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Chemosphere 41 (2000) 12711277

Contribution of free radicals to chlorophenols decomposition by several advanced oxidation processes


F. Javier Benitez *, Jesus Beltran-Heredia, Juan L. Acero, F. Javier Rubio
Departamento de Ingenieria Quimica y Energetica, Universidad de Extremadura, 06071, Badajoz, Spain Received 18 June 1999; accepted 29 October 1999

Abstract The chemical decomposition of aqueous solutions of various chlorophenols (4-chlorophenol(4-CP), 2,4-dichlorophenol (2-DCP), 2,4,6-trichlorophenol (2,4,6-TCP) and 2,3,4,6-tetrachlorophenol (2,3,4,6-TeCP)), which are environmental priority pollutants, is studied by means of single oxidants (hydrogen peroxide, UV radiation, Fenton's reagent and ozone at pH 2 and 9), and by the Advanced Oxidation Processes (AOPs) constituted by combinations of these oxidants (UV/H2 O2 , UV/Fenton's reagent and O3 /UV). For all these reactions the degradation rates are evaluated by determining their rst-order rate constants and the half-life times. Ozone is more reactive with higher substituted CPs while OH radicals react faster with those chlorophenols having lower number of chlorine atoms. The improvement in the decomposition levels reached by the combined processes, due to the generation of the very reactive hydroxyl radicals, in relation to the single oxidants is clearly demonstrated and evaluated by kinetic modeling. 2000 Elsevier Science Ltd. All rights reserved.
Keywords: Chlorophenols; Hydroxyl radicals; Advanced oxidation processes; UV radiation/hydrogen peroxide; UV radiation/Fenton's reagent; Ozone/UV radiation

1. Introduction The chemical oxidation of toxic and hazardous organic pollutants, which frequently are present in surface waters and wastewaters, is often carried out by using single oxidants such as chlorine, ozone, UV radiation, hydrogen peroxide, etc. However, sometimes this decomposition by conventional treatments may be dicult if these pollutants are present at low concentrations or if they are especially refractory to the oxidants. For these situations, it has been necessary to develop more eective processes for the destruction of such contaminants. Among them, some systems based on the generation

Corresponding author. Tel.: +34-924-289384; fax: +34924-271304. E-mail address: javben@unex.es (F.J. Benitez).

of very reactive and oxidizing free radicals, especially hydroxyl radicals, have experimented an increasing interest due to their high oxidant power. These systems are commonly named Advanced Oxidation Processes (AOPs), and the production of those radicals is achieved by the combinations of ozone, hydrogen peroxide and UV radiation (Glaze et al., 1987; Glaze and Kang, 1989; Masten and Davies, 1994); and also, with the combination of hydrogen peroxide with ferrous ions in the socalled Fenton's reagent (Walling, 1975). Chlorophenols (CPs) constitute a group of organic substances that are introduced into the environment as a result of several man-made activities, such as water disinfection, waste incineration, uncontrolled used of pesticides and herbicides, etc., and also as byproducts in the bleaching of paper pulp with chlorine (Ahlborg and Thunberg, 1980). Because of their numerous origins, they can be found in industrial wastewaters, soils and surface waters, and several of them have been listed

0045-6535/00/$ - see front matter 2000 Elsevier Science Ltd. All rights reserved. PII: S 0 0 4 5 - 6 5 3 5 ( 9 9 ) 0 0 5 3 6 - 6

