Pilot scale study of a photo-fenton process for pharmaceutical effluents

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1 Pilot scale study of a photo-fenton process for pharmaceutical effluents Irina Daniela Gaspar Nunes da Cruz Marques The aim of this work was to study the effects of an Advanced Oxidation Process in a pharmaceutical effluent, namely in its content of organic matter, Active Pharmaceutical Ingredients (API) and other relevant pollutants, namely, dichloromethane. A photo Fenton pilot system was tested in situ. In this unit, several types of effluent were tested from general effluent to specific aqueous phases; and several tests were performed internally and externally, including COD analysis and API identification through LC-MS. In total 30 batches were performed. The 19 batches considered revealed an average COD removal yield of 78%; biodegradability improvement (ratio BOD 5 /COD); API destruction and AOX reduction. This investigation allowed concluding that this technology is effective in the treatment of the studied effluent. However, it is highly expensive and, consequently, unsustainable for the company. The system also revealed weaknesses. The turbidity of the effluent can have a major impact on the efficiency of the process due to the inability of the UV radiation to penetrate the liquid and radicalize the hydrogen peroxide molecules. Keywords: Advanced Oxidation Processes; Ultra-violet radiation; Hydrogen Peroxide; Industrial Wastewater; Chemical Oxygen Demand; Pharmaceutical industry; Fenton 1. Scope and objectives 1.1. Water Pollution about the presence of pharmaceuticals in surface and ground water (in orders of ng/l), Liquid effluents containing toxic namely Germany, United States, China and substances are generated by a variety of industrial processes, as well as by a number of common household or agricultural activities Brazil, thus leading to the conclusion that these substances are distributed all over the world. However it is not reasonable to demand (Machulek Jr, Quina, & Gozzi, 2010). absolutely no API in water as these Over the last years, pharmaceuticals have been gaining attention as potential bioactive compounds are excreted by humans and animals after ingestion and traditional WWTP chemicals in the environment. The designation (primary physico-chemical treatment and Active Pharmaceutical Ingredients (API) is biological second step) are unable to remove used to describe compounds that are or destroy them. Additionally, nowadays pharmacologically active. These chemicals are generally resistant to degradation and are potentially able to produce adverse events in water organisms and on the health of humans analytical technologies allow the detection of these compounds even at trace levels A Pharmaceutical Industry Facility The investigated industrial facility is a through drinking water consumption multipurpose pharmaceutical factory, and this (Muruganandham et al., 2014). Rivera-Utrilla and coworkers 2013, collected several data means that the production is extremely variable resulting in an also very variable 1

2 aqueous effluent. On average, 200 m 3 /day of wastewater are produced in this site, including process wastewaters, equipment washes, domestic effluents and other liquid wastes. Due to its variability and constant changes of production, effluent characterization in detail is exceptionally complex, often impossible. For the same reason, finding a suitable and efficient treatment for this effluent is a major challenge. The Chemical Oxygen Demand (COD) levels measured in the raw wastewater are on average around 9000 mgo 2 /L. Besides the process by-products and solvents and domestic wastewater constituents, this effluent also contains pharmaceutical products. Presently, the wastewater treatment procedure involves two main units, namely, a steam stripping unit and a thermal oxidizer. The stripping unit has the purpose of removing solvents with a normal boiling point under 100⁰C from the wastewater. The thermal oxidizer allows the treatment of a part of the industrial effluent while producing steam, an efficient form of waste valorization. The produced steam covers about 60% of the factory s steam needs. The investigated treatment should be able to degrade all types of contaminations, either it is solvents, dissolved solids, suspended solids or others, reducing the COD to the desired levels i.e. under 1500 ppm. Previous studies at lab scale (Agostinho & Dias, 2011), had showed that this company s effluent could be treated successfully using Advanced Oxidation Processes (AOP). 