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Environ Dev Sustain

DOI 10.1007/s10668-017-0053-3

Treatment of landfill leachate by integrated sequence


of air stripping, coagulation–flocculation and adsorption

Sushmita De1 • Tumpa Hazra1 • Amit Dutta1

Received: 30 April 2017 / Accepted: 30 October 2017


 Springer Science+Business Media B.V. 2017

Abstract This research work has been performed to institute a proper landfill leachate
treatment program by the integrated sequence of air stripping, coagulation–flocculation
(CF), and adsorption. In this study, air stripping removes up to 96.3% of NH3–N, 49.3% of
COD, and 74.1% of BOD5 within an optimum retention period of 36 h. Optimization of CF
and adsorption were accomplished by employing central composite design of response
surface methodology. The application of CF resulted in the removal of COD by 55.3%,
BOD5 by 83.9%, color by 91.8%, and Hg by 42.2% at the optimized state of pH 5.2 and
FeCl3 dose of 3.1 g/L. In case of adsorption, about 56.1% of COD and 89.2% of Hg
removal were observed at the optimum conditions of pH 7, adsorbent dose of 0.6 g/L of
chitosan beads, and 66.4 min of contact time. Langmuir isotherm model satisfactorily
described adsorption isotherm and fitted with pseudo-second-order kinetic model. Adsor-
bent was characteristically specified by FTIR and SEM with EDAX analysis. Desorption
study showed that 77.2% of adsorbed Hg could be recovered effectively by EDTA. The
overall treatment schedule demonstrates a net removal of 96.3% of NH3–N, 91.8% of
color, 95.8% of BOD5, 90.0% of COD, and 95.8% of Hg.

Keywords Landfill leachate  Air stripping  Coagulation–flocculation  Adsorption 


Response surface methodology  Chitosan beads

Electronic supplementary material The online version of this article (https://doi.org/10.1007/s10668-017-


0053-3) contains supplementary material, which is available to authorized users.

& Sushmita De
shushmitaa2010@gmail.com; sde@research.jdvu.ac.in
1
Department of Civil Engineering, Jadavpur University, Kolkata 700032, India

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S. De et al.

1 Introduction

Landfill leachate is categorized as a complex wastewater containing of toxic organic and


inorganic pollutants. The compositional variations of leachate are primarily due to the
influence of the age of the landfill, nature of disposed waste mass, rainfall pattern, per-
colation, and hydrogeology of the area (Li et al. 2010; Moradi and Ghanbari 2014).
Leachate contaminates surface water and groundwater resources as it seeps and disperses
through the soil (Maiti et al. 2016; De et al. 2017a). Thus landfill leachate treatment is
inevitable to protect the natural ecosystem. Leachate treatment predominantly depends on
the biodegradability factor, i.e., BOD5/COD ratio (Mahmud et al. 2012). Biological pro-
cesses have its wide applications in treating young leachate with a high biodegradability
index, i.e., [ 0.5 (Renou et al. 2008). Moreover, biological methods are not efficient
enough in eliminating heavy metals as compared to organic matter and nutrients (Modin
et al. 2011). Otherwise, physicochemical processes are largely employed to treat stabilized
landfill leachate having biodegradability value of less than 0.1(Li et al. 2010). Thus the
sequential operation of different physicochemical processes can be a viable option to treat
intermediate landfill leachate having medium biodegradability value in between 0.1 and
0.5 in presence of toxic pollutants (NH3–N and heavy metals).
Mahmud et al. (2012) perceived the combination of biological and physicochemical
processes (extended aeration-Fenton) was highly efficient to treat intermediate landfill
leachate. Other combined treatments of physicochemical processes like coagulation-ad-
sorption (Li et al. 2010), coagulation-Fenton (Moradi and Ghanbari 2014), air stripping,
and adsorption (Kalčı́ková et al. 2015) were largely applied to treat stabilized landfill
leachate. Yet, very few studies were conducted with the integrated system of air stripping,
coagulation–flocculation and adsorption to treat intermediate landfill leachate.
Air stripping is the most cost-effective physicochemical method used for NH3–N
removal from landfill leachate (Abood et al. 2014). Ammonia stripping follows a first-order
reaction as the mass transfer rate from the aqueous to gaseous phase is dependent on the
initial values of ammonia. Air stripping also enhances the elimination of organic loads
from landfill leachate (Gotvajn et al. 2009; Mahmud et al. 2012).
Coagulation–flocculation (CF), a basic physicochemical method, has been applied
favorably to remove COD (Amokrane et al. 1997; Liu et al. 2012), color (Aziz et al. 2007;
Liu et al. 2012), turbidity (Amokrane et al. 1997; Liu et al. 2012), and so on, in the
treatment of landfill leachate. Lu et al. (2014) utilized CF for removing heavy metal like
mercury from natural surface water and simulated solutions. However, very few studies
have been done on the application of CF to weed out BOD5 and heavy metal from landfill
leachate. Among the conventional coagulants, iron salts prove superior to aluminum salts
in the CF process (Amokrane et al. 1997; Li et al. 2010).
Adsorption is a common physicochemical process for the post-treatment of landfill
leachate (Foo and Hameed 2009). Adsorption is also largely effective to remove heavy
metals from liquid medium. Activated carbon, though an extremely effective adsorbent for
the abatement of organic and inorganic compounds from both gaseous and aqueous
mixtures, limits its application for high operational costs (Oloibiri et al. 2015). Thus,
inexpensive counterpart of activated carbon should be used to treat landfill leachate.
Deacetylated chitin, i.e., chitosan, is a natural low-cost adsorbent extensively known for
the removal of heavy metals ions (Ngah and Fatinathan 2010) as well as COD (Chung et al.
2005). Chitosan is a biopolymer of D-glucosamine highly efficient in scavenging heavy
metal ions by the reactive amine groups (Kousalya et al.2010). Gamage and shahidi (2007)
used chitosan for the abatement of Hg, Fe, Ni, Pb, Cu, and Zn from industrial wastewater.

