A Review on the Degradation of Organic Pollutants in Waters by UV Photoelectro ‐ Fenton and Solar Photoelectro

Este artigo apresenta uma revisão sobre os emergentes processos eletroquímicos de oxidação avançada (PEOAs) tais como UV fotoeletro-Fenton (FEF) e fotoeletro-Fenton solar (SPEF) em que a irradiação do efluente com a luz UV e solar, respectivamente, causa um efeito sinérgico sobre o processo de degradação dos poluentes orgânicos pela formação de mais •OH e/ou da fotólise dos complexos de Fe com a geração de ácidos carboxílicos. Fundamentos destes PEOAs são explicados para clarificar seu desempenho na remoção de produtos químicos industriais, pesticidas, corantes e fármacos. Exemplos com reatores de mistura perfeita em escala de bancada equipados com ânodos de Pt ou boro dopado de diamante (BDD) e cátodos de difusão à gás, feltro de carbono ou fibra de carvão ativado são discutidos. Tratamentos com uma planta piloto de recirculação acoplada a um fotoreator solar são também explicados. Um método de combinação envolvendo FEF e fotocatálise é descrito. A influência dos parâmetros experimentais sobre a taxa de mineralização, eficiência de corrente da mineralização e custo energético dos métodos FEF e FEFS é detalhada. A cinética de degradação dos contaminantes e a evolução de seus intermediários e íons inorgânicos finais são discutidas. O processo FEFS se mostrou mais eficiente e menos caro que outros PEOAs como a oxidação anódica com eletrogeração de H2O2, eletro-Fenton e FEF.


Introduction
Water is essential for the subsistence of all the living beings, but its pollution with organic and inorganic compounds remains a pervasive threat.The water quality is merely a concept reflecting the kind and quantity of contaminants contained in it.2][3][4][5] This pollution comes from urban, industrial and agricultural human activities and cannot be significantly removed by means of conventional wastewater treatment plants because most compounds are recalcitrant, showing a high stability to sunlight irradiation and resistance to microbial attack and temperature.As a result, low amounts of many synthetic organics, usually in µg L -1 , have been detected in rivers, lakes, oceans and even drinking water all over the world.Research efforts are then made to develop simple, safe, effective and economical technologies for the removal of organic pollutants from waters and wastewaters in order to avoid their toxic consequences and potential hazardous health effects on living organisms including human beings.
][8][9][10] AOPs are environmental friendly chemical, photochemical, photocatalytic, electrochemical and photoelectrochemical methods, which present the common feature of the in situ production of hydroxyl radical ( • OH) as the main oxidant.• OH has so high standard reduction potential (Eº( • OH/H 2 O) = 2.80 V vs. SHE) that non-selectively reacts with most organics yielding dehydrogenated or hydroxylated derivatives, which can be in turn mineralized to CO 2 , water and inorganic ions. 8,10The simplest and most typical chemical AOP is the Fenton method in which a mixture of Fe 2+ and H 2 O 2 (Fenton's reagent) is used to degrade organics.The oxidation power of this technique can be significantly improved by illuminating the treated effluent with UV light (photo-Fenton method) or sunlight (solar photo-Fenton method). 11The coupling of the Fenton method with electrochemistry is another way to enhance its decontamination efficiency.
A large variety of electrochemical AOPs (EAOPs) has been recently developed. 7,8EAOPs present environmental compatibility, versatility, high efficiency, amenability of automation and safety because they operate at mild conditions. 4They are mediated electrochemical treatments based on the destruction of organics at the anode and/or using the Fenton's reagent partially or completely generated from electrode reactions.The simplest of the former EAOPs is the electro-oxidation or anodic oxidation (AO) method, which can also be carried out with cathodic H 2 O 2 generation, then being so-called AO with electrogenerated H 2 O 2 (AO-H 2 O 2 ). 7When the Fenton's reagent is electrogenerated, the electrochemical methods constitute the so-called EAOPs based on Fenton's reaction chemistry and are useful for the treatment of acidic wastewaters. 8,10The most popular technique among them is the electro-Fenton (EF) process, in which an iron catalyst (Fe 2+ , Fe 3+ or iron oxides) is added to the effluent while H 2 O 2 is produced at the cathode with O 2 or air feeding.The degradation ability of the EF method on organic pollutants has been improved by combining it with other oxidizing processes.Among them, the most effective methods have been found when the effluent treated by EF is simultaneously exposed to UV or solar radiation, corresponding to the so-called UV photoelectro-Fenton (PEF) and solar PEF (SPEF) methods. 8s far as we know, only few papers 4,8,10 have summarized some data on the performance of the latter EAOPs for the degradation of few organic contaminants.
The aim of this paper is to present a general review on the application of the PEF and SPEF methods to the degradation of organic pollutants in waters including industrial chemicals, pesticides, dyes and pharmaceuticals.Fundamentals of these methods are initially described to better analyze their characteristics and oxidation ability.Systems in which PEF is combined with heterogeneous photocatalysis (PEF-PC) are also described.Special attention is made on SPEF, which is an emerging EAOP that is being developed in our laboratory since 2007.

Fundamentals of the PEF and SPEF Methods
Hydrogen peroxide is a green chemical since it leaves oxygen gas and water as byproducts.It is widely used to bleach pulp and paper and textiles, clean electronic circuits and delignify agricultural wastes, as well as for disinfection in medical and industrial applications and as an oxidant in synthesis and wastewater treatment. 12However, the treatment of wastewaters with H 2 O 2 is limited by its low oxidation ability because it can only attack reduced sulfur compounds, cyanides and certain organics such as aldehydes, formic acid and some nitro-organic and sulfo-organic compounds.For this reason, H 2 O 2 is commonly activated in acidic effluents with Fe 2+ ion as catalyst of the Fenton's reagent to produce homogenous • OH as strong oxidant of organics in the traditional chemical Fenton method. 8t is known since 1882 that H 2 O 2 can be accumulated in aqueous medium from the cathodic two-electron reduction of dissolved O 2 gas at carbonaceous electrodes with high surface area. 13In acidic solutions, this reaction with Eº = 0.68 V vs. SHE can be written as follows: O 2(g) + 2 H + + 2 e − → H 2 O 2 (1)   Reaction 1 takes place more easily than the four-electron reduction of O 2 to water (Eº = 1.23 V vs. SHE).The production and stability of H 2 O 2 depend on several factors such as cell configuration, cathode properties used and operational conditions.Electrochemical reduction at the cathode surface from reaction 2 and, in much lesser extent, disproportion in the bulk from reaction 3 are parasitic reactions that result in the loss of oxidant or a lowering of current efficiency: 14 When an undivided cell is utilized, H 2 O 2 is also oxidized to O 2 at the anode via hydroperoxyl radical (HO 2 • ) as intermediate, a weaker oxidant than • OH, by the following reactions: 15 H 2 O 2 → HO 2 • + H + + e − (4) HO 2 • → O 2(g) + H + + e − The PEF treatment of acidic aqueous solutions of organic contaminants involves the continuous generation of H 2 O 2 from O 2 directly injected as pure gas or compressed air, which is efficiently reduced at cathodes like carbon nanotubes-polytetrafluoroethylene (PTFE), 16,17 carbon nanotubes immobilized onto graphite plates, 18,19 carbon felt, 20,21 activated carbon fiber (ACF) 22,23 and carbon-PTFE gas diffusion electrodes [24][25][26][27][28] via reaction 1.A small catalytic quantity of Fe 2+ is added to the acidic effluent to react with electrogenerated H 2 O 2 giving Fe 3+ and • OH in the bulk according to the classical Fenton's reaction with optimum pH of 2.8: 29 Reaction 6 can be propagated by the catalytic behavior of the Fe 3+ /Fe 2+ pair. 30Table 1 collects the main reactions related to the Fenton system and their corresponding absolute second-order rate constant (k 2 ) value. 31After the initiation reaction 6, Fe 2+ can be regenerated by H 2 O 2 from the Fenton-like reaction 7, by HO 2 • from reaction 8 and/or by the superoxide ion (O 2 •− ) from reactions 9 and 10.The propagation reactions involve the production of HO 2 • by reaction 11 and O 2 •− by reaction 12, along with the attack of • OH to saturated or aromatic organics yielding dehydrogenated or hydroxylated derivatives via reactions 13 or 14, respectively.The inhibition reactions 15-22 promote the removal of reactive radicals and can restrict the range of several experimental parameters.For example, the existence of the parasitic reaction 15 prevents the use of a high Fe 2+ concentration, which usually is < 1.0 mmol L -1 in PEF.
A key advantage of the PEF process compared to the chemical Fenton method is that Fe 2+ is continuously regenerated from the electroreduction of Fe 3+ at the cathode according to reaction 23, with Eº = 0.77 V vs. NHE: 8 Fe 3+ + e − → Fe 2+ (23)   In an undivided electrolytic cell, the slow oxidation of Fe 2+ to Fe 3+ at the anode by reaction 24 is also feasible: 30 Fe 2+ → Fe 3+ + e − In undivided electrolytic systems, the quicker degradation rate of organics in PEF is achieved at pH near 3.These compounds are not only destroyed by reactive oxygen species (ROS), pre-eminently by   , etc., but also by the action of heterogeneous • OH produced at a high O 2 -overvoltage anode (M) from water oxidation by reaction 25: 7,32 M + H The degradation action of M( • OH) is very ineffective for active electrodes such as Pt, being much more efficient when a non-active boron-doped diamond (BDD) thin layer is used as anode.Operating at high current, within the water discharge region, reactive BDD( • OH) is produced in much greater amount than Pt( • OH) and can mineralize completely aromatics and unsaturated compounds such as carboxylic    acids. 32The main loss of BDD( • OH) is its oxidation to O 2 gas via reaction 26, although the low adsorption ability of • OH on BDD favors its dimerization to H 2 O 2 by reaction 27. 33,34[34] 2 BDD( The use of a BDD anode is currently preferred in AO and comparison with EF and PEF can be made by means of the AO-H 2 O 2 method without Fe 2+ addition to the contaminated water. Apart from the electrogeneration of oxidant hydroxyl radicals, the PEF process involves the simultaneous illumination of the acidic treated effluent with UV light.UVA (λ = 315-400 nm), UVB (λ = 285-315 nm) and UVC (λ < 285 nm) lights supplied by artificial lamps as energy sources are commonly employed.The intensity and wavelength of such radiations have significant effect on the destruction rate of organic pollutants.The degradation action of an UV irradiation can be associated with: (i) a higher Fe 2+ regeneration and production of additional • OH from photoreduction of Fe(OH) 2+ , the predominant Fe 3+ species at pH 2.8-3.5, according to photo-Fenton reaction 30: 8,29 Fe(OH) 2+ + hν → Fe 2+ + • OH (30)   and/or (ii) the photodecarboxylation of complexes of Fe(III) with generated carboxylic acids allowing the regeneration of Fe 2+ as depicted in the general reaction 31.
As an example, reaction 32 shows the photolytic processes for Fe(III)-oxalate complexes (Fe( ), 35 which are formed as ultimate by-products of aromatics: When UVC light is applied, its high energetic photons are able to photolyze some organics and promote the generation of more The main drawback of PEF in practice is the high electrical cost of the UV lamps utilized in it.To solve this problem, we have proposed the alternative use of the SPEF method in which the solution is directly irradiated with sunlight as a cheap and renewable energy source with λ > 300 nm. 36,37The higher intensity of UV radiation supplied by sunlight and the additional absorption at λ > 400 nm, e.g., for the photolysis of Fe(III)-carboxylate complexes, enhance the degradation rate of SPEF compared with the PEF process.
The aforementioned synergistic characteristics of the PEF method were confirmed by studying the accumulation of H 2 O 2 in different electrolytic systems.As an example, Figure 1a illustrates a bench-scaled stirred tank reactor with an O 2 -diffusion cathode for H 2 O 2 generation used for the PEF treatment of organic pollutants. 15,24Figure 1b shows the evolution of accumulated H 2 O 2 during the electrolysis of 100 mL of 0.05 mol L -1 Na 2 SO 4 solutions at pH 3.0 in an undivided Pt/O 2 cell like of Figure 1a equipped with a 10 cm 2 Pt anode and a 3 cm 2 carbon-PTFE O 2 -diffusion cathode. 24 gradual accumulation of H 2 O 2 can be observed for 3 h up to reach a steady concentration, which increased with rising applied current from 100 mA (curve e) to 450 mA (curve a).The steady H 2 O 2 concentration under these AO-H 2 O 2 conditions was attained just when its generation rate from reaction 1 becomes equal to its oxidation rate to O 2 from reactions 4 and 5.When 1.0 mmol L -1 Fe 2+ was added to this system (EF conditions), H 2 O 2 destruction was accelerated by action of reactions 6, 7 and 11, as can be deduced by comparing curves b and c of Figure 1b, determined at 300 mA.The acceleration of H 2 O 2 destruction mainly from Fenton reaction 6 owe to the additional Fe 2+ regeneration under UVA illumination from photo-Fenton reaction 30, i.e., operating under PEF conditions, can be confirmed from the slight decay in the steady H 2 O 2 concentration that can be observed by comparing curves c (without UVA light) and d (under 6 W UVA light) of Figure 1b.The above results confirm that the rate of H 2 O 2 production in the Pt/O 2 cell is high enough to destroy relatively concentrated solutions of organic contaminants.

