Fate of pharmaceuticals in contaminated urban wastewater effluent under ultrasonic irradiation

The application of sonolysis (US) for remediation of wastewater is an area of increasing interest. The aim of this study was to evaluate the ultrasonic (US) process on the degradation of pharmaceuticals (diclofenac (DCF), amoxicillin (AMX), carbamazepine (CBZ)) in single solutions and also in three mixtures spiked in urban wastewater effluent. Several operating conditions, such as power density (25-100 W L⁻¹), initial substrate concentrations (2.5-10 mg L⁻¹), initial solution pH (3-11), and air sparging were varied for the evaluation and understanding of the process. The degradation (as assessed by measuring UV absorbance), the generation of hydroxyl radicals (as assessed measuring H₂O₂ concentration), the mineralization (in terms of TOC and COD removal), and the aerobic biodegradability (as assessed by the BOD₅/COD ratio) were monitored during sonication. Ecotoxicity to Daphnia magna, Pseudokirchneriella subcapitata and Lepidium sativum before and after treatment was also evaluated. It was found that the pharmaceuticals conversion is enhanced at increased applied power densities, acidic conditions and in the presence of dissolved air. The reaction rate increases with increasing initial concentration of single pharmaceuticals but it remains constant in the mixtures, indicating different kinetic regimes (i.e. first and zero order respectively). Mineralization is a slow process as reaction by-products are more stable than pharmaceuticals to total oxidation; nonetheless, they are also more readily biodegradable. The toxicity of the wastewater samples before and after contamination with pharmaceuticals both in mixtures and in single substance-containing solutions was observed more severely on P. subcapitata; a fact that raises concerns in regards to the discharge of such effluents. D. magna displayed less sensitivity compared to P. subcapitata because it belongs in a lower taxonomic species than D. magna. The germination index of L. sativum in the presence of the drugs' mixture was stimulated instead of inducing any toxicity effect and this might be attributed to the fact the sample, laden with very low drug concentrations was able to act as a provider of additional nutrient elements.     

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.     

Degradation of sulfamethoxazole in water by solar photo-Fenton. Chemical and toxicological evaluation

In this work, the photocatalytic degradation of the antibiotic sulfamethoxazole (SMX) by solar photo-Fenton at pilot plant scale was evaluated in distilled water (DW) and in seawater (SW). Degradation and mineralization of SMX were strongly hindered in SW compared to DW. The influence of H₂O₂ and iron concentration on the efficiency of the photocatalytic process was evaluated. An increase in iron concentration from 2.6 to 10.4 mg L⁻¹ showed only a slight improvement in SMX degradation and mineralization. However, an increase in H₂O₂ concentration up to 120 mg L⁻¹ during photo-Fenton in DW decreased SMX solution toxicity from 85% to 20%, according to results of Daphnia magna bioassays. The same behaviour was not observed after photo-Fenton treatment in SW. Despite 45% mineralization in SW, toxicity increased from 16% to 86% as shown by Vibrio fischeri bioassays, which suggests that the intermediates generated in SW are different from those in DW. A SMX degradation pathway during the photo-Fenton treatment in DW is 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.     

Coupling membrane separation and photocatalytic oxidation processes for the degradation of pharmaceutical pollutants

The coupling of membrane separation and photocatalytic oxidation has been studied for the removal of pharmaceutical pollutants. The retention properties of two different membranes (nanofiltration and reverse osmosis) were assessed. Comparable selectivity on the separation of pharmaceuticals were observed for both membranes, obtaining a permeate stream with concentrations of each pharmaceutical below 0.5 mg L⁻¹ and a rejected flux highly concentrated (in the range of 16–25 mg L⁻¹ and 18–32 mg L⁻¹ of each pharmaceutical for NF-90 and BW-30 membranes, respectively), when an initial stream of six pharmaceuticals was feeding to the membrane system (10 mg L⁻¹ of each pharmaceutical). The abatement of concentrated pharmaceuticals of the rejected stream was evaluated by means of heterogeneous photocatalytic oxidation using TiO₂ and Fe₂O₃/SBA-15 in presence of hydrogen peroxide as photo-Fenton system. Both photocatalytic treatments showed remarkable removals of pharmaceutical compounds, achieving values between 80 and 100%. The nicotine was the most refractory pollutant of all the studied pharmaceuticals. Photo-Fenton treatment seems to be more effective than TiO₂ photocatalysis, as high mineralization degree and increased nicotine removal were attested. This work can be considered an interesting approach of coupling membrane separation and heterogeneous photocatalytic technologies for the successful abatement of pharmaceutical compounds in effluents of wastewater treatment plants.     

