Degradation of 32 emergent contaminants by UV and neutral photo-fenton in domestic wastewater effluent previously treated by activated sludge

This study focuses on the removal of 32 selected micropollutants (pharmaceuticals, corrosion inhibitors and biocides/pesticides) found in an effluent coming from a municipal wastewater treatment plant (MWTP) based on activated sludge. Dissolved organic matter was present, with an initial total organic carbon of 15.9 mg L⁻¹, and a real global quantity of micropollutants of 29.5 μg L⁻¹. The treatments tested on the micropollutants removal were: UV-light emitting at 254 nm (UV₂₅₄) alone, dark Fenton (Fe^2+,3+/H₂O₂) and photo-Fenton (Fe^2+,3+/H₂O₂/light). Different irradiation sources were used for the photo-Fenton experiences: UV₂₅₄ and simulated sunlight. Iron and H₂O₂ concentrations were also changed in photo-Fenton experiences in order to evaluate its influence on the degradation. All the experiments were developed at natural pH, near neutral. Photo-Fenton treatments employing UV₂₅₄, 50 mg L⁻¹ of H₂O₂, with and without adding iron (5 mg L⁻¹ of Fe²⁺ added or 1.48 mg L⁻¹ of total iron already present) gave the best results. Global percentages of micropollutants removal achieved were 98 and a 97% respectively, after 30 min of treatments. As the H₂O₂ concentration increased (10, 25 and 50 mg L⁻¹), best degradations were observed. UV₂₅₄, Fenton, and photo-Fenton under simulated sunlight gave less promising results with lower percentages of removal.The highlight of this paper is to point out the possibility of the micropollutants degradation in spite the presence of DOM in much higher concentrations.     

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 emerging contaminant ibuprofen in water by photo-Fenton

In this study the degradation of the worldwide Non-Steroidal Anti-Inflammatory Drug (NSAID) ibuprofen (IBP) by photo-Fenton reaction by use of solar artificial irradiation was carried out. Non-photocatalytic experiments (complex formation, photolysis and UV/Vis-H₂O₂ oxidation) were executed to evaluate the isolated effects and additional differentiated degradation pathways of IBP. The solar photolysis cleavage of H₂O₂ generates hydroxylated-IBP byproducts without mineralization. Fenton reaction, however promotes hydroxylation with a 10% contamination in form of a mineralization. In contrast photo-Fenton in addition promotes the decarboxylation of IBP and its total depletion is observed. In absence of H₂O₂ a decrease of IBP was observed in the Fe(II)/UV-Vis process due to the complex formation between iron and the IBP-carboxylic moiety. The degradation pathway can be described as an interconnected and successive principal decarboxylation and hydroxylation steps. TOC depletion of 40% was observed in photo-Fenton degradation. The iron-IBP binding was the key-point of the decarboxylation pathway. Both decarboxylation and hydroxylation mechanisms, as individual or parallel process are responsible for IBP removal in Fenton and photo-Fenton systems. An increase in the biodegradability of the final effluent after photo-Fenton treatment was observed. Final BOD₅ of 25 mg L⁻¹ was reached in contrast to the initial BOD₅ shown by the untreated IBP solution (BOD₅ < 1 mg L⁻¹). The increase in the biodegradability of the photo-Fenton degradation byproducts opens the possibility for a complete remediation with a final post-biological treatment.     

Effect of pesticide concentration on the degradation process by combined solar photo-Fenton and biological treatment

The influence of pesticide concentration, expressed as dissolved organic carbon (DOC), on combined solar photo-Fenton and biological oxidation treatment was studied using wastewater containing a mixture of five commercial pesticides, Vydate, Metomur, Couraze, Ditumur and Scala. Two initial DOC concentrations, 200 mg L⁻¹ and 500 mg L⁻¹ were assayed. Variation in biodegradability with photocatalytic treatment intensity was tested using Pseudomonas putida. Thus the mineralisation required for combining with biodegradation of intermediates by activated sludge was 33% and 55% at 200 mg L⁻¹ and 500 mg L⁻¹, respectively. Biotreatment was carried out in a stirred tank in sequencing batch reactor (SBR) mode. As revealed by the biodegradation kinetics, intermediates generated at the higher pesticide concentration caused lower carbon removal rates in spite of the longer photo-Fenton treatment time applied. One strategy for treating water with high concentrations of pesticides and overcoming the low biodegradability of photo-Fenton intermediates is to mix it with a biodegradable carbon source before biological oxidation. This combination of photo-Fenton and acclimatized activated sludge in several SBR cycles led to complete biodegradation of a concentrated pesticide solution of 500 mg L⁻¹ DOC in 5 h with a carbon removal efficiency of 90%.     

