Environmental Management (2021) 68:226–239

https://doi.org/10.1007/s00267-021-01489-4

Landfill Leachate Treatment Through Coagulation-flocculation with

Lime and Bio-sorption by Walnut-shell
Milad Ghaffariraad1 Mehdi Ghanbarzadeh Lak
●
2

Received: 11 February 2021 / Accepted: 25 May 2021 / Published online: 7 June 2021
© The Author(s), under exclusive licence to Springer Science+Business Media, LLC, part of Springer Nature 2021

Abstract
Due to the environmental consequences corresponding to leachate penetration, a sequence of inexpensive conventional processes
proposed leachate treatment. The main objective was maximizing the COD and heavy metal removal efficiencies while
minimizing generated sludge volume and material consumption rate. Walnut-shell adsorption complements lime treatment by
eliminating heavy metals and low molecular-weight organic compounds. Samples gathered from Nazlou-landfill, Urmia, Iran. The
relative significance of independent variables (lime and walnut-shell dosages and pH) on the removal efficiency was investigated
using response surface methodology. By estimating the gradient of relative equations of the experimental results, the ideal
1234567890();,:
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direction of independent variable change was found as such increasing COD removal. A new variable called OSVLDR was
utilized for measuring the ratio of the observed sludge volume to used lime dosage. The proposed sequence resulted in 43.24%
COD removal under optimal conditions (i.e., 6.83, and 25 g/L of lime and walnut-shell dosage and pH values of 6, and 4 for two
sets). Furthermore, effective removal in heavy metal concentrations was observed, i.e., 98.17, 67.45, 91.03, and 88.02% for nickel,
cadmium, zinc, and lead, respectively. The results showed that a change in variables’ amount affects associated costs while
making a variation at removal efficiency. Reducing the initial pH value of leachate to 3.50 might decrease the consumed raw
materials and OSVLDR value, resulting in a considerable decline in material costs (by 10%). Also, the inactive walnut-shell
surface with a more crushing degree was used to reduce costs in walnut-shell set experiments rather than the activated surface.

Supplementary information The online version contains

supplementary material available at https://doi.org/10.1007/s00267-
021-01489-4.

* Mehdi Ghanbarzadeh Lak Engineering Department, Urmia University, Urmia, Iran

m.ghanbarzadehlak@urmia.ac.ir 2
School of Engineering, Civil Engineering Department, Urmia
1 University, Urmia, Iran
Environmental Engineering, School of Engineering, Civil
Environmental Management (2021) 68:226–239 227

Graphical Abstract

Keywords Landfill leachate treatment Lime Walnut-shell RSM Coagulation-flocculation Urmia

● ● ● ● ●

Highlights
● Coagulation-flocculation and bio-sorption processes used for raw-leachate treatment.
● Introducing a new parameter for calculating the amount of settled sludge (OSVLDR).
● Ideal change direction of independent variables found using the gradient of equations.
● More crushing walnut-shell instead of activating its surface to increase efficiency.
● Over 43% of COD removal was achieved under optimal conditions.
● Major metal removals were Ni 98.17%, Zn 91.03%, Pb 88.02%, and Cd 67.45%.

Introduction waste type, moisture content, operational conditions, and

An integrated municipal solid waste management system
involves all aspects of waste management, including
temporary storage, collection, transportation, processing,
and final disposal, so that imposes an acceptable cost on
urban management while does not adversely affect
humans, plants, animals, and the environment in general
(Agwu 2012). The municipal solid waste disposal can be
partly or wholly handled by applying conventional pro-
cedures such as recycling processes, composting, or
incineration. However, the final disposal of remaining
waste from these processes (such as incineration ash), as
well as non-recyclable, non-degradable, and non-
combustible wastes, requires the landfilling method
(Qasim and Chiang 1994; Sharholy et al. 2008).
One of the main problems associated with the landfill
process is leachate generation. Landfill leachate is a highly
contaminated liquid produced during the waste stabilization
stage (Ghanbarzadeh Lak et al. 2018) with a variety of
physical and chemical compositions mainly depends on
the height and the age of buried materials (Renou et al.
2008; Moody and Townsend 2017). However, leachate
generally contains organic matter, mineral salts, ammo-
nium, halogenated organic compounds, and heavy metals.
Consequently, leachate penetrating beneath the landfill liner
might cause significant environmental problems (Renou
et al. 2009; Gautam et al. 2019).
Leachate treatment methods are mainly classified into
leachate transfer (recirculation and co-treatment with
municipal sewage) (Townsend et al. 1995), physicochem-
ical, and aerobic and/or anaerobic biodegradation categories
(El-Gohary and Kamel 2016; Augusto et al. 2019). Flota-
tion, neutralization, precipitation, adsorption (Mahdavi et al.
2018), coagulation-flocculation (Renou et al. 2008), nano-
filtration (NF) (de Almeida et al. 2020c), reverse osmosis
(RO) (Şchiopu et al. 2012; de Almeida et al. 2020a), che-
mical oxidation (Ghanbarzadeh Lak et al. 2012, 2018;
Sabour et al. 2011) and air stripping (Smaoui et al. 2020)
are among the physicochemical treatment methods recently
used by some researchers.
228 Environmental Management (2021) 68:226–239

Table 1 Design matrix of lime

Observation number in lime Coded values Lime set experiments Walnut-shell set experiments
and walnut-shell experiments in
(walnut-shell) experiments (for both lime
the current study
and walnut-shell
experiments)
X1 X2 Dosage (g/L) Initial pH Dosage (g/L) Influent pH
(L1) (L2) (W1) (W2)

1 (12) 1 1 6 8 25 8
2 (13) 1 −1 6 4 25 4
3 (14) −1 1 2 8 15 8
4 (15) −1 −1 2 4 15 4
5 (16) 1.414 0 6.83 6 27.07 6
6 (17) −1.414 0 1.17 6 12.93 6
7 (18) 0 1.414 4 8.83 20 8.83
8 (19) 0 −1.414 4 3.17 20 3.17
9 (20) 0 0 4 6 20 6
10 (21) 0 0 4 6 20 6
11 (22) 0 0 4 6 20 6
For lime set experiments, coded values could be calculated as: X 1 ¼ Lime dosage4
2 (lime dosage in g/L);
X 2 ¼ Initial pH2value6
For walnut-shell experiments, coded values could be calculated as X 1 ¼ WalnutShell
5
dosage20
(walnut-shell
dosage in g/L); X 2 ¼ Influent pH2 value6

