Decolorization and mineralization of reactive dyes by a photocatalytic process using ZnO and UV radiation

Reactive dyes are one of the major pollutants in textile wastewater and a concern because they are not easily degraded by conventional wastewater treatments. Heterogeneous photocatalysis has been considered an effective option for treating wastewater containing those dyes. This research work assesses the photocatalytic degradation of reactive dyes using UV irradiation and pure or impregnated ZnO. In addition to photocatalysis, separate photolysis and adsorption experiments were conducted but showed low efficiency. The dye degradation was monitored by UV-Vis spectroscopy and mineralization was determined by total organic carbon (TOC) analyses. Total color removal was achieved after 30 min of irradiation using pure ZnO. The Black 5 dye photocatalytic decolorization reaction followed first-order kinetics, while Yellow 145, Red 4 and Blue 21 dyes followed zero-order kinetics. TOC removals in the range of 70-80% were achieved after 240 min of individual photocatalytic treatment with ZnO. The performance of each photocatalyst was also compared when the four dyes were mixed together and the order of efficiency in the mineralization process was as follows: Fe/ZnO > ZnO > Co/ZnO. This result was explained by the crystal field theory.     

Optimised photocatalytic degradation of a mixture of azo dyes using a TiO(2)/H(2)O(2)/UV process

The aim of the present study was to optimise the photocatalytic degradation of a mixture of six commercial azo dyes, by exposure to UV radiation in an aqueous solution containing TiO(2)-P25. Response surface methodology, based on a 3(2) full factorial experimental design with three replicates was employed for process optimisation with respect to two parameters: TiO(2) (0.1-0.9 g/L) and H(2)O(2) (1-100 mmol/L). The optimum conditions for photocatalytic degradation were achieved at concentrations of 0.5 g TiO(2)/L and 50 mmol H(2)O(2)/L, respectively. Dye mineralisation was confirmed by monitoring TOC, conductivity, sulfate and nitrate ions, with a sulfate ion yield of 96% under optimal reactor conditions. Complete decolorisation was attained after 240 min irradiation time for all tested azo-dyes, in a process which followed a pseudo-first kinetic order model, with a kinetic rate constant of approximately 0.018 min(-1). Based on these results, this photocatalytic process has promise as an alternative for the treatment of textile effluents.     

Comparison of the photoconversion of para-chlorophenol under simulated sunlight and UV irradiation in ice

The photochemistry of para-chlorophenol (4-CP) was studied under simulated sunlight (lambda > 300 nm) and UV irradiation by using a 125 W high-pressure mercury lamp with or without a hard glass as light source in an ice matrix. The experiments were carried out in a photochemical cold chamber reactor at -14 to -12 degrees C. The photoconversion rate, photoproducts and photoconversion mechanism of 4-CP were all inspected and compared. The results show that the 4-CP photoconversion obeys the first order kinetic model and its photoconversion rate is highly affected by the initial concentration of 4-CP, light intensity and water quality. It is found that the conversion rate of 4-CP under UV irradiation is higher than that under simulated sunlight irradiation. The intermediate products of 4-CP were characterized by GC-MS, HPLC-ESI-MS and HPLC techniques and the possible photoconversion mechanism was proposed accordingly. It is concluded that the mechanism and photoproducts of 4-CP photolysis in ice are different from those in water, and the photoproducts and photoconversion pathways of 4-CP in ice varied with different light sources.     

Parathion degradation and toxicity reduction in solar photocatalysis and photolysis.

The solar photocatalytic degradation of methyl parathion was investigated using a circulating TiO2/solar light reactor. Under solar photocatalysis condition, parathion was more effectively degraded than solar photolysis and TiO2-only conditions. With solar photocatalysis, 20 mg/L of parathion was completely degraded within 60 min with a TOC decrease of 63% after 150 min. The main ionic byproducts during photocatalysis recovered from parathion degradation were mainly as NO3-, NO2- and NH4+, 80% of the sulphur as SO4(2-), and 5% of phosphorus as PO4(3-). The organic intermediates 4-nitrophenol and methyl paraoxon were also identified, and these were further degraded in solar photocatalytic condition. Two different bioassays (Vibrio fischeri and Daphnia magna) were used to test the acute toxicity of solutions treated by solar photocatalysis and photolysis. The Microtox test using V. fischeri showed that the toxicity expressed as EC50 (%) value increased from 5.5% to >82% in solar photocatalysis, indicating that the treated solution is non-toxic, but only increased from 4.9 to 20.5% after 150 min in solar photolysis. The acute toxicity test using D. magna showed that EC50 (%) increased from 0.05 to 1.08% under solar photocatalysis, but only increased to 0.12% after 150 min with solar photolysis, indicating the solution is still toxic. The pattern of toxicity reduction parallels the decrease in TOC and the parathion concentrations.     

