Photochemical degradation of the antidepressant sertraline in aqueous solutions by UVC, UVC/H2O2, and UVC/S2O82.

Antidepressants are released into the aquatic environment because of their incomplete removal from wastewater treatment plants. In the present work, we investigated the photochemical degradation of a commonly prescribed antidepressant, namely sertraline, in aqueous matrices. The molar absorption coefficient of sertraline at 254 nm and at various pH values in the range from 4.0 to 9.0 was 444±65 L•mol-1•cm-1, while the quantum yield of its direct photolysis under UVC radiation (λ = 254 nm) was (1.7±0.1) × 10-2 mol∙einstein-1 (i.e., both values were relatively low). Next, we investigated the photochemical degradation of sertraline under UVC radiation in the presence of hydrogen peroxide, H2O2 (i.e., UVC/H2O2) or persulfate ions, S2O82- (i.e., UVC/PS). Several parameters were studied, such as the initial concentrations of the oxidants, solution pH, and the composition of the aqueous matrix (experiments were carried out in aqueous phosphate buffers, in synthetic wastewater, as well as in synthetic fresh and hydrolyzed human urine). It was found that, in all aqueous matrices, the photochemical degradation of sertraline followed pseudo first-order kinetics. The values of the observed pseudo first-order rate constants in the UVC/H2O2 and UVC/PS processes were from one to three orders of magnitude higher than the corresponding value in the UVC process. The UVC/PS process was more efficient than the UVC/H2O2 process, either in aqueous phosphate buffer solutions or in synthetic wastewaters, despite the comparable reactivity of sertraline towards hydroxyl and sulfate radicals. However, both processes resulted in partial mineralization of the compound after prolonged irradiation. In the UVC/H2O2 process, there was an optimum H2O2 concentration which depended on the aqueous matrix, while in the UVC/PS process, there was an almost linear increase in treatment efficiency as a function of PS concentration, at least in the range of concentrations studied in the present work. Solution pH in the range from 6.0 to 9.0 had a relatively negligible effect on treatment performance for both processes. In synthetic urine matrices, despite the reduction in reaction rate (the observed pseudo first-order rate constants were reduced by approximately one to two orders of magnitude), the photochemical degradation of sertraline proceeded to a relatively satisfactory degree. Finally, the calculations of the electrical energy per order and the associated cost showed that the UVC/H2O2 and UVC/PS processes are cost-efficient and suitable for full-scale applications.

TiO2 photocatalysis under natural solar radiation for the degradation of the carbapenem antibiotics imipenem and meropenem in aqueous solutions at pilot plant scale.

This paper deals with the removal of two last-resort antibiotics, namely imipenem and meropenem, in aqueous solutions employing heterogeneous photocatalysis with TiO2 under natural solar radiation at pilot plant scale. It was found that TiO2 photocatalysis is a very efficient technique for the degradation of both compounds in aqueous solutions, albeit it's relatively low quantum efficiency. At the experimental conditions employed in the present work (compound parabolic collectors photoreactor) the optimal TiO2 concentration was about 50 mg L-1. Experiments conducted in various aqueous matrices lead to the conclusion that the method can be applied to real aqueous matrices, such as natural waters and wastewaters. The comparison of TiO2 photocatalysis and natural photolysis showed an important decrease of the accumulated energy required to achieve the complete removal of both antibiotics which, in terms of normalized illumination time (t30W), represented a reduction of 50 min for imipenem and 60 min for meropenem.

Photochemical degradation of the carbapenem antibiotics imipenem and meropenem in aqueous solutions under solar radiation.

