Characterization and photo-Fenton treatment of used tires leachate

In this study the leachates derived from used tires were firstly characterized by means of the evaluation of their organic matter content. The leachate from tire powder presented a COD value of 508 mg O(2) l(-1) and a TOC of 214 mg Cl (-1). The main identified organic substances were constituents of the rubber structure: benzothiazole derivatives, phthalates, phenolic derivatives, hydrocarbons and fatty acids. The application of photo-Fenton treatment was investigated in order to obtain the maximum organic matter removal. When a solar chamber as light source was used (light intensity=500 Wm(-2)), the best operational conditions were the following: [H(2)O(2)]=3703 mg l(-1), [Fe(2+)]=92.1 mg l(-1), initial pH 2.7-3.0, reaction time=100 min. After the photo-Fenton treatment at optimum conditions, the reached COD and TOC reduction was 64% and 48%, respectively. The main initial organic substances were eliminated after the reaction and no significant by-products were identified. A complementary treatment consisted of coagulation-flocculation carried out with FeCl(3) x 6H(2)O at pH 12 produced a maximum organic matter removal of 43% as COD and 39% as TOC. A combination of photo-Fenton followed by coagulation-flocculation enhanced the organic matter removal: a reduction of 77% of COD and 64% of TOC was attained.     

A comparative study of the advanced oxidation of 2,4-dichlorophenol

Advanced oxidation processes (AOPs) using UV, UV/H2O2, Fenton and photo-Fenton treatment were investigated at laboratory scale for aqueous solutions of 2,4-dichlorophenol (DCP). The effects on degradation of different reactant concentrations, irradiation time, temperature and pH were assessed. DCP removal, TOC mineralization, dechlorination and change in oxidation state were monitored. UV photolysis was less efficient for total DCP degradation than other AOPs. In contrast, photo-Fenton reaction in acidic conditions led to a higher DCP degradation in a short time. Sixty minutes of treatment were sufficient for 100% DCP removal with 75 mg l(-1) H2O2 and 10 mg l(-1) Fe(II) initial concentrations. In these conditions, a first-order degradation constant for DCP of 0.057 min(-1) was obtained.     

Solubilization of excess sludge in activated sludge process using the solar photo-Fenton reaction

The solubilization of excess sludge by the solar photo-Fenton reaction has been investigated for the reduction of excess sludge in the activated sludge process. The solubilization kinetics depended on the dosages of the Fenton reagents, Fe and H(2)O(2). Increases of initial Fe and H(2)O(2) concentrations in their ranges studied in this work continuously enhanced the sludge solubilization. Cell lysis by the photo-Fenton reaction caused the increase in dissolved chemical oxygen demand (COD) in the first step of sludge solubilization. The further oxidative decomposition of the discharged organic compounds by the photo-Fenton reaction led to the decrease in the dissolved COD as the second step of sludge solubilization. The increase of dissolved COD in the first step of sludge solubilization and the consumption of H(2)O(2) could be described by the pseudo-zero order kinetics based on the accumulated light energy. About 40% reduction of mixed-liquor suspended solids (MLSS) by the solar photo-Fenton reaction was found. It was found that solar light used as a light energy source instead of costly and hazardous artificial UV light was very effective. The dissolved COD for solar photo-Fenton reaction increased faster and by 1.5 times as compared with that by artificial UV light.     

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.     

Degradation and detoxification of formaline wastewater by advanced oxidation processes

In this study, advanced oxidation processes (AOPs) utilizing the combinations of UV/H(2)O(2), Fenton, photo-Fenton and the combination of Fenton/photo-Fenton reactions were investigated in lab-scale experiments for the degradation of formaline wastewater. The studied toxic chemicals were formaldehyde and methanol in mixture solution, so-called formalin, which is the embalming agent in mortuaries. The experimental results showed that the photo-Fenton process was the most effective treatment process among the studied AOPs. Pseudo-first-order degradation rate constants of formaldehyde and methanol were obtained from batch experimental data. In the combination of Fenton/photo-Fenton reactions, the results show that applying UV light at an early stage of the reaction might not be necessary for a speedy oxidation reaction of the Fenton process. With Fenton and photo-Fenton processes, mineralization of formaline wastewater can be achieved, as no residual TOC is detected in the effluent after the reaction period. It is suggested that Fenton and photo-Fenton processes are viable techniques for the formaline wastewater treatment as they were able to provide high degradation of formaldehyde and methanol with relatively low toxicity of the by-products in the effluent.     