The biological processes could not be applicable in this
case for several reasons including (a) the volume and
intensity of leachate produced in the Nazlou landfill and
land restrictions associated with the mentioned site, man-
dates the application of a rapid treatment sequence for
previously stacked leachate in the field; and (b) as the
generated leachate has been collected in several ponds in
the Nazlou landfill without any treatment since 1997, this
heterogeneous complex mixture is containing large amounts
of recalcitrant substances, heavy metals, and non-
biodegradable-toxic contents. Accordingly, biological
treatments may not be convincing in handling mentioned
raw mature leachate unless primarily undergoes physico-
chemical treatments (Amor et al. 2015; Kargi and Pamu-
koglu 2003; Ghanbarzadeh Lak et al. 2018; Robinson 2017;
Sabour et al. 2011). The coagulation-flocculation process is
regarded as a relatively simple method for leachate treat-
ment (Ye et al. 2017, Renou et al. 2009, Tatsi et al. 2003).
Aluminum sulfate (alum), iron sulfate, iron chloride, ferric
chloride, ferric sulfate, and lime are typical coagulants
(Tatsi et al. 2003), among which lime is known as an
inexpensive compound with acceptable efficiency in lea-
chate treatment (Renou et al. 2009; de Almeida et al.
2020b). According to Table 1 of Supplementary material
file #1 (Tables S1-1), lime can reduce the chemical oxygen
demand (COD) of leachate from 0.4% up to 66%.
Although lime as a coagulant agent can partly remove
heavy metals from leachate in addition to COD removal
(Tables S1-1), in most cases, it requires a complementary
method to eliminate heavy metals (Renou et al.
2008, 2008, 2009; Zazouli et al. 2010; Slater et al. 1983; de
Almeida et al. 2019, 2020a, b, c; Chaouki et al. 2017; Kılıç
et al. 2007; Tatsi et al. 2003). The efficiency of lime in
removing organic compounds with low molecular weight is
limited (Renou et al. 2009). Also, the amount of sludge
(chemically ineffective) increases with the dose of lime
(usually considered for more efficient heavy metal
removal), causing the management to economically unaf-
fordable (Renou et al. 2008). Finally, achieving high
removal percentages of heavy metals such as lead and zinc
using lime is difficult because of the low solubility of metal
hydroxides and the high alkalinity of lime (Wang et al.
2016). Based on the facts mentioned above, adsorption was
implemented to complete the treatment sequence in this
research. Adsorption, as an operationally simple method,
has beneficial effects on removing organic compounds,
heavy metals, and leachate odor (Li et al. 2019), while
producing limited sludge volume (Pan et al. 2011).
The conventional absorbents are activated carbon and
zeolite (Halim et al. 2010), nanomaterials (Sadegh et al.
2017), carbon mesoporous, clay materials, industrial
substances, and agricultural wastes (Li et al. 2019). The
application of agricultural wastes (bio-sorption process)
as low-cost adsorbents is suggested among all (Bozecka
et al. 2016). Natural adsorbents are environmentally
friendly and affordable. These compounds are readily
available in nature, and their cellulosic content increases
the adsorption capacity of heavy metals (Jain et al. 2016).
Some of the agricultural (natural) waste adsorbents used
in recent researches include orange peel (Xie et al. 2014),
Environmental Management (2021) 68:226–239
compressed coconut and palm fibers (Abdul Kadir et al.
2014), wheat bran, walnut-shell (Mahdavi et al. 2018;
Karimi-Jashni and Saadat 2014; Altun and Pehlivan
2012), hazelnut shell, almond shell, rice bran, banana
peel, cherry kernel, apricot kernel, sugarcane bagasse (Pan
et al. 2011) and grape seeds (Shehzad et al. 2015). walnut-
shell is known as a natural adsorbent for leachate treat-
ment due to its significant adsorption capacity of COD
and heavy metals. Furthermore, Iran is the fourth largest
walnut producer in the world with a production rate of
more than 290,000 t of walnuts per year, and walnut-shell
as an agricultural by-product is widely available (Karimi-
Jashni and Saadat 2014).
The results of some previous studies are summarized in
Tables S1-1 and S1-2. Lime dosage, leachate pH before
adding lime, stirring speed and time (fast and slow), and
sedimentation duration are the independent variables con-
sidered in lime tests. In walnut-shell tests, the valid para-
meters are walnut-shell dosage, leachate pH before adding
adsorbent, the size of the crushed walnut-shell, and stirring
speed and time. The experimental conditions and output
results of previous studies showed that changes in dosage
and pH in both experiments significantly affect the results
(de Almeida et al. 2019, 2020b). The difference between
pH before and after the coagulation-flocculation experi-
ment (Tables S1-1) was due to the alkalinity of lime. Since
the increased rate of pH does not follow a general rule by
lime addition, therefore, in the present study, the relation-
ship between leachate initial pH value and lime dosage
with the consequent pH value was investigated. Besides,
the sludge resulted from the coagulation-flocculation pro-
cess as a by-product of liming has not been addressed in
previous studies, while it is a necessary factor in simulating
the operational conditions.
Although there are many studies on the treatment of
landfill leachate (Cheng et al. 2021), limited studies were
found on the optimization and the mechanism of
coagulation-flocculation and bio-sorption combination in
landfill leachate treatment (Bazrafshan and Ahmadi 2017).
In the present paper, leachate samples collected from
Nazlou landfill were analyzed to determine COD, pH,
alkalinity, and heavy metals concentrations (Ni, Cd, Zn, and
Pb). The efficiency of coagulation-flocculation (lime) and
bio-sorption (walnut-shell) sequence in leachate treatment
was evaluated using RSM. The main objectives of the
current study are (1) to provide a quick pre-treatment
method for accumulated leachate at the studied area; (2) to
increase the efficiency of leachate treatment considering the
independent variables of the processes including initial pH,
lime dosage (g/L), influent pH and walnut-shell dosage
(g/L); (3) to find ideal change direction of independent
variables, where COD removal was considered as the main
target response.
229
Materials and Methods
Leachate Sampling
The studied leachate was obtained from Nazlou landfill,
21 km of Urmia, West Azerbaijan, Iran. The Nazlou muni-
cipal waste landfill is located in the northeast of Urmia City,
close to Nazlou village, with about 77.5 ha of area. This
center has been accepting the urban waste of Urmia and
surrounding towns (Serow, Silvana, Qushchi, Nooshinshahr),
and affiliated villages since 1997. The generated leachate has
been collected in several ponds in the Nazlou landfill without
any treatment since 1997. A sample was taken from the
stacked leachate pound to measure its characteristics. Other
samples were stabilized using 1 M sulfuric acid (Merck
group) for further experiments. According to the standard
methods, samples were kept in polyethylene bottles at 4 °C
until the tests (Rice et al. 2017). The characteristics of the
leachate used in this study are presented in Tables S1-3.
Analytical methods were according to “Standard methods for
the examination of water and wastewater” specified by the
American public health association (APHA), American water
works association (AWWA), and Water Environment Fed-
eration (WEF) (Rice et al. 2017).
Municipal landfills handling a mixture of household,
commercial, and industrial wastes, and treatment sludges
usually produce leachate with COD and heavy metal con-
centrations in the microgram per liter to low milligram per