This paper deals with the photochemical fate of two representative carbapenem antibiotics, namely imipenem and meropenem, in aqueous solutions under solar radiation. The analytical method employed for the determination of the target compounds in various aqueous matrices, such as ultrapure water, municipal wastewater treatment plant effluents, and river water, at environmentally relevant concentrations, was liquid chromatography coupled with hybrid triple quadrupole-linear ion trap-mass spectrometry. The absorption spectra of both compounds were measured in aqueous solutions at pH values from 6 to 8, and both compounds showed a rather strong absorption band centered at about 300 nm, while their molar absorption coefficient was in the order from 9 × 103-104 L mol-1 cm-1. The kinetics of the photochemical degradation of the target compounds was studied in aqueous solutions under natural solar radiation in a solar reactor with compound parabolic collectors. It was found that the photochemical degradation of both compounds at environmentally relevant concentrations follows first order kinetics and the quantum yield was in the order of 10-3 mol einsten-1. Several parameters were studied, such as solution pH, the presence of nitrate ions and humic acids, and the effect of water matrix. In all cases, it was found that the presence of various organic and inorganic constituents in the aqueous matrices do not contribute significantly, either positively or negatively, to the photochemical degradation of both compounds under natural solar radiation. In a final set of photolysis experiments, the effect of the level of irradiance was studied under simulated solar radiation and it was found that the quantum yield for the direct photodegradation of both compounds remained practically constant by changing the incident solar irradiance from 28 to 50 W m-2.

Removal of faecal indicator pathogens from waters and wastewaters by photoelectrocatalytic oxidation on TiO(2)/Ti films under simulated solar radiation.

PURPOSE: The disinfection efficiency of water and secondary treated wastewater by means of photoelectrocatalytic oxidation (PEC) using reference strains of Enterococcus faecalis and Escherichia coli as faecal indicators was evaluated. Operating parameters such as applied potential (2-10 V), initial bacterial concentration (10(3)-10(7) CFU/mL), treatment time (up to 90 min) and aqueous matrix (pure water and treated effluent) were assessed concerning their impact on disinfection. METHODS: PEC experiments were carried out using a TiO(2)/Ti film anode and a zirconium cathode in the presence of simulated solar radiation. Bacterial inactivation was monitored by the culture method and real-time SYBR green PCR. RESULTS: A 6.2 log reduction in E. faecalis population was achieved after 15 min of PEC treatment in water at 10 V of applied potential and an initial concentration of 10(7) CFU/mL; pure photocatalysis (PC) led to only about 4.3 log reduction, whilst negligible inactivation was recorded when the respective electrochemical oxidation process was applied (i.e. without radiation). PEC efficiency was generally improved increasing the applied potential and decreasing initial bacterial concentration. Regarding real wastewater, E. coli was more susceptible than E. faecalis during treatment at a potential of 5 V. Wastewater disinfection was affected by its complex composition and the contained mixed bacterial populations, yielding lower inactivation rates compared to water treatment. Screening the results obtained from both applied techniques (culture method and real-time PCR), there was a discrepancy regarding the recorded time periods of total bacterial inactivation, with qPCR revealing longer periods for complete bacterial reduction. CONCLUSIONS: PEC is superior to PC in terms of E. faecalis inactivation presumably due to a more efficient separation and utilization of the photogenerated charge carriers, and it is mainly affected by the applied potential, initial bacterial concentration and the aqueous matrix.

Degradation, mineralization and antibiotic inactivation of amoxicillin by UV-A/TiO2 photocatalysis.