Photo-assisted Fenton type processes for the degradation of phenol: a kinetic study

In this study the application of advanced oxidation processes (AOPs), dark Fenton and photo-assisted Fenton type processes; Fe(2+)/H(2)O(2), Fe(3+)/H(2)O(2), Fe(0)/H(2)O(2), UV/Fe(2+)/H(2)O(2), UV/Fe(3+)/H(2)O(2) and UV/Fe(0)/H(2)O(2), for degradation of phenol as a model organic pollutant in the wastewater was investigated. A detail kinetic modeling which describes the degradation of phenol was performed. Mathematical models which predict phenol decomposition and formation of primary oxidation by-products: catechol, hydroquinone and benzoquinone, by applied processes were developed. The study also consist the modeling of mineralization kinetic of the phenol solution by applied AOPs. This part, besides well known reactions of Fenton and photo-Fenton chemistry, involves additional reactions which describe removal of iron from catalytic cycle through formation of ferric complexes and its regeneration induced by UV radiation. Phenol decomposition kinetic was monitored by HPLC analysis and total organic carbon content measurements (TOC). Complete phenol removal was obtained by all applied processes. Residual TOC by applied Fenton type processes ranged between 60.2 and 44.7%, while the efficiency of those processes was significantly enhanced in the presence of UV light, where residual TOC ranged between 15.2 and 2.4%.     

Environmental assessment of different photo-Fenton approaches for commercial reactive dye removal

An environmental study using life cycle assessment (LCA) has been applied to three bench-scale wastewater treatments for Cibacron Red FN-R hetero-bireactive dye removal: artificial light photo-Fenton process, solar driven photo-Fenton process and artificial light photo-Fenton process coupled to a biological treatment. The study is focused on electricity and chemicals consumption, transports and atmosphere and water emissions generated by the different processes involved. Results show that the artificial light photo-Fenton process is the worst treatment in terms of environmental impact. On the other hand, both solar driven and coupled to biological photo-Fenton processes reduce significantly the environmental damage, although none can be identified as the best in all impact categories. The major environmental impact is attributed to the H2O2 consumption and to the electrical energy consumption to run the UVA lamp. An economic analysis of the different photo-Fenton processes has also been performed and the results are discussed together with those obtained from the environmental assessment.     

Effects of reaction conditions on nuclear laundry water treatment in Fenton process

This study presents the efficiency of Fenton process in the degradation of organic compounds of nuclear laundry water. The influence of Fe(2+) and hydrogen peroxide ratio, hydrogen peroxide dose, pH and treatment time were investigated. The degradation of non-ionic surfactant and other organic compounds was analysed as COD, TOC and molecular weight distribution (MWD). The most cost-effective degradation conditions were at H(2)O(2)/Fe(2+) stoichiometric molar ratio of 2 with 5 min mixing and H(2)O(2) dose of 1000 mg l(-1). With the initial pH of 6, the reductions of COD and TOC were 85% and 69%, respectively. However, the removal of the organic compounds was mainly carried out by Fenton-based Fe(3+) coagulation rather than Fenton oxidation. Fenton process proved to be much more efficient than previously performed ozone-based oxidation processes.     