Treatment of a sanitary landfill leachate using combined solar photo-Fenton and biological immobilized biomass reactor at a pilot scale

A solar photo-Fenton process combined with a biological nitrification and denitrification system is proposed for the decontamination of a landfill leachate in a pilot plant using photocatalytic (4.16 m² of Compound Parabolic Collectors - CPCs) and biological systems (immobilized biomass reactor). The optimum iron concentration for the photo-Fenton reaction of the leachate is 60 mg Fe²⁺ L⁻¹. The organic carbon degradation follows a first-order reaction kinetics (k = 0.020 L kJ_UV⁻¹, r₀ = 12.5 mg kJ_UV⁻¹) with a H₂O₂ consumption rate of 3.0 mmol H₂O₂ kJ_UV⁻¹. Complete removal of ammonium, nitrates and nitrites of the photo-pre-treated leachate was achieved by biological denitrification and nitrification, after previous neutralization/sedimentation of iron sludge (40 mL of iron sludge per liter of photo-treated leachate after 3 h of sedimentation). The optimum C/N ratio obtained for the denitrification reaction was 2.8 mg CH₃OH per mg N-NO₃⁻, consuming 7.9 g/8.2 mL of commercial methanol per liter of leachate. The maximum nitrification rate obtained was 68 mg N-NH₄⁺ per day, consuming 33 mmol (1.3 g) of NaOH per liter during nitrification and 27.5 mmol of H₂SO₄ per liter during denitrification. The optimal phototreatment energy estimated to reach a biodegradable effluent, considering Zahn-Wellens, respirometry and biological oxidation tests, at pilot plant scale, is 29.2 kJ_UV L⁻¹ (3.3 h of photo-Fenton at a constant solar UV power of 30 W m⁻²), consuming 90 mM of H₂O₂ when used in excess, which means almost 57% mineralization of the leachate, 57% reduction of polyphenols concentration and 86% reduction of aromatic content.     

Decolorization of dark brown colored coffee effluent by solar photo-Fenton reaction: effect of solar light dose on decolorization kinetics

The decolorization of dark brown colored coffee effluent by solar photo-Fenton process has been studied. Effects of accumulated solar light energy and dosage of Fenton reagents (iron and hydrogen peroxide) on the color removal have been examined. With increasing Fe dosage the rate of the decolorization increased but the enhancement was not pronounced beyond 10 mg L⁻¹. Although addition of H₂O₂ increased the decolorization rate up to around 1000 mg L⁻¹ of H₂O₂, further addition of H₂O₂ could not enhance the color removal. At excess dosages of Fenton reagents, the color removal was not improved due to their scavenging of hydroxyl radicals. It was found that the pseudo-first order decolorization kinetic constant based on the accumulated solar energy is a sole parameter unifying solar photo-Fenton decolorization processes under the different weather conditions. The kinetic constant can be readily used to calculate the amount of solar energy required to achieve a certain degree of color removal. The mineralization was rather slower as compared with the decolorization. The decolorization capability with solar irradiation was found to be comparable to UV light irradiation. The present results suggest that abundant solar energy driving decolorization of coffee effluent by photo-Fenton reaction is highly efficient.     

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 a four-pesticide mixture by combined photo-Fenton and biological oxidation

Complete degradation of a pesticide mixture by a combination of a photo-Fenton pretreatment and an activated-sludge batch reactor is demonstrated. Four commercial pesticides, Laition, Metasystox, Sevnol and Ultracid were chosen for this experiment. The active ingredients are, respectively, dimethoate, oxydemeton-methyl, carbaryl and methidathion. The original pesticide concentration was 200 mg L⁻¹. Biotreatment began after 31% photocatalytic mineralization, which after 5 h in a 6-L stirred batch-mode tank reactor with non-acclimated activated sludge, leaves the photo-Fenton effluent completely degraded. This biotreatment time is shorter than commonly found in municipal wastewater treatment plants (∼8-10 h). Therefore, the combined process is effective for rapid pesticide degradation in wastewater with complete removal of parent compounds and the associated DOC concentration. Nonetheless, assessment of this technology should take into account higher pesticide concentrations and how this factor affects both the photocatalytic and the biological oxidation.     