Application of cuprous oxide synthesized from copper-containing waste liquid to treat aqueous reactive dye

Cuprous oxide that was prepared from Cu-containing waste liquid from a printed circuit board manufacturer was used to carry out Fenton-like and photo-Fenton-like oxidation reactions to decolorize a reactive dye (RB19). A microwave hydrothermal method was applied in the synthesis. The highest recovery rate of Cu from wastewater was 87% and was obtained when the synthesis was performed at a power of 200 W for 15 min. An RB19 decolorization efficiency of 99.9% was achieved when the Fenton-like reaction was conducted with 50 mmol/L H(2)O(2) and 0.9 g/L of Cu(2)O. The decolorization of RB19 was more effective when the system was irradiated with visible light than with UV light. Under irradiation, the decolorization rate was the highest when the decolorization was performed in the RB19 solution that contained 50 mmol/L H(2)O(2) and 0.9 g/L CuO(2) in the Fenton-like and the 365 nm-irradiated photo-Fenton-like reactions. In the case of irradiation under 410 nm visible light, the system was operated with lower H(2)O(2) (30 mmol/L) and Cu(2)O (0.5 g/L) to achieve a decolorization rate higher than 365 nm-irradiated photo-Fenton-like reactions.     

Frequency effect on p-nitrophenol degradation under conditions of strict acoustic and electric control

The process of decomposing p-nitrophenol (PNP) with power ultrasound requires strict control of acoustic and electric conditions. In this study, the conditions, including acoustic power and acoustic intensity, but not ultrasonic frequency, were controlled strictly at constant levels. The absorbency and the COD concentrations of the samples were measured in order to show the variation of the sample concentration. The results show significant differences in the trend of the solution degradation rate as acoustic power increases after the PNP solution (with a concentration of 114 mg/L and a pH value of 5.4) is irradiated for 60 min with ultrasonic frequencies of 530.8 kHz, 610.6 kHz, 855.0 kHz, and 1130.0 kHz. The degradation rate of the solution increases with time and acoustic power (acoustic intensity). On the other hand, the degradation rate of the solution is distinctly dependent on frequency when the acoustic power and intensity are strictly controlled and maintained at constant levels. The degradation rate of the PNP solution declines with ultrasonic frequencies of 530.8 kHz, 610.6 kHz, 855.0 kHz, and 1130.0 kHz;the COD concentration, on the contrary, increase.     

Evaluation of hybrid treatments to produce high quality reuse water

Four tertiary hybrid treatments to produce high quality reused water, fulfilling Brazilian drinking water regulations, from a slaughterhouse's secondary treated effluent were evaluated. The pilot plant with a capacity of 500 L h(-1) was set up and consisted of these stages: pre-filtration system (cartridge filter 50 micron, activated carbon filter, cartridge filter 10 micron), oxidation (H2O2) or second filtration (ceramic filter, UF) followed by UV radiation (90 L h(-1)). The best combination was T4: pre-filtration followed by H2O2 addition and UV radiation (AOP H2O2/UV). Disinfection kinetics by T4 followed pseudo first-order kinetics: k(T4) = 0.00943 s(-1) or 0.00101 cm2 mJ(-1). Three different zones (A, B, C) were observed in the UV254 degradation kinetics (pseudo-first order kinetics): k' decreased over time (k'(A) > k'(B) > k'(C)).     

草酸铁络合物／H2O2／UV体系对靛红染料废水脱色的研究

以草酸铁络合物/H2O2作光氧化剂,利用紫外光对水溶性染料靛红进行了光氧化降解试验研究。结果表明,在pH值为3,[Fe(Ⅲ)]/[C2O42-]=1/3,H2O2为100 mg/L条件下,光照30 min后,质量浓度为30 mg/L的染料溶液其脱色率达到98.5%,COD去除率为54.4%。与UV/Fe3+、UV/H2O2、UV/草酸等光氧化体系相比,脱色效果较为明显。     

Waste fly ash–ZnO as a novel sunlight-responsive photocatalyst for dye discoloration

