Photocatalytic Decolorization Kinetics and Mineralization of Reactive Black 5 Aqueous Solution by UV/TiO2 Nanoparticles

The photocatalytic decolorization and mineralization of Reactive Black 5 (RB5) dye in presence of TiO₂ Degussa P25 has been studied using artificial light radiation in a shallow pond slurry reactor. The equilibrium adsorption of dye, influence of pH (3–11), catalyst load (0.5–3.0 g/L), and dye concentration (20–100 mg/L) on decolorization kinetics were studied. The effect of area to volume ratio of photoreactor on decolorization kinetics has been also studied. Mineralization studies were performed at optimized conditions of pH (3) and catalyst load (1.5 g/L). The maximum adsorption (26.5 mg/g) of dye was found to occur at pH 3. The apparent pseudo first order decolorization rate constant (k_app) value followed the order pH 3 > pH 11 > pH 9 > pH 7. As compared to available literature reduction in total organic carbon (TOC) was minimal by the time there was complete decolorization. Initial reduction in TOC was followed by subsequent increasing trend till complete decolorization. Final decreasing trend in TOC was observed only after complete decolorization. Twelve hours of treatment under experimental conditions reduced TOC content by 70% only. Discussion of results suggest that photocatalytic treatment of colored effluent under low UV intensity, and low A/V ratio may result in completely decolorized effluent but still having high COD.     

The Effect of Oxygen on Anaerobic Color Removal of Azo Dye in a Sequencing Batch Reactor

In this study, various amounts of oxygen were added to the anaerobic phase of an anaerobic‐aerobic sequencing batch reactor (SBR) receiving azo dye remazol brilliant violet 5R to mimic the input of oxygen into the anaerobic zones of biological textile wastewater treatment plants. The effect of oxygen on the anaerobic biodegradative capability of the mixed microbial culture for remazol brilliant violet 5R was investigated. To investigate the effect of oxygen on anaerobic azo dye biodegradation, the anaerobic phase of the SBR cultures were exposed to a very low limited amount of oxygen for various air flow rates. Initially, an air flow rate of 20 mL/min was applied, further on the air flow rate in the anaerobic phase was increased up to 40 mL/min. System performance was determined by monitoring chemical oxygen demand, color removal rate, activities of anaerobic (azo reductase) and aerobic enzymes (catechol 2,3‐dioxygenase, catechol 1,2‐dioxygenase). The results of percentage COD reduction at each stage were similar for all runs, giving an overall reduction of 96%. Anaerobic color removal efficiency and azo reductase activity of anaerobic microorganisms were adversely affected by the addition of oxygen. Color removal efficiencies of the anaerobic phases decreased from 80% down to 42 and 38% for the limited oxygen conditions of 20 mL/min and 40 mL/min, respectively. It was observed that the activity of catechol 2,3‐dioxygenase and catechol 1,2‐dioxygenase, involved in breakage of aromatic rings, increased after they are exposed to oxygen limited conditions compared to fully anaerobic conditions. It was also observed that catechol 1,2‐dioxygenase enzyme activity increased by increasing the oxygen level on oxygen limited conditions in the anaerobic zone.     

Biologische Behandlung von synthetischen Abwässern mit Azofarbstoffen

Purification of Wastewaters Containing Azo Dyes This study describes the degradability of the azo dye C.I. Reactive Violet 5 by a continuous flow biological treatment system consisting of three rotating disc reactors. The azo dye was first decolorized in an anaerobic reactor. Decolorization was improved by adding an auxiliary substrate (yeast extract and acetic acid). Although severe operating conditions were experienced due to failures in the temperature and pH-controllers, the reactor recovered quickly and continued to decolorize reliably. The removal of the auxiliary substrate in the anaerobic reactor was not satisfactory, probably due to the copper in the azo dye. Batch experiments showed that copper was removed from the dye molecule and precipitated during the decolorization. In the continuous flow reactor, the copper precipitate on the disc can redissolve due to a pH-gradient in the fixed biomass becoming toxic again for the bacteria. In the following two aerobic reactors, the auxiliary substrate was degraded, but mineralization of the dye metabolites was insufficient. The aromatic amines produced by the anaerobic decolorization are more toxic in the bacterial luminescence test than the azo dye. Therefore, decolorization alone cannot be used to treat colored wastewater. Since the amines can also be produced in anaerobic parts of rivers, the dyes have to be removed in a more efficient way. That is the reason why in further experiments ozonation is being tested to increase the biological degradability of the azo dye for a following aerobic stage. Either ozonation can be used after the two stage treatment of the dye in anaerobic/aerobic reactors or the dye can be oxidized directly, making the addition of auxiliary substrate unnecessary. These configurations are being tested with the goal to degrade the dye with the least ozone consumption.     

