A comparative study among different photochemical oxidation processes to enhance the biodegradability of paper mill wastewater

Advanced oxidation processes including UV, UV/H(2)O(2), Fenton reaction (Fe(II)/H(2)O(2)) and photo-Fenton process (Fe(II)/H(2)O(2)/UV) for the treatment of paper mill wastewater will be investigated. A comparison among these techniques is undertaken with respect to the decrease of chemical oxygen demand (COD) and total suspended solids (TSS) and the evolution of chloride ions. Optimum operating conditions for each process under study revealed the effect of the initial amounts of Fe(II) and hydrogen peroxide. Of the tested processes, photo-Fenton process was found to be the fastest one with respect to COD and TSS reduction of the wastewater within 45 min reaction time under low amounts of Fe(II) and hydrogen peroxide of 0.5 and 1.5mg/L, respectively, and amounted to 79.6% and 96.6% COD and TSS removal. The initial biodegradability of the organic matter present in the effluent, estimated as the BOD(5)/COD, was low 0.21. When the effluent was submitted to the different types of AOPs used in this study, the biodegradability increases significantly. Within 45 min of reaction time, the photo-Fenton process appears as the most efficient process in the enhancement of the biodegradability of the organic matter in the effluent and the BOD(5)/COD ratio increased from 0.21 to 0.7.     

Evaluation of biodegradability and oxidation degree of hospital wastewater using photo-Fenton process as the pretreatment method

In this work, the photo-Fenton process was used for the pretreatment of hospital wastewater with the objective of improving its overall biodegradability and determining the degree of increased oxidation. The chemical oxygen demand (COD), 5-day biochemical oxygen demand (BOD5), total organic carbon (TOC) and toxicity towards the gram negative marine bioluminescent bacteria of the species V. fischeri were selected as the environmental sum parameters to follow the performance of this process. The enhancement of biodegradability, evaluated in terms of the BOD5/COD ratio, increased from 0.3 to 0.52 and the oxidation degree, calculated in terms of AOS, leveled up from -1.14 to +1.58 at the optimum conditions; a dosage ratio of COD:H2O2:Fe(II) at 1:4:0.1, and a reaction pH of 3. The reduction in the inhibition percentage from the toxicity test indicated the safe levels for micro-organisms in degrading the residual organic substance in this method. Almost total removal percentages of COD, BOD5, and TOC were found by a sequential activated sludge process for the pre-treated wastewater. Results obtained from this work indicated that the photo-Fenton process could be a suitable pretreatment method in reducing toxicity of pollutants and enhancing biodegradability of hospital wastewaters treated in a coupled photochemical-biological system.     

Pre-treatment of penicillin formulation effluent by advanced oxidation processes

A variety of advanced oxidation processes (AOPs; O3/OH-, H2O2/UV, Fe2+/H2O2, Fe3+/H2O2, Fe2+/H2O2/UV and Fe3+/H2O2/UV) have been applied for the oxidative pre-treatment of real penicillin formulation effluent (average COD0 = 1395 mg/L; TOC0 = 920 mg/L; BOD(5,0) approximately 0 mg/L). For the ozonation process the primary involvement of free radical species such as OH* in the oxidative reaction could be demonstrated via inspection of ozone absorption rates. Alkaline ozonation and the photo-Fenton's reagents both appeared to be the most promising AOPs in terms of COD (49-66%) and TOC (42-52%) abatement rates, whereas the BOD5 of the originally non-biodegradable effluent could only be improved to a value of 100 mg/L with O3/pH = 3] treatment (BOD5/COD, f = 0.08). Evaluation on COD and TOC removal rates per applied active oxidant (AOx) and oxidant (Ox) on a molar basis revealed that alkaline ozonation and particularly the UV-light assisted Fenton processes enabling good oxidation yields (1-2 mol COD and TOC removal per AOx and Ox) by far outweighed the other studied AOPs. Separate experimental studies conducted with the penicillin active substance amoxicillin trihydrate indicated that the aqueous antibiotic substance can be completely eliminated after 40 min advanced oxidation applying photo-Fenton's reagent (pH = 3; Fe(2+):H2O2 molar ratio = 1:20) and alkaline ozonation (at pH = 11.5), respectively.     