Treating waste with a waste material using freely available solar energy is the most effective way towards sustainable future. In this study, a novel photocatalyst, partly derived from waste material from the coal industry, was developed. Fly ash hybridized with ZnO (FA—Zn) was synthesized as a potential photocatalyst for dye discoloration. The synthesized photocatalyst was characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, and ultraviolet—visible/near infra-red spectroscopy. The photocatalytic activity was examined with the discoloration of methylene blue used as synthetic dye wastewater. All the experiments were performed in direct sunlight. The photocatalytic performance of FA—Zn was found to be better than that of ZnO and the conventionally popular TiO₂. The Langmuire—Hinshelwood model rate constant values of ZnO, TiO₂, and FA—Zn were found to be 0.016 min^-1, 0.017 min^-1, and 0.020 min^-1, respectively. There were two reasons for this: (1) FA—Zn was able to utilize both ultraviolet and visible parts of the solar spectrum, and (2) its Brunauere—Emmette—Teller surface area and porosity were significantly enhanced. This led to increased photon absorption and dye adsorption, thus exhibiting an energy-efficient performance. Therefore, FA—Zn, partly derived from waste, can serve as a suitable material for environmental remediation and practical solar energy applications.     

UV/H2O2和UV/TiO2/H2O2去除水中微量硝基苯的比较研究

研究比较了UV/H2O2和UV/TiO2/H2O2对水中微量硝基苯的降解效果,并考察了水中常见HCO-3和腐殖酸对硝基苯降解的影响.结果表明,薄膜状TiO2的存在对UV/H2O2降解硝基苯有显著的促进作用,在最佳H2O2投加量2.1 mg/L时,UV/TiO2/H2O2的反应速率常数比UV/H2O2高32.8%;2 min内UV/TiO2/H2O2对硝基苯的去除率达到80%以上.HCO-3和腐殖酸对硝基苯降解有很强的抑制作用,HCO-3和腐殖酸浓度分别为2 mmol/L和3.2 mg/L时,UV/TiO2/H2O2对硝基苯的反应速率常数分别下降84.6%和92.2%.     

Development and validation of a UPLC-MS/MS method for studying the degradation kinetics of ofloxacin and trimethoprim during the application of solar Fenton process in secondary treated sewage

In this work, a sensitive and highly selective method was developed and validated to study the degradation of two antibiotic compounds (ofloxacin (OFX) and trimethoprim (TMP)), spiked in secondary treated domestic effluents, by the solar Fenton process. Three different chromatographic columns were tested on a ultra performance liquid chromatography-tandem mass spectrometric (UPLC-MS/MS) instrument working in the electrospray ionization (ESI) mode with twelve combinations of eluting solvents. Samples were enriched prior to the analysis by solid phase extraction using the hydrophilic-lipophilic balanced (HLB) reversed phase polymeric sorbent. The method was optimized and showed very good performance characteristics and was successfully applied to study the degradation kinetics of the selected antibiotics during the solar Fenton process applied. The degradation was found to follow a pseudo first-order kinetics for both compounds at initial concentration of 100 μg L(-1) with k = 0.0345 min(-1) for OFX and k = 0.0768 min(-1) for TMP, whereas the complete removal was achieved after 120 min of treatment for both compounds.     

Photodegradation of sulphadimethoxine in water by medium pressure UV lamp

The photodegradation rate of sulphadimethoxine (SMT) in water was studied under polychromatic UV light, in a bench scale apparatus. SMT photolysis was carried out at pH levels of 2.5, 6.5 and 10 to study the impact of acid base properties on the degradation of SMT. The highest SMT photolysis fluence based rate was found at pH=2.5 (k=7.22x10(-4) cm2/mJ) and the lowest rate at pH=10 (k=4.72x10(-4) cm2/mJ), thus the reaction rate decreases with an increase in pH between pH values of 2.5-10. Results indicated that direct photolysis is not satisfactory for degradation of SMT by polychromatic UV lamp as a fluence of approximately 7,000 mJ/cm2 is needed to break down 99% of SMT at pH 6.5. The photodegradation products of SMT were studied at various pH values. Photodegradation of SMT results in dissimilar relative amounts of intermediates formed at different pH values which may exert a photon demand and impact on SMT photodegradation rate.     

Advanced H2O2 oxidation for diethyl phthalate degradation in treated effluents: effect of nitrate on oxidation and a pilot-scale AOP operation

