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.     

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.     

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%.     

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.     

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.     

Degradation of DMSO by ozone-based advanced oxidation processes

The present study investigates the oxidation of dimethyl sulfoxide (DMSO) by conventional ozonation and the advanced oxidation processes (AOPs). The major degradation products identified were methanesulfinate, methanesulfonate, formaldehyde, and formic acid in ozonation process. The subsequent degradation of intermediates shows that methanesulfonate is more resistance to ozonation, which reduces the mineralization rate of DMSO. The effect of t-butanol addition and ozone gas flow dosage on the degradation rate was evaluated. The rate constant of the reaction of ozone (k(D)) with DMSO was found to be 0.4162 M(-1)S(-1). In the second part of this study, DMSO degradation and TOC mineralization were investigated using O(3)/UV, O(3)/H(2)O(2) and UV/H(2)O(2) processes. In all theses processes the degradation of target organics is more pronounced than TOC removal. The efficiencies of these processes were evaluated and discussed. The formation of sulfate ion in all AOPs have been identified and compared with other processes. Overall it can be concluded that ozonation and ozone-based AOPs are promising processes for an efficient removal of DMSO in wastewater.     

Degradation of sodium dodecyl sulphate in water using solar driven Fenton-like advanced oxidation processes

Synthetic wastewater samples containing a model surfactant were treated using two different Fenton-like advanced oxidation processes promoted by solar radiation; the photo-Fenton reaction and Co/PMS/UV processes. Comparison between the different experimental conditions was performed by means of the overall surfactant degradation achieved and by obtaining the initial rate in the first 15 min of reaction (IR15). It was found that, for dark Fenton reaction, the maximum surfactant degradation achieved was 14% under low iron and oxidant concentration. Increasing Fenton reagents by one magnitude order, surfactant degradation achieved 63% in 60 min. The use of solar radiation improved the reaction rate by 17% under same conditions and an additional increase of 12.5% was obtained by adjusting initial pH to 2. IR15 values for dark and irradiated Fenton reactions were 0.143 and 0.154 mmol/min, respectively, for similar reaction conditions and this value increased to 0.189 mmol/min when initial pH was adjusted. The use of the Co/PMS system allow us to determine an increase in the degradation rate, for low reaction conditions (1 mM of transition metal; 4 mM oxidant) similar to those used in dark Fenton reaction. Surfactant degradation increased from 3%, for Fenton reaction, to 44.5% in the case of Co/PMS. When solar irradiation was included in the experiments, under same reaction conditions described earlier, surfactant degradation up to 64% was achieved. By increasing Co/PMS reagent concentration by almost 9 times under irradiated conditions, almost complete (>99%) surfactant degradation was reached in 5 min. Comparing IR15 values for Co/PMS and Co/PMS/UV, it allow us to observe that the use of solar radiation increased the degradation rate in one magnitude order when compared with dark experiments and further increase of reagent concentration increased reaction rate twice.     

Degradation of carbofuran by using ozone, UV radiation and advanced oxidation processes.

The degradation of carbofuran (2,3-dihydro-2,2-dimethylbenzofuran-7-yl methylcarbamate), a frequently used carbamate derivative pesticide that is considered a priority pollutant, is carried out in batch reactors by means of single oxidants: ozone, UV radiation and Fenton's reagent; and by the advanced oxidation processes (AOPs) constituted by combinations of ozone plus UV radiation, UV radiation plus H(2)O(2), and UV radiation plus Fenton's reagent (photo-Fenton system). For all these reactions, the apparent pseudo-first-order rate constants are evaluated in order to compare the efficiency of each process. In addition and by means of a competition kinetic model, the rate constants for the reaction of carbofuran with ozone and with hydroxyl radicals are also determined. The improvement in the decomposition levels of carbofuran reached by the combined processes in relation to the single oxidants, due to the generation of the very reactive hydroxyl radicals, is also established in every process. For the oxidant concentrations applied, the most effective process in removing carbofuran was the photo-Fenton system.     

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.     