2. Bibliographic review 2.1. Advanced Oxidation Processes In 1987, Glaze defined AOPs as near ambient temperature and pressure water treatment processes which involve the generation of hydroxyl radicals in sufficient quantity to effect water purification. The hydroxyl radical is one of the most reactive species known in aqueous solution, surpassed only by fluorine atoms, and reacts with the majority of organic substances with little or no selectivity and at rates often approaching the diffusion-controlled limit (unit reaction efficiency per encounter) (Machulek Jr et al., 2010). Unlike air stripping and adsorption, which are phase-transfer processes, AOPs are destructive processes. Despite that advantage, as with all treatment technologies, the effectiveness of AOPs will be largely determined by the specific water quality matrix of the contaminated water. However, in the case of AOPs, the effects of background water quality on contaminant removal are much less well understood than for other technologies. Despite most AOP use O 3, H 2 O 2 and/or UV light to produce the hydroxyl radicals, the exact method that forms the radicals differs from technology to technology. According to US- EPA (1998), AOP technologies can be broadly divided into the following groups: (1) Vacuum UV (VUV) photolysis, (2) UV/oxidation processes, (3) the photo-fenton process, and (4) sensitized APO processes. After the formation of the hydroxyl radicals, there will be an attack to organic substrates. These reactions generate organic radicals as transient intermediates, which then undergo further reactions, eventually resulting in final products (P oxid ) corresponding to the net oxidative degradation of the starting molecule (R), as represented in Eq. 1. HO + R P oxid Eq. 1 The principal modes of reaction of HO with organic compounds include hydrogen abstraction from aliphatic carbon, addition to 2

3 double bonds and aromatic rings, and electron transfer. Most of the technical difficulties associated with AOPs stem from the fact that oxidation processes are non-selective with the potential for significant interference. To compensate for these limitations, more energy or higher chemical dosages may be required, potentially resulting in higher costs (Komminemi et al., 2000). Another possible negative point is the possibility of forming toxic compounds which can lead to an increase of the overall toxicity of the effluent with the treatment. These treatment technologies are rising and gaining more a more customers due to their efficiency and destructive (rather than phase changing) capacity of pollutants Process in study: Photo-Fenton Over a century ago, it was discovered by Fenton that the dark reaction of ferrous iron Fe 2+ with H 2 O 2 in acidic medium, known as Fenton s reaction had very powerful oxidizing properties. Although the precise mechanism of this reaction is still the subject of some discussion, it is generally assumed to be an important chemical source of hydroxyl radicals (Machulek Jr et al., 2010). Fe 2+ + H 2 O 2 Fe 3+ + OH + OH Eq. 2 Fe 3+ + H 2 O 2 Fe H + + O 2 Eq. 3 Fe 3+ + O 2 Fe 2+ + O 2 Eq. 4 The rate of removal of organic pollutants and the extent of mineralization with the Fe 2+ /H 2 O 2 and Fe 3+ /H 2 O 2 reagents are improved considerably by irradiation with near- UV radiation and visible light. The peroxide is colorless, it does not absorb visible radiation and it merely absorbs UV radiation with a wave length above 280 nm. Given this, to activate the hydrogen peroxide, meaning to cause photolysis H 2 O 2, the useful approach is applying short-wave radiation, i.e. energy from UV-C band (Brito, Borges, & Silva, 2012). The rate of photolysis of H 2 O 2 depends directly on the incident power or intensity. Beside its part in the formation of hydroxyl radicals, UV light can