Solar Photocatalytic Decolorization and Detoxification of Industrial Batik Dye Wastewater Using P(3HB)‐TiO2 Nanocomposite Films

Solar photocatalytic decolorization and detoxification of batik dye wastewater using titanium dioxide (TiO₂) immobilized on poly‐3‐hydroxybutyrate (P(3HB)) film was studied. The effects of initial dye concentration, catalyst concentration, P(3HB) film thickness, and fabrication methods of the nanocomposite films were evaluated against methylene blue, a standard organic dye. It was observed that 0.4 g of P(3HB)‐40 wt% TiO₂ removed 96% of the color under solar irradiation. P(3HB) and TiO₂, mixed concurrently in chloroform followed by stirring for 24 h showed a more even distribution of the photocatalyst on the polymer surface and yielded almost 100% color removal. The photocatalytic films were able to completely decolorize real industrial batik dye wastewater in 3 h and induced a chemical oxygen demand (COD) reduction of 80%. Reusability of the 0.4 g P(3HB)‐40 wt% TiO₂ film in decolorizing the batik dye wastewater was also possible as it gave a high consistent value of decolorization percentage (>80%) even after the sixth repeated usage. Recovery step of the photocatalysts was also not required in this simple treatment system. The decolorized batik dye wastewater had less/no toxic effects on mosquito larvae, Aedes aegypti, and microalgae, Scenedesmus quadricauda indicating simultaneous detoxification process along with the decolorization process.     

Treatment of Malting Wastewater in a Granular Sludge Sequencing Batch Reactor (SBR)

Aerobic granular sludge was successfully cultivated in a sequencing batch reactor (SBR) treating wastewater from the malting process with a high content of particulate organic matter. At an organic loading rate of 3.2 kg/(m³ d) COD_total and an influent particle concentration of 0.95 g/L MLSS an average removal of 50% in COD_total and 80% in COD_dissolved could be achieved. A comparison of granular and flocculent sludge grown under the same operating conditions showed no significant difference in removal efficiency although granules exhibited a higher metabolic activity in terms of specific oxygen uptake rate (r_{O2, X}). Two distinct mechanisms of particle removal were observed for granular sludge: during initial granule formation, particles were incorporated into the biofilm matrix. For mature granules, a high level of protozoa growth on the granule surface accounted for the ability to remove particulate COD. Combined evaluation of the development in MLSS content and sludge bed settling rate (i.e., mean derivative of the normalized sludge volume) was found to be an adequate method for monitoring the characteristic settling properties of a granulizing sludge bed. By means of this method, a distinct substrate gradient out of several operating conditions was concluded to have the biggest impact on the formation of aerobic granular sludge.     

Degree of Sulfate‐Reducing Activities on COD Removal in Various Reactor Configurations in Anaerobic Glucose and Acetate‐fed Reactors