A statistical experiment design approach for advanced oxidation of Direct Red azo-dye by photo-Fenton treatment

Advanced oxidation of an azo-dye, Direct Red 28 (DR 28) by photo-Fenton treatment was investigated in batch experiments using Box-Behnken statistical experiment design and the response surface analysis. Dyestuff (DR 28), H(2)O(2) and Fe(II) concentrations were selected as independent variables in Box-Behnken design while color and total organic carbon (TOC) removal (mineralization) were considered as the response functions. Color removal increased with increasing H(2)O(2) and Fe(II) concentrations up to a certain level. High concentrations of H(2)O(2) and Fe(II) adversely affected the color and TOC removals due to hydroxyl radical scavenging effects of high oxidant and catalyst concentrations. Both H(2)O(2) and Fe(II) concentration had profound effects on decolorization. Percent color removal was higher than TOC removal indicating formation of colorless organic intermediates. Complete color removal was achieved within 5min while complete mineralization took nearly 15min. The optimal reagent doses varied depending on the initial dyestuff dose. For the highest dyestuff concentration tested, the optimal H(2)O(2)/Fe(II)/dyestuff ratio resulting in the maximum color removal (100%) was predicted to be 715/71/250 (mgL(-1)), while this ratio was 1550/96.5/250 for maximum mineralization (97.5%).     

Photo-Fenton process as an efficient alternative to the treatment of landfill leachates

Advanced oxidation processes (AOPs), namely photo-Fenton, Fenton-like, Fenton and UV/H(2)O(2), have been investigated in the removal of organic matter and colour from landfill leachates. The leachate was characterised by high COD, low biodegradability and intense dark colour. Evaluation of COD removal as a function of the operation variables (H(2)O(2), Fe(2+), Cu(2+), UV) led to results that ranged between 30% and 77% and it was observed that the removal efficiencies decreased in the order: photo-Fenton>Fenton-like>Fenton>UV/H(2)O(2)>UV. Thus, a detailed experimental analysis was carried out to analyse the effect of the hydrogen peroxide and iron concentrations and the number of reagent additions in the photo-Fenton process, observing that: (i) the COD removal ranged from 49% to 78% depending on the H(2)O(2) dose, (ii) the total amount of organic matter removed was increased by adding the reagent in multiple steps (86%), (iii) iron concentration corresponding to a Fe(2+)/COD mass ratio=0.33 was found to be the most favourable and, (iv) after a neutralization step, the colour and residual concentrations of iron and H(2)O(2) were practically negligible in the final leachate solution.     

Combined Fenton oxidation and aerobic biological processes for treating a surfactant wastewater containing abundant sulfate

The present study is to investigate the treatment of a surfactant wastewater containing abundant sulfate by Fenton oxidation and aerobic biological processes. The operating conditions have been optimized. Working at an initial pH value of 8, a Fe2+ dosage of 600mgL(-1) and a H2O2 dosage of 120mgL(-1), the chemical oxidation demand (COD) and linear alkylbenzene sulfonate (LAS) were decreased from 1500 and 490mgL(-1) to 230 and 23mgL(-1) after 40min of Fenton oxidation, respectively. Advanced oxidation pretreatment using Fenton reagent was very effective at enhancing the biodegradability of this kind of wastewater. The wastewater was further treated by a bio-chemical treatment process based on an immobilized biomass reactor with a hydraulic detention time (HRT) of 20h after Fenton oxidation pretreatment under the optimal operating conditions. It was found that the COD and LAS of the final effluent were less than 100 and 5mgL(-1), corresponding to a removal efficiencies of over 94% and 99%, respectively.     

A simple methodology to evaluate influence of H2O2 and Fe(2+) concentrations on the mineralization and biodegradability of organic compounds in water and soil contaminated with crude petroleum

