Exposisicon Martes-13 - Marc Pera-AOPs

Applied Catalysis B: Environmental 47 (2004) 219256
Degradation of chlorophenols by means of advanced oxidation processes: a general review

Marc Pera-Titus a , Vernica Garc a-Molina a , Miguel A. Baos b,1 , a Jaime Gimnez , Santiago Esplugas a,
a
Department of Chemical Engineering and Metallurgy, Faculty of Chemistry, University of Barcelona, Mart i Franqus 1, 08028 Barcelona, Spain b Department of Physical Chemistry, Faculty of Chemistry, University of Barcelona, Mart i Franqus 1, 08028 Barcelona, Spain Received 20 April 2003; received in revised form 25 July 2003; accepted 9 September 2003
Abstract Advanced oxidation processes (AOPs) constitute a promising technology for the treatment of wastewaters containing non-easily removable organic compounds. Chlorophenols (CPs) are a group of special interest due to their high toxicity and low biodegradability. Data concerning the degradation of CPs by means of AOPs reported during the period 19952002 are evaluated in this work. Among the AOPs, the following techniques are studied: processes based on hydrogen peroxide (H2 O2 + UV, Fenton, photo-Fenton and Fenton-like processes), photolysis, photocatalysis and processes based on ozone (O3 , O3 + UV and O3 + catalyst). Half-life times and kinetic constants for CP degradation are reviewed and the different mechanistic degradation pathways are taken into account. 2003 Elsevier B.V. All rights reserved.
Keywords: Chlorophenol; AOP; Photolysis; Fenton; Photo-Fenton; Ozone; Photocatalysis; Radiation; Pathway; Half-life time; Kinetic constant
1. Introduction In the beginning of the 21st century, the mankind has to face the problem of water as an important threat. According to WHO [135], the shortage or even lack of water affects more than 40% of the world population due to political, economical and climatological reasons. Besides, more than 25% of the world population suffers from health and hygienic problems related to water. Despite the plans carried out by UNO in recent years, 1100 million people have still no access to improved water supply and sanitation, especially concentrated in underdeveloped countries of Africa, Asia and Latin America [248]. On the other hand, the domestic use and industrial activity, of especially impact among the developed countries, generate high amounts of residual wastewater, whose direct disposal to natural channels causes a considerable effect in the environment. This fact, together with the need to restore this water for new uses, makes practically essential the
purication of wastewater to achieve the desired degree of quality. Because of an increasing social and political concern on environment, the research eld of water purication has been extensively growing in the last decades, comprising both polluted wastewaters and groundwaters from seas, rivers and lakes, as water quality control and regulations against hazardous pollutants have become stricter in many countries. More recently, reecting a new environmental conscience, the European Directive 2000/60/CE [60] stresses the need to adopt measures against water pollution in order to achieve a progressive reduction of pollutants. On this way, chlorophenols2 (CPs) constitute a particular group of priority toxic pollutants listed by the US EPA in the Clean Water Act [67,102,131] and by the European Decision 2455/2001/EC [57], because most of them are toxic and hardly biodegradable, and are difcult to remove from the environmentthe half-life in water can reach 3.5 months in aerobic waters for PCP and some years in organic sediments
2 As generally submitted in the literature, the general nomenclature used for CPs is the following one: monochlorophenol (MCP), dichlorophenol (DCP), trichlorophenol (TCP), tetrachlorophenol (TTCP) and pentachlorophenol (PCP).
Corresponding author. Tel.: +34-93-4021288; fax: +34-93-4021291. E-mail address: esplugas@angel.qui.ub.es (S. Esplugas). 1 Tel.: +34-93-4021220; fax: +34-93-4021231.
0926-3373/$ see front matter 2003 Elsevier B.V. All rights reserved. doi:10.1016/j.apcatb.2003.09.010
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M. Pera-Titus et al. / Applied Catalysis B: Environmental 47 (2004) 219256
[1]. Because of their numerous origins, they can be found in ground waters, wastewaters and soils [244] and even in the trophic chain of places with very low pollution levels [193,247]. As pointed out in Table 1, they might produce disagreeable taste and odor to drinking water at concentrations below 0.1 g l1 [238] and adverse effects on the environment [79]. All CPs possess bactericidal activities, phytotoxicity and ability to bioaccumulate in organisms that increase with increasing the chlorination and substitution away from the ortho-(2-) position (see Table 1). The higher toxicity of the more chlorinated CPs may be ascribed to an increase in lypophility which leads to a greater potential for uptake into the organism. The ortho-substituted congeners are generally of lower toxicity than the meta- and para-ones, because ortho-substituted chlorine seems to shield OH group, which apparently interacts with the active site in aquatic organisms [92]. On the other hand, toxicity also depends on the extent to which CP molecules are dissociated, with an increasing toxicity when the pH decreases, because the more toxic non-dissociated forms predominate at lower pH. The presence of CPs has been detected in both surface and ground waters [114]. Toxic reference values of 43.8, 36.5 and 13.0 g l1 are, respectively, suggested for 2-MCP, 2,4-DCP and PCP in surface waters, and maximum average values should not exceed 2.020, 4.380 and 0.055 mg l1 [68,125]. The limiting permissible concentration of CPs in drinking water should not exceed 10 g l1 [220].
CPs are introduced into the environment as a result of several man-made activities. Because of their broad-spectrum antimicrobial properties, CPs have been used as preservative agents for wood, paints, vegetable bers and leather and as disinfectants. In addition, they have been widely employed in many industrial processes as synthesis intermediates or as raw materials in the manufacturing of herbicides, fungicides, pesticides, insecticides, pharmaceuticals and dyes. CPs may be also generated as by-products during waste incineration, the bleaching of pulp with chlorine, and in the dechlorination of drinking water [259]. According to [235], the world market for CPs is fairly stable and is ca. 100 kt per year. The production of heavy and light CPs is ca. 2530 and 60 kt per year, respectively. M-, Dand TCPs which have no chlorine atoms in meta position relative to OH are industrially produced by direct chlorination of phenol with chlorine gas; CPs having at least one chlorine atom in the meta position must be produced by other types of reactions, such as hydrolysis, sulfonation, hydrodechlorination, hydroxylation, and alkylation; and TTCPs and PCP are produced batchwise by means of the chlorination of less chlorinated CPs in the presence of aluminum or iron trichloride. Emissions are mainly due to the manufacture, storage, transportation and application of CPs. The need to restore contaminated sites to avoid further risks to the environment has aroused in the last few years the development of effective methods for CP removal. The main goal is to achieve a complete mineralization to CO2
Table 1 Literature guidelines for CPs in drinking water [6971] and toxicity based on Daphnia magnaa [58] and Rat [70,235] CP congeners Guidelines (g l1 ) Daphnia magna 24 h-LC50 b (mg l1 ) Range 2-MCP 3-MCP 4-MCP 2,3-DCP 2,4-DCP 2,5-DCP 2,6-DCP 3,4-DCP 3,5-DCP 2,3,4-TCP 2,3,5-TCP 2,3,6-TCP 2,4,5-TCP 2,4,6-TCP 3,4,5-TCP 2,3,4,5-TTCP 2,3,4,6-TTCP 2,3,5,6-TTCP PCP 0.10 0.10 0.04 0.101.00 0.50 0.20 0.30 1.00 0.122.00 1.00 30.0 16.6019.30 13.8017.79 5.7910.34 4.096.30 2.482.89 8.6910.08 2.552.98 1.852.33 2.002.48 2.062.50 6.258.52 1.882.29 4.936.01 0.820.93 1.521.98 1.872.66 0.620.89 Mean 17.95 15.78 8.07 5.19 2.68 4.50 9.38 2.77 2.09 2.24 2.28 7.38 2.08 5.47 0.88 1.76 2.70 2.27 0.76 Rat 24 h-LC50 c (mg kg1 ) Oral 670 570 261 580 2940 820 2800 572 140 109 50 Subcutaneous 950 1030 1390 1730 1730 2260 210 100
a The Daphnia magna were all >72 h old. The water hardness was 200 mg l1 as CaCO , dissolved oxygen >2.27 mg l1 , pH 7.88.2 and temperature 3 20 C. b At this concentration of CP, 50% of Daphnia magna die after 24 h contact with pollutant. c Estimated oral 24 h-LD 1 50 for human beings is between 50 and 500 mg kg .
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and H2 O in addition to smaller amounts of some ions, e.g. chloride anions, or at least to produce less harmful intermediates. The conventional pollutant destructive technologies include biological, thermal and chemical treatments [124]. The former usually require a long residence time for microorganisms to degrade the pollutant, because they are affected by CP toxicity; thermal treatments present considerable emission of other hazardous compounds; and the latter, which include processes as occulation, precipitation, adsorption on granular activated carbon (GAC), air stripping or reverse osmosis (RO), require a post-treatment to remove the pollutant from the newly contaminated environment [54]. Alternative methods to these well-established techniques involve the oxidation of CPs with reagents such as air or oxygen in wet oxidation and supercritical wet oxidation [146,149,152], electrons in electrochemical oxidation [52,117,205], potassium permanganate, chlorine, hydrogen peroxide and ozone [42,256]. Among these techniques, the so-called advanced oxidation processes (AOPs) [86,89] appear to be a promising eld of study, which have been reported to be effective for the near ambient degradation of soluble organic contaminants from waters and soils, because they can provide an almost total degradation [6,25,26,39,40,86,95,111,112,147,171,179,181,195,235]. Even though these techniques can provide the conversion of contaminants to less harmful compounds, usually oxygenated organic products and low molecular acids [83,104,145], they are limited to treat waters which contain low concentrations of organic or inorganic scavenging material [88]. Experiences with different oxidation technologies and substrates have shown that a partial oxidation of toxic water may increase its biodegradability up to high levels [133,214]. Highly reactive hydroxyl radicals (HO ) are traditionally thought to be the active species responsible for the destruction of pollutants [34,86,87,97,195]. Thanks to its high standard reduction potential of 2.8 V vs. NHE3 in acidic media (see Table 2) [77,245], these radicals would be able to oxidize almost all organic compounds to carbon dioxide and water, except for some of the simplest organic compounds, such as acetic, maleic and oxalic acids, acetone or simple chloride derivatives as chloroform [28], which are of a very interesting kind because they are typical oxidation products of larger molecules after fragmentation and they take part in energetic cycles of most living organisms. They should be extremely unstable and continuously generated by chemical, photochemical or electrochemical reactions. Depending on the nature of organic species, two types of initial attack might be possible: it might abstract a hydrogen atom in the case of alkanes and alcohols, or it might attach itself to a molecule in the case of aromatic compounds, such as CPs. Even though AOPs for water and wastewater treatment show high efciencies, they actually work at high cost
Table 2 Standard reduction potentials of some oxidants in acidic media [120] Oxidant Fluorine (F2 ) Hydroxyl radical (HO ) Atomic oxygen Ozone (O3 ) Hydrogen peroxide (H2 O2 ) Potassium permanganate (KmnO4 ) Hypobromous acid (HbrO) Chlorine dioxide (ClO2 ) Hypochlorous acid (HClO) Chlorine (Cl2 ) Bromine (Br2 ) Standard reduction potential (V vs. NHE) 3.03 2.80 2.42 2.07 1.77 1.67 1.59 1.50 1.49 1.36 1.09
[190]. They only appear to be suitable for COD contents lower than 5 g l1 , since higher COD contents would require the consumption of too large amounts of reactantsin those cases, it would be more convenient to use wet oxidation or incineration [184]. Furthermore, the combination of an AOP as a preliminary treatment, followed by an inexpensive biological process, seems to be an interesting option from an economical point of view [129,169,213,254]. A scheme of this kind of processes is depicted in Fig. 1. This work is devoted to summarize the main aspects dealing with their degradation and mineralization of CPs by means of AOPs. It is specially focused on the collection of half-life times and kinetic constants for the processes considered, which appear in the literature in the period 19952002, and on the comparison between the different mechanistic pathways concerning CP degradation. Among the various AOPs proposed in the literature, which even include techniques based on ultrasound (Lin et al., 2000), plasma [231], or electrohydraulic discharge [249], the main ones taken into account in this work are based on the following ones [89,199]: (1) Photolysis (UV or VUV). (2) Hydrogen peroxide (H2 O2 ): H2 O2 + UV; Fenton: H2 O2 + Fe2+ /Fe3+ ; Fenton-like reagents: H2 O2 + Fe2+ -solid/Fe3+ -solid; photo-Fenton: H2 O2 + Fe2+ /Fe3+ + UV. (3) Ozone (O3 ): ozonation: O3 ; photo-ozonation: O3 + UV; ozonation + catalysis: O3 + H2 O2 and O3 + Fe2+ /Fe3+ . (4) Heterogeneous catalysis + UV and photocatalysis. Heterogeneous catalysts and photocatalysts reviewed: TiO2 + CdS + combinations.
Normal standard hydrogen electrode.
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Fig. 1. Scheme of a process which combines an AOP with a biological process for wastewater treatment [190].
2. Analytical topics Different analytical methods based on particular analytical techniques have been proposed for qualitative and quantitative analysis of CPs and reagents concerning their degradation. These methods usually involve aeration or desaeration, extraction of the aqueous sample with an organic solvent and ltration in case a heterogeneous catalyst or solid reactant is employed. The most popular techniques for qualitative and quantitative analysis of CPs and the organic and inorganic species involved in their degradation by AOPs are summarized in Table 3.
3. Reactor and lamp conguration 3.1. Reactor conguration for direct photolysis and AOPs based on hydrogen peroxide As reported in most of the papers reviewed [21,22,143, 166,220,257], completely mixed batch cylindrical glass vessels constitute the most popular reactor conguration for the studies of degradation of CPs for Fenton studies. Other batch congurations concern erlenmeyers or cylindrical glass asks [17,119,161,208] (Lu et al., 2002) or glass bottles [163]. As shown in Fig. 2a, a typical batch operation would consist in a chemical storage and dosing
modules (for H2 O2 , FeSO4 , acid, and lime/NaOH) and a reactor, provided with the required elements to allow the introduction of probes and reagents, and usually surrounded by a cooling jacket. The materials of construction for the reactor and holding tank are typically types 304 or 316 stainless steel, while those for the chemical storage systems may also be HDPE [242]. On the other hand, tubular congurations are usually employed for direct photolysis and photo-Fenton processes, and processes based on H2 O2 /UV reagent, in order to achieve a good interaction between CPs and other intermediates and radiation [17,220]. All experimental measures must be taken from treated stream, due to the concentration proles which appear inside the reactor. A scheme for the photo-Fenton process is shown in Fig. 2b. 3.2. Reactor conguration for AOPs based on ozone According to the literature, semi-batch stirred reactors glass bottles or cylindrical vesselsare typical reactor congurations for ozonation processes [1,2224,53,140,141]. On the other hand, bubble columns, wetted-sphere adsorbers, and other special designs have also been employed [55,100,186,233,239] to improve the contact between the gaseous ozone stream and the liquid and polluted stream. An ozone generator must be located near the reactor to supply continuously the ozone required for the reactionozone
Fig. 2. Flow chart for (a) the Fenton process and (b) the photo-Fenton process [17,22].
M. Pera-Titus et al. / Applied Catalysis B: Environmental 47 (2004) 219256 Table 3 Analytical techniques employed in degradation of CPs with AOPs Compound CPs and intermediates Analytical techniques GC GC/MS HPLC Ion chromatography Spectroscopy TOC analysis Ion selective electrode Colorimetry Potentiometric titration Capillary electrophoresis Ion chromatography Spectrophotometry Iodometry Photometry Colorimetry DPD method Spectrophotometry Iodometry DO meter Oxygen electrode Gas: Spectrophotometry Iodometry Colorimetry Electro-magnetically Dissolved Indigo method Titration method Iodometry Cationic chromatography pH-meter AAS XRD Actiometry Radiometry References
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[7,45,55,59,125,154,173,177,204,253,255,257] [44,103,119,124,143,239] [1,7,2123,43,46,61,93,100,105,106,124,156,172,188,210,233] [7] [220,255] (Hautaniemi, 1998) [1,17,24,46,61,93,105,124,139,163,166,203,230,260] (Chen and Chan, 1996) [100,140,166] [141] [45,260] [119] [1,105,139,174,233] [51,100,233] [22,166] [10] [119] Lu et al. (2002) [17,163,166,208] [119,257] (Lu et al., 2002) [43,143] [61,166] [99,100,233] [23,204] [24,170] [188] [11,12,23,44,55,100,188,233] Kuo (1999) [24] [17] [163] [59] [100,233,257] [59]
Cl
H2 O 2
Fe2+ /Fe3+ O2 O3
Cations pHa Metals TiO2 Light intensity

