Science of the Total Environment 407 (2009) 34733481

Contents lists available at ScienceDirect

Science of the Total Environment

j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / s c i t o t e n v

Optimizing the treatment of landll leachate by conventional Fenton and photo-Fenton processes
Daphne Hermosilla a,, Manuel Cortijo b, Chin Pao Huang c
a b c

Departamento de Ingeniera Qumica, Facultad de Ciencias Qumicas, Universidad Complutense de Madrid, Ciudad Universitaria s/n, 28040 Madrid, Spain U.D. Operaciones Bsicas, Departamento de Ingeniera Forestal, E.T.S.I. Montes, Universidad Politcnica de Madrid, Avda. Ramiro de Maeztu s/n, 28040 Madrid, Spain Department of Civil and Environmental Engineering, 352C DuPont Hall, University of Delaware, Newark, DE 19716, USA

a r t i c l e

i n f o

a b s t r a c t
Landll, a matured and economically appealing technology, is the ultimate approach for the management of municipal solid wastes. However, the inevitable generation of leachate from landll requires further treatment. Among the various leachate treatment technologies available, advanced oxidation processes (AOPs) are among powerful methods to deal with the refractory organic constituents, and the Fenton reagent has evolved as one promising AOPs for the treatment of leachates. Particularly, the combination of UV-radiation with Fenton's reagent has been reported to be a method that allows both the photo-regeneration of Fe2+ and photodecarboxylation of ferric carboxylates. In this study, Fenton and photo-Fenton processes were ne tuned for the treatment of leachates from the Colmenar Viejo (Madrid, Spain) Landll. Results showed that it is possible to dene a set of conditions under which the same COD and TOC removals ( 70%) could be achieved with both the conventional and photo-Fenton processes. But Fenton process generated an important quantity of iron sludge, which will require further disposal, when performed under optimal COD removal conditions. Furthermore conventional Fenton process was able to achieve slightly over an 80% COD removal from a young leachate, while for old and mixed leachates was close to a 70%. The main advantage showed by the photoassisted Fenton treatment of landll leachate was that it consumed 32 times less iron and produced 25 times less sludge volume yielding the same COD removal results than a conventional Fenton treatment. 2009 Elsevier B.V. All rights reserved.

Article history: Received 4 November 2008 Received in revised form 3 February 2009 Accepted 4 February 2009 Available online 10 March 2009 Keywords: Landll leachate Fenton process Photo-assisted Fenton Iron role Advanced oxidation processes

1. Introduction Sanitary landll is one of the most commonly used methods for the management of municipal solid wastes due to technological maturity and economic merits even though generation of landll leachate is an important drawback (Lema et al., 1988; Robinson and Maris, 1985). This high-strength wastewater is produced by physiochemical and biological decomposition of solid wastes and the percolation of rainwater through the waste layers (EPA, 2008). It has been reported that landll leachate has both acute and chronic toxicity (Deng and Englehardt, 2006). Lack of proper site and capacity design has led to contamination of surface water, soil and groundwater (Chian and Dewalle, 1997; Christensen et al., 1992); and then it is difcult and expensive to clean it up. Recently, groundwater pollution by leachate seepage has become a major environmental concern worldwide (Kurniawan et al., 2006). The characteristics of landll leachates are dependent on the composition of the deposited wastes, soil properties, rainfall patterns, and the age of the landll (Chen,1996; Di Laconi et al., 2006; Park et al.,

Corresponding author. Tel.: +34 91 394 4645; fax: +34 91 394 4243. E-mail address: dhermosilla@quim.ucm.es (D. Hermosilla). 0048-9697/$ see front matter 2009 Elsevier B.V. All rights reserved. doi:10.1016/j.scitotenv.2009.02.009

2001). Generally, young leachates (b12 years) have a high organic fraction of relatively low molecular weight such as volatile organic acids, high COD, TOC, BOD5, and a BOD5/CODN 0.6 (Calace et al., 2001; Di Laconi et al., 2006; Zhang et al., 2005b). In contrast, as a result of the anaerobic decomposition, old leachates (N10 years old) have a high organic fraction of relatively high molecular weight, such as humic and fulvic substances, which are refractory and not easily degradable. Usually old leachates have lower COD, TOC, DBO5, and a BOD5/ CODb 0.3 (Calace et al., 2001; Di Laconi et al., 2006; Zhang et al., 2005b). Various biological and physiochemical processes have been studied for the treatment of landll leachates. It has been reported that biological processes are effective in treating young leachates (Chian and Dewalle, 1997; Ehrig, 1985; Mndez et al., 1989) but are relatively ineffective for the treatment of old leachates due to the presence of biorefractory compounds (Kim and Huh, 1997; Zhang et al., 2005b). Particularly, advanced oxidation processes (AOPs) have been reported as powerful technologies capable of degrading a wide variety of refractory compounds from stabilized leachates (Kim et al., 1997; Kurniawan et al., 2006; Parsons, 2004) and are excellent alternatives for the treatment of high-strength wastewaters. Furthermore, It has been demonstrated that AOPs can achieve a considerably high efciency on the removal of organic compounds from leachates compared to other physiochemical technologies (coagulation, activated carbon adsorption, membrane

3474

D. Hermosilla et al. / Science of the Total Environment 407 (2009) 34733481

ltration, and/or other separation processes) which only bring about phase transfer of the contaminants in question and do not involve chemical destruction (Deng and Englehardt, 2006). AOPs are oxidation processes that generate hydroxyl radicals in sufcient quantity to affect chemical transformation of contaminants (Glaze et al., 1987). It is known that hydroxyl radicals are almost twice as reactive as chlorine with an oxidation potential only next to uorine (Bigda, 1995). The catalytic decomposition of hydrogen peroxide by ferrous ion (i.e., Fenton's reagent) was rst described by Fenton (1894) and is one of the most commonly used AOPs for wastewater treatment. Huang et al. (1993) discussed the advantages and disadvantages of AOPs and suggested that methods like the Fenton process are the most promising technologies for the treatment of wastewaters. Moreover, the Fenton method is more efcient and implies a lower capital cost than other AOPs (Esplugas et al., 2002; Rivas et al., 2004; Tang, 2004). The Fenton process is based on the electron transfer between hydrogen peroxide and ferrous ion, which acts as a homogenous catalyst, yielding hydroxyl radicals (OH.) that can degrade organic compounds (Harber and Weiss, 1934). This process could be described by the following equations (Pignatello et al., 2006): Fe Fe
2