Sulfate‐reduction data from various anaerobic reactor configurations, e. g., upflow anaerobic sludge blanket reactor (UASBR), completely stirred tank reactor (CSTR), and batch reactor (BR) with synthetic wastewaters, having glucose and acetate as the substrates and different levels of sulfate, were evaluated to determine the level of sulfate‐reducing activity by sulfate‐reducing bacteria coupled to organic matter removal. Anaerobic reactors were observed for the degree of competition between sulfate‐reducing sulfidogens and methane producing bacteria during the degradation of glucose and acetate. Low sulfate‐reducing activity was obtained with a maximum of 20% of organic matter degradation with glucose‐fed upflow anaerobic sludge bed reactors (UASBRs), while a minimum of 2% was observed with acetate‐fed batch reactors. The highest sulfate removal performance (72–89%) was obtained from glucose fed‐UASB reactors, with the best results observed with increasing COD/SO₄ ratios. UASB reactors produced the highest level of sulfidogenic activity, with the highest sulfate removal and without a performance loss. Hence, this was shown to be the optimum reactor configuration. Dissolved sulfide produced as a result of sulfate reduction reached 325 mg/L and 390 mg/L in CST and UASB reactors, respectively, and these levels were tolerated. The sulfate removal rate was higher at lower COD/SO₄ ratios, but the degree of sulfate removal improved with increasing COD/SO₄ ratios.     

Studies on the Treatment of Distillery Effluents by Anaerobic Filters

In the present work the kinetics and the feasibility of batch anaerobic filter operations for the treatment of beet molasses distillery slops have been investigated. Up to 50% of the influent COD up to 25 g/l are removed after 5… 10 h and up to 80% after 24… 40 h treating time. Highest removal rates were obtained for 50% removal and influent COD concentration ≧13 kg. m^?3. The highest methane productivity was observed in the same range of COD influent concentration during the first 10 hours (initial velocity) of the treatment. The benefits of the anaerobic treatment of waste water applying systems with biomass retention are discussed.     

Photooxidation Degradation of Reactive Brilliant Red K‐2BP in Aqueous Solution by Ultraviolet Radiation/Sodium Hypochlorite

Photooxidation degradation of Reactive Brilliant Red K‐2BP (K‐2BP) aqueous solution by ultraviolet irradiation/sodium hypochlorite (UV/NaClO) was investigated. The effects of NaClO dosage, pH, temperature and initial dye concentrations were studied. A possible degradation pathway of K‐2BP was investigated. Acidic or neutral conditions were beneficial to the decolorization of K‐2BP aqueous solution. However, alkaline conditions facilitated chemical oxygen demand (COD) removal. Increasing the solution temperature from 20 to 50°C increased the removal of color and COD. However, at 60°C, the final percentage color and COD removal decreased by approximately 17 and 10%, respectively. Based on the products indentified and theoretical analysis, N=N cleavage and C‐N cleavage were possible initial steps in the degradation of K‐2BP. From the results of this work, we conclude that treatment of UV/NaClO is an efficient method to degrade K‐2BP in aqueous solution.     

Response Surface Optimization of Acid Red 119 Dye Adsorption by Mixtures of Dried Sewage Sludge and Sewage Sludge Ash

The mixtures of dried sewage sludge (DSS) and sewage sludge ash were studied for removal of acid red 119 (AR119) dye as a new, more environmental friendly, and low cost adsorbent. For this purpose, response surface methodology was applied to optimize the dye removal efficiency and turbidity of treated dye solutions as two individual responses. Results revealed that an optimum condition under specified constraints (dye removal efficiency >95% and turbidity <50 NTU) was obtained at a contact time of 60 min, 40 wt% DSS in the mixture, an initial pH of 6, and an initial dye concentration of 200 mg dye/L in distilled water. Under the optimal condition, dye removal efficiency of 94.98% and effluent turbidity of 24.9 NTU was observed. In further studies, at optimum condition, the effect of some additives on adsorption process and desorption/reusability of adsorbent was investigated. It was observed that removal efficiency was significantly decreased to 83.76% when a simulated dye wastewater (containing the selected dye, acetic acid, and Glauber's salt dissolved in tap water) was used. Desorption studies revealed that AR119 dye could be well removed from dye‐loaded adsorbent by 0.3 M NaOH solution.     

