Optimizing the treatment of landll leachate by conventional Fenton and

photo-Fenton processes
Daphne Hermosilla
a,
, Manuel Cortijo
b
, Chin Pao Huang
c
a
Departamento de Ingeniera Qumica, Facultad de Ciencias Qumicas, Universidad Complutense de Madrid, Ciudad Universitaria s/n, 28040 Madrid, Spain
b
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
c
Department of Civil and Environmental Engineering, 352C DuPont Hall, University of Delaware, Newark, DE 19716, USA
a b s t r a c t a r t i c l e i n f o
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
Landll, a matured and economically appealing technology, is the ultimate approach for the management of
municipal solid wastes. However, the inevitable generation of leachate fromlandll requires further treatment.
Among the various leachate treatment technologies available, advanced oxidationprocesses (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 Fe
2+
and photo-
decarboxylation of ferric carboxylates. Inthis study, Fentonand photo-Fentonprocesses 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 Fentonprocess was able toachieve slightlyover an 80%CODremoval froma young
leachate, while for old and mixed leachates was close to a 70%. The main advantage showed by the photo-
assisted 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.
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,
andthe age of the landll (Chen, 1996; Di Laconi et al., 2006; Park et al.,
2001). Generally, young leachates (b12 years) have a high organic
fractionof relatively lowmolecular weight suchas volatile organic acids,
high COD, TOC, BOD
5
, and a BOD
5
/CODN0.6 (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, DBO
5
, and a BOD
5
/
CODb0.3 (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, advancedoxidationprocesses (AOPs) have beenreportedas
powerful technologies capable of degrading a wide variety of refractory
compounds fromstabilized leachates (Kimet al., 1997; Kurniawan et al.,
2006; Parsons, 2004) and are excellent alternatives for the treatment of
high-strengthwastewaters. Furthermore, It has beendemonstratedthat
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
Science of the Total Environment 407 (2009) 34733481
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
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j our nal homepage: www. el sevi er. com/ l ocat e/ sci t ot env
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 oxidationpotential 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 Fentonprocess is basedonthe electrontransfer betweenhydrogen
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
2
H
2
O
2
Fe
3
OH

OH
U
k
1
70:0 M
1
d s
1
1
Fe
3
H
2
O
2
Fe
2
HO
U
2
H

k
2
bbb k
1
2
H
2
O
2
OH
U
HO
U
2
H
2
O k
3
3:3d 10
7
M
1
d s
1
3
Fe
2
OH
U
Fe
3
OH

k
4
3:2d 10
8
M
1
d s
1
4
Fe
3
HO
U
2
Fe
2
O
2
H

k
5
b 2:0d 10
3
M
1
d s
1
5
Fe
2
HO
U
2
H

Fe
3
H
2
O
2
k
6
1:20d10
6
M
1
d s
1
6
HO
U
2
HO
U
2
H
2
O
2
O
2
k
7
8:3d 10
5
M
1
d s
1
7
HO
U
2
H
2
O
2
OH
U
H
2
O O
2
k
8
3:0 M
1
d s
1
8
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 hydrogenperoxide to molecular oxygenandwater. 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 thanwhenthe oxidationof ferrous to
ferric iron occurs in the presence of hydrogen peroxide. In addition, HO
U
2
and its conjugate base O
2
U
can both reduce Fe
3+
and oxidize Fe
2+
at the
[Fe
3+
]/[Fe
2+
] ratio of N2.5 and b2.5, respectively (Pignatello et al.,
2006). Typically, ferric iron becomes a predominant species when the
molar ratio of hydrogen peroxide to total iron is high. Regardless, HO
U
2
(O
2
U
) 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:
OH
U
R ROH
U
hydroxylated products k
9
10
7
10
10
M
1
d s
1
9
b) hydrogen atom abstraction:
OH
U
RR
U
H
2
Ooxidized products k
10
10
7
10
10
M
1
d s
1
10
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 forma 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 (centrifuga-
tion); 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 O
2
L
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 pre-
treated 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 FeSO
4
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
h Fe
2
OH
U
11
and (b) the photo-decarboxylation of ferric carboxylates (Kavitha and
Palanivelu, 2004; Safarzadeh et al., 1997), namely:
FeIIIRCO
2