a
pH change during degradation processes are often monitored to ensure that they are progressing as planned.
cannot be stored due to the potential ammable character of ozoneoxygen mixtures. The gaseous ozone stream is usually introduced into the reactor through a porous glass-plate diffuser, where it dissolves, and the residual one in the outow stream must be removed. In addition, a lamp or several ones must be added in the contact system to allow matter interact with both ozone and radiation, a scheme which is shown in Fig. 3. Ozone can be generated from pre-treated air or oxygen by irradiating with UV or by means of an electrical discharge [65,235]. In both cases, high energy is required and the efciency of ozone generation is lowlower than 0.25 wt.% for the rst technique, with a top ow rate of 0.5 g/h [14]. The concentration in the ozonated gas is low, usually between 1 and 5 wt.%. The rst technique is the most ex-
tended for ozone generation in the most recent references [141,142,188]. 3.3. Reactor conguration for AOPs based on photocatalysis Some laboratory and pilot plant photo-reactor congurations have been proposed for photocatalysis. The most typical laboratory-scale congurations include vigorously stirred batch photochemical cells (see Fig. 4), cylindrical asks or vessels, glass dishes, and annular differential photo-reactors [46,61,85,99,106,124,125,139,172,191,203, 208,228,255]. On the other hand, pilot plant congurations may be based on a continuous rotating disk photo-catalytic reactor (RDPR)
224
Fig. 3. Flow chart for an ozonation process together with or without radiation [17,22].
[59], which are set up with a semicircular shape vessel with the water to be treated and the catalytic pellets are loaded on the surface of the rotating disk by using a UV resistant adhesive. Moreover, these congurations may also be based on several continuous compound parabolic collectors (CPC) at Plataforma Solar de Almeria (PSA), connected in series,
with a total reective surface of 9 m2 and 37 of inclination [93,106,203] and on cylindrical tanks (at reactor of PSA) with several tubes located at the bottom of the reactor, through which circulates an air-ow [84,165]. Fig. 4b and c shows the schemes of the two reactor congurations at PSA.
Fig. 4. (a) Scheme of a photocatalytic reactor (adapted from Chen et al. [46]). Schematic view of PSA detoxication loop (b) with CPCs modules and (c) with at reactor [84].
225
3.4. Lamp conguration: general topics Different sorts of lamps are employed for the generation of radiation supplied to CP samples for direct UV-photolysis and for techniques based on UV/H2 O2 , UV/O3, photo-Fentons reagents and photocatalysis. Among the various commercial radiation sources, high-, mediumand low-pressure mercury vapor lamp for the generation of UV radiation [17,21,22,166,257] and solar-simulated xenon lamps as a source of visible radiation [208,220] are widely employed. Among the different congurations, the lamp can be located in an axial position housed by a sleeve [21] or in its center in a vertical manner [257].
4. UV-photolysis Direct photolysis involves the interaction of light with moleculesin addition to waterto bring about their dissociation into fragments, with the following mechanistic pathways [34]: CP degradation CP + h Intermediates Intermediates + h CO2 + H2 O + Cl
of chlorine atoms in alkali medium at constant values of initial CP concentration, radiation intensity and temperature; the values of half-life times are between 1.1 and 30.6 min dealing with the results of Ben tez et al. [23]. The results seem to be conrmed by the series indicated in Fig. 5, where higher kinetic constants for less chlorinated CPs at alkaline pH can be observed. Otherwise, this trend seems not to be conrmed in acidic conditions, where the kinetic constant for 2,4,6-TCP degradation is higher than the one for 2,4-DCP. The trend mentioned for the degradation of CPs is also observed for the evolution of quantum yield respect to the chlorination of the aromatic ring of different CPs, as indicated in Fig. 6. On this way, as the chlorination of the aromatic ring increases, a lower amount of radiation intensity is employed in its degradation to less harmful compounds or to a complete mineralization. The quantum yield for these species also tends to increase with temperature and to be reduced with the pH, because of a lower interaction of dissociated species with the radiation instead of the non-dissociated ones. An equation obtained by Ben tez et al. [24], which can be applied for 2,4,6-TCP between 10 and 40 C is the following one: = 5.85 exp 1521 T (3)
(1) (2)
Earlier studies on direct UV-photolysis illustrated rapid degradation of pollutants, such as CPs, in dilute aqueous solutions [33,252], which were subsequently conrmed by further studies [19,90,123,128,147,219]. On the other hand, direct photolysis has been reported to lead primarily to inert non-chlorinated benzenoid compounds [261]. However, it appears to be less effective than other processes where radiation is combined with hydrogen peroxide or ozone, or where homogeneous, heterogeneous catalysis or photocatalysis are employed. As shown in Table 4, half-life times and pseudo-rst kinetic constants change depending on the initial concentration of CP, pH, temperature and radiation intensity.4 As initial CP concentration increases and the other variables remain constant, the half-life times decrease, namely the degradation of CP improves. Moreover, as pH increases for constant values of the other variables, half-life times tend to decrease and kinetic constants referred to CP degradation tend to increase, but the kinetic constants referred to TOC degradation tend to decrease. Finally, even though the effect of radiation intensity cannot be deduced directly form data in Table 4, an increase in CP degradation can be proposed with an increase in radiation intensity. On the other hand, as reported in Table 4, the degradation of different CPs is faster when decreasing the number
Flux of photons per volume unit is measured in einstein l1 s1 , where 1 einstein = 1 mol of photons of a particular wavelength. The values given in Table 5 and in the other ones in this work are mean values for the wavelength ranges supplied by the lamps employed in each study reviewed.
4
(mol einstein1 , T in K, = 185436 nm)
5. AOPs based on hydrogen peroxide Hydrogen peroxide is a safe, efcient and easy to use chemical oxidant suitable for wide usage on contamination prevention. Discovered by Thenard in 1818, it was rst used to reduce odor in wastewater treatment plants, and from then on, it became widely employed in wastewater treatment [66]. However, since hydrogen peroxide itself is not an excellent oxidant for many organic pollutants, it must be combined with UV light, salts of particular metals or ozone to produce the desired degradation results. 5.1. Fentons reagent (H2 O2 /Fe2+ ) The Fenton reaction is a widely used and studied catalytic process based on an electron transfer between H2 O2 and a metal acting as a homogeneous catalyst [163,209]. By far, the most common of these ones is iron [28,242]. The reactivity of this system was rst observed in 1894 by its inventor Fenton [76], but its utility was not recognized until the 1930s once a mechanism based on hydroxyl radicals (HO ) was proposed [200,242]. Fentons reagent can be employed to treat a variety of industrial wastes containing a range of organic compounds like phenols, formaldehyde, pesticides, wood preservatives, plastic additives, and rubber chemicals [16,29,64,77,78,80,156159,180,185,187,196,221]. The process may be applied to wastewaters, sludges, and contaminated soils [160,162,136,180,234,240] with a reduction
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Table 4 Half-life times and pseudo-rst kinetic constants for degradation of CPs by direct UV-photolysis for different initial concentrations of CP CP congener 2-MCP 2-MCP 2-MCP 2-MCP 4-MCP 4-MCP 4-MCP 4-MCP 4-MCP 4-MCP 4-MCP 4-MCP 2,4-DCP 2,4-DCP 2,4-DCP 2,4-DCP 2,4-DCP 2,4-DCP 2,4-DCP 2,4-DCP 2,3,5-TCP 2,3,6-TCP 2,4,6-TCP 2,4,6-TCP 2,4,6-TCP 2,4,6-TCP 2,4,6-TCP 2,3,4,6-TTCP PCP PCP
a b c
[CP]0 (mM) 0.78 0.78 0.40 0.40 0.30 0.30 0.30 0.40 0.40 0.78 0.78 0.5b 0.30 0.30 0.30 0.78 0.78 0.40 0.40 0.49 0.04 0.12 0.24 0.30 0.30 0.40 0.40 0.30 0.04 0.04
pH 6.0 9.0 2.5 9.5 2.0 2.0 9.0 2.5 9.5 6.0 9.0 7.0 2.0 2.0 9.0 6.0 9.0 2.5 9.5 7.0 7.0 7.0 2.0 2.0 2.5 9.5 2.0 2.5 9.5
T ( C) Room Room Room Room Room 25 25 Room Room Room Room 20 Room 25 25 Room Room Room Room Room Room Room Room Room 25 Room Room Room Room Room
Rad. intensity (einstein l1 s1 ) 5.97 5.97 6.45 6.45 4.80 4.80 3.52 6.45 6.45 5.97 5.97 9.74 4.80 3.52 3.52 5.97 5.97 6.45 6.45 2.04 8.08 8.08 8.08 4.80 3.52 6.45 6.45 105 105 107 107 104 104 105 107 107 105 105 105 104 105 105 105 105 107 107 104 105 105 105 104 105 107 107
(nm) 320400 320400 250 250 185436 185436 185436 250 250 320400 320400 172 185436 185436 185436 320400 320400 250 250 185436 185436 250 250 185436 250 250
CP t1/2 (min) 12.0 8.5 25.0 1.1 1.2 1.2 27.3 13.4 8.6 7.4 48.0, 200c 17.5 10.3 6.2.0 70.0 14.7 20.0 Not reached 35.0 22.0 25.2 63.0 34.3 30.6
kCP (min1 ) 1.52 9.00 8.76 4.04 0.564 0.539 0.432 2.52 5.08 9.32 5.10 0.832 3.80 3.80 0.173 5.90 7.00 6.95 4.98 0.130 2.60 2.60 9.48 2.03 103 a 104 a 103 102
Reference [140] [140] [233] [233] [23] [21] [21] [233] [233] [140] [140] [98] [23] [21] [21] [140] [140] [233] [233] [19] [239] [239] [239] [23] [21] [233] [233] [23] [233] [233]
102 102 103 a 104 a 102 102 104 a 104 a 103 102
102 102 103 102
4.80 104 6.45 107 6.45 107
2.10 102 8.16 102 5.39 102
Rate constants referred to TOC. This CP concentration corresponds to TOC = 36 mg l1 . Half-times referred to TOC.
of toxicity, an improvement of biodegradability, and odor and color removal. Some initial works have been issued about the degradation of CPs in ground waters, wastewaters and soils. These
works differ in the way hydrogen peroxide is supplied to the system. Among them, the ones that use an external supply [82,197,241] and with an electrochemical production (electro-Fenton) [35,36,115] are of particular interest. On the
Fig. 5. Evolution of ln[CP] with respect to time for 4-MCP, 2,4-DCP and 2,4,6-TCP for [4-MCP] = 0.40 mM, I = 6.45 107 einstein l1 s1 , and = 250 nm at pH 2.5 and 9.5 [233]. It can be observed a linear correlation, which indicates that kinetics of the degradation of these CPs by direct UV-photolysis follows a pseudo-rst order kinetics.
227
Fig. 5. (Continued ).
other hand, Fenton/ultrasound technologies have also been surveyed [151]. As a result of the mineralization or degradation of CPs into intermediates, the pre-oxidized efuent is generally more amenable to conventional treatment, e.g. occulation and bio-treatment. Signicantly, this may be achieved with a hydrogen peroxide dose of 5075% of the stoichiometry [242]. However, small chlorinated alkanes, n-parafns and short-chain carboxylic acids show resistance to oxidation [28]. On the other hand, removal of pollutants in turbid waters appears to be not feasible for solutions with a high absorbance. As reported by several authors [227,228,143], the degradation and dechlorination of CPs by Fentons reagent follows a pseudo-rst order kinetics. Half-life times and pseudo-rst kinetic constants for degradation of CP and TOC are summarized in Table 5. As indicated previously by Barbeni et al. [16], the degradation rates of MCPs decrease in the order 3-MCP > 2-MCP > 4-MCP for the same experimental conditions, which seems to be opposite to the ones related to CP biodegradability, ortho > para > meta [62,246]. This result may suggest that OH and Cl substituents at ortho and para positions on the aromatic ring inhibit the organic oxidation. Half-life times and kinetic
constants for the degradation of 2,4,5-TCP are identical to those for 4-MCP under the same experimental conditions, respectively. On the other hand, as reported in Table 5 and shown in Fig. 7, the degradation of different CPs is higher for series 2,3,4,6-TTCP < 2, 4, 6-TCP < 2, 4-DCP < 4-MCP at constant values of initial CP, hydrogen peroxide and ferrous concentrations, pH and temperature. The time needed to complete a CP degradation reaction with Fentons reagent depends on many variables, most notably pH and catalyst and hydrogen peroxide concentrations. As indicated in Table 5, for MCP oxidation (less than 2 mM), typical half-life times are between 0.8 and 74 min. For more chlorinated phenols, the reaction may take hours. In such cases, performing the reaction in steps (adding both iron and hydrogen peroxide) may be more effective than increasing the initial charges. 5.1.1. Studies of dechlorination kinetics of CPs In addition to the studies of CPs degradation by Fentons reagent, some studies concerning its dechlorination kinetics have also been reported [227,228]. The kinetic rate of dechlorination by Fentons reagent is assumed to follow a pseudo-rst kinetic order, with an analogous dependence with initial concentrations of catalytic ferrous ions, hydrogen