Magnetic Removal of Reactive Black 5 from Wastewater Using Ionic Liquid Grafted‐Magnetic Nanoparticles

Due to the unique chemical properties and therefore wide range of applications, significant amounts of reactive dyes often end up in waste waters and this issue raises the need for more efficient treatment technologies. This work investigates the ability of magnetite nanoparticles functionalized with imidazolium based ionic liquid (IL) as an efficient sorbent for the removal of the Reactive black 5 from wastewater. Fourier transform infrared spectroscopy, X‐ray diffraction, transmission electron microscopy, thermo‐gravimetric analysis, and zeta potential measurement were used to characterize the synthesized nanosorbent. The results showed that under optimal conditions, the dye removal efficiency of the grafted IL is 98.5% after a single run. Regeneration of the used sorbent could be possible and the modified magnetic nanoparticles exhibited good reusability. The isothermal data of RB5 sorption conformed well to the Langmuir model and the maximum sorption capacity of IL@Fe₃O₄ for RB5 was 161.29 mg g^?1. Thermodynamic study indicated that the adsorption is endothermic and spontaneous. The use of such a system can provide fast and efficient removal of the reactive dyes from wastewater by using an external magnetic field.     

Treatment of Domestic Sewage in an Anaerobic–Aerobic Fixed‐bed Reactor with Recirculation of the Liquid Phase

This study reports the performance of a combined anaerobic–aerobic packed‐bed reactor that can be used to treat domestic sewage. Initially, a bench‐scale reactor was operated in three experimental phases. In the first phase, the anaerobic reactor was operated with an average organic matter removal efficiency of 77% for a hydraulic retention time (HRT) of 10 h. In the second phase, the reactor was operated with an anaerobic stage followed by an aerobic zone, resulting in a mean value of 91% efficiency. In the third and final phase, the anaerobic–aerobic reactor was operated with recirculation of the effluent of the reactor through the anaerobic zone. The system yielded mean total nitrogen removal percentages of 65 and 75% for recycle ratios (r) of 0.5 and 1.5, respectively, and the chemical oxygen demand (COD) removal efficiencies were higher than 90%. When the pilot‐scale reactor was operated with an HRT of 12 h and r values of 1.5 and 3.0, its performance was similar to that observed in the bench‐scale unit (92% COD removal for r = 3.0). However, the nitrogen removal was lower (55% N removal for r = 3.0) due to problems with the hydrodynamics in the aerobic zone. The anaerobic–aerobic fixed‐bed reactor with recirculation of the liquid phase allows for concomitant carbon and nitrogen removal without adding an exogenous source of electron donors and without requiring any additional alkalinity supplementation.     

Effect of Sludge Retention Time on Nitrifiers' Biomass and Kinetics in an Anaerobic/Oxic Process

In this study, the effect of sludge retention time on ammonia oxidizing bacteria (AOB) and nitrite oxidizing bacteria (NOB) in an anaerobic/oxic (AO) process, was explored. The results indicated that the growth rate constants of AOB were 0.97, 0.88, and 0.79 d^–1, respectively, meanwhile, those of NOB were 1.22, 1.03, and 0.93 d^–1, respectively, when the sludge retention time (SRT) was 15 days, 10 days and 5 days. The relation between the growth rate constant and the SRT could be best described using a simple exponential curve and a second type hyperbolic curve. The lysis rate constants for AOB and NOB were 0.13 and 0.18 d^–1, respectively. The yield coefficients values of AOB and NOB were 0.22 and 0.21, respectively. The percentage of AOB to mixed liquid suspended solids (MLSS) was 0.64%, 0.53%, and 0.35%, respectively. Meanwhile, the percentage of NOB was 2.24%, 1.87%, and 1.11%, respectively, at SRT values of 15 days, 10 days and 5 days. When the SRT value decreased, the AOB and NOB biomass levels decreased by 12.75 and 47.01 mg L^–1, respectively. Meanwhile the removal efficiency of NH₄⁺‐N decreased from 90 to 26%, while the removal efficiency of total nitrogen (TN) decreased from 14 to 8%.     