also play a direct part in the degradation of organic molecules Photo-degradation (Schrank, 2003). Naturally, turbidity lowers the transmittance of the source water and, thus, lowers the penetration of the UV radiation into the source water which decreases the efficiency of the process (Komminemi et al., 2000). According to Machulek Jr and others (2010) more detailed studies of the ph dependence of the photo-fenton reaction have shown that the optimum ph range is about ph 3. This is due to the abundance of different iron species in solution which depends on ph: At ph < 2, the dominant species is Fe 3+ which absorbs weakly in the ultraviolet above 300 nm; At ph 3, the predominant specie is Fe(OH) 2+, which absorbs throughout much of the ultraviolet spectral region; And at ph > 3, solution are supersaturated with respect to formation of colloidal iron hydroxide, Fe(OH) 3 and prone to precipitation of hydrated iron oxides upon standing for a prolonged period. Moreover, ph controls the equilibrium between carbonate, bicarbonate and carbonic acid radical scavengers a lower ph favors the equilibrium to form carbonic acid lowering the concentration of scavengers in solution (Machulek Jr et al., 2010). Taking into account all these factors, generally, photo-fenton systems work at a ph between 2,5 and 3. Usually the increase in temperature affects positively the Fenton and photo-fenton processes because occurs an increase of kinetic energy and consequently, the reaction rate also increases. However, it is also 3

4 possible to occur acceleration in the hydrogen peroxide decomposition process, decreasing the amount available for reaction (Homem & Santos, 2011). The minimum concentration of iron for the Fenton reaction to start is between 3 and 15 mg/l. With the increase of iron concentration, the degradation rate of organic compounds also increases, however, at a certain stage the increase in iron concentration becomes inefficient. This fact suggests the existence of an optimal iron concentration for a given system (Agostinho & Dias, 2011). According to Muruganandham et al. (2014), for many chemicals the optimum catalyst to peroxide ratio is usually 1:5 w/w. Also, Kusic (2007) states that studies show that the optimal ratio Fe:H 2 O 2 is between 1:5 to 1:25. It should be noted that the dose of H 2 O 2 and the concentration of Fe 2+ are two relevant and closely related factors affecting the Fenton process. An excess of peroxide will have a negative effect, as it has a scavenging behavior but low peroxide concentration will not generate enough radicals, so an optimal concentration has to be found. The choice of the optimal concentration of hydrogen peroxide in Fenton and photo-fenton Processes is important from a practical and economical point of view, nevertheless there is no agreement on which concentration provides better results (Alaton 2007). An amount of H 2 O 2 corresponding to the theoretical stoichiometric H 2 O 2 to chemical oxygen demand (COD) ratio is frequently used (Bautista et. al., 2008), although it depends on the response of the specific contaminants to oxidation and on the objective pursued in terms of reducing the contaminant load (Muruganandham et al., 2014). The H 2 O 2 dose has to be fixed according to the initial pollutant concentration and the most frequent approach is to adjust it through several lab tests. The treatment is negatively affected by the presence, in relevant concentrations, of chloride; nitrates and nitrites; phosphates and sulphates; and iron and copper Industrial Effluent Analysis In industrial setting the quantification and characterization of an effluent is quite complicated. In fact, due to the variety and complexity, the determination of contaminations has to be performed in an aggregated form. That is, instead of investigate the content of compounds X, Y and Z individually, one investigates the content of a general family of these compounds, per example, organic compounds or suspended solids Organics To measure and quantify organic compounds in wastewater several approaches can be used, such as Total Organic Carbon (TOC), Theoretical Oxygen Demand (ThOD), Chemical Oxygen Demand (COD) and Biochemical Oxygen Demand (BOD). 