Simple measurements of H2O2 concentration or CO2 evolution were used to evaluate the effectiveness of the use of Fenton's reagent to mineralize organic compounds in water and soil contaminated by crude petroleum. This methodology is suitable for application in small treatment and remediation facilities. Reagent concentrations of H2O2 and Fe(2+) were found to influence the reaction time and temperature, as well as the degree of mineralization and biodegradability of the sample contaminants. Some H2O2/Fe(2+) combinations (H2O2 greater than 10% and Fe(2+) greater than 50mM) resulted in a strong exothermic reaction, which causes peroxide degradation and violent gas liberation. Up to 75% TOC removal efficiency was attained in water and 70% in soil when high H2O2 (20%) and low Fe(2+) (1mM) concentrations were used. Besides increasing the degree of mineralization, the Fenton's reaction enhances the biodegradability of petroleum compounds (BOD5/COD ratios) by a factor of up to 3.8 for contaminated samples of both water and soil. Our experiments showed that low reagent concentrations (1% H2O2 and 1mM Fe(2+)) were sufficient to start the degradation process, which could be continued using microorganisms. This leads to a decrease in reagent costs in the treatment of petroleum-contaminated water and soil samples. The simple measurements of H2O2 concentration or CO2 evolution were effective to evaluate the Fenton's reaction efficiency.     

Improvement of COD and color removal from UASB treated poultry manure wastewater using Fenton's oxidation

The applicability of Fenton's oxidation as an advanced treatment for chemical oxygen demand (COD) and color removal from anaerobically treated poultry manure wastewater was investigated. The raw poultry manure wastewater, having a pH of 7.30 (+/-0.2) and a total COD of 12,100 (+/-910) mg/L was first treated in a 15.7 L of pilot-scale up-flow anaerobic sludge blanket (UASB) reactor. The UASB reactor was operated for 72 days at mesophilic conditions (32+/-2 degrees C) in a temperature-controlled environment with three different hydraulic retention times (HRT) of 15.7, 12 and 8.0 days, and with organic loading rates (OLR) between 0.650 and 1.783 kg COD/(m3day). Under 8.0 days of HRT, the UASB process showed a remarkable performance on total COD removal with a treatment efficiency of 90.7% at the day of 63. The anaerobically treated poultry manure wastewater was further treated by Fenton's oxidation process using Fe2+ and H2O2 solutions. Batch tests were conducted on the UASB effluent samples to determine the optimum operating conditions including initial pH, effects of H2O2 and Fe2+ dosages, and the ratio of H2O2/Fe2+. Preliminary tests conducted with the dosages of 100 mg Fe2+/L and 200 mg H2O2/L showed that optimal initial pH was 3.0 for both COD and color removal from the UASB effluent. On the basis of preliminary test results, effects of increasing dosages of Fe2+ and H2O2 were investigated. Under the condition of 400 mg Fe2+/L and 200 mg H2O2/L, removal efficiencies of residual COD and color were 88.7% and 80.9%, respectively. Under the subsequent condition of 100 mg Fe2+/L and 1200 mg H2O2/L, 95% of residual COD and 95.7% of residual color were removed from the UASB effluent. Results of this experimental study obviously indicated that nearly 99.3% of COD of raw poultry manure wastewater could be effectively removed by a UASB process followed by Fenton's oxidation technology used as a post-treatment unit.     

Use of Fenton reaction for the treatment of leachate from composting of different wastes

The oxidation of leachate coming from the composting of two organic wastes (wastewater sludge and organic fraction of municipal solid wastes) using the Fenton's reagent was studied using different ratios [Fe(2+)]/[COD](0) and maintaining a ratio [H(2)O(2)]/[COD](0) equal to 1. The optimal conditions for Fenton reaction were found at a ratio [Fe(2+)]/[COD](0) equal to 0.1. Both leachates were significantly oxidized under these conditions in terms of COD removal (77 and 75% for leachate from wastewater sludge composting and leachate from organic fraction of municipal solid wastes, respectively) and BOD(5) removal (90 and 98% for leachate from wastewater sludge composting and leachate from organic fraction of municipal solid wastes, respectively). Fenton's reagent was found to oxidize preferably biodegradable organic matter of leachate. In consequence, a decrease in the biodegradability of leachates was observed after Fenton treatment for both leachates. Nevertheless, Fenton reaction proved to be a feasible technique for the oxidation of the leachate under study, and it can be considered a suitable treatment for this type of wastewaters.     

