Waste Management 33 (2013) 89–101

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Waste Management
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Evaluation of landfill leachate treatment by advanced oxidative process

by Fenton’s reagent combined with membrane separation system
Wagner G. Moravia ⇑, Míriam C.S. Amaral, Liséte C. Lange
Sanitary and Environmental Engineering Department, Federal University of Minas Gerais, Presidente Antônio Carlos Avenue, 6627, Engineering School, 4° Floor, Pampulha,
CEP: 31.270-901 Belo Horizonte, MG, Brazil

a r t i c l e i n f o a b s t r a c t

Article history: A high content of refractory organic matter, ammonia and toxic compounds is characteristic of landfill
Received 31 October 2011 leachate. Advanced oxidative processes (AOPs) are an attractive alternative for landfill leachate treat-
Accepted 14 August 2012 ment. However, when applied as a unique process treatment, they do not provide a complete solution
Available online 9 October 2012
for the effluent treatment. Combining AOP with a membrane separation process (MSP) presents a number
of benefits and provides an adequate solution for this problem. With this in mind, the present work aims
Keywords: to evaluate, using a bench scale, leachate treatability through AOP by Fenton’s reagent (AOP/Fenton)
Landfill leachate
combined with microfiltration (MF) and nanofiltration (NF). A high efficient removal of COD (63%), true
Fenton’s reagent
Microfiltration
color (76%) and humic substances (50%) was observed during AOP/Fenton under optimized conditions
Nanofiltration (1.7 g H2O2/g CODraw leachate; FeSO47H2O:H2O2 = 1:5.3; pH = 3.8; reaction conditions = 115 rpm/28 min).
According to the evaluated parameters, MSP presented an efficient complementary treatment, in which
the integrity of the stages was sufficient for reaching regulatory levels in the effluent (Deliberação Norma-
tiva Conjunta COPAM/CERH-MG No. 1, May 5, 2008).
Ó 2012 Elsevier Ltd. All rights reserved.

1. Introduction (aromatic hydrocarbons, phenols, pesticides, etc.) (Christensen

Landfill leachate is the liquid produced by natural humidity and
water present in the residue of organic matter, the result of the
biological degradation of organic matter present and by water infil-
tration in the covering and inner layers of landfill cells, supple-
menting dissolved or suspended material originating from the
residue mass.
The chemical and microbiological composition of landfill leach-
ate is complex and variable, since apart from being dependent
upon features of residual deposit, it is influenced by environmental
conditions, the operational manner of the landfill and by the
dynamics of the decomposition process that occurs inside the cells
(El-Fadel et al., 2002; Kjeldsen et al., 2002).
Landfill leachate is generally a dark colored liquid, with a strong
smell, which carries a high organic and inorganic load. One of its
characteristic features is an aqueous solution in which four groups
of pollutant are present: dissolved organic matter (volatile fatty
acid and more refractory organic matter such as humic sub-
stances), macro inorganic compounds (Ca2+, Mg2+, Na+, K+, NH4+,
Fe2+, Mn2+, Cl, SO24 , HCO 2+ 3+ 2+
3 ), heavy metals (Cd , Cr , Cu , Pb ,
2+
Ni2+, Zn2+), and xenobiotic organic compounds originating from
chemical and domestic residue present at low concentrations
⇑ Corresponding author. Tel.: +55 31 3409 1714; fax: +55 31 3409 1879.
E-mail address: moravia@desa.ufmg.br (W.G. Moravia).
and Kjeldsen, 1991; apud Kjeldsen et al., 2002), and microorgan-
isms that indicate, predominantly total and thermotolerant coli-
form (Machado, 2004).
The most common techniques for leachate treatment are the
ones based on biological mechanisms. Nevertheless, difficulties oc-
cur with the utilization of these treatments for leachate. This is due
to the extremely variable organic loads and flow, requiring vast
areas for construction, and owing to low efficiency to established
leachate because of its refractory features. An alternative for this
type of leachate is treatment by the combination of physico-
chemical processes, which can cause the degradation, or even min-
eralization of refractory pollutant matter (Kurniawan et al., 2006).
Advanced oxidative processes (AOPs) are currently popular in
effluent treatment to degrade recalcitrant compounds, which are
difficult to remove by biological processes. Despite being highly
efficient, when applied in an isolated way in leachate treatment,
AOP do not reach effluent discharge standards established by the
existing legislation, requiring post-treatment techniques to also
be applied.
Fenton’s reagent (AOP/Fenton) is process that involve the gen-
eration of hydroxyl radicals (OH), which are highly reactive and
which have the capacity to totally destroy many organic pollutants.
The free radicals (OH) which are formed attack the organic com-
pound leading to its partial or complete oxidation and producing
CO2 and H2O. During the AOP/Fenton, hydrogen peroxide (H2O2)