H2 O2 Fe H2 O2 Fe

U OH OH U HO2 H

k1 70:0 M k2 bbb k1

ds

1 2

U U H2 O2 OH HO2 H2 O Fe Fe Fe
2

k3 3:3d 10 M k4 3:2d 10 M
3 8

ds

3 4 5 6 7 8

U 3 OH Fe OH
2 U HO2 Fe O2 H 3 U HO 2 H Fe H2 O2

ds

k5 b 2:0d 10 M
6

ds

k6 1:20d10 M d s k7 8:3d 10 M k8 3:0 M

1 5 1

Organic free radicals (RU) are formed as transient intermediates and are further oxidized by ferric iron, oxygen, hydrogen peroxide, hydroxyl radicals, or other intermediates to form a stable and oxidized product (Huang et al., 1993). Typically, Fenton treatment is performed in the following four stages (Bigda, 1995): pH adjustment, oxidation reaction, neutralizationcoagulation, and precipitation (centrifugation); so organic substances are removed by both oxidation and coagulation. It has been reported that the Fenton process can achieve 6090% of COD removal in the treatment of landll leachate. Particularly, Zhang et al. (2005a) achieved a 70% COD removal in a leachate of 1000 mg O2L 1 COD under the best tuned conditions for the treatment, while Di Laconi et al. (2006) reported an 85% COD removal. Moreover, Bae et al. (1996) reported that, when leachates were pretreated by biological processes, the Fenton process can achieve an additional 63% COD removal; and Lpez et al. (2004) reported a maximum COD removal of 60% in the Fenton treatment of an old landll. Finally, Kang and Hwang (2000) reported a constant 70% maximum COD removal at different FeSO4 dosages, differentiating between oxidation and coagulation contributions to COD removal. A 4555% COD removal was attributed to the oxidation process efciency, while the rest 1525% was removed by coagulation. Regardless its high COD removal efciency and environmental friendliness, Fenton treatment of wastewater is mired by the nal production of iron sludge, which requires ultimate disposal (e.g. Kim and Vogelpohl, 1998; Pignatello et al., 2006). In order to deal with this problem, it has been suggested that the conventional Fenton process could be modied by the combined application of electricity, i.e. electro-Fenton (Brillas and Casado, 2002; Qiang et al., 2002, 2003), and/or UV-light, i.e. photo-Fenton/photoelectron-Fenton (Brillas et al., 1998, 2003; Kavitha and Palanivelu, 2004). The photo-Fenton process has two major features: (a) the reduction of ferric to ferrous iron as to produce additional hydroxyl radicals via photolysis (Faust and Hoigne, 1990; Kavitha and Palanivelu, 2004; Kim and Vogelpohl, 1998), i.e.: FeIIIOH
2

U U HO2 HO2 H2 O2 O2 U HO2 H2 O2 OH H2 O O2 U

ds

h Fe

OH

11

ds

Ferrous ions oxidation to ferric iron initiate and catalyze the decomposition of hydrogen peroxide molecules, resulting in the rapid generation of hydroxyl radicals (Eq. (1)); so in the absence of any other oxidable substance, the net reaction results in the iron-catalyzed conversion of hydrogen peroxide to molecular oxygen and water. Several authors have also reported how the reduction of ferric to ferrous iron occurs consuming hydrogen peroxide (Eq. (2); Alegria et al., 2003; Lipczynskakochany, 1991; Pignatello et al., 2006), but the reaction rate is several orders of magnitude slower than when the oxidation of ferrous to U ferric iron occurs in the presence of hydrogen peroxide. In addition, HO 2 3+ 2+ U and its conjugate base O2 can both reduce Fe and oxidize Fe at the [Fe3+]/[Fe2+] ratio of N2.5 and b2.5, respectively (Pignatello et al., 2006). Typically, ferric iron becomes a predominant species when the U molar ratio of hydrogen peroxide to total iron is high. Regardless, HO2 U (O2 ) radicals are decomposed to give ferrous ion and hydrogen peroxide, and thereby further propagate the Fenton reaction. The highly reactive hydroxyl radicals produced in the Fenton process initiate the oxidative destruction of organic substances (RH) typically present in the wastewater (Huang et al., 1993), namely: a) hydroxyl radical addition reaction:
7 10 1 1 U U OH R ROH hydroxylated products k9 10 10 M d s

and (b) the photo-decarboxylation of ferric carboxylates (Kavitha and Palanivelu, 2004; Safarzadeh et al., 1997), namely: FeIIIRCO2
2

h Fe

U CO2 R

12 13

U U R O2 RO 2 Products

b) hydrogen atom abstraction:

7 10 1 1 U U 10 OH RR H2 Ooxidized products k10 10 10 M d s

As shown above, the amount of catalytic iron required, and consequently the volume of sludge produced, could be strongly reduced and, moreover, some additional organic compounds (carboxylates) may also be effectively treated. Several authors have studied the photo-Fenton treatment of different types of wastewater (e.g. Bali et al., 2003; Ghaly et al., 2001; Brillas et al., 2003; Sarasa et al., 2006), including landll leachate (Kim et al., 1997; Kim and Vogelpohl, 1998). Results of all these studies indicated better treatment efciencies in the presence than in the absence of UV light under the same reaction conditions. Particularly, Kim et al. (1997) reported an additional 35 and 50% TOC removal by applying 80 and 160 kW/m3 UV radiation, respectively, when treating leachate by the Fenton reagent ([H2O2] 72 mM, [Fe2+] 1.2 mM). Despite the existent several studies carried on the treatment of landll leachates by the Fenton process, there has been little effort to ne-tune the operation conditions so as to achieve the maximum removal efciency. There is a lack of systematic evaluation of the operational conditions of conventional Fenton process (Kurniawan et al., 2006; Zhang et al., 2005a); and, moreover, photo-assisted Fenton reaction in landll leachate has been little studied. The optimum COD removal performing conditions have not been reported and the real