liter level. Assessment of leachate quality in more than 13
landfills around the world shows that the concentrations of
COD, Ni, Cd, Zn, and Pb are between 10–62000,
0.001–3.2, 0.00002–0.13, 0.00005–7.2, and
0.0005–1.5 mg/L, respectively. According to Tables 1–3,
the leachate of Nazlou Landfill has a similar quality to other
sanitary landfills. Therefore, landfill leachates might con-
tain, among many other constituents, heavy metals in con-
siderable concentrations. The heavy metals may constitute
an environmental problem and must be treated prior to
discharge (Baun and Christensen 2004; Edokpayi et al.
2018; Al Raisi et al. 2014).
Designing the Lime and Walnut-Shell Experiments
The number of experiments required to achieve the desired
accuracy could be reduced using response surface metho-
dology (RSM) (Moradi and Ghanbari 2014; Roudi et al.
2020). This technique will eventually lead to polynomial
models (similar to Eq. (1)) between objective functions (i.e.,
response: Yj; j = 1, 2,…, m) and the respective input vari-
ables (i.e., Xi; i = 1, 2,…, k) (Wu et al. 2010; Ghanbarzadeh
Lak et al. 2018).
Yj ¼ f ðX1 ; X2 ; ¼ ; Xk Þ þ ε ð1Þ
230
Where f is a polynomial function of degree 2 (maximum),
and ε denotes statistically possible errors in the system
(assumed with a normal distribution, mean of zero, and
variance of σ2).
As mentioned earlier, two variables, i.e., initial/influent
pH values and lime/walnut-shell dosages, were identified as
independent parameters in both experimental sets (it should
be noted that here the initial pH value means the pH value
of raw leachate after pH adjustment prior to lime tests, and
influent pH value stands for the pH of samples entering to
the bio-sorption stage). The temperature was determined
according to room temperature in both tests. The pH values
variations from 4 to 8, and the dosage range from 2 to 6 and
from 15 to 25 g/L, were determined for lime and walnut-
shell tests, respectively. Based on Table 1, 11 experiments
were designed using the RSM methodology.
As the experiments were completed, the experimental
data were analyzed using the RSM method to fit a second-
order poly-nominal model (Eq. (2)).
X X XX
Y ¼ β0 þ β i Xi þ βii Xi2 þ βij Xi Xj ð2Þ
i i i j
Where Y is the prediction function (in lime experiments
includes COD removal percentage, final pH value, and
observed sludge volume to used lime dosage ratio (OSVLDR
value); and in walnut-shell experiments includes COD removal
percentage), β0 is a constant-coefficient (independent); βi; i = 1,
2, …, k is the first-order coefficient for factor i; βii; i = 1, 2, …,
k is the second-order coefficient for factor
i; βij; i, j = 1, 2, …, k, i ≠ j is the linear model coefficient
for the interaction of factors i, and j and Xi; i = 1, 2, …, k, is the
encoded value referring to factor i. The term “final pH” is used
instead of the pH of leachate obtained from lime treatment. The
meaning of OSVLDR is discussed in detail in parts 2-4-1.
In this study, a combination of central composite
design (CCD) and RSM was used to analyze the data
using operational variables of dose (lime and walnut-
shell) and pH. CCD is one of the widely used methods for
designing experiments (especially in consecutive experi-
ments). This experiment design method includes 2k
second-order factorial points, 2k axial points, and 3–5
center point iterations for error calculation (k is the
number of operational variables of the experiment). In this
study, the value of independent variables was encoded
between +1 and −1, and the amount of parameter α was
selected equal to 1.414 pffiffiffito cover the full range of opera-
tional variables (α ¼ k ).
In lime set experiments, the experimental variables
included in equations for calculating the percentage of COD
removal and the final pH are lime dosage and the initial pH.
However, the practical factors in the equation for estimating
the OSVLDR include lime dosage and final pH. In walnut-
shell experiments, the factors influential in the equations are
Environmental Management (2021) 68:226–239
walnut-shell dosage and influent pH value entering the bio-
sorption process.
Preparing Walnut-Shell
Walnut-shell samples were obtained from the fruits of
Chandler walnut trees cultivated in Urmia, Iran. A 0.2 M
NaOH solution (Merck group) was used to remove the
impurities. Subsequently, shells were washed out with dis-
tilled water to neutralize the pH value and placed in an oven
at 105 °C for 24 h for drying (Mahdavi et al. 2018).
For better performance, the hard shell of the walnut
should be crushed into smaller pieces (by a ball mill). Then,
the parts were powdered using a crusher machine. The
particle size in this study varied between 100 and 200 sieve
mesh (ranges from 0.075 to 0.15 mm). These particles were
then kept in a suitable container until the experiment.
Experiments
Lime experiments
For lime set experiments, some 400 mL leachate samples
were prepared. Then, their pH was adjusted according to the
design (Table 1). In the next step, for each experiment, some
lime was dissolved in distilled water based on the desired
concentration (the purity percentage of hydrated lime used
was 90–92% and was supplied by Azarshahr Lime Factory,
Iran). The reason for obtaining the lime from local factories
is to the practical feasibility study of its application in lea-
chate treatment as well as to facilitate the economic calcu-
lations of the process. The prepared lime solution was then
added to the leachate, and stirring was begun according to
the determined experimental conditions (the final reactor
volume varies from about 420 to 466 mL depending on the
concentration of the lime solution and the amount of sulfuric
acid consumed). The leachate was first stirred at 300 rpm for
5 min and then at 30 rpm for 30 min. The pH of the solution
was measured (and recorded as the final pH) immediately
after stirring was completed. Then, the leachate was trans-
ferred to a graduated cylinder to settle for 30 min. During
settling, the sludge to leachate volume ratio was recorded at
5-min intervals defining a new parameter called OSVLDR.
This parameter refers to the amount of sludge produced
(mL) to the amount of lime used (g) per liter of leachate. It
may be useful for achieving the optimal conditions of lime
experiments in terms of reduction in the amount of sludge
formed and, consequently, the operating costs. Then, sam-
ples were collected from the supernatant to measure the
COD and the heavy metal concentrations. To measure COD
and heavy metals, the methods, 5220 D. Closed Reflux,
Colorimetric, and 3111 B. Direct air-acetylene flame method
were used, respectively (Rice et al. 2017).
Environmental Management (2021) 68:226–239
Walnut-Shell experiments
Following the measurement of the COD output from lime
experiments, the results of all eleven lime coagulation-
flocculation experiments were compared, and the best
experimental conditions were determined to achieve the
maximum COD removal percentage. Then, the output of the
optimal conditions of lime experiments is used in walnut-
shell experiments. As in lime experiments, the pH of the
leachate was adjusted (influent pH). The walnut-shells were
then added to the leachate (weighed using a scale with a
precision of 0.001 g). The resulting solution was stirred at
150 rpm for 30 min. As the adsorption process was com-
pleted, the clear liquid was separated from the walnut-shell
using filter paper. It was used to measure the COD and
heavy metal concentrations (similar to the procedure in
“Lime experiments”). To better evaluate the adsorption
capacity of walnut-shell, the qe (i.e., COD removed during
Fig. 1 An overview of lime and walnut-shell experiments
231
the bio-sorption process (mg) per g of adsorbent used) was
calculated using (Eq. (3)).
 