Degradation of aldrin in adsorbed system using advanced oxidation processes: comparison of the treatment methods

In this study, Fenton, UV/Fenton, UV/H2O2, UV/Fe2+ advanced oxidation processes have been applied for degradation of aldrin adsorbed on Na-montmorillonitte and activated carbon. Aldrin adsorbed on Na-montmorillonitte was degraded more efficiently than that of on activated carbon. For example, in UV/Fenton technique 95% of aldrin was removed from Na-montmorillonitte while 50% degradation was observed on activated carbon. Degradation of aldrin adsorbed on Na-montmorillonitte has also been achieved effectively using UV/Fe2+ technique despite the absence of H2O2. All AOPs but Fenton have been observed nearly equally effective for degradation of aldrin on Na-montmorillonitte sorbent. Fenton reaction exhibited least activity in degradation aldrin adsorbed on Na-montmorillonitte. The experiments with activated carbon sorbent indicated that phenyl groups in activated carbon structure and aldrin molecules exhibited competitive behavior on reaction with OH* radicals. The results of infrared spectroscopy support this assumption. The degradation efficiency of aldrin using activated carbon sorbent was determined in the following order: UV/Fenton > UV/H2O2 > Fenton > UV/Fe2+.     

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.     

The decolorization and mineralization of acid orange 6 azo dye in aqueous solution by advanced oxidation processes: a comparative study

The comparison of different advanced oxidation processes (AOPs), i.e. ultraviolet (UV)/TiO(2), O(3), O(3)/UV, O(3)/UV/TiO(2), Fenton and electrocoagulation (EC), is of interest to determine the best removal performance for the destruction of the target compound in an Acid Orange 6 (AO6) solution, exploring the most efficient experimental conditions as well; on the other hand, the results may provide baseline information of the combination of different AOPs in treating industrial wastewater. The following conclusions can be drawn: (1) in the effects of individual and combined ozonation and photocatalytic UV irradiation, both O(3)/UV and O(3)/UV/TiO(2) processes exhibit remarkable TOC removal capability that can achieve a 65% removal efficiency at pH 7 and O(3) dose=45mg/L; (2) the optimum pH and ratio of [H(2)O(2)]/[Fe(2+)] found for the Fenton process, are pH 4 and [H(2)O(2)]/[Fe(2+)]=6.58. The optimum [H(2)O(2)] and [Fe(2+)] under the same HF value are 58.82 and 8.93mM, respectively; (3) the optimum applied voltage found in the EC experiment is 80V, and the initial pH will affect the AO6 and TOC removal rates in that acidic conditions may be favorable for a higher removal rate; (4) the AO6 decolorization rate ranking was obtained in the order of O(3)相似文献   

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.     

Comparison of various advanced oxidation processes for the degradation of 4-chloro-2 nitrophenol

In the present study an attempt is made efficiently to degrade USEPA listed 4-chloro-2-nitrophenol (4C-2-NP), widely available in bulk drug and pesticide wastes using various advanced oxidation processes (AOPs). A comparative assessment using various AOPs (UV, H(2)O(2,) UV/H(2)O(2), Fenton, UV/Fenton and UV/TiO(2)) was attempted after initial optimization studies, viz., varying pH, peroxide concentration, iron concentration, and TiO(2) loading. The degradation of the study compound was estimated using chemical oxygen demand (COD) reduction and compound reduction using spectrophotometric methods and further validated with high performance liquid chromatography (HPLC). The degradation trends followed the order: UV/Fenton > UV/TiO(2) > UV/H(2)O(2) > Fenton > H(2)O(2) > UV(.) It can be inferred from the studies that UV/Fenton was the most effective in partial mineralization of 4C-2-NP. However, lower costs were obtained with H(2)O(2). Kinetic constants were evaluated using first order equations to determine the rate constant K.     

Pre-ozonation coupled with UV/H2O2 process for the decolorization and mineralization of cotton dyeing effluent and synthesized C.I. Direct Black 22 wastewater

The decolorization and mineralization of cotton dyeing effluent containing C.I. Acid Black 22 as well as synthesized C.I. Acid Black 22 wastewater by means of advanced oxidation processes (AOPs), such as UV/H2O2, O3 and pre-ozonation coupled with UV/H2O2 processes, were evaluated in this study. It was observed that the UV/H2O2 process took longer retention time than ozonation for color removal of dye bath effluent. Reversely, the total organic carbon (TOC) removal showed different phenomena that ozonation and UV/H2O2 process obtained 33 and 90% of removal efficiency for 160 min of retention time, respectively. Additionally, laboratory synthesized dye wastewater was substantially more efficient in the decolorization process than dye bath effluent. Therefore, in this work, pre-ozonation coupled with UV/H2O2 process was employed to enhance the reduction of both color and TOC in dye bath effluent at the same time. At the same time, the retention time demand was reduced to less than 115 min for 90% removal of TOC and color by this combined process.     

