Effect of UV dose on degradation of venlafaxine using UV/H2O2: perspective of augmenting UV units in wastewater treatment.

Many water and wastewater treatment plants (WWTPs) are fitted with a UV system that provides post treatment disinfection before the water is released to receiving water. This paper presents a study on expected removal for the pharmaceutical venlafaxine (VEN) in a typical UV unit at a municipal WWTP with analysis of removal rates of an advanced oxidation process using UV irradiation with injection of H2O2. The study is supported by bench scale degradation experiments on VEN. Results demonstrated that UV can completely degrade VEN, but the addition of H2O2 increased pseudo first order rate constant by up to 2.5 times. Extrapolations of the lab data indicated that removal rates of VEN at the UV disinfection unit of a typical municipal WWTP are approximately 0.4% at standard operating conditions. With the addition of 10 mg/L of H2O2, degradation of VEN can be increased by ten times over existing UV treatment. By studying the impact of adjusting parameters such as UV intensity, UV dosage, and H2O2 dosage, a framework is set to allow researchers and engineers to move forward with developing UV/H2O2 systems that meet their future design needs for pharmaceutical removal.

Influence of UV dose on the UV/H2O2 process for the degradation of carbamazepine in wastewater.

This study evaluates the influence of UV dose on degradation of carbamazepine (CBZ) in wastewater under UV-C (λ = 254 nm) photolysis with and without H2O2. The rate of degradation of CBZ exhibited a direct dependence on the intensity of incident UV irradiation as the rate of degradation was observed to increase linearly (R2 = 0.98) with UV intensity between 1.67 and 8.95 × 1017 photons/s. More than 95% of the CBZ that spiked in wastewater rapidly degraded within 4 min with a first-order rate constant of 1.2 min-1 for an optimum H2O2 dose of 100 mg/L. Bench-scale continuous flow reactor experiments also showed that CBZ degraded with first-order kinetics at a rate constant of 1.02 min-1. The kinetic parameters obtained for a continuous bench-scale reactor were in good agreement with the relationships developed through batch experiments with only a marginal deviation of ± 6.5%. The relationship between UV intensity and CBZ degradation rate obtained in this study was extrapolated to the UV disinfection unit of a wastewater treatment plant to predict possible degradation of CBZ during UV disinfection. The addition of 100 mg/L of H2O2 to the secondary-treated effluent entering the UV disinfection unit is predicted to achieve over 60% degradation of CBZ. Abbreviations: CBZ carbamazepine; AOPs advanced oxidation processes; UV ultraviolet radiation; UV-C ultraviolet C (λ = 254 nm) radiation; NZVI non-zerovalent iron; WWTP wastewater treatment plant; HPLC high-performance liquid chromatography.

Fate of Zinc Oxide Nanoparticles in a Biosolid Slurry Characterized for Metal Complexation Characteristics.

Zinc oxide nanoparticles (NPs) present in domestic wastewaters may accumulate in biosolids used as fertilizer. In this paper, metal complexation by typical biosolids is explored using methods from the humics literature. Uptake of Zn from NPs in the biosolids is evaluated. Finally, the kinetics of release of Zn species are reported as a function of (i) pH and (ii) the presence of strong binding ligands (e.g., ion exchange resin promoting release). The investigation revealed that (i) metal binding sites of biosolids are analogs of humic substances, (ii) ZnO NPs do not survive in the digestion environment, and (iii) any ZnO NPs dissolve to aqueous Zn in <10 d. Kinetics of Zn in biosolids revealed that Zn release is a function of biosolid protonation. At pH 8, Zn is retained in the biosolids, whereas at pH 4.5, 10% of Zn is released from the biosolids. Adding a chelating resin to the system at pH 5.0 led to Zn release from the biosolids as per Noyes-Whitney kinetics, releasing 85% of the bound Zn in 360 h. Fifteen percent of Zn appeared to be irreversibly bound.

Mineralization of sulfolane in aqueous solutions by Ozone/CaO2 and Ozone/CaO with potential for field application.