Influence of pharmaceutical residues on the structure of activated sludge bacterial communities in wastewater treatment bioreactors

Concern is growing over contamination of the environment with pharmaceuticals because of their widespread use and incomplete removal during wastewater treatment, where microorganisms drive the key processes. The influence of pharmaceuticals on bacterial community structure in activated sludge was assessed in small-scale wastewater treatment bioreactors containing different concentrations (5, 50, 200 and 500 μg L⁻¹) of several commonly used pharmaceuticals (ibuprofen, naproxen, ketoprofen, diclofenac and clofibric acid). T-RFLP analyses of the bacterial 16S rRNA genes indicated a minor but consistent shift in the bacterial community structure in the bioreactor R50 supplied with pharmaceuticals at a concentration of 50 μg L⁻¹, compared to the control reactor R0, which was operated without addition of pharmaceuticals. In the reactors operated with higher concentrations of pharmaceuticals, a greater structural divergence was observed. Bacterial community composition was further investigated by preparation of two clone libraries of bacterial 16S rRNA genes from reactors R0 and R50. Most clones in both libraries belonged to the Betaproteobacteria, among which Thauera, Sphaerotilus, Ideonella and Acidovorax-related spp. dominated. Nitrite-oxidizing bacteria of the genus Nitrospira sp., which are key organisms for the second stage of nitrification in wastewater treatment plants, were found only in the clone library of the reactor without pharmaceuticals. In addition, diversity indices were calculated for the two clone libraries, indicating a reduced diversity of activated sludge bacterial community in the reactor supplied with 50 μg L⁻¹ of each of selected pharmaceuticals.     

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.     

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.     

Solar photo-Fenton process on the abatement of antibiotics at a pilot scale: Degradation kinetics, ecotoxicity and phytotoxicity assessment and removal of antibiotic resistant enterococci

This work investigated the application of a solar driven advanced oxidation process (solar photo-Fenton), for the degradation of antibiotics at low concentration level (μg L⁻¹) in secondary treated domestic effluents at a pilot-scale. The examined antibiotics were ofloxacin (OFX) and trimethoprim (TMP). A compound parabolic collector (CPC) pilot plant was used for the photocatalytic experiments. The process was mainly evaluated by a fast and reliable analytical method based on a UPLC-MS/MS system. Solar photo-Fenton process using low iron and hydrogen peroxide doses ([Fe²⁺]₀ = 5 mg L⁻¹; [H₂O₂]₀ = 75 mg L⁻¹) was proved to be an efficient method for the elimination of these compounds with relatively high degradation rates. The photocatalytic degradation of OFX and TMP with the solar photo-Fenton process followed apparent first-order kinetics. A modification of the first-order kinetic expression was proposed and has been successfully used to explain the degradation kinetics of the compounds during the solar photo-Fenton treatment. The results demonstrated the capacity of the applied advanced process to reduce the initial wastewater toxicity against the examined plant species (Sorghum saccharatum, Lepidium sativum, Sinapis alba) and the water flea Daphnia magna. The phytotoxicity of the treated samples, expressed as root growth inhibition, was higher compared to that observed on the inhibition of seed germination. Enterococci, including those resistant to OFX and TMP, were completely eliminated at the end of the treatment. The total cost of the full scale unit for the treatment of 150 m³ day⁻¹ of secondary wastewater effluent was found to be 0.85 € m⁻³.     