0956-053X/$ - see front matter Ó 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.wasman.2012.08.009
90 W.G. Moravia et al. / Waste Management 33 (2013) 89–101
is applied as an oxidizing agent, however, the addition of activators
such as iron, to produce a high rate of required radicals, is neces-
sary (Li et al., 2010; Bull and Zeff, 1991). Reaction occurs in a sim-
ple reactor, without the need for more complex equipment and
extreme conditions of temperature and pressure. Another feature
of the AOP/Fenton is its ease of operation when compared with
other AOP techniques, such as processes based on ozone and ultra-
violet radiation in which respectively an O3 generator and a UV
source are needed.
Combining the AOP/Fenton with membrane separation process
(MSP) provides a range of advantages. The use of microfiltration
(MF) can eliminate the decantation stage used for separation of
mud produced during AOP/Fenton, drastically reducing the time
of treatment. The combination of AOP/Fenton – MF with nanofil-
tration also allows for greater efficiency in pollutant removal, since
it offers a complementary treatment enabling the guidelines for
legislation standards of effluent to be followed, besides reducing
costs in area requirements for the implementation of a treatment
plant.
MSP can be understood to be a group of methods or processes
that involve the use of synthetic membranes intended for separa-
tion substances. Such operations can be used for effluent treatment
and are based on the selective permeability of one or more compo-
nents through the membrane.
Habert et al. (2006) define membranes as a barrier that sepa-
rates two phases and restricts, under action of a driving force, total
or partial transportation of one or more chemical species present.
Molecules smaller than the membrane pores pass through it, while
those which are greater in size are rejected by the retention effect
or by the repulsive force acting on the membrane surface. The fluid
that traverse the membrane is called permeate and that which re-
mains in the other side of the membrane containing the solute is
referred to as the concentrate (Giraldo-Zuñiga et al., 2004; Ordó-
nez, 2005).
Membrane fouling has, in some cases, been a limiting factor for
MSP application. Over time, such a phenomenon leads to a decline
in permeate flux, causing the flux to become independent of the
pressure across the membrane. Appropriate selection of feeding
characteristics, the hydrodynamic conditions of the system and
cleaning techniques can minimize fouling (Judd, 2006). Several
techniques exist to control fouling but what use and how to use
will depend on the characteristics of the system and feed that will
influence the mechanism of fouling. Thus knowledge of fouling
mechanisms is necessary to adequately select methods for mitiga-
tion of fouling.
Regarding the benefits of combining the AOP/Fenton with MSP
in synergy, AOP/Fenton also serves to minimize MSP fouling, since
during oxidation reaction, colloidal particle coagulation occurs,
which can reduce the penetration of such particles within the mem-
brane pores, thus increasing sustainable flux by modifying the
characteristics of the deposited material (Chiu and James, 2006).
Therefore, the objective of this research was to evaluate landfill
leachate treatment in Belo Horizonte/MG through the combination
of the AOP/Fenton and microfiltration (MF), for removal of mud
generated by AOP/Fenton, and nanofiltration (NF) as a form of final
polishing to bring effluent levels into legislation standards.
2. Materials and methods
2.1. Sampling
The leachate utilized for the experiments was provided by the
landfill of Central de Tratamento de Resíduos Sólidos – CTRS (Treat-
ment Center for Solid Waste) in Belo Horizonte/MG – Brazil. Occu-
pying an area of 133 ha, the landfill contains cells of different ages
and characteristics. The sanitary landfill of the CTRS-BR-040 oper-
ated for 33 years, since it was created in 1975. Received in recent
years approximately 4200 t/day of waste until its closure in
2008. Currently generates 300 m3/day of leachate and serves as
transshipment area. The leachate generated is transported and
treated along with domestic wastewater using activated sludge
system.
For this research, the raw leachate was collected from the
equalization tank which receives leachate from a 9-year-old
AC05 cell.
2.2. Physicochemical characterization of raw leachate
Raw leachate characterization lasted for a period of four months
over different seasons (water surplus period – January/February
2009; water deficit period – May/June 2009), in which five
monthly samples were collected composing a total of 20 samples.
The following physicochemical parameters were taken into
account: true and apparent color, chemical oxygen demand –
COD (method 5220 C), biochemical oxygen demand – BOD (meth-
od 5210 B), pH, alkalinity (method 2320 B), series solids – total and
dissolved (method 2540 B and 2540 D), total and ammoniacal
nitrogen – NKT and N–NH3 (method 4500 – N B and method
4500 – NH3 B, C), phosphorus total (method 4500 P C), chlorides
(method 4500 Cl C) and metals. Analyses were performed in accor-
dance with Standard Methods for the Examination of Water and
Wastewater (APHA, 2005).
2.3. Experimental unit
The AOP/Fenton–MF–NF experimental unit consists of the reac-
tor (V = 10 L), agitator of blades, feeding reservoir, diaphragm
pump (Qmáx = 456 L h1), MF hollow-fiber membrane modules
(manufacturer: PAM Membranas Seletivas) for optimization
(0.1 m2 by module/0.1–0.4 lm) and operation (1.0 m2 by mod-
ule/0.1–0.4 lm), NF spiral-wound modules (NF90-2540 manufac-
tured by DOW Water & Process Solutions) for operation (2.6 m2
by module/retention of 97% stabilized salts), regulator valves,
manometers (permeate and backwashing), rotameters (feeding
and permeate), thermometer and reservoirs for the collection of
permeate and concentrate. The unit also features a permeate back-
wash cleaning (system) for MF membranes. Fig. 2.1 shows the dia-
gram schematic of AOP/Fenton–MF–NF experimental unit.
MF and NF main characteristics are presented in Tables 2.1 and
2.2, respectively. Table 2.1 – MF Module main characteristics.
2.4. AOP/Fenton optimization and operation
The landfill leachate used in the AOP/Fenton optimization and
operation was collected during water deficit period – May/June
2009, for to represent the most critical situation, since the pollu-
tants concentration in the leachate in this period is the highest that
can be found over the year.
For each test, the oxidation stage consisted of pH adjustment/
reaction of the slow addition of sulfuric acid to 1-L of raw leachate,
followed by the addition of solid iron sulfate heptahydrate and a
hydrogen peroxide solution. The system was agitated throughout
the reaction. Aliquots of the sample, pre and post-treatment were
collected and analyzed with regard to COD and TS parameters. Jar
Test equipment was used for the tests. The reagents hydrogen
peroxide solution (H2O2, 30% v/v – VETEC) and ferrous sulfate
heptahydrate (FeSO47H2O – SYNTH) were also employed for the
AOP tests.
The optimization of AOP/Fenton operational conditions empha-
sized the percentage removal of COD organic matter and mud
generation measured in TS. A 25–1 fractional factorial design was
 W.G. Moravia et al. / Waste Management 33 (2013) 89–101 91

C
CONCEN NTRA
ATE
DIISPO
OSAL
L
V
VAL
LVE VA
ALV
VE
(CH
HARA
ACT
TERIZ
ZAT
TION
N)

L
LAN
NDFFILL
L RE
ETAIINED
D
AC
CIDIIFICAATIO
ON
L
LEAC
CHAATE
E and
REAAGEENT MEM
MBRRANEE
DOOSAG GE MO
ODUULE PER
RMEA
ATE
(H
H2O2 and F
FeSO
O4) VAL
LVE (M
MF/N
NF)

MA
ANOM
MET
TER

P
R
REACCTOR
(AO
OP)
P
PUM
MP VA
ALV
VE

Fig. 2.1. Diagram schematic of AOP/Fenton–MF–NF experimental unit.

Table 2.1 Table 2.4

MF module main characteristics. Variation levels of central composite 22 rotational design factors in AOP/Fenton
testing when determining sludge production critical values (minimum).
Characteristics MF
Condition Vm (rpm)a t (min)a
Optimization phase Operational phase
+1.414 150 60
Material Polyamide Polyamide
+1 135 53.5
Fiber length (mm) 240 800
0 100 37.5
Fiber external diameter (mm) 0.8–0.9 0.8–1.0
1 65 21.5
Packing density (m2/m3) 1100 600
1.414 50 15
Number of fibers 189 428
Pore diameter 0.1–0.4 lm 0.1–0.5 lm a
Vm: mixing velocity; t: reaction time.
Effective filtration area (m2) 0.100 1.0
Module useful diameter (m) 0.02 0.05

Table 2.5
Variation levels of 23 central composite rotational design factors in AOP/Fenton
Table 2.2 testing for critical value (maximum) for COD removal.
NF module main characteristics.
Condition H2O2 Fe:H2O2 pH
Characteristics NF Factora Value (g L1) Proportionb Value (g L1)
Nomenclature NF90-2540 +1681 1.5 30 1:1 6.0 5
Selective layer material Polyamide +1 1.3 26 1:2 3.0 4.6
Module length (mm) 1016 0 1.0 20 1:5 1.2 4
Module diameter (mm) 61 1 0.7 14 1:8 0.8 3.4
Selective ability (% stabilized salt retention) 97 1.681 0.5 10 1:10 0.6 3
Filtration effective area (m2) 2.6
a
Multiplying factor  2.125 g for each COD gram of raw leachate
(CODraw leachate = 3.141 mg L1).
b
FeSO47H2O:H2O2 (30% v/v) proportion considering O2 stoichiometric quantities
Table 2.3 necessary for total COD stabilization.
Variation levels of 251 fractional factorial design factors to AOP/Fenton testing.