Combined electrocoagulation and TiO(2) photoassisted treatment applied to wastewater effluents from pharmaceutical and cosmetic industries

The treated wastewater consists of refractory materials and high organic content of hydrolyzed peptone residues from pharmaceutical factory. The combination of electrocoagulation (EC) followed by heterogeneous photocatalysis (TiO(2)) conditions was maximized. The EC: iron cathode/anode (12.50 cmx2.50 cmx0.10 cm), current density 763Am(-2), 90min and initial pH 6.0. As EC consequence, the majority of the dissolved organic and suspended material was removed (about 91% and 86% of the turbidity and chemical oxygen demand (COD), respectively). After EC, refractory residues still remained in the effluent. The subsequent photocatalysis: UV/TiO(2)/H(2)O(2) (mercury lamps), pH 3.0, 4h irradiation, 0.25gL(-1) TiO(2) and 10mmolL(-1) H(2)O(2) shows high levels of inorganic and organic compounds eliminations. The obtained COD values: 1753mgL(-1) for the sample from the factory, 160mgL(-1) after EC and 50mgL(-1) after EC/photocatalyzed effluents pointed out that the combined treatment stresses this water purification.     

Treatability of a simulated disperse dye-bath by ferrous iron coagulation, ozonation, and ferrous iron-catalyzed ozonation

Dyeing and finishing of textile yarns and fabrics are extremely important processes in terms of both quality and environmental concerns. Among the commercial textile dyes, particularly disperse dyestuffs are of environmental interest because of their widespread use, their potential for formation of toxic aromatic amines and their low removal rate during aerobic waste treatment as well as advanced chemical oxidation. Thus, in the present paper ferrous iron coagulation, ozonation and ferrous iron-catalyzed ozonation were employed at varying pH (3-13) and Fe(II)-ion doses (0.09-18mM) for the treatment of a simulated disperse dye-bath (average initial apparent color as absorbance at 566nm=815.4m(-1); COD(0)=3784mgl(-1); TOC(0)=670mgl(-1); BOD(5,0)=58mgl(-1)) that more closely resembled an actual dyehouse effluent than an aqueous disperse dye solution. Coagulation with 5000mgl(-1) FeSO4-7H2O (18mM Fe(2+)) at pH 11 removed up to 97% color and 54% COD, whereas oxidation via ozonation alone (applied ozone dose=2300mgl(-1)) was only effective at pH 3, resulting in 77% color and 11% COD removal. Fe(II)-ion-catalyzed ozonation (3.6mM Fe(2+) at pH 3; Fe(2+):O3 molar ratio 1:14) eliminated 95% color and 48% COD and appeared to be the most attractive option among the investigated chemical treatment methods as for its applicability at the natural acidic pH of the disperse dye-bath effluent and at relatively low Fe(2+)-ion doses as compared to ferrous sulfate coagulation. However, no TOC reduction was observable for ozonation and catalytic ozonation at the investigated reaction conditions (14gl(-1) O3 at pH 3). An average six-fold enhancement in the biodegradability parameter of the synthetic dye wastewater expressed in terms of the BOD(5)/COD ratio could be achieved by the investigated chemical treatment methods.     

Photooxidation processes for an azo dye in aqueous media: modeling of degradation kinetic and ecological parameters evaluation

Three photooxidation processes, UV/H(2)O(2), UV/S(2)O(8)(2-) and UV/O(3) were applied to the treatment of model wastewater containing non-biodegradable organic pollutant, azo dye Acid Orange 7 (AO7). Dye degradation was monitored using UV/VIS and total organic carbon (TOC) analysis, determining decolorization, the degradation/formation of naphthalene and benzene structured AO7 by-products, and the mineralization of model wastewater. The water quality during the treatment was evaluated on the bases of ecological parameters: chemical (COD) and biochemical (BOD(5)) oxygen demand and toxicity on Vibrio fischeri determining the EC(50) value. The main goals of the study were to develop an appropriate mathematic model (MM) predicting the behavior of the systems under investigation, and to evaluate the toxicity and biodegradability of the model wastewater during treatments. MM developed showed a high accuracy in predicting the degradation of AO7 when considering the following observed parameters: decolorization, formation/degradation of by-products and mineralization. Good agreement of the data predicted and the empirically obtained was confirmed by calculated standard deviations. The biodegradability of model wastewater was significantly improved by three processes after mineralizing a half of the initially present organic content. The toxicity AO7 model wastewater was decreased as well. The differences in monitored ecological parameters during the treatment indicated the formation of different by-products of dye degradation regarding the oxidant type applied.     