Fig. 6. Evolution of quantum yield () with pH for 4-MCP, 2,4-DCP, 2,4,6-TCP and 2,3,4,6-TTCP. [CP] = 0.30 mM, I = 3.52 105 einstein l1 s1 , and = 185436 nm [21].
228
Table 5 Half-life times and pseudo-rst kinetic constants for degradation of CPs by Fentons reagent for different initial concentrations of CP, H2 O2 and Fe2+ CP congener 2-MCP 2-MCP 3-MCP 4-MCPa 4-MCP 4-MCP 4-MCP 4-MCP 4-MCP 4-MCP 2,4-DCP 2,4-DCP 2,4-DCP 2,4-DCP 2,4-DCP 2,4,5-TCP 2,4,6-TCP 2,4,6-TCP 2,4,6-TCP 2,4,6-TCP 2,4,6-TCP 2,4,6-TCP 2,3,4,6-TTCP PCP
a b c
[CP]0 (mM) 0.50 0.39 0.80 0.50 0.80 2.00 0.30 10.00 0.30 2.27 0.50 0.30 0.51 0.51 0.30 0.80 0.50 0.50 0.30 0.51 0.51 0.30 0.30 0.80
[H2 O2 ]0 (mM) 5.00 2.20 4.00 4.00 4.00 6.00 7.50 30.00 0.50 8.20 5.00 7.50 5.90 5.90 0.50 4.00 5.00 5.00 7.50 5.90 5.90 0.50 7.50 4.00
[Fe2+ ]0 (mM) 0.20 0.008 0.020 0.040 0.020 0.30 0.10 0.005 0.010 0.054 0.20 0.010 0.20 2.00 0.010 0.020 0.20 0.10 0.010 0.20 2.00 0.010 0.010 0.020
,
pH 3.5 3.0 2.0 7.18.2 2.0 3.0 2.0 3.5 2.0 4.0 3.5 2.0 7.1 7.1 2.0 2.0 3.5 2.0 2.0 7.1 7.1 2.0 2.0 2.0
T ( C) Room 30 25 22 25 20 25 Room 25 Room Room Room 22 22 25 25 Room 30 Room 22 22 25 Room 25
CP t1/2 (min) 1.0 46.0 50.0 2.2, 2.5, 9.5 66.0 0.8 0.4 Not reached 74.0 82.0, 1440b 2.4 4.0c 87.0c Not reached 63.0 5.5 9.0 5.1 96.0c 37.0c Not reached 49.5 Not reached
kCP (min1 ) 1.67 1.92 102 0.320, 0.280, 1.20 103 1.55 1.88 7.00 103 7.25 103 0.995 0.209 7.00 104 0.15 1.02 9.80 102 5.00 104 9.00 103
Reference [227] [161] [220] [155] [220] [143] [22] [257] [21] [41] [227] [23] Yeh et al. (2000) Yeh et al. (2000) [21] [220] [227] [24] [23] Yeh et al. (2000) Yeh et al. (2000) [21] [23] [220]
Reactions underwent in the presence of ClO4 Data referred to TOC. Time in hours.
NO3
and
Cl
anions with a concentration of 3.00 mM in all cases.
peroxide and CP for 3-MCP, which are shown in Figs. 810, and the dechlorination rates for different degrees of chlorination for the same initial concentrations are depicted in Fig. 11. On the other hand, the evolution of the kinetic constants of the dechlorination of several CPs with the ratio H2 O2 /CP is also shown in Fig. 12. Generally speaking, these evolutions have a non-linear trend, especially for more chlorinated CPs. When the ratio H2 O2 /CP is 20, the dechlorination constants for 2-MCP, 2,4-DCP, and 2,4,6-TCP are 3.00,
9.60, and 39.60 min1 , respectively. The number of available sites not occupied by chlorine atoms is the major factor responsible for dechlorination [227]. Furthermore, the position of chlorine atoms on the aromatic ring has different effects on dechlorination kinetics of the CP isomers with the same chlorine content. For MCPs, the different evolution observed in Fig. 14 can be ascribed to the ortho- and para-directory nature of OH and Cl groups [16,227]. It is found that the dechlorination of 3-MCP is
Fig. 7. Evolution of ln[CP] with respect to time for 4-MCP, 2,4-DCP, 2,4,6-TCP and 2,4,6-TCP for [CP] = 0.30 mM, [H2 O2 ] = 0.50 mM, [Fe2+ ] = 0.010 mM, pH 2.0 [21]. It can be observed a pseudo-rst order kinetics for the degradations of these CPs with Fentons reagent.
229
Fig. 8. Evolution of normalized Cl concentration with time for 3-MCP for different initial concentrations of ferrous ions ([3-MCP] = 0.25 mM, [H2 O2 ] = 5.00 mM, pH 3.5) [228,229].
faster than that of 4-MCP, which is dechlorinated more easily than 2-MCP. As the number of chlorine atoms increases, steric hindrance becomes more important in determining the dechlorination kinetic rates, which is thought to be the most important one for TCPs instead of ortho- and para-directory effects. 5.1.2. Mechanistic pathway Even though a mechanism based on hydroxyl radicals is the most popular for the description of the degradation of CPs by Fenton reaction, some authors have recently
pointed out that there may other mechanisms responsible for the degradation of CPs [32,148,209,250,251]. For instance, an intermediate suggested for Fenton reaction is a high-oxidized and unstable form of Fe (Fe(IV)). Because of the indiscriminate nature by which radicals degrade organic pollutantsboth hydroxyl radicals or other intermediate radicalsit is important to prole the degradation of each waste in the laboratory to be treated. For example, in a typical application the series indicated in Fig. 13 will occur. Each transformation in this series has its own reaction rate and there may occur build-up of undesirable
Fig. 9. Evolution of normalized Cl concentration with time for 3-MCP different initial concentrations of hydrogen peroxide ions ([CP] = 0.50 mM, [H2 O2 ] = 5.00 mM, pH 3.5) [228,229].
230
Fig. 10. Evolution of normalized Cl concentration with time for 3-MCP for different initial concentrations of 3-MCP ([Fe2+ ] = 0.20 mM, [H2 O2 ] = 5.00 mM, pH 3.5) [228,229].
intermediates (quinones), which require sufcient hydrogen peroxide to be added to push the reaction beyond that point [48,126,243,250]. The main stages are the following ones: Initial reactions: H2 O2 H2 O + H2 O2 + Fe
2+ 1 2 O2 3+
H2 O2 + Fe3+ Fe(OOH)2+ + H+ Fe2+ + HO2 + H+ HO + Fe3+ Fe(OH)2+ Fe2+ + HO Propagation: HO + H2 O2 HO2 + H2 O (8) (6) (7)
(4) + HO
Fe
+ HO
(5)
Fig. 11. Evolution of normalized Cl concentration with time for 3-MCP, 2,3-DCP and 2,3,4-TCP ([CP] = 0.50 mM, [Fe2+ ] = 0.50 mM, [H2 O2 ] = 5.00 mM, pH 3.5) [228,229].
Fig. 12. The effect of chlorine position in dechlorination constants at different H2 O2 /CP ratios ([CP] = 0.50 mM, [H2 O2 ] = 5.00 mM, [Fe2+ ] = 0.20 mM, pH 3.5) [227229].
231
232
Fig. 13. Typical series for the mineralization of an organic substrate by means of reaction with Fentons reagent.
HO2 + H2 O2 HO + H2 O + O2 HO2 + HO2 HO + HO + O2 Termination: Fe2+ + HO Fe3+ + HO HO2 + Fe3+ Fe2+ + H+ + O2 HO + HO2 H2 O + O2 HO + HO H2 O2 + O2 CP degradation: CP + H2 O2 Intermediates + H2 O CP + HO Intermediates Intermediates + H2 O2 CO2 + H2 O + Cl Intermediates + HO CO2 + H2 O + Cl
(9) (10)
(11) (12) (13) (14)
(15) (16) (17) (18)
5.1.2.1. Effect of pH. As shown in Fig. 15, pH signicantly inuences the decomposition of 4-MCP, which progresses at higher rates at pH 24. This agrees with the results reported in previous studies [262]. At a pH above 4, the decomposition signicantly decreases as the pH increases probably because the dissolved fraction of iron species decreases [132], as colloidal ferric species appear. On the other hand, at a pH below 2, no decomposition is observed. Optimal pH occurs between 2 and 4 for 4-MCP and for other CPs [21]. Oxygen concentration remains stable at pH 1, probably because hydrogen peroxide solvates protons to form oxonium ions (H3 O2 + ), which enhance the stability of hydrogen peroxide and reduce its reactivity with ferrous ions [211]. A second aspect of pH deals with its shift as the reaction progresses. The pH tends to decrease as ferrous ions as FeSO4 are added, because it typically contains residual H2 SO4 . On the other hand, it also tends to decrease as hydrogen peroxide is added, and continues gradually at a rate which is largely dependent on Fe2+ concentration, because CPs fragmentate into organic acids. 5.1.2.2. Effect of hydrogen peroxide concentration [H2 O2 ]. As shown in Table 5, the concentration of hydrogen peroxide has an important inuence in the degradation of CPs. The stoichiometric coefcient for the Fenton reaction has been found to be approximately 0.5 mol organic compound/mol H2 O2 [41]. As concentration of hydrogen peroxide increases, the degradation of CPs
As has been pointed out in the mechanistic pathway, ferric ions (Fe3+ ) may be regenerated by means of reactions (6) and (7), which are assumed to be developed by intermediates Fe(OOH)2+ and Fe(OH)2+ , respectively. This regeneration process is summarized in Fig. 14, which is suitable for both Fenton and photo-Fentons reactions.
Fig. 14. Mechanism for degradation of CPs in Fenton and photo-Fenton reactions (adapted from Mazellier et al. [175]). Scavenging of radicals in termination reactions are not included. The nal products of degradation should be CO2 , H2 O and Cl if complete mineralization is achieved.
233
Fig. 15. Optimal 4-MCP degradation takes place at pH 24. (b) Evolution of ln(kCP ) with respect to time for different pH. Linear correlations are observed at pH 2.0, 3.0 and 4.0 [143]. (a) 4-MCP decomposition at pH range of 24 for [4-MCP] = 2.00 mM; [H2 O2 ] = 6.00 mM; [Fe2+ ] = 0.30 mM.
also increases, because the amount of oxidant present in the reaction system is higher for the same initial concentration of CP and catalytic ferrous ions. On the other hand, as indicated in Fig. 16, the inverse of the kinetic constant for CP degradation (1/kCP ) can be linearly correlated with the inverse of concentration of hydrogen peroxide (1/[H2 O2 ]) at constant CP and ferrous ion concentration in excess for data provided from different authors, as indicated for kinetic constant for CP dechlorination [227,228]. Otherwise, when the reaction evolves, this linear correlation seems to disappear. This suggests that the linear dependence is only achieved when hydrogen peroxide is in excess compared to other CP and when it begins to be consumed, then the degradation becomes lower. Because of the series of intermediates that take place in the process, sufcient hydrogen peroxide must be added in order to push the reaction beyond that point. This fact is frequently seen when pre-treating a complex organic wastew-
ater for toxicity reduction. As the H2 O2 dose is increased, a steady reduction in COD may occur with little or no change in toxicity until a threshold is attained, whereupon further addition of hydrogen peroxide results in a rapid decrease in wastewater toxicity [242]. As reported by Chamarro et al. [41], contaminants with a ratio of BOD5 /COD > 0.4 may be considered thoroughly biodegradable. Acetic acid and phenol are hardly biodegradable, but 4-CP and 2,4-DCP are refractory to biological treatments. 5.1.2.3. Effect of catalytic ferrous ion concentration [Fe2+ ]. In the absence of iron, there is no evidence of radical or other intermediate active species formation when, for example, hydrogen peroxide is added to a wastewater which contains CPs. As the concentration of iron is increased, CP removal accelerates until a point is reached where further addition of iron becomes inefcient. The feature of an optimal dose range for iron catalyst is characteristic of Fentons
234
Fig. 16. Evolution of 1/kCP with respect to 1/[H2 O2 ] for the degradation of 4-MCP with Fentons reagent. (a) [4-MCP] = 2.00 mM, [Fe2+ ] = 0.30 mM, pH 3.0 [143]. (b) [4-MCP] = 2.33 mM, [Fe2+ ] = 8.20 mM, pH 4.0 [41].
reagent, although the denition of the range varies between contaminated waters. Typical ranges are 1 part iron per 525 parts of hydrogen peroxide (w/w) [242] [263]. For most applications, it does not matter whether ferrous (Fe2+ ) or ferric (Fe3+ ) ions are used to catalyze the reactionthe catalytic cycle indicated in Fig. 14 begins quickly if hydrogen peroxide and organic pollutants are abundant. However, if low doses of Fentons reagent are used (e.g. <1025 mg l1 H2 O2 ), some research suggests that ferrous ions may be preferred [242]. On the other hand, neither does it matter whether chloride or sulfate salts of iron are used, although chlorine may be generated at high rates. As summarized in Table 5, the inuence of ferrous ions in CP degradation is similar to the one already cited for hydrogen peroxide. On this way, as this concentration increases, the degradation of CPs also increases, because the amount of catalyst present in the reaction system is higher for the same initial concentration of CP and hydrogen peroxide. As indicated in Fig. 17, the inverse the kinetic constant for CP degradation (1/kCP ) can be linearly correlated with the inverse of surplus concentration of ferrous ions (1/[Fe2+ ])
for data provided from different authors, as indicated previously for the dependence of the inverse of the kinetic constant respect to the inverse of concentration of ferrous ions. 5.1.2.4. Effect of initial concentration of CP. As focused in Table 5 and Fig. 18, the initial concentration of 4-MCP enhances the pseudo-rst kinetic constant for its degradation. Since this kinetic constant can depend on the CP concentration, it is obvious that the degradation of CP does not rigorously present a pseudo-rst kinetic order mentioned, but an undened kinetic order. Therefore, the proposal of a pseudo-rst kinetic constant in the study of CP degradation must be revised and the chances when this proposal is feasible must be taken into account. 5.1.2.5. Effect of temperature. The studies concerning the evolution of the pseudo-rst kinetic constant with the temperature reveal that it follows an Arrhenius dependence. According to Ben tez et al. [24], the following equation can be proposed for the degradation of 2,4,6-TCP for a range of