C0  Cf V
qe ¼ ð3Þ
W
Where C0 is the influent COD (mg/L), Cf is the COD at the
end of the experiment (mg/L), V is the leachate volume (L),
and W is the walnut-shell used (g). A schematic of all
experiments and analyzes performed in this study is
presented in Fig. 1.
Results and Discussion
Table 2 summarizes the lime and walnut-shell experiments’
outputs. Through lime addition, cations interact with surface
negative-charged colloids, neutralizing them and promoting
colloid destabilization. However, after reaching the
232 Environmental Management (2021) 68:226–239

Table 2 Summary of experiments results

Lime set test Walnut-shell set tests
Observation number Final a
OSVLDR (mL/g) COD removal Observation number qe (mg/g) COD removal
pH Value efficiency (%) efficiency (%)

1 10.73 75.00 22.16 12 160.00 15.46

2 4.90 0.00 24.59 13 198.00 19.08
3 9.06 37.50 11.89 14 86.67 4.93
4 4.29 0.00 10.41 15 116.67 6.75
5 10.48 50.51 29.86 16 155.15 16.12
6 6.82 0.00 6.49 17 34.80 1.81
7 9.78 41.25 15.95 18 82.50 6.41
8 4.27 0.00 16.49 19 150.00 11.51
9 7.43 10.00 16.76 20 140.00 10.86
10 7.61 26.25 17.57 21 125.00 9.54
11 7.59 23.13 17.84 22 110.00 8.55
Note that the initial COD value at lime set tests and walnut-shell set tests were 37,000 and 25,950 mg/L, respectively. The COD removal efficiency
numbers (%) are rounded to two decimal places
a
Observed sludge volume (mL) to used lime dosage (g) ratio (per 1-L of leachate)

optimum lime dosage, the re-stabilization of colloidal par-
ticulates would occur (Chaouki et al. 2017) resulting in a
noticeable increase in the volume of generated sludge. As it
is evident from Table 2, the best result of lime experiments
occurred in observation No. 5 (according to Table 1, in this
observation, the lime dosage was 6.83 g/L, and the initial
pH of leachate was 6).
The increase in the adsorption percentage with an
increase in adsorbent dosage is due to the availability of
larger surface areas and more adsorption sites (Almasi et al.
2012). However, in walnut-shell experiments, observation
No.13 resulted in the maximum COD removal (i.e., walnut-
shell dosage of 25 g/L and influent pH of 4).
It should be noted that the input fluid to bio-sorption
experiments is the same as the effluent from observation No.
5 (with the highest COD removal efficiency). In other words,
following the coagulation-flocculation experiments and
determining the best removal rate of COD, the coagulation-
flocculation process was repeated in conditions similar to
observation No. 5 with a larger volume of leachate. The
resulted supernatant is then extracted to following up the
bio-sorption experiments. To check the efficiency of the
sequence for the removal of heavy metals, the outputs of
observations No. 5 and No. 13 (the best conditions in lime
and walnut-shell experiments) were considered (Table S1-4).
Table S1-4 shows the usefulness of the proposed
sequence in heavy metals removal as reducing the initial
concentrations to acceptable levels according to the US EPA
standard. For example, according to the US EPA standard,
the maximum daily and monthly average concentrations of
zinc in treated effluent should not exceed 0.2 mg/L and
0.11 mg/L, respectively (U.S. EPA 2000). In this study, the
treated leachate met these requirements. The sequence also
reduced the concentration of zinc to 0.02 mg/L. The cad-
mium removal rate is lower than other studied heavy metals
because of its strong structure and the presence of hydroxide
complex (Keenan et al. 1983; Çeçen and Gürsoy 2000).
In general, the experimental study shows that a combi-
nation of coagulation-flocculation and bio-sorption process
may provide a high-efficiency sequence in Nazlou landfill
leachate treatment. However, more efficiency can be
achieved by analyzing the independent variables of the
process. In addition to the COD and heavy metals removal
efficiency, there are limiting parameters such as sludge
volume and treatment cost. In the continuation of the pre-
sent study, equations are presented that can achieve high
efficiency with the lowest consumption of raw materials.
Curve Fitting
According to Table 2, the question arises as to whether it was
possible to achieve the same amount of COD removal by
selecting the independent values other than what was con-
sidered in observation No. 5? Also, in the latter case, in what
conditions could we incur the lowest cost while maintaining
the highest COD removal efficiency, mostly when the
influent pH to the bio-sorption experiments was a value other
than 4 (relating to the optimal state of these series of tests)? A
proper curve fitting to the results of the experiments is
required to answer the above questions. For this purpose, the
RSM methodology has been used. Using polynomial
regression between the independent variables of dosage and
pH and dependent variables, equations of COD removal
efficiency, final pH, and sludge volume for lime experiments
Environmental Management (2021) 68:226–239
as well as the COD removal efficiency for walnut-shell
experiments were obtained (Eqs. (4)–(7)). The characteristics
of the regression process (sum of squares, mean squares, P-
values, lack of fit, pure error, R2, Adj. R2, PRESS, and pre-
dicted R2) are also presented in Tables S1-5–S1-8.
COD Removal Efficiency ð%Þ ¼ ð8:047Þ þ ð5:064  L1 Þ þ ð2:942  L2 Þ
 
 ð0:245  L1  L2 Þ  0:172  L22
ð4Þ
pH Final Value ¼ ð3:263Þ  ð0:344  L1 Þ þ ð2:371  L2 Þ
    ð5Þ
þ 0:101  L21  0:102  L22
OSVLDRðmL=gÞ ¼ ð6:493Þ þ ð10:820  L1 Þ  ð12:530  L3 Þ
    ð6Þ
 1:294  L21 þ 1:520  L23
Where L1 is the lime dosage (g/L), L2 and L3 are the initial
and the final pH of the leachate in the lime experiments,
respectively.
 
COD Removal Efficiencyð%Þ ¼ ð8:939Þ þ ð1:029  W1 Þ þ 0:011  W12
 
 ð0:063  W1  W2 Þ þ 0:039  W22
ð7Þ
Where W1 is the walnut-shell dosage (g/L), and W2 is the
influent pH to the walnut-shell experiments.
The diagram of changes in COD removal efficiency, final
pH, and OSVLDR in lime experiments, as well as the changes
in COD removal percentage in walnut-shell experiments
obtained from (Eqs. (4)–(7)), are shown in Fig. 2.
Conferring to Figs. 2a, b, various lime dosage, and pH
values can be used for a specific rate of COD removal in
lime and walnut-shell experiments. Accordingly, the lower
lime dosage application requires an initial pH of leachate
adjusted in a basic range to achieve higher COD removal
efficiencies. On the other hand, in the case of using a higher
lime dosage, the appropriate initial pH range of leachate is
acidic. Also, the best performance of the bio-sorption pro-
cess is observed in the acidic range of the input fluid
(minimum application of walnut-shell). According to
Fig. 2c, the pH of the leachate will increase, following the
treatment by lime, proportionally to the lime dosage used,
and the initial leachate pH. Compared to previous studies
(Tables S1-1), the rate of pH increase is different in various
leachate (or other wastewater) samples, which can be due to
the type and composition of leachate in addition to the lime
dosage, purity, and alkalinity of lime. In the present study,
the increased final pH value is considerable due to the
alkalinity of the leachate and the coagulant used, especially
at high leachate initial pH values. For example, in experi-
mental conditions of the lime dosage of 4 g/L and an initial
pH of 3.50, the final pH is 4.03 (|ΔpH| = 0.53, and COD
removal efficiency is 16.97% in a series of lime experi-
ments). While, at the same dosage and initial pH of 7.90
233
(which will result in a similar efficiency of COD removal by
lime), the final pH will be about 9.34 (|ΔpH| = 1.44). By
comparing Fig. 2a, c, it can be cleared that by applying
lower lime dosage as a coagulant to achieve a specific COD
removal, the final pH of the lime treatment effluent will
increase significantly. While to increase the efficiency of the
subsequent bio-sorption process (according to Fig. 2b), it is
necessary to reduce this amount by using acidic substances
(to achieve the appropriate COD removal efficiency with
minimal application of walnut-shell).
Figure 2d shows the amount of OSVLDR based on lime
dosage and final pH in lime experiments. Here, the final pH is
used instead of the initial leachate pH for two reasons. First,
the sludge is formed following the stirring (the pH value is not
the same as at the beginning of the experiment). The other is
because the regression between OSVLDR and both pH (initial
and final) determined that by using the initial pH, the value of
R2 is equal to 0.903, and using the final pH resulted in an R2
value of 0.952. Therefore, there is a more significant correla-
tion between the final pH and the amount of OSVLDR.
According to this diagram, the amount of OSVLDR will
increase with the amount of lime dosage and the final pH in
the lime experiments (simultaneously), so that at the final pH
less than 6, the amount of sludge produced is minimal for all
lime dosage. However, OSVLDR can be increased up to
69 mL/g with pH as well as lime dosage.
Analysis of Coagulation-flocculation Experiments
Results
In “Analysis of coagulation-flocculation experiments results”
and “Analyzing of bio-sorption experiments results”, the
changes in the experimental variables (lime dosage and pH) to
achieve the highest efficiency of leachate COD removal are
analyzed and addressed using the theory of calculus of var-
iations and the equations obtained (Eqs. (4)–(7)). The main
purpose of the analysis of experimental results is to provide the
conditions to increase the efficiency so that at a specific lime
dosage and pH, it can achieve more COD removal by chan-
ging the variables (increase or decrease). Therefore, by cal-
culating the gradient, a trend can be found between lime
dosage and pH in which the rate of change of COD removal
efficiency is the highest. Calculation of the gradient of Eq. (4)
for constant COD removal percentage of 30% relative to both
lime dosage and initial pH of leachate, it is suggested that up
to the leachate initial pH values of 3.5, the initial pH should be
increased to enhance the efficiency. However, at the higher
values, a more COD removal rate will be possible by reducing
the pH value. Besides, in both changing patterns in the pH
values (increase or decrease), the amount of lime used should
be increased to improve the COD removal efficiency (see
Supplementary material file #2). For more analysis, the sen-
sitivity analysis of COD removal percentage to changes in
234
Fig. 2 a COD removal efficiencies (%) relative to initial pH value of
leachate and lime dosage (g/L) in lime set experiments. b COD
removal efficiencies (%) relative to influent pH value and walnut-shell
dosage (g/L) in bio-sorption set experiments. c pH final value relative
lime dosage and pH value was performed using Eq. (3), and
the results are reflected in Fig. 3.
According to Fig. 3a, a reduction in the pH value to 3.50
while the lime dosage is constant increases the COD
removal percentage. However, further declines in pH values
cause a decrease in removal efficiency. At the adjusted
values of the initial leachate pH to ~2, the solution will
become acidic, and the performance of the lime will be
affected. In other words, the leachate is in a stabilized state
under these conditions, and its colloidal particles retain their
form. Therefore, according to Fig. 3a, it can be stated that
the optimal pH (before the beginning of the experiment) is
3.5, and an increase or decrease in the pH value will reduce
the COD removal efficiency.
As mentioned, the optimum pH in the lime experiments
was about 3.50. Therefore, using this initial pH value and
(Eq. (4)), the effects of changing the lime dosage on COD
Environmental Management (2021) 68:226–239
to initial pH value and lime dosage (g/L) in lime set experiments.
d OSVLDR (mL/g) relative to final pH value and lime dosage (g/L) in
lime set experiments
removal were addressed in Fig. 3b. It shows that the COD
removal percentage increases linearly with the amount of
lime. Therefore, there are no optimal conditions for the lime
dosage, and an increase in the lime dosage will increase the
COD removal rate. However, there are two reasons for a
limited increase in the lime dosage: according to Table S1-
4, lime is not efficient enough to remove heavy metals,
especially Cd, Pb, and Zn, therefore, applying com-
plementary methods is essential to increase the removal
efficiency of lime and achieve low concentrations of these
metals; on the other hand, an increase in the lime dosage
resulted in more sludge produced, the consequences of
which will practically complicate the scenario of increasing
the lime dosage. To better analyze using the optimal pH of
3.50 to achieve a higher COD removal efficiency, the lime
dosage was increased. Then, the graph of the COD removal
rate against OSVLDR was drawn in Figs. S1-1. For this
Environmental Management (2021) 68:226–239 235