2
h Fe
2
CO
2
R
U
12
R
U
O
2
RO
U
2
Products 13
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 (carbox-
ylates) 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 (Kimet al., 1997; Kimand 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/m
3
UV radiation,
respectively, when treating leachate by the Fenton reagent ([H
2
O
2
]
72 mM, [Fe
2+
] 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 Fentonprocess (Kurniawanet 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
3474 D. Hermosilla et al. / Science of the Total Environment 407 (2009) 34733481
comparisonwithanoptimal conventional Fenton has not beenprovided
(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 fromlight, 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 TOC-
analyzer (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, [Fe
2+
], 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 [Fe
2+
] (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 [Fe
2+
] was determined as described above. For Method B,
the total iron was directly determined by an atomic absorption
spectrometer (Perkin-Elmer 3100). [Fe
3+
] was estimated by subtract-
ing [Fe
2+
] 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, [Fe
2+
], 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-mlter membrane to collect
the ltrate for the determination of the residual [H
2
O
2
], [Fe
2+
], and
total iron. The other portion, not ltered, was neutralized to about
pH=8.00 with 10 Msodiumhydroxide 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 [H
2
O
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 (pb0.05).
Table 1
Properties of the leachates used in different experiments (Colmenar Viejo Landll, Madrid, Spain, 20042006).
Experiment
T pH Reagents
ratio
Reagents dose. Leachate type Feeding
mode
Iron role and
photo-Fenton
Mixed Old Young
pH 8.20 8.14 8.43 8.36 8.47 8.34 8.09 8.41
Conductivity (Scm
1
) 7.85 11.71 13.62 9.62 8.04 32.74 26.44 15.46
TDS (gL
1
) 3.90 5.85 6.80 4.80 4.02 16.36 12.19 7.15
BOD
5
(mgO
2
L
1
) 1400.00 258.00 175.00 175.00 42.50 100.00 620.00 362.57
COD (mgO
2
L
1
) 2414.17 1497.50 1747.50 1320.63 836.50 6118.75 3299.00 2072.00
TOC (mgCL
1
) 834.00 536.00 626.00 458.00 223.00 1481.00 1094.00 769.00
Alcalinity (mgCaCO
3
L
1
) 3345.21 4725.77 6159.43 3477.95 2203.59 14442.79 11734.77 6862.44
NNH
3
(mgNL
1
) 540.00 1000.00 1000.00 260.50 199.50 1965.00 2100.00 12281.07
CI (mgClL
1
) 1340.00 1735.00 1900.00 1470.00 1335.00 4430.00 3260.00 1906.43
Fe (mgFeL
1
) 10.69 10.81 9.19 10.92 12.99 6.62 10.23 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.
3475 D. Hermosilla et al. / Science of the Total Environment 407 (2009) 34733481
When linear and non-linear regressions between variables and CODor
TOC removal were tted (SigmaPlot 2000, SPSS Inc.), correlation
coefcients (R
2
) 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(H
2
O
2
) =0.000020[H
2
O
2
]
2
+0.393239[H
2
O
2
];
R
2
=99.92%; pb0.0001) was used to t the H
2
O
2
versus COD relation-
ship, 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 tothe optimal conditions as reportedby
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 experi-
ments 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 Fentonprocess inthe 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 pHwas 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 pHof 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 ([H
2
O
2
]/[Fe
2+
]). 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. 2A shows the effect of the reagents concentration ratio ([H
2
O
2
]/
[Fe
2+
]) on COD removal. Results were in good agreement with those
reported by Zhang et al. (2005a). A [H
2
O
2
]/[Fe
2+
]=1.5 provided the best
operation condition for the conventional Fenton treatment of landll
leachates. COD removal increased rapidly to 60% at [H
2
O
2
]/[Fe
2+
]=
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[H
2
O
2
]/[Fe
2+
]=1.5). Harber andWeiss (1934)
reported that the reaction was second order with respect to hydrogen
peroxide and ferrous iron at low[H
2
O
2
]/[Fe
2+
]; but became zero order at
high[H
2
O
2
]/[Fe
2+
], whenoneor moresidereactions wouldoccur (mainly
Eqs. (3) and(4)). Moreover, when[H
2
O
2
]/[Fe
2+
]2.0, sludgesettlingwas
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[H
2
O
2
]/[Fe
2+
] rangeof 5to7, under whichconditions the CODremoval
Fig. 1. A. COD removal with respect to temperature in the treatment of landll leachate
by conventional Fenton process. Experimental conditions: initial COD=2414 mgO
2
L
1
;
T=25 C; pH=3; [H
2
O
2
] =0.213 M; [Fe
2+
] =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 msd (n=3). B. COD removal with respect to pH
in the treatment of landll leachate by conventional Fenton process. Experimental
conditions: COD=1498 mgO
2
L
1
; T=25 C; [H
2
O
2