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among the 65 priority pollutants by the US EPA (Keith and Telliard, 1979). Their conventional destructive technologies include biological treatments, incineration, adsorption over activated carbon, air stripping, etc. (Jardin et al., 1997). Some of these treatments, like the biological treatments, can be aected by the toxicity of some substances; others, like incineration, present considerable emission of other hazardous compounds; and adsorption or air stripping requires a post-treatment to remove the pollutants from the newly contaminated environment. Therefore, a promising technology could be the use of single chemical oxidants, or the more eective destruction by the AOPs, which can provide an almost total degradation as has been reported by several authors in the decomposition of a wide variety of organic contaminants (Peyton et al., 1982; Guittonneau et al., 1988; Legrini et al., 1993). According to these considerations, a research program was designed which focused on the oxidation of several chlorophenols (4-chlorophenol (4-CP), 2,4-dichlorophenol (2,4-DCP), 2,4,6-trichlorophenol (2,4,6TCP) and 2,3,4,6-tetrachlorophenol (2,3,4,6-TeCP)) by single oxidants and by dierent AOPs. The objectives were to provide data about the removal obtained, to report values of the rate constants for the global processes, and to compare the eciency of the dierent AOPs tested. Also, the enhancements reached in the degradation levels in these combined oxidations compared to the single oxidation processes are determined, and the partial contributions of the OH radical pathway to the global oxidation process are calculated for the dierent AOPs studied. 2. Materials and methods Analytical grade 4-CP, 2,4-DCP, 2,4,6-TCP and 2,3,4,6-TeCP were obtained from Sigma, hydrogen peroxide (33% v/v) was purchased from Panreac and ferrous sulfate heptahydrate was from Merck. Ozone was produced from an oxygen stream in an ozone generator (Yemar, mod. HPA), and the radiation source was a Heraeus TQ150 high pressure mercury vapor lamp which emitted a polychromatic radiation in the range from 185 to 436 nm. The reactor used in all the experiments consisted of a 500 ml cylindrical glass reactor provided with the necessary elements for the development of the dierent processes: photodecomposition, Fenton's reagent oxidation, ozonation, and the dierent combinations of these oxidants. In the photochemical experiments, the radiation source was located in the reactor in axial position. The reactor was lled with 350 ml of an aqueous solution of the selected CP (initial concentration of 3 104 M in all cases), and the selected pH (2 or 9) was

obtained by adding orthophosphoric acid and sodium hydroxide. The required amounts of ferrous sulfate and hydrogen peroxide were added to the reactor in Fenton's reagent oxidation experiments and in the photo-Fenton experiments, and only the required amounts of hydrogen peroxide in the UV/H2 O2 experiments. In the ozonation experiments and combined UV/ozone experiments, the ozoneoxygen mixture was fed to the reactor through a porous plate gas sparger located at the bottom of the reactor. The temperature was kept constant at 25C. The CPs concentrations in the samples withdrawn from the reactor at regular reaction times were analyzed by HPLC using a Waters Chromatograph equipped with a 996 Photodiode Array Detector and a Nova-Pak C18 Column. The detection was made at 290 nm with a mobile phase composed of a mixture methanolwater acetic acid (65/33/2 in volume) and with a ow rate of 1 ml/min. Ozone concentration was measured in the gas stream iodometrically by bubbling the gas in a potassium iodide solution. The concentration of H2 O2 was determined by the colorimetric method proposed by Bader et al. (1988). 3. Results and discussion 3.1. Decomposition by single oxidants In a rst stage, the decomposition of all four selected CPs was performed by the action of the following single oxidants: UV radiation, Fenton's reagent and ozone. A previous set of degradation experiments by using hydrogen peroxide alone was also conducted, but no signicant CPs degradation was obtained with this oxidant. Therefore, it can be concluded that H2 O2 does not oxidize the studied organic compounds, this eect being already observed by several authors with some refractory pollutants (Masten and Davies, 1994; Benitez et al., 1995). 3.1.1. UV radiation The photooxidation of CPs by a polychromatic UV radiation was conducted at pH 2. Fig. 1 shows the decrease in concentration as a function of irradiation time: As can be observed, 4-CP was rapidly degraded; decreasing rates are obtained for 2,4-DCP, 2,4,6-TCP, and for 2,3,4,6-TeCP. It suggests that the addition of substituent chlorine atoms decreases the susceptibility of the aromatic ring to be attacked by the photons generated by the UV radiation. It can be explained by taking into account that during photochemical treatments, electronically excited states of polychlorinated phenols are generated (Skurlatov et al., 1998). In these excited states, the CP molecules undergo intramolecular transformations and stabilize states with dierent electron

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rine atoms also increase, corroborating the sequence obtained for the decomposition rates. 3.1.2. Fenton's reagent In a second step, the decomposition of the four selected CPs was explored by means of the very reactive and oxidizing hydroxyl radicals, which are generated by Fenton's reagent, a mixture of hydrogen peroxide and ferrous ions, according to the reaction (Walling and Kato, 1971; Walling, 1975)
Fig. 1. CPs decomposition curves by direct photolysis.