Condition H2O2 Fe:H2O2 pH Vm t

(rpm) (min) for statistical analysis of data. The adopted configurations in each
Factor a
Value Proportion b
Value fractional factorial test and central composite rotational designs
(g L1) (g L1) are summarized, respectively, in Tables 2.3–2.5.
+1 1.5 33 1:1 6.6 5 150 60
0 1.0 22 1:5 1.3 4 100 30
1 0.5 11 1:10 0.7 3 50 15 2.5. Evaluation of sedimentability in AOP/Fenton generated mud
a
Multiplying factor 2.125 g H2O2 for each COD gram of raw leachate
(CODraw leachate = 3.141 mg L1). The sedimentation velocity was determined by sedimentation
b
FeSO47H2O:H2O2 (30% v/v) proportion considering O2 stoichiometric quantities in a measuring cylinder test that relates the dates of height inter-
necessary for total COD stabilization.
face versus sedimentation settling time. A 1-L glass beaker with the
same volume sample (post-AOP/Fenton effluent) was added and
left to stand until the solid/liquid interface height variation
utilized for the sequential strategy planning, in which the effects of reached an end. A sedimentation curve was drawn by obtaining
five major factors involved in the AOP/Fenton were examined the height of the solid/liquid interface every 3 min.
(H2O2 dosage, FeSO47H2O:H2O2 proportion, pH, mixing velocity Finally, sedimentation velocity was determined as the average
and reaction time) and their interactions. After this stage was com- speeds achieved before the critical time of sedimentation. Tests
pleted, a rotational central composite design was decided upon, were carried out with post-AOP/Fenton effluent neutralized at pH
with the variables which showed significance a < 0.05 (auxiliary 7.0 favoring optimal sedimentation conditions.
factors) and significance a > 0.05 (main factors) for the chosen pro- The Sludge Volume Index (SVI) also was evaluated. The interface
cess responses. MINITABÒ Release 15 Statistical Software was used height value used for Sludge Volume Index (SVI) determination
92 W.G. Moravia et al. / Waste Management 33 (2013) 89–101

Table 3.1
Raw leachate characterization.

Physicochemical parameters Unit Hydric surplus Hydric deficit

Max. Min. Average STD Max. Min. Average STD
True color lH 568 420 467 60 1579 1229 1374 155
Apparent color lH 748 519 590 94 1845 1536 1711 154
COD mg L1 2428 2220 2354 94 3156 2886 2990 130
BOD5 mg L1 85 50 68 15 130 70 99 28
BOD20 mg L1 130 75 105 23 195 100 154 44
BOD5/COD – 0.04 0.02 0.03 0.01 0.04 0.02 0.03 0.01
pH – 8.44 8.10 8.26 0.15 8.55 8.07 8.30 0.22
NKT mg L1 1172 1036 1105 57 1731 1054 1429 308
N–NH3 mg L1 1144 941 1055 85 1547 1062 1250 317
Alkalinity mg L1 6041 4791 5263 557 8089 7137 7576 430
Chlorides mg L1 2333 2033 2190 124 2533 2155 2325 172
Total phosphorus mg L1 19.6 11.3 14.5 3.7 43.0 28.0 34.5 6.9
TS mg L1 9408 8120 8801 591 13,100 9310 11,255 1927
FTS g L1 6002 5114 5595 370 7702 5602 6707 1020
VTS g L1 3736 2452 3227 614 5378 3678 4528 931
TSS g L1 26.5 17.0 22.4 4.1 43.0 24.5 34.0 8.4
FSS mg L1 4.5 1.5 3.1 1.4 13.0 1.8 7.7 5.5
VSS mg L1 22.0 15.5 19.3 2.8 30.0 22.7 26.3 3.3
Cadmium mg L1 0.524 <0.005 0.466 0.264 0.605 <0.005 0.366 0.111
Lead mg L1 <0.02 <0.02 <0.02 – <0.02 <0.02 <0.02 –
Chrome mg L1 0.49 <0.05 0.23 0.23 0.56 0.07 0.29 0.23
Iron mg L1 10.35 2.20 5.68 3.60 11.36 3.56 7.54 3.49
Zinc mg L1 0.14 0.07 0.10 0.03 0.21 0.07 0.13 0.07

COD – chemical oxygen demand; BOD – biochemical oxygen demand); TOC – total organic carbon; NKT – nitrogên Kjeldahl total; N–NH3 – ammoniacal nitrogen; TS – totais
solids; FTS – fixed total solids; VTS – volatile total solids; TSS – total suspended solids; FSS – fixed suspended solids Fixos; VSS – volatile suspended solids.

corresponded to a 30 min time span. SVI was determined by the directly of the hydrodynamics of the system, and other factors that
concentration of suspended solids in the sample. SVI values were are also important, the evaluation of the frequency of cleaning in
calculated according to Eq. (1), as established by von Sperling (2001). bench scale is difficult to be transfer to the real scale. Moreover
all tests performed in this work were developed in batch mode
Z 030  106 and an assessment of frequency of cleaning would have to be
SVI ¼ ð1Þ developed continuously.
Z 00  TSS

where SVI is the Sludge Volume Index (mL g1); Z 030 the interface
height 30 min after test onset (m); Z 00 the interface height at test on-
set (m); and TSS is the total suspended solids concentration
(mg L1).
2.6. Evaluation of MF in AOP/Fenton generated mud removal
2.6.1. Optimization
MF operating conditions were optimized by monitoring the per-
meate flux profile versus time throughout the different evaluated
conditions of operation, except for operating pressure, which was
assessed through critical pressure. The operating conditions evalu-
ated were operating pressure and crossflow velocity. To determine
critical pressure, tests were performed in which the pressure was
fixed and the permeate flux was monitored for 18 min, time re-
quired for compressing the membrane pores and stabilization of
the flow. Pressure was increased every 3 min following the perme-
ate flux. Evaluated pressure values were 0.25, 0.5, 0.75, 1.0,
1.25 bar (0.025, 0.05, 0.075, 0.1, 0.125 MPa). The effect of flow
velocity was evaluated by varying the feed flow rate corresponding
to the variation of hydraulic regimes related to a Reynolds (Re)
number range of 2600, 4400 and 5700 (operational limitation of
the experimental unit). Tests were carried out with effluent at
room temperature. Upon completion of each test, the module
was subjected to physical and chemical cleaning processes using
solution of citric acid at pH 3 for 20 min, sodium hypochlorite
(NaClO – 2% solution) for 60 min and water recirculation until
complete recovery of the membrane.
The cleaning procedure and frequency of cleaning was not
evaluated in this article, although it is an important aspect to be
evaluated and optimized. As the frequency of cleaning will depend
2.6.2. Investigation of fouling
The evaluation of fouling of the MF process was carried out
through the evaluation of the profile of the effluent permeate flux
(Jv) in relation to the pure water permeate flux for the new mem-
brane (Ji). In addition total fouling resistance and the resistance of
each part constituting the total resistance (membrane resistance –
Rm, static adsorption – Ra, pore blockage – Ra and gel formation
layer – Rg) were evaluated. To calculate these resistances, it was
necessary to determine the fluxes Ji, Ja, Jf e Jv as follows: the Ji flux
was determined for pure water permeation to the new membrane,
such a step being performed to characterize membrane permeabil-
ity. Ja flux was determined for pure water permeation after a 2-h
static adsorption of the effluent (unpressurized). Jf flux was deter-
mined by pure water permeation in the encrusted membrane and
Jv was determined by permeation of the effluent under conditions
to be established based on the determination of the critical pres-
sure for 2 h. Resistance values were calculated using Eqs. (2)–(5),
corresponding to the Resistances in Series Model.
DP
Rm ¼ ð2Þ
lJi
where Ji is the pure water permeate flux to the new membrane
(m3 m2 s1); DP the pressure difference applied through the mem-
brane (Pa); l the fluid viscosity (Pa s); and Rm is the membrane
resistance (m1).
 