The UV-A/TiO(2) photocatalytic decomposition of amoxicillin (AMX) in aqueous suspensions was investigated. Experiments were performed at antibiotic concentrations between 2.5 and 30 mg/L, eight commercially available TiO(2) catalysts at loadings between 100 and 750 mg/L, acidic or near-neutral conditions (pH 5 or 7.5) and two different matrices (ultrapure water and secondary treated effluent) at a photon flux of 8 × 10(-4) E/(L min). Of the various catalysts tested, Degussa P25 was highly active, i.e. complete AMX degradation and 93% mineralization could be achieved after 25 and 90 min of reaction, respectively at 10 mg/L AMX and 250 mg/L titania. In general, mineralization was slower than degradation due to the formation of stable transformation by-products. For the range of concentrations studied, initial degradation rates can be approached by a Langmuir-Hinshelwood kinetic model, while the reaction order with respect to AMX shifts from first to zeroth as initial concentration increases from 2.5 to 5 mg/L to higher values. Degradation in treated effluent was partly impeded compared to pure water due to the inherent presence of organic and inorganic constituents that compete for hydroxyl radicals. Although increasing solution pH from 5 to 7.5 had no effect on degradation, it retarded mineralization. The antibiotic activity of AMX prior to and after photocatalytic degradation was tested to three reference bacterial strains, namely Escherichia coli (ATCC 23716), Klebsiella pneumoniae (NCTC 5056) and Enterococcus faecalis (ATCC 14506). The first two were found to be highly resistant at AMX concentrations up to 25 mg/L, while the latter could partly be inactivated at lower AMX concentrations (i.e. 10 mg/L) and/or in the presence of photocatalytic by-products.

Pilot treatment of olive pomace leachate by vertical-flow constructed wetland and electrochemical oxidation: an efficient hybrid process.

A hybrid process comprising biological degradation in a vertical-flow constructed wetland (CW) and electrochemical oxidation over boron-doped diamond electrodes to decolorize, mineralize and detoxify a leachate from olive pomace processing (OPL) was investigated. Two alternative treatment schemes were compared: According to the first treatment scheme, OPL was treated by electrochemical oxidation followed by treatment in a constructed wetland pilot unit (CW-A). The second scheme comprised of treatment in a constructed wetland followed by electrochemical treatment (CW-B). The constructed wetlands units were planted with Phragmites australis (reeds) and were fed intermittently at organic loadings between 5 and 15 g COD m(-2) d(-1) and a residence time of 3 d. Electrochemical oxidation (EO) was performed for 360 min at 20 A. Treatment of OPL in the wetland at 15 g COD m(-2) d(-1) led to mean COD and color reduction of 86% and 77%, respectively; the wetland effluent with a COD of about 800 mg L(-1) was polished electrochemically for 360 min after which the overall COD and color removal of the combined process (i.e. CW-B/EO) was around 95%, while the final effluent was not toxic against the marine bacteria Vibrio fischeri. Electrochemical oxidation of the original OPL at COD values between 6250 and 14 100 mg L(-1) led to moderate COD and color reduction (i.e. less than 40%) through zero order kinetics. When this was coupled to constructed wetland post-treatment (i.e. EO/CW-A), the overall COD and color removal was 81% and 58%, respectively. The decreased efficiency may be assigned to the increased toxicity of the electrochemically treated effluent which was only partially removed in the natural treatment system.

Treatment of ink effluents from flexographic printing by lime precipitation and boron-doped diamond (BDD) electrochemical oxidation.

Effluent treatment from flexographic printing was investigated by precipitation/coagulation and electrochemical oxidation over boron-doped diamond electrodes. Precipitation with 3 g/L of lime led to complete removal of effluent turbidity (initial value of about 410 NTU) but only about 20% chemical oxygen demand (COD) decrease (initial value of about 1,900 mg/L). Higher lime dosages (up to 15 g/L) had no effect on separation. On the other hand, coagulation with alum in the range 0.05-1 mM failed to enhance the extent of solids separation achieved by gravity settling alone (i.e. about 60%). Preliminary electrochemical oxidation experiments in the presence of sulphuric acid as supporting electrolyte showed that treatment performance (in terms of COD removal and decrease in sample absorbance at 300 nm) increased with increasing applied current. The latter was more efficiently utilized at shorter treatment times and lower currents with efficiency reaching 30%. Following lime precipitation, the effluent was electrochemically oxidized at alkaline conditions for 360 min yielding 64% absorbance reduction and 50% COD removal (this corresponds to 60% overall COD removal for the combined process). The rather low electrochemical treatment performance may be attributed to limestone deposition and fouling of electrodes and other electrochemical reactor components as evidenced by the gradual drop in conductivity/current throughout the operation.