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Jeon and Höll (2003); Ngah and Fatinathan (2010) and Kousalya et al. (2010) used chi-
tosan to remove Hg, Pb and Cr from their respective metal solutions. However, treatment
of landfill leachate with chitosan as an adsorbent is not yet studied.
In order to attain a more accurate and efficient system of leachate treatment, opti-
mization of the treatment processes is highly significant. Traditionally, one variable at a
time (OVAT) method has been practiced for the optimization process which considers
changing only a single variable at a time keeping all other variables constant (Bezerra et al.
2008). However, this method is incapable of attaining the maximum accuracy as it does not
involve the effects of interactions among the variables. Thus response surface methodology
(RSM) can be successfully applied to optimize the response variables as it is able to
involve the effects of each input variables along with their interactive effects using min-
imum experimental runs (Ghafari et al. 2009). RSM is an optimization tool based on
mathematical and statistical techniques. The method involves second order polynomial
model and uses designed experiments for best fitting of the model equations to the
experimental data (Bas and Boyacı 2007; Bezerra et al. 2008). In leachate treatment, RSM
were applied in very few studies to optimize the CF process for the abatement of COD,
color, turbidity, TSS and HA (Ghafari et al. 2009; Liu et al. 2012; Moradi and Ghanbari
2014). Till date, limited research work have been performed by implementing RSM to
remove COD, BOD5, color and Hg by CF followed by adsorption processes from landfill
leachate.
Thus the aim of the present study was to evaluate the effectiveness of sequential
processes of physicochemical methods like air stripping, CF, and adsorption to treat
intermediate landfill leachate in terms of removal of crucial pollutants. This research
investigated the process of air stripping at natural pH of landfill leachate to eliminate COD,
BOD5 and NH3–N. Moreover, this work examined the optimization of CF using RSM to
remove COD, BOD5, color, and Hg. Further, RSM was also employed for optimizing the
adsorption process using chitosan to remove COD and Hg from the leachate sample.

2 Materials and method

2.1 Leachate sample collection

Leachate samples for the present research work were collected from an uncontrolled
municipal solid waste (MSW) landfill in Kolkata, India. In Kolkata, about 3000 tons of
MSW are being disposed off daily at Dhapa landfill site which has been working since
1981 (Chattopadhyay et al. 2009). Leachate samples were collected from the peripheral
leachate drains as the landfill site is devoid of leachate collection systems and any kind of
bottom liners (De et al. 2016). After collection, the representative leachate samples are
immediately transported to the laboratory and preserved at 4 C for subsequent charac-
terization and treatment analyses. The physicochemical characteristics of Dhapa landfill
leachate are presented in Table 1 and compared with the Indian standards (MoEFCC
2016).