Mineralization of sulfolane in aqueous systems by CaO2/O3 and CaO/O3 was investigated in this study. If 1.6 g/L of oxidants (CaO2 and CaO) were used along with 5 L/min of O3 in a batch reactor, degradation of sulfolane followed a pseudo-first order kinetics model. Both sulfolane and TOC were totally removed in less than 40 and 150 min respectively. For these treatments, the pH of the aqueous solutions was above 11, which made O3 more effective in removing sulfolane. However, the high pH of the solution didn't improve TOC removal. For TOC removal the presence of CaO2 and CaO was necessary. Once these conditions were optimised in the lab, field experiments were designed and evaluated to treat contaminated ground water samples. The field tests were successful in mineralization of sulfolane within a reasonable time (4 h). Sulfolane degradation took 150 min in these experiments. The pH of the water samples was brought to near neutral (pH = 6.5) by bubbling CO2.

Impact of support characteristics and preparation method on photocatalytic activity of TiO2/ZSM-5/silica gel composite photocatalyst.

Titanium dioxide (Degussa P25) was supported onto two different aluminosilicate zeolites (ZSM-5) and anchored on three silica gels using two separate preparation methods to study the effect of the catalyst components and the preparation method on the photoactivity of composite catalysts. The photoactivity was investigated by tracking phenol disappearance in a batch UVA light-emitting diode reactor. An easily separable photocatalyst with higher photoactivity than commercial Degussa P25 was developed using Degussa P25, ZSM-5 (SiO2/Al2O3 = 280) and silica gel (particle size 0.2-0.5 mm and pore size 40 Å). The optimum composition was found to be P25:ZSM-5:silica gel = 0.3 : 0.5 : 0.5 g l-1. SEM photographs show that the distribution of the composite catalyst components prepared without a binder was better than that prepared with a binder. The efficiency of photocatalytic ozonation of sulfamethoxazole (SMX) using the new photocatalyst was assessed and compared to that of commercially available Degussa P25. It was found that photocatalytic ozonation promoted the SMX disappearance and mineralization. PZS was superior to Degussa P25 with respect to photocatalysis and photocatalytic ozonation. The enhancement was attributed to the synergetic effect between adsorption, ozonation and/or photocatalytic oxidation.

Degradation of sulfolane using activated persulfate with UV and UV-Ozone.

This study investigates the degradation of sulfolane in aqueous system by (NH4)2S2O8/UVC and (NH4)2S2O8/O3/UVC. While bubbling O3 significantly decreased the reaction time, the experimental results in both cases were consistent: firstly, the degradation of sulfolane followed pseudo-first order kinetic models, secondly, the reaction rates were affected by persulfate dosages, UV light intensity, initial pH and concentration of carbonate/bicarbonate present. Low concentration of chloride (less then 100 ppm) had no effect on the reaction rate. Application of (NH4)2S2O8/O3/UVA for degradation of sulfolane was also investigated. It was found that for higher sulfolane degradation kinetics, higher concentrations of persulfate was required under UVA irradiation. Finally, (NH4)2S2O8/UVC was evaluated for its applicability for degradation of sulfolane in groundwater samples.

Photocatalytic ozonation of pesticides in a fixed bed flow through UVA-LED photoreactor.

In this study, a fixed bed flow through UVA-LED photoreactor was used to compare the efficiency of ozone, photocatalysis and photocatalysis-ozone degradation, and mineralization of two pure pesticides, 2,4-dichlorophenoxyacetic acid (2,4-D) and 2-methyl-4-chlorophenoxyacetic acid (MCPA), and a commercial one, Killex®. For the degradation of the parent compounds, ozone-based processes were more effective. While for mineralization, photocatalytic processes were more effective. Photocatalytic ozonation was the most efficient process for both the degradation and mineralization of the parent compounds. The degradation rates and mineralization by photocatalytic ozonation were higher than the summation of the corresponding rates by ozonation and photocatalysis, indicating a symbiotic relationship.Overall, the photocatalytic ozonation process with the fixed bed TiO2 reduces the time needed for the degradation and mineralization of the pesticides, reduces the costs of powder catalyst separation and overcomes the reduced efficiency of immobilized catalysts, which makes the process quite attractive for practical applications.

Application of UV based advanced oxidation to treat sulfolane in an aqueous medium.