Boron-doped diamond anodic treatment of olive mill wastewaters: statistical analysis, kinetic modeling and biodegradability.

The electrochemical treatment of olive mill wastewaters (OMW) over boron-doped diamond (BDD) electrodes was investigated. A factorial design methodology was implemented to evaluate the statistically important operating parameters, amongst initial COD load (1000-5000 mg/L), treatment time (1-4h), current intensity (10-20A), initial pH (4-6) and the use of 500 mg/L H(2)O(2) as an additional oxidant, on treatment efficiency; the latter was assessed in terms of COD, phenols, aromatics and color removal. Of the five parameters tested, the first two had a considerable effect on COD removal. Hence, analysis was repeated at more intense conditions, i.e. initial COD values up to 10,000 mg/L and reaction times up to 7h and a simple model was developed and validated to predict COD evolution profiles. The model suggests that the rate of COD degradation is zero order regarding its concentration and agrees well with an electrochemical model for the anodic oxidation of organics over BDD developed elsewhere. The treatability of the undiluted effluent (40,000 mg/L COD) was tested at 20A for 15h yielding 19% COD and 36% phenols' removal respectively with a specific energy consumption of 96 kWh/kg COD removed. Aerobic biodegradability and ecotoxicity assays were also performed to assess the respective effects of electrochemical treatment.

Simultaneous photocatalytic oxidation of As(III) and humic acid in aqueous TiO2 suspensions.

The simultaneous photocatalytic oxidation of As(III) and humic acid (HA) in aqueous Degussa P25 TiO(2) suspensions was investigated. Preliminary photocatalytic studies of the binary As(III)/TiO(2) and HA/TiO(2) systems showed that As(III) was oxidized more rapidly than HA and the extent of photocatalytic oxidation of each individual component (i.e. As(III) or HA) increased with decreasing its initial concentration and/or increasing catalyst loading. The simultaneous photocatalytic oxidation of As(III) and HA in the ternary As(III)/HA/TiO(2) system showed that both As(III) and HA oxidation was reduced in the ternary system compared to the corresponding binary systems. The effect of operating conditions in the ternary system, such as initial As(III), HA and TiO(2) concentrations (in the range 3-20mg/L, 10-100mg/L and 50-250 mg/L respectively), initial solution pH (3.6-6.7) and reaction time (10-30 min), on photocatalytic As(III) and HA oxidation was assessed implementing a two-level factorial experimental design methodology. Seven and ten factors were found statistically important in the case of photocatalytic As(III) and HA oxidation respectively. Based on these statistically significant factors, a first order polynomial model describing As(III) and HA photocatalytic oxidation was constructed and a very good agreement was obtained between the experimental values and those predicted by the model, while the observed differences may be readily explained as random noise.

Wet air oxidation of table olive processing wastewater: determination of key operating parameters by factorial design.

The wet air oxidation of an effluent from edible olive processing was investigated. Semibatch experiments were conducted with 0.3L of effluent loaded into an autoclave and pure oxygen fed continuously to maintain an oxygen partial pressure of 2.5MPa. The effect of operating conditions, such as initial organic loading (from 1240 to 5150mg/L COD), reaction time (from 30 to 120min), temperature (from 140 to 180 degrees C), initial pH (from 3 to 7) and the use of 500mg/L H(2)O(2) as an additional oxidant, on treatment efficiency was assessed implementing a factorial experimental design. All five parameters had a statistically considerable effect on COD removal, alongside second order interactions of COD with reaction temperature, contact time and effluent pH. In most cases, high levels of phenols degradation (up to 100%) and decolorization (up to 90%) were achieved followed by low to moderate mineralization (up to 70%). The oxidation of phenols was affected to a considerable level by the initial COD, reaction temperature and contact time, as well as the second order interaction between COD and temperature, while all other effects were insignificant.