2.2 Analytical reagents and methods

Analytical-grade reagents were used in all the experiments. Chemical reagent such as
coagulant FeCl3 was bought from Merck Company. Adsorbent chitosan was purchased

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Table 1 Comparison of physicochemical characteristics of Dhapa landfill leachate with Indian standard
Parameters Unit Mean ± SDa Indian leachate discharge standards (MoEFCC 2016)

pH – 8.2 ± 0.09 5.5–9.0


Color Abs. 1.7 ± 0.02 –
COD mg/L 2235 ± 68 250
BOD5 mg/L 683.2 ± 13 30
BOD5/COD – 0.31 –
NH3–N mg/L 1265 ± 7 50
Cd mg/L 0.1 ± 0.002 2.0
Cr mg/L 0.5 ± 0.02 2.0
Fe mg/L 9.4 ± 0.07 –
Hg mg/L 2.4 ± 0.08 0.01
Mn mg/L 2.7 ± 0.13 –
Ni mg/L 0.3 ± 0.02 3.0
Pb mg/L 0.1 ± 0.01 0.1
Zn mg/L 3.5 ± 0.06 5.0
a
Standard deviation

from Sisco Research Laboratories Pvt. Ltd, India. Different physicochemical parameters
including heavy metals were determined as per the standard methods (APHA 1999). pH of
the leachate sample was assessed by digital portable meter (HI9813-5), color was analyzed
from the absorbance value of landfill leachate at 400 nm wavelength considering as
maximum absorbance of solution (Moraes and Bertazolli 2005; Atmaca 2009; Moradi and
Ghanbari 2014), chemical oxygen demand (COD) was evaluated by closed reflux digestion
method, biochemical oxygen demand (BOD5) was determined by Azide modification of
the Winkler method, ammoniacal nitrogen (NH3–N) was examined using Expandable ion
analyzer EA940, and heavy metals like cadmium (Cd), chromium (Cr), iron (Fe), mercury
(Hg), manganese (Mn), nickel (Ni), lead (Pb), and zinc (Zn) were estimated using atomic
absorption spectrophotometer equipped with Graphite furnace (GFAAS) (Perkin Elmer
AAnalyst 400). Hg was specifically measured with a mixture of chemical modifiers
(magnesium nitrate and palladium nitrate). All the experimental analyses were conducted
in duplicate for accuracy of the analytical results. However, leachate characterizations
were repeatedly determined before the subsequent treatment analyses to observe the
treatment efficiency precisely.

2.3 Air stripping

In this experiment, unfiltered leachate samples (2L) were aerated at natural pH (8.2) using
air diffusers at the rate of 10 L/min according to modified protocol of Guo et al. (2010).
The aeration setup was operated for a retention period of 48 h. Aerated samples of leachate
were collected at regular time intervals to quantify removal percentage of COD, BOD5,
and NH3–N. The concentrations of all heavy metals were also analyzed at the optimum
retention time.

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2.4 Coagulation–flocculation (CF)

The CF process was conducted in the commonly used jar test apparatus using six glass jars
of 500 mL volume. Prior to adding the coagulant in the leachate sample, the pH of the
optimized air-stripped leachate sample was adjusted to different target values using 5 N
H2SO4 and NaOH solutions. Afterward, different doses of ferric chloride (FeCl3) were
added to each of the beakers containing leachate sample. Rapid mixing and slow mixing
were carried out for 3 min at 150 rpm and 20 min at 50 rpm, respectively. Finally, the
solutions were left for a settling period of 1 h before the supernatant was sampled for the
subsequent analysis of COD, BOD5, color, and Hg. Other heavy metals were also mea-
sured at the optimized condition of CF.

2.5 Preparation of adsorbent (chitosan beads)

Chitosan flakes (2 g) were dissolved in 5% (v/v) solution of glacial acetic acid (60 mL)
and kept it for whole night at room temperature to gel formation. Chitosan beads were
prepared by adding the chitosan gel drop wise in 0.5 M NaOH solution. The beads were
continuously stirred for 24 h to neutralize the acetic acid. Afterward pH of the gel beads
was brought down to neutral point by repeatedly washing with distilled water (Ngah and
Fatinathan 2010).

2.6 Characterization of adsorbent

Chitosan beads were characterized by Fourier transform infrared spectroscopy (FTIR) for
ascertaining the functional groups present on adsorbent. FTIR spectra were obtained by
Shimadzu IR Prestige-21. Surface morphological changes of the chitosan beads before and
after leachate treatment were observed by JEOL-JSM-6360—scanning electron micro-
scope (SEM)—with platinum coating. Energy-dispersive X-ray analyzer (EDAX) equip-
ped with SEM was also used to detect the corresponding elemental peaks adsorbed on the
chitosan beads.