235
Fig. 17. Evolution of 1/kCP with respect to 1/[Fe2+ ] for the degradation of 4-MCP with Fentons reagent. [4-MCP] = 2.00 mM, [Fe2+ ] = 0.30 mM, pH 3.0 [143].
temperatures between 10 and 40 C: k = 1.84 1010 exp 8267 (min1 , T in K, T [TCP]0 = 0.50 mM, [H2 O2 ]0 = 5.0 mM, (19)
5.2. Fenton-like reagent s (H2 O2 /Fe2+ -solid) Even though the degradation of CPs with Fentons reagent appears to be promising, its disadvantage is that the homogeneous catalyst, added as iron salt, cannot be retained in the degradation process. In some early attempts made,
[TCP]0 = 0.10 mM, = 185436 nm)
Fig. 18. Evolution of kCP with respect to [CP] for the degradation of 4-MCP with Fentons reagent ([H2 O2 ] = 6.00 mM, [Fe2+ ] = 0.30 mM, pH 3.0) [143].
236
homogeneous catalysts are replaced by heterogeneous metal supported ones [5,73,153,236]. The catalytic activity can be related to hydroxyl radicals generated from hydrogen peroxide activated by iron ions simultaneously leached from the support material, which act homogeneous catalysts. Among the various catalysts studied, goethite (-FeOOH) is one of the most efcient catalysts for Fenton-like degradation of CPs due to the catalysis of its surface and ferrous ion generation. It is thought to be suitable in removal of hazardous pollutants as it exists in soil and can be recycled to further use, as has been reported by several authors [153,264]. Ferrous ions can be regarded to be produced from the reductive dissolution of goethite shown below [258]: -FeOOH(s) + 3H+ + e Fe2+ + 3H2 O H2 O2 2H+ + O2 + 2e (20)
On the other hand, the following equation provides electrons: (21)
Combining both equations, the following equation is obtained: 2-FeOOH(s) + 4H+ + H2 O2 2Fe2+ + O2 + 4H2 O (22) Hydroxyl radicals are therefore produced by Fenton reaction: Fe2+ + H2 O2 Fe3+ + HO + HO (23)
Previous studies indicated that the dissolution reaction was facilitated under reducing conditions and inuenced by complex-forming organic ligands [223,258]. Moreover, Lu et al. [160] examined the behavior of CP oxidation by using a mixture of H2 O2 and goethite and found that it increased with an increase in goethite dissolution. Some data concerning the degradation of several CPs by Fenton-like reagents involving different catalytic solids with ferrous ions are summarized in Table 6. In addition to goethite, some other solid supports for ferrous ions have been studied, for instance, GAC or Naon membranes, as well as iron powder. As indicated in Table 6, goethite performs a better degradation of 2-MCP when solved ferrous ions are added, because half-life times are reduced from 174 to 252 min for the experimental conditions assayed, but pseudo-rst kinetic constants remain invariable. On the other hand, the comparison of the performance of several GAC-Fe, iron powder and graphite-Fe for the same experimental conditions reveals a better degradation of 4-MCP for iron powder, because half-life time is remarkably lower than the ones corresponding to other solids. 5.3. H2 O2 /UV reagent This AOP is based on the formation of HO radicals by means of the photolysis of hydrogen peroxide and the subsequent propagation reactions: H2 O2 + h 2HO (24)
As it is widely assumed, the dissolution of goethite plays an important role in the goethite/H2 O2 Fenton-like process. It can interact chemically with H+ , HO , cations, and anions, followed by a series of dissolution reactions.
The molar absorptivity of hydrogen peroxide at 253.7 nm is low, about 20 M1 cm1 and HO radicals are formed per incident photon absorbed [86]. At this wavelength, the
Table 6 Half-life times and pseudo-rst kinetic constants for degradation of CPs by Fenton-like reagent for different initial concentrations of CP, H2 O2 and Fe2+ charge on the surface of the solid at pH 3.0 CP congener 2-MCPb 2-MCP 2-MCP 2-MCP 2-MCP 4-MCP 4-MCP 4-MCP 4-MCP 4-MCP 4-MCP 2,4,5-TCPd
a b c d e
Solid GAC-Fe Goethite Goethite Goethite Goethite Iron powder Graphite-Fe GAC GAC GAC GAC F-300 GCW ROW RFZ
A (m2 g1 ) (BET) 194215 194215 194215 208 1000.0 1000.0 950.0 800.0 48.0
dp (mm) 0.0440.21 0.0440.21 0.0440.21 0.0800.15 70100 <100 <50 <50 <50 <50
[Solid]a (g l1 ) 1.0 0.2 0.2 0.2 0.2 1.0 1.0 1.0 1.0 1.0 1.0
[CP]0 (mM) 0.39 0.39 0.39 0.31 7.78 7.78 7.78 7.78 7.78 7.78 68.0e
Total Fe (g kg1 ) 5.5 c c 4.9 4.9 0.6 90.2 No data
[H2 O2 ]0 (mM) 280 2.20 2.20 2.20 1.96 155.8 155.8 155.8 155.8 155.8 155.8 10.0
CP t1/2 (min) 426 174 36 30 252 1.5 Not reached 810 311 240 59 Not reached
kCP (min1 ) 2.27 2.47 2.75 2.24 1.33 1.40 5.38 1.32 3.30 6.14 2.52 103 102 102 102 102 102 105 105 105 105 104
Reference [119] [161] [161] [161] Lu et al. (2002) [163] [163] [163] [163] [163] [163] [208]
Naon membrane
Concentration of the solid suspension. Values are usually between 0.2 and 1.0 g l1 . Data referred to pH 4.6. Additional solved Fe2+ was added. Data referred to pH 5.4. Data referred to TOC.
237
rate of photolysis of aqueous hydrogen peroxide is about 50 times slower than ozone. This technique requires a relatively high dose of H2 O2 and/or a much longer UV-exposure time than, for example, UV/O3 process. On the other hand, the rate of photolysis of hydrogen peroxide has been found to be pH dependent and increases when more alkaline conditions are used, because, at 253.7 nm, peroxide anions HO2 may be formed, which display a higher molar absorptivity than hydrogen peroxide, 240 M1 cm1 [86], by the following reaction: HO2 + h HO + O (25)
The absorptivity of hydrogen peroxide may be increased by using UV lamps with output at lower wavelengths. The main reactions of the system are the following ones [22,88]: Initial reaction: H2 O2 + h 2HO
kp 1 H2 O2 H2 O + 2 O2 kp
Propagation: HO + H2 O2 HO2 + H2 O HO2 + H2 O2 HO + H2 O + O2 HO2 + HO2 HO + HO + O2 Termination: HO + HO2 H2 O + O2 HO + HO H2 O2 + O2 CP degradation: Intermediates, CP + HO CP + H2 O2 Intermediates + H2 O, CP + h Intermediates Intermediates + H2 O2 CO2 + H2 O + Cl , Intermediates + HO CO2 + H2 O + Cl , Intermediates + h CO2 + H2 O + Cl (27) (26)
kr
rates achieved by the H2 O2 /UV process in alkaline conditions with DCP were comparable to those achieved by direct DCP irradiation, while at acidic pH the addition of hydrogen peroxide increased the reaction rate by one order of magnitude. Ultimate oxidation of CPs to carbon dioxide and water has rarely been obtained under typical test conditions. As summarized in Table 7, typical values for half-life times are between 0.3 and 20.1 min for CP degradation, depending on the initial concentration of CP and hydrogen peroxide, the intensity of radiation and the degree of chlorination. It is observed that the degradation rates increase when the number of chlorine substituents decreases. On the other hand, data concerning with pseudo-rst order kinetic constants are also included. As reported by Ben tez et al. [23], this rate constants present moderate higher values than those obtained in the single photolytic process (see Table 5), which demonstrate an additional contribution to the photolytic reaction, which can be related to the action of hydroxyl radicals generated by the presence of hydrogen peroxide. According to Ben tez et al. [22,23], the total kinetic constant, kt , may be assumed to be constituted by two contributions (kt = kp + kr ). Some constants related to the second reaction (kr ) are summarized in Table 8. It can be observed that these constants tend to decrease when the degree of chlorination increases. Specically, Sundstrom et al. [228] proposed for the ratio kt /kp values of 2.0 and 1.3 for 2,4-DCP and 2,4,6-TCP, respectively. 5.4. Photo-Fentons reagent (H2 O2 /Fe2+ /UV) The photo-Fenton reaction is also well-known in the literature [134,207,209], which is an efcient and inexpensive method for wastewater and soil treatment [18,48,132,138,206,210]. Photo-Fenton is known to be able to improve the efciency of dark Fenton or Fenton-like reagents, respectively, by means of the interaction of radiation (UV or Vis) with Fentons reagent [107,196,226,221,265]. This technique has been suggested to be feasible and promising to remove pollutants from natural and industrial waters and increase the biodegradability of CPs being used as a pre-treatment method to decrease the toxicity of water [74,75,167,181]. Some innovative applications dealing with photo-Fentons reagent include oxalate as a ligand of iron ions [8]. As summarized in Table 9, typical values for half-life times are between 0.3 and 50 min for CP degradation, depending on the initial concentration of CP, hydrogen peroxide and ferrous ions, the intensity of radiation and the degree of chlorination. It is observed that the degradation rates increase when the number of chlorine substituents decreases. As reported by Ben tez et al. [23], pseudo-rst kinetic constants this rate present moderate higher values than those obtained in the single photolytic process (see Table 5), as indicated for UV/H2 O2 reagent. On this way, an additional contribution to the photolytic reaction may be considered,
If there are other strong UV absorbers different than hydrogen peroxide, the observed effect will be the same as if the incident ux were decreased, i.e. there is less radiation intensity available for the photolysis of hydrogen peroxide, or the amount of radiation transformed into HO radicals will be lower if such absorbents are present. Furthermore, CPs can be hydroxylated by the photolysis of hydrogen peroxide [158,217,218]. However, Hivronen et al. [108] reported that
238
Table 7 Half-life times and pseudo-rst kinetic constants for degradation of CPs by H2 O2 /UV reagent for different initial concentrations of CP and H2 O2 and for different radiation intensities CP congener 2-MCP 2-MCP 4-MCP 4-MCP 4-MCP 4-MCP 4-MCP 4-MCPa 2,4-DCP 2,4-DCP 2,4-DCP 2,4-DCP 2,4-DCP 2,4,6-TCP 2,4,6-TCP 2,4,6-TCP 2,4,6-TCP 2,3,4,6-TTCP 2,3,4,6-TTCP PCP PCP
a
[CP]0 (mM) 0.40 0.40 0.30 10.00 0.30 0.40 0.40 1.00 0.30 0.30 0.40 0.40 0.74 0.30 0.30 0.40 0.40 0.30 0.30 0.04 0.04
[H2 O2 ]0 (mM) 40.00 40.00 0.50 30.00 0.50 40.00 40.00 10.00 0.50 0.50 40.00 40.00 0.74 0.50 0.50 40.00 40.00 0.50 0.50 40.00 40.00
pH 2.5 9.5 2.0 3.5 2.0 2.5 9.5 3.0 2.0 2.0 2.5 9.5 2.0 2.0 2.5 9.5 2.0 2.0 2.5 9.5
T ( C) Room Room 25 20 Room Room Room 25 Room 25 Room Room 25 Room 25 Room Room Room 25 Room Room
Rad. intensity (einstein l1 s1 ) 6.45E07 6.45E07 3.52E05 1.04E06 4.80E04 6.45E07 6.45E07 3.34E04 4.80E04 4.80E04 6.45E07 6.45E07 4.87E04 4.80E04 4.80E04 6.45E07 6.45E07 4.80E04 4.80E04 6.45E07 6.45E07
Wavelength range (nm) 250 250 185436 320400 185436 250 250 185436 185436 250 250 240570 185436 185436 250 250 185436 185436 250 250
CP t1/2 (min) 0.3 Not reached 1.0 9.9 10.1 1420 14.5 7.9 11.0 110.0 19.2 7.7 16.5 20.1
kCP (min1 ) 5.07 5.11 0.549 0.601 5.07 5.11 2.80 4.40 2.54 8.64 5.22 102 102
Reference [233] [233] [21] [257] [23] [233] [233] [17] [23] [21] [233] [233] [118] [23] [21] [233] [233] [23] [21] [233] [233]
102 102 102 102 102 102 102
3.30 102 1.80 102 0.109 5.46E02 2.90 102 2.90 102 0.458 0.267
Data referred to TOC.
which can be related to the action of hydroxyl radicals generated by the presence of hydrogen peroxide. As pointed out by Ben tez et al. [22,23], in the degradation of CPs by photo-Fentons reagent, additionally to the photolysis of hydrogen peroxide, the production of hydroxyl radicals by the Fentons reagent must be taken into account. On this way, it must be expected that the hydroxyl attack reaction must improve the removal obtained by the UV/H2 O2 reagent, because in this case two different pathways contribute to the generation of free radicals and, therefore, their concentration must be higher. All initial, propagation, termination and CP degradation steps for CP removal are the same as the ones exposed for reactions with Fentons and UV/H2 O2 reagents. Nevertheless, another step for initial reactions must be added [48,242,243], which does not take place in Fenton reaction, because there is no radiation: Initial reactions: H2 O2 + Fe2+ + h Fe3+ + HO + HO (28)