Color, TOC and AOX removals from pulp mill effluent by advanced oxidation processes: a comparative study

Pulp mill effluent containing toxic chemicals was treated by different advanced oxidation processes (AOPs) consisting of treatments by hydrogen peroxide, Fenton's reagent (H2O2/Fe2+), UV, UV/H2O2, photo-Fenton (UV/H2O2/Fe2+), ozonation and peroxone (ozone/H2O2) in laboratory-scale reactors for color, total organic carbon (TOC) and adsorbable organic halogens (AOX) removals from the pulp mill effluent. Effects of some operating parameters such as the initial pH, oxidant and catalyst concentrations on TOC, color, AOX removals were investigated. Almost every method used resulted in some degree of color removal from the pulp mill effluent. However, the Fenton's reagent utilizing H2O2/Fe2+ resulted in the highest color, TOC and AOX removals under acidic conditions when compared with the other AOPs tested. Approximately, 88% TOC, 85% color and 89% AOX removals were obtained by the Fenton's reagent at pH 5 within 30 min. Photo-Fenton process yielded comparable TOC (85%), color (82%) and AOX (93%) removals within 5 min due to oxidations by UV light in addition to the Fenton's reagent. Fast oxidation reactions by the photo-Fenton treatment makes this approach more favorable as compared to the others used.     

Photodegradation of Reactive Black 5, Direct Red 28 and Direct Yellow 12 using UV, UV/H(2)O(2) and UV/H(2)O(2)/Fe(2+): a comparative study

The photodegradation of three commercially available dyestuffs (C.I. Reactive Black 5, C.I. RB5, C.I. Direct Yellow 12, C.I. DY12, and C.I. Direct Red 28, C.I. DR28) by UV, UV/H(2)O(2) and UV/H(2)O(2)/Fe(II) processes was investigated in a laboratory-scale batch photoreactor equipped with an 16W immersed-type low-pressure mercury vapour lamp. The experimental results were assessed in terms of absorbance and total organic carbon (TOC) reduction. The initial concentration was kept constant at 100 mg l(-1) for all dyes. Initial results showed that, color removal efficiencies by UV or H(2)O(2) alone were negligible for all dyes. Almost complete disappearance of C.I. RB5 (99%) and DY12 (98%) in UV/H(2)O(2) process was possible to achieve after 60 min of irradiation. The maximum color removal efficiency of C.I. DR28 after 60 min of irradiation, however, was only 40% and reached a maximum value of 70% after 120 min of irradiation. Corresponding mineralization efficiencies were 50, 55 and 7-12%, respectively. The addition of Fe(II) to the system, so-called the photo-Fenton process, greatly enhanced the color removal, the efficiencies being 98, 88 and 85% for C.I. RB5, C.I. DY12 and C.I. DR28 only after 5 min of irradiation. Corresponding mineralization efficiencies were 98% for 45 min irradiation, 100% for 60 min irradiation and 98% for 90 min irradiation, respectively. However, marginal benefit was less significant in the higher range of both H(2)O(2) and Fe(II). Furthermore, decreases in both decolorization and mineralization were observed at higher concentrations of oxidant and catalyst due to the scavenging effect of excess H(2)O(2) and OH radicals. The degradation of all dyes was found to follow first-order reaction kinetics.     

Effects of ozonation process on lignin-derived compounds in pulp and paper mill effluents

The effect of ozonation process on pulp and paper mill effluents was investigated. The objectives were to: (1) identify various compounds in wastewater from a pulp and paper mill, (2) evaluate decolorization and organic removal efficiency by conventional bubble reactor and (3) evaluate the biodegradability at various progressive stages of ozonation. The qualitative GC/MS analyses were performed before and after the biological treatment and ozonation process. Two groups of compounds were observed in this wastewater: lignin-derived compounds and aliphatic compounds used in the pulp and paper production process (i.e. n-alkanes, fatty alcohols, fatty acid and ester). Treatment efficiency was measured by decolorization and TOC removal rates. Additionally, the utilization coefficient (k) and BOD/COD ratio were determined to observe the biodegradability of ozonized effluents. The results indicated that after 45 min, the ozonation of effluents yielded almost colorless effluent with over 90% decolorization efficiency and with corresponding ozone capacity rate of 20.0 mg O(3)L(-1). This decolorization was not always accompanied by the mineralization of the organic matters therefore ozonation was not related to TOC removal rates. The BOD/COD ratio increased from 0.10 to a maximum value of 0.32 with ozone flow rate (O/F) of 4.0 L min(-1). It was confirmed by the utilization coefficient as first order BOD equation, the magnitude k value increased from 0.21 day(-1) to maximum value of 0.47 day(-1) as the ozonation time was raised to 60 min with O/F 4.0 L min(-1).     