D. Hermosilla et al. / Science of the Total Environment 407 (2009) 34733481

3475

comparison with an optimal conventional Fenton has not been provided (Kim et al., 1997; Kim and Vogelpohl, 1998). The objective of this study was to determine the optimal conditions for maximizing treatment efciency and minimizing iron sludge production in the treatment of landll leachate by the conventional Fenton and photo-Fenton processes. 2. Material and methods 2.1. Material and analytical methods Leachate samples from Colmenar Viejo Landll in Madrid (Spain) taken between January 2004 and December 2006 were used in the study. After sampling, the leachate was preserved in polyethylene bottles and kept in a refrigerator protected from light, according to the Standard Methods for the Examination of Water and Wastewater (APHA, AWWA and WPCF, 1989). It was a mixed waste of old leachate from a closed landll area in the main basin of the Colmenar Viejo Landll, and a much younger one from the current phase of operation. Particularly, old and young leachates were also sampled separately in the experiment to ne-tune the optimal conditions of the Fenton treatment. Table 1 shows the main characteristics of the leachates used in the experiments. All analyses were made according to the Standard Methods (APHA, AWWA and WPCF, 1989). The characteristics of the leachate used in the present study were similar and consistent with those reported by others (Keenan et al., 1984; Lpez et al., 2004; De Morais and Zamora, 2005). All chemicals used were of analytical grade and supplied by either Merck KGaA (Darmstadt, Germany) or PANREAC S.A. (Madrid, Spain). Chemical oxygen demand (COD) was measured, according to the Standard Methods for the Examination of Water and Wastewater (APHA, AWWA and WPCF, 1989), using the colorimetric method at 600 nm with a Hach-spectrophotometer (Hach DR/2000). A TOCanalyzer (Shimadzu 5000A) was used to determine the total organic carbon (TOC) by the combustion-infrared method. TOC was estimated by the difference between the total carbon (TC) and the inorganic carbon (IC) in the samples. Hydrogen peroxide concentration was analyzed using the titanium sulphate spectrophotometric method (Pobiner, 1961). Ferrous ion concentration, [Fe2+], was determined using the 1,10-phenanthroline colorimetric method (Tamura et al., 1974). Ammonium uoride was chosen as a masking agent for ferric iron, so the interference due to its presence was avoided when determining [Fe2+] (Tamura et al., 1974). Two methods, both considered in the Standard Methods (APHA, AWWA and WPCF, 1989), were used for measuring total iron concentration in the samples. For Method A, ferric iron was rst reduced to ferrous one by hydroxylamine under acidied conditions, and then [Fe2+] was determined as described above. For Method B, the total iron was directly determined by an atomic absorption

spectrometer (Perkin-Elmer 3100). [Fe3+] was estimated by subtracting [Fe2+] from the total iron concentration. 2.2. Experimental procedures The total solution volume of the reactor was 4 L. The leachate was mixed throughout the experiments with a magnetic device. The following operational parameters were optimized: temperature, pH, reagent concentrations, reaction time and dosage mode. Temperature was adjusted to the desired value with a water heater and circulator. The pH was continuously and automatically adjusted to the desired value (0.1) along the treatment using 1 molL 1 sodium hydroxide or 1 molL 1 sulphuric acid. After temperature and initial pH adjustment, ferrous sulphate was added to reach the targeted ferrous ion concentration. Hydrogen peroxide was then added in batch mode until the designated concentration was reached. Just before the addition of hydrogen peroxide, [Fe2+], total iron concentration, COD, and TOC were measured (note: this was set as reaction time = 0). For continuous dosage mode, the selected amounts of reagents were continuously added along a 30 minute treatment. Aliquots of treated leachate were taken at pre-selected time intervals with a syringe. The samples were split into two portions. The rst portion was ltered through a 0.45-m lter membrane to collect the ltrate for the determination of the residual [H2O2], [Fe2+], and total iron. The other portion, not ltered, was neutralized to about pH = 8.00 with 10 M sodium hydroxide and then mixed in a beaker for 20 min with a magnetic stirring bar. The sample was centrifuged for 10 min at 2000 rpm to collect the supernatant for the analysis of COD, TOC, and [H2O 2]. This information was used to correct COD determination removing the contribution of hydrogen peroxide (Kang et al., 1999; Kuo, 1992; Talinli and Anderson, 1992). When applying the photo-Fenton process, all experimental procedures were the same except that a 450-W high-pressure mercury immersion lamp from ACE-glass was used. This lamp was enclosed inside a quartz glass vessel through which water was circulated in order to reduce the excessive heat generated during the UV irradiation. The lamp was located vertically in the centre of the reactor. The entire assembly was covered with aluminium foil and thick black tape and placed on top of a magnetic stirring stand. The UV-lamp was switched on simultaneously as hydrogen peroxide was added (time = 0). All experiments were repeated 34 times to allow the calculated a posteriori standard deviation to be less than 5% in terms of COD and TOC removal. 2.3. Statistical analysis One-way ANOVA was run (SigmaStat 2.0, SPSS Inc.) to determine the signicant level of differences among experimental runs. Post hoc all pairwise comparisons were performed using Tukey's test (p b 0.05).

Table 1 Properties of the leachates used in different experiments (Colmenar Viejo Landll, Madrid, Spain, 20042006). Experiment T pH Conductivity (Scm 1) TDS (gL 1) BOD5 (mgO2L 1) COD (mgO2L 1) TOC (mgCL 1) Alcalinity (mgCaCO3L 1) NNH3 (mgNL 1) CI (mgClL 1) Fe (mgFeL 1) 8.20 7.85 3.90 1400.00 2414.17 834.00 3345.21 540.00 1340.00 10.69 pH 8.14 11.71 5.85 258.00 1497.50 536.00 4725.77 1000.00 1735.00 10.81 Reagents ratio 8.43 13.62 6.80 175.00 1747.50 626.00 6159.43 1000.00 1900.00 9.19 Reagents dose. Leachate type Mixed 8.36 9.62 4.80 175.00 1320.63 458.00 3477.95 260.50 1470.00 10.92 Old 8.47 8.04 4.02 42.50 836.50 223.00 2203.59 199.50 1335.00 12.99 Young 8.34 32.74 16.36 100.00 6118.75 1481.00 14442.79 1965.00 4430.00 6.62 Feeding mode 8.09 26.44 12.19 620.00 3299.00 1094.00 11734.77 2100.00 3260.00 10.23 Iron role and photo-Fenton 8.41 15.46 7.15 362.57 2072.00 769.00 6862.44 12281.07 1906.43 10.78

Analyses were made according with the standard methods (APHA, AWWA and WPCF, 1989). TDS = Total dissolved solids; BOD = Biological oxygen demand; COD = Chemical oxygen demand; TOC = Total organic carbon; Alcalinity at pH = 4.5.