According to Benitez et al. [22,23], as has been pointed for the H2 O2 /UV process, the total kinetic constant, kt , may be assumed to be constituted by two contributions (kt = kp + kr ). Some constants related to this reaction (kr ) are summarized in Table 10. It can be observed that these constants tend to decrease when the degree of chlorination increases. Specically, Sundstrom et al. [226] proposed for the ratio kt /kp values of 2.0 and 1.3 for 2,4-DCP and 2,4,6-TCP, respectively. Due to this additional generation of hydroxyl radical in the degradation of CPs by the photo-Fenton reaction, the degree of degradation is higher compared to direct photolysis or degradation with UV/H2 O2 reagent for the same system of reaction, as shown in Fig. 19. In fact, this improvement is more important for chlorinated CPs instead of MCPs, which show a similar degradation for the three oxidation processes.
6. AOPs based on ozonation 6.1. Ozone (O3 ) There has been an increasing interest in the last decades in using ozone to treat efuents containing hazardous pollutants with the development of large-scale ozone generators along with reduced installation and operating costs [14,96,176,189,199,201,202]. Compared to other oxidizing reagents, ozonated water is more efcient in pollutant degradation and it is not harmful for most of the organisms,
Table 8 Values for kt and kr pseudo-rst kinetic constant for the degradation of CP with H2 O2 /UV reagent [22,23] CP 4-MCP 2,4-DCP 2,4,6-TCP 2,3,4,6-TTCP kt 103 601 44 33 29 kr 103 36.0 6.9 7.2 7.9
239
Table 9 Half-life times and pseudo-rst kinetic constants for degradation of CPs by photo-Fentons reagent for different initial concentrations of CP and H2 O2 and for different radiation intensities CP congener 4-MCP 4-MCP 4-MCP 4-MCP 4-MCP 2,4-DCP 2,4-DCP 2,4-DCP 2,4,5-TCP 2,4,6-TCP 2,4,6-TCP 2,3,4,6-TTCP 2,3,4,6-TTCP PCP
a
[MCP]0 (mM) 0.30 10.00 0.80 0.30 1.00a 0.80 0.30 0.30 0.80 0.30 0.30 0.30 0.30 0.80
[H2 O2 ]0 (mM) 0.50 30.00 4.00 0.50 10.00 4.00 0.50 0.50 4.00 0.50 0.50 0.50 0.50 4.00
[Fe2+ ]0 (mM) 0.010 0.005 0.020 0.010 0.25 0.020 0.010 0.010 0.020 0.010 0.010 0.010 0.010 0.020
pH 2.0 3.5 2.0 2.0 3.0 2.0 2.0 2.0 2.0 2.0 2.0 12.0 50 73 mg l1 .
T ( C) 25 20 25 Room 25 25 Room 25 25 Room 25 Room 25 25
Rad. intensity (einstein l1 s1 ) 3.52E05 1.04E06 7.30E02 3.76E04 3.34E04 No data 4.80E04 3.52E05 No data 4.80E04 3.52E05 4.80E04 3.52E05 No data
(nm) 185436 320400 >300 185436 >300 185436 185436 >300 185436 185436 185436 185436 >300
CP t1/2 (min) 0.25 22.0 28.0 0.9 13.0 25.0 0.9 Not reached 8.5 12.0 50.0
kCP (min1 ) 0.642 0.642 1.25 8.80 102 8.80 102 7.80 102 7.80 102 5.80 102 5.80 102
Reference [21] [257] [220] [23] [17] [220] [23] [21] [220] [23] [21] [23] [21] [220]
This CP concentration corresponds to TOC =
Table 10 Values for k and kr pseudo-rst kinetic constant for the degradation of CP with photo-Fentons reagent CP 4-MCP 2,4-DCP 2,4,6-TCP 2,3,4,6-TTCP kt 103 642 88 78 58 kr 103 16.0 56.8 66.7 63.8
because no strange compounds are added to treated waters. Ozonation has been widely used for drinking water disinfectionbacterial sterilization, odor, algae, and trihalomethane removal and organic compound degradation [2,91], but its application to wastewater treatment is limited due to its high energy demand. Thanks to its oxidizing power and the absence of hazardous decomposition products, ozone is a potential pre-treatment agent to transform refractory compounds into substances that can be further removed by conventional methods [13,116]. Thus, the ozona-
tion of dissolved compounds in water can constitute an AOP by itself, as hydroxyl radicals can be generated from the decomposition of ozone, which might be catalyzed by hydroxyl ions or initiated by the presence of traces of other substances, like transition metal cations [224]. As pH increases, so does the rate of decomposition of ozone in water. The reaction of aqueous phenol with ozone has been extensively studied and the kinetics and many of the products of the reaction have been determined [2,9,111,112,150]. The specic application of ozonation to degrade CPs has been also studied by several authors [31,49,63,81,121,127,142,233]. As reported by several authors [23,143,188,233], the degradation and dechlorination of CPs by ozone reagent follows a pseudo-rst order kinetics. Half-life times and pseudo-rst rate constants for degradation of CP and TOC are summarized in Table 11. The degradation of CPs is favored at high pH [22,101,140, 141,233]. The faster degradation of this compounds in alkali media can be due to the fast production of HO radicals and the dissociation of CPs to chlorophenolate ions that are
Fig. 19. Degradation of CPs by different AOPs ([CP] = 0.30 mM, [H2 O2 ] = 0.50 mM, [Fe2+ ] = 0.010 mM, pH 2.0) [21,23].
240
Table 11 Half-life times and pseudo-rst kinetic constants for degradation of CPs by ozone reagent for different initial concentrations of CP Pollutant 2-MCPa 2-MCP 2-MCP 2-MCP 2-MCP 2-MCP 4-MCP 4-MCP 4-MCP 4-MCP 4-MCP 4-MCPa 4-MCP 4-MCPa,d 4-MCP 4-MCPe 2,4-DCP 2,4-DCP 2,4-DCP 2,4-DCPa 2,4-DCP 2,4-DCP 2,4,6-TCP 2,4,6-TCP 2,4,6-TCP 2,4,6-TCP 2,4,6-TCP 2,3,4,6-TTCP 2,3,4,6-TTCP 2,3,4,6-TTCP
a b c d e
[CP]0 (mM) 0.78 0.40 0.78 0.78 0.78 0.18 0.30 0.30 0.10 0.30 0.40 0.78 0.40 1.38 0.18 0.50 0.30 0.30 0.40 0.78 0.18 0.30 0.30 0.40 0.18 0.16 0.30 0.30 0.40
O3 feed ow rate (mg min1 ) 5.0 107.3 18.0 18.0 18.0 8.3 107.3 8.3 8.3 ? 5.0 8.3 1.2 8.3 ?
pH 6.0 2.5 3.0 7.0 9.0 3.4 2.0 9.0 2.0 2.0 2.0 6.0 2.5 3.3 3.4 7.0 2.0 9.0 2.0 6.0 3.4 7.0 2.0 9.0 2.0 3.4 4.9 2.0 9.0 2.0
CP t1/2 (min) 17.0 14.0 7.5 28.8 38.5 3.4 8.3c 3.6c 2.4c 6.0 19.0a 7.0, 22.0a 16.2 12.7, 170.0a 30.4 3.3 6.0 22.4 300.0 20.6 3.1 156.0 10.6 1.9
kCP (min1 ) 1.49 103 4.78 102 5.60 102 8.69 102b 0.137 2.30 103 3.64 102 0.163, 1.19 102 a 2.55 3.67 103 1.07 103 0.552
kO3 (min1 ) 1.70 102 0.239 4.48 11.3 13.9 2.40 102 0.315 45.3 4.40 102 0.314 228.0 9.40 102 0.415 361.0
Reference [140] [233] [188] [188] [188] [1] [23] [23] [22] [22] [22] [140] [233] [210] [1] [98] [23] [23] [22] [140] [1] [266] [23] [23] [22] [1] [55] [23] [23] [22]
Data referred Half-time for Half-times in Data referred Data referred
to TOC. TOC not reached. seconds. to TOC = 100 mg l1 . to TOC = 36 mg l1 .
able to react with ozone faster than non-dissociated species [111]. However, according to the results of Hautaniemi et al. [101], reactions with HO radicals did not appear to make any contribution to the rate of oxidation at pH 9, which was related to the high rate of the reaction between phenolate ions with ozone at pH conditions which usually favor oxidation by means HO radicals. Not much data are present in the literature for the degradation of CPs. Otherwise, an interesting work concerning this subject was carried out by Ben tez et al. [22], who studied the ozonation process of several CPs in alkali media and found that the degradation curves were very close for all CPs. Pseudo-rst order kinetic constants and half-life times also conrmed the small differences in the removal of the CPs at this pH as depicted in Fig. 20. A similar conclusion was reached by Hong and Zeng [113], who found that the rates of disappearance of PCP were very similar at pH between 7 and 12, reecting a small inuence of pH.
6.1.1. Mechanistic pathway for ozonation One of the most important facts to mention when studying the oxidation of CP by ozone is the high inuence of the pH in the kinetics and pathways of the reaction. This arises from the fact that pH affects the double action of ozone on the organic matter, that may be a direct or an indirect (free radical) ozonation pathway [20,110], as shown in Fig. 21. These different reaction pathways lead to different oxidation products and are controlled by different kinetic models. At low pH, ozone exclusively reacts with compounds with specic functional groups through selective reactions such as electrophilic, nucleophilic or dipolar addition reactions (i.e. direct pathway) [144]. On the other hand, at basic conditions, ozone decomposes yielding hydroxyl radicals, which are high oxidizing species [147] that react in a non-selectively way with a wide range of organic and inorganic compounds in water (i.e. indirect ozonation) [37]. Normally, under acidic conditions (pH <4) the
241
Fig. 20. Decomposition curves for the ozonation of 4-CP, 2,4,6-TCP and 4-CGC (4-chloroguaiacol; 4-chloro-2-methoxy phenol) in experiments at pH 9 [22].
direct ozonation dominates, in the range of pH 49 both are present, and above pH >9 the indirect pathway prevails. 6.1.1.1. Direct ozonation. When the ozonation is carried out in acidic media (pH 2) the decomposition of ozone, which is initiated by the action of HO ions [225], is much too low and consequently the formation of hydroxyl radicals is limited. According to this, the main pathway in the degradation of CPs at these conditions is the direct ozonation, which is a selective reaction with quite slow kinetic constants, which lie in the range of 11000 M1 s1 . Trapido et al. [233] have reported that an increase in the number of chlorine atoms in the aromatic ring provides an increase in the degradation rate, since the presence of chlorine enhances the dechlorination step, and therefore, the degradation is faster. This statement agrees with the results obtained by Ben tez et al. [22]. The results obtained, shown in Figs. 22 and 23, indicate that the higher is the pH, the faster are the degradation of these CPs. In addition, the slowest degradation when the ozonation was undertaken at pH 2 and 4 belonged to 4-CP, whereas no signicant differences between the three compounds were found at the highest pH. Similar results were found by Kuo et al. (1999), who studied the ozonation of 2-CP, 4-CP and 2,4-DCP at pH 6 and 9. After 10 min of reaction at pH 6 the degradation of 2,4-DCP, 4-CP and 2-CP were 79.2, 63.9 and 34.3%, respectively. 6.1.1.2. Indirect ozonation. The indirect reaction pathway involves radicals. The rst step is the decay of ozone, accelerated by initiators HO ions, to form secondary oxidants such as HO radicals, which react non-selectively and immediately (k = 108 1011 M1 s1 ) with solutes. The radical pathway is very complex and inuenced by many substances. The mechanism can be divided in three different parts: Initial reactions: O3 + HO O2 + HO2 , k1 = 70 M1 s1 (29)
Propagation: O3 + O2 O3 + O2 , O3 + H+ HO3 , HO3 HO + O2 , HO + O3 HO4 , HO4 HO2 + O2 , HO2 O2 + H+ , Termination: HO + CO3 2 HO + CO3 , k6 = 4.2 108 M1 s1 HO + HCO3 HO + CO3 , k7 = 1.5 107 M1 s1 CP degradation: CP + HO Intermediates, CP + O2 CPOO Intermediates + HO2 Intermediates + HO CO2 + H2 O + Cl , Intermediates + O2 IOO CO2 + H2 O + Cl 6.2. O3 /UV reagent Photolytic ozonation (O3 /UV process) is an effective method for the oxidation and destruction of toxic and refractory organics in water [20,55,72,86,130,194,198,206,267 269] and has a signicant potential as a wastewater treat(39) (38) (37) (36) k2 = 1.6 109 M1 s1 (30) pKa = 6.2 k3 = 1.1 108 M1 s1 k4 = 2.0 109 M1 s1 k5 = 2.8 104 s1 pKa = 4.8 (31) (32) (33) (34) (35)
242
Fig. 21. General scheme of reactions for ozonation of CPs in an aqueous solution, including the effect of radiation and H2 O2 , in case they are employed. The nal products of degradation should be CO2 , H2 O and Cl if complete mineralization is achieved [111].
Fig. 22. Decomposition curves for the ozonation of 4-CP, 2,4,6-TCP and 4-CGP in experiments at pH 2 [22].
243
Fig. 23. Decomposition curves for the ozonation of 4-CP, 2,4,6-TCP and 4-CGP in experiments at pH 6 [22].
ment process. Basically, aqueous systems saturated with ozone are irradiated with UV light of 253.7 nm. The extinction coefcient of ozone at 253.7 nm is 3300 M1 cm1 , much higher than that of hydrogen peroxide. The decay rate of ozone is around 1000 times higher than that of hydrogen peroxide [94]. It was shown that photolytic ozonation is more effective for the destruction of some organic compounds than either UV-photolysis or ozonation alone. However, some researchers [148] have found photolytic ozona-
tion to be only more effective than ozonation alone in some cases. The photodegradation of CPs by ozone and UV radiation, alone or combined with hydrogen peroxide or ferrous and ferric ions, has been reported by several authors [1,27,168,206,217,218,226]. The initial concentrations of CP, O3 ow rates, half-life times and pseudo-rst kinetic constants for degradation of CPs by photo-ozonation are show in Table 12.
Table 12 Half-life times and pseudo-rst kinetic constants for degradation of CPs by O3 /UV reagent for different initial concentrations of CP and O3 ow rates and for different radiation intensities Pollutant 2-MCPa 2-MCP 2-MCP 4-MCP 4-MCPa 4-MCP 4-MCPb 4-MCP 4-MCPa,c 4-MCP 2,4-DCP 2,4-DCPa 2,4-DCP 2,4-DCP 2,3,5-TCP 2,3,6-TCP 2,4,6-TCP 2,4,6-TCP 2,4,6-TCP 2,4,5-TCP 2,4,5-TCP 2,3,4,6-TTCP 2,3,4,6-TTCP PCP
a b c
[MCP]0 (mM) 0.78 0.40 0.18 0.30 0.78 0.40 1.38 0.18 0.78 0.18 0.30 0.78 0.40 0.18 0.04 0.12 0.30 0.18 0.24 6.0 0.18 0.30 0.05 0.05