Ji
Ra ¼  1 Rm ð3Þ
Ja
!
Ji
Rb ¼  1 Rm  Ra ð4Þ
Jf
 W.G. Moravia et al. / Waste Management 33 (2013) 89–101 93

Table 3.2
Factor condition and response values obtained in AOP tests using 25–1 fractional factorial design.

Tests Order test Factors/codes Responses

1 1
H2O2 (g L ) Fe:H2O2 (g L ) pH Vm (rpm) T (min) Ef. COD (%) STD Gen. TS (g L1) STD
1 18 11 (1) 0.7 (1) 3 (1) 50 (1) 60 (+1) 63.2 3.0 12.4 4.5
2 7 33 (+1) 0.7 (1) 3 (1) 50 (1) 15 (1) 64.7 2.9 9.2 0.6
3 12 11 (1) 6.6 (+1) 3 (1) 50 (1) 15 (1) 83.7 1.5 9.8 1.3
4 3 33 (+1) 6.6 (+1) 3 (1) 50 (1) 60 (+1) 73.2 3.4 7.4 0.1
5 1 11 (1) 0.7 (1) 5 (+1) 50 (1) 15 (1) 50.2 2.2 14.9 7.4
6 10 33 (+1) 0.7 (1) 5 (+1) 50 (1) 60 (+1) 42.3 1.7 7.2 1.6
7 16 11 (1) 6.6 (+1) 5 (+1) 50 (1) 60 (+1) 66.2 0.4 14.6 6.8
8 13 33 (+1) 6.6 (+1) 5 (+1) 50 (1) 15 (1) 53.0 4.2 31.1 6.2
9 11 11 (1) 0.7 (1) 3 (1) 150 (+1) 15 (1) 49.1 1.9 9.4 0.8
10 6 33 (+1) 0.7 (1) 3 (1) 150 (+1) 60 (+1) 53.8 2.1 7.5 0.7
11 9 11 (1) 6.6 (+1) 3 (1) 150 (+1) 60 (+1) 90.9 0.6 9.6 2.0
12 17 33 (+1) 6.6 (+1) 3 (1) 150 (+1) 15 (1) 65.9 2.9 8.5 1.0
13 15 11 (1) 0.7 (1) 5 (+1) 150 (+1) 60 (+1) 57.3 1.5 4.4 5.5
14 19 33 (+1) 0.7 (1) 5 (+1) 150 (+1) 15 (1) 40.8 1.7 6.5 0.3
15 5 11 (1) 6.6 (+1) 5 (+1) 150 (+1) 15 (1) 53.8 2.5 4.9 6.8
16 2 33 (+1) 6.6 (+1) 5 (+1) 150 (+1) 60 (+1) 54.0 1.1 6.6 2.1
17 4 22 (0) 1.3 (0) 4 (0) 100 (0) 30 (0) 74.4 4.7 10.4 0.7
18 14 22 (0) 1.3 (0) 4 (0) 100 (0) 30 (0) 76.4 2.8 7.9 0.5
19 8 22 (0) 1.3 (0) 4 (0) 100 (0) 30 (0) 76.8 3.8 9.4 1.5

where H2O2 = H2O2 solution concentration corresponding to the H2O2 fraction in relation to the stoichiometric quantity of O2 required for COD total stabilization; Fe:H2-
O2 = ferrous sulfate heptahydrate concentration, with reference to the FeSO47H2O:H2O2 proportion; pH = hydrogenionic potential; Vm = mixing velocity; T = reaction time.

Fig. 3.1. (a) Main effects and (b) interactions among effects on response efficiency of COD removal during determination of the significant factors.

 
Ji carried out according to Standard Methods for the Examination of
Rg ¼  1 Rm  Ra  Rb ð5Þ
Jv Water and Wastewater (APHA, 2005).

where RT is the total resistance (m1); Rm the transport resistance
through membrane (m1); Ra the additional resistance due to static
adsorption (m1); Rb the additional resistance due to physical
blockage of pores (m1); Rg the additional resistance due to gel layer
formation (cake) (m1); Ji the pure water permeate flux to the new
membrane (m3 m2 s1); Ja the pure water permeate flux after the
effluent static adsorption (m3 m2 s1); Jf the pure water permeate
flux into fouled membrane (m3 m2 s1); and Jv is the permeate flux
with effluent (m3 m2 s1).
2.6.3. Evaluation of the removal of mud generated in the AOP/Fenton
The evaluation of MF performance in the removal of mud from
the effluent post-AOP/Fenton at different pH (3, 5 and 7) took into
consideration the hydraulic permeability and selectivity through
the effectiveness in color, total iron, TS and COD removal, where
total iron and TS were the prioritized parameters and the main
objectives of this stage. Adjustment of pH was performed with
sodium hydroxide avoiding damage to membranes. Analyses were
2.7. Evaluation of complete treatment cycle
After the optimum conditions were established, MF and NF
processes were operated under such conditions in order to jointly
assess efficiency of AOP mud removal by MF and final polishing of
the effluent through the NF process. Samples from each stage of
treatment were collected and analyzed according to the parame-
ters: COD, BOD, total carbon (TC), inorganic carbon (IC), TOC, pH,
true and apparent color, total and ammoniacal nitrogen, alkalinity,
chloride, total phosphorus, series solids (total and dissolved) and
metals.
3. Results and discussion
3.1. Physicochemical characterization of raw leachate
Table 3.1 shows the maximum, minimum and average values
and their respective deviations, obtained from the analyzed param-
eters of raw leachate in different seasons. It is noteworthy that the
94 W.G. Moravia et al. / Waste Management 33 (2013) 89–101
Fig. 3.2. (a) Main effects and (b) interactions between effects for response of mud generation in terms of TS during significant factors.
average monthly rainfall was 270 mm in the water surplus period
in contrast to 30 mm during the water deficit period, showing sig-
nificant climatic differences between the monitored periods.
As expected, it can be observed that the organic matter in terms
of COD of the generated leachate is strongly affected by rainfall
patterns, being approximately 66% lower during high rainfall peri-
ods due to dilution. Nevertheless, the high values of the color pre-
sented confirm the pollution potential of the leachate in relation of
this parameter. The small difference between the real and apparent
color values means that the color of the effluent is associated with
the dissolved substances in the leachate; a statement that is rein-
forced by the low solids concentration and significant presence of
humic substances.
A high concentration of organic matter in terms of COD
throughout the characterization can be observed. The low BOD/
COD ratio indicates low leachate biodegradability, confirming the
advanced stabilization stage, and also demonstrating the high
leachate oxidation condition, i.e., the microbiological reactions of
BOD degradation are limited. This suggesting that the physical–
chemical mechanisms are most suitable for the treatment of this
effluent.
It is observed that the pH encountered was elevated in compar-
ison to similar leachate found in literature with similar character-
istics (Gomes et al., 2009), substantiated by the high values of
alkalinity, derived from the large amount of construction
  waste
which was disposed, where the carbonate ions CO2 and bicar-
  3
bonate ions HCO 3 can be leaching from ceramic materials.
The BOD/NKT ratio is the quantity of organic matter related to
the amount of the macronutrient nitrogen, similar to the C/N rela-
tionship. The values for this ratio are very low (1/16) indicating
that excess nitrogen is present mainly in the form of ammonia,
probably generated by the degradation of protein material consti-
tuting the major fraction of biodegradable organic matter in leach-
ate. As BOD5/COD ratio is very low (0.03 < 0.4), microbial
degradation in the landfill aerobic cell may still be limited due to
lack of easily biodegradable organic matter or the presence of toxic
compounds in the effluent. Additionally, the limitation of phospho-
rus concentration is not observed when compared to the ratio indi-
cated as favorable for the development of microorganisms
(C:N:P = 100:5:2) (Metcalf and Eddy, 2003).
It can also be seen that the content of suspended and total solids
is low, also explaining the small difference between true and
apparent color of the effluent (low turbidity). VSS/FSS represents
the ratio between volatile solids amount (organic fraction) and
fixed suspended solids (inorganic fraction). Besides the low solids
concentration, a VSS/FSS relationship ranging from 3 to 6 is
observed in high and low rainfall periods respectively, indicating
development and stability of community microbiological, since
VSS can be directly associated to the existing biomass in the
leachate.
Metals concentration is low and shows no evidence of toxicity
that can be attributed to these elements. The concentration of iron
superior to other metals can be explained by the abundant pres-
ence of iron oxides in the soil of the region.
3.2. AOP/Fenton optimization and operation
3.2.1. Determination of main factors of process
Table 3.2 shows coded levels of variation, actual values of each
factor involved in the process as well as analytical responses
obtained by the 25–1 fractional factorial design.
It is interesting to note that all COD tests at this and later stages
were corrected for the presence of H2O2 residual interference in the
analysis (obtained results <5.0 mg COD L1). The analyses for resid-
ual hydrogen peroxide were performed through the iodometric
method (Kolthoff, 1920), which is less susceptible to organic com-
pound interference.
3.2.1.1. Determination of the significant factors involved in COD
removal efficiency. Fig. 3.1 shows the estimated main effects of fac-
tors involved in the AOP, when change occurs from the lowest level
(–) to the highest level (+) of each factor, and Pareto chart of
Standardized effects for the COD removal efficiency response.
According to the Main Effects charts, a marked curvature in the
model can be observed, which means, the intermediate values of
the chosen limits produced a favorable response. This fact also
indicates that the fractional factorial design (linear fit) is not rec-
ommended for optimization of this model.
Analyzing the effect of H2O2 concentration at extreme limits, its
increase from the lowest to the highest level reduced the COD re-
moval efficiency by 8.4%. This reduction can be explained by the
fact that better results of oxidation are obtained for hydrogen per-
oxide excess in the reaction (>25 mg L1 H2O2 solution) with a fer-
ric ion in the media instead of ferrous ions. H2O2 excess also favors
self-decomposition reactions of this reagent and sequestration of
hydroxyl radical, generating radicals with lower oxidation power.
Nevertheless, the lack of this reagent may result in failure of OH
evolved in the oxidation of organic compounds.
The addition of Fe in the form of solid ferrous sulfate heptahy-
drate improved COD removal efficiency by 14.8% when considering
the variation limits of this factor. The increase of Fe concentration
accelerates Fenton reaction, causing H2O2 concentration to rapidly
decrease, minimizing OH sequestration (Villa et al., 2007). How-
ever, for the values of this factor close to the center points, higher
 W.G. Moravia et al. / Waste Management 33 (2013) 89–101 95