2.7 Adsorption

In this experiment, 100 mL of the optimized coagulated leachate samples were further
introduced into the adsorption process. Varying dosage of chitosan beads were mixed with
the leachate samples at different pH and stirred at 150 rpm for different time periods at
room temperature. Then leachate samples were filtered to measure the residual concen-
tration of COD and Hg. At the optimized state of adsorption, the concentrations of other
heavy metals were also evaluated to observe the efficiency of the chitosan beads.
Adsorption capacity qe (mg/g) of chitosan to remove COD and Hg were determined as
follows:
C0  Ce
qe ¼ V ð1Þ
W
where C0 indicates initial and Ce (mg/L) equilibrium concentration of pollutants,
V (L) denotes leachate volume, and W (g) indicates adsorbent weight.

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2.8 Experimental designing and optimization of CF and adsorption

The statistical designing of experiments were conducted with Design Expert (7.0.0) soft-
ware, and a five-level rotatable central composite design (CCD) of RSM was approached to
optimize CF and adsorption processes. For CF process, two independent variables were
selected (pH and coagulant dose), and for adsorption process, three independent variables
were selected (pH, adsorbent dose, and contact time). Initially, preliminary experiments
were performed by OVAT method with a broad range of independent variables for CF and
adsorption processes to screen out the effective range of the variables before statistically
designing the experiments. Prior to experimental design, pH in the range of 3–10 and
coagulant dose of 1–10 g/L were examined to identify the effective range of independent
variables for the CF process. On the basis of the primary screening the effectual range of
pH and coagulant dose for statistical analysis were observed to be 4–7 and 1–4 g/L,
respectively, for CF. While for the process of adsorption pH in the range of 3–9, adsorbent
dose of 0.1–1.5 g/L and contact time of 5–180 min were chosen for the preliminary study.
Consequently, the productive range identified for pH, adsorbent dose and contact time
were 6–8, 0.3–0.9 g/L and 30–90 min, respectively. Afterward, the effective range of the
independent variables for both the processes were provided as the input to obtain the
design matrix of experimental runs by applying CCD of RSM. The levels of the inde-
pendent variables (coded and decoded) are shown in Table 2. The response variables
considered in the CF process were COD, BOD5, color and Hg removal, whereas for
adsorption process only COD and Hg removal was considered. The experimental data were
examined to fit the following quadratic Eq. (2) establishing relationship among indepen-
dent variables and dependent responses.
X
k X
k k X
X k
Y ¼ b0 þ bi Xi þ bii Xi2 þ bij Xi Xj þ    þ e ð2Þ
i¼1 i¼1 ij j

where Y denotes predicted response variable, Xi and Xj indicate coded independent vari-
ables, k denotes number of factors, e indicates random error, b0 designates constant
coefficient, whereas bi, bii, bij specify linear, quadratic, and interaction coefficient,
respectively.
Analysis of variance (ANOVA) was also evaluated for data analysis representing
interactive effects in between independent variables and dependent responses.

Table 2 Coded and decoded


Independent variable Coded levels
levels of the independent vari-
ables for central composite –a –1 0 ?1 ?a
design (CCD)
Decoded levels
CF
pH 3.4 4 5.5 7 7.6
Coagulant dose (g/L) 0.4 1 2.5 4 4.6
Adsorption
pH 5.3 6 7 8 8.7
Adsorbent dose (g/L) 0.1 0. 3 0.6 0.9 1.1
Contact time (min) 9.6 30 60 90 110.5

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2.9 Desorption study

The chitosan beads used for the Hg removal from landfill leachate were repeatedly washed
using distilled water. Then beads were mixed with 100 mL of various concentrations of
desorbing solution of ethylenediaminetetraacetic acid (EDTA). Desorption was carried out
for a time period of 60 min at 150 rpm. Finally the concentration of Hg in the desorbing
solution was analyzed as mentioned above.

3 Results and discussion

3.1 Characterization of Dhapa landfill leachate

The characteristics of raw leachate from the Dhapa landfill showed that the initial values of
COD and BOD5 of leachate were 2235 and 683.2 mg/L, respectively. BOD5/COD ratio
was around 0.31 and pH was 8.2 indicating that landfill leachate were of intermediate
biodegradability (Foo and Hameed 2009). The concentration of NH3–N (1265 mg/L) and
among the analyzed heavy metals, Hg (2.4 mg/L), was significantly high and much above
the leachate discharge standards. Thus, in presence of high level of NH3–N and Hg, landfill
leachate treatment through biological processes could not be a convenient option.
Physicochemical treatment would be needed since BOD5/COD ratio was within 0.1–0.5
signifying that leachate samples were composed of medium biodegradable complexes
(Mahmud et al. 2012) along with high levels of NH3–N and Hg. Even though the landfill
site has been working for about 36 years, this medium biodegradability can be as a result
of the continuous process of waste disposal (De et al. 2017b).