3. Materials and Methods 3.1. Effluent assembly and sampling Regarding the tests where the target was real effluent generated in the industrial plant, this wastewater was retrieved from the different sources to specific containers, with a capacity of one cubic meter, called TAM. For the tests, the wastewater was retrieved from the entrance of the stripping unit using pumps, directly to TAMs. The amount of effluent was roughly 6 m 3 in every test. In some batches, the goal was to treat specific types of process effluent, per example, aqueous phases from different process. In these situations, the effluent was isolated directly on the source and collected to TAMs using hoses and pumps. 4

5 Lastly, in some other cases the tests were to treat mixtures specifically prepared for the test in a stirred tank using water and target compounds per example, API. The coagulation/flocculation procedure used Multifloc 320 at a concentration of 4-5g/L and followed the suppliers guidelines. The collected effluent was stored in TAM or tanks for a maximum period of 2 days before it was analyzed and tested. In Table 4 there is a resumed description of the tests performed Photo oxidation pilot unit The complete operating manual of the pilot unit as well as the P&I diagram, are not public due to confidentiality. For this reason, in the present work and in the present chapter, only a reduced description of the equipment and its functions is done. The treatment unit was equipped with a ph monitoring and correcting system that worked throughout the entire treatment process. Table 1 - Pilot unit characteristics. Mode of operation Batch - UV reactors 2 - UV power 16 (4 and 12) kw Tanks 2 x 4 m 3 Total treatment capacity 8 m 3 The system worked in batch mode, the effluent was transferred to the container tank to be analyzed COD Merck Kit. With base on this measurement the adequate Program Sequence Plan (PAP) was selected. Table 2 Reagents and suppliers. Reagents Concentration Supplier H 2 O 2 35% w/w RNM FeCl 3 40% w/w RNM NaOH 20% w/w Quimitécnica H 2 SO 4 38% w/w Quimitécnica The PAP had the variables of the process pre-defined: ph, temperature, amount of peroxide to add in each step, amount of catalyst, energy density to deliver and other parameters. These programs were prepared by the pilot unit s supplier, through several studies and tests taking into account certain effluent characteristics and goals COD of treated waste water lower than 1500 ppm. For more details see Table 3. Figure 1 - Reactors of the pilot unit during a test (UV lights on). Table 3 - Final PAP pre-defined parameters. H 2 O 2 FeCl 3 Energy density ph (ppm) (L/m 3 ) (L/m 3 ) (kwh/m 3 ) ,3 62 2,5 COD initial ,3 71 2, ,3 81 2, , , , ,5 The pilot system was equipped with several control and security systems, namely ph, flow, level, ventilation and temperature Analyses During this work, samples were taken from the pilot unit tank to 100ml glass flasks with glass cap, filling the flask as much as possible to avoid the contact of the liquid with air. The samples were kept at room temperature until the internal analysis this period was always less than 24 hours. COD was measured internally (using Merck Spectroquant cell test and, in some batches, by external labs (by oxidation with potassium dichromate, in acidic medium). Internally, due to the interference of H 2 O 2 in COD measurements, when the peroxide concentration was higher than 10 mg/l, sodium sulphite was added to the 5

6 Table 4 - Description of the different types of wastewater tested, applied pre-treatments and storage. Batch Type of effluent Pre-treatment Storage HQ0001 Raw general effluent - TAM HQ0002 Raw general effluent - TAM HQ0003 Raw general effluent - TAM HQ0004 Raw general effluent - TAM HQ0005 Raw general effluent - TAM HQ0006 Raw general effluent - TAM HQ0007 Raw general effluent - TAM HQ0009 Raw general effluent - TAM HQ00010 Raw general effluent - TAM HQ00011 Raw general effluent - TAM HQ00012 Raw general effluent - TAM HQ00013 Raw general effluent - TAM HQ00014 Raw general effluent - TAM HQ00015 Raw general effluent - TAM HQ00016 Raw general effluent - TAM HQ00018 Process aqueous phase DCM - TAM HQ00019 Raw general