] =0.075 M; [Fe
2+
] =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 ViejoLandll (Madrid, Spain) was used. Values are msd(n=3). Letters (a, b)
identify different statistically signicant groups (Tukey's test, pb0.05).
3476 D. Hermosilla et al. / Science of the Total Environment 407 (2009) 34733481
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 Fe
3+
to Fe
2+
with the
generation of hydroxyl radicals.
We have therefore selected a [H
2
O
2
]/[Fe
2+
] 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,
[H
2
O
2
] 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
consistent higher COD removal of about 10% with respect to results
achieved with old and mixed leachates at [H
2
O
2
] 0.0050.01 M.
While the conventional Fentonprocess was able to achieve slightly over
an80%CODremoval fromthe young leachate, CODremoval fromold
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 bementionedthat 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 mgO
2
L
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 [H
2
O
2
]/[Fe
2+
] levels, namely, 1.5 (the
optimal value) and 12 (extremely high value). Fig. 3 shows the
residual [H
2
O
2
] and COD removal as a function of time under the
above dosage conditions. Results showed that at [H
2
O
2
]/[Fe
2+
] =1.5
(or [Fe
2+
] =0.05 Mand [H
2
O
2
] =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 [H
2
O
2
]/[Fe
2+
] =12 (or
[Fe
2+
] =0.00625 M and [H
2
O
2
] =0.075 M; Fig. 3B) a substantial
amount of H
2
O
2
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 [H
2
O
2
]/[Fe
2+
] ratio in the treatment of landll
leachate byconventional Fentonprocess. Experimental conditions: COD=1748mgO
2
L
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 (R
2
99%; pb0.0001) were
used for curve ttings illustrating conventional Fenton treatment results at different
[H
2
O
2
]/[Fe
2+
] ratios. Values are msd (n=4). Letters (a,b,c) identify different statistically
signicant groups (Tukey's test, pb0.05). B. CODremoval with respective to H
2
O
2
dosage in
the treatment of various landll leachates by conventional Fenton process. Experimental
conditions: COD=6119, 837 and 1321 mgO
2
L
1
for young, old and mixed leachate,
respectively; T=25 C; pH=2.5; [H
2
O
2
]/[Fe
2+
]=1.5; treatment time=60 min. Mixed
leachate was sampled from Colmenar Viejo Landll (Madrid, Spain). 4-parametric double
exponential rise to maximum models (R
2
99%; pb0.0001) were used for curve ttings
illustrating conventional Fenton treatment results at different [H
2
O
2
]. Values are msd
(n=4). Letters (a,b,c) identify different statistically signicant groups (Tukey's test,
pb0.05).
Fig. 3. Effect of Fe
2+
dosage on COD removal and change in [H
2
O
2
] as a function of time
in the treatment of landll leachate by conventional Fenton. Experimental conditions:
COD=2072 mgO
2
L
1
; T=25 C; pH=2.5; [H
2
O
2
] =0.075 M; [Fe
2+
] =0.05 M (A)
and 0.00625 M (B). Mixed leachate was sampled fromColmenar Viejo Landll (Madrid,
Spain). Values are msd (n=3).
3477 D. Hermosilla et al. / Science of the Total Environment 407 (2009) 34733481
(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 reactionproceeds
when ferrous iron regeneration by hydrogen peroxide becomes
predominant. According to Bishop et al. (1998), OE is dened as
100(COD/available O
2
), where available O
2
is the theoretical
amount of reactive oxygen equivalent to the added hydrogenperoxide.
At initial [H
2
O
2
] =0.075 M and [Fe
2+
] =0.05 M (or [H
2
O
2
]/[Fe
2+
] =
1.5), an average 1.71 mgL
1
of hydrogen peroxide were required to
remove 1 mgO
2
L
1
of COD over a 180-minute treatment time (Fig.
3A). When [Fe
2+
] was lowered to 0.00625 M (or [H
2
O
2
]/[Fe
2+
] =12);
2.87mgL
1
of hydrogenperoxidewere neededtoremove 1mgO
2
L
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
1.65mgH
2
O
2
L
1
were respectivelyrequiredtoremove every mgO
2
L
1
of COD for both [H
2
O
2
]/[Fe
2+
] values. In this context, Rivas et al. (2004)
applied a Fenton-like process to treat landll leachate using ferric iron
instead of Fe
2+
and reported that 10 mgH
2
O
2
L
1
was consumed for
the removal of 1 mgO
2
L
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 showedthat at a hydrogenperoxidedosage of 0.075M,
the conventional Fenton process was able to achieve a COD removal of
17.04.0% (n=3) in 6 h. Additionally, by simply lowering the pHto 2.5,
there was only an additional COD removal of 15.04.5% (n=3)
with respect to centrifuged samples. This result was in agreement
with those reported by Rivas et al. (2003), who demonstrated that at
pHb3 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 HO
2
U 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).
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
(H
2
O
2
or Fe
2+
) 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, [Fe