3476

D. Hermosilla et al. / Science of the Total Environment 407 (2009) 34733481

When linear and non-linear regressions between variables and COD or TOC removal were tted (SigmaPlot 2000, SPSS Inc.), correlation coefcients (R2) and p-values for the selected models were reported. 3. Results and discussion 3.1. Conventional Fenton treatment Results regarding the contribution of hydrogen peroxide to COD agreed well with those reported by other researchers (Kang et al., 1999; Kuo, 1992; Talinli and Anderson, 1992). A second-power polynomial equation (DQO(H2O2) = 0.000020[H2O2]2 + 0.393239[H2O2]; R2 = 99.92%; p b 0.0001) was used to t the H2O2 versus COD relationship, according to the theoretical approximation provided by Kang et al. (1999). In order to assess the effect of UV on the performance of the Fenton process, it was rst necessary to study the optimal operational conditions of the conventional Fenton process. This was conducted one variable at a time by modifying the value of one particular variable while keeping all other variables close to the optimal conditions as reported by various authors (Bae et al., 1996; Di Laconi et al., 2006; Kang and Hwang, 2000; Lpez et al., 2004; Zhang et al., 2005a). Treatments were run until maximum COD removal was achieved. 3.1.1. Effect of temperature Fig. 1A shows the effect of temperature on COD removal. Results indicated that there was no signicant increase in COD removal when temperature was increased from 25 to 45 C by the conventional Fenton process. COD removal achieved resulted constant at 64% in the temperature range studied. Accordingly, all remaining experiments were performed at 25 C, so less heating energy should be consumed. Several authors have studied the effect of temperature on COD removal when treating leachate by the Fenton method reporting similar results (Kang and Hwang, 2000; Rivas et al., 2003; Zhang et al., 2005a). 3.1.2. Effect of pH Several authors have demonstrated that pH is one of the major factors limiting the performance of the Fenton process in the treatment of wastewater due to its role in controlling the activity of the oxidant and the substrate, the speciation of iron, and the stability of hydrogen peroxide (Bigda, 1995; Gulsen and Turan 2004; Zhang et al., 2005a). In this study, the effect of pH was also assessed. Fig. 1B shows the effect of pH on the treatment of leachate by the conventional Fenton method. Results agreed well with those reported by other authors (Gulsen and Turan 2004; Zhang et al., 2005a). An optimal pH of 2.5 was established in this study, even though there was no signicant difference in COD removal in the pH range between 2.0 and 4.0. 3.1.3. Effect of chemical reagents Chemical reagents are major operational cost items for many wastewater treatment facilities (Gulsen and Turan 2004; Zhang et al., 2005a). Dosage requirement can be assessed readily in terms of both the absolute concentration of reagents (i.e. hydrogen peroxide and ferrous ions) and the molar ratio ([H2O2]/[Fe2+]). It should be noted that although the removal of specic organic contaminants is improved as the concentration of reagents increases, the extent of increase becomes negligible when the dosage is increased above a certain threshold level (Deng and Englehardt, 2006; Zhang et al., 2005a). Naturally, an excessive dosage of iron can contribute to a signicant increase in total dissolved solids (TDS) and electrical conductivity in the efuent. Excessive iron salt dosing requires further treatment of the efuent before its discharge to the receiving water (Gogate and Pandit, 2004). Excessive application of hydrogen peroxide generates gas bubbles, which inhibits sludge sedimentation (Deng and Englehardt, 2006; Lau et al., 2001) and may be detrimental to biological treatments a posteriori (Gogate and Pandit, 2004).

Fig. 1. A. COD removal with respect to temperature in the treatment of landll leachate by conventional Fenton process. Experimental conditions: initial COD = 2414 mgO2L 1; T = 25 C; pH = 3; [H2O2] = 0.213 M; [Fe2+] = 0.065 M. Although treatments were run up to 23 h, from 60 min onwards COD removal was not signicantly improved. To perform these experiments mixed leachate sampled from Colmenar Viejo Landll (Madrid, Spain) was used. Values are m sd (n = 3). B. COD removal with respect to pH in the treatment of landll leachate by conventional Fenton process. Experimental conditions: COD = 1498 mgO2L 1; T = 25 C; [H2O2] = 0.075 M; [Fe2+] = 0.05 M. Although treatments were run up to 23 h, from 60 min onwards COD removal was not signicantly improved. To perform these experiments mixed leachate sampled from Colmenar Viejo Landll (Madrid, Spain) was used. Values are m sd (n = 3). Letters (a, b) identify different statistically signicant groups (Tukey's test, p b 0.05).

Fig. 2A shows the effect of the reagents concentration ratio ([H2O2]/ [Fe2+]) on COD removal. Results were in good agreement with those reported by Zhang et al. (2005a). A [H2O2]/[Fe2+]=1.5 provided the best operation condition for the conventional Fenton treatment of landll leachates. COD removal increased rapidly to 60% at [H2O2]/[Fe2+]= 1.52.0 and remained relatively constant upon further increases in this reagents ratio even above 5 (COD removal 65% with no statistically signicant difference from [H2O2]/[Fe2+]=1.5). Harber and Weiss (1934) reported that the reaction was second order with respect to hydrogen peroxide and ferrous iron at low [H2O2]/[Fe2+]; but became zero order at high [H2O2]/[Fe2+], when one or more side reactions would occur (mainly Eqs. (3) and (4)). Moreover, when [H2O2]/[Fe2+]2.0, sludge settling was hindered by the oxygen bubbling produced from the decomposition of excess hydrogen peroxide. Furthermore, the results shown in Fig. 2A also demonstrated that there was no signicant difference in COD removal in the [H2O2]/[Fe2+] range of 5 to7, under which conditions the COD removal

D. Hermosilla et al. / Science of the Total Environment 407 (2009) 34733481

3477

consistent higher COD removal of about 10% with respect to results achieved with old and mixed leachates at [H2O2] 0.0050.01 M. While the conventional Fenton process was able to achieve slightly over an 80% COD removal from the young leachate, COD removal from old and mixed leachates was less than 70%. Zhang et al. (2005b) have attributed the difference to the chemical characteristics of the organic contaminants present. Furthermore, it must be mentioned that although the COD removal from the young leachate was higher than that from the other leachates, the residual COD in this young leachate was also higher than in the other leachates (e.g. 1162, 436, and 284 mgO2L 1 for young, mixed, and old leachate, respectively). To assess the rate-limiting step in the mineralization of the organic compounds in the wastewater (as reported by Alegria et al., 2003), experiments on the treatment of leachate by the conventional Fenton process were conducted at two [H2O2]/[Fe2+] levels, namely, 1.5 (the optimal value) and 12 (extremely high value). Fig. 3 shows the residual [H2O2] and COD removal as a function of time under the above dosage conditions. Results showed that at [H2O2]/[Fe2+] = 1.5 (or [Fe2+] = 0.05 M and [H2O2] = 0.075 M; Fig. 3A) hydrogen peroxide was consumed quickly in 60 min, and consequently no more increase in COD removal would be possible. When [H2O2]/[Fe2+] = 12 (or [Fe2+] = 0.00625 M and [H2O2] = 0.075 M; Fig. 3B) a substantial amount of H2O2 remained in the solution until 180 min. COD removal at high ferrous iron concentration was much faster in rate and greater in extent than at the lower lever. At the beginning of the Fenton process, all ferrous iron reacted quickly with hydrogen peroxide according to Eq. (1), with a rate constant much higher than that of the reaction shown in Eq. (2). As a result, there was rapid generation of hydroxyl radicals, which in turn led to quick and extensive oxidation of the organic compounds and quick depletion of ferrous ions. The availability of ferrous iron becomes the main rate-limiting step in the process as the reduction