Mineralization and Energetic Parameters
When dyes wastewaters are treated by PEF and SPEF, the decay in their color is usually determined from the decolorization efficiency or percentage of color removal by equation 34: 4 (34)  where ABS 0 M and ABS t M are the average absorbances before electrolysis and after an electrolysis time t, respectively, at the maximum visible wavelength (λ max ) of the wastewater.
The decontamination process of organic pollutants is usually monitored from the abatement of its total organic carbon (TOC), which is preferable to the measurement of the chemical oxygen demand (COD) to avoid the interference of generated H 2 O 2 .From these data, the percentage of TOC removal is calculated from equation 35: 4 (35)   where DTOC is the experimental TOC decay (mg L -1 ) at electrolysis time t and TOC 0 is the initial value before treatment.The mineralization current efficiency (MCE) for electrolyzed solutions at a given time t (h) is estimated from equation 36: 36,38 (36) where n is the number of electrons exchanged in the mineralization process of the organic compound, F is the Faraday constant (96485 C mol -1 ), V s is the solution volume (L), 4.32 × 10 7 is a conversion factor for units homogenization (= 3600 s h -1 × 12000 mg carbon mol -1 ), m is the number of carbon atoms of the molecule under study and I is the applied current (A).
Energetic parameters are essentials figures-of-merit to assess the viability of PEF and SPEF for industrial application. 39Operating at constant I, the energy consumption per unit volume (EC) and unit TOC mass (EC TOC ) are obtained from equations 37 and 38, respectively: 39,40 (37) (38)   where E cell is the average potential difference of the cell (V).

Degradation of Organic Pollutants by PEF
Since the proposal of the PEF process by our group in 1996, 41 a high number of industrial chemicals, pesticides, dyes and pharmaceuticals has been treated by this EAOP.In this section, the main aspects of such treatment are described.

Industrial chemicals
The former works of our group were focused to show the better performance of the PEF process compared with AO-H 2 O 2 and EF for the mineralization of 100 mL of aniline 41,42 and 4-chlorophenol 43 solutions at pH 3.0 using a stirred tank reactor like of Figure 1a with a 10 cm 2 Pt foil anode and a 3 cm 2 carbon-PTFE O 2 -diffusion cathode at 100 mA.Figures 2a and 2b depict that the AO-H 2 O 2 treatment yielded a very slow degradation of both contaminants for 6 h, reaching 25-30% mineralization.The low oxidation ability of AO-H 2 O 2 can be ascribed to the small concentration of reactive Pt( • OH) formed at the Pt surface from reaction 25, which is the main oxidant of organics.In contrast, the EF treatment with 1 mmol L -1 Fe 2+ was much more potent, leading to 68 and 92% decontamination for aniline and  (c and d) with 1.0 mmol L -1 Fe 2+ and (d) under a 6 W UVA irradiation.Applied current: (a) 450 mA, (b, c and d) 300 mA and (e) 100 mA. 24-chlorophenol, respectively.A faster TOC decay can be observed for PEF giving > 92% mineralization from 4 h in both cases.The quick decontamination found for EF can be related to the reaction of organics with the great amounts of • OH produced from Fenton's reaction 6, remaining in the solution products that are not attacked by this radical.The photolysis of such products by UVA light can then account for by the highest mineralization rate of the most potent PEF process.It was also found that the decay of both contaminants followed a pseudo-first-order kinetics and the mineralization rate was enhanced with rising current.For aniline, nitrobenzene and p-benzoquinone were detected as aromatic intermediates by GC-MS (gas chromatographymasss spectrometry) and reversed-phase HPLC (high performance liquid chromatography), but only maleic and fumaric acids were identified as generated carboxylic acids by ion-exclusion HPLC.The release of about 80% of initial N as NH 4 + , along with a smaller proportion of 11% of N as NO 3