3.2 Air stripping

Aeration increases the pH of raw leachate from 8.2 to 9.3 within 36 h of retention period
by CO2 stripping. This process of aeration stripped out 96.3% of NH3–N from leachate
since free NH3–N forms above pH 7 (Abood et al. 2014). COD and BOD5 showed a
maximum removal efficiency of 49.3 and 74.1%, respectively, with an optimum retention
time of 36 h. The removal percentage of NH3–N, COD and BOD5 remained more or less
constant beyond 36 h as shown in Fig. 1. Similar findings were observed by Mahmud et al.
(2012) with the removal of 36% for COD; 95% for BOD5 and NH3–N within 7 days of

Fig. 1 Effect of air stripping on COD, BOD5 and NH3–N removal for an aeration period of 48 h

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retention period with extended aeration. As a result of air stripping, Fe and Mn of landfill
leachate were oxidized with the aeration process at or above pH 7 and pH 9, respectively,
(sletten et al. 1995). The oxidized form of Fe and Mn precipitate out representing a
decrease in concentration of 23.0 and 17.1%, respectively. Consequently, Hg and Pb
showed a maximum removal of 8.4 and 18.2% in concentration, respectively, by adsorbing
onto Fe and Mn oxides. The surface hydroxyl groups of these oxides predominantly take
part in adsorption of heavy metals (Lu et al. 2014). Furthermore, the concentration of other
heavy metals in leachate were also evaluated which denoted removal of Cd by 9.2%, Cr by
15.1%, Ni by 12.7%, and Zn by 14.3% (Supplementary Table 1).

3.3 Optimization of CF using RSM

The relationship between two variables (pH and coagulant dose) and four important
responses (COD, BOD5, color, and Hg removal efficiency) for CF process was analyzed
using RSM. The design matrix of experimental runs along with the removal percentage
(experimental and predicted) of the dependent response variables is demonstrated in
Table 3 for CF process. On the basis of the experimental results, the quadratic equations to
predict the percent removal of the following four responses as a function of coded variables
are as follows:
COD removal ð%Þ ¼ 59:82 þ 7:71A  4:86B þ 2:05AB  9:82A2  8:87B2 ð3Þ

BOD5 removal ð%Þ ¼ 82:88 þ 5:17A  3:15B  0:55AB  6:76A2  8:88B2 ð4Þ

Color removal ð%Þ ¼ 88:16 þ 6:17A  3:49B þ 1:18AB  10:24A2  10:37B2 ð5Þ

Hg removal ð%Þ ¼ 40:78 þ 7:46A  6:07B þ 1:55AB  7:02A2  8:55B2 ð6Þ


where A and B represent pH and coagulant dose (g/L), respectively.
In the statistical optimization, run no. 3 showed the minimum percent of removal,
whereas run no. 12, 10, 11, and 13 represented the maximum removal percentage for COD,
BOD5, color, and Hg, respectively (Table 3). ANOVA of the CF experimental results
demonstrated that the model was significant as the p value was less than 0.05 with F values
for COD, BOD5, color, and Hg were 174.3, 58.2, 363.1, and 850.7, respectively, and 0.01%
of chance exists to occur as a result of noise (Table 5). The p values of lack of fit (LOF) for
all the responses of CF processes signify that the experimental data fitted the regression
models well as p [ 0.05. Adequate precision (AP) of signal-to-noise ratio of responses
indicates adequate signal as all the values were more than 4. The coefficient of variance
(CV) of less than 10% for all the responses also helps to establish reproducibility and
reliability of the models. The goodness of fit of the models was confirmed by the coeffi-
cient of determination (R2). R2 values of responses were close to 1 and were in good
agreement with the adjusted R2 value. Moreover, the adjusted and predicted R2 values were
also represented reasonable accordance among experimental and predicted values for all
CF responses.
To represent the interactive influences along with the optimized state of the variables,
3D response surface plots were developed for CF (Fig. 2). The figures showed the impact
of the independent variables for percent removal of response variables. With respect to
response surface plots of CF process, the optimum conditions obtained for the four
responses were pH 5.2 and coagulant dose 3.1 g/L. Thus, at the optimum conditions, the
predicted values for the highest percent removal of COD, BOD5, color and Hg were 56.8,