Use of advanced oxidation processes to improve the biodegradability of mature landfill leachates

Two advanced oxidative processes (Fe2+/H2O2/UV and H2O2/UV systems) were used for the pre-treatment of mature landfill leachate with the objective of improving its overall biodegradability, evaluated in terms of BOD5/COD ratio, up to a value compatible with biological treatment. At optimized experimental conditions (2000 mgL(-1) of H2O2 and 10 mgL(-1) of Fe2+ for the photo-Fenton system, and 3000 mgL(-1) of H2O2 for the H2O2/UV system), both methods showed suitability for partial removal of chemical oxygen demand (COD), total organic carbon (TOC) and color. The biodegradability was significantly improved (BOD5/COD from 0.13 to 0.37 or 0.42) which allowed an almost total removal of COD and color by a sequential activated sludge process. In addition, gel permeation chromatography (GPC) has showed a substantial agreement on the cleavage of large organic compound into smaller ones.     

Evaluation of the influences of solution path length and additives concentrations on the solar photo-Fenton degradation of 4-chlorophenol using multivariate analysis

This study reports the photodegradation of 4-chlorophenol (4-CP) in aqueous solution by the photo-Fenton process using solar irradiation. The influence of solution path length, and Fe(NO(3))(3) and H(2)O(2) concentrations on the degradation of 4-CP is evaluated by response surface methodology. The degradation process was monitored by the removal of total organic carbon (TOC) and the release of chloride ion. The results showed a very important role of iron concentration either for TOC removal or dechlorination. On the other hand, a negative effect of increasing solution path length on mineralization was observed, which can be compensated by increasing the iron concentration. This permits an adjustment of the iron concentration according to the irradiation exposure area and path length (depth of a tank reactor). Under optimum conditions of 1.5 mM Fe(NO(3))(3), 20.0 mM H(2)O(2) and 4.5 cm solution path length, 17 min irradiation under solar light were sufficient to reduce a 72 mg CL(-1) solution of 4-CP by 91%.     

Treatment of petroleum refinery sourwater by advanced oxidation processes

The performance of several oxidation processes to remove organic pollutants from sourwater was investigated. Sourwater is a specific stream of petroleum refineries, which contains slowly biodegradable compounds and toxic substances that impair the industrial biological wastewater treatment system. Preliminary experiments were conducted, using the following processes: H2O2, H2O2/UV, UV, photocatalysis, ozonation, Fenton and photo-Fenton. All processes, except Fenton and photo-Fenton, did not lead to satisfactory results, reducing at most 35% of the sourwater dissolved organic carbon (DOC). Thus, further experiments were performed with these two techniques to evaluate process conditions and organic matter removal kinetics. Batch experiments revealed that the Fenton reaction is very fast and reaches, in a few minutes, an ultimate DOC removal of 13-27%, due to the formation of iron complexes. Radiation for an additional period of 60 min can increase DOC removal up to 87%. Experiments were also conducted in a continuous mode, operating one 0.4L Fenton stirred reactor and one 1.6L photo-Fenton reactor in series. DOC removals above 75% were reached, when the reaction system was operated with hydraulic retention times (HRT) higher than 85 min. An empirical mathematical model was proposed to represent the DOC removal kinetics, allowing predicting process performance quite satisfactorily.     

Decontamination of soil washing wastewater using solar driven advanced oxidation processes

Decontamination of soil washing wastewater was performed using two different solar driven advanced oxidation processes (AOPs): the photo-Fenton reaction and the cobalt/peroxymonosulfate/ultraviolet (Co/PMS/UV) process. Complete sodium dodecyl sulphate (SDS), the surfactant agent used to enhance soil washing process, degradation was achieved when the Co/PMS/UV process was used. In the case of photo-Fenton reaction, almost complete SDS degradation was achieved after the use of almost four times the actual energy amount required by the Co/PMS/UV process. Initial reaction rate in the first 15 min (IR₁₅) was determined for each process in order to compare them. Highest IR₁₅ value was determined for the Co/PMS/UV process (0.011 mmol/min) followed by the photo-Fenton reaction (0.0072 mmol/min) and the dark Co/PMS and Fenton processes (IR₁₅ = 0.002 mmol/min in both cases). Organic matter depletion in the wastewater, as the sum of surfactant and total petroleum hydrocarbons present (measured as chemical oxygen demand, COD), was also determined for both solar driven processes. It was found that, for the case of COD, the highest removal (69%) was achieved when photo-Fenton reaction was used whereas Co/PMS/UV process yielded a slightly lower removal (51%). In both cases, organic matter removal achieved was over 50%, which can be consider proper for the coupling of the tested AOPs with conventional wastewater treatment processes such as biodegradation.     