Fig. 3 Sensitivity analysis of COD removal efficiencies (%) relative to (a) initial pH value at lime dosage = 6.83 g/L; and (b) lime dosage (g/L) at
initial pH value = 3.5

purpose, the final pH value was calculated using Eq. (5),

and the OSVLDR was measured using Eq. (6).
According to Figs. S1-1, achieving higher COD removal
percentages using lime causes a sharp increase in OSVLDR,
making it difficult to control and consequently may disrupt
the overall treatment process.
One of the evident efficiencies of lime other than COD
and heavy metals removal is in leachate color removal
(Renou et al. 2009). The leachate color changes slowly
during lime treatment. However, the color varies from dark
brown to light brown and then light yellow after settling and
separation of the resulting sediment. The changes in the
leachate color after the lime treatment compared to the raw
sample are shown in Figs. S1-2.
Fig. 4 Changing trends of lime dosage and pH value to increase the
Gradient measures in results analysis COD removal efficiency

In this section, Eq. (4) is analyzed, and the change trends of

the lime dosage and pH to achieve the maximum COD
removal efficiency are evaluated using the gradient calcu-
lation. In the mentioned equations in Supplementary
material file #2, a certain COD removal percentage can be
obtained for different values of lime dosage and pH value.
For example, in the lime experiments, a removal rate of
30% could be achieved using a lime dosage of 7.11 g/L and
an initial leachate pH of 3.00. Whereas, a lime dosage of
8.92 g/L and an initial pH of 9.00 could lead to the same
COD removal efficiency. Based on the results of the
experiments, in the first conditions, the lime dosage and pH
should be increased to achieve a COD removal efficiency
by more than 30%. However, in the latter, this efficiency
increase could be obtained by increasing the lime dosage
and decreasing the pH value.
Given the calculations in Supplementary material file #2,
it can be found that the ratio of increase in the pH value to
  
 ΔpH 
increase in the lime dosage of 0.04 Δdosage  ¼ 0:04
should be considered to enhance the COD removal effi-
ciency in the first conditions (i.e., the lime dosage of 7.11 g/
L and initial leachate pH of 3.00). However, in the latter, the
COD removal efficiency will increase by increasing
the lime dosage and decreasing the pH value by 0.82 times
  