Several oxidative methods were studied to degrade sulfolane in an aqueous medium. These include UVA and UVC irradiation with suitable photoactive oxidants, including ozone, H2O2, and TiO2 based photocatalysis and their combinations. Since sulfolane lacks absorption bands in the UV range beyond 200 nm, initiation of reactions depends on the spectra and photochemistry of the oxidants. Among all the advanced oxidation processes investigated, combinations of (a) UVC with H2O2 and O3 (b) UVC with H2O2 and (c) UVC with O3 led to the highest rate of sulfolane loss in synthetic water samples. Experiments on sulfolane contaminated groundwater samples also indicated that these three combinations can efficiently degrade sulfolane. Furthermore, a synergistic effect was observed in the combination of H2O2 and O3 photolysis.

Design and evaluation of a UV LED Photocatalytic Reactor Using Anodized TiO2 Nanotubes.

A bench-scale flow-through photocatalytic reactor using light emitting diodes (LED) as light source and a TiO2 nanotube array (TN) as immobilized catalyst has been designed, fabricated and tested on commonly studied contaminants. The photoreactor is comprised of 144, 365-nm UV-LED lamps mounted along the inner periphery of an annular cylinder. An ordered array of TN, as catalyst, was immobilized by electrochemical anodization of a titanium cylinder and placed in the center of the reactor. Synthesized TN was characterized by scanning electron microscopy (SEM) and energy-dispersive X-ray spectroscopy (EDX). Laboratory investigations were conducted on the photoreactor to treat 4-chlorophenol (4-CP), atrazine and methylene blue. The performance of the photoreactor at different flow rates and at varying distances of photocatalyst from the light source was monitored. The photocatalytic reaction rates increased with bubbling oxygen into the reservoir. Significant improvement was observed when H2O2 was added and degradation to detection limits was observed.

Preparation and characterization of humic acid-carbon hybrid materials as adsorbents for organic micro-pollutants.

The present work involves the preparation of novel adsorbent materials by the insolubilization and hybridization of humic acid (HA) with carbon. The prepared materials were characterized by N2 adsorption, elemental analysis, Fourier transform infrared spectroscopy, scanning electron microscopy, transmission electron microscopy, solid-state (13)C cross polarization magic angle spinning nuclear magnetic resonance, and low-field nuclear magnetic resonance (NMR) relaxometry on wetted samples. The water solubility of these materials and the lack of effect of oxidants were also confirmed. With this background, the adsorption capacities toward phenol, 2,4,6-tricholrophenol, and atrazine were evaluated, using these as model compounds for organic micropollutants of concern in water. Experimental results show that the prepared materials are mesoporous and have a higher surface area than humic acid and even than the porous carbon in the case of carbon coating. They retain the basic features of the starting materials with lowered functional group content. Moreover, there are interesting new features. NMR relaxometry shows that equilibration of water uptake is very fast, making use in water simple. They have higher adsorption capacities than the pure materials, and they can be applied under a wide range of environmental conditions.

Photocatalytic degradation of agricultural antibiotics using a UV-LED light source.

With a view to developing a UV-LED photocatalytic reactor for small and remote water systems, the degradation of three representative agriculturally produced contaminants, two antibiotics and an endocrine disruptor hormone, was evaluated in a bench 365 nm LED photoreactor using a slurry of the well-known Degussa P25® (TiO2) as photocatalyst. Use of an additional electron capture additives O2 and H2O2 was also assessed. Loss of the parent organic compounds was tracked by HPLC or UV absorbance and mineralization, where feasible, was studied with TOC analysis with conventional instrumentation. In all cases, degradation is significant with moderate light dose. Lab data suggest log reduction with light delivery less than 2.2 kWhr per cubic meter light delivery.

Dechlorination of polychlorinated biphenyls in transformer oil using UV and visible light.

A study on dechlorination of PCB138 in transformer oil (TO) and 2-propanol (IPA) using 254 nm ultraviolet (UV) light as well as dye sensitized visible light has been conducted. Studies on dechlorination of polychlorinated biphenyls (PCBs) in TO using visible light in the presence of methylene blue (MB) and triethylamine (TEA) (providing a 'photocatalytic' cycle) in both deaerated and aerated conditions have been conducted to determine effects of TO, MB and TEA on reaction rates. The results show that photolytic methods are effective in treating PCBs in TO, and that the oil plays a limited adverse role. Under UV irradiation, PCB 138 can be >99% dechlorinated in the presence 0.06% (w/w) TO in IPA within 1 h with a rate constant of 0.0853 min(-1), while 47% of PCB138 can be dechlorinated in 92.1% (w/w) TO in IPA within 2 h with a rate constant of 0.0051 min(-1). In the 'photocatalytic' system, 94% reduction of PCB 138 was achieved within 30 min with a rate constant of 0.0968 min(-1) when the solvent was 60.70% (w/w) TO in IPA, while 71% dechlorination of PCB138 was achieved within 30 min with a rate constant of 0.0382 min(-1) when 81.62% (w/w) TO was present. In treatment of 30-73 ppm PCBs in TO, the optimal concentration of MB and TEA were found to be 0.5 g/L and 58.08 g/L respectively. Because of quenching by oxygen, deaeration of the solution is necessary for an efficient reaction. The photocatalytic system is especially adapted for treating lower concentration of PCBs in TO.