effluent - TAM HQ00020 Raw general effluent - TAM HQ00021 Raw general effluent - TAM HQ00022 Process aqueous phase NY - TAM HQ00023 Prep. solution of iopamidol (1,85 g/l) and iohexol (0,68 g/l) - Tank HQ00024 Prep. solution of monoethylene glycol (3,7 g/l) - Tank HQ00025 Process aqueous phase NY Coag. / Floc. Tank HQ00026 Process aqueous phase NY - Tank HQ00027 Raw general effluent - TAM HQ00028 Process aqueous phase MEG - TAM HQ00029 Process aqueous phase NY - TAM wastewater for hydrogen peroxide elimination until its concentration was between 0 and 10 mg/l. This concentration was measured using Merckoquant Peroxide test strips (1 to 100 mg H 2 O 2 /L). In the present work, the equipment used to measure this parameter internally was TOC analyzer Fisher- Rosemount model 2100 C. Besides the analyses to the initial and final sample, in some batches, COD was measured throughout several separation steps for better understanding of the sample s composition (see Figure 2). Table 5 Methods performed externally (LAIST). COD SMEWW* D* Sulphur SMEWW 4500-S2- F* BOD SMEWW 5210 B Iron ISO* :2007 TOC SMEWW 5310 C Chloride SMEWW 4110 B TS SMEWW 2540 B* AOX SMEWW 5320* TDS SMEWW C Dichloromethane SPME TSS SMEWW D Iodine SMEWW 4110 B* VSS SMEWW 2540 E* API search LCMS VDS SMEWW 2540 E* *This analysis is based on the named standard method; * 2 SMEWW - Standard Methods for Examination of Water and Waste Water * 3 ISO stands for International Organization for Standardization. 6

7 COD (ppm) (g/l) representation of the COD values and H 2 O 2 concentration measured during the treatment. Figure 2 - Scheme of additional COD analysis Cost estimation At a first stage of the investigation, the conditions for dimensioning a full photo-fenton treatment unit are described at Table 6. Table 6 - Initial presupposes. Mode of operation Continuous Initial COD 9000 ppm Final COD 1500 ppm Average flowrate 8 to 10 m 3 /h Maximum flowrate 15 m 3 /h ph 2-10 T ⁰C Chloride concentration Other possible contaminants >1500 ppm Ethylene glycol (MEG), Active Pharmaceutical Ingredients (API), Dichloromethane (DCM), methanol and others In this task, the costs were calculated in terms of m 3 of effluent and in terms of kg of COD removed. Also, the costs were determined separately for the different treatment programs (PAP) and taking into account the prices of Table 7. Table 7 - Prices of energy and hydrogen peroxide supported by the company where the study was performed. Electrical energy [ / kwh] H 2 O 2 (35%) [ / L] 4. Results 0,1011 0,32 Therefore, from a total of 30 batches performed, for investigation purposes, the first 10 were neglected and the final batch was also taken out since it was a very peculiar effluent Concentrated mixture (JO). In Figure 3 and Figure 5 is possible to see the treatment effect throughout time. Additionally, in Figure 4 there is the Figure 3 - Batch HQ00015 samples from different times throughout the treatment (1A - initial sample; 2A 8 hours; 3A 17 hours; 4A treated sample in 27 hours) HQ ppm Time (h) Figure 4 - Evolution of COD and H 2 O 2 concentration throughout batch HQ Figure 5 - Samples from batch HQ00025 (first bottle from the left - initial sample; second bottle - sample after flocculation; 1A 11 hours; 2A 17 hours; 3A 26 hours; 4A treated sample in 35 hours. At Table 8 it is possible to see the sources of effluent of each batch, also the external analysis performed at LAIST. H 2 O

8 HQ HQ HQ HQ HQ HQ HQ HQ HQ HQ HQ HQ HQ HQ HQ HQ HQ HQ HQ00030 % COD removal Table 8 - All batches performed in the pilot unit. Each test is described effluent source, abbreviation of the source name and the different analysis performed. External Analysis Effluent Source Name Batches Solids Organics LC-MS-MS Before Stripping ES 19 X X After Stripping SS 2 NY aqueous phase FA-NY 3 X X NY aqueous phase after coagulation FA-NY (C) 1 X X Monoethylene glycol (MEG) solution (prepared in the lab) MEG 1 X (minocicline) Iopamidol solution (prepared in the lab) XR 1 X (iopamidol) MEG recovery aqueous phase Dest-MEG 1 DCM recovery aqueous phase Dest-DCM 1 Concentrated mixture from R6001 JO 1 TOTAL % 90% 80% 70% 60% 50% 40% 30% 20% 10% 0% Dest-MEG ES FA-NY MEG XR JO Dest-DCM Figure 6 - COD