−
, was determined in all methods by ion chromatography.For 4-chlorophenol, its hydroxylated derivative 4-chloro-1,2-dihydroxybenzene was always formed, which was subsequently oxidized to maleic and fumaric acids with loss of Cl − ion.It was proposed that these acids were finally transformed into oxalic acid, which forms Fe(III)-oxalate acids that are not attacked by hydroxyl radicals in EF and quickly photodecomposed via reaction 32 in PEF, thus justifying the best oxidation ability of this procedure.
Further work was devoted to the degradation of nitrobenzene, a well-known toxic pollutant in industrial wastewaters, to evidence the synergistic catalytic action of Fe 2+ and Cu 2+ in EF and PEF using the above Pt/O 2 tank reactor. 44It has been proposed that Cu 2+ can be reduced to Cu + with HO 2 • from reaction 39 and then, Cu 2+ is regenerated either from the Fenton-like reaction 40 yielding more • OH or from reaction 41 producing more Fe 2+ to enhance Fenton's reaction 6: 45,46 Cu 2+ + HO 2 Figure 3 highlights the slow and continuous mineralization of 100 mg L -1 nitrobenzene at pH 3.0 using 1 mmol L -1 Cu 2+ as catalyst up to yield 53% TOC removal in 360 min at 100 mA, indicating a low • OH production from reactions 39 and 40.EF with 1 mmol L -1 Fe 2+ also promoted the same TOC decay but with much higher initial mineralization rate, while the combined use of 1 mmol L -1 Fe 2+ and 1 mmol L -1 Cu 2+ upgraded the organic destruction up to 88% mineralization.The same trend was found for the most potent PEF technique, which required 360 min for overall mineralization with 1 mmol L -1 Fe 2+ and only 240 min when 1 mmol L -1 Cu 2+ was also added to the medium.The nitrobenzene decay always followed a pseudo-first-order reaction.2-Nitrophenol, 3-nitrophenol, 4-nitrophenol, 4-nitrocatechol and maleic, fumaric and oxalic acids were identified by HPLC as intermediates.The increase in oxidation ability of the  (EF process), () 1 mmol L -1 Cu 2+ + 1 mmol L -1 Fe 2+ , () 1 mmol L -1 Fe 2+ + 6 W UVA light (PEF process) and () 1 mmol L -1 Cu 2+ + 1 mmol L -1 Fe 2+ + 6 W UVA light. 44ethods tested was related to the formation of stable Fe(III)-oxalate complexes in EF with 1 mmol L -1 Fe 2+ , which were photolyzed by UVA irradiation in PEF, and of competitive Cu(II)-oxalate complexes in EF and PEF with 1 mmol L -1 Fe 2+ and 1 mmol L -1 Cu 2+ that can be quickly removed with • OH.In all cases, the initial N was completely converted into NO 3 − ion.More information about the PEF process of other industrial chemicals has been obtained in more recent studies for a polyhydroxy compound such as gallic acid (3,4,5-trihydroxybenzoic acid) 47 and sulfanilic acid (4-aminobenzenesulfonic acid), 48 which is widely used to synthesize pesticides, sulfonamide pharmaceuticals, sulfonated azo dyes, dye mordants, species, and food pigments.In the former case, 200 mL of solutions containing up to 6 mmol L -1 gallic acid in 2.0 g L -1 KCl at pH 3.0 were treated at 80 mA and room temperature.The EF method with 1 mmol L -1 Fe 2+ in an undivided Pt/O 2 cell promoted 70% TOC removal in 240 min, whereas the comparable PEF with UVA light led to 90% mineralization.This behavior was explained by the expected production of stable Fe(III)-oxalate complexes that can only be photodecarboxylated under UVA irradiation via reaction 31.For sulfanilic acid, a stirred tank reactor like of Figure 1a with a 3 cm 2 BDD anode was used, because it showed greater oxidation ability than Pt, as will be discussed below for other kinds of contaminants.However, 100 mL of 1.39 mmol L -1 sulfanilic acid only underwent a partial decontamination of 85% by EF until 100 mA cm -2 at optimum conditions of 0.4 mmol L -1 Fe 2+ and pH 3.0.The increase in current density and substrate content led to an almost total mineralization.In contrast, the PEF process was more powerful giving almost complete mineralization in less electrolysis time under comparable conditions.The kinetics for sulfanilic acid decay always followed a pseudo first-order reaction.Hydroquinone and p-benzoquinone were detected as aromatic intermediates, whereas acetic, maleic, formic, oxalic and oxamic acids were identified as generated carboxylic acids.The fast photolysis of Fe(III)-carboxylate complexes, especially of the ultimate Fe(III)-oxalate and Fe(III)-oxamate species, under UVA radiation explained the greater oxidation ability of the PEF method.NH 4 + ion was preferentially released in both treatments, along with NO 3 − ion in much smaller proportion.Erbatur et al. 20 investigated the characteristics of another PEF process using a three-electrode divided cell under an UVC radiation to degrade 4-chloro-2-methoxyphenol, emitted from the industrial production of phenoxy herbicides, and three representative toxic phenolics in olive mill wastewater such as vanillic, o-coumaric and protocatechuic acids. 21The divided cell was a stirred tank reactor equipped with a Nafion 117 membrane as separator of the anolyte containing a Pt gauze anode and the catholyte with a carbon-felt cathode of 3 cm × 5 cm area in contact with a SCE reference electrode.The catholyte contained 300 mL of an O 2 -saturated solution at pH 2.7 by adding 0.05 mol L -1 H 2 SO 4 .H 2 O 2 was generated in it by applying a cathodic potential (E cat ) of −0.55 V vs. SCE and a 15 W UVC lamp was used as energy source in PEF.In the case of 4-chloro-2-methoxyphenol, the best decay rate for a 0.6 mmol L -1 solution under EF conditions was found using 2.4 mmol L -1 Fe 2+ that allowed its total disappearance in 360 min.A large enhancement of the substrate removal was determined by means of PEF, ascribed to its additional photolysis by UVC irradiation and a greater production of • OH from H 2 O 2 dissociation by reaction 33.Total disappearance of 4-chloro-2-methoxyphenol, with 42% TOC removal and complete dechlorination was achieved in PEF with 1.8 mmol L -1 Fe 2+ by consuming 141.4 C electrical charge in 300 min.In the comparable EF process, however, 280.7 C electrical charge were consumed during 450 min of electrolysis to completely remove the substrate with 15% TOC removal and 89% dechlorination.Similar results were also obtained for vanillic, o-coumaric and protocatechuic acids.Interestingly, these authors showed that 4-chloro-2-methoxyphenol decayed more rapidly by using 1.8 mmol L -1 Mn 2+ instead of 1.8 mmol L -1 Fe 2+ in EF.This was explained by the catalytic effect of the Mn 3+ /Mn 2+ pair with • OH production from the Fenton-like reaction 42 and cathodic regeneration of Mn 2+ via reaction 43.
Apart from the alternative use of homogeneous Cu 2+ and Mn 2+ catalysts instead of Fe 2+ , other varieties of the EF and PEF treatments for organic pollutants have been proposed.Expósito et al. 26 explored the action of several low-soluble mineral iron oxides as an iron source for the production of • OH from Fenton's reaction 6.The experiments were conducted with a stirred tank reactor similar to that of Figure 1a with a 6.5 cm 2 Pt spiral anode and a 5 cm 2 carbon-PTFE air-diffusion cathode.Solutions of 250 mL of 100 mg L -1 aniline in 0.2 mol L -1 Na 2 SO 4 at pH 3.0 were comparatively treated by EF and PEF with UVA and UVC light at 250 mA by adding 0.5 mmol L -1 Fe 2+ and 1 g L -1 of iron oxides like hematite (α-Fe 2 O 3 ), wustite (FeO), magnetite (Fe 3 O 4 ) and goethite (α-FeOOH).Among them, magnetite was the most efficient catalyst in PEF and its action was postulated to be the result of its possible photocatalytic action because similar Fe contents of ca.20 mg L -1 to the other iron oxides were released to the medium during 300 min of electrolysis.However, more work is needed to confirm the possible use of magnetite as iron source in EAOPs based on Fenton's reaction chemistry.

Pesticides
The study of the PEF degradation of pesticides was initiated by considering the performance of common chlorophenoxy herbicides present in the aquatic environment such as (2,4-dichlorophenoxyacetic acid (2,4-D), 24 4-chlorophenoxyacetic acid (4-CPA), 49 4-chloro-2-methylphenoxyacetic acid (MCPA), 50 2,4,5-trichlorophenoxyacetic acid (2,4,5-T) 51 and 3,6-dichloro-2-methoxybenzoic acid (dicamba). 52A stirred Pt/O 2 tank reactor equipped with a 10 cm 2 Pt sheet anode and a 3 cm 2 carbon-PTFE cathode fed with pure O 2 at a flow rate of 20 mL min -1 was used to electrolyze 100 mL of herbicide solutions in 0.05 mol L -1 Na 2 SO 4 at pH in the range 2.0-6.0 by applying a constant current between 100 and 450 mA and keeping the temperature at 25 or 35 ºC.In EF and PEF, 0.2-2.0mmol L -1 FeSO 4 was added to the starting solutions, while in the latter method, the solution was irradiated with 6 W UVA light of λ max = 360 nm.
Figure 4a illustrates the degradation behavior for 190 mg L -1 of 4-CPA, at pH 3.0, 100 mA and 35 ºC, showing that the oxidation ability of the EAOPs increased in the sequence AO-H 2 O 2 < EF with 1 mmol L -1 Fe 2+ < PEF with 1 mmol L -1 Fe 2+ .The AO-H 2 O 2 process only allows 29% TOC reduction in 360 min because of the small concentration of reactive Pt( • OH) formed at the anode surface from reaction 25.In contrast, EF with 1 mmol L -1 Fe 2+ promoted 74% mineralization at the same time owe to the additional • OH production from Fenton's reaction 6, whereas total mineralization in 180-240 min took place by PEF with 1 mmol L -1 Fe 2+ as a result of the quick photodecomposition of byproducts and/or the enhancement of • OH generation induced by photo-Fenton reaction 30.The fact that PEF is the most potent EAOP was also found for all the other herbicides, as deduced from the percentages of TOC removal obtained after 1 and 3 h of electrolysis of solutions with 100 mg L -1 TOC for 4-CPA, MCPA, 2,4-D and 2,4,5-T at pH 3.0 and 100 mA summarized in Table 2 (experiments denoted as Pt).The MCE values determined from equation 36 are also collected and at 3 h of electrolysis, they were 4.4-8.3%for AO-H 2 O 2 -Pt, 14-20% for EF-Pt with 1 mmol L -1 Fe 2+ and 25-29% for PEF-Pt with 1 mmol L -1 Fe 2+ , related to 16-28, 53-65 and 90-99% mineralization, respectively.It was found that increasing current caused higher mineralization rate in all the EAOPs by the concomitant production of more oxidizing agents, but with gradual decay in MCE by the Table 2. Percentage of TOC removal, mineralization current efficiency (MCE) and pseudo first-order rate constant (k 1 ) for the degradation of 100 mL of solutions containing 100 mg L -1 TOC of chlorophenoxyacetic acid herbicides in 0.05 mol L -1 Na 2 SO 4 at pH 3.0 by several EAOPs at 100 mA 24,49,[51][52][53]