2+
] =
0.05 M, [H
2
O
2
] =0.075 M (or [H
2
O
2
]/[Fe
2+
] =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 hydrogenperoxide over a fewminutes 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 mgO
2
L
1
; T=25 C; pH=2.5; [H
2
O
2
] =0.075 M; [Fe
2+
] =0.05 M).
Mixed landll leachate was sampled from Colmenar Viejo (Madrid, Spain) main pond.
Values are msd (n=3). Letters (a,b) identify different statistically signicant groups
at 1-h treatment (Tukey's test, pb0.05).
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 mgO
2
L
1
; TOC=769 mgCL
1
; pH=2.5; T=25 C; [H
2
O
2
] =
0.075 M dosed every 20 min; [Fe
2+
] =0.05 M. COD and TOC removals were generally
monitoredjust before andafter H
2
O
2
addition. Arrows indicate whenH
2
O
2
was added(20-
min intervals). A 400 W UV-lamp was used, total volume of leachate treated was 4-L.
Values are msd (n=3). There were no statistical signicant differences among
treatments at any time (One-way ANOVA; pN0.05).
3478 D. Hermosilla et al. / Science of the Total Environment 407 (2009) 34733481
no improvement in either COD or TOC removal in the presence of UV-
light. 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 Fe
3+
to Fe
2+
(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 Fe
3+
to Fe
2+
, 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 themhave 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 compen-
sated 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 con-
centration. Results indicated that COD and TOC removals remained
high and relatively independent of [Fe
2+
] in the photo-Fentonprocess.
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 [Fe
2+
] 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 oxidationwhen 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 conven-
tional 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. 6. Change of [H
2
O
2
] as a function of time at various concentrations of Fe
2+
during the
treatment of mixed landll leachate by photo-Fenton process. Experimental conditions:
COD=2072 mgO
2
L
1
; TOC=769 mgCL
1
; pH=2.5; T=25 C; [H
2
O
2
] =0.075 M;
[Fe
2+
] =501.563 mM; one-step initial addition of reagents; 400 W UV-lamp; 4-L
leachate). Values are msd (n=3).
Fig. 7. Effect of Fe
2+
on the removal of COD and TOC by conventional Fenton and
photo-Fenton treatments of mixed landll leachate. Experimental conditions:
COD=2072 mgO
2
L
1
; TOC=769 mgCL
1
; pH=2.5; T=25 C; [H
2
O
2
] =0.075 M;
[Fe
2+
] =501.563 mM; one-step initial addition of reagents). A 400 W UV-lamp was
used; total leachate treatedwas 4 L. CODandTOCremovals were estimatedwhenall H
2
O
2
was exhausted. 4-parametric double exponential rise to maximum models (R
2
99%;
pb0.05) were used for curve ttings illustrating conventional Fenton treatment results at
different [Fe
2+
]. Upper specication reference lines for photo-Fenton treatment indicate
mean removal results. Values are msd (n=3). Letters (a,b,c) identify different
statistically signicant groups at 1-h treatment (Tukey's test, pb0.05).
3479 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
[Fe
2+
], 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 [H
2
O
2
] =0.075 M without the addition of Fe
2+
, only an average
174% 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
reportedthat ina biologically treatedleachate (COD=1150mgO
2
L
1
),
it was able to achieve up to 35% of COD and TOC removal by simply
adding hydrogenperoxide incombinationwithUVlight. Theyattributed
the results to the photolysis of both hydrogen peroxide and organic
compounds. Since the oxidation rate of the H
2
O
2
-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 lowas 1.562 mMas shown in Fig. 6, radically changes
the process performance; for example, it is possible to achieve an
additional 3545% CODremoval (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 UV-
light. 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 mgFe
2+
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 ([Fe
2+
] =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 ([H
2
O
2
] and [Fe
2+
]) can be
nely tuned to maximize the efciency of the treatment. COD removal
at higher ferrous iron dosages (or [H
2
O
2
]/[Fe
2+
] =1.5) was much
faster in rate and greater in extent than at lowferrous iron dosages (or
[H
2
O
2
]/[Fe
2+
] =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 [Fe
2+
] in the photo-Fenton process; but the ferrous
iron concentration used can be reduced about 32 times obtaining the
same results in terms of CODand TOC removals thanwhenperforming
a conventional Fenton treatment under optimal conditions. Iron
sludge production was reduced from 25% to 1% of the total nal
volume. Using lower [Fe
2+
] 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.
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