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.     

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.     

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.     

Treatment of 1,10-phenanthroline laboratory wastewater using the solar photo-Fenton process

The red Fe(2+)-phenanthroline complex is the basis of a classical spectrophotometric method for determination of iron. Due to the toxicity of this complexing agent, direct disposal of the wastewaters generated in analytical laboratories is not environmentally safe. This work evaluates the use of the solar photo-Fenton process for the treatment of laboratory wastewaters containing phenanthroline. Firstly, the degradation of phenanthroline in water was evaluated at two concentration levels (0.1 and 0.01%, w/v) and the efficiencies of degradation using ferrioxalate (FeOx) and ferric nitrate were compared. The 0.01% w/v solution presented much higher mineralization, achieving 82% after 30min of solar irradiation with both iron sources. The solar photo-Fenton treatment of laboratory wastewater containing, in addition to phenanthroline, other organic compounds such as herbicides and 4-chlorophenol, equivalent to 4,500mgL(-1) total organic carbon (TOC) resulted in total degradation of phenanthroline and 25% TOC removal after 150min, in the presence of either FeOx or ferric nitrate. A ratio of 1:10 dilution of the residue increased mineralization in the presence of ferrioxalate, achieving 38% TOC removal after 120min, while use of ferric nitrate resulted in only 6% mineralization over the same period.     

Application of Fenton oxidation to cosmetic wastewaters treatment

The removal of organic matter (TOC and COD) from a cosmetic wastewater by Fenton oxidation treatment has been evaluated. The operating conditions (temperature as well as ferrous ion and hydrogen peroxide dosage) have been optimized. Working at an initial pH equal to 3.0, a Fe(2+) concentration of 200 mg/L and a H(2)O(2) concentration to COD initial weight ratio corresponding to the theoretical stoichiometric value (2.12), a TOC conversion higher than 45% at 25 degrees C and 60% at 50 degrees C was achieved. Application of the Fenton oxidation process allows to reach the COD regional limit for industrial wastewaters discharges to the municipal sewer system. A simple kinetic analysis based on TOC was carried out. A second-order equation describes well the overall kinetics of the process within a wide TOC conversion range covering up to the 80-90% of the maximum achievable conversion.     

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.     

Oxidative decomposition of p-nitroaniline in water by solar photo-Fenton advanced oxidation process

The degradation of p-nitroaniline (PNA) in water by solar photo-Fenton advanced oxidation process was investigated in this study. The effects of different reaction parameters including pH value of solutions, dosages of hydrogen peroxide and ferrous ion, initial PNA concentration and temperature on the degradation of PNA have been studied. The optimum conditions for the degradation of PNA in water were considered to be: the pH value at 3.0, 10 mmol L(-1) H(2)O(2), 0.05 mmol L(-1) Fe(2+), 0.072-0.217 mmol L(-1) PNA and temperature at 20 degrees C. Under the optimum conditions, the degradation efficiencies of PNA were more than 98% within 30 min reaction. The degradation characteristic of PNA showed that the conjugated pi systems of the aromatic ring in PNA molecules were effectively destructed. The experimental results indicated solar photo-Fenton process has more advantages compared with classical Fenton process, such as higher oxidation power, wider working pH range, lower ferrous ion usage, etc. Furthermore, the present study showed the potential use of solar photo-Fenton process for PNA containing wastewater treatment.     

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.