H2 O2 Fe2 3 Fe3 OH OHX

distributions, followed by decomposition to radical or molecular products. A higher level of chlorine substitution must bother the formation of the excited state or the stabilization of the intermediate state. Since reaction mechanisms are complex for the photodegradation of organic compounds, a rigorous kinetic study cannot be performed. However, the shape of the lines in Fig. 1 looks like a rst-order reaction with respect to CPs degradation. Therefore, an approach to this kinetic study can be performed by assuming that the photochemical decomposition reaction follows a rstorder kinetics, and can be represented by the simple expression P hm 3 Poxid Y
kp

The hydroxyl radicals formed attack any organic compound P, and thus, cause its chemical decomposition P OH 3 Poxid Y
kr

where Poxid symbolizes intermediates and nal products, and kp is the rst-order rate constant. This approach is frequently used by several authors in similar studies (Sundstron et al., 1989; Shen et al., 1995). In order to evaluate these rate constants, the terms ln (CP 0 /CP ) are plotted versus reaction time, and after linear regression analysis, the rst-order rate constants are determined and showed in Table 1 with the correlation coecients. Obviously, they follow the trend already commented for the degradation rates: 4-CP >2,4-DCP >2,4,6-TCP >2,3,4,6-TeCP. Table 1 also summarizes another interesting kinetic parameter, the half-life times t1a2 or time necessary to reduce the initial concentration of the CPs in solution by a factor of two. As can be observed, these t1a2 increase when the substituent chlo-

where Poxid again symbolizes dierent intermediates and nal products of the chain degradation reactions that take place, and kr is the rst-order rate constant for the reaction of CPs with OH. In these experiments, the initial concentrations of Fe2 and H2 O2 were respectively 1 104 and 7X5 103 M, and the pH 2. The degradation curves obtained versus reaction time again suggest that a rstorder kinetics perfectly approaches the real kinetics of this Fenton's reagent oxidation process. Fig. 2 shows the plot of ln (CP 0 /CP ) against reaction time: as can be seen points lie satisfactorily around straight lines. After regression analysis, the results obtained for kr and for the half-life times are depicted in Table 1. The sequence of oxidation rates is the same as in the photodegradation process, that is: 4-CP >2,4-DCP >2,4,6-TCP >2,3,4,6TeCP. Hydroxyl radicals usually attack the aromatic ring at the sites which are not occupied by chlorine atoms, and therefore, hydroxylation is the rst elementary step which precedes the dissociation of chlorine atoms (Tang and Huang, 1996). So, the increase in the chlorine atoms number in the aromatic ring decreases the reactivity towards the hydroxyl radicals, and subsequently, the trend in the t1a2 values is inverse: they increase when the substituent chlorine atoms also increase.

Table 1 Rate constants and half-life times for the decomposition of CPs by single oxidants Compound UV kp 10 (min1 ) 4-CP 2,4-DCP 2,4,6-TCP 2,3,4,6-TeCP 564 38 26 21
3

Fenton t1a2 (min) 1.1 17.5 25.2 30.6 kr 10 (min1 ) 1877 209 98 9
3

O3 pH 2 t1a2 (min) 0.4 2.4 5.1 49.5 kO3 10 (min1 ) 17 24 44 94


3

O3 pH 9 t1a2 (min) 38.5 30.4 20.6 10.6 kO3 103 (min1 ) 239 315 314 415 (0.99) (0.98) (0.98) (0.99) t1a2 (min) 3.4 3.3 3.1 1.9

(0.99) (0.99) (0.99) (0.99)

(0.99) (0.99) (0.99) (0.98)

(0.99) (0.99) (0.98) (0.98)

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Fig. 2. Determination of rst-order rate constants kr in CPs decomposition experiments by Fenton's reagent.