 ΔpH 
the lime dosage Δdosage  ¼ 0:82 . The mentioned process
is the optimal condition for changing the values of the
variables to increase the efficiency so that with the least
changes in the lime dosage and initial pH, the rate of COD
removal could be improved. Figure 4 shows the changes in
lime dosage and pH values on the COD removal efficiency
diagram. A similar analysis could be a subject of discussion
in walnut-shell experiments.
Analyzing of Bio-sorption Experiments Results
The results of analyzing the gradient in Eq. (7) for the
constant COD removal percentage equal to 20%, relative to
236
Fig. 5 Sensitivity analysis of COD removal efficiency (%) relative to (a) influent pH value at walnut-shell dosage = 25 g/L; and (b) walnut-shell
dosage (g/L) at influent pH value = 3.5
the influent pH and walnut-shell dosage, showed that the
conditions of decreasing the influent pH and increasing the
walnut-shell dosage should always be followed to increase
the COD removal efficiency (refer to Supplementary
material file #2).
The optimal conditions of the walnut-shell experiment
were used to evaluate the contribution of experimental
variables in COD removal. Accordingly, walnut-shell
dosage was considered 25 g/L. Then, the pH value was
changed. The sensitivity analysis diagram of COD removal
percentage to pH is shown in Fig. 5a.
According to Fig. 5a, the rate of COD removal increases as
the influent pH decreases. As reported in the literature, the
charges on the absorbent surface tend to be neutralized at pH
4, enhancing the adsorption of humic acid. On the contrary, at
a pH higher than 7 the absorbent tends to present a negative
charge, repulsing ionized humic acid molecules (Mahdavi
et al. 2018; Ferraz and Yuan 2020). According to Fig. 5a, the
COD removal trend is ascending at low pH values. However,
because of the alkalinity of the leachate, a reduction in pH
required more acidic substance application. Therefore, the
optimal pH value of 3.50 was selected to achieve a higher
percentage of COD removal.
The effect of walnut-shell dosage on COD removal was
investigated as follows. First, the influent pH value was set to
3.50. Then, the effect of changes in walnut-shell dosage on the
rate of COD removal was calculated using Eq. (7). The results
of the sensitivity analysis of COD removal percentage to
walnut-shell dosage are presented in Fig. 5b, indicating a quite
ascending trend. Accordingly, the walnut-shell dosage must be
significantly increased to achieve a higher COD removal.
Although walnut-shell has a high capacity to remove heavy
metals (Table S1-4), a much higher amount of crushed walnut-
shell is required to remove a higher percentage of COD. For
instance, the qe is calculated 191.48 mg/g and 304.80 mg/g at
walnut-shell dosages of 25 g/L and 50 g/L, respectively.
Environmental Management (2021) 68:226–239
It should be noted that the size of the crushed walnut-shell
affects the results of the experiments. In some studies, the
activated carbon obtained from walnut-shell under pressure
and heat has been used to achieve more efficiency (Mahdavi
et al. 2018; Yang and Oiu 2010). In a study on leachate
COD removal using activated carbon synthesized from
walnut-shell, the maximum adsorption capacity (qe) of
123.2 mg/g in COD removal was obtained under experi-
mental conditions of pH: 4.00, walnut-shell dosage: 15 g/L
and walnut-shell size: 0.2–0.3 mm (Mahdavi et al. 2018). In
the present study with a similar experimental condition but
with a non-activated walnut-shell crushed to the size of
0.075–0.15 mm, the adsorption capacity was obtained
116.67 mg/g, which will increase to 198 mg/g by increasing
the walnut-shell dosage to 25 g/L. The reduction in the size
of the crushed walnut-shell (increase in its specific surface
area) in addition to the differences in the conditions and type
of leachate compounds leads to the negligible difference
between the efficiency of the activated and non-activated
walnut-shell surfaces. Therefore, in situations where it is
possible to crush walnut-shell into smaller sizes, this pro-
cedure is suggested as a proper solution rather than acti-
vating Walnut surfaces due to simpler operating conditions.
Optimization of the Experiment Variables From an
Economic Point of View
According to the diagrams in Fig. 2, different doses and pH
values can be used to achieve various COD removal effi-
ciencies. Therefore, in terms of pH, the optimal conditions
from the economic point of view are to maintain the lea-
chate initial pH value. In terms of dosage, the optimal
conditions are defined as using less lime or walnut-shell. It
should be noted here that all bio-sorption experiments were
performed only in the same input COD value (according to
Table 2, which is equal to 25,950 mg/L). Since the
Environmental Management (2021) 68:226–239
efficiency of COD removal in the bio-sorption process is
affected by its initial value, it was assumed in economic
calculations that the selected conditions for the lime
experiments should lead to an output COD of 25,950 mg/L.
Thus, by making selective changes in the lime dosage and
the initial leachate pH (to achieve the mentioned output
COD) as well as the pH input to the bio-sorption process
and the walnut-shell dosage, the best conditions can be
determined from an economic point of view.
According to the results, the best conditions for COD
removal in the lime and walnut-shell experiments were
about 30 and 20%, respectively. Consequently, two differ-
ent scenarios were defined to optimize the experimental
conditions and compare the outputs. In the first scenario,
using the optimization of (Eq. (4)), the lowest lime dosage
effective in 30% COD removal was calculated as 7.10 (by
adjusting the initial leachate pH to 3.50). Then, considering
the final conditions of the lime experiment, the initial con-
ditions for the walnut-shell experiment in terms of the pH of
the solution were defined. Here we calculate the walnut-
shell dosage using (Eq. (7)) to achieve the COD removal
efficiency of 20%. In the second scenario, the pH of raw
leachate (8.26) was used to achieve a COD removal of 30%
in lime experiments. Then, the walnut-shell experiment
conditions were determined similarly to the first scenario to
achieve a 20% efficiency. The results of the first and second
scenarios are presented in Table 3.
According to Table 3, achieving the desired efficiency by
reducing the initial pH (first scenario) is more affordable
because the amount of lime and walnut-shell consumed in
this scenario is less than in the second scenario. Further-
more, another advantage of reducing the pH in the first
scenario is the reduction of sediments during the lime
experiments compared to the second one, with the OSVLDR
as 0.36 and 116.26 mL/g, respectively. In contrast, in the
first scenario, an average of 1.88 mL of 97% sulfuric acid
was used per 1 L of leachate to reduce the pH by 1 unit.
Using H2S increases the cost in the second scenario by
16.22%. Economic analysis showed that the treatment of
1 m3 leachate would cost 2.34 and 2.58 USD (based on raw
materials cost including lime, walnut-shell, and sulfuric
Table 3 Analysis of initial conditions for both test sets
Lime set tests
a
Initial pH |ΔpH| Lime Final
dosage (g/L) pH value
Sc.1b 3.50 4.76 7.10 6.43
Sc.2c 8.26 0.00 8.38 13.57
a
|ΔpH| = the absolute value of initial leachate pH minus the value of adjusted pH in the scenario
b
With respect to lime optimal dosage
c
With respect to initial leachate pH
237
acid) for investigated scenarios, respectively (price inquiry
based on the domestic market of Iran—May 2021).
Conclusions
One of the essential measures to treat the landfill’s leachate is to
choose a suitable process to remove organic compounds and