Fig. 2. A. COD removal with respect to [H2O2]/[Fe2+] ratio in the treatment of landll leachate by conventional Fenton process. Experimental conditions: COD = 1748 mgO2L 1; T = 25 C; pH = 2.5; [Fe 2 + ] = 0.05 M; [H 2 O 2 ] = 0.0250.35 M; treatment time = 60 min). Leachates were sampled from Colmenar Viejo Landll (Madrid, Spain). 4-parametric double exponential rise to maximum models (R2 99%; p b 0.0001) were used for curve ttings illustrating conventional Fenton treatment results at different [H2O2]/[Fe2+] ratios. Values are m sd (n= 4). Letters (a,b,c) identify different statistically signicant groups (Tukey's test, pb 0.05). B. COD removal with respective to H2O2 dosage in the treatment of various landll leachates by conventional Fenton process. Experimental conditions: COD= 6119, 837 and 1321 mgO2L 1 for young, old and mixed leachate, respectively; T = 25 C; pH= 2.5; [H2O2]/[Fe2+]= 1.5; treatment time = 60 min. Mixed leachate was sampled from Colmenar Viejo Landll (Madrid, Spain). 4-parametric double exponential rise to maximum models (R2 99%; pb 0.0001) were used for curve ttings illustrating conventional Fenton treatment results at different [H2O2]. Values are m sd (n = 4). Letters (a,b,c) identify different statistically signicant groups (Tukey's test, pb 0.05).

remained at 6568%. This was not a signicant increase in COD removal due to the slow mineralization of highly refractory organic compounds (Zhang et al., 2005b) and the reduction of Fe3+ to Fe2+ with the generation of hydroxyl radicals. We have therefore selected a [H2O2]/[Fe2+] value of 1.5 for the remaining experiments in the treatment of three different types of leachates, i.e. old, young and mixed. As shown in Fig. 2B, all three leachates exhibited similar behaviour in COD removal efciency with respect to the dosage of hydrogen peroxide. Results were in good agreement with those reported by Zhang et al. (2005a). Moreover, [H2O2] over 0.075 M did not lead to signicantly high COD removals, although a slight improvement of about 5% was observed when the hydrogen peroxide concentration reached 0.225 M. Among the various types of leachate treated, young leachate exhibited a signicantly

Fig. 3. Effect of Fe2+ dosage on COD removal and change in [H2O2] as a function of time in the treatment of landll leachate by conventional Fenton. Experimental conditions: COD = 2072 mgO2L 1; T = 25 C; pH = 2.5; [H2O2] = 0.075 M; [Fe2+] = 0.05 M (A) and 0.00625 M (B). Mixed leachate was sampled from Colmenar Viejo Landll (Madrid, Spain). Values are m sd (n = 3).

3478

D. Hermosilla et al. / Science of the Total Environment 407 (2009) 34733481

Finally, the mode of reagent addition was also tested following the same procedures as those studied by Zhang et al. (2005a). These authors reported that there was an additional increase of about 10% in COD removal when the reagents were added in a continuous mode rather than when all reagents were added simultaneously in batch mode, as it is also veried by our results, showed in Fig. 4. Lower differences where found with respect to when adding one reagent (H2O2 or Fe2+) at the beginning of the treatment and the other one continuously. 3.2. Effect of photo-irradiation The combination of UV-radiation with Fenton's reagent is a promising advanced oxidation process for the treatment of landll leachates, as UV light may promote photo-decarboxylation of ferric carboxylates and reduce ferric to ferrous iron yielding additional hydroxyl radicals by photolysis. UV light was applied together with a conventional Fenton process under a one-step dosing operation at the optimal reagent concentration established above, that is, [Fe2+] = 0.05 M, [H2O2] = 0.075 M (or [H2O2]/[Fe2+] = 1.5), pH = 2.5, and T = 25 C. Results (similar to those reported in Fig. 5) showed no signicant improvement in COD and TOC removal upon the application of UV light to conventional Fenton process. This can be attributed to the rapid consumption of hydrogen peroxide over a few minutes of reaction time (Fig. 3A). A separate experiment was conducted by adding hydrogen peroxide in batch mode every 20 min keeping its concentration equal to 0.075 M at all successive steps. Again, results (Fig. 5) showed

Fig. 4. Effect of reagent feeding mode on COD removal as a function of time in the treatment of landll leachate by conventional Fenton process. Experimental conditions: COD = 3299 mgO2L 1; T = 25 C; pH = 2.5; [H2O2] = 0.075 M; [Fe2+] = 0.05 M). Mixed landll leachate was sampled from Colmenar Viejo (Madrid, Spain) main pond. Values are m sd (n = 3). Letters (a,b) identify different statistically signicant groups at 1-h treatment (Tukey's test, p b 0.05).

(regeneration) of ferric to ferrous forms (Eq. (2)) is slower than the consumption of ferrous iron (Eqs. 12 and 14; Alegria et al., 2003; Lipczynskakochany, 1991; Pignatello et al., 2006). As shown in Fig. 3B, as long as there was presence of hydrogen peroxide, the slow ferrous iron regeneration process (Eq. (2)) was able to maintain the function of the Fenton process. It is important to note that the oxidation efciency (OE) of the process also deteriorates as the reaction proceeds when ferrous iron regeneration by hydrogen peroxide becomes predominant. According to Bishop et al. (1998), OE is dened as 100(COD/available O2), where available O2 is the theoretical amount of reactive oxygen equivalent to the added hydrogen peroxide. At initial [H2O2] = 0.075 M and [Fe2+] = 0.05 M (or [H2O2]/[Fe2+] = 1.5), an average 1.71 mgL 1 of hydrogen peroxide were required to remove 1 mgO2L 1 of COD over a 180-minute treatment time (Fig. 3A). When [Fe2+] was lowered to 0.00625 M (or [H2O2]/[Fe2+] = 12); 2.87 mgL 1 of hydrogen peroxide were needed to remove 1 mgO2L 1 of COD over a 180-minute treatment time (Fig. 3B). But during the rst 10 min of reaction, the OE remained constant; that is, 1.70 and 1.65 mgH2O2L 1 were respectively required to remove every mgO2L 1 of COD for both [H2O2]/[Fe2+] values. In this context, Rivas et al. (2004) applied a Fenton-like process to treat landll leachate using ferric iron instead of Fe2+ and reported that 10 mgH2O2L 1 was consumed for the removal of 1 mgO2L 1 of COD in the treated landll leachate. Moreover, Wang et al. (2000) showed that the mere presence of hydrogen peroxide was able to remove 24% of organic compounds in the leachate. Our data showed that at a hydrogen peroxide dosage of 0.075 M, the conventional Fenton process was able to achieve a COD removal of 17.0 4.0% (n= 3) in 6 h. Additionally, by simply lowering the pH to 2.5, there was only an additional COD removal of 15.0 4.5% (n = 3) with respect to centrifuged samples. This result was in agreement with those reported by Rivas et al. (2003), who demonstrated that at pH b 3 about a 25% COD removal was possible to achieve from an intermediately stabilized landll leachate. In conclusion, even though hydrogen peroxide is theoretically effective as an oxidizing agent, its effectiveness in removing organic pollutants is highly related to its conversion to OH and HO2U radicals (Neyens and Baeyens, 2003). Great improvements in COD removal were obtained when ferrous iron was available as a catalyst. Hydrogen peroxide alone is not considered effective in degrading recalcitrant compounds in leachates that are stabilized (e.g., old) and have high strength in organic loadings (Kurniawan et al., 2006).