Herbicide
Method a Temperature / ºC After 1 h of treatment After 3 h of treatment greater acceleration of reactions 26-29.In contrast, a higher efficiency was obtained with rising initial herbicide content owing to the quicker destruction of organics with hydroxyl radical and the decay in rate of the previous non-oxidizing parasitic reactions.In EF and PEF, all the compounds were more effectively degraded at pH 3.0-4.0and similar degradation rates were obtained up to 1 mmol L -1 Fe 2+ , but less TOC removal was found for higher Fe 2+ contents due to the acceleration of reaction 15.
Figure 4b highlights that the 4-CPA decay is very slow in AO-H 2 O 2 , whereas a much faster removal with similar disappearance in 25 min can be observed for EF-Pt and PEF-Pt because of the production of very high quantities of • OH from Fenton's reaction 6.This is indicative of a very small participation of photo-Fenton reaction 30.All concentration decays for the aforementioned herbicides agreed with a pseudo-first-order reaction kinetic equation.The corresponding pseudo-first-order rate constants (k 1 ) are collected in the last column of Table 2, being about two magnitude orders higher for EF and PEF than for AO-H 2 O 2 .
GC-MS and HPLC analyses of treated solutions revealed the formation of several aromatic intermediates and a high number of short-chain carboxylic acids coming from the cleavage of the benzenic ring of such aromatics and the release of aliphatic lateral chains.Figure 5 exemplifies the time course of selected compounds detected during the treatments of 190 mg L -1 4-CPA solutions at pH 3.0 and 100 mA.As expected, the primary byproducts, 4-chlorophenol (Figure 5a) and glycolic acid (Figure 5b) were slowly destroyed in AO-H 2 O 2 , but very quickly degraded in EF and PEF.Glycolic acid disappeared more rapidly in PEF, probably because of the fast photodegradation of its Fe(III) complexes.The same trends were found for the other intermediates, except oxalic acid that is accumulated in EF and rapidly removed in PEF (see Figure 5c), which can be explained by the photolysis of Fe(III)-oxalate complexes via reaction 32.This process accounts for the total mineralization attained in PEF and its higher oxidation ability compared to EF. Figure 5d evidences that all the initial chlorine of 4-CAP was converted into Cl − after 30-40 min of EF and PEF, when chlorinated byproducts are totally destroyed, but the slower removal of such intermediates caused a progressive Cl − accumulation in AO-H 2 O 2 .From the products detected for 4-CPA degradation, the reaction sequence of Figure 6 was proposed for the different EAOPs tested in a Pt/O 2 cell.The initial breaking of the lateral chain of 4-CPA via C(1)-O bond gives 4-chlorophenol and glycolic acid.4-chlorophenol then leads to 4-chlorocatechol, as well as hydroquinone and p-benzoquinone with release of Cl − , which are oxidized to a mixture of malic, maleic and fumaric acids.Glycolic acid yields glyoxylic acid and both acids produce formic acid that is transformed into CO 2 .Oxalic acid formed from precedent acids is slowly mineralized to CO 2 by AO-H 2 O 2 and its Fe(III) species are slowly destroyed in EF and quickly photodecarboxylated, with loss of Fe 2+ , in PEF.
The influence of a BDD anode on the AO-H 2 O 2 and EF treatments of 100 mg L -1 TOC of 4-CPA, MCPA, 2,4-D and 2,4,5-T at pH 3.0 was investigated at 100 mA and 35 ºC using an undivided BDD/O 2 cell like of Figure 1a equipped with a 3 cm 2 BDD thin layer. 53Table 2 shows a much quicker TOC removal for both treatments with BDD compared to Pt.The use of BDD then allowed more efficient processes leading to total mineralization which was not attained with Pt (see Figure 4a).However, this situation was achieved practically at the same time for both AO-H 2 O 2 and EF processes, which cannot be related to a faster reaction of aromatic intermediates with the higher amount of reactive BDD( • OH) formed from reaction 25, since initial herbicides always followed a pseudo-first-order decay with a quite similar k 1 -value for each method in both Pt/O 2 and BDD/O 2 cells (see Table 2).Worth highlighting,   these results corroborate the quicker reaction of herbicides with • OH in the medium rather than at the Pt or BDD surface.Analysis of generated carboxylic acids revealed the very slow reaction of Fe(III)-oxalate complexes with BDD( • OH) in EF, accounting for the long time needed for the total decontamination of herbicides by EF-BDD.This occurs at similar times to those needed using AO-H 2 O 2 in which oxalic acid was practically removed at the same rate as produced.It was also found that Cl − ion released in all treatments was slowly oxidized to Cl 2 on BDD.The great oxidation ability of EAOPs with BDD was confirmed from the degradation of other chlorophenoxy herbicide such as 2,4-dichlorophenoxypropionic acid (2,4-DP) under similar conditions. 25The EF and PEF processes with 1 mmol L -1 Fe 2+ in a BDD/O 2 cell led to complete mineralization of 100 mL of 217 mg L -1 2,4-DP solutions at pH 3.0, 300 mA and 35 ºC, with overall loss of chloride ion.Nevertheless, the UVA light in PEF had little effect on the degradation rate of pollutants compared with the fast oxidation produced by BDD( • OH) and • OH.The comparative procedures with Pt promoted slower decontamination because of the lower oxidizing power of this anode.
A further research of our group was devoted to the degradation of several s-triazinic herbicides such as atrazine (2-chloro-4-ethylamino-6-isopropylamino-1,3,5-triazine), 54 desmetryne (2-isopropylamino-4-methylamino-6-methylthio-1,3,5-triazine) 55 and cyanacine (2-(4-chloro-6-ethylamino-1,3,5-triazin-2-ylamino)-2-methylpropiononitrile). 56These products are widely used as pre-and post-emergency herbicides for combating grassy and broadleaf weeds in sorghum, corn, rangeland and sugar cane, but their removal by AOPs is very difficult because they are transformed into cyanuric acid (2,4,6-trihydroxy-1,3,5-triazine), which cannot be destroyed by • OH.The treatment of the three s-triazines with a stirred BDD/O 2 tank reactor demonstrated that an almost total mineralization was always achieved by AO-H 2 O 2 , EF and PEF since cyanuric acid can be removed by generated BDD( • OH).This behavior can be observed in Figure 7a for 30 mg L -1 atrazine, where 90-92% mineralization was attained in AO-H 2 O 2 and PEF after 540 min of electrolysis at 100 mA and 360 min at 300 and 450 mA.The increase in current caused the spent of more specific charge, also reflected in the gradual fall in MCE, shown in Figure 7b, owe to the higher increase in rate of waste reactions 26-29.The low rise of TOC removal when using PEF compared to AO-H 2 O 2 was explained considering that the limiting oxidation reaction involved the attack of BDD( • OH) over cyanuric acid.For desmetryne and cyanazine, the effect of UVA light was more apparent because higher amounts of carboxylic acids like formic, oxamic and oxalic were produced from the degradation of their lateral groups.The optimum pH for all the processes was 2.0-4.0.From the HPLC analysis of treated solutions, aromatic intermediates like desethylatrazine and desethyldesisopropylatrazine for atrazine, ammeline for desmetryne and deisopropylatrazine, desethyldeisopropylatrazine and ammeline for cyanazine, which further evolved to cyanuric acid, were detected.As an example, Figure 7c shows the reaction sequence proposed for the formation of this recalcitrant byproduct from atrazine. 54In all cases, the initial N was pre-eminently released as NO 3 − ion and the initial chlorine was lost as Cl − ion, which was oxidized to Cl 2 at the BDD anode.
On the other hand, Dhaouadi and Adhoum 57 reported a 97 and 94% COD reduction for 100 mL of 20 mg L -1 of the herbicide paraquat (1,1'-dimethyl-4,4'-bipyridinium chloride) in 0.05 mol L -1 Na 2 SO 4 and 0.2 mmol L -1 Fe 2+ at pH 3.0 and 100 mA by PEF with 6W UVA light and EF, respectively, using a stirred tank reactor containing a 5 cm 2 Pt anode and a carbon-felt cathode of (3 cm × 5 cm) area.The small accumulation of succinic, acetic, formic and oxalic acids justified the little effect of UVA light when the most potent PEF process was applied, so that, • OH formed from Fenton's reaction 6 was the main oxidizing agent under the experimental conditions tested.The paraquat decay kinetics obeyed a pseudo-first-order model and its absolute second-order rate constant with • OH was determined as k 2 = 2.55 × 10 9 mol -1 L s -1 .These authors also showed that comparable Ag + concentration to that of Fe 2+ in EF favored slightly the decontamination rate of the herbicide, thus opening the doors for the possible application of Ag + as alternative catalyst in EAOPs.