removal efficiency in each batch from HQ00011 to HQ Batches organized according to its initial COD. Each color represents a different effluent source. A resume of the efficiencies in terms of COD removal from batches HQ00011 to HQ00029 is shown in Figure 6, the batches are organized according to their initial contamination, COD lower than 10 g/l; COD between 10 and 20 g/l; finally wastewaters with a COD greater than 20 g/l. Also each color represents a different effluent source the names of the sources are explained at Table 8. Through the analysis of this chart, there seems to be a tendency of lower COD removal for FA-NY effluents, namely at HQ00025, HQ00026 and HQ However, there is a contradicting result as the same type <10 [10-20] >20 Initial COD (g/l) of effluent was tested at batch HQ00022 with a COD removal of 89%. Beside the analyses performed internally using Merck kit, several analyses from COD and other parameters were ordered, namely, TOC, dichloromethane, chloride, iodine, BOD 5, total iron and others. Biodegradability is a very important parameter as the target effluent, after leaving the industrial complex is still to be treated at the local Waste Water Treatment Plant (WWTP). It is expected that biodegradability of the effluent is increased by the treatment, due to the degradation of recalcitrant and toxic 8

9 compounds into molecules that are, frequently, more accessible for microorganisms. Table 9 - Biodegradability of the effluent (BOD/COD) calculated for initial effluent and for samples after the treatment in the pilot unit (based on values from LAIST). Batch HQ Initial 55,2 46,5 40,6 Biodegradability (%) Final 68,8 68,3 67,2 Biodegradability (%) Ratio 1,25 1,47 1,65 LC-MS analyses on batches HQ00023 and HQ00025, confirmed that the treatment was able to degrade API, respectively iopamidol and minocycline. In fact, the presence of certain small molecules in the final samples is concurring with the degradation of the initial compounds Cost Projection Considering the amounts of H 2 O 2 and energy needed (Table 6) and the costs showed in Table 7, the approximate price of treatment was calculated and is shown in Table 10. Table 10 - Theoretical energy cost and peroxide cost for cubic meter of treated effluent (depending on the used PAP). PAP Energy Cost Peroxide Cost Total Price H 2 O 2 contribution 6,3 7,2 8,2 11,2 12,7 11,5 15,4 17,9 27,5 35,5 17,8 22,5 26,1 38,7 48,3 65% 68% 69% 71% 73% Table 11- Theoretical energy and H 2 O 2 costs for kg of removed COD considering a final COD of 1500ppm (depending on PAP). PAP COD removed [kg/m 3 ] Total Price [ / kg COD] 3,5 5,5 7,5 13,5 18,5 5,1 4,1 3,5 2,9 2,6 Through these calculations, it is possible conclude that hydrogen peroxide represents more than 60% of the total costs. Note that the higher initial COD is, the bigger the contribution of peroxide costs gets. Another cost projection was done taking into account pilot tests - Table 12, Table 13 and Table 14. Table 12 - Average values based on data from the tests (total energy consumption, % COD removal, initial COD, number of batches). PAP Energy measured [kwh / m 3 ] % COD reduction COD in [ppm] Nr of batches 46,9 58,2 64,8 94,4 No data available Table 13 - Measured energy cost and H 2 O 2 cost for cubic metter of treated effluent (depending on the used PAP). PAP Energy Cost Peroxide Cost Total Price No data 5,9 6,6 9,5 No data 11,5 15,4 17,9 27,5 35,5-21,2 24,5 37,1 - H 2 O 2-72,6% 73,1% 74,1% - contribution Results from Table 11 and Table 14 are quite similar indicating that theoretical values are accurate. Table 14 - Energy and H 2 O 2 costs for kg of removed COD considering an average removal (depending on the treatment programs). PAP COD removed [kg/m 3 ] Total Price [ / kg COD] - 6,1 8,2 18, ,5 3,0 2,1 - These values are an estimation that does not take into account the costs of others reagents like catalyst, acid and base but these volumes were minor compared to H 2 O Discussion This study was conditioned by several limitations, namely, time and schedule limited renting and long batches; resources consumables and effluent; security handling peroxide and danger effluents requires planning, also the pilot unit usage presented 9