Color Removal from Synthetic Textile Wastewater by Sono‐Fenton Process

In this study, the oxidative decolorization of C.I. reactive yellow 145 (RY 145) from synthetic textile wastewater including RY 145 and polyvinyl alcohol by Fenton and sono‐Fenton processes which are the combination of Fenton process with ultrasound has been carried out. The effects of some operating parameters which are the initial pH of the solution, the initial concentration of Fe²⁺, H₂O₂, and the dye, temperature, and agitation speed on the color and chemical oxygen demand (COD) removals have been investigated. The optimum conditions have been found as [Fe²⁺] = 20 mg/L, [H₂O₂] = 20 mg/L, pH 3 for Fenton process and [Fe²⁺] = 20 mg/L, [H₂O₂] = 15 mg/L, pH 3 for sono‐Fenton process by indirectly sonication at 35 kHz ultrasonic frequency and 80 W ultrasonic power. The color and COD removal efficiencies have been obtained as 91 and 47% by Fenton process, and 95 and 51% by sono‐Fenton processes, respectively. Kinetic studies have been performed for the decolorization of RY 145 under optimum conditions at room temperature. It has been determined that the decolorization has occurred rapidly by sono‐Fenton process, compared to Fenton process.     

UV/H2O2 Process Under High Intensity UV Irradiation: A Rapid and Effective Method for Methylene Blue Decolorization

This study examined the UV/H₂O₂ decolorization efficiency under high UV photon flux (intensity normalized by photon energy) irradiation; the incident UV was ranging from 3.13 × 10^?8 to 3.13 × 10^?6 einstein cm^?2 s^?1. The experimental results showed that complete decolorization of 20 mg L^?1 methylene blue (MB) can be achieved within 5 s and 99% decolorization of 1000 mg L^?1 MB can be achieved in 180 s under the best condition of high UV intensity UV/H₂O₂ process. To the best of our knowledge, UV/H₂O₂ decolorization process in such a short time has not been reported. The electrical energy per order of the process was 16.21 kWh m^?3 order^?1 and it is relatively economical compared with other advanced oxidation processes. The kinetics of decolorization follows pseudo‐first order. There is a linear relationship between rate constant and UV intensity, which indicates that increasing UV intensity does not cause decline in light utilization efficiency. The experiment related to initial substrate concentration shows decolorization rate of different substrate concentration (20–1000 mg L^?1) are closed to each other. Besides, optimal H₂O₂ concentration, comparative study with low photon flux light, decolorization of other types of dyes and TOC removal were also studied.     

Central Composite Design Optimization of Biological Dye Removal in the Presence of Macroalgae Chara sp.

Response surface methodology (RSM) was employed to investigate the effects of different operational parameters on the biological decolorization of a dye solution containing malachite green (MG) in the presence of macroalgae Chara sp. The investigated variables were the initial pH, initial dye concentration, algae amount, and reaction time. Central composite design (CCD) was used for the optimization of biological decolorization process. Predicted values were found to be in good agreement with experimental values (R² = 0.982 and Adj‐R² = 0.966), which indicated suitability of the employed model and the success of RSM. The results of optimization predicted by the model showed that maximum decolorization efficiency was achieved at the optimum condition of the initial pH 6.8, initial dye concentration 9.7 mg/L, algae amount 3.9 g, and reaction time 75 min. UV–VIS spectra and FT‐IR analysis showed degradation of MG.     

Removal of the Alphazurine FG Dye from Simulated Solution by Electrocoagulation

The removal of Alphazurine FG (AF) dye from water by an electrocoagulation process has been studied. The effect of some operational parameters, such as anode material, current density, initial dye concentration, pH of solution, conductivity, and inter‐electrode distance, on the removal efficiency was investigated. Iron and aluminum were used as anodes in the electrocoagulation cell. It was found that the efficiency of the iron anode was better than that of the aluminum anode for AF removal. The factors that affected the removal efficiency were the current density and the initial dye concentration. The removal efficiency increased from about 35% at 25 A m^–2 to about 97% at 100 A m^–2, during 4 min of electrocoagulation. The results exhibited pseudo‐first‐order kinetics for AF removal by electrocoagulation. In addition, a mathematical model was successfully established for predicting the removal efficiency. A comparison between the model results and experimental data gave a high correlation coefficient (R² = 0.9925), which indicates that the model is able to predict the removal efficiency of AF.     