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Table 3 CCD design matrix, experimental, and predicted removal percentage of the response variables in coagulation–flocculation
Experimental runs Independent variables Removal percentage

pH Coagulant dose (g/L) COD BOD5 Color Hg

Experimental Predicted Experimental Predicted Experimental Predicted Experimental Predicted

1. 4.0 1.0 36.0 35.3 63.0 64.7 65.9 66.0 25.7 25.4
2. 4.0 4.0 45.7 46.7 75.5 76.1 75.3 76.0 36.6 37.2
3. 7.0 1.0 21.3 21.5 57.3 59.5 56.1 56.7 10.4 10.1
4. 7.0 4.0 39.2 41.0 67.6 68.7 70.2 71.4 27.5 28.2
5. 5.5 0.4 23.7 24.3 64.2 62.1 59.2 59.0 15.7 16.2
Treatment of landfill leachate by integrated sequence of…

6. 5.5 4.6 47.8 46.1 77.3 76.7 77.5 76.4 38.1 37.3
7. 3.4 2.5 43.9 44.0 70.6 69.6 72.7 72.4 32.4 32.3
8. 7.6 2.5 31.4 30.2 62.4 60.7 63.5 62.5 15.3 15.1
9. 5.5 2.5 54.4 54.8 82.4 82.9 87.3 88.2 41.0 40.8
10. 5.5 2.5 55.0 54.8 84.6 82.9 88.2 88.2 40.8 40.8
11. 5.5 2.5 54.3 54.8 83.7 82.9 89.1 88.2 40.2 40.8
12. 5.5 2.5 56.6 54.8 82.7 82.9 88.4 88.2 40.7 40.8
13. 5.5 2.5 53.8 54.8 81.0 82.9 87.8 88.2 41.2 40.8

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Fig. 2 Response surface plot for optimizing CF at pH 4–7 and coagulant dose 1–4 g/L a COD removal,
b BOD5 removal, c Color removal, d Hg removal

84.2, 89.2 and 43.4%, respectively. However, the corresponding experimental response
values were 55.3, 83.9, 91.8 and 42.2% for COD, BOD5, color, and Hg removal,
respectively, which was close to the predicted values. The removal efficiencies were found
to reduce when moving away from these optimum conditions, meaning that either increase
or decrease in any of the tested variables results in decline of the response. At the opti-
mized condition of CF, the concentration of other heavy metals present in the landfill
leachate was determined which signified a maximum removal of 34.0% of Cd, 58.2% of
Cr, 36.4% of Mn, 37.1% of Ni, 40.6% of Pb and 33.1% of Zn (Supplementary Table 1).

3.4 Characterization of the adsorbent

FTIR analysis was carried out for the chitosan beads to determine the functional groups
involved in heavy metal binding with chitosan beads. The chemical changes of chitosan
beads before and after the leachate treatment are shown in Fig. 3. The significant peak
detected for the chitosan beads at 3427 cm-1 is the characteristic extending vibrations of –
NH2 and –OH groups. The 2872 cm-1 peak can be attributed to the extending vibrations of
–CH methyl groups. The peaks at 1593 and 1421 cm-1 can be ascribed to the –NH
distorting vibration. The peak at 1379 cm-1 can be imputed to the –CH bending mode,
whereas the peak at 1319 cm-1 denoted –CN deforming mode. The peak at 1256 cm-1 can

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Treatment of landfill leachate by integrated sequence of…

Fig. 3 FTIR specter of chitosan beads before and after adsorption

be accredited to the –OH extending vibration. Following the leachate treatment with
chitosan beads, the extent of transmittance got reduced at 3427, 1593, and 1421 cm-1,
which are the characteristic wave numbers of –NH2 and –OH groups. Thus amino (–NH2)
and hydroxyl (–OH) groups are the predominant groups in chitosan beads which take part
in heavy metal adsorption.
SEM image of unutilized chitosan beads along with image of beads subsequent to
leachate treatment is presented in Fig. 4. Alterations in the chitosan bead’s external
morphology can be clearly observed after leachate treatment. Moreover, EDAX analysis
demonstrates that the chitosan beads adsorb Hg and other ions. The peaks of Hg in the
EDAX spectrum confirm the adsorption of Hg on chitosan beads (Fig. 5).