Removal of organic carbon from wastepaper pulp effluent by lab-scale solar photo-Fenton process

The bleaching wastewater effluent from a pulp and paper mill (located in Tianjin, China) was treated with solar photo-Fenton process in a lab-scale reactor (22 cm x 15 cm thermostatic dish). The mill used wastepaper as raw material and the effluent contained 332 mgL(-1) of total organic carbon (TOC) and 1286 mg L(-1) of COD. The treatment involved a constant intensity of irradiation (0.2 kW/m(2)) with a solar simulator of 250 W xenon lamp and various conditions of pH, temperature, and initial concentrations of H(2)O(2) and Fe(II). The better treatment conditions were searched for in the ranges of initial Fe(II) concentration from 31 to 310 mgL(-1) (initial pH 3.0, 30 degrees C), initial H(2)O(2) concentration from 0.5 to 3 Dth (1 Dth=1883 mg L(-1) for TOC mineralization) (initial pH 3.0, 30 degrees C), initial pH from 2.0 to 6.0 (1 and 2 Dth, 10:1 of H(2)O(2)/Fe(II), 30 degrees C), and temperature from 30 to 50 degrees C (1 Dth, 10:1 of H(2)O(2)/Fe(II), initial pH 2.8). TOC removal generally showed the initial fast increase stage within the first sampling time of 15 min, followed by the gradual increase stage in the remaining sampling time of 180 min experimental time course. The highest percentage of TOC removal in the first stage was about 60% when the initial pH was either 2.8 (H(2)O(2)=1 Dth, ratio=10:1, temperature=30-50 degrees C) or 3.5 (H(2)O(2)=2 Dth, ratio=10:1, temperature=30 degrees C). Also under the latter condition, the value reached 82% at 120 min and was projected to reach 94% at 180 min. According to the positive effect of temperature increase on TOC removal observed in this experiment, further increase above these maximum values is possible if the temperature of the above condition were increased from 30 to 40 degrees C or 50 degrees C. Furthermore, under most of the treatment conditions, the TOC removal reached or was projected to reach over 60% toward the end of the experiments. The result indicated that the solar photo-Fenton process has a potential to effectively remove TOC from the wastepaper pulp effluent on a large scale.     

Application of the central composite design and response surface methodology to the advanced treatment of olive oil processing wastewater using Fenton's peroxidation

The central composite design (CCD) technique was used to study the effect of the Fenton's peroxidation on the removal of organic pollutants from olive oil mill wastewater (OMW). The ratio of hydrogen peroxide-to-Fe(II) (x1) was between 1.67 and 8.33. Fe(II) concentration was constant at 0.03 M while the H2O2 concentration was set at three levels: 0.05, 0.15 and 0.25 M. Based on the molarity ratio, the selected ratio were in the low range of Fe(II)-to-H2O2 ratio (<1). While based on the wt/wt ratio, the tested Fe(II)-to-H2O2 ratios were in the range of < or =1:5. pH (x2) was between 3 and 5. The concentration of OMW (x3) was varied between 40 and 100%. The influence of these three independent variables on the four dependent variables, i.e. COD, total phenolics (TP), color and aromaticity removal was evaluated using a second-order polynomial multiple regression model. Analysis of variance (ANOVA) showed a high coefficient of determination (R2) value of 0.902-0.998, thus ensuring a satisfactory adjustment of the second-order regression model with the experimental data. H2O2-to-Fe(II) ratio had significant effect on all the four dependent variables. The positive sign for the regression coefficient of this regressor variable indicated that the level of the pollutant removal increased with the increased levels of factor x1 from 1.67 to 8.33 and this effect was the most pronounced for TP removal. pH had also significant effect on the pollutant removal and the effect was the most noticeable for TP reduction. The negative coefficient of this variable (pH) indicated that level of the pollutant removal decreased as the pH increased from 3 to 5. The negative coefficient of the interaction between variable x1 and x2 indicated that a simultaneous increase in H2O2-to-Fe(II) ratio with decrease in the pH of the reaction led to an increase in the COD, TP and color removal. Quadratic models were predicted for the response variable, i.e. pollutant removal, and the maximum model-predicted removals were 56, 100, 33 and 32% for COD, TP, color and aromaticity, respectively. Optimum conditions for this wastewater treatment was obtained based on the performance of the Fenton's peroxidation in the experiment where the H2O2-to-Fe(II) ratio was at its high level (8.33) and the pH and OMW concentration were 4 and 70%, respectively.     