Table 3.3
Factor conditions and chosen response values for the applied 22 central composite rotational design in AOP for determination of critical values during the optimization phase of
the AOP auxiliary factors.

Tests Order test Factors/codes Responses

Vm (rpm) T (min) Ef. COD (%) STD Gen. TS (g L1) STD
1 4 65 (1) 21.5 (1) 33.7 3.6 7.7 0.8
2 6 135 (+1) 21.5 (1) 49.6 2.5 4.7 0.2
3 10 65 (1) 53.5 (+1) 58.8 1.0 10.4 1.7
4 7 135 (+1) 53.5 (+1) 52.5 1.6 5.0 0.9
5 1 50 (1.414) 37.5 (0) 73.8 0.4 8.9 0.1
6 2 150 (+1.414) 37.5 (0) 78.9 1.5 4.8 0.3
7 9 100 (0) 15 (1.414) 67.8 0.8 4.1 0.2
8 13 100 (0) 60 (+1.414) 57.2 1.5 5.3 0.5
9 12 100 (0) 37.5 (0) 76.2 0.5 4.5 0.3
10 5 100 (0) 37.5 (0) 72.7 0.9 4.6 0.3
11 11 100 (0) 37.5 (0) 74.3 1.3 4.7 0.1
12 8 100 (0) 37.5 (0) 74.0 0.9 4.4 0.5
13 3 100 (0) 37.5 (0) 74.5 0.1 4.7 0.1

where Vm = mixing velocity; T = reaction time.

Fig. 3.3. (a) Response surface and (b) contours curves for mud generation in terms of TS as a function of temperature and mixing velocity during optimization stage of AOP
auxiliary factors.

Table 3.4
Factor conditions and chosen response values for 23 central composite rotational design applied in AOP tests to determine critical values during optimization phase of AOP main
factors.

Tests Order test Factors/codes Responses

H2O2 (g L1) Fe:H2O2 (g L1) pH Ef. COD (%) STD Gen. TS (g L1) STD
1 2 14 (1) 0.8 (1) 3.4 (1) 68.7 0.3 6.8 0.9
2 5 26 (+1) 0.8 (1) 3.4 (1) 53.3 2.3 10.3 0.0
3 15 14 (1) 3.0 (+1) 3.4 (1) 82.1 1.6 6.3 0.2
4 8 26 (+1) 3.0 (+1) 3.4 (1) 78.1 0.5 6.1 0.4
5 16 14 (1) 0.8 (1) 4.6 (+1) 61.8 4.6 5.6 0.1
6 10 26 (+1) 0.8 (1) 4.6 (+1) 41.8 4.0 5.3 0.1
7 9 14 (1) 3.0 (+1) 4.6 (+1) 77.5 0.9 4.4 0.3
8 12 26 (+1) 3.0 (+1) 4.6 (+1) 66.3 5.9 10.3 2.4
9 3 10 (1.682) 1.2 (0) 4 (0) 80.4 2.2 6.4 0.5
10 13 30 (+1.682) 1.2 (0) 4 (0) 59.8 3.4 4.9 0.4
11 20 20 (0) 0.6 (1.682) 4 (0) 51.5 8.9 5.1 0.7
12 18 20 (0) 6.0 (+1.682) 4 (0) 81.4 0.1 6.4 0.4
13 6 20 (0) 1.2 (0) 3 (1.682) 70.4 0.0 7.5 1.8
14 7 20 (0) 1.2 (0) 5 (+1.682) 58.9 1.7 5.8 0.3
15 11 20 (0) 1.2 (0) 4 (0) 76.7 0.7 6.4 0.1
16 19 20 (0) 1.2 (0) 4 (0) 78.5 0.1 6.3 0.2
17 17 20 (0) 1.2 (0) 4 (0) 74.7 1.0 5.9 0.2
18 1 20 (0) 1.2 (0) 4 (0) 78.5 0.1 6.3 0.7
19 4 20 (0) 1.2 (0) 4 (0) 74.7 1.0 6.4 0.9
20 14 20 (0) 1.2 (0) 4 (0) 76.7 0.7 5.9 0.6

where H2O2 = H2O2 solution concentration corresponding to the fraction of the quantity of H2O2 in relation to the quantity of stoichiometric O2 required for COD total
stabilization; Fe:H2O2 = concentration of ferrous sulfate heptahydrate, with reference to the FeSO47H2O:H2O2 proportion; pH = hydrogenionic potential.
96 W.G. Moravia et al. / Waste Management 33 (2013) 89–101

Fig. 3.4. (a) Response surface and (b) contour curves for COD removal efficiency as a function of H2O2 and Fe during optimization phase of AOP/Fenton main factors.