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.     

Formation of bromoform in irradiated titanium dioxide suspensions with varying photocatalyst, dissolved organic carbon and bromide concentrations

We report the formation of bromoform in TiO₂ suspensions (P25) under simulated solar UV irradiation at different concentrations of photocatalyst (0.5-1.5 g L⁻¹) as well as initial concentrations of bromide ions (1-3 mg L⁻¹) and 2,4-dihydroxybenzoic acid (2-10 mg L⁻¹). The extent of bromoform formation (3-17 μg L⁻¹) was most strongly affected by the amount of photocatalyst present and by the initial bromide concentration, increasing either of which leads to increased bromoform formation. Important interaction effects were observed when simultaneously increasing the concentrations of TiO₂ and bromide as well as of bromide and DHBA. The time it takes for bromoform to appear in measurable concentrations in the irradiated TiO₂ suspensions was between 10 and 90 min and most strongly depended on the initial concentration of dissolved organic carbon present in the suspensions, along with the amount of photocatalyst, also in interaction with the initial bromide concentration.     

Degradation of carbamazepine in environmentally relevant concentrations in water by Hydrodynamic-Acoustic-Cavitation (HAC)

The antiepileptic drug carbamazepine is one of the most abundant pharmaceuticals in the German aquatic environment. The effect of low carbamazepine concentrations (1-50 μg L⁻¹) is discussed controversially, but ecotoxicological studies revealed reproduction toxicity, decreased enzymatic activity and bioaccumulation in different test organisms. Therefore, as a preventive step, an efficient and cost-effective technique for wastewater treatment plants is needed to stop the entry of pharmaceuticals into the aquatic environment. Cavitation, the formation, growth, and subsequent collapse of gas- or vapor-filled bubbles in fluids, was applied to solve this problem. The technique of Hydrodynamic-Acoustic-Cavitation was used showing high synergistic effect. Under optimized conditions carbamazepine (5 μg L⁻¹) was transformed by pseudo-first order kinetics to an extent of >96% within 15 min (27% by hydrodynamic cavitation, 33% by acoustic cavitation). A synergistic effect of 63% based on the sum of the single methods was calculated. Carbamazepine concentrations were monitored by a sensitive and selective immunoassay and after 60 min no known metabolites were detectable by LC-MS/MS.     

Contribution of the ozonation pre-treatment to the biodegradation of aqueous solutions of 2,4-dichlorophenol

The effect of ozonation on the biodegradability of 100-ppm aqueous solutions of 2,4-dichlorophenol has been investigated. BOD at 5, 10 and 21 days, BOD/COD and BOD/TOC ratios and the average oxidation state are presented. Biodegradability measured as BOD₅/COD ratio was increased from 0 of the original solution to 0.25 at the moment of removing all the initial compound (corresponding to an ozone dose of 0.12 g L⁻¹, 0.48 for BOD₂₁/COD ratio). To test the effect of this pre-treatment, the biological oxidation of these pre-ozonated solutions was performed in two semi-continuous stirred tank reactors, one with non-acclimated sludge and one with acclimated-to-phenol sludge. The study showed that the TOC content of the pre-treated solution could be removed up to 68% by an aerobic biological treatment as well as co-digested with municipal wastewater (TOC removal up to 82%), with similar operating retention times to a municipal wastewater plant (12-24 h). Kinetic studies based on Monod model have also been carried out. Pseudo-first-order kinetic constants were found to be in the range of 0.5-0.8 L g TVSS⁻¹ h⁻¹.     