O3 feed ow rate (mg min1 ) 5.0 107.3 8.3 107.3 8.3 8.3 5 107.3 8.3 8.3 8.3
pH 6.0 2.5 3.4 2.0 6.0 2.5 3.3 3.4 7.0 7.0 2.0 6.0 2.5 3.4 3.0 3.0 2.0 3.4 3.0 3.0 3.4 2.0 3.0 3.0
Rad. intensity (einstein l1 s1 ) 5.97 6.45 2.50 1.76 5.97 6.45 1.38 2.50 4.33 2.56 1.76 5.97 6.45 2.50 8.08 8.08 1.76 2.50 8.08 8.08 2.50 105 107 105 105 105 107 108 105 105 104 105 105 107 105 105 105 105 105 105 105 105
(nm) 320400 250 185436 320400 250
CP t1/2 (min) 15.0 9.9 1.3 4.5 7.2, 46.0a 9.3 10.0 10.5, 92a 15.6 8.8 16.8 11.8 39.5 25.0 9.7
kCP (min1 ) 7.68 103 3.83 102 1.18 102 3.65 102 0.112, 5.42 102 a 5.20 103 3.87 6.50 102 8.59 103 5.16 102 6.80 102 7.10 102
References [140] [233] [1] [23] [140] [233] [210] [1] [141] [98] [23] [140] [233] [1] [239] [239] [23] [1] [239] [239] [1] [23] [239] [239]
320400 172 185436 320400 250 185436 185436
1.76 105 8.08 105 8.08 105
Data referred to TOC. Data referred to TOC = 100 mg l1 . Data referred to TOC = 54.6 mg l1 .
244
Several authors have compared the O3 /UV system with the direct photolysis or simple ozonation. Some of them [23,72,139141,168] concluded that the combination O3 /UV improves the efciency of the single processes. Kuo [140,141] compared the destruction of 2-CP, 4-CP and 2,4-DCP by combination of photolysis + ozonation, direct photolysis and ozonation alone. As a result of this research it was found that the synergistic effects of the combined procedure increased obviously with increasing initial pH of solution to basic levels. This fact was attributed to that the initiation of ozonation could be catalyzed by OH ions. The experimental results also proved that the potentialities of photolytic ozonation compared to direct photolysis and ozonation alone was remarkable for the treatment of industrial wastewaters containing CPs. Ben tez et al. [23] studied the degradation of four CPs by the combined process UV/O3 at 25 C and pH 2. When comparing their results with single photodecomposition or pH 2 ozonation, it was found that the combined system accelerated the decomposition with an extremely high rate constant for 4-CP. The other CPs studied (2,4-DCP, 2,4,6-TCP and 2,3,4,6-TTCP) presented slightly increasing rate constants when the substituent chlorine atoms increased (this sequence was also observed in the single ozonation). Esplugas et al. [72] applied the photolytic ozonation to degrade 4-CP. It was concluded that UV on its own produced negligible degradation of the compound and some degradation was achieved by single ozonation. The mineralization of 4-CP was more effective when it was subjected to photolytic ozonation. Despite the conclusions reached by the above mentioned authors, Trapido et al. [233] afrmed that although the molar absorptivity of CPs in known to be relatively high in the UV, the combination of UV with ozone did not accelerate the degradation of CPs further. In this research, the degradation of 4-CP, 2-CP, 2,4-DCP, 2,4,6-TCP, 2,3,4,6-TTCP and PCP was studied by several AOPs. From this study, it was concluded that CPs can be degraded at quite signicant rates by all the methods studied, while traditional ozonation at high pH was determined to be the most effective method to treat CPs. 6.2.1. Mechanistic pathway The degradation of CPs by O3 /UV reagent follows a mechanism similar to the one described for simple ozonation. Nevertheless, a synergistic effect between direct ozonation, direct photolysis and hydroxyl radical decomposition is observed in this system [23]. On this way, some other elemental stages have to be added to take into account the interaction between radiation and matter (see Fig. 21). First of all, a stage the photolysis of ozone must be added, which leads to two hydroxyl radicals, which do not act as they recombine producing hydrogen peroxide [194]: H2 O + O3 + h H2 O2 + O2 (40)
Hydrogen peroxide, on being exposed to UV radiation can then decompose directly into hydroxyl radicals: H2 O2 + h 2HO (41)
In addition, H2 O2 accelerates O3 decomposition into hydroxyl radicals [225]: 2O3 + H2 O2 2HO + 3O2 (42)
6.3. Ozonation + homogeneous/heterogeneous catalysis: O3 /H2 O2 , O3 /Fe2+ and O3 /Fe2+ /UV Some approaches have been taken into account in order to improve the oxidizing power of ozone or ozone/UV leading to the reduction of time required for the reaction and hence, decreasing its energy cost. Several works indicate that a combination of ozone with hydrogen peroxide (O3 /H2 O2 ), which actually acts as a homogeneous catalyst, improves CP degradation [3,192,210,270]. In this case, in addition to the general pathway for ozonation exposed in Fig. 21, ozone reacts with H2 O2 when present as anion HO2 and the direct reaction of ozone with the undissociated H2 O2 is negligible due to a very low kinetic constant: H2 O2 + O3 H2 O + O2 , k < 0.01 M1 s1 (43)
Other propagation reactions that must be added are the following ones: H2 O2 HO2 + H+ O3 + HO HO2 + O2 H2 O2 + H2 O HO2 + H3 O+ O3 + HO2 HO + O2 + O2 O3 + HO HO2 + O2 (44) (45) (46) (47) (48)
In absence of any contaminant, the chain reaction may be terminated by the major step below: HO + HO2 H2 O + O2 , k = 3.7 1010 M1 s1 (49) In most cases, the optimum ratio H2 O2 /O3 is considered to be 0.5 mol/mol or more. Chamarro et al. [41] found the stoichiometric coefcients for 4-MCP degradation in the range 0.601 0.044 (mol removed/mol active reagent). Despite the good results shown by this method, it is not always advantageous to add H2 O2 with O3 , even when HO radical chemistry is necessary for the oxidation of the target organic. On the other hand, promising experiments involving ferrous or ferric ion homogeneous catalysis together with ozonation in presence or in absence of radiation are also reported in the literature [2,271]. Some data concerning this processes are shown in Table 13. As indicated in Fig. 24, the presence of ferrous ions seems to improve the mineralization of CPs
245
Table 13 Half-life times and pseudo-rst kinetic constants for degradation of CPs by O3 /Fe2+ /UV reagent for different initial concentrations of CP and O3 ow rates and for different radiation intensities Pollutant 2-MCP 4-MCP 4-MCP 2,4-DCP 2,4,6-TCP 2,4,5-TCP
a
[CP]0 (mM) 0.18 1.38 0.18, 100a 0.18 0.18 0.18
[Fe2+ ]0 (mM) 0.067 1.00 0.067 0.067 0.067 0.067
O3 feed ow rate (mg min1 ) 8.3 8.3 8.3 8.3 8.3 8.3
pH 3.4 3.3 3.4 3.4 3.4 3.4
Rad. intensity (einstein l1 s1 ) 2.50 105 1.38 108 2.50 105 2.50 105 105 2.50 2.50 105
(nm)
CP t1/2 (min) 7.1 7.0, 22.0a 5.8 12.4 19.0 10.5
kCP (min1 ) 0.113, 6.42 102 a
References [1] [210] [1] [1] [1] [1]
Data referred to TOC. Concentrations are measured in mg l1 .
Fig. 24. Evolution of Ln[TOC] with time for the degradation of 4-CP in presence of O3 /Fe2+ /UV reagent ([4-CP] = 0.18 mM, [TOC]0 = 100 mg l1 , [Fe2+ ]0 = 1.00 mM, pH 3.3, I = 1.38 108 einstein l1 s1 ) [210]. Table 14 Half-life times and pseudo-rst kinetic constants for degradation of CPs by heterogeneous ozonation [188] Solid -Alumina -Alumina -Alumina a (m2 g1 ) (BET) 120190 120190 120190 dp (mm) 0.0600.200 0.0600.200 0.0600.200 Conc. susp. (g l1 ) 1.7 1.7 1.7 [2-CP]0 (mM) 0.78 0.78 0.78 pH 3.0 7.0 9.0 CP t1/2 (min) 7.0 TOC t1/2 (min) 79 kCP (min1 ) 0.0653 0.1269 0.1390
when it is compared to single ozonation, and in presence of UV radiations, the action of these ions also seems to improve the efciency O3 /UV process. On the other hand, Ni and Chen [188] have reported the use of heterogeneous catalytic ozonation of 2-CP by employing -alumina as a solid catalyst, as summarized in Table 14. The research showed that the rate of degradation of TOC could increase from 21 to 43% by using this method instead of single ozonation, and the pseudo-rst reaction constant could also increase from 0.8688 to 0.127 min1 at pH 7.0 for particles with the general features exposed in Table 14.
ics [38,50,56,212,232] and more than 1700 references have been recently collected on this discipline [30]. Compared with other conventional chemical oxidation methods, photacatalysis may be more effective because semiconductors are inexpensive and capable of mineralizing various refractory compounds [139], however this technique is still in the developmental stage for many cases [59]. 7.1. Mechanistic pathways Photocatalytic reactions occur when charge separation are induced in a large bandgap semiconductor by excitation with ultra bandgap radiations [203]. This way, the absorption of light by the photocatalyst greater than its bandgap energy excites an electron from the valence band of the irradiated particle to its conduction band, producing a positively charged hole in the valence band and
7. Photocatalysis Photocatalytic degradation has proven to be a promising technology for degrading refractory chlorinated aromat-
246
Fig. 25. Conduction and valence bands and electronhole pair generation in semiconductors.
an electron in the conduction band [122] as shown in Fig. 25. The hole in the valence band may react with water absorbed at the surface to form hydroxyl radicals and on the other hand, the conduction band electron can reduce absorbed oxygen to form peroxide radicals anions that can further disproportionate to form HO through various pathways [4]. During the photocatalytic process, other oxygen containing radicals are also formed including superoxide radical anion and the hydroperoxide radical [59]. In addition, the band electron may also react directly with the contaminant via reductive processes [125]. It is not clear under which experimental conditions, one reaction pathway is more important than the other. It is generally accepted that the substrate adsorption in the surface of semiconductors plays and important role in photocatalytic oxidation [272]. Therefore if the surface of the catalyst is covered with the CP, the direct oxidation by positive holes could be the major oxidation pathway since the adsorption of organic compounds on the surface of the catalyst is the prerequisited step for direct charge transfer. On the other hand, indirect oxidation by hydroxyl radicals requires the adsorption of water or hydroxide ions on the surface to form the hydroxyl radicals [228,229]. 7.1.1. Direct photocatalytic pathway The literature suggests two different direct photocatalytic reaction mechanisms. 7.1.1.1. The LangmuirHinshelwood process. This mechanism is based on production of electrons and holes by the photoexcitation of the catalyst. The hole is then trapped by the adsorbed molecule (CP) to form a reactive radical state. On one side, this reactive specie (CPads + ) can decay when recombination with and electron occurs and on the other hand its chemical reaction yields to the products and regenerates the original state of the catalyst surface (S). Reactions (50)(55) show the reaction mechanism of the LangmuirHinshelwood process (adapted from Serpone and Emelie [215]): M + S CPads (adsorption/desorption Langmuir equilibrium) (50)
CPads M + S (adsorption/desorption Langmuir equilibrium) Cat + h e + h+ (51)
(photoexcitation of the catalyst) (52)
CPads + h+ CPads + (hole trapping by adsorbed molecule) CPads + + e CPads (decay of the reactive state) (53) (54) (55)
CPads + product + S (chemical reaction)
7.1.1.2. The EleyRideal process. This process starts with the photogeneration of free carriers and the subsequent trapping of the holes by surface defects (i.e. potential surface active centers) S to produce surface active centers S+ . These surface active centers can then react with the CP (chemisorption) to form species (SCP)+ that further decompose yielding the photoreaction products or can recombine with electrons, which represents their physical decay. The reactions involved in the process are shown below (adapted from Serpone and Emelie [215]): Cat + h e + h+ S + h+ S+ S+ + e S (photogeneration of free carriers) (56) (hole trapping by surface defects) (physical decay of active centers) (chemisorption) (57) (58) (59)
S+ + CP (SCP)+
(SCP)+ S + products (reaction to form photoreaction products) (60)
7.1.2. Indirect photocatalytic pathway The radical photodegradation mechanism is shown in reactions (61)(67) (adapted from Yue et al. [255]). The process starts with the photogeneration of electronhole pairs
247
on the surface of the catalyst particles when irradiated by the light in the region of absorption charge-transfer bands. The hole is trapped by the water molecules leading the formation of HO radicals and H+ and the electrons allow the formation of H2 O2 which further decomposes in more OH radicals by means of its reaction with the oxygen supplied in the medium. Finally, the radicals formed during this mechanism are responsible for the oxidation of the CPs yielding some intermediate compounds and mineralization products: h e + h+ h+ + H2 O(ads) HO(ads) + H(ads) + O2 + 2e O2 (ads)