Fig. 3.5. (a) Response surface and (b) contour curves for COD removal efficiency as a function of H2O2 and pH during optimization phase of AOP/Fenton main factors.

Fig. 3.6. (a) Response surface and (b) contour curves for COD removal efficiency as a function of Fe concentration and pH during optimization phase of AOP main factors.

performance was obtained, suggesting an optimal concentration of
this element in the process.
The pH effect on Fenton’s reaction was the most significant
within the factors studied. Efficiency of COD removal decreased
by 15.8% when operated at this factor upper level in relation to
its lowest level. The influence of pH on oxidation is a consequence
of Fe precipitation at pHs above 4, drastically reducing its interac-
tion with hydrogen peroxide and consequently the OH production,
and by hydrogen peroxide decomposition. It is also noteworthy
that for very acidic pH values (<2), degradation efficiency also
decreases in spite of iron species remaining soluble, since high
concentrations of H+ can sequester hydroxyl radicals.
For an a = 0.05 significance level, Fig. 3.1b shows that for the
COD removal efficiency, all evaluated factors (except interactions)
were significant in the process. Thus, pH factors, Fe and H2O2
concentration, in this order, presented the greater degree of
 W.G. Moravia et al. / Waste Management 33 (2013) 89–101 97

Fig. 3.7. Evaluation of AOP/Fenton generated mud sedimentability: (a) sedimentation curve and (b) velocity of sedimentation curve.

Fig. 3.8. (a) Relationship between permeate flux and operating pressure to determine critical pressure in MF proccess; (b) profile of MF permeate flux profile for different flow
velocities during the operation.

significance for the response under study. These factors were con-
sidered as the main process, taking into account the principle
objective of this treatment (AOP).
3.2.1.2. Determination of significant factors involved in mud genera-
tion. Fig. 3.2 shows the estimated main effects of factors involved
in the AOP, in which changes occur from the lowest () to the high-
est level (+) of each factor, and also the Pareto chart of effects
according to the standardized response for mud generation in
terms of TS.
For the mud generation response in terms of TS, a low effect of
curvature was observed, which indicates a linear pattern of behav-
ior regarding the response when varying each factor values be-
tween established maximum and minimum levels. Note also that
mixing velocity and reaction time factors have impacted more inci-
sively on the process for mud generation response. The other fac-
tors interfered less severely in the response process of the study.
At the fastest mixing velocity (150 rpm), mud production was
reduced by 6.2%. This factor mainly affects the AOP on mud
generation and separation, since it influences flake formation and
characteristics. At very low mixing velocities (slow agitation), flake
formation decreases due to a smaller number of collisions between
solid particles in suspension. With regards to mixing at very high
velocities (violent agitation), there is formation of flakes followed
by their breaking into smaller particles due to the high kinetic
energy involved.
Prolonged reaction time contributed to a 3.1% lower mud gener-
ation. A longer reaction time creates more opportunities for more
flakes to break during agitation, leaving released particles more
prone to oxidation.
For an a = 0.05 significance level, it is observed that by the Par-
eto charts, only mixing speed and reaction time were significant in
the process for mud generation in terms of TS. These factors were
considered as process auxiliaries and were later optimized, in order
to determine the critical operating condition (optimal).
3.2.2. Optimization of process auxiliary factors
With the objective of determining the critical values (which en-
able the minimum generation of mud) of the factors considered to
be auxiliary to AOP, a model was optimized using a 22 central
composite rotational design. Table 3.3 shows the coded levels of
variation and actual values of each factor involved in the process,
as well as analytical responses obtained from the 22 CCRD.
Fig. 3.3 shows the surface response and contour lines for mud
generation response in terms of TS as a function of reaction time
and mixing velocity.
The identification of the critical point coordinates of the re-
sponse surface were determined by the resolution of a system with
two linear equations and two unknowns (Eqs. (6) and (7)), result-
ing from the application of derivative equations obtained for the
surfaces.
@YðXÞ
¼ 0:2455 þ 0:0024X 1  0:0011X 2 ð6Þ
@X 1
Table 3.5
SVI for post-AOP/Fenton generated sludge.
Sample TSS (mg L1) Z00 (m) Z300 (m) SVI (mL g1)
Post-AOP/Fenton + sludge 1067 0.400 0.137 321
98 W.G. Moravia et al. / Waste Management 33 (2013) 89–101

Fig. 3.9. (a) Ji, Ja, Jf and Jv flux values; (b) relationship between Ja/Ji, Jf/Ji and Jv/Ji; (c) Rm, Ra, Rb, Rg and Rtotal resistance values, (d) resistance fraction in relation to Rtotal in MF
being fed at pH 7, 0.25 bar (0.025 mPa) operating pressure and flow Re equal to 5700.