Ecotoxicological assessment of a polyelectrolyte flocculant

Flocculant blocks are commonly used as a component of (passive) water treatment systems to reduce suspended sediment loads in the water column. This study investigated the potential for aquatic biological impacts of a flocculant block formulation that contained an anionic polyacrylamide (PAM) active ingredient and a polyethylene glycol (PEG) based carrier. The toxicity of the whole flocculant block was assessed and the individual components of the block were also tested separately. Five Northern Australian tropical freshwater species (i.e. Chlorella sp. Lemna aequinoctialis, Hydra viridissima, Moinodaphnia macleayi and Mogurnda mogurnda) were exposed to a range of concentrations of the whole flocculant block, and of the individual PAM and PEG components. The concentration of Total Organic Carbon (TOC) in solution was used to provide a measure of the total amount of PAM and PEG present. An extremely wide range of toxic responses were found, with the flocculant blocks being essentially non-toxic to the duckweed, fish and algae (IC₅₀ > 1880 mg l⁻¹ C TOC, IC₁₀ > 460 mg l⁻¹ C TOC), slightly toxic to the hydra (IC₅₀ = 610-2180 mg l⁻¹ C TOC, IC₁₀ = 80-60 mg l⁻¹ C TOC) and significantly more toxic to the cladoceran (IC₅₀ = 10 mg l⁻¹ C TOC, IC₁₀ = 4 mg l⁻¹ C TOC). More detailed investigation of the two components indicated that the PAM was the primary “toxicant” in the flocculant blocks. Derived Protective Concentrations (PCs) for the flocculant blocks, expressed as equivalent TOC concentrations, were found to be lower than typically measured natural environmental concentrations of TOC. It will thus be possible to use TOC as measure of the concentration of PAM only in those situations where lower levels of ecosystem protection (i.e. higher PCs) are applicable.     

Mechanism and kinetics of sulfamethoxazole photocatalytic ozonation in water

The photocatalytic ozonation of sulfamethoxazole (SMT) has been studied in water under different experimental conditions. The effect of gas flow rate, initial concentration of ozone, SMT and TiO₂ has been investigated to establish the importance of mass transfer and chemical reaction. Under the conditions investigated the process is chemically controlled. Both, SMT and TOC kinetics have been considered. Fast and slow kinetic regime of ozone reactions have been observed for SMT and TOC oxidation, respectively. Application of different inhibitors allows for the establishment of reaction mechanism involving direct ozonation, direct photolysis, hydroxyl radical reactions and photocatalytic reactions. Rate constants of the direct reaction between ozone and protonated, non-protonated and anionic SMT species have been determined to be 1.71 × 10⁵, 3.24 × 10⁵ and 4.18 × 10⁵ M⁻¹ s⁻¹, respectively. SMT quantum yield at 313 nm was found to be 0.012 moles per Einstein at pH 5 and 0.003 moles per Einstein at pHs 7 and 9. Main contributions to SMT removal were direct ozone reaction, positive hole oxidation and hydroxyl radical reactions. For TOC removal, main contributions were due to positive hole oxidation and hydroxyl radical reactions.     

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.     

Using magnetic seeds to improve the aggregation and precipitation of nanoparticles from backside grinding wastewater

Backside grinding (BG) wastewater treatment typically requires large quantities of chemicals, i.e. polyaluminum chloride (PAC) coagulant and produces considerable amounts of sludge, increasing the loading and cost of subsequent sludge treatment and disposal processes. This study investigated the effects of the addition of magnetic seeds (FeO*Fe₂O₃) of selected particle sizes and of optimized combinations of magnetic seeds and PAC on the aggregation of silica nanoparticles from BG wastewater and on the sedimentation time at various pH values (5-9). The results show that the turbidity of BG wastewater was significantly reduced by the magnetic aggregation treatment. The dosage of PAC combined with 2.49 g L⁻¹ or 1.24 g L⁻¹ of magnetic seeds was reduced by 83% (from 60 to 10 mg L⁻¹) compared to the conventional process of using only PAC as a coagulant. The turbidity of the BG wastewater, initially 1900-2500 NTU, could also be successfully decreased about to 23 NTU by the addition of 3.74 g L⁻¹ magnetite (FeO*Fe₂O₃) only at pH 5 with an applied magnetic field of 1000 G. Different coagulation conditions using magnetic seeds combined with coagulant resulted in different aggregation performances. The treatment performance was more effective by using two-stage dosing, in which magnetic seeds and PAC were added separately, than that with one-stage dosing, where the magnetic seeds and PAC were added simultaneously during rapid mixing. The two-stage dosing allowed for a reduction in the optimum dosage of magnetic seeds from 3.74 g L⁻¹ to 2.49 g L⁻¹ or 1.24 g L⁻¹ without affecting performance when coupled with 0.01 g L⁻¹ of PAC coagulant. The developed method effectively reduced the production of waste sludge.     