(61) (62) (63) (64) (65) (66)
O2 (ads) + H+ HO2 (ads) HO2 (ads) H2 O2 (ads) + O2 H2 O2(ads) 2HO(ads) HO
2HO(ads) + CPs Intermediates + HCl HO CO2 + H2 O 7.2. Studies of degradation of CPs
(67)
Numerous photocatalytic semiconductors have been recently investigated for the destruction of several CPs in water, including TiO2 , CdS, ZnS and active carbon [139,164,279,280]. However, titanium dioxide, has been studied more extensively because of its low cost, stable nature and high photoactivity when exposed to near-UV light [84,109,125,139,237,203,273]. The experimental results obtained by Jardim et al. [124] and shown in Fig. 26 reinforce the viability of heterogeneous photocatalysis using TiO2 in the detoxication process, especially when chorinatedphenols are the target compounds since degradation
of DCP, TCP and PCP was shown to be feasible and almost complete. The applicability of some photocatalysts for CP degradation is summarized in Table 15. For instance, Doong et al. [61] reported that cadmium sulde had a higher rate constant than titanium dioxide for the degradation of 2-CP. This fact was attributed to that the average particle size of cadmium sulde is larger than that of titanium dioxide. Other researchers [15] studied the photocatalytic degradation of 2,4,6-trichlorophenol, 2,3-dichlorophenol, 2-chlorophenol and 2,4-dichlorophenol on aqueous suspensions of -Fe2 O3 and -FeOOH and TiO2 . -FeOOH was found to be inactive for CPs degradation with exception of 2,4-DCP where a modest effect was observed. The most active photocatalysis (-Fe2 O3 ) was compared with TiO2 . Total mineralization of CPs was observed on TiO2 while only partial mineralization was observed on Fe2 O3 . The effectiveness of TiO2 has been also compared with Na4 W10 O32 [230]. The results of the solar degradation of 2-CP and 2,4-DCP in the presence of TiO2 and Na4 W10 O32 showed that the degradation of the pollutants was twice faster in the presence of TiO2 . One possible way to enhance the degradation efciency of photocatalytic reactions consist of adding heavy metals, such as platinum (Pt), palladium (Pd), gold (Au) or other semiconductors [47,182,183]. The increase in the photoactivity when metallic ions are present can be justied by taking into account that the presence of a photoreduced metal on TiO2 would improve charge separation. Rideh et al. [203] have reported that the 2-CP photodegradation rate increases remarkably when they are saturated by oxygen and metallic ions such as Ag+ , Cr2 O7 2 , Cu2+ and Fe2+ . Chen et al. [46] studied the photocatalytic degradation of 2-CP, 2,4-DCP and 2,4,6-TCP in the presence of manganese ions at pH 3. The results indicate that dissolved manganese ions can increase the rate of CPs oxidation in the TiO2 photocatalytic system. Another technique to improve the degradation of CPs by photocatalysis consists of coupled semiconductors
Fig. 26. Photodegradation of PCP, 2,3,5-TCP, 3,5-DCP and 2,4-DCP and TOC values during irradiation. Experiments carried out in a cylindrical photoreactor of 800 ml capacity with a high-pressure 125 W mercury lamp, 0.1 g l1 of TiO2 and air supplied at 560 ml min1 [124].
248
Table 15 Half-life times and pseudo-rst kinetic constants for degradation of CPs by photocatalysis Pollutant 2-CP Pollutant conc. (mM) 0.78 Catalyst TiO2 (2.0 g l1 ) Lamp 100 W medium pressure Hg CP t1/2 (min) 170 200 80 48 48 20 80 110 140 200 59 53 36 27 15 420 8 8,8 7,3 180 160 60 256 108 256 900 22 845 1368 634 433 1061 499 416 252 354 173 145 528 234 238 300 8,4 10,4 5,8 5,3 165 59 10 Not reached 106 kCP (mol l1 min1 ) 3.89 3.27 1.01 1.25 2.80 2.10 7.78 6.38 4.51 3.66 9.10 7.71 7.47 5.04 3.72 2.57 8.60 8.20 9.50 2.70 6.40 5.24 2.70 6.40 2.70 2.33 4.03 2.82 2.98 6.24 8.93 3.93 8.17 9.59 1.50 1.07 2.11 2.66 7.56 1.65 1.61 2.68 8.60 6.60 1.26 1.28 9.32 106 106 105 105 105 106 107 107 107 107 106 106 106 106 106 106 105 105 105 104 104 105 104 104 104 106 106 107 107 107 107 107 107 107 106 106 106 106 107 106 106 106 105 105 104 104 107 106 pH 2.5 4.5 7.1 9.5 12.5 3.0 5.0 7.0 9.0 11.0 2.83.0 Reference [61]
2-CP
0.078
TiO2 (2 g l1 )
15 W black ue uorescent
[139]
2-CP
2-CP 2-CP 3-CP 4-CP 4-CP
0.78 0.54 0.39 0.19 0.077 0.50 1.00
TiO2
600 W high pressure xenon lamp
[43]
-Fe2 O3 (1.5 g l1 ) PW12 O40 3 (7.0 104 mol l1 )
Solar simulator Oriel 1000 W Xe arc lamp
6.0 1.0
[15] [7]
1.00
4-CP
1.00
TiO2 TiO2 /AC-M TiO2 /AC-PC TiO2 TiO2 -ACM TiO2 -ACpc -Fe2 O3 (1.5 g l1 ) TiO2 (0.1 g l1 ) TiO2 (g l1 ) 0.1 0.2 0.5 0.5 1.0 2.0 0.1 0.1 0.2 0.5 0.5 1.0 2.0 -Fe2 O3 (1.5 g l1 ) PW12 O40 3 (7.0 104 mol l1 )
125 W high pressure Hg lamp
[105]
High pressure Hg lamp 125 W
[172]
2,3-DCP 2,4-DCP 2,4-DCP
2,4-DCP 2,4-DCP 2,6-DCP 3,4-DCP 3,5-DCP 3,5-DCP 2,3,5-TCP 2,4,6-TCP 2,4,6-TCP PCP
0.50 0.12 0.34 0.59 0.57 0.56 0.60 0.59 0.58 0.55 0.55 0.53 0.56 0.58 0.56 0.55 0.50 1.00
Solar simulator 125 W high pressure Hg lamp Solar light in at reactor
Solar light in CPCs modules
Solar simulator Oriel 1000 W Xe arc lamp
6.0 6.0 6.6 6.2 5.9 6.2 7.6 5.9 5.6 4.6 5.9 4.2 4.2 5.9 6.0 5.1 6.0 1.0
[15] [124] [84]
[15] [7]
0.30 0.43 1.00 0.50 0.65
TiO2 (0.1 g l1 ) TiO2 PW12 O40 3 (7.0 104 mol l1 ) -Fe2 O3 (1.5 g l1 ) TiO2 (0.1 g l1 ) (0.1 g l1 )
125 W high pressure Hg lamp 125 W high pressure Hg lamp Oriel 1000 W Xe arc lamp Solar simulator 125 W high pressure Hg lamp
7.0 7.0 1.0 6.0 7.0
[124] [124] [7] [15] [124]
2.32 7.50 105 1.17 106 2.96 106
249
[155,216]. One possibility of coupled conductors is based on a combination of TiO2 /CdS which allows higher degradation efciency of 2-CP than the single semiconductor system [61]. The enhancement of photodegradation efciency of 2-CP in TiO2 /CdS/UV system may be attributed to the rapid transfer of the photogenerated electrons from the cadmium sulde to the titanium dioxide conduction band, resulting in the effective separation of the electrons and holes [216]. The addition of activated carbon to titania has been also studied and the results shows that the addition of a commercial H-type activated carbon to titania under UV radiation induces a benecial effect on the photocatalytic degradation of 4-CP whereas the addition of L-type carbon is rather detrimental [172]. 7.2.1. Effect of pH The pH has a great effect on the photodegradation efciency of CPs. The literature [182,183,222] suggests that TiO2 surface carries a net positive charge at low pH value, while the CPs and intermediates are primarily negatively and neutrally charged. Therefore, low pH values can facilitate the adsorption of the organic molecule and promote better photocatalytic degradation. This statement is in agreement with the results obtained by Ku et al. [139], where the photodegradation of 2-CP in the presence of TiO2 under various solution pH showed higher pseudo-rst order photolytic rate constant at pH 3. However, better removal efciency of CPs in TiO2 /UV system under alkali condition has been also reported [212,216,222]. One possible explanation is that the photocatalytic transformation of CPs does not involve hydroxyl radical oxidation exclusively and direct electron transfer and surface sorption reactions also contribute signicantly to the disappearance of CPs in TiO2 suspensions [212,222]. Another possible explanation is that TiO2 has an amphoteric character with a point zero charge around pH 6 [274], and the substrate can undergo acidbasic equilibrium. Consequently, the adsorption of the substrate may be affected, strongly inuencing the degradation rate [137]. The results presented by Doong et al. [61] and Rideh et al. [203] show that the rate constant is lower in acid medium than in basic medium for the photodegradation of 2-CP in the presence of TiO2 . Tang and Huang [228] studied the photodegradation of 2,4-DCP and found that the optimal pH for this system was pH 5. 7.2.2. Effect of the dose of semiconductor The inuence of the dose of the semiconductor in the photocatalytic reaction has been studied in the last years. At low photocatalyst loadings, the removal of organic compounds increased linearly with the catalyst loading; however, the presence of excess photocatalyst in the aqueous solutions could cause a shielding effect on the penetration light [84] [275]. After the achievement of the maximum reaction rate, increased turbidity of the solution reduced the light transmission through the solution, while below this level, it is assumed that the catalyst surface and the
absorption light by TiO2 were limiting [203]. Doong et al. [61] observed that increasing the TiO2 dosage decreased the photodegradation efciency of 2-CP. Removal of 71% was observed with the illumination time of 150 min when 0.1 g l1 was amended into the system. However, only 50% of 2-CP were decomposed when the dosage of TiO2 increased to 1 g l1 . Rideh et al. [203] carried out a series of experiments to nd out an optimum catalyst concentration by varying the concentration of TiO2 on the reaction with 2-CP from 1.2 102 to 0.3 kg m3 . The results showed that the initial photodegradation rate increases linearly with catalyst concentration up to 0.2 kg m3 . 7.2.3. Effect of the initial concentration of CP Many researchers have studied the effect of the initial concentration of the pollutant in the photocatalysis. In all the cases it was found that an increase in the concentration of the contaminant involves a decrease in the photocatalytic reaction rate. A plausible explanation can be that since the initial concentration increases, more and more organic substances are adsorbed on the surface of TiO2 , but the intensity of light and illumination time are constant; consequently, the OH formed on the surface of TiO2 is constant, the relative number of OH attacking the CPs decreases, and thus the photodegradation efciency decreases too [178]. Chan et al. [43] and Rideh et al. [203] observed that an increase in the initial concentration of 2-CP when degraded photocatalytically by TiO2 involved a decrease in the rate of degradation. Chen et al. [46] studied the photocatalytic degradation of 2-CP, 2,4-DCP and 2,4,6-TCP in the presence of manganese ions at pH 3 varying the concentration of the CPs. In all the cases, the rate constant of the photodegradation decreases when increasing the initial concentration of the CPs. 7.2.4. Effect of temperature Temperature has been proved to be an important aspect when studying the photocatalysis of CPs. Rideh et al. [203] and Chen et al. [46] studied the inuence of temperature on the rate of degradation of 2-CP. Rideh et al. [203] afrm that the oxidation rate of 2-CP did not change signicantly in the range of 1565 C. Chen et al. [46] reported that the rate increases following Eq. (67): k = 0.0043T 1.2146 (min1 , T in K) (68)
7.2.5. Effect of the oxygen concentration Axelsson et al. [276], Barbeni et al. [16] and Chan et al. [43] have reported that the partial pressure of oxygen is a crucial factor in the photocatalytic reaction, in fact, photocatalysis is commonly carried out with a source of oxygen or air [124,139,203,276278]. The limitation of the rate of photocatalytic degradation is attributed by most researchers to the recombination of photogenerated holeelectron pairs. Oxygen absorbed on the surface of TiO2 prevents the recombination process by trapping electrons according to the
250
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reaction [203]: O2 + e O2 Rideh et al. [203], found that the degradation rate of 2-CP increases non-linearly with oxygen partial pressure. It was assumed that the reaction rate is a function of the fraction of adsorption sites occupied by oxygen; hence oxygen adsorption becomes a limiting factor at very low dissolved oxygen concentrations. 8. Conclusions Taking into account only the half reaction time data between the different AOPs studied for the degradation of CPs (shown in Tables 57, 9, 11, 12 and 15) it can be concluded that single ozonation appears to be the most suitable method for the treatment of aqueous solutions containing CPs. In fact, by means of single ozonation, the lowest half-times have been reported for the degradation of MCPs, TCPs and TTCPs. However, AOPs based on H2 O2 (Fenton, photo-Fenton and H2 O2 -UV) have been also reported to achieve the degradation of this compounds in a short period of time. Moreover, these techniques are also of interest because they involve less cost expenses than ozonation. As for the degradation of TTCPs, besides ozonation, the combination O3 /UV and photo-Fenton techniques have been reported to achieve high reaction kinetic rates. On the other hand, the photo-Fenton process seems to be a suitable technique for the treatment of DCP, jointly with single ozonation and Fenton which have also shown reasonable results for its degradation. According to the literature, photocatalytic processes have shown higher half reaction times than the rest of the AOPs for the treatment of most of the CPs. However, photocatalysis displays also some advantages with respect to the other AOPs, since no oxidant is consumed during the oxidation and it does not require any further separation after the reaction (like in the case of Fenton-like processes, where Fe2+ ions are dissolved in the medium during the reaction). Acknowledgements The authors wish to express their gratitude for the economic support given by the Spanish Ministry of Education and Culture (CICYT projects PPQ 2001-3046 and PPQ 2002-00565). M. Pera-Titus and V. Garc a-Molina are thankful to Prof. Juha Kallas from Lappeenranta University of Technology (Finland) and Dr. Sandra Contreras for the aid given in this work. References
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Applied Catalysis B: Environmental 47 (2004) 219256