10 risks; analyses COD measurements present several limitations and interferences. Despite the presence of small carboxylic acids after treatment, these should be easily degraded by the action of UV light. Besides, these organic compounds are, normally, easy to degrade in natural environments so they do not represent a problem. The rate of radicals formation is crucial and will be directly related with the rate of degradation. However, if the rate of radicalization is too high, radicals will be lost in parallel and secondary reactions resulting in useless peroxide consume. The influence of turbidity was confirmed as for darker, more opaque and muddy effluents, the process did not work as well as with clearer effluents. The amount of hydrogen peroxide required for the treatment depends on multiple factors. Certain compounds are more recalcitrant than others, whether it is because of its size, bonds or geometry. Nevertheless, with the right adjustment in terms of operation (volumes of H 2 O 2, ph, UV irradiation, catalyst concentration and others) the system can treat an effluent with a wide variety of compounds without a selectivity problem. 6. Conclusions The average of COD removal was 78% with a standard deviation of 14%. LC-MS analysis proved that API molecules (Iopamidol and Minocicline) were degraded. The treatment system showed to be versatile and efficient, however, the estimated running costs are too elevated. This way, an alternative plan was proposed effluent will be labelled and segregated to the adequate treatment, meaning AOP system will be used in parallel with stripping and URIS. Part of the organic compounds are lost by evaporation due to their volatile characteristics, meaning that a full scale plant would require a vent system. 7. Bibliography Agostinho, J. & Dias, F., Tratamento de Efluentes da Indústria Farmacêutica por Processos Avançados de Oxidação Engenharia Química. Instituto Politécnico de Bragança. Alaton, I.A., Teksoy, S., Acid dyebath effluent pretreatment using Fenton's reagent: Process optimization, reaction kinetics and effects on acute toxicity. Dyes and Pigments, (1): p Bautista P., Mohedano A. F,. Casas J. A,. Zazo J. A, and Rodriguez J. J An overview of the application of Fenton oxidation to industrial wastewaters treatment, Journal of Chemical Technology and Biotechnology, vol. 83, no. 10, pp Brito, N.N. De, Borges, V. & Silva, M., Advanced oxidative process and environmental application. Revista Eletrônica de Engenharia Civil, 1(3), pp Glaze, W.H., Kang, J.-W. & Chapin, D.H., The Chemistry of water treatment processes involving ozone, hydrogen peroxide and ultraviolet radiation. Ozone Science & Engineering, 9, pp Homem, V. and Santos, L., Degradation and removal methods of antibiotics from aqueous matrices--a review. Journal of environmental management, 92(10), pp Komminemi, S. et al., Treatment Technologies for Removal of Methyl Tertiary Butyl Ether ( MTBE ) from Drinking Water 2nd ed. G. Melin, ed., California: Center for Groundwater Restoration and Protection. Kusic, H., A. Bozic, L., Koprivanac, N., Fenton type processes for minimization of organic content in coloured wastewaters: Part I: Processes optimization. Dyes and Pigments, (2): p Machulek Jr, A., Quina, F.H. & Gozzi, F., Silva V., Friedrich L. and Moraes J Fundamental Mechanistic Studies of the Photo-Fenton Reaction for the Degradation of Organic Pollutants. Organic Pollutants Ten Years After the Stockholm Convention - Environmental and Analytical Update, Dr. Tomasz Puzyn (Ed.), ISBN: , InTech MetCalf & Eddy, Wastewater Engineering Treatment Disposal Reuse, third edition mcgraw-hill international editions Muruganandham, M. et al., Recent Developments in Homogeneous Advanced Oxidation Processes for Water and Wastewater Treatment, International Journal of Phototechnology, Rivera-Utrilla, J. et al., Pharmaceuticals as emerging contaminants and their removal from water. A review. Chemosphere, 93(7), pp Schrank, S.G., Tratamento de efluentes da indústria de couros através de processos avançados de oxidação. Universidade Federal de Santa Catarina. US-Environmental Protection Agency, Handbook Advanced Photochemical Oxidation Processes, Washington DC,