Photooxidation and subsequent biodegradability of recalcitrant tri-alkyl phosphates TCEP and TBP in water

Biodegradable organic carbon (BDOC) from OH radical oxidation (UV-H₂O₂) of the recalcitrant industrial anti-foaming agents and flame retardants, tri-n-butyl phosphate (TBP) and tris(2-chloroethyl) phosphate (TCEP), was quantified with respect to the fraction of the TBP or TCEP photooxidized. For 50-96% contaminant oxidation via OH, BDOC was similar in solutions of either compound, and ranged from 0.25 to 0.5 mg L⁻¹ (TBP₀ and TCEP₀ = 5 mg L⁻¹). In addition, for this contaminant oxidation range, complete dehalogenation of TCEP was observed, along with a significant change in pH. Oxidation of TCEP results in both H⁺ and Cl⁻ release, while the TBP mineralization pathway results in CO₂, H₂O, H⁺, and PO₄³⁻. For low μg/L levels of TCEP contamination in treated surface waters, UV-H₂O₂ oxidation of TCEP or TBP would not be expected to impact pH or chloride concentrations, however, a portion of the TCEP or TBP oxidation products, likely in non-halogenated aldehyde form, would become an available carbon source for bacterial growth in storage, distribution, or during further physical treatment.     

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.     

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.     

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.     

Decontamination industrial pharmaceutical wastewater by combining solar photo-Fenton and biological treatment

Characterization and treatment of a real pharmaceutical wastewater containing 775 mg dissolved organic carbon per liter by a solar photo-Fenton/biotreatment were studied. There were also many inorganic compounds present in the matrix. The most important chemical in this wastewater was nalidixic acid (45 mg/L), an antibiotic pertaining to the quinolone group. A Zahn-Wellens test demonstrated that the real bulk organic content of the wastewater was biodegradable, but only after long biomass adaptation; however, the nalidixic acid concentration remained constant, showing that it cannot be biodegraded. An alternative is chemical oxidation (photo-Fenton process) first to enhance biodegradability, followed by a biological treatment (Immobilized Biomass Reactor - IBR). In this case, two studies of photo-Fenton treatment of the real wastewater were performed, one with an excess of H₂O₂ (kinetic study) and another with controlled H₂O₂ dosing (biodegradability and toxicity studies). In the kinetic study, nalidixic acid completely disappeared after 190 min. In the other experiment with controlled H₂O₂, nalidixic acid degradation was complete at 66 mM of H₂O₂ consumed. Biodegradability and toxicity bioassays showed that photo-Fenton should be performed until total degradation of nalidixic acid before coupling a biological treatment. Analysis of the average oxidation state (AOS) demonstrated the formation of more oxidized intermediates. With this information, the photo-Fenton treatment time (190 min) and H₂O₂ dose (66 mM) necessary for adequate biodegradability of the wastewater could be determined. An IBR operated in batch mode was able to reduce the remaining DOC to less than 35 mg/L. Ammonium consumption and NO₃⁻ generation demonstrated that nitrification was also attained in the IBR. Overall DOC degradation efficiency of the combined photo-Fenton and biological treatment was over 95%, of which 33% correspond to the solar photochemical process and 62% to the biological treatment.     

Greywater treatment by UVC/H2O2

Greywater treatment by UVC/H₂O₂ was investigated with regard to the removal of chemical oxygen demand (COD). A COD reduction from 225 to 30 mg l⁻¹ (overall removal of 87%) was achieved after settling overnight and subsequent irradiation for 3 h with 10 mM H₂O₂. Most of the contaminants were removed by oxidation since only 13% COD was removed by settlement.The removal of COD in the greywater followed a second-order kinetic equation, r = 0.0637[COD][H₂O₂], up to 10 mM H₂O₂. A slightly enhanced COD removal was observed at the initial pH of 10 compared with pH 3 and 7. This was attributed to the dissociation of H₂O₂ to O₂H⁻. The treatment was not affected by total concentration of carbonate (c_T) of at least 3 mM, above which operation between pH 3 and 5 was essential. The initial biodegradability of the settled greywater (as BOD₅:COD) was 0.22. After 2 h UVC/H₂O₂ treatment, a higher proportion of the residual contaminants was biodegradable (BOD₅:COD = 0.41) which indicated its potential as a pre-treatment for a biological process.     