Fig. 5. The removal of COD and TOC as a function of time by conventional Fenton and photo-Fenton methods in the treatment of mixed landll leachate. Experimental conditions: COD = 2072 mgO2L 1; TOC= 769 mgCL 1; pH= 2.5; T = 25 C; [H2O2] = 0.075 M dosed every 20 min; [Fe2+] = 0.05 M. COD and TOC removals were generally monitored just before and after H2O2 addition. Arrows indicate when H2O2 was added (20min intervals). A 400 W UV-lamp was used, total volume of leachate treated was 4-L. Values are m sd (n = 3). There were no statistical signicant differences among treatments at any time (One-way ANOVA; p N 0.05).

D. Hermosilla et al. / Science of the Total Environment 407 (2009) 34733481

3479

Fig. 6. Change of [H2O2] as a function of time at various concentrations of Fe2+ during the treatment of mixed landll leachate by photo-Fenton process. Experimental conditions: COD= 2072 mgO2L 1; TOC = 769 mgCL 1; pH= 2.5; T = 25 C; [H2O2] = 0.075 M; [Fe2+] = 501.563 mM; one-step initial addition of reagents; 400 W UV-lamp; 4-L leachate). Values are m sd (n = 3).

no improvement in either COD or TOC removal in the presence of UVlight. It was noticed, however, that there was an abrupt COD and TOC removal during the rst 10 min of treatment by these Fenton processes. This could be attributed to the rate-limiting step of the reduction of Fe3+ to Fe2+ (Eq. (2)) as reported by Lipczynskakochany (1991) and Alegra et al. (2003). Considering that UV light may aid in the recycling of ferrous iron, which will favour the Fenton process via the formation of additional hydroxyl radicals, the most plausible explanation to these results might be that, at this level of ferrous iron content, the observed brown turbidity generated in the solution was high enough to severely hinder UV light transmission through the media; so much so that the photo-reduction of Fe3+ to Fe2+, which is strongly dependent on the intensity of the radiation and the speciation of ferric iron, was hindered signicantly (Kim et al., 1997). Furthermore, it is also important to note that landll leachates contain a great diversity of organic and inorganic ligands. As a result, a great variety of ferric complexes are formed, with each complex having a different capacity to absorb UV light (Kim and Vogelpohl, 1998). Consequently, at this ferrous iron concentration (0.05 M), there was no improvement in COD and TOC removals in comparison with the conventional Fenton treatment. Lpez et al. (2004) also reported that the end and intermediate products of Fenton reaction consisted mostly of carboxylic acids, and the higher the extent of the Fenton's oxidation (50% COD removal in 10 min as shown in Fig. 5), the greater the amount of acid by-products formed. Gau & Chang (1996) also showed how biological treatment could remove only 16% COD equivalent of organic compounds with molecular weight over 10,000 Da, but a posteriori Fenton treatment could remove almost all of these organics. Only 1% of the residual organics have a molecular weight N10,000 Da and 90% of them have a molecular weight b600 Da. These residual carboxylic acids are supposedly difcult to remove with the conventional Fenton process (Bigda, 1995). Aplin et al. (2001) reported also that oxalates were relatively unreactive with hydroxyl radicals and that a reduced light intensity led to slower photolysis of ferric-oxalate complexes and subsequently slower ferrous iron photo-regeneration rates. Hence, the production of hydroxyl radicals was strongly decreased when hydrogen peroxide was consumed to recycle the ferric to ferrous ion as was taking place in the conventional Fenton process. Assuming that the hindrance to UV radiation could be compensated using lower iron dosage, separate experiments were run at low iron concentrations in the range of 1.562 to 50 mM (32 times higher) while keeping the hydrogen peroxide concentration constant at 0.075 M. Fig. 6 shows the change in hydrogen peroxide concentration

as a function of time. Results indicated that the consumption of hydrogen peroxide depends on the concentration of ferrous iron used in the different experiments. When more ferrous ions are added in the process, more quickly the hydrogen peroxide is consumed. Fig. 7 shows COD and TOC removals as a function of ferrous iron concentration. Results indicated that COD and TOC removals remained high and relatively independent of [Fe2+] in the photo-Fenton process. As it has already been remarked, the amount of iron added determines the operation time. For the conventional Fenton method, both COD and TOC removals were lower when [Fe2+] was less than 0.05 M, which is the optimal value for running a conventional Fenton treatment, as reported above. The maximum COD and TOC removals were not signicantly different between these two processes under otherwise optimal dosage conditions. It is worth mentioning that it is possible to dene a set of conditions under which the same COD and TOC removals could be achieved with both the conventional and photo-Fenton processes by simply adding an adequate amount of hydrogen peroxide and ferrous iron. Finally, COD removal can just be attributed to oxidation when applying the photo-Fenton treatment, so the coagulation fraction considered in the conventional Fenton treatment (Kang and Hwang, 2000) can be oxidized. Therefore, as far as the treatment cost is concerned, the conventional Fenton process implies a higher cost in chemicals, associated to higher ferrous iron consumption levels, and also has to deal with iron sludge disposal; while the photo-Fenton treatment will require higher

Fig. 7. Effect of Fe2+ on the removal of COD and TOC by conventional Fenton and photo-Fenton treatments of mixed landll leachate. Experimental conditions: COD=2072 mgO2L 1; TOC= 769 mgCL 1; pH = 2.5; T = 25 C; [H2O2] = 0.075 M; [Fe2+] = 501.563 mM; one-step initial addition of reagents). A 400 W UV-lamp was used; total leachate treated was 4 L. COD and TOC removals were estimated when all H2O2 was exhausted. 4-parametric double exponential rise to maximum models (R2 99%; p b 0.05) were used for curve ttings illustrating conventional Fenton treatment results at different [Fe2+]. Upper specication reference lines for photo-Fenton treatment indicate mean removal results. Values are m sd (n = 3). Letters (a,b,c) identify different statistically signicant groups at 1-h treatment (Tukey's test, p b 0.05).