Dyes
Large volumes of industrial wastewaters with high dye contents are discharged into lakes and rivers over the world, causing esthetic problems and serious health and environmental risks because of the toxicity, carcinogenic and mutagenic properties of dyes and their byproducts. 4Despite that powerful AOPs are needed to destroy dyes because they are difficultly removed under conventional aerobic treatments in wastewater treatment plants, only few papers have reported the PEF treatment of acidic dyestuffs solutions.
The first study on these toxic organics was centered on the characteristics of the EF and PEF treatments of 100 mL of aqueous solutions containing 220 mg L -1 of Indigo Carmine (C.I.Acid Blue 64) and Fe 2+ and/or Cu 2+ as catalysts at pH 3.0 with Pt/O 2 and BDD/O 2 cells like of Figure 1a, with electrodes of 3 cm 2 area, at 100 mA and 35.0 ºC. 58While EF with Pt and 1.0 mmol L -1 Fe 2+ gave poor mineralization, only attaining 49% TOC removal in 540 min, EF with BDD promoted 91% TOC reduction at the same time, reaching total mineralization with loss of NH 4 + ion in 780 min.Indigo Carmine obeyed a pseudo-zero-order reaction kinetics, as determined by HPLC, and disappeared at the same time as its aromatic derivatives isatin 5-sulphonic acid, indigo and isatin, mainly by reaction with • OH produced from Fenton's reaction 6.The most persistent byproducts were oxalic and oxamic acids, present in the medium as Fe(III)-oxalate and Fe(III)-oxamate complexes.As can be seen in Figures 8a and 8b, both complexes were poorly attacked with • OH formed from Fenton's reaction 6 and Pt( • OH) generated from reaction 25 in EF with Pt, but they were completely destroyed with BDD( • OH) in EF with BDD, in agreement with the greater oxidation power of the latter radical.In PEF with Pt under a 6 W UVA light, TOC was reduced by 84% in 540 min and Fe(III)-oxalate complexes disappeared in 480 min  54 (see Figure 8a), but Fe(III)-oxamate complexes attained a steady concentration (see Figure 8b).Consequently, the superiority of PEF compared to EF was related to the quick photolysis of Fe(III)-oxalate complexes from reaction 32.Cu 2+ was then added as co-catalyst trying to produce additional quantity of • OH from Fenton-like reaction 40.Surprisingly, it was obtained that PEF with Pt and 1.0 mmol L -1 Fe 2+ + 0.25 mmol L -1 Cu 2+ promoted almost total mineralization (> 97% TOC removal) in 450 min due to a faster and total destruction of both oxalic and oxamic acids (see Figures 8a and 8b).The synergistic effect of Fe 2+ and Cu 2+ was explained by: (i) the photolysis of Fe(III)-oxalate complexes and (ii) the simultaneous reaction of competitively formed Cu(II)-oxalate and Cu(II)-oxamate complexes with • OH in the bulk.Figures 8c and 8d present the proposed reaction pathways to describe the mineralization processes of oxalic and oxamic acids, respectively, in the presence of both catalysts.
More recently, the action of UVA light in the PEF process was clarified by treating 100 mL of a 200 mg L -1 Direct Yellow 4 solution in 0.05 mol L -1 Na 2 SO 4 with 0.5 mmol L -1 Fe 2+ at pH 3.0, 33.3 mA cm -2 and 35 ºC in a BDD/air-diffusion cell like of Figure 1a. 59Figure 9a highlights that the dye was not photodecomposed under a 6 W UVA irradiation, while the solution TOC was reduced by 84 and 97% after 360 min of EF and PEF, respectively.When the EF process was carried out for 60 min, 31% TOC was removed, but the Fenton's reagent remaining in the solution had oxidation ability enough to reduce the TOC by 45% during a longer time of 180 min, thus demonstrating the oxidation role of • OH formed from Fenton's reaction 6 in EF.In contrast, if the solution treated during 60 min in PEF was subsequently submitted to UVA irradiation, TOC removal gradually rose up to 81%, whereas if the UVA light was applied after 120 min of EF, 97% TOC decay, equal to using PEF, was found (see Figure 9b).This is a very interesting finding, because it clearly shows that the photolytic action of UVA light, also involving the photodegradation of the ultimate Fe(III)-oxalate complexes, yields the predominant mineralization process of the PEF method at long electrolysis time.Further research on this point is necessary to use less expensive processes to degrade organic pollutants.
The superiority of PEF over EF has also been shown for other dyes. 22,60,61Thus, Wang et al. 22 used the undivided RuO 2 /ACF cell of Figure 10a with an 11 W UVC lamp positioned in a hollow quartz tube between the electrodes to treat the azo dye Acid Red 14.A reduction of about 94% TOC was found after 360 min of PEF treatment of 450 mL of an O 2 -saturated solution containing 200 mg L -1 of dye in 0.05 mol L -1 Na 2 SO 4 with 1 mmol L -1 Fe 2+ at pH 3.0 and 500 mA, a value much greater than 73% TOC decay obtained for the similar EF treatment.An interesting Figure 8. Evolution of the concentration of (a) oxalic and (b) oxamic acids during the degradation of 100 mL of 220 mg L -1 Indigo Carmine solutions in 0.05 mol L -1 Na 2 SO 4 at pH 3.0, 33 mA cm -2 and 35.0 ºC using a Pt/O 2 or BDD/cell with 3 cm 2 electrodes.Process: () EF with Pt and 1.0 mmol L -1 Fe 2+ , () PEF with Pt, 1.0 mmol L -1 Fe 2+ under 6 W UVA light, () EF with BDD and 1.0 mmol L -1 Fe 2+ and () PEF with Pt and 1.0 mmol L -1 Fe 2+ + 0.25 mmol L -1 Cu 2+ .Proposed pathways for the mineralization of (c) oxalic and (d) oxamic acids. 58tudy has been reported by Peralta-Hernández et al. 60 for the treatment of 400 mL of a solution with 50 mg L -1 of the azo dye Orange II with 0.05 mol L -1 Na 2 SO 4 and 0.2 mmol L -1 Fe 2+ at pH 3.0 using a concentric annular undivided graphite cloth/graphite cloth flow reactor with 164 cm 2 cathode area operating at 300 mA cm -2 and liquid flow rate of 100 mL min -1 .The effluent was irradiated with a central 75 mW cm -2 UVA lamp under O 2 -bubbling for H 2 O 2 electrogeneration.Complete decolorization in less than 5 min and 80% TOC removal in 60 min were obtained by PEF from the great production of • OH from Fenton's reaction 6 and photo-Fenton reaction 30.Similar decolorization rate, but with smaller 63% TOC decay was found for the comparable EF treatment.However, Almeida et al. 61 showed a quicker and total decolorization by PEF compared to EF for 100 mL of a 244 mg L -1 Acid Red 29 solution in 0.05 mol L -1 Na 2 SO 4 under optimum conditions of 0.5 mmol L -1 Fe 2+ and pH 3.0 at 35 ºC using a stirred BDD/air-diffusion tank reactor like of Figure 1a with 3 cm 2 electrode area.The decay kinetics for the dye followed a pseudo-first-order reaction with similar rate for EF and PEF.
Since it disappeared much more rapidly than solution color, it was proposed that the decolorization process involved the destruction of colored conjugated byproducts with λ max similar to that of Acid Red 29, which was enhanced in PEF by the production of more • OH from photo-Fenton reaction 30.Almost total mineralization was found for PEF, whereas poorer degradation was achieved by EF.In the PEF process, Fe(III)-oxalate complexes were efficiently photolyzed, but tartronic and oxamic acids were the most persistent byproducts because of the larger stability of their Fe(III) complexes.The initial N of the azo dye yielded NO 3 − ion, along with NH 4 + ion in smaller quantity.