Another group of CPs ozonation experiments were conducted in basic media (pH 9). In this case, the degradation curves were very close for all the CPs studied, with similar conversions for every CP. Table 1 also shows the values obtained for the rst-order rate constants kO3 and the half-life times which conrm the small dierences in the removal of the CPs at this pH. However, the most important fact that can be observed when comparing the results at pH 2 and pH 9 is the further increase in the rate constant (and decrease in the half-life time) with increasing the pH. This nding can be explained by the faster production of OH radicals at basic pH and the dissociation of phenols to phenolate ions that are able to react with ozone faster than the non-dissociated species (Hoigne and Bader, 1983). 3.2. Decomposition by advanced oxidation processes In the second part of this research, the Advanced Oxidation Processes constituted by the combinations of UV radiation plus H2 O2 , UV radiation plus Fenton's reagent, and UV radiation plus ozone, have been used for the study of CPs decomposition. As was mentioned in Section 1, these processes are characterized by the generation of free radicals, mainly hydroxyl radicals (Glaze et al., 1987; Glaze and Kang, 1989; Peyton et al., 1982). Therefore, the objectives of this study are focused on the evaluation of the enhancements caused in the oxidation reactions by these radicals in comparison to the reduction levels reached by the single oxidants at similar operating conditions. 3.2.1. UV/H2 O2 system Photodegradation experiments of the four selected CPs in the presence of hydrogen peroxide (with a H2 O2 initial concentration of 5 104 M in these experiments) were conducted at 25C and pH 2, and the sequence of degradation rates achieved was just the same as that obtained for the single photochemical process (showed in Fig. 1): the degradation rates increase when the number of chlorine substituents decreases. This sequence can be observed in Table 2, where the conversions obtained at three selected reaction times (2.5, 5 and 30 min) are summarized, as well as the rst-order rate constants for this combined process kt and the half life times t1a2 . It is seen that these rate constants present a

3.1.3. Ozone Finally, the CPs were oxidized by ozone (with an ozone partial pressure in the ozoneoxygen gas stream of 90 Pa) at 25C and in acidic media pH 2. At this pH the decomposition of ozone, which is initiated by the action of hydroxide ions (Staehelin and Hoigne, 1982), is too low and consequently the formation of hydroxyl radicals is limited. This decomposition of organic compounds by ozone can be represented by a single global reaction which follows a rst-order kinetics: P O3 3 Poxid X
K O3

When the four CPs were ozonated, the rate constant kO3 for the reaction represented by Eq. (4) was in the following decreasing rate of magnitude: 2,3,4,6-TeCP >2,4,6-TCP >2,4-DCP >4-CP as can be observed in Table 1. Similar results were obtained by Trapido et al. (1997) in the ozonation of several CPs. Therefore, it can be concluded that the sequence of degradation is the inverse to that found in the photodegradation and Fenton's reagent processes; that is, the increase in the number of chlorine atoms in the aromatic ring provides an increase in the degradation rate. The pathways proposed by Chen and Ni (1998) to describe the complete ozonation of 2,4-dichlorophenol were hydroxylation, dechlorination and ring-cleavage. According to this mechanism, the presence of more atoms of chlorine enhances the dechlorination step, and therefore, the degradation is faster.

Table 2 Conversions reached, rate constants and half-life times in the decomposition of CPs by UV/H2 O2 Compound 4-CP 2,4-DCP 2,4,6-TCP 2,3,4,6-TeCP
a

X2X5 (%) 70 15 11 10

X5 (%) 89 25 18 21

X30 (%) a 74 66 63

kt 103 (min1 ) 601 44 33 29

t1a2 (min) 1.0 14.5 19.2 20.1

kr 103 (min1 ) 36 6.9 7.2 7.9

Total conversion reached at 9 min.