@YðXÞ X 1 ¼ 16:0616; X 2 ¼ 3:0501 and X 3 ¼ 3:8092 ! H2 O2

¼ 0:0476 þ 0:0028X 2  0:0011X 1 ð7Þ
@X 2
¼ 16:0 g L1 ; Fe ¼ 3:0 g L1 j and pH ¼ 3:8:
@YðXÞ @YðXÞ
Considering, @X 1
¼ 0 and @X 2
¼ 0, the system solution is:
    Note that the optimal value of the H2O2 solution concentration
 X 1   115:25  (16.0 g L1) obtained for raw leachate with a concentration of
 ¼ 
 X   28:27  ! V m ¼ 115 rpm and T ¼ 28 min: 2834 mg L1 corresponds to the multiplication factor of the oxidiz-
2
ing agent in the AOP/Fenton with 1.7 g H2O2 for each CODraw leachate
gram. Nevertheless, when analyzing the FeSO47H2O:H2O2 propor-
3.2.3. Optimization main factors of the process tion for critical values found in the optimization model, the opti-
With the objective of determining the critical values (which en- mum value for the proportion of reagents is 1:5.3. The results are
able maximum efficiency of COD removal) of the AOP/Fenton main specific to the leachate used. The values optimize are compatible
factors, the model was optimized using a central composite with the literature (Cortez et al., 2011; US Peroxide, 2010).
rotational design. Table 3.4 shows the coded levels of variation
and actual values for each factor involved in the process, as well 3.3. Evaluation of AOP/Fenton generated mud sedimentability
as the analytical responses obtained in the 23 CCRD.
Figs. 3.4–3.6 show the response surface and contour curves for The profile of sedimentation of AOP/Fenton mud was evaluated
response of COD removal efficiency as a function of H2O2 and Fe through the sedimentation and velocity of sedimentation curves
concentrations, H2O2 concentration and pH, and Fe concentration obtained in the test beaker. Fig. 3.7 shows the test response curves.
and pH, respectively. Note that the critical time of sedimentation, i.e., the one from
The identification of the critical point coordinates of the re- which only two phases in the liquid are seen, was 27 min while
sponse surface were determined by the resolution of a system with mud compression completion time was close to 70 min (speed of
three linear equations and three unknowns (Eqs. (8)–(10)), result- sedimentation is constant and close to zero). The average velocity
ing from the application of derivative equations obtained for the of sedimentation (calculated on the basis of the velocity of
surfaces. sedimentation curve) was 0.56 m h1. These results indicate low
@YðXÞ sedimentability of AOP/Fenton generated mud. According to von
¼ 2:4695  0:1316X 1 þ 0:3864X 2  0:4028X 3 ð8Þ Sperling (2001), the post-AOP/Fenton mud presented a SVI classifi-
@X 1
cation as poor sedimentability (>300 mL g1). Table 3.5 shows the
results obtained.
@YðXÞ
¼ 10:6638  6:0512X 2 þ 0:3864X 1 þ 0:4167X 3 ð9Þ
@X 2
3.4. Evaluation of MF in the removal of mud generated in the AOP/
Fenton
@YðXÞ
¼ 96:3290  23:9232X 3  0:4028X 1 þ 0:4167X 2 ð10Þ
@X 3
3.4.1. Optimization
@YðXÞ @YðXÞ @YðXÞ
Considering @X 1
¼ 0, @X 2
¼ 0 and @X 3
¼ 0, the system solution Initially operating pressure was evaluated through determining
is found to be: critical pressure by the flux-step method (BACCHIN et al., 2006).
 W.G. Moravia et al. / Waste Management 33 (2013) 89–101
Critical pressure is defined as that in which the relationship be-
tween pressure and permeate flux becomes nonlinear, i.e., from
which membrane fouling is observed. Fig. 3.8a and b shows the
relationship between permeate flux and operating pressure used
to determine critical pressure and the MF permeate flux profile
when operated at different Re.
The critical flux test could have been carried out with constant
pressure or constant flux. In this study, the choice of setting pres-
sure and not the flux is due to the fact that system has more sen-
sibility to measure the flux than the pressure. The loss of flux
indicates the occurrence of fouling, and then the indication of the
critical pressure or critical flux.
It is observed that the flux declines from the lower values of
applied pressure, thus indicating considerable potential for mem-
brane fouling and that is not possible to determine the critical flux.
It is also observed that applied pressure higher than 0.75 bar did
not produce a higher permeate flux indicating the occurrence of
limit flux. This fouling is most likely due to the characteristics of
feeding and represents the actual process conditions of this appli-
cation. Probably due to the fact that colloidal solids, the convective
forces toward the membrane surface brought by the pressure gra-
dient, albeit low, are sufficient to raise the solids concentration
next to the membrane selective layer, and thus promote the forma-
tion of cake, possibly due to chemical precipitation of soluble com-
pounds. These results suggest that improved performance of this
process can be achieved through the operation of the system at
low pressure.
These results suggest that improved performance of this pro-
cess can be achieved through the operation of the system at low
pressure and using fouling mitigation strategies. However it is
noteworthy that this test was realized in the worst situation that
can be found in real scale since it does not use any technique to
minimize fouling (e.g. backwash, relaxation and pulse). Even in
these conditions, the results show that although there is a great
loss of initial permeability, the permeability after stabilization is
Fig. 3.10. Pollutant concentration in the feed and permeate in MF process during different times of operation and their respective removal efficiencies (a) apparent color; (b)
total iron; (c) total solids and (d) total COD.
99
high when compared to that found in systems that operate with
solids concentration similar to this system, reinforcing the viability
of applying this process.
Using techniques to minimize fouling, the increased flux can be
used in the design stage to reduce the demand for membrane area,
in the other way, the minimum flux may be considered to design
and increased flux be used to make the process more sustainable
by providing lower energy requirement, lower cleaning frequency
and therefore longer life of the membrane since the frequency of
cleaning directly influences the lifetime of the membrane and
increased productivity.
According to the results, if compared with Re of 5700, the stabi-
lized permeate flux of the MF system increased from 16.3 to
32.7 L m2 h1 when operated with Re of 2600 compared to Re of
5700. These results can be explained by greater turbulence and
shearing next to the membrane surface, resulting in stronger drag,
and consequently, lower particle concentration next to the mem-
brane selective layer, thus increasing operational permeability.
The results also demonstrate a permeate recovery coefficient next
to the flow velocity evaluated. Re equal to 5700 (pressure = 0.25 -
bar–0.025 MPa/Qa = 5.2 L min1) was adopted as the system opti-
mal flow velocity.
3.4.2. Investigation of fouling
The evaluation of the MF fouling process was performed through
assessment of the total fouling resistance (Rtotal) and the resistance
of each part that constitutes Rtotal (membrane resistance – Rm, static
adsorption – Ra, pore blockage – Rb and cake – Rg), by determining
the pure water permeation flux towards the new membrane (Ji),
the pure water permeation after static adsorption of effluent (Ja),
pure water permeation in the fouled membrane (Jf) and the effluent
permeation under the established conditions (Jv).
The operational conditions of the MF process during the evalu-
ation of fouling mechanisms were fed at pH 7, a 0.25 bar
(0.025 MPa) operating pressure and Re equal to 5700. Fig. 3.9a–d
100 W.G. Moravia et al. / Waste Management 33 (2013) 89–101

Table 3.6
Specific collective characterization of raw leachate, post-AOP/Fenton effluent and permeate produced by MF and NF.

Physicochemical parameters Unit Raw leachate Post-AOP/Fentona MF NF Standardb

Average STD Average STD Average STD Average STD
True color lH 1200 86 284 72 197 42 4 2 –
Apparent color lH 1242 107 5476 652 209 40 4 2 –
1
COD mg L 2863 426 1073 120 781 63 45 13 180
BOD5 mg L1 85 22 182 30 121 16 26 12 60
BOD20 mg L1 197 85 248 41 160 25 31 14 –
BOD5/COD mg L1 0.03 0.01 0.17 0.01 0.16 0.01 0.56 0.11 –
Total Carbon mg L1 1764 107 273 53 272 61 22 6 –
Inorganic Carbon mg L1 915 44 14 8 15 7 4 1 –
TOC mg L1 850 66 259 46 257 54 17 6 –
pH – 7.65 0.29 7.13 0.52 7.02 0.06 7.32 0.36 6.0–9.0
TKN mg L1 1132 13 1059 54 904 54 95 23 –
N–NH3 mg L1 1099 19 1037 53 884 52 78 7 –
Chlorides mg L1 2154 194 2055 99 1904 275 366 156 –
Alkalinity mg L1 5492 361 322 28 179 30 0 0 –
Total phosphorus mg L1 13.5 5.6 6.5 1.0 0.5 0.2 0.0 0.0 –
TS mg L1 7725 1807 14,831 641 1301 109 45 11 –
FS mg L1 5410 569 9867 328 797 35 32 11 –
VS mg L1 2.315 1.248 4.971 338 507 79 13 1 –
TSS mg L1 48.8 25.0 1534.6 178.1 0.0 0.0 0.0 0.0 100
FSS mg L1 12.8 8.0 1020.0 131.7 0.0 0.0 0.0 0.0 –
VSS mg L1 36.1 17.5 530.7 83.2 0.0 0.0 0.0 0.0 –
Cadmium mg L1 <0.02 – <0.02 – <0.02 – <0.02 – 0.1
Lead mg L1 <0.08 – <0.08 – <0.08 – <0.08 – 0.1
Chrome mg L1 0.07 – <0.02 – <0.02 – <0.02 – 0.5
Iron mg L1 5.22 3.74 559.63 44.53 2.08 0.16 <0.08 – 15.0
Zinc mg L1 0.17 0.08 0.07 0.04 0.07 0.02 0.05 0.03 5.0

COD – chemical oxygen demand; BOD – biochemical oxygen demand; TOC – total organic carbon; TKN – Total Kjeldahl nitrogên; N–NH3 – ammoniacal nitrogen; TS – totals
solids; FTS – fixed total solids; VTS – volatile total solids; TSS – total suspended solids; FSS – fixed suspended solids; VSS – volatile suspended solids.
a
Supernatant + sludge – after neutralization.
b
Deliberação Normativa Conjunta COPAM/CERH-MG No. 1, May 5, 2008 (Brazil).

the total resistance, while 20% of the resistance was due to cake
formation. Despite being very low, fouling due to static adsorption
was also observed (3.5% of the membrane total resistance). The
most significant resistance was the membrane resistance repre-
senting more than 50% of the total.