Pharmaceuticals
Our group has investigated the PEF degradation process of several aromatic drugs including analgesics/ anti-inflammatories such as paracetamol, 62 ibuprofen 63 and salicylic acid, 64 the blood lipid regulator metabolite clofibric acid, 65,66 antimicrobials such as chloroxylenol, 38 enrofloxacin, 67 flumequine 68 and sulfamethazine, 28 and β-blockers such as atenolol, 69 propranolol 70,71 and metoprolol. 27All these compounds have been detected in the aquatic environment because of their inefficient removal   11) dark box. 22In plot (b), (1) RuO 2 /Ti anode, (2) ACF cathode, (3) UVA lamp, (4) O 2 in pipe, (5) magnetic stirrer and (6) dark box. 23n wastewater treatment plants and can induce adverse health problems on living beings since they can develop multi-resistant strains of microorganisms, can affect the endocrine systems of fishes and invertebrates and can be toxic on algae and small invertebrates.4 Table 3 summarizes the time needed for the total disappearance of pharmaceuticals (t TD ) and the percentage of TOC removal at the end of comparative EF and PEF treatments of relevant drug solutions in 0.05 mol L -1 Na 2 SO 4 at pH 3.0.Experiments were performed with stirred tank reactors like of Figure 1a containing a Pt or BDD anode and a gas (O 2 or air) diffusion electrode (GDE) as cathode, applying a 6 W UVA lamp for PEF.Trials with two pairs of electrodes, also using a CF cathode to enhance the Fe 2+ regeneration in the system from Fe 3+ reduction by reaction 23, were checked for the β-blockers.[69][70][71] Data of Table 3 corroborate the higher oxidation ability of the PEF method compared to EF for all pharmaceuticals tested, since greater percentages of TOC abatement (> 95% related to almost total mineralization) were always obtained for the former process under comparable conditions.A greater mineralization degree was usually attained by using a BDD anode instead of Pt, as expected for the higher oxidation power of generated BDD( • OH).The drugs followed pseudo-first-order decays and in most cases, Table 3 evidences practically the same t TD values for both EF and PEF degradations, regardless of the anode (Pt or BDD) used.This is indicative again of the pre-eminent reaction of aromatics with • OH formed from Fenton's reaction 6, but with poor production of this radical from photo-Fenton reaction 30.The greater TOC removal achieved in PEF is then due to the synergistic action of UVA light that is able to photolyze intermediates like Fe(III)-carboxylate complexes.In these works, it was also found that increasing current led to quicker mineralization due to the generation of more oxidizing species (Pt( • OH) or BDD( • OH) and • OH), but with the concomitant loss of MCE owe to the higher rates attained for the waste reactions 26-29.In contrast, the presence of more organic matter enhanced the current efficiency, although longer time was required for a given TOC decay.Besides, it was confirmed that optimum degradation processes were obtained with 0.5-1.0 ml L -1 Fe 2+ and at pH 3.0.
Based on previous studies made with nitrobenzene (see subsection 4.1), the effect of Cu 2+ as a co-catalyst in the EF and PEF treatments of paracetamol was investigated with a Pt/O 2 (or Pt/GDE) cell. 62Results of Table 3 show that the oxidation ability of the EF system with 1 mmol L -1 Fe 2+ and 1 mmol L -1 Cu 2+ was greater than with 1 mmol L -1 Fe 2+ alone.The lower mineralization found using 1 mmol L -1 Fe 2+ was ascribed to the formation of stable Fe(III)-oxalate and Fe(III)-oxamate complexes, which cannot be attacked neither by Pt( • OH) nor by • OH formed from Fenton's reaction 6.In contrast, when Cu 2+ is added, the competitively Cu(II) complexes formed can be oxidized by • OH.When analogous PEF treatments were applied, the mineralization rate was accelerated by the photodecarboxylation of Fe(III) complexes.This behavior can be deduced from Figure 11, where the evolution of both acids is depicted.Their scarce accumulation using 1 mmol L -1 Cu 2+ and 1 mmol L -1 Cu 2+ + 6 W UVA light agrees with the small mineralization of paracetamol by means of • OH generated from reactions 39-41.The initial N was mainly transformed into NH 4 + ion during all treatments.From the intermediates detected by GC-MS and HPLC, it was concluded that the initial hydroxylation of paracetamol produces hydroquinone releasing acetamide, which is converted into oxamic acid.The opening of the benzenic ring of p-benzoquinone coming from hydroquinone degradation leads to ketomalonic, maleic and fumaric acids, which are further oxidized to oxalic acid.Figure 12 presents the proposed reaction pathway.The removal of oxalic and oxamic acids followed the pathways suggested in Figures 8c and 8d, respectively.
0][71] Thus, shorter disappearance times and higher percentages of TOC removal for atenolol and propranolol were attained for the combined Pt/GDE-Pt/carbon felt and BDD/GDE-Pt/carbon felt cells rather than for the single Pt/GDE and BDD/GDE ones in EF (see Table 3).Both drugs obeyed a pseudo first-order kinetics with a rate at least 2.5 times higher in combined than in single cells.However, the fast destruction of Fe(III) complexes by UVA light in the analogous PEF processes led to similar mineralization degree for combined and single cells when the most potent BDD anode was utilized.This corroborates again the powerful synergistic influence of UVA irradiation in the latter method, which is even more potent to mineralize organic matter than the acceleration of Fenton's reaction 6 by increasing the rate of Fe 2+ regeneration at the cathode.
On the other hand, Wang et al. 23 utilized the cell of Figure 10b equipped with a Ti/RuO 2 anode and an ACF cathode to treat 125 mL of an O 2 -saturated solution of 200 mg L -1 of the antibiotic sulfamethoxazole with 0.05 mol L -1 Na 2 SO 4 and 1 mmol L -1 Fe 2+ at pH 3.0 and 360 mA.After 360 min, TOC was reduced by 63 and 80% in EF and PEF with an 11 W UVA lamp, respectively (see Table 3).Nevertheless, the same time (75 min) was needed to remove the drug in both cases, indicating that the 158 mg L -1 with 0.5 mmol L -1 Fe 2+ , 35 ºC, at 50 mA for two-electrode cells and 50-12 mA for four-electrode cells during 360 min 100 mg L -1 drug with 1 mmol L -1 Fe 2+ at 100 mA and 35 ºC for 360 min 179 mg L -1 drug with 1 mmol L -1 Fe 2+ at 300 mA and 35 ºC for 240 min 158 mg L -1 drug with 0.5 mmol L -1 Fe 2+ at 100 mA and 35 ºC for 360 min 62 mg L -1 drug with 2 mmol L -1 Fe 2+ at 100 mA and 35 ºC for 360 min 41 mg L -1 drug (near saturation) with 0.5 mmol L -1 Fe 2+ at 100 mA and 35 ºC for 360 min 157 mg L -1 of drug at 35 ºC for 240 min.Catalyst: 154 mg L -1 propranolol hydrochloride with 0.5 mmol L -1 Fe 2+ , 35 ºC, at 120 mA for two-electrode cells and 120-12 mA for four-electrode cells during 420 min 164 mg L -1 drug with 0.5 mmol L -1 Fe 2+ at 100 mA and 35 ºC for 180 min 193 mg L -1 drug with 0.5 mmol L -1 Fe 2+ at 100 mA and 35 ºC for 360 min.200 mg L -1 of drug with 1 mmol L -  superiority of PEF is due to the synergistic effect of UVA light.HPLC-MS analysis allowed detecting six aromatic intermediates during sulfamethoxazole degradation by PEF process, formed from the hydroxylation of the aromatic and/or isoxazole ring, accompanied by the substitution of the amine group (on aromatic cycle) or methyl group (on isoxazole ring) by • OH.Oxalic, maleic, oxamic, formic and acetic acids were detected and the initial N was converted into NH 4 + .

Combination of PEF with Photocatalysis
The Khataee's group has proposed and presented relevant results on the coupling of PEF with heterogeneous photocatalysis (PC) for the decolorization of acidic dyestuff solutions.Two kinds of photocatalysts, TiO 2 18,19,[72][73][74] and ZnO, 16,75,76 were employed for these authors.8][79] TiO 2 nanoparticles as suspended powder or immobilized onto a substrate are the most used catalysts in this technique.When TiO 2 is illuminated with UV photons of λ < 380 nm, an electron from the filled valence band is promoted to the empty conduction band (e − cb ) with an energy gap of 3.2 eV, generating a positively charged vacancy or hole (h + vb ) by reaction 44.The holes thus produced at the TiO 2 surface can oxidize either water or OH − giving • OH from reactions 45 and 46, respectively, which can subsequently attack the organic species. 79O The major loss of efficiency in PC is due to the recombination of electrons promoted to the conduction band either with unreacted holes by reaction 47 or with adsorbed • OH by reaction 48: Similar reactions are proposed when ZnO is used as catalyst in PC. 16 Figure 13a shows a sketch of the stirred tank reactor used by Zarei et al. 72 for the decolorization of 2 L of a  20 mg L -1 Basic Red 46 solution in 0.05 mol L -1 Na 2 SO 4 with 0.1 mmol L -1 Fe 3+ at pH 3.0.The CNT-PTFE cathode was fed with O 2 to generate H 2 O 2 from reaction 1 and the inner walls of the cell were covered with TiO 2 nanoparticles immobilized onto glass plates.Figure 13b illustrates that the direct PC during 90 min only promoted 19% color removal at λ max = 530 nm of the dye.In contrast, when EF at 100 mA was applied, the decolorization efficiency rose to 45%, meaning that more amounts of • OH are formed from Fenton's reaction 6 compared to those produced by reactions 45 and 46 in PC.The analogous PEF process with a 6 W UVC light enhanced strongly the decolorization rate to 88% color removal due to the additional generation of • OH from the photolysis of H 2 O 2 via reaction 33.The most potent method was then the combined PEF-PC where 94% decolorization efficiency was attained as a result of the sum of the amounts of • OH generated by reactions 6, 33, 45 and 46.For this method, the authors showed that the optimum pH was 3.0 within the pH range 2.0-6.0 and that the decolorization efficiency increased with increasing the applied current from 50 to 500 mA and decreasing the dye content from 20 to 5 mg L -1 .Besides, a strong decay in color removal was observed by applying a 6 W UVB light in PEF-PC because of the inhibition of reaction 33 to produce • OH that took place when the 6 W UVC lamp was employed.
The optimum conditions for the PEF-PC treatment of dyes such as Acid Red 17 73 and Basic Red 46 74 using the same cell of Figure 13a were determined by means of response surface methodology (RSM).In the case of Acid Red 17, for example, 15 mg L -1 dye, 0.2 mmol L -1 Fe 3+ , applied current of 100 mA and reaction time of 36 min were found optimal to obtain its quickest almost total decolorization.A further study on a mixture of Acid Yellow 36, Acid Red 14 and Basic Yellow 28 18 treated with a modified cell containing a CNT/graphite cathode fed with air injected to the solution at 2.5 L min -1 allowed concluding that RSM was able to optimize the experimental values of PEF-PC for the decolorization of each dye.For Acid Yellow 36 degraded alone in the above system, 19 this methodology gave 25 mg L -1 dye concentration, 0.15 mmol L -1 Fe 3+ , applied current of 115.62 mA and reaction time of 127 min as optimum experimental parameters to achieve the maximum decolorization of 84%.
The cell of Figure 13a was also utilized to examine the performance of the decolorization process of Basic Yellow 28 75 and Direct Yellow 12 76 using ZnO nanoparticles immobilized onto glass plates.For 2 L of 20 and 50 mg L -1 dye solutions, respectively, in 0.05 mol L -1 Na 2 SO 4 with 0.1 mmol L -1 Fe 3+ at pH 3.0 and 100 mA, the oxidation ability of processes increased in the sequence PC < EF < PEF < PEF-PC, i.e., the same order as found using TiO 2 nanoparticles.After 90 min of the PEF-PC degradation, 97 and 90% color removal for Basic Yellow 28 and Direct Yellow 12, respectively, was obtained.GC-MS analysis of the treated solutions of the former dye allowed the identification of 1,2,3,3-tetramethylindoline, 4-methoxybenzenamine, hydroquinone and maleic, propionic and glyoxylic acids like intermediates.On the other hand, it was demonstrated that RSM was able to predict the decolorization of the diazo dye Direct Yellow 12 by PEF-PC with ZnO nanoparticles immobilized onto glass plates. 16The result of optimization showed the maximum decolorization efficiency at the optimal condition of 50 mg L -1 dye concentration, 0.2 mmol L -1 Fe 3+ , applied current of 400 mA and reaction time of 70 min.By prolonging the process for 360 min, an almost complete mineralization (97% TOC reduction) was achieved.All these findings indicate that both photocatalysts, immobilized TiO 2 and ZnO  72 nanoparticles, are useful in the PEF-PC treatment of dyestuff solutions, not only for decolorization but also for upgrading the mineralization of organics.