heavy metals. Selecting an inexpensive with high-efficiency
treatment process is of particular importance. Therefore, in the
present study, the efficiency of two complementary approaches,
coagulation-flocculation, and bio-sorption, were evaluated as
inexpensive and natural techniques for leachate treatment. The
results show the ability of this sequence to remove 43.24,
98.17, 67.45, 91.03, and 88.02% for COD, nickel, cadmium,
zinc, and lead, respectively. According to the outputs, in lime
experiments, increasing the lime dose to achieve greater effi-
ciency will be problematic due to the limitations caused by the
sludge. Therefore, applying a complementary method to
complete the treatment is required. On the other hand, the use
of the bio-sorption process using walnut-shell can be significant
due to its high competency, especially in the adsorption of
heavy metals. Based on the results, more crushing of walnut-
shell instead of activating its surface can be a more appropriate
solution due to more simple operating conditions.
Accurate evaluation of process efficiency requires sen-
sitivity analysis of the outputs to the test variables. The
equations for COD removal efficiency, dosage, and pH
were obtained using the RSM methodology. Using the
gradient of proposed equations, the way to achieve higher
efficiency with the least change of the mentioned variables
was expressed. The results showed that under optimal
conditions, operating costs would be reduced by 54,324
IRR per treatment of 1 m3 of leachate while achieving
affordable COD removal efficiency. Also, the amount of
sludge formed as one of the limiting parameters of lime tests
will be significantly reduced. Finally, it can be said that the
use of RSM is not limited to designing experiments as well
as presenting the governing relationships. Still, relationship
analysis can play an essential role in reducing operating
costs and increasing efficiency.
Walnut-shell set tests
COD removal Influent Walnut-shell COD removal
efficiency (%) pH value dosage (g/L) efficiency (%)
30.00 6.43 29.17 20.00
30.00 13.57 37.61 20.00
238
Availability of Data and Materials
The datasets used and/or analyzed during the current study
including codes prepared on MATLAB environment and
Microsoft Excel are available from the corresponding
author on reasonable request. Moreover, other data gener-
ated or analyzed during this study are included in this
published article [and its supplementary information files].
Author Contributions All authors contributed to the study’s concep-
tion and design. Material preparation, data collection and analysis were
performed by Milad Ghaffariraad and Mehdi Ghanbarzadeh Lak. The
first draft of the manuscript was written by Milad Ghaffariraad and
Mehdi Ghanbarzadeh Lak commented on previous versions of the
manuscript. All authors read and approved the final manuscript.
Compliance with Ethical Standards
Conflict of Interest The authors declare no competing interests.
Publisher’s note Springer Nature remains neutral with regard to
jurisdictional claims in published maps and institutional affiliations.
References
Abdul Kadir A, Al Bakri Abdullah MM, Sandu AV, Mohamed Noor
N, Latif A, Lisanah A, Hussin K (2014) Usage of palm shell
activated carbon to treat landfill leachate. Int J Convers Sci 5
(1):117–126
Agwu MO (2012) Issues and challenges of solid waste management
practices in Port-Harcourt City, Nigeria-A behavioural perspec-
tive. Am J Soc Manag Sci 3(2):83–92. https://doi.org/10.5251/a
jsms.2012.3.2.83.92
Almasi A, Omidi M, Khodadadian M, Khamutian R, Gholivand MB
(2012) Lead (II) and cadmium (II) removal from aqueous solution
using processed Walnut shell: kinetic and equilibrium study.
Toxicological Environ Chem 94(4):660–671. https://doi.org/10.
1080/02772248.2012.671328
Al Raisi SAH, Sulaiman H, Suliman FE, Abdallah O (2014) Assess-
ment of heavy metals in leachate of an unlined landfill in the
Sultanate of Oman. Int J Environ Sci Dev 5(1):60. https://doi.org/
10.7763/IJESD.2014.V5.451
Altun T, Pehlivan E (2012) Removal of Cr (VI) from aqueous solu-
tions by modified Walnut-Shells. Food Chem 132(2):693–700.
https://doi.org/10.1016/j.foodchem.2011.10.099
Amor C, De Torres-Socías E, Peres JA, Maldonado MI, Oller I,
Malato S, Lucas MS (2015) Mature landfill leachate treatment by
coagulation/flocculation combined with Fenton and solar photo-
Fenton processes. J Hazard Mater 286:261–268. https://doi.org/
10.1016/j.jhazmat.2014.12.036
Augusto PA, Castelo-Grande T, Merchan L, Estevez AM, Quintero X,
Barbosa D (2019) Landfill leachate treatment by sorption in
magnetic particles: preliminary study. Sci Total Environ
648:636–668. https://doi.org/10.1016/j.scitotenv.2018.08.056
Baun DL, Christensen TH (2004) Speciation of heavy metals in
landfill leachate: a review. Waste Manag Res 22(1):3–23. https://
doi.org/10.1177/0734242X04042146
Bazrafshan E, Ahmadi S (2017) Removal COD of landfill leachate
using coagulation and activated tea waste (ZnCl2) adsorption. Int
J Innovative Sci, Eng Technol 4(4):339–47
Environmental Management (2021) 68:226–239
Bozecka A, Bozecki P, Sanak-Rydlewska S (2016) Removal of Pb (II)
and Cd (II) ions from aqueous solutions with selected organic
wastes. Physicochemical Probl Miner Process 52(1):380–396.
https://doi.org/10.5277/ppmp160132
Çeçen F, Gürsoy G (2000) Characterization of landfill leachates and
studies on heavy metal removal. J Environ Monit 2(5):436–442.
https://doi.org/10.1039/B004729P
Chaouki Z, El Mrabet I, Khalil F, Ijjaali M, Rafqah S, Anouar S,
Nawdali M, Valdés H, Zaitan H (2017) Use of coagulation-
flocculation process for the treatment of the landfill leachates of
Casablanca city (Morocco). J Mater Environ Sci 8(8):2781–2791
Cheng SY, Show PL, Juan JC, Chang JS, Lau BF, Lai SH, Ng EP,
Yian HC, Ling TC (2021) Landfill leachate wastewater treatment
to facilitate resource recovery by a coagulation-flocculation pro-
cess via hydrogen bond. Chemosphere 262:127829. https://doi.
org/10.1016/j.chemosphere.2020.127829
de Almeida R, Bila DM, Quintaes BR, Campos JC (2020a) Cost
estimation of landfill leachate treatment by reverse osmosis in a
Brazilian landfill. Waste Manag Res 38(10):1087–1092. https://
doi.org/10.1177/0734242X20928411
de Almeida R, Campos J, de Almeida Oroski F (2020b) Techno-
economic evolution of landfill leachate treatment by hybrid Lime
application and Nano filtration process. Detritus 1(9):1–12.
https://doi.org/10.31025/2611-4135/2020.13897
de Almeida R, de Souza Couto JM, Gouvea RM, de Almeida Oroski
F, Bila DM, Quintaes BR, Campos JC (2020c) Nanofiltration
applied to the landfill leachate treatment and preliminary cost
estimation. Waste Manag Res 38(10):1119–1128. https://doi.org/
10.1177/0734242X20933333
de Almeida R, Moraes Costa A, de Almeida Oroski F, Carbonelli
Campos J (2019) Evaluation of coagulation–flocculation and
nanofiltration processes in landfill leachate treatment. J Environ
Sci Health, Part A 54(11):1091–1098. https://doi.org/10.1080/
10934529.2019.1631093
Edokpayi, J. N., Durowoju, O. S., Odiyo, J. O., 2018. Assessment of
heavy metals in landfill leachate: a case study of Thohoyandou
landfill, Limpopo Province, South Africa. Heavy Met.
El-Gohary FA, Kamel G (2016) Characterization and biological
treatment of pre-treated landfill leachate. Ecol Eng 94:268–274.
https://doi.org/10.1016/j.ecoleng.2016.05.074
Ferraz FM, Yuan Q (2020) Performance of oat hulls activated carbon
for COD and color removal from landfill leachate. J Water Pro-
cess Eng 33:101040. https://doi.org/10.1016/j.jwpe.2019.101040
Gautam P, Kumar S, Lokhandwala S (2019) Advanced oxidation
processes for treatment of leachate from hazardous waste landfill:
a critical review. J Clean Prod 237:117639. https://doi.org/10.