Stabilization Ponds Design as a function of Organic Removal Coefficient (K1)

The effluent from biological treatment plants of cane sugar factories undergoes a final purification in laboratory models with a Chlorella culture at volume loads of 76… 325 mg/l. d BOD₅ or 121… 555 mg/l-d COD. The coefficient of removal on the basis of BOD₅ is found to be linearly negatively correlated with the retention time, but independent of the substrate concentration and composition as well as of the pre-treatment of the wastewaters (aerobic or anaerobic). A dimensioning on the basis of the COD is not possible because of the high phytoplankton content in the effluent of the ponds.     

Adsorption Characteristics of Reactive Black 5 from Aqueous Solution onto Chitosan

Adsorption of reactive black 5 (RB5) from aqueous solution onto chitosan was investigated in a batch system. The effects of solution pH, initial dye concentration, and temperature were studied. Adsorption data obtained from different batch experiments were modeled using both pseudo first‐ and second‐order kinetic equations. The equilibrium adsorption data were fitted to the Freundlich, Tempkin, and Langmuir isotherms over a dye concentration range of 45–100 µmol/L. The best results were achieved with the pseudo second‐order kinetic and Langmuir isotherm equilibrium models, respectively. The equilibrium adsorption capacity (q_e) was increased with increasing the initial dye concentration and solution temperature, and decreasing solution pH. The chitosan flakes for the adsorption of the dye was regenerated efficiently through the alkaline solution and was then reused for dye removal. The activation energy (E_a) of sorption kinetics was estimated to be 13.88 kJ/mol. Thermodynamic parameters such as changes in free energy (ΔG), enthalpy (ΔH), and entropy (ΔS) were evaluated by applying the van't Hoff equation. The thermodynamics of reactive dye adsorption by chitosan indicates its spontaneous and endothermic nature.     

Bio-augmented activated sludge treatment of potato wastewaters

A laboratory study was conducted to determine the effect of bacterial augmentation with LLMO (liquid live microorganisms) on the activated sludge treatment of potato wastewaters. Completed mixed activated sludge bench scale reactors were used in this study. Parameters varied during the continuous reactor run included hydraulic detention time, LLMO addition, and powdered activated carbon addition. The hydraulic detention time lasted 1, 2, and 3 days, while the sludge age was maintained at 10 days for both reactors. The bio-augmented reactor had a better COD removal than the non-bio-augmented reactor at a lower MLVSS level in the reactor. It is concluded that bacterial augmentation with LLMO improved slightly the COD removal efficiency in treating potato wastewaters with the activated sludge process. The bio-augmentation increased the substrate removal rate, increased the oxygen utilization, and decreased the excess sludge production.     

Biodegradation Studies on Acid Violet 19, a Triphenylmethane Dye,by Pseudomonas aeruginosa BCH

Acid violet 19 (AV) belongs to the triphenylmethane (TPM) class of dyes which are potentially mutagenic or carcinogenic. However, very little studies on biodegradation of AV were reported as compared to other TPM dyes such as malachite green and crystal violet. In this study, AV was decolorized up to 98% within 30 min by Pseudomonas aeruginosa BCH. The decolorization depends on the initial dye concentration, pH, and temperature. However, the dye was decolorized under wide pH and temperature ranges with an optimum of pH 7 and 30°C. Up to 250 mg L^?1 of dye was found to be tolerated and decolorized by this strain. It showed decolorization ability for seven repeated dye addition cycles. The effect of additional carbon sources on dye decolorization was studied in which mannitol containing medium showed decolorization in 15 min. Induction in the enzyme activities of laccase, NADH‐DCIP reductase, and veratryl alcohol oxidase (VAO) indicates their involvement in AV degradation. Various analytical studies viz. UV–VIS, HPTLC, HPLC, and FTIR confirmed the biodegradation of AV by the bacterium. Based on GC‐MS analysis, a possible degradation pathway for AV was proposed. The phytotoxicity studies using Phaseolus mungo and Sorghum vulgare revealed the less toxic nature of metabolites formed after AV degradation.