SPEF Treatment of Organic Pollutants
The SPEF process was recently proposed by our group to avoid the excessive energetic cost of the UVA lamp utilized in the PEF method, making a less expensive and more viable EAOP.The assays with SPEF have been made at two levels, with stirred tank reactors and further, with recirculation pre-pilot plants as a first step for its possible application at industrial scale.
The degradation of the drugs ibuprofen, 63 salicylic acid 64 and enrofloxacin 67 , as well as the azo dye Sunset Yellow FCF, 80 was comparatively studied by SPEF and other EAOPs (see Table 3) using a stirred tank reactor like of Figure 1a equipped with a Pt or BDD anode and a GDE cathode, all with 3 cm 2 area.In SPEF, the solution was submitted to solar irradiation with an average UV intensity of about 30-32 W m -2 and a mirror was placed at the bottom of the cell to better collect the solar energy.Figure 14a exemplifies the TOC abatement with electrolysis time for the comparative EF, PEF and SPEF treatments of 100 mL of 41 mg L -1 ibuprofen in 0.05 mol L -1 Na 2 SO 4 with 0.5 mmol L -1 Fe 2+ at pH 3.0, 33.3 mA cm -2 and 25.0 ºC.As expected, each process was enhanced using a BDD anode instead of Pt due to the greater oxidizing power of BDD( • OH) than Pt( • OH) to remove the contaminants.A quicker degradation process can be observed when UV light was applied, reaching more rapidly an almost total mineralization in SPEF by the higher intensity of UV radiation from sunlight.Similar results were found for the other organics tested, showing that SPEF with BDD is always the best EAOP yielding quicker mineralization.In all cases, pH 3.0 was found optimal for the EF, PEF and SPEF treatments, near the optimum pH of 2.8 for Fenton's reaction 6, as expected if • OH is the main oxidant of organic pollutants.Besides, higher amounts of TOC were removed with increasing current density and substrate concentration.
GC-MS, reversed-phase HPLC and/or LC-MS analysis of treated solutions revealed the formation of aromatic intermediates like 4-ethylbenzaldehyde, 4-isobutylacetophenone, 4-isobutylphenol and 1-(1-hydroxyethyl)-4-isobutylbenzene for ibuprofen, 2,3-, 2,5-and 2,6-dihydroxybenzoic acids for salicylic acid, polyols, ketones and N-derivatives for enrofloxacin and 14 aromatic products and 34 hydroxylated derivatives, including benzenic, naphthalenic and phthalic acid compounds, for Sunset Yellow FCF.Ion-exclusion HPLC allowed the identification and quantification of different generated carboxylic acids, oxalic acid being the ultimate by-product accumulated in larger extent.Figure 14b illustrates the stability of the Fe(III)-oxalate complexes in EF, which were quickly removed in PEF and much more rapidly in SPEF by their fast photolysis from reaction 32.This behavior accounts for by the greatest mineralization degree attained in SPEF.Inorganic ions released from the mineralization of heteroatoms in SPEF were identified by ion chromatography.The initial F of enrofloxacin The inset panel presents the kinetic analysis assuming a pseudo-first-order reaction for the drug. 63as totally transformed into F − ion and its initial N was primordially transformed into NH 4 + ion and in smaller proportion into NO 3 − ion.In contrast, the major part of the initial N (73-79%) of the azo dye Sunset Yellow FCF was released from the solution, probably as N 2 and N x O y species, suggesting a complex destruction of N-derivatives formed.
Figure 14c shows a similar rate for the decay of ibuprofen concentration in EF and PEF, in agreement with a pseudo-first-order reaction (see the inset panel), yielding a k 1 value of about 2.1 × 10 -3 s -1 .A strong enhancement of the ibuprofen decay can be observed for the SPEF treatment, as expected if much more • OH is produced from the action of the photo-Fenton reaction 30 as a result of the higher UV intensity of sunlight.This can also explain the higher oxidation ability of SPEF because primary products can be more rapidly destroyed leading intermediates that can be more quickly photolyzed by sunlight.
2][83][84] Figure 15 shows a sketch of the flow plant and the cell used for these trials. 37he electrodes with 20 cm 2 area were separated about 1.2 cm.The solar photoreactor was a polycarbonate box of 600 mL of irradiated volume, built-up with a mirror at the bottom and tilted 30° from the horizontal.The study of the SPEF process was lately extended to a 10 L pre-pilot plant, schematized in Figure 16a. 85This plant had the same components as those shown in Figure 15a, but with a reactor of 90.3 cm 2 electrode area coupled to a 1.57L compound parabolic collectors (CPCs) as the solar photoreactor.Solutions with 50-300 mg L -1 of TOC in 0.05-0.10mol L -1 Na 2 SO 4 with 0.5 mmol L -1 Fe 2+ at pH 3.0, 50-100 mA cm -2 and liquid flow rate of 180-200 L h -1 were usually tested in both systems.The high TOC removals with excellent MCE values, along with the corresponding EC TOC values, determined for selected SPEF assays of several organic pollutants are collected in Table 4.
Similarly to found in the stirred tank reactor, SPEF was found much more potent to mineralize organics than EF in the 2.5 L pre-pilot plant.As can be seen in Table 4, several organics like the pesticide mecoprop were hardly removed in this system, since 95% TOC reduction was reached after 540 min of SPEF treatment of 100-637 mg L -1 of this compound at 50 mA cm -2 . 36However, much faster degradation was found for the SPEF process of o-, m-and  p-cresol, which attained 95-98% mineralization in only 180 min. 37Analogous almost total mineralization was also easily achieved for the dyes Acid Yellow 36, 39 Acid Red 88, 40 Acid Yellow 9, 40 Disperse Red 1 81 and Disperse Red 3 81 and for the pharmaceuticals enrofloxacin 67 and sulfanilamide. 84For all these compounds, the MCE values increased at lower current density and higher contaminant concentration.For example, a maximum efficiency of 480% was obtained for the treatment of 1024 mg L -1 of o-cresol at 50 mA cm -2 , which was reduced to 140% for 128 mg L -1 .The very high MCE value found for this product evidences the great synergistic power of sunlight in SPEF.The same trend was obtained for EC TOC .While this parameter was as high as 0.259 kWh g -1 TOC after 240 min of EF degradation of 100 mg L -1 TOC of Disperse Red 1 at 50 mA cm -2 , it was reduced to 0.151 kWh g -1 TOC (EC = 14.2 kWh m -3 ) for the comparative SPEF with 97% mineralization and 82% current efficiency. 81This corroborates that the SPEF method is much more economic than the EF one.
RSM was applied to optimize the SPEF process of sulfanilic acid. 82For 240 mg L -1 of this acid in 0.05 mol L -1 Na 2 SO 4 with a Pt/air-diffusion cell, optimum variables of 100 mA cm -2 , 0.5 mmol L -1 Fe 2+ and pH 4.0 were determined after 120 min of treatment, giving rise to 76% mineralization with 0.275 kWh g -1 TOC of EC and 52% current efficiency (see Table 4).The performance of SPEF was enhanced from the combined use of Fe 2+ and Cu 2+ as co-catalysts for Disperse Blue 3 degradation in 0.10 mol L -1 Na 2 SO 4 with a BDD/airdiffusion cell in the 2.5 L flow plant. 83The best conditions were found for 0.5 mmol L -1 Fe 2+ + 0.1 mmol L -1 Cu 2+ .Figures 17a and 17b illustrate that this co-catalyst led to > 95% TOC abatement in the presence and absence of 200 mg L -1 dye with EC TOC < 0.080 kWh g -1 TOC, more rapidly and less expensive than using 0.5 mmol L -1 Fe 2+ alone.This confirms the attack of • OH on Cu(II) complexes of generated carboxylic acids like oxalic and oxamic (see Figures 8c and 8d), competitively formed with Fe(III)-carboxylate ones.
All the organic pollutants tested in the 2.5 L pre-pilot plant decayed at similar rate in EF and SPEF obeying a pseudo-first-order kinetics and their k 1 value increased with rising current density and decreasing pollutant concentrations.Aromatic intermediates were detected in several cases, like 2-methyl-p-benzoquinone for o-and m-cresol, 5-methyl-2-hydroxy-p-benzoquinone for p-cresol, 2-methylhydroquinone, 2-methylp-benzoquinone and 4-chloro-o-cresol for mecoprop and up to 15 anthraquinonic and phthalic acid derivatives for DB3.
Analysis of final carboxylic acids confirmed the quick removal of oxalic acid by photolysis of its Fe(III) complexes, but the formation of other more recalcitrant acids like acetic and oxamic slowed the mineralization process. 36,39,40,81,82,84Cl − ion was loss in mecoprop degradation, 36  − ions were loss in the mineralization of dyes, 39,40,81 sulfanilic acid 82 and sulfanilamide. 84he research in the 10 L pre-pilot plant was mainly focused on the optimization of the treatment of the herbicide MCPA 86 and the drug paracetamol 87 by RSM.A Pt/air-diffusion cell was chosen for these trials since less energy cost than using a BDD anode was required, because of its lower E cell .For example, optimum variables of 5 A, 0.4 mmol L -1 Fe 2+ and pH 3.0 were found for 157 mg L -1 paracetamol with 0.05 mol L -1 Na 2 SO 4 , leading to 75% TOC removal, 0.093 kWh g -1 TOC energy consumption (EC = 7.2 kWh m -3 ) and 71% current efficiency at 120 min (see Table 4).HPLC analysis of electrolyzed solutions allowed detecting hydroquinone, p-benzoquinone, 1,2,4-trihydroxybenzene, 2,5-dihydroxyp-benzoquinone and tetrahydroxy-p-benzoquinone as aromatic intermediates, which were removed by • OH in the bulk, whereas maleic, fumaric, succinic, lactic, formic, oxalic and oxamic acids were identified as carboxylic acids, which form Fe(III) complexes that are photolyzed under sunlight radiation.Recently, the SPEF treatment of 297 mg L -1 of the azo dye Sunset Yellow FCF in 0.05 mol L -1 Na 2 SO 4 and 0.5 mmol L -1 Fe 2+ at pH 3.0 using the same system at 7 A demonstrated that total decolorization was feasible at 120 min and that about 94% mineralization with 0.197 kWh g -1 TOC energy consumption (EC = 16.6 kWh m -3 ) was attained at 150 min. 80ollowing their research in stirred tank reactors with two or four electrodes (see subsection 4.4.),Isarain-Chávez et al. 85 extended the study to the SPEF degradation of 10 L of 100 mg L -1 TOC of solutions with the β-blockers atenolol, metoprolol tartrate and propranolol hydrochloride in 0.10 mol L -1 Na 2 SO 4 with 0.5 mmol L -1 Fe 2+ at pH 3.0 using single Pt/ADE and BDD/ADE cells and their combination with a Pt/CF cell to enhance Fe 2+ regeneration from Fe 3+ reduction.Figure 16b shows a sketch of the combined BDD/ADE-Pt/CF cell used.Figure 18a exemplifies the superiority of combined cells over single ones, BDD over Pt and SPEF over EF regarding the TOC abatement of a 0.246 mmol L -1 metoprolol tartrate solution.This can be accounted for by the greater production of • OH from Fenton's reaction 6 in the combined cells, the higher oxidizing power of BDD( • OH) and the photolytic action of sunlight in SPEF, as can be deduced from the pseudo-first-order decay kinetics shown in Figure 18b for Cu 2+ , () 0.5 mmol L -1 Fe 2+ and 200 mg L -1 Disperse Blue 3 (DB3) and () 0.5 mmol L -1 Fe 2+ + 0.1 mmol L -1 Cu 2+ and 200 mg L -1 DB3. 83he different cells checked.Nevertheless, the combined Pt/ADE-Pt/CF cell allowed the lowest EC TOC of 0.080 kWh g -1 TOC for 88-93% mineralization, thereby being the most viable system for industrial application.