3.5 Optimization of adsorption using RSM

In case of adsorption, the relationship between three independent variables (pH, adsorbent
dose, and contact time) and two target response variables (COD and Hg) was studied using
RSM. The experimental and predicted percent removal of the response variables for the
experimental runs in adsorption process is summarized in Table 4. On the basis of batch

Fig. 4 SEM images of chitosan beads a before and b after adsorption

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Fig. 5 EDAX specter of chitosan beads a before and b after adsorption

Table 4 CCD design matrix, experimental, and predicted removal percentage of the response variables in
adsorption
Experimental Independent variables Removal percentage
runs
pH Adsorbent Contact COD Hg
dose (g/L) time (min)
Experimental Predicted Experimental Predicted

1. 6.0 0.3 30 14.5 13.3 45.3 44.1


2. 8.0 0.3 30 25.6 26.1 56.9 57.4
3. 6.0 0.9 30 17.8 18.0 48.7 49.0
4. 8.0 0.9 30 36.7 35.4 67.9 66.5
5. 6.0 0.3 90 32.7 34.5 63.8 65.6
6. 8.0 0.3 90 38.7 38.9 70.0 70.1
7. 6.0 0.9 90 40.9 40.8 72.0 71.9
8. 8.0 0.9 90 48.1 49.7 79.0 80.6
9. 5.3 0.6 60 7.5 7.3 38.4 38.2
10. 8.7 0.6 60 25.9 25.5 57.0 56.7
11. 7.0 0.1 60 41.0 40.4 72.1 71.6
12. 7.0 1.1 60 53.5 53.5 84.7 84.6
13. 7.0 0.6 9.6 20.7 22.0 51.5 52.8
14. 7.0 0.6 110.5 53.7 51.8 84.5 82.7
15. 7.0 0.6 60 54.5 55.1 85.9 86.1
16. 7.0 0.6 60 54.4 55.1 85.1 86.1
17. 7.0 0.6 60 55.2 55.1 86.6 86.1
18. 7.0 0.6 60 54.4 55.1 85.3 86.1
19. 7.0 0.6 60 55.5 55.1 87.1 86.1
20. 7.0 0.6 60 56.6 55.1 86.2 86.1

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Treatment of landfill leachate by integrated sequence of…

adsorption experiments, the quadratic equation to predict the percent removal of COD and
Hg as a function of coded variables (Table 3) are as follows:
COD removal ð%Þ ¼ 55:12 þ 5:43A þ 3:88B þ 8:88C þ 1:12AB  2:1AC þ 0:4BC
 13:69A2  2:89B2  6:44C 2 ð7Þ

Hg removal ð%Þ ¼ 86:05 þ 5:51A þ 3:87B þ 8:9C þ 1:05AB  2:2AC þ 0:35BC


 13:65A2  2:8B2  6:47C2 ð8Þ

where A, B and C represent pH, adsorbent dose (g/L) and contact time (min), respectively.
In the statistical optimization of adsorption process, run no. 9 showed the minimum
percent of removal, whereas run no. 20 and 19 represented the maximum percentage of
COD and Hg removal, respectively (Table 4). ANOVA of the adsorption experimental
results showed that the model F values for COD and Hg removal were 285.7 and 305.3,
indicating that this model was also significant and only 0.01% of chance exists to occur as
a result of noise (Table 5). The fitting of the regression models by the experimental data
was also can be determined from the p values of LOF for all the responses of adsorption
processes as p [ 0.05. Adequate signal-to-noise ratio for the responses was observed as all
the values of AP were more than 4. The models were observed to be reliable as well as
precise since the value of CV was less than 10% for all the responses. R2 values of
responses were close to 1 and were in good agreement with the adjusted R2 value. Fur-
thermore, the adjusted and predicted R2 values were well in accord since the experimental
and predicted values for all adsorption responses were observed to be in reasonable
concurrence.
Three-dimensional response surface plots were also generated for adsorption to repre-
sent the interactive influences along with the optimized state of the variables (Figs. 6, 7). In
case of response surface plots of adsorption process, the optimum conditions observed for
COD and Hg removal were pH 7, adsorbent dose 0.6 g/L, and contact time 66.4 min. Thus,
at the optimum conditions, the predicted values for the highest percentage of COD and Hg
removal were 56.7 and 87.7%, respectively. However, the corresponding experimental
response values were 56.1 and 89.2% for COD and Hg removal, respectively, which
denotes that the experimental values are similar to the predicted results. Before the onset of
the process of adsorption, leachate was adjusted to the optimum pH of 7. At this stage the
concentration of Fe decreases to 3.3 mg/L as the residual Fe?3 hydroxides produced during