3480

D. Hermosilla et al. / Science of the Total Environment 407 (2009) 34733481

equipment and energy costs, associated to the use of UV light. At lower [Fe2+], more photo-regeneration cycles will be required to produce the same amount of hydroxyl radicals in order to yield the same COD and TOC removals. At [H2O2] = 0.075 M without the addition of Fe2+, only an average 17 4% of COD removal was observed. The application of UV light improved the COD removal by only 10% over a reaction time of 4 h. This could be explained by the presence of iron in the leachate, which was about 10 mgL 1, as shown in Table 1. Similarly, Kim et al. (1997) have reported that in a biologically treated leachate (COD = 1150 mgO2L 1), it was able to achieve up to 35% of COD and TOC removal by simply adding hydrogen peroxide in combination with UV light. They attributed the results to the photolysis of both hydrogen peroxide and organic compounds. Since the oxidation rate of the H2O2-UV process was extremely slow, it is expected that the energy cost will be very high. The treatment cost can be drastically reduced by the addition of a small amount of ferrous iron to the leachate to be treated with the application of UV light, as just described above. The addition of a very small amount of ferrous ions, as low as 1.562 mM as shown in Fig. 6, radically changes the process performance; for example, it is possible to achieve an additional 3545% COD removal (total of 7080%) with the addition of a very small amount of ferrous iron. In short time, the photo-regeneration can self-regenerate and replenish a signicant amount of iron. Finally, we can assess the signicant decrease in the production of iron sludge that can be achieved assisting the Fenton process with UVlight. In order to yield the same level of COD removal produced by a photo-Fenton process run with a 32 times lower ferrous iron addition, 2750 mgFe2+L 1 will be required by the conventional Fenton process. This is equivalent to about a 25% of the total nal volume of the treated leachate under the optimal performance conditions of the conventional Fenton process. The sludge volume was less than 1% when the lowest iron content ([Fe2+] = 1.5625 mM) was used in the photo-Fenton process. This obviously represents a tremendous saving in iron sludge disposal cost. 4. Conclusions The optimal conditions for the treatment of landll leachate by the Fenton and photo-Fenton processes were veried and results demonstrated that the selected optimal conditions were statistically signicant. At pH = 2.5 and room temperature, COD removal rates were typically high. Chemicals dosages ([H2O2] and [Fe2+]) can be nely tuned to maximize the efciency of the treatment. COD removal at higher ferrous iron dosages (or [H2O2]/[Fe2+] = 1.5) was much faster in rate and greater in extent than at low ferrous iron dosages (or [H2O2]/[Fe2+] = 12) in the absence of UV irradiation. Under the optimal conditions and in the absence of UV light, the conventional Fenton process was able to achieve slightly over an 80% COD removal from a young leachate; while the COD removal from the old and mixed leachates resulted less than a 70%. A mere 10% increase in COD removal was possible when all chemicals were added in continuous mode. Under the optimal conditions of conventional Fenton process, the application of UV light did not increase COD and TOC removals signicantly. COD and TOC removals remained high and relatively independent of [Fe2+] in the photo-Fenton process; but the ferrous iron concentration used can be reduced about 32 times obtaining the same results in terms of COD and TOC removals than when performing a conventional Fenton treatment under optimal conditions. Iron sludge production was reduced from 25% to 1% of the total nal volume. Using lower [Fe2+] implied that more photo-regeneration cycles will be required to produce the same amount of hydroxyl radicals in order to yield the same COD and TOC removals. Resuming, it is possible to dene a set of conditions under which the same COD and TOC removal could be achieved with both the conventional and photo-Fenton processes by simply adding an adequate amount of

hydrogen peroxide and ferrous iron. As far as the treatment cost is concerned, the conventional Fenton process will require higher chemical and sludge disposal costs while the photo-Fenton one will ask for a higher cost in equipment and energy. Acknowledgments This research was developed in the framework of projects GR/ AMB/0269/2004 and M0500204133 funded by Univ. Politcnica de Madrid and Comunidad Autnoma de Madrid (Spain), who also sponsored Daphne Hermosilla's visit to Univ. of Delaware. We would also like to thank Dra. Ma Paz Andrs for technical support. We wish to thank Diane Kukich, Univ. of Delaware, for her editorial assistance. References
Alegria Y, Liendo F, Nuez O. On the Fenton degradation mechanism. The role of oxalic acid. Arkivoc 2003;10:53849. APHA, AWWA, WPCF. Standard methods for the examination of water and wastewater; 1989. Washington DC. Aplin R, Feitz AJ, Waite TD. Effect of Fe(III)-ligand properties on effectiveness of modied photo-Fenton processes. Water Sci Technol 2001;44:2330. Bae JH, Kim SK, Chang HS. Treatment of landll leachates: ammonia removal via nitrication and denitrication and further COD reduction via Fenton's treatment followed by activated sludge. Water Sci Technol 1996;36:3418. Bali U, Catalkaya EC, Sengul F. Photochemical degradation and mineralization of phenol: a comparative study. J Environ Sci Heal A 2003;38:225975. Bigda RJ. Consider Fenton's chemistry for wastewater treatment. Chem Eng Prog 1995;12:626. Bishop DF, Stern G, Fleischman M, Marshall LS. Hydrogen peroxide catalytic oxidation of refractory organics in municipal wastewaters. Ind Eng Chem Proc Des Dev 1998;7:1107. Brillas E, Casado J. Aniline degradation by Electro-Fenton and peroxi-coagulation processes using a ow reactor for wastewater treatment. Chemosphere 2002;47: 2418. Brillas E, Baos MA, Garrido JA. Mineralization of herbicide 3,6-dichloro-2-methoxybenzoic acid in aqueous medium by anodic oxidation, electro-Fenton and photoelectro-Fenton. Electrochim Acta 2003;48:1697705. Brillas E, Mur E, Sauleda R, Snchez L, Peral J, Domenech X, et al. Aniline mineralization by AOP's: anodic oxidation, photocatalysis, electro-Fenton and photo-electroFenton processes. Appl Catal B-Environ 1998;16:3142. Calace N, Liberatori A, Petronio BM, Pietroletti M. Characteristics of different molecular weight fractions of organic matter in landll leachate and their role in soil sorption of heavy metals. Environ Pollut 2001;113:3319. Chen PH. Assessment of leachates from sanitary landlls: impact of age, rainfall and treatment. Environ Int 1996;2:22537. Chian ESK, Dewalle FB. Evaluation of leachate treatment. Characterization of leachate, vol. 1. Cincinnati: United States Environmental Protection Agency; 1997. Christensen TH, Cossu R, Stegmann R. Landll leachate: an introduction. In: Christensen TH, Cossu R, Stegmann R, editors. Landlling of waste: leachate. London: Taylor and Francis; 1992. p. 1-17. De Morais JL, Zamora PP. Use of advanced oxidation processes to improve the biodegradability of mature landll leachates. J Hazard Mater 2005;123:1816. Deng Y, Englehardt JD. Treatment of landll leachate by the Fenton process. Water Res 2006;40:368394. Di Laconi C, Ramadori R, Lopez A. Combined biological and chemical degradation for treating a mature municipal landll leachate. Biochem Eng J 2006;31:11824. Ehrig HJ. Biological treatment of sanitary landll leachate with special aspects on high ammonia concentration. Water Qual Res J Can 1985;20:23248. Environmental Protection Agency (EPA), Urban watershed management research terminology. http://www.epa.gov/ednnrmrl/terminology.htm. October, 2008 Esplugas S, Gimnez J, Contreras S, Pascual E, Rodrguez M. Comparison of different advanced oxidation processes for phenol degradation. Water Res 2002;36:103442. Faust BC, Hoigne J. Photolysis of Fe(III)-hydroxy complexes as sources of OH radicals in clouds, fog and rain. Atmos Environ 1990;24:7989. Fenton HJH. Oxidation of tartaric acid in the presence of iron. J Chem Soc 1894;65: 899910. Gau SH, Chang FS. Improved Fenton method to remove recalcitrant organics in landll leachate. Water Sci Technol 1996;34:44562. Ghaly MY, Hrtel G, Mayer R, Haseneder R. Photochemical oxidation of p-chlorophenol by UV/H2O2 and photo-Fenton process. A comparative study. Waste Manage 2001;21:417. Glaze WH, Kang JW, Chapin DH. The chemistry of water-treatment processes involving ozone, hydrogen-peroxide and ultraviolet-radiation. Ozone: Sci Eng 1987;9: 33552. Gogate PR, Pandit AB. A review of imperative technologies for wastewater treatment I: oxidation technologies at ambient conditions. Adv Environ Res 2004;8:50151. Gulsen H, Turan M. Treatment of sanitary landll leachate using a combined anaerobic uidized bed reactor and Fenton's oxidation. Environ Eng Sci 2004;21:62736. Harber F, Weiss JJ. The catalytic decomposition of hydrogen peroxide by iron salts. J Am Chem Soc 1934;45:33851. Huang CP, Dong C, Tang Z. Advanced chemical oxidation: its present role and potential future in hazardous waste treatment. Waste Manage 1993;13:36177.