Conclusions
The recent development of PEF and SPEF processes has confirmed their viability to remove toxic and refractory aromatic pollutants such as industrial chemicals, pesticides, dyes and pharmaceuticals from acidic wastewaters.High mineralization with good current efficiency is usually found for these EAOPs.They are simple, safe and environmentally friendly technologies that can be easily scaled-up to industrial level using recirculation flow plants.The current electrochemical technology permits the use of very stable anodes like BDD and several carbonaceous cathodes for an efficient H 2 O 2 generation.However, the main drawback for industrial application is the electrical cost that is spent for running the electrochemical cell since the energy cost required for the UV lamp in PEF can be avoided when sunlight is used in SPEF.The possible coupling of photovoltaic systems to provide inexpensive electrical energy to the electrochemical reactor could be an excellent alternative way that may be tested in the next future to solve this problem.The coupling of the reactor with efficient solar CPCs photoreactors is another interesting possibility for enhancing the degradation process.It has then been shown that the SPEF treatment of organic pollutants with a BDD anode is more efficient and less expensive than other EAOPs like AO, EF and PEF operating under comparable conditions.The coupling with PC can also enhance the oxidation ability of the method, as recently demonstrated for the PEF process by the Khataee's group.In PEF and SPEF, the mineralization rate was slowed as applied current falls, but with greater MCE and lower energy consumption.This trend was also found when pollutant concentration increased since parasitic reactions of oxidant • OH are inhibited due to its quicker reaction with higher amounts of organics.The decay kinetics of contaminants usually obeyed a pseudo-first-order reaction.Aromatic intermediates were oxidized by generated • OH giving short-linear carboxylic acids that form Fe(III) complexes, most of which are much more rapidly photolyzed by the more potent UV radiation supplied by sunlight in SPEF than by typical artificial lamps in PEF.Heteroatoms present in organics are also mineralized and released as inorganic ions such as F − , Cl − , SO 4 2− , NH 4 + and NO 3 − .

Figure 1 .
Figure 1.(a) Sketch of the bench-scaled open and stirred undivided tank reactor used for the PEF treatment with a carbon-PTFE diffusion cathode directly fed with pure O 2 to generate H 2 O 2 (adapted from reference 15). 24(b) Evolution of the concentration of hydrogen peroxide accumulated during the electrolysis of 100 mL of 0.05 mol L -1 Na 2 SO 4 solutions at pH 3.0 at 25 ºC in a Pt/O 2 diffusion cell.(a, b and e) Without Fe 2+ , (c and d) with 1.0 mmol L -1 Fe 2+ and (d) under a 6 W UVA irradiation.Applied current: (a) 450 mA, (b, c and d) 300 mA and (e) 100 mA.24

Figure 5 .
Figure 5. Evolution of the concentration of selected intermediates detected during the degradation of 4-CPA solutions under the conditions of Figure 4 by () AO-H 2 O 2 , () EF and () PEF.Plots correspond to: (a) 4-chlorophenol, (b) glycolic acid, (c) oxalic acid and (d) chloride ion (adapted from reference 49).

Figure 6 .
Figure 6.Reaction sequence for 4-CPA degradation by EAOPs in a Pt/O 2 tank reactor (adapted from reference 49).

Figure 7 .
Figure 7. Effect of applied current on (a) TOC abatement and (b) mineralization current efficiency with consumed specific charge for the degradation of 100 mL of a 30 mg L -1 atrazine solution in 0.05 mol L -1 Na 2 SO 4 at pH 3.0 at 35 ºC by (,,) AO-H 2 O 2 and (, , ) PEF with a BDD/O 2 cell.Current: (, ) 100 mA, (, ) 300 mA and (, ) 450 mA.(c) Proposed reaction sequence for the degradation of atrazine to cyanuric acid by EAOPs with a BDD anode.54

Figure 9 .
Figure 9. TOC abatement vs electrolysis time for 100 mL of a 200 mg L -1 Direct Yellow 4 solution in 0.05 mol L -1 Na 2 SO 4 with 0.5 mmol L -1 Fe 2+ at pH 3.0, 33.3 mA cm -2 and 35 ºC using a BDD/air-diffusion cell.In plot (a), () 6 W UVA irradiation, () EF and () PEF with 6 W UVA light.()EF process up to 60 min, whereupon the resulting solution remained without any treatment.In plot (b), () EF process and photo-assisted EF degradation where only UVA irradiation was applied to the solution after: () 30 min, () 60 min and () 120 min of electrolysis.59

a
Experiments carried out with 100 mL solution in 0.05 mol L -1 Na 2 SO 4 at pH 3.0 in a stirred tank reactor and with a 6 W UVA light for PEF.b Treatment of 125 mL of an O 2 -saturated solution in 0.05 mol L -1 Na 2 SO 4 at pH 3.0 in a stirred tank reactor with a 8 W UVA light.

Figure 12 .
Figure 12.Proposed reaction sequence for paracetamol degradation in acidic aqueous medium by EAOPs based on Fenton's reaction chemistry using a Pt/O 2 cell (adapted from reference 62).

Figure 13 .
Figure 13.(a) Sketch of the stirred cubic tank reactor used for the combined PEF-PC treatment of dyes.(b) Percentage of color removal with time for 2 L of a 20 mg L -1 Basic Red 46 solution in 0.05 mol L -1 Na 2 SO 4 with 0.1 mmol L -1 Fe 3+ at pH 3.0 and 25 ºC.In the center of the cell, a 11.5 cm 2 Pt anode, a 11.5 cm 2 CNT-PTFE O 2 -diffusion cathode and a 6 W UVC lamp were placed, surrounded by the TiO 2 nanoparticles immobilized onto glass plates covering its four inner walls.Applied current 100 mA.Method: () TiO 2 /UV photocatalysis (PC), () EF, () PEF and () PEF-PC.72

Figure 14 .
Figure14.(a) TOC decay and (b) evolution of generated oxalic acid for the degradation of 100 mL of 41 mg L -1 ibuprofen (near saturation) with 0.05 mol L -1 Na 2 SO 4 and 0.5 mmol L -1 Fe 2+ at pH 3.0, 33.3 mA cm -2 and 25.0 ºC using stirred tank reactors with 3 cm 2 electrode area and an O 2 -diffusion cathode.() EF with Pt, () EF with a BDD anode, () PEF with Pt under 6 W UVA light, () PEF with BDD under 6 W UVA irradiation, () SPEF with Pt and () SPEF with BDD.(c) Decay of ibuprofen concentration.The inset panel presents the kinetic analysis assuming a pseudo-first-order reaction for the drug.63

Table 1 .
31solute second-order rate constant for the main general reactions involved in a Fenton system at pH close to 331 7

Table 3 .
Time needed for the total disappearance of pharmaceuticals (t TD ) and percentage of TOC removal for drug solutions treated by EF and PEF processes using two-electrode or four-electrode cells with Pt, BDD or Ti/RuO 2 anode and CF, ACF or gas (O 2 or air) diffusion electrode (GDE) cathode under selected conditions

Table 4 .
Percentage of TOC removal, mineralization current efficiency and energy consumption per unit TOC mass determined for the degradation of several organic pollutants solutions by the SPEF process using a recirculation pre-pilot plant coupled to a solar photoreactor submitted to an average UV irradiation of about 30 W m -2 under selected conditions