Gallic acid degradation in aqueous solutions by UV/H2O2 treatment, Fenton's reagent and the photo-Fenton system

Gallic acid (3,4,5-trihydroxybenzoic acid) is a major pollutant present in the wastewater generated in the boiling cork process, as well as in other wastewaters from food manufacturing industries. Its decay in aqueous solutions has been studied by the action of several oxidation systems: monochromatic UV radiation alone and combined with hydrogen peroxide, Fenton's reagent and the combination Fenton's reagent with UV radiation (photo-Fenton system). The influence of the pH is discussed and the quantum yields are determined in the UV radiation system. Also, the influence of operating variables (initial concentrations of H2O2 and Fe(II), and pH) is established in the Fenton's reaction. The apparent pseudo-first-order rate constants are evaluated in all the experiments conducted in order to compare the efficiency of each one of the processes. Increases in the degradation levels of gallic acid are obtained in the combined processes in relation to the single UV radiation system, due to reactions of the very reactive OH*. These improvements are determined in every process by calculating the partial contribution to the overall decomposition rate of the radical pathways. For the oxidant concentrations applied, the most effective process in removing gallic acid was found to be the photo-Fenton system. The rate constant for the reaction of gallic acid with OH was also determined by means of a competition kinetics model, being its value 11.0+/-0.1 x 10(9)l mol(-1)s(-1).     

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.     

Alkydic resin wastewaters treatment by fenton and photo-Fenton processes

Advanced oxidation processes are an emerging option to treatment of the painting industry effluents. The aim of this study was to compare the effectiveness of the Fenton and photo-Fenton processes in chemical oxygen demand (COD), total organic carbon (TOC) and phenolic compounds removal from wastewaters generated during alkydic resins manufacture. The optimized treatment conditions are the following: pH 3.0, 15.15x10(-3)molL(-1) FeSO(4) and 0.30molL(-1) H(2)O(2) for a reaction time of 6h. photo-Fenton experiments were carried out in the presence of sunlight or artificial radiation and complementary additions of H(2)O(2) were made for all experiments. The best results were obtained with photo-Fenton process assisted with solar radiation, with reductions of 99.5 and 99.1% of COD and TOC levels, respectively. Fenton and photo-Fenton (with artificial irradiation) processes presented lower but not insignificant removals, within 60-80% reduction for both COD and TOC. In addition, an excellent removal (95%) of total phenols was obtained using photo-Fenton process assisted with artificial irradiation. This study demonstrated that the use of photo-Fenton process on alkydic resins wastewater treatment is very promising especially when solar light is used.     

Treatment of gasoline-contaminated waters by advanced oxidation processes

In this study, the efficiency of advanced oxidative processes (AOPs) was investigated toward the degradation of aqueous solutions containing benzene, toluene and xylenes (BTX) and gasoline-contaminated waters. The results indicated that BTX can be effectively oxidized by near UV-assisted photo-Fenton process. The treatment permits almost total degradation of BTX and removal of more than 80% of the phenolic intermediates at reaction times of about 30 min. Preliminary investigations using water contaminated by gasoline suggest a good potentiality of the process for the treatment of large volumes of aqueous samples containing these polluting species. Heterogeneous photocatalysis and H2O2/UV system show lower degradation efficiency, probably due to the heterogeneous character of the TiO2-mediated system and lost of photonic efficiency of the H2O2/UV system in the presence of highly colored intermediated.     

Degradation of p-nitrophenol using acoustic cavitation and Fenton chemistry

Due to increasing human requirements, newer chemical species are being observed in the effluent streams with higher loadings such that efficacy of conventional treatment techniques is decreased and a combination of advanced oxidation processes is implemented for enhanced treatment ability and better energy efficiency. In the present work, the efficacy of combination of sonochemistry and Fenton chemistry has been investigated for wastewater treatment considering p-nitrophenol as model pollutant at pilot scale operation. Degradation of p-nitrophenol has been investigated under various operating conditions based on the use of ultrasound, Fenton process, ultrasound and H₂O₂, ultrasound and Fe, ultrasound and FeSO₄, ultrasound and conventional Fenton process and ultrasound and advanced Fenton process. Two different initial concentrations of 0.5 and 1% of p-nitrophenol have been used for the experiments. In conventional Fenton and advanced Fenton process, two loadings of FeSO₄ and Fe powder 0.5 and 1 g/l and three ratios of FeSO₄:H₂O₂ and Fe:H₂O₂ (1:5, 1:7.5 and 1:10) were investigated respectively. In all the systems investigated, maximum extent of degradation (66.4%) was observed for 0.5% p-nitrophenol concentration (w/v) using a combination of ultrasound and advanced Fenton process. The novelty of the work is in terms of investigating the efficacies of combined advanced oxidation processes based on the use of cavitation and Fenton chemistry at pilot scale operation and tries to establish the missing design related information for large scale operation of wastewater treatment.