3.4.3. Evaluation of removal of AOP/Fenton generated mud

Fig. 3.11. Appearance of samples during treatment stages (a) raw leachate; (b)
post-AOP/Fenton effluent; (c) MF permeate; (d) NF permeate.
shows the Ji, Ja, Jf and Jv flux values, the relationships between
fluxes, Rm, Ra, Rb, Rg and Rtotal resistances and fraction of resistance
in relation to Rtotal respectively.
It is observed that membrane fouling was mainly due to pore
blockage and consequently cake formation. The main resistance
attributed to the blocking of membrane pores can be explained
by the favorability of obstruction by the particles present in the
feeding, whose colloidal nature favors their own deposition in
the membrane pores. The expression of resistance due to cake for-
mation can be associated with the accumulation of particles on the
membrane surface and also by the occurrence of chemical precip-
itation. The resistance due to pore blockage accounted for 24% of
The MF stage aimed primarily at the removal of mud generated
during the AOP/Fenton and the iron used as catalyst for Fenton
reaction. As previously shown, cake formation was significant in
the process, where it became necessary to evaluate MF selectivity
during different times of operation with the purpose of verifying
the impact of formed cake on the quality of permeate from the
MF process. Fig. 3.10 presents the concentration of pollutants in
the feed and permeate of the MF process during different times
of operation, as well as removal efficiencies obtained.
The results showed that the MF process was satisfactory for the
objective of this stage, where the average mud removal efficiencies
in terms of TS and total iron were 90.8 (<1150 mg L1) and 99.8%
(<1.0 mg L1) respectively. It was found that for the iron parame-
ter, MF was sufficient for inclusion in the regulatory standards
for effluent discharge according to Deliberação Normativa Conjunta
COPAM/CERH-MG No. 1, May 5, 2008 (Regulatory Determination),
where the maximum allowed is 15.0 mg L1. The decreasing con-
centrations of total iron (more evident) and TS in the feed may
be explained by the accumulation of these substances within the
membrane module. MF presented high removal efficiency of
apparent color, though the true color of the effluent still remained
above the limit established by law. MF did not present satisfactory
removal of total COD where permeate concentrations were close to
1000 mg L1. Such results reinforce the necessity for final polishing
of the effluent.
 W.G. Moravia et al. / Waste Management 33 (2013) 89–101
3.5. Evaluation of full cycle treatment
The NF process was employed as the final polishing stage of the
effluent. The manner of NF operation occurred as a single stage and
employed the optimized operational conditions previously estab-
lished, where operating pressure was 12.5 bar (1.25 MPa) and flow
rate equivalent to a Re of 1800 (Qa = 4.0 L min1). For an integrated
evaluation of NF performance, samples were characterized in trip-
licate in all stages of treatment. Table 3.6 shows the obtained aver-
age values and respective deviations of parameters. Fig. 3.11
illustrates the appearance of raw leachate samples after each stage
of treatment.
Note that the AOP has significantly contributed to the removal
of true color from raw leachate, reaching an average efficiency of
76.4%. The remaining percentage was almost completely removed
by NF (99.4%). In contrast, the MF process removed 91.2% of solids
in the post-AOP/Fenton effluent. This effluent, when considered as
mud and supernatant, presented a 92%-increase in TS concentra-
tion due to the oxidation reaction, which also played an important
role in conditioning the effluent for the later treatment stage (NF).
Regarding the removal of organic pollutants, average removal
efficiencies of 62.5% for COD and 71.0% for TOC respectively were
obtained in the AOP/Fenton. The MF process had little significance
for this type of effluent, as expected by the results of the molecular
weight distribution. Nonetheless, the NF process was effective as
effluent polishing causing an average removal efficiency of 98.4%
and 98.1% for COD and TOC, respectively in a complete treatment
cycle.
The membrane separation processes were effective in removing
nutrients. The nitrogen, due to a neutral pH (<8.0) presented as vir-
tually ionized ammonia NHþ 4 , was significantly removed by the
NF process. This was expected, as the literature already asserts
the fact that the NF membrane is effective in rejection ions (Habert
et al., 2006). Regarding phosphorus, the removal of approximately
52% during AOP/Fenton, is probably due to its adsorption by the
mud generated in the process, which was retained by MF, explain-
ing the average removal of phosphorus of 92.3% by MF. Yet, consid-
ering the effect of effluent polishing, the NF stage was able to
remove almost this nutrient.
The alkalinity, probably due to bicarbonates present in the
leachate (pH < 8.3), was also significantly removed during the
AOP/Fenton (94.1%). According to EPA (1998), oxidative processes
tend to consume alkalinity as carbonate and bicarbonate ions are
 Kjeldsen, P.I. et al., 2002. Present and long-term composition of MSW landfill
OH sequestering agents. The NF process was enough to remove
the remaining AOP alkalinity which had not been previously re-
moved by MF. With regards to chloride parameters, similar to
the removal of ammonia in the ionized form, the NF process was
effective in retaining these ions, enabling an average removal effi-
ciency close to 80%.
4. Conclusion
Regarding the properties of the leachate from the Belo Horizon-
te landfill, the results showed that the leachate in the study pre-
sented characteristics of stabilized landfill. The treatment of the
leachate using all of the proposed stages was sufficient for reach-
ing, with the exception of nitrogen, all parameters according to
current legislation (Deliberação Normativa Conjunta COPAM/CERH-
MG No. 1, May 5, 2008). Despite nitrogen concentration above the
limits, the removal of this pollutant was significant. Thus, the
AOP system in conjunction with MPS proved to be a potential
alternative for landfill leachate treatment with a focus on reuse
101
of water, characterized as a superior solution for fast, compact
and efficient removal of pollutants when compared to conven-
tional systems.
Acknowledgements
The authors gratefully aknowledge the Conselho Nacional de
Desenvolvimento Científico e Tecnológico – CNPq (Brazilian National
Council for Scientific and Technological Development) and Fun-
dação de Amparo a Pesquisa do Estado de Minas Gerais – FAPEMIG
(Research and Support Foundation of Minas Gerais) for granting
financial resources, and Superintendência de Limpeza Urbana da Pre-
feitura Municipal de Belo Horizonte – SLU/PBH (Cleaning and Landfill
Management Department of the Belo Horizonte’s City Council) for
the supply of leachate and operational support.
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