One of the objectives of this study was to delineate the effect of nitrate on diethyl phthalate (DEP) oxidation by conducting a bench-scale ultraviolet (UV)/H2O2 and O3/H2O2 operations as suggested in a previous study. We also aim to investigate DEP oxidation at various UV doses and H2O2 concentrations by performing a pilot-scale advanced oxidation processes (AOP) system, into which a portion of the effluent from a pilot-scale membrane bioreactor (MBR) plant was pumped. In the bench-scale AOP operation, the O3 oxidation alone as well as the UV irradiation without H2O2 addition could be among the desirable alternatives for the efficient removal of DEP dissolved in aqueous solutions at a low DEP concentration range of 85+/-15 microg/L. The adverse effect in the UV/H2O2 process was significantly greater than that in the UV oxidation alone, and its oxidation was almost halved by the nitrate. However, the nitrate clearly enhanced the DEP oxidation in the O3 oxidation and O3/H2O2 process. Especially, the addition of nitrate almost doubled the DEP oxidation efficiency in the O3/H2O2 process. The series of pilot-scale AOP operations confirmed that about 30-50% of DEP dissolved in the treated MBR effluent streams was, at least, oxidized by the O3 oxidation alone as well as the UV irradiation without H2O2 addition. The UV photolysis of H2O2 was most effective for DEP degradation with an H2O2 concentration of 40 mg/L at a UV dose of 500 mJ/cm2.     

UV disinfection of wastewater effluents for unrestricted irrigation.

Wastewater reuse in arid regions is important for the production of a water resource to be utilised for non-potable purposes and to prevent the environmental transmission of disease-causing agents. This study was conducted to evaluate the effect of water quality on the comparative disinfection efficiency of viruses, bacteria and spores by UV irradiation. Furthermore, the microbial quality of effluent produced by coagulation, high rate filtration (HRF) and either UV irradiation or chlorination was determined. Using low pressure collimated beam, a UV dose of 80 mWs/cm2 was needed to achieve a 3-log10 inactivation of either rotavirus SA-11 or coliphage MS2, whereas over 5-log10 inactivation of E. coli was reached with a dose of only 20 mWs/cm2. B. subtilis inactivation was found to be linear up to a dose of 40 mWs/cm2 and then a tailing up to a UV dose of 120 mWs/cm2 was observed. It is worth noting that effluent turbidity of < 5 NTU did not influence the inactivation efficiency of UV irradiation. Operation of a pilot plant to treat secondary effluent by coagulation, HRF and UV disinfection at a UV dose of 80 mWs/cm2 resulted in the production of high quality effluent in compliance with the Israel standards for unrestricted irrigation (< 10 CFU/100 mL faecal coliform and turbidity of < 5 NTU). Sulphite reducing clostridia (SRC) were found to be more resistant than coliphages and F coliform for UV irradiation. The results of this study indicated that UV disinfection is suitable for the production of effluents for unrestricted irrigation of food crops.     

Solar degradation of Direct Blue 71 using surface modified iron doped ZnO hybrid nanomaterials

This paper reports photodegradation of Direct Blue 71 under irradiation by sunlight. We synthesized Fe:ZnO nanomaterials under mild hydrothermal conditions (P = autogenous, T = 100 °C, t = 18 h). The precursors were Fe(2)O(3) as dopant, n-butylamine as surface modifier, NaOH as mineralizer and reagent grade ZnO. The systematic experiments on the photodegradation of Direct Blue 71 were carried out by changing different effective parameters. The variables in this study were type of nanomaterials synthesized (4 types), nanomaterial dosage (0.4-1.0 g/L), contact time (30-120 min), pH (3-11), and dye concentration (20-100 ppm). The photodegradation efficiency was determined using a UV-Vis spectrophotometer. Determination of total organic carbon (TOC) amount was used to find out mineralization efficiency. Our experimental results revealed that the nanomaterials synthesized had higher efficiency compared with the reagent grade ZnO. The best efficiency was achieved at the following conditions: 1.0 g/L nanomaterials loading, 120 min contact time, pH 5, and photodegradation efficiency from more than 75 up to 99% depending upon the dye concentration.     

Treatment of an ECF effluent by combined use of activated sludge and advanced oxidation process.

The combined biological and chemical treatments of the cellulose effluents have been studied aiming to promote a more significant degradation of their recalcitrant compounds and to reduce their toxicity, as compared with the isolated treatments. In this work the effluent from acid stages of the ECF bleaching of Eucalyptus urograndis pulp was treated by using separately activated sludge and UV radiation and its combination. The treatment efficiency was evaluated by colour, total phenol, COD, BOD, UV spectroscopy, molar weight distribution and toxicity. The untreated effluent presented 587 +/- 18 CU, 19.3 +/- 0.6 mg.L(-1) of total phenol, 2246 +/- 137 mgO2.L(-1) of COD and 904 +/- 48 mgO2.L(-1) of BOD. It did not show acute toxicity to Escherichia coli, but presented chronic toxicity to Selenastrum capricornutum (EC50 = 25%). The sludge treatment resulted in a colour increasing of 42% and decreasing of total phenol, COD and BOD of 33%, 64% and 92%, respectively. The UV radiation treatment for 120 min resulted in a decrease of colour, total phenol, BOD and COD of 70%, 43%, 62% and 43%, respectively. The combined treatment promoted an expressive decrease for colour and total phenol. The UV absorption indicated a degradation of the aromatic compounds. The biological treatment did not remove chronic toxicity and after UV radiation treatment, a 10 times improving toxicity was noticed.     