Use of Fenton oxidation to improve the biodegradability of a pharmaceutical wastewater

The applicability of Fenton's oxidation to improve the biodegradability of a pharmaceutical wastewater to be treated biologically was investigated. The wastewater was originated from a factory producing a variety of pharmaceutical chemicals. Treatability studies were conducted under laboratory conditions with all chemicals (having COD varying from 900 to 7000 mg/L) produced in the factory in order to determine the operational conditions to utilize in the full-scale treatment plant. Optimum pH was determined as 3.5 and 7.0 for the first (oxidation) and second stage (coagulation) of the Fenton process, respectively. For all chemicals, COD removal efficiency was highest when the molar ratio of H(2)O(2)/Fe(2+) was 150-250. At H(2)O(2)/Fe(2+) ratio of 155, 0.3M H(2)O(2) and 0.002 M Fe(2+), provided 45-65% COD removal. The wastewater treatment plant that employs Fenton oxidation followed by aerobic degradation in sequencing batch reactors (SBR), built after these treatability studies provided an overall COD removal efficiency of 98%, and compliance with the discharge limits. The efficiency of the Fenton's oxidation was around 45-50% and the efficiency in the SBR system which has two reactors each having a volume of 8m(3) and operated with a total cycle time of 1 day, was around 98%, regarding the COD removal.     

Development and optimization of dark Fenton oxidation for the treatment of textile wastewaters with high organic load

The examination of the effectiveness of the chemical oxidation using Fenton's reagent (H(2)O(2)/Fe(2+)) for the reduction of the organic content of wastewater generated from a textile industry has been studied. The experimental results indicate that the oxidation process leads to a reduction in the chemical oxygen demand (COD) concentration up to 45%. Moreover, the reduction is reasonably fast at the first stages of the process, since the COD concentration is decreased up to 45% within four hours and further treatment time does not add up to the overall decrease in the COD concentration (48% reduction within six hours). The maximum color removal achieved was 71.5%. In addition, the alterations observed in the organic matter during the development of the process, as indicated by the ratios of COD/TOC and BOD/COD and the oxidation state, show that a great part of the organic substances, which are not completely mineralized, are subjected to structural changes to intermediate organic by-products.     

Decolorization kinetics of Procion H-exl dyes from textile dyeing using Fenton-like reactions

The decolorization kinetics of three commercially used Procion H-exl dyes was studied using a Fenton-like reagent. The effect of the major system parameters (pH, concentration of H(2)O(2) and Fe(3+) and initial dye concentration) on the kinetics was determined. For comparison, the effect of the use of UV irradiated Fenton-like reagent and of Fenton reagent on the kinetics was also examined. In addition, mineralization rates and the biodegradability improvement as well as the effect of the addition of Cl(-), CO(3)(2-) or HCO(3)(-) on the decolorization rates was studied. The reactions were carried out in a 300 ml stirred cylindrical reactor with the capability of UV irradiation. The dye half-life time goes through a minimum with respect to the solution pH between 3 and 4. It also exhibits a broad minimum with respect to Fe(3+) and H(2)O(2) at molar ratios of H(2)O(2)/Fe(3+) from about 100 to 10. The addition of CO(3)(2-) and HCO(3)(-) substantially reduces the decolorization rates, while this effect is significantly less pronounced with Cl(-). At an optimum range of parameters, the mineralization rate (TOC reduction) is very slow for the Fenton-like process (TOC decrease from an initial 49.5 to 41.1 mg/l after 30 min and to only 35.2 mg/l after 600 min), but it increases significantly for the photo-Fenton-like process (to TOC values of 39.7 and 11.4 mg/l, respectively). The biodegradability, as expressed by the BOD/COD ratio, increases significantly from an initial value of 0.11-0.55 for the Fenton-like and to 0.72 for the photo-Fenton-like processes.