Electron transfer sensitized photodechlorination of surfactant solubilized PCB 138.

Sensitized photodechlorination of polychlorinated biphenyl, PCB 138, in three different surfactant solutions was studied. The sensitizer of choice was leuco-methylene blue, which was produced in situ from methylene blue using either triethylamine or sodium borohydride. Three types of surfactants, anionic (SDS), neutral (TWEEN 80), and cationic (CTAB) at different concentrations were investigated. The neutral and cationic surfactants were found to be more effective than anionic. In each case the surfactant concentration was found to play a significant role in the rate of dechlorination. For different sensitized systems (triethylamine or sodium borohydride), a different product distribution and a different pathway of dechlorination was observed.

An alternative process to treat boiler feed water for reuse.

A bench-scale process to treat boiler feed water for reuse in steam generation was developed. Industrial water samples from a steam-assisted gravity drainage plant in northern Alberta, Canada, were obtained and samples characterized. The technology, which consists of coagulation-settling to remove oil/grease and particulates followed by an advanced oxidative treatment, led to clean water samples with negligible organic carbon. Coagulation followed by settling removed most particulates and some insoluble organics. The advanced oxidative treatment removed any remaining color in the samples, decreased the organic content to near-zero, and provided water ready for reuse.

An integrated performance assessment framework for water treatment plants.

An innovative framework for the performance assessment of a traditional water treatment plant (WTP) is presented that integrates the concepts of reliability, robustness, and Quantitative Microbial Risk Assessment (QMRA). Performance assessment for a WTP comprised of three units (i.e., unit 1: Coagulation/Flocculation and Sedimentation; unit 2: Filtration, and unit 3: Disinfection) was conducted. Performance functions for units 1, 2, and units 1 and 2 combined, were constructed by integrating turbidity robustness indices. Performance function for chlorine disinfection was developed based on the difference between achieved and required CT values. A health-based performance function was developed by comparing the target daily infection rate to the site-specific infection rate. It was used to identify whether the health-based target was met during the failures of units 1 to 3. Results obtained from the proposed performance functions can be used by operators to ensure that multiple barriers perform successfully under variable conditions.

Photocatalytic dechlorination of polychlorinated biphenyls using leuco-methylene blue sensitization, broad spectrum visible lamps, or light emitting diodes.

Photocatalytic routes to dechlorinate polychlorinated biphenyls (PCBs) have considerable potential for development. This paper describes efficient dye-photocatalyzed processes which can be driven by long wavelength light sources including light-emitting diodes (LEDs), fluorescent lamps, and quite probably sunlight. The reduced form of methylene blue (MB), leuco-methylene blue (LMB), has previously been found to photoinduce dechlorination of chloroaromatics with an electron transfer from its triplet excited state. Sodium borohydride, used in this case is an efficient sacrificial reductant, which can maintain LMB as the major species in competition with air oxidation of LMB to MB. There is also evidence that it plays a further (chain reaction) role in promoting the LMB photodechlorination process as well. The generality of the photoelectron transfer from reduced members of the phenothiazine dye family is demonstrated with phenothiazine and leuco-methylene green when a wavelength (UV) is chosen to produce the highly reductive triplet. It is likely that dechlorination can be initiated by many triplet excited states with adequate reduction potential.

Photocatalytic dechlorination of PCB 138 using leuco-methylene blue and visible light; reaction conditions and mechanisms.