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moderate higher values than those obtained in the single photodecomposition process (see Table 1, values of kp ). These ndings demonstrate the additional contribution to the single photoreaction of the hydroxyl radicals generated by the presence of hydrogen peroxide. This supplementary contribution can be determined by considering the mechanism of the combined process. Thus, in addition to the direct photoreaction (1), the following reactions must be taken into account: Direct photolysis of hydrogen peroxide with the formation of hydroxyl radicals: H2 O2 hm 3 2 OH 5

Radical reaction between the organic compound and the hydroxyl radicals generated in (5), which is given by Eq. (3). According to this mechanism, the reaction rate for the global photodecomposition rT can be proposed as the addition of the direct rP (reaction (1)) and radical rR (reaction (3)) reaction rates in the form ! dCP rT rP rR kp kr CP kt CP X dt 6 According to Eq. (6), the rate constants for the radical reaction kr are easily deduced by subtracting the previously determined kp from kt , and Table 2 also depicts the kr obtained. When comparing these values to those of kp in Table 1, it is shown that the direct photolysis provides

a contribution to the total reaction higher than that of the radical reaction. In order to validate the proposed mechanism which allows to calculate the rate constants, Fig. 3 presents the theoretically calculated degradation curves of 2,4,6-TCP (taken as example, similar results for other CPs) for the single radical and photochemical reactions, and for the combined UV/H2 O2 reaction. These theoretical curves were calculated by means of computer simulations by using the program ACUCHEM, which solves complicated systems of chemical reactions (Braun et al., 1988). For these calculations, the evaluated rate constants kp and kr have been used, and the global degradation is determined as the sum of both contributions. In the combined reaction, the experimental concentrations obtained are also plotted. The excellent agreement between model calculations and experimental data supports the proposed mechanism. 3.2.2. Photo-Fenton system Decomposition experiments of the CPs were carried out by the simultaneous action of UV radiation and Fenton's reagent (with initial concentrations of Fe2 1 105 M and H2 O2 5 104 M), and the same sequence of degradation rates as in the single photodecomposition or Fenton's reagent processes, or as in the combined UV/H2 O2 system was obtained. Table 3 depicts the conversions obtained at three reaction times, as well as the rst-order rate constants kt and the half-life times. When compared these rate constants kt to the single photodecomposition rate constants (kp in Table 1), higher values for kt can be seen which again conrm the additional contribution of the radical reaction due to the generation of the hydroxyl radicals by Fenton's reagent and by the H2 O2 . To evaluate the contribution of OH radical in this process, in addition to reactions (1) and (2), corresponding to the direct photodecomposition and the generation of hydroxyl radicals by Fenton's reagent respectively, another hydroxyl radicals generation reaction must be considered due to the photolysis of H2 O2 which is represented by Eq. (5). According to this mechanism described by Eqs. (1), (2), (5) and (3), Eq. (6) can be used to determine the hydroxyl radicals contribution to the global reaction. Table 3 depicts the kr values obtained after using Eq. (6) and higher values of kr for this system

Fig. 3. Decomposition curves for 2,4,6-TCP in the UV/H2 O2 system. ( ) theoretical values. (e) experimental values.

Table 3 Conversions reached, rate constants and half-life times in the decomposition of CPs by the photo-Fenton system Compound 4-CP 2,4-DCP 2,4,6-TCP 2,3,4,6-TeCP
a

X2X5 (%) 81 24 21 16

X5 (%) 96 39 37 28

X20 (%) a 84 79 67

kt 103 (min1 ) 642 88 78 58

t1a2 (min) 0.9 7.4 8.5 12.0

kr 103 (min1 ) 79 50 52 37

Total conversion reached at 8 min.