Photocatalytic degradation of parathion in aqueous TiO2 dispersion: the effect of hydrogen peroxide and light intensity

The photodegradation of parathion in the direct photolysis, UV/TiO₂, UV/H₂O₂ and UV/TiO₂/H₂O₂ systems was investigated at 25°C. The effect of light intensity was also examined to clarify the relationship between the photo flux and decomposition rate of parathion. Results of the study demonstrated that no obvious degradation of parathion in dark reaction occurred within 24 hours. However, the addition of TiO₂ and/or H₂O₂ promotes the degradation efficiency of parathion. Adding H₂O₂ was more effective in the photocatalytic oxidation of parathion than TiO₂. Also, hydrogen peroxide was found as an intermediate with the maximum concentration of 55 μM in UV/TiO₂ system during the photodegradation of parathion. A higher intensity of lamp could increase the degradation rale of parathion. However, the quantum efficiency for degradation of parathion decreased from 0.053 to 0.006 when light intensity increased from 100 W to 450W. Photodecomposition followed a pseudo-first-order reaction. The rate constants of parathion ranged from 0.003 min^-1 for direct photolysis to 0.023 min^-1 for UV/TiO₂/H₂O₂ system. This study indicated that photocatalytic degradation is a highly promising technology for detoxifying parathion.     

A bifunctionalized dye-sensitized TiO(2) film for efficient degradation of methyl orange under visible light irradiation

A new bifunctionalized TiO(2) film containing a dye-sensitized region and a degradation region was described. A similar structure of dye-sensitized solar cell (DSSC) was fabricated in the dye-sensitized region to accomplish separation of electrons from positive charges, and separation of dye from pollutants to avoid dye decomposition. The bifunctionalized TiO(2) film electrode and anode electrode can degrade methyl orange (MO) in reactors A and B, respectively. The degradation efficiency was enhanced remarkably by an external electrical potential. The decolorization of MO reaches as high as 95% after 2 h visible light irradiation at an external potential of 0.5 V along with a loss of 41% total organic carbon (TOC). The possible reason for the improvement of degradation by external DC potential was discussed. Effects of pH and inorganic salts on the decolorization are present.     

Noble metal modified titania catalysts in the degradation of reactive black 5: a kinetic approach

The photocatalytic degradation of Reactive Black 5 (RB 5), a di-azo dye was investigated over M/TiO2 (M = Ag, Au and Pt) photocatalysts irradiated with UV and visible light. TiO2 was prepared by sol-gel technique (Syn-TiO2). Photodeposition of metal salt precursors over Syn-TiO2 was carried out so as to obtain 1 wt% of M/TiO2 catalysts. The photodecolourization and photodegradation reactions were also compared with commercial TiO2 (Degussa P25) catalyst. Kinetic studies for the decolourization of RB 5 showed that it followed pseudo first order. Recycling of catalysts was performed to check the economic feasibility of the photocatalytic process. In order to check the applicability of M/TiO2 catalyst in the treatment of industrial effluent, real textile effluent was collected from an industry and subjected to photodegradation and the results are presented. Enhanced activity of M/TiO2 catalyst under visible light irradiation highlights its importance in the field of photocatalysis.     

Biofilm control in water by advanced oxidation process (AOP) pre-treatment: effect of natural organic matter (NOM)

The main goal of this study was to examine the influence of natural organic matter (NOM) on the efficiency of H?O?/UV advanced oxidation process (AOP) as a preventive treatment for biofilm control. Pseudomonas aeruginosa PAO1 biofilm-forming bacteria were suspended in water and exposed to various AOP conditions with different NOM concentrations, and compared to natural waters. H?O?/UV prevented biofilm formation: (a) up to 24 h post treatment - when residual H?O? was neutralized; (b) completely (days) - when residual H?O? was maintained. At high NOM concentrations (i.e. 25 mg/L NOM or 12.5 mg/L DOC) an additive biofilm control effect was observed for the combined H?O?/UV system compared to UV irradiation alone, after short biofilm incubation times (<24 h). This effect was H?O? concentration dependent and can be explained by the high organic content of these water samples, whereby an increase in NOM could enhance (?)OH production and promote the formation of additional reactive oxygen species. In addition, maintaining an appropriate ratio of bacterial surviving conc.: residual H?O? conc. post-treatment could prevent bacterial regrowth and biofilm formation.