A study of dechlorination of PCB 138, under visible light employing methylene blue (MB) and triethylamine (TEA) in acetonitrile/water has been conducted to investigate the details of the mechanism of dechlorination and to determine the efficiency of the process for this representative congener. Two other amines, N-methyldiethanolamine (MEDA) and (triethanolamine) TEOA also replaced TEA and two other solvents, methanol and ethanol replacing acetonitrile were examined for effects on reaction rates. The results show that PCB 138 can be dechlorinated efficiently in this photocatalytic reaction. Clarifying ambiguities in several previous reports, the reduced form of MB, leuco-methylene blue (LMB) was identified as responsible for the photoreaction with its excited state transferring an electron to PCBs; oxidized LMB (i.e. MB) is reduced back to LMB by the excess amine present. The reaction depends on a cycle driven by the amine as a sacrificial electron donor. MEDA proved to be the most efficient electron donor; apparently in consequence of the most favourable steady state concentration of LMB. Methanol and ethanol may be used to replace acetonitrile with little change in the efficiency of the reaction.

A comparison of several nanoscale photocatalysts in the degradation of a common pollutant using LEDs and conventional UV light.

A comparative study on the photocatalytic activities of four different catalysts, P-25 TiO(2), TiO(2) nanofibers, tin-doped TiO(2) nanofibers under UV light irradiation at 350 nm, and coumarin (C-343) coated TiO(2) nanofibers at 436 nm light emitting diodes (LED) is reported. Catalysts performance has been compared based on their reflectance spectrum and activity. A common water contaminant 4-chlorophenol was used as a substrate to compare the activity of the different catalysts under both direct and dye sensitized conditions. Results indicated that amongst the four different catalysts the activity of P-25 was the highest. However the activity of C-343 coated TiO(2) nanofibers in the LED (436 nm) based reactor was competitive. Identification of reaction intermediates implied that the reaction pathways under UV (band gap) and visible (dye sensitized) irradiation were different. Nonetheless, ring opening took place in all reactions with both maleic and dihydroxymaleic have been identified as intermediates. The study indicates that ordered arrays of TiO(2) irradiated by panels of arrays of low cost high intensity LEDs might be used for the design of reactors. The near monochromaticity, long life, and operation under direct currents are advantages of using LEDs.

Characterization of an LED based photoreactor to degrade 4-chlorophenol in an aqueous medium using coumarin (C-343) sensitized TiO2.

A detailed performance evaluation of a simple high intensity LED based photoreactor exploiting a narrow wavelength range of the LED to match the spectrum of a dye in a photocatalysis system is reported. A dye sensitized (coumarin-343, lambda max = 446 nm) TiO 2 photocatalyst was used for the degradation of 4-chlorophenol (4-CP) in an aqueous medium using the 436 nm LED based photoreactor. The LED reactor performed competitively with a conventional multilamp reactor and sunlight in the degradation of 4-CP. Light intensities entering the reaction vessel were measured by conventional ferrioxalate actinometry. The results can be fitted by approximate first order kinetic behavior in this system. Hydroxyl radicals were detected by spin trapping EPR, and effects of OH radical quenchers on kinetics suggest that the reaction is initiated by these radicals or their equivalents. LEDs operating at competitive intensities offer a number of advantages to the photochemist or the environmental engineer via long life, efficient current to light conversion, narrow bandwidth, forward directed output, and direct current power for remote operation. Matching light source spectrum to chromophore is a key.

The pathway of dechlorination of PCB congener by a photochemical chain process in 2-propanol: the role of medium and quenching.

As part of a program aimed at developing a field process for cleanup of PCB contaminated soils using photochemistry in basic 2-propanol, additional details of the dechlorination pathway are presented. The mechanism involves a chain reaction with both homolytic photochemical C-Cl bond fission and electron transfer steps producing PCB anion radicals. Kinetics of dechlorination of various congeners show patterns of relative rates associated with the basic 2-propanol medium that are not found in other media because both electron transfer and photochemical homolysis steps determine overall rates of dechlorination and govern the pathways and relative concentrations of intermediates. The electron transfer steps display opposite structure-reactivity correlations to the photo-homolysis, C-Cl bond fission steps. Oxygen quenching is shown to differentially affect both types of steps. In contrast to the suggestion that inter system crossing can be highly efficient with reaction originating from a PCB triplet, oxygen quenching data suggest that a significant minimum of the quantum yield is non-quenchable, presumably because of a reaction path from the PCB singlet. This may help to explain why exclusion of air is not entirely necessary in practice.