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in comparison to the AOP UV/H2 O2 are observed. Furthermore, the contribution to the global reaction of the radical reaction is higher than that of the direct photodecomposition (comparison between kr of Table 3 and kp of Table 1), except for 4-CP whose direct photolysis is really fast. Similar to the former UV/H2 O2 system, Fig. 4 shows the theoretical degradation curves for 2,3,4,6-TeCP (taken as example), calculated as described above, and the experimental concentrations obtained in this combined system: again a perfect agreement is observed between experimental results and model calculations. In addition, is also seen the higher degradation rate corresponding to the radical reaction in comparison to the direct photolysis. 3.2.3. O3 /UV system Finally, degradation experiments of the four CPs by the combined process UV/O3 were conducted at 25C and pH 2. The results obtained for the conversions at three reaction times (2.5, 5 and 20 min), the global rstorder rate constants kt (with correlation coecients higher than 0.99 in all cases) and the half-life times t1a2 are depicted in Table 4. When comparing these results to those of the single photodecomposition or pH 2 ozonation processes (Table 1), it is observed that this combination accelerates the decomposition rate as could be expected, with an extremely high rate constant kt for 4-CP (as a consequence of its extremely high rate for the single photolysis), and lower rates for the rest of CPs.

These remaining CPs (2,4-DCP, 2,4,6-TCP and 2,3,4,6TeCP) present slightly increasing rate constants when the substituent chlorine atoms increase, which was the sequence observed in the single ozonation. As Peyton et al. pointed out (Peyton et al., 1982), ozone absorbs UV radiation and produces hydrogen peroxide O3 hm 3 H2 O2 7

and then, there is a photolysis of hydrogen peroxide to generate hydroxyl radicals in the form described by reaction (5). In addition, H2 O2 accelerates O3 decomposition into OH radicals (Staehelin and Hoigne, 1982) O3 H2 O2 3 OHX 8

These radicals generated by reactions (5) and (8) constitute the principal active species in the photolytic ozonation. Thus, in the O3 /UV process, there is a synergistic eect of several individual reactions: direct ozonation (reaction (4)), direct photolysis (reaction (1)) and hydroxyl radical decomposition (reaction (3)). However, this synergism cannot be accounted for on the basis of an additive eect as in the former cases (UV/ H2 O2 and photo-Fenton), and its magnitude varies from substrate to substrate.

4. Conclusions Several single oxidants and combined systems have been used for the decomposition of some CPs, like 4-CP, 2,4-DCP, 2,4,6-TCP and 2,3,4,6-TeCP, being the degradation rates evaluated by means of rst-order rate constants. In the decomposition by single UV radiation and Fenton's reagent, 4-CP is the most rapidly degraded and 2,3,4,6-TeCP presents the lowest rate, while in the single ozonation process the sequence of degradation is inverse: 2,3,4,6-TeCP >2,4,6-TCP >2,4-DCP >4-CP, with a clear increase in the degradation rate when the pH is increased from 2 to 9. Therefore, ozone attacks to these CPs with a dierent mechanism than OH radicals, being this study the goal of current investigations. In the decomposition experiments by the advanced oxidation processes, an enhancement in the degradation is observed due to the generation of the hydroxyl radi-

Fig. 4. Decomposition curves for 2,3,4,6-TeCP in the photoFenton system. ( ) theoretical values. (h) experimental values.

Table 4 Conversions reached, rate constants and half-life times in the decomposition of CPs by O3 /UV Compound 4-CP 2,4-DCP 2,4,6-TCP 2,3,4,6-TeCP
a

X2X5 (%) 78 3 16 22

X5 (%) 96 14 28 37

X20 (%) a 64 73 77

kt 103 (min1 ) 644 65 68 71

t1a2 (min) 1.3 15.6 11.8 9.7

Total conversion reached at 7 min.

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cals. This improvement is moderate in the UV/H2 O2 system and signicant in the UV/Fenton's reagent system. In the last one, the contribution of the radical reaction to the global reaction is higher than that of the direct photolysis. In the O3 /UV system an improvement of the degradation rate is also observed, but in this case the synergistic eect is not possible to be determined as a result of an additive eect.

Acknowledgements Authors wish to thank CICYT of Spain for its nancial support under Project AMB97-339, and Junta de Extremadura for its Project IPR98A014. F. Javier Rubio also thanks Junta de Extremadura for being granted with a PhD Grant.

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