Table 5 ANOVA analysis for CF and adsorption


Response variables F value p value p-LOF SD AP CV (%) R2 Adj R2 Pred R2

CF
COD 174.3 \ 0.0001 0.1818 1.4 34.5 3.3 0.992 0.986 0.958
BOD5 58.2 \ 0.0001 0.1415 1.9 18.0 2.6 0.976 0.959 0.870
Color 363.1 \ 0.0001 0.1272 1.0 47.6 1.3 0.996 0.993 0.978
Hg 850.7 \ 0.0001 0.0907 0.6 75.9 1.9 0.998 0.997 0.990
Adsorption
COD 285.7 \ 0.0001 0.0775 1.4 49.4 3.5 0.996 0.992 0.973
Hg 305.3 \ 0.0001 0.0504 1.3 51.1 1.9 0.996 0.993 0.974

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S. De et al.

Fig. 6 Response surface plot for optimizing adsorption to remove COD at pH 6–8, adsorbent dose
0.30–0.90 g/L and contact time 30–90 min a pH and adsorbent dose interaction, b pH and contact time
interaction, c adsorbent dose and contact time interaction

the process of CF in the form of polynuclear cations precipitate out from the leachate
sample which leads to decrease in concentration of Fe. After the treatment of adsorption,
apart from the target pollutants of COD and Hg, the concentration of all other heavy metals
in the final effluent were quantified to observe the removal efficiency of the adsorbent
which indicated a removal of 72.6% of Cd, 77.1% of Cr, 76.2% of Fe, 67.7% of Mn, 75.4%
of Ni, 81.0% of Pb, and 64.3% of Zn (Supplementary Table 1).

3.6 Adsorption isotherms

To understand the association governing the adsorbate and adsorbent surface, the exper-
imental data were validated by the various adsorption isotherm models. Three isotherm
models, namely Langmuir, Freundlich, and Temkin, were used for validating the experi-
mental values.
The linearized form of Langmuir isotherm model can be represented as follows: (Foo
and Hameed 2010)
ce 1 ce
¼ þ ð9Þ
qe KL Qo Qo

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Treatment of landfill leachate by integrated sequence of…

Fig. 7 Response surface plot for optimizing adsorption to remove Hg at pH 6–8, adsorbent dose
0.30–0.90 g/L and contact time 30–90 min a pH and adsorbent dose interaction, b pH and contact time
interaction, c adsorbent dose and contact time interaction

where Ce (mg/L) denotes equilibrium concentration, qe (mg/g) indicates quantity of


adsorbate adsorbed per unit mass of the adsorbent at equilibrium condition, Qo (mg/g)
denotes highest amount of adsorbate adsorbed forming monolayer and KL (L/mg) desig-
nate Langmuir constant associated with the affinity of the adsorption sites.
The linearized form of Freundlich isotherm model can be represented as follows:
(Sohbatzadeh et al. 2016)
1
log qe ¼ log KF þ log Ce ð10Þ
n
where KF and n are Freundlich constants. KF denotes adsorption capacity and n indicates
adsorption intensity. A value of n in between 1 and 10 denotes favorable adsorption
(Chowdhury et al. 2009).
The linearized form of Temkin isotherm model can be represented as follows: (Foo and
Hameed 2010)
qe ¼ B ln A þ ðBÞ ln Ce ð11Þ
where B = RT/b, with b (J/mol) and A (L/g) are the sorption heat and equilibrium binding
constants.
The isotherm parameters of different isotherm models and their corresponding coeffi-
cient of determination (R2) are described in Table 6. It can be summarized as adsorption of
COD and Hg from landfill leachate onto chitosan beads can be expressed by Langmuir
isotherm model since maximum R2 of 0.998 and 0.997 was obtained for Langmuir

123
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Table 6 Isotherm parameters for the adsorption of Hg on chitosan beads
Adsorbate Langmuir isotherm Freundlich isotherm Temkin isotherm
2 2 1/n 2 2
Qo (mg/g) KL (L/mg) RL R v 1/n n KF (mg/g).(L/mg) R v A (L/g) B R2 v2

COD 555.6 0.03 0.07 0.999 0.03 0.1026 9.75 1.3 0.972 0.06 55.2 51.0 0.974 0.05
Hg 2.4 43.33 0.02 0.997 0.019 0.102 9.8 2.4 0.764 0.022 0.07 9 106 0.2 0.768 0.020
S. De et al.
Treatment of landfill leachate by integrated sequence of…

isotherm, respectively. Langmuir isotherm constants Qo and KL were obtained by plotting


Ce
Qe versus Ce . The favorability of adsorption of COD and Hg on the chitosan beads was
determined by calculating the equilibrium parameter