Complete treatment of olive pomace leachate by coagulation, activated-carbon adsorption and electrochemical oxidation.

A battery scheme comprising sequential alum coagulation, activated-carbon adsorption and electrochemical oxidation over boron-doped diamond electrodes to mineralize a leachate from olive pomace processing is demonstrated. The effect of coagulant and adsorbent concentration on treatment efficiency was assessed in the range 0.1-50 mM Al(3+) and 2.5-50 g/L activated-carbon and optimal conditions were established. Coagulation at 7.5mM Al(3+) resulted in substantial solids and color removal (i.e. 80% and 93%, respectively). This was accompanied by only 30% chemical oxygen demand (COD) reduction (initial COD was about 3,500 mg/L). The latter increased to 80% though when coagulation was coupled with adsorption at 25 g/L activated carbon. Electrochemical oxidation of the original effluent for 360 min led to 63% and 82% COD reduction at 10 and 20A current intensity, respectively. When this process was tested as a polishing stage following coagulation and adsorption, overall COD removal reached values of 92% and 97%, respectively. The final effluent was also colorless and solids free. However, the treated effluent still exhibited ecotoxicity possibly due to the formation of ecotoxic oxidation products.

Photocatalytic treatment of black table olive processing wastewater.

The photocatalytic treatment of an effluent from black table olive processing over TiO2 suspensions was investigated. The study focused on the effect of various operating parameters on the treatment efficiency including initial organic load, catalyst type, concentration and reuse, and addition of hydrogen peroxide. Initial organic load, expressed in terms of chemical oxygen demand (COD), was studied in the range 1-8 g/L, anatase TiO2 concentrations in the range 0.25-2 g/L and H2O2 concentrations in the range 0.025-0.15 g/L. Treatment efficiency, which was assessed in terms of COD, total phenols, aromatics and color reduction, generally increased with decreasing initial COD and increasing contact time, catalyst and H2O2 concentrations; however, for H2O2 there was a maximum dosage above which performance deteriorated. Depending on the conditions employed, nearly complete decoloration (>90%) could be achieved, while mineralization never exceeded 50%. Shake-flask tests with non-acclimated activated sludge showed that both the original and photocatalyzed effluents were degradable aerobically with the biodegradation rate of the original effluent being three times greater than the oxidized one. On the other hand, photocatalytic oxidation of the original effluent was at least two orders of magnitude faster than its biological oxidation to achieve comparable levels of degradation.

Electrochemical oxidation of table olive processing wastewater over boron-doped diamond electrodes: treatment optimization by factorial design.

The electrochemical treatment of an effluent from edible olive processing over boron-doped diamond electrodes was investigated. The effect of operating conditions, such as initial organic loading (from 1340 to 5370 mg/L chemical oxygen demand (COD)), reaction time (from 30 to 120 min), current intensity (from 5 to 14 A), initial pH (from 3 to 7) and the use of 500 mg/L H2O2 as an additional oxidant, on treatment efficiency was assessed implementing a factorial experimental design. Of the five parameters tested, the first three had a considerable effect on COD and total phenols removal, while the other two were statistically insignificant. In most cases, high levels of phenols degradation and decolorization were achieved followed by moderate mineralization. The analysis was repeated at more intense conditions, i.e., initial COD up to 10,000 mg/L, reaction times up to 240 min and current up to 30 A; at this level, the effect of treatment time and applied current was far more important than the starting COD concentration. Treatment for 14 h at optimal conditions (30 A and an initial loading of about 10,000 mg/L) led to 73% COD removal with a zero-order kinetic constant of 8.5mg/(L min) and an energy consumption efficiency of 16.3 g COD/(m3 A h).

Photocatalytic degradation of reactive black 5 in aqueous solutions: Effect of operating conditions and coupling with ultrasound irradiation.