1016/j.jclepro.2019.117639
Ghanbarzadeh Lak M, Sabour MR, Amiri A, Rabbani O (2012)
Application of quadratic regression model for Fenton treatment of
municipal landfill leachate. Waste Manag 32(10):1895–1902.
https://doi.org/10.1016/j.wasman.2012.05.020
Ghanbarzadeh Lak M, Sabour MR, Ghafari E, Amiri A (2018) Energy
consumption and relative efficiency improvement of Photo-
Fenton–Optimization by RSM for landfill leachate treatment, a
case study. Waste Manag 79:58–70. https://doi.org/10.1016/j.wa
sman.2018.07.029
Halim AA, Aziz HA, Johari MAM, Ariffin KS (2010) Comparison
study of ammonia and COD adsorption on zeolite, activated carbon
and composite materials in landfill leachate treatment. Desalination
262(1-3):31–35. https://doi.org/10.1016/j.desal.2010.05.036
Jain CK, Malik DS, Yadav AK (2016) Applicability of plant based
biosorbents in the removal of heavy metals: a review. Environ
Process 3(2):495–523. https://doi.org/10.1007/s40710-016-0143-5
Kargi F, Pamukoglu MY (2003) Powdered activated carbon added
biological treatment of pre-treated landfill leachate in a fed-batch
Environmental Management (2021) 68:226–239
reactor. Biotechnol Lett 25(9):695–699. https://doi.org/10.1023/
A:1023456116291
Karimi-Jashni A, Saadat S (2014) Investigation of factors affecting
removal of nickel by pre-treated Walnut-Shells using factorial
design and univariate studies. Iranian Journal of Science and
Technology. Trans Civ Eng 38(C1+):309–324. https://doi.org/
10.22099/IJSTC.2014.1872
Keenan JD, Steiner RL, Fungaroli AA (1983) Chemical-physical
leachate treatment. J Environ Eng 109(6):1371–1384. 10.1061/
(ASCE)0733-9372(1983)1096(137)
Kılıç MY, Kestioglu K, Yonar T (2007) Landfill leachate treatment by
the combination of physicochemical methods with adsorption
process. J Biol Environ Sci 1(1):37–43
Li S, Qiu M, Zeng Z, Xue W (2019) Effective Modified Walnut-Shell
Adsorbent: Synthesis and Adsorption Behavior for Pb2+ and Ni2+
from Aqueous Solution. Environ Eng Sci 36(11):1421–1432.
https://doi.org/10.1089/ees.2019.0227
Mahdavi AR, Ghoresyhi AA, Rahimpour A, Younesi H, Pirzadeh K
(2018) COD removal from landfill leachate using a high-
performance and low-cost activated carbon synthesized from
Walnut-Shell. Chem Eng Commun 205(9):1193–1206. https://
doi.org/10.1080/00986445.2018.1441831
Moody CM, Townsend TG (2017) A comparison of landfill leachates
based on waste composition. Waste Manag 63:267–274. https://
doi.org/10.1016/j.wasman.2016.09.020
Moradi M, Ghanbari F (2014) Application of response surface method
for coagulation process in leachate treatment as pretreatment for
Fenton process: biodegradability improvement. J Water Process
Eng 4:67–73. https://doi.org/10.1016/j.jwpe.2014.09.002
Pan, Y., Zhu, Y., Xu, Z., Lu, R., Zhang, Z., Liang, M., Liu, H.,
2011. Adsorption removal of COD from wastewater by the
activated carbons prepared from sugarcane bagasse. In 5th
International Conference on Bioinformatics and Biomedical
Engineering, iCBBE.
Qasim, S.R., Chiang, W., 1994. Sanitary landfill leachate: generation,
control and treatment. CRC Press.
Renou S, Givaudan JG, Poulain S, Dirassouyan F, Moulin P (2008)
Landfill leachate treatment: Review and opportunity. J Hazard Mater
150(3):468–493. https://doi.org/10.1016/j.jhazmat.2007.09.077
Renou S, Poulain S, Givaudan JG, Moulin P (2008) Treatment process
adapted to stabilized leachates: Lime precipitation–prefiltration–
reverse osmosis. J Membr Sci 313(1-2):9–22. https://doi.org/10.
1016/j.memsci.2007.11.023
Renou S, Poulain S, Givaudan JG, Sahut C, Moulin P (2009) Lime
treatment of stabilized leachates. Water Sci Technol 59
(4):673–685. https://doi.org/10.2166/wst.2009.014
Rice EW, Baird RB, Eaton AD, Clesceri LS (2017) Standard methods
for the examination of water and wastewater, 23rd ed. American
Public Health Association, American Water Works Association,
Water Environment Federation, Washington, DC, USA
Robinson T (2017) Removal of toxic metals during biological treat-
ment of landfill leachates. Waste Manag 63:299–309. https://doi.
org/10.1016/j.wasman.2016.12.032
Roudi AM, Kamyab H, Chelliapan S, Ashokkumar V, Kumar A,
Yadav KK, Gupta N (2020) Application of response surface
method for Total organic carbon reduction in leachate treatment
using Fenton process. Environ Technol Innov 19:101009. https://
doi.org/10.1016/j.eti.2020.101009
Sabour MR, Ghanbarzadeh Lak M, Rabbani O (2011) Evaluation of
the main parameters affecting the Fenton oxidation process in
239
municipal landfill leachate treatment. Waste Manag Res 29
(4):397–405. https://doi.org/10.1177/0734242X10375332
Sadegh H, Ali GA, Gupta VK, Makhlouf ASH, Shahryari-
ghoshekandi R, Nadagouda MN, Sillanpää M, Megiel E (2017)
The role of nanomaterials as effective adsorbents and their
applications in wastewater treatment. J Nanostructure Chem 7
(1):1–14. https://doi.org/10.1007/s40097-017-0219-4
Şchiopu AM, Piuleac GC, Cojocaru C, Apostol I, Mămăligă I, Gav-
rilescu M (2012) Reducing environmental risk of landfills: lea-
chate treatment by reverse osmosis. Environ Eng Manag J 11
(12):2319–2331
Sharholy M, Ahmad K, Mahmood G, Trivedi RC (2008) Municipal
solid waste management in Indian cities–A review. Waste Manag
8(2):459–467. https://doi.org/10.1016/j.wasman.2007.02.008
Shehzad A, Bashir MJ, Sethupathi S, Lim JW (2015) An overview of
heavily polluted landfill leachate treatment using food waste as an
alternative and renewable source of activated carbon. Process Saf
Environ Prot 98:309–318. https://doi.org/10.1016/j.psep.2015.09.005
Slater CS, Ahlert RC, Uchrin CG (1983) Treatment of landfill lea-
chates by reverse osmosis. Environ Prog 2(4):251–256. https://
doi.org/10.1002/ep.670020411
Smaoui Y, Bouzid J, Sayadi S (2020) Combination of air stripping and
biological processes for landfill leachate treatment. Environ Eng
Res 25(1):80–87. https://doi.org/10.4491/eer.2018.268
Tatsi AA, Zouboulis AI, Matis KA, Samaras P (2003)
Coagulation–flocculation pretreatment of sanitary landfill lea-
chates. Chemosphere 53(7):737–744. https://doi.org/10.1016/
S0045-6535(03)00513-7
Townsend TG, Miller WL, Earle JFK(1995) Leachate-recycle infil-
tration ponds J Environ Eng 121(6):465–471. https://doi.org/10.
1061/(ASCE)0733-9372(1995)121:6.(465)
U.S. Environmental Protection Agency, 2000. Development
Document for Find Effluent Limitations Guidelines and Stan-
dards for the Landfill Point Source Category. EPA-821-R-99-
019.
Wang W, Hua Y, Li S, Yan W, Zhang WX (2016) Removal of Pb (II)
and Zn (II) using Lime and nanoscale zero-valent iron (nZVI): a
comparative study. Chem Eng J 304:79–88. https://doi.org/10.
1016/j.cej.2016.06.069
Wu Y, Zhou S, Qin F, Ye X, Zheng K (2010) Modeling physical and
oxidative removal properties of Fenton process for treatment of
landfill leachate using response surface methodology (RSM). J
Hazard Mater 180(1-3):456–465. https://doi.org/10.1016/j.jha
zmat.2010.04.052
Xie, Z., Guan, W., Ji, F., Song, Z., Zhao, Y., 2014. Production of
biologically activated carbon from orange peel and landfill
leachate subsequent treatment technology. Journal of Chem-
istry. 2014. https://doi.org/10.1155/2014/491912.
Yang J, Qiu K (2010) Preparation of activated carbons from Walnut-
Shells via vacuum chemical activation and their application for
methylene blue removal. Chem Eng J 165(1):209–217. https://doi.
org/10.1016/j.cej.2010.09.019
Ye ZL, Hong Y, Pan S, Huang Z, Chen S, Wang W (2017) Full-
scale treatment of landfill leachate by using the mechanical
vapor recompression combined with coagulation pretreatment.
Waste Manag 66:88–96. https://doi.org/10.1016/j.wasman.
2017.04.026
Zazouli MA, Maleki A, Izanloo H (2010) Assessment of raw leachate
characteristics and its pretreatment by Lime. Asian J Chem 22
(8):6155–6163