D. Hermosilla et al. / Science of the Total Environment 407 (2009) 34733481 Kang YW, Hwang K. Effects of reaction conditions on the oxidation efciency in the Fenton process. Water Res 2000;34:278690. Kang YW, Cho M, Hwang K. Correction of hydrogen peroxide interference on standard chemical oxygen demand test. Water Res 1999;33:124751. Kavitha V, Palanivelu K. The role of ferrous ion in Fenton and photo-Fenton processes for the degradation of phenol. Chemosphere 2004;55:123543. Keenan JD, Steiner RL, Fungaroli AA. Landll leachate treatment. J Water Poll Control Fed 1984;56:2733. Kim YK, Huh IR. Enhancing biological treatability of landll leachate by chemical oxidation. Environ Eng Sci 1997;14:739. Kim S, Vogelpohl A. Degradation of organic pollutants by the photo-Fenton process. Chem Eng Technol 1998;21:18791. Kim S, Geissen S, Vogelpohl A. Landll leachate treatment by a photoassisted Fenton reaction. Water Sci Technol 1997;35:23948. Kuo WG. Decolorizing dye wastewater with Fenton's reagent. Water Res 1992;26: 8816. Kurniawan TA, Lo WH, Chan GYS. Radicals-catalyzed oxidation reactions for degradation of recalcitrant compounds from landll leachate. Chem Eng J 2006;125:3557. Lau IWC, Wang P, Fang HHP. Organic removal of anaerobically treated leachate by Fenton coagulation. J Environ Eng 2001;27:6669. Lema JM, Mndez R, Blzquez R. Characteristics of landll leachates and alternatives for their treatment: a review. Water Air Soil Poll 1988;40:22350. Lipczynskakochany E. Novel method for a photocatalytic degradation of 4-nitrophenol in homogeneous aqueous-solution. Environ Technol 1991;12:8792. Lpez A, Pagano M, Volpe A, Di Pinto AC. Fenton's pre-treatment of mature landll leachate. Chemosphere 2004;54:100510. Mndez R, Lema JM, Blzquez R, Pan M, Forjn C. Characterization, digestibility and anaerobic treatment of leachates from old and young landlls. Water Sci Technol 1989;21:14555. Neyens E, Baeyens J. A review of classic Fenton's peroxidation as an advanced oxidation technique. J Hazard Mater 2003;98:3350. Park S, Choi KS, Joe KS, Kim WH, Kim HS. Variations of landll leachate's properties in conjunction with the treatment process. Environ Technol 2001;22:63945. Parsons SA. Advanced oxidation processes for water and wastewater treatment. London: IWA Publishing; 2004.

3481

Pignatello JJ, Oliveros E, MacKay A. Advanced oxidation processes for organic contaminant destruction based on the Fenton reaction and related chemistry. Crit Rev Env Sci Tec 2006;36:1-84. Pobiner H. Determination of hydroperoxides in hydrocarbon by conversion to hydrogen peroxide and measurement by titanium complexing. Anal Chem 1961;33:14238. Qiang ZM, Chang JH, Huang CP. Electrochemical generation of hydrogen peroxide from dissolved oxygen in acidic solutions. Water Res 2002;36:8594. Qiang ZM, Chang JH, Huang CP. Electrochemical regeneration of Fe2+ in Fenton oxidation processes. Water Res 2003;37:130819. Rivas FJ, Beltrn F, Carvalho F, Acedo B, Gimeno O. Stabilized leachates: sequential coagulationoculation + chemical oxidation process. J Hazard Mater 2004;116: 95-102. Rivas FJ, Beltrn F, Gimeno O, Carvalho F. Fenton-like oxidation of landll leachate. J Environ Sci Heal A 2003;38:3719. Robinson HD, Maris PJ. The treatment of leachates from domestic waste in landll sites. J Water Pollut Control Fed 1985;57:308. Safarzadeh A, Bolton JR, Cater SR. Ferrioxalate-mediated photodegradation of organic pollutants in contaminated water. Water Res 1997;31:78798. Sarasa J, Llabrs T, Ormad P, Mosteo R, Ovelleiro JL. Characterization and photo-Fenton treatment of used tires leachate. J Hazard Mater 2006;36:7488. Talinli I, Anderson GK. Interference of hydrogen peroxide on the standard COD test. Water Res 1992;26:10710. Tamura H, Goto K, Yotsuyanagi T, Nagayama M. Spectrophotometric determination of iron (II) with 1,10-phenanthroline in the presence of large amounts of iron (III). Talanta 1974;21:3148. Tang WZ. Physicochemical treatment of hazardous wastes. Boca Raton, FL: Lewis Publishers; 2004. Wang P, Lau IWC, Fang HHP, Zhou D. Landll leachate treatment with combined UASB and Fenton coagulation. J Environ Sci Heal A 2000;35:19818. Zhang H, Choi HJ, Huang CP. Optimization of Fenton process for the treatment of landll leachate. J Hazard Mater 2005a;125:16674. Zhang H, Choi HJ, Huang CP. Landll leachate treatment by Fenton's reagent. The variation of leachate characteristics. Fresen Environ Bull 2005b;14:117883.