The degradation of reactive black 5 (RB 5), a representative diazo dye found in textile effluents, by means of ultraviolet irradiation (9W UVA) over TiO(2) suspensions, ultrasound irradiation (80kHz, 135W) and their combined application was investigated. Several commercial TiO(2) catalysts were screened and an anatase Hombicat UV 100 sample exhibited considerable activity in terms of solution decoloration, COD and ecotoxicity reduction. Photocatalytic degradation increased with increasing TiO(2) loading (in the range 0.05-1g/L) and decreasing dye concentration (in the range 120-20mg/L) and solution pH (in the range 9-2.6). At the typical conditions employed in this study (60mg/L dye, 0.25mg/L catalyst, ambient pH=5.8, oxygen sparging), complete decoloration was achieved after 60min of reaction. Addition of H(2)O(2) up to 0.01M hindered degradation, scavenging the photogenerated holes and hydroxyl radicals. Ultrasound irradiation resulted in low decoloration, e.g. less than 10% after 60min at 60mg/L dye and oxygen sparging and slightly improved under an argon atmosphere. The simultaneous application of ultraviolet and ultrasound irradiation resulted in increased decoloration compared to that achieved by photocatalysis and sonolysis operating separately; moreover, the overall sonophotocatalytic effect was greater than the additive effect of the two processes, implying possible synergy.

Electrochemical treatment of textile dyes and dyehouse effluents.

The electrochemical oxidation of textile effluents over a titanium-tantalum-platinum-iridium anode was investigated. Batch experiments were conducted in a flow-through electrolytic cell with internal recirculation at current intensities of 5, 10, 14 and 20A, NaCl concentrations of 0.5, 1, 2 and 4% and recirculation rates of 0.81 and 0.65 L/s using a highly colored, synthetic effluent containing 16 textile dyes at a total concentration of 361 mg/L and chemical oxygen demand (COD) of 281 mg/L. Moreover, an actual dyehouse effluent containing residual dyes as well as various inorganic and organic compounds with a COD of 404 mg/L was tested. In most cases, quantitative effluent decolorization was achieved after 10-15 min of treatment and this required low energy consumption; conversely, the extent of mineralization varied between 30 and 90% after 180 min depending on the operating conditions and the type of effluent. In general, treatment performance improved with increasing current intensity and salinity and decreasing solution pH. However, the use of electrolytes not containing chloride (e.g. FeSO4 or Na2SO4) suppressed degradation. Although the acute toxicity of the actual effluent to marine bacteria Vibrio fischeri was weak, it increased sharply following treatment, thus suggesting the formation of persistent toxic by-products.

Treatment of textile dyehouse wastewater by TiO2 photocatalysis.

The oxidative degradation of an actual textile dyehouse wastewater was investigated by means of photocatalysis in the presence of TiO2. The UV-A-induced photocatalytic oxidation over TiO2 suspensions was capable of decolorizing the effluent completely, as well as reducing chemical oxygen demand (COD) sufficiently (COD reduction generally varied between about 40% and 90% depending on the operating conditions) after 4 h of treatment. Two crystalline forms of TiO2, viz. anatase and rutile, were tested for their photocatalytic activity and anatase was found to be more active than rutile. The extent of photocatalytic degradation was found to increase with increasing TiO2 concentration up to 0.5 g/L TiO2, above which degradation remained practically constant, reaching a plateau. Furthermore, textile effluent degradation was enhanced at acidic conditions (i.e. pH = 3) and in the presence of hydrogen peroxide. To assess catalyst activity on repeated use, experiments were performed where the catalyst was recovered and reused; after three successive uses, TiO2 had sufficiently retained its photocatalytic activity. Finally, the luminescent marine bacteria Vibrio fischeri was used to assess the acute ecotoxicity of samples prior to and after the photocatalytic treatment and it was found that ecotoxicity was fully eliminated following photocatalytic oxidation.