment from wastewater reuse facilities.     

Heterogeneous photocatalytic removal of toluene from air on building materials enriched with TiO2

This paper reports the potential of heterogeneous photocatalysis as an advanced oxidation technology for removal of toluene from air using TiO₂ as a photocatalyst in building materials. First, the photocatalytic activity of two types of TiO₂ containing building materials, i.e. roofing tiles and corrugated sheets, has been investigated at ambient conditions (T=25.0 °C; relative humidity RH=47%; toluene inlet concentration [TOL]_in=17–35 ppbv). Toluene removal efficiencies up to 63% were observed at a gas residence time (τ) of 17 s. Second, the effect of RH (1–77%), [TOL]_in (23–465 ppmv) and τ (17–115 s) on toluene removal has been systematically investigated using TiO₂ containing roofing tiles as photocatalytic building materials. Results revealed lower toluene removal efficiencies at higher RH and [TOL]_in, whereas a positive effect was observed with increased τ. Under optimal conditions, toluene removal efficiencies up to 78±2% and elimination rates higher than 100 mg h⁻¹ m⁻² roofing tile were obtained. A decline in photocatalytic activity by a factor of 2 was observed after operation at gas residence times shorter than 69 s and [TOL]_in higher than 76 ppmv. Washing the building materials with deionized water, simulating rainfall, could partially (i.e. by a factor 1.3) regenerate the catalyst activity.