Comparative effect of simulated solar light,UV, UV/H2O2 and photo-Fenton treatment (UV–Vis/H2O2/Fe) in the Escherichia coli inactivation in artificial seawater

Innovative disinfection technologies are being studied for seawater, seeking a viable alternative to chlorination. This study proposes the use of H₂O₂/UV₂₅₄ and photo-Fenton as disinfection treatment in seawater. The irradiations were carried out using a sunlight simulator (Suntest) and a cylindrical UV reactor. The efficiency of the treatment was compared for Milli-Q water, Leman Lake water and artificial seawater. The presence of bicarbonates and organic matter was investigated in order to evaluate possible effects on the photo-Fenton disinfection treatment. The photo-Fenton treatment, employing 1 mg L⁻¹ Fe²⁺ and 10 mg L⁻¹ of H₂O₂, led to the fastest bacterial inactivation kinetics. Using H₂O₂/UV₂₅₄ high disinfection rates were obtained similar to those obtained with photo-Fenton under UV₂₅₄ light. In Milli-Q water, the rate of inactivation for Escherichia coli was higher than in Leman Lake water and seawater due to the lack of inorganic ions affecting negatively bacteria inactivation. The presence of bicarbonate showed scavenging of the OH^• radicals generated in the treatment of photo-Fenton and H₂O₂/UV₂₅₄. Despite the negative effect of inorganic ions, especially HCO₃^-, the disinfection treatments with AOPs in lake water and seawater improved significantly the disinfection compared to light alone (simulated sunlight and UV₂₅₄). In the treatment of photo-Fenton with simulated sunlight, dissolved organic matter had a beneficial effect by increasing the rate of inactivation. This is associated with the formation of Fe³⁺-organo photosensitive complexes leading to the formation of ROS able to inactivate bacteria. This effect was not observed in the photo-Fenton with UV₂₅₄. Growth of E. coli surviving in seawater was observed 24 and 48 h after treatment with UV light. However, growth of surviving bacteria was not detected after photo-Fenton with UV₂₅₄ and H₂O₂/UV₂₅₄ treatments.     

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.     

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.     

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.     

Development of a TiO2 modified optical fiber electrode and its incorporation into a photoelectrochemical reactor for wastewater treatment

Electrochemical advanced oxidation processes (EAOPs) are used to chemically burn non biodegradable complex organic compounds that are present in polluted effluents. A common approach involves the use of TiO₂ semiconductor substrates as either photocatalytic or photoelectrocatalytic materials in reactors that produce a powerful oxidant (hydroxyl radical) that reacts with pollutant species. In this context, the purpose of this work is to develop a new TiO₂ based photoanode using an optic fiber support. The novel arrangement of a TiO₂ layer positioned on top of a surface modified optical fiber substrate, allowed the construction of a photoelectrochemical reactor that works on the basis of an internally illuminated approach. In this way, a semi-conductive optical fiber modified surface was prepared using 30 μm thickness SnO₂:Sb films on which the photoactive TiO₂ layer was electrophoretically deposited. UV light transmission experiments were conducted to evaluate the transmittance along the optical fiber covered with SnO₂:Sb and TiO₂ showing that 43% of UV light reached the optical fiber tip. With different illumination configurations (external or internal), it was possible to get an increase in the amount of photo-generated H₂O₂ close to 50% as compared to different types of TiO₂ films. Finally, the electro-Fenton photoelectrocatalytic Oxidation process studied in this work was able to achieve total color removal of Azo orange II dye (15 mg L⁻¹) and a 57% removal of total organic carbon (TOC) within 60 min of degradation time.     

Performance of a passive treatment system for net-acidic coal mine drainage over five years of operation

A full-scale passive treatment system (PTS) was commissioned in 2003 to treat two net-acidic coal mine water discharges in the Durham coalfield, UK. The principal aim of the PTS was to decrease concentrations of iron (< 177 mg L⁻¹) and aluminium (< 85 mg L⁻¹) and to increase pH (> 3.2) and alkalinity (≥ 0 mg L⁻¹ CaCO₃ eq). Secondary objectives were to decrease zinc (< 2.8 mg L⁻¹), manganese (< 20.5 mg L⁻¹) and sulfate (< 2120 mg L⁻¹). Upon treatment, water qualities were improved by 84% in the case of Fe, 87% Al, 83% acidity, 51% Zn, 23% Mn and 29% SO₄²⁻. Alkalinity (74%) and pH (95% as H⁺) were increased. Area adjusted removal rates (Fe = 1.49 ± 0.66 g d⁻¹ m⁻²; acidity = 6.7 ± 4.9 g d⁻¹ m⁻²) were low compared to design criteria, mainly due to load limitation. Disregarding seasonality effects, acidity removal and effluent pH were stable over time. A substantial temporal decrease in calcium and alkalinity generation suggests that limestone is increasingly armoured. Once pH is no longer buffered by the carbonate system, metals could be remobilized, putting treatment efficiency at risk.