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.     

Solar treatment of cork boiling and bleaching wastewaters in a pilot plant

This paper reports on cork boiling and bleaching wastewaters treatment by solar photocatalytic processes, TiO₂/UV and Fe²⁺/H₂O₂/UV (TiO₂-only for bleaching wastewater), in a pilot plant with compound parabolic collectors. The photo-Fenton reaction (k = 0.12 L/kJ_UV, r₀ = 59.4 mg/kJ_UV) is much more efficient that TiO₂ photocatalysis and TiO₂ + S₂O₈²⁻ (k = 0.0024 L/kJ_UV, r₀ = 1.36 mg/kJ_UV), leading to 94% mineralization of the bleaching wastewater after 31.5 kJ_UV/L, consuming 77.1 mM of H₂O₂ (3.0 mmol/kJ_UV) and using 20 mg/L of iron. For the cork boiling wastewater, after a slow initial reaction rate, the DOC degradation curve shows a first-order kinetics behaviour (k = 0.015 L/kJ_UV, r₀ = 20.8 mg/kJ_UV) until 173 kJ_UV/L (≈300 mg C/L). According to the average oxidation state (AOS), toxicity profiles, respirometry and kinetic results obtained in two solar CPCs plants, the optimal energy dose estimated for phototreatment to reach a biodegradable effluent is 15 kJ_UV/L and 114 kJ_UV/L, consuming 33 mM and 151 mM of H₂OT:/PGN/ELSEVIER/WR/web/00007490/₂, achieving almost 49% and 48% mineralization of the wastewaters, respectively for the cork bleaching and boiling wastewaters.     

Effect of ozone exposure on the oxidation of trace organic contaminants in wastewater

Three tertiary-treated wastewater effluents were evaluated to determine the impact of wastewater quality (i.e. effluent organic matter (EfOM), nitrite, and alkalinity) on ozone (O₃) decomposition and subsequent removal of 31 organic contaminants including endocrine disrupting compounds, pharmaceuticals, and personal care products. The O₃ dose was normalized based upon total organic carbon (TOC) and nitrite to allow comparison between the different wastewaters with respect to O₃ decomposition. EfOM with higher molecular weight components underwent greater transformation, which corresponded to increased O₃ decomposition when compared on a TOC basis. Hydroxyl radical (OH) exposure, measured by parachlorobenzoic acid (pCBA), showed that limited OH was available for contaminant destruction during the initial stage of O₃ decomposition (t < 30 s) due to the effect of the scavenging by the water quality. Advanced oxidation using O₃ and hydrogen peroxide did not increase the net production of OH compared to O₃ under the conditions studied. EfOM reactivity impacted the removal of trace contaminants when evaluated based on the O₃:TOC ratio. Trace contaminants with second order reaction rate constants with O₃ (kO3) > 10⁵ M⁻¹ s⁻¹ and OH (k_OH) > 10⁹ M⁻¹ s⁻¹, including carbamazepine, diclofenac, naproxen, sulfamethoxazole, and triclosan, were >95% removed independent of water quality when the O₃ exposure () was measurable (0-0.8 mg min/L). O₃ exposure would be a conservative surrogate to assess the removal of trace contaminants that are fast-reacting with O₃. Removal of contaminants with and k_OH > 10⁹ M⁻¹ s⁻¹, including atrazine, iopromide, diazepam, and ibuprofen, varied when O₃ exposure could not be measured, and appeared to be dependent upon the compound specific k_OH. Atrazine, diazepam, ibuprofen and iopromide provided excellent linear correlation with pCBA (R² > 0.86) making them good indicators of OH availability.