Degradation of chlorophenols by means of advanced oxidation processes: a general review

M. Pera-Titus et al. / Applied Catalysis B: Environmental 47 (2004) 219256

M. Pera-Titus et al. / Applied Catalysis B: Environmental 47 (2004) 219256

Normal standard hydrogen electrode.

M. Pera-Titus et al. / Applied Catalysis B: Environmental 47 (2004) 219256

Cations pHa Metals TiO2 Light intensity

M. Pera-Titus et al. / Applied Catalysis B: Environmental 47 (2004) 219256

M. Pera-Titus et al. / Applied Catalysis B: Environmental 47 (2004) 219256

(mol einstein1 , T in K, = 185436 nm)

M. Pera-Titus et al. / Applied Catalysis B: Environmental 47 (2004) 219256

102 102 103 102

4.80 104 6.45 107 6.45 107

2.10 102 8.16 102 5.39 102

M. Pera-Titus et al. / Applied Catalysis B: Environmental 47 (2004) 219256

M. Pera-Titus et al. / Applied Catalysis B: Environmental 47 (2004) 219256

T ( C) Room 30 25 22 25 20 25 Room 25 Room Room Room 22 22 25 25 Room 30 Room 22 22 25 Room 25

anions with a concentration of 3.00 mM in all cases.

M. Pera-Titus et al. / Applied Catalysis B: Environmental 47 (2004) 219256

M. Pera-Titus et al. / Applied Catalysis B: Environmental 47 (2004) 219256

M. Pera-Titus et al. / Applied Catalysis B: Environmental 47 (2004) 219256

M. Pera-Titus et al. / Applied Catalysis B: Environmental 47 (2004) 219256

(11) (12) (13) (14)

(15) (16) (17) (18)

M. Pera-Titus et al. / Applied Catalysis B: Environmental 47 (2004) 219256

M. Pera-Titus et al. / Applied Catalysis B: Environmental 47 (2004) 219256

M. Pera-Titus et al. / Applied Catalysis B: Environmental 47 (2004) 219256

[TCP]0 = 0.10 mM, = 185436 nm)

M. Pera-Titus et al. / Applied Catalysis B: Environmental 47 (2004) 219256

On the other hand, the following equation provides electrons: (21)

Total Fe (g kg1 ) 5.5 c c 4.9 4.9 0.6 90.2 No data

M. Pera-Titus et al. / Applied Catalysis B: Environmental 47 (2004) 219256

M. Pera-Titus et al. / Applied Catalysis B: Environmental 47 (2004) 219256

102 102 102 102 102 102 102

Data referred to TOC.

M. Pera-Titus et al. / Applied Catalysis B: Environmental 47 (2004) 219256

T ( C) 25 20 25 Room 25 25 Room 25 25 Room 25 Room 25 25

This CP concentration corresponds to TOC =

M. Pera-Titus et al. / Applied Catalysis B: Environmental 47 (2004) 219256

Data referred Half-time for Half-times in Data referred Data referred

to TOC. TOC not reached. seconds. to TOC = 100 mg l1 . to TOC = 36 mg l1 .

M. Pera-Titus et al. / Applied Catalysis B: Environmental 47 (2004) 219256

M. Pera-Titus et al. / Applied Catalysis B: Environmental 47 (2004) 219256

M. Pera-Titus et al. / Applied Catalysis B: Environmental 47 (2004) 219256

(nm) 320400 250 185436 320400 250

320400 172 185436 320400 250 185436 185436

1.76 105 8.08 105 8.08 105

M. Pera-Titus et al. / Applied Catalysis B: Environmental 47 (2004) 219256

M. Pera-Titus et al. / Applied Catalysis B: Environmental 47 (2004) 219256

[CP]0 (mM) 0.18 1.38 0.18, 100a 0.18 0.18 0.18

[Fe2+ ]0 (mM) 0.067 1.00 0.067 0.067 0.067 0.067

pH 3.4 3.3 3.4 3.4 3.4 3.4

CP t1/2 (min) 7.1 7.0, 22.0a 5.8 12.4 19.0 10.5

kCP (min1 ) 0.113, 6.42 102 a

References [1] [210] [1] [1] [1] [1]

Data referred to TOC. Concentrations are measured in mg l1 .

M. Pera-Titus et al. / Applied Catalysis B: Environmental 47 (2004) 219256

CPads M + S (adsorption/desorption Langmuir equilibrium) Cat + h e + h+ (51)

(photoexcitation of the catalyst) (52)

CPads + product + S (chemical reaction)

(SCP)+ S + products (reaction to form photoreaction products) (60)

M. Pera-Titus et al. / Applied Catalysis B: Environmental 47 (2004) 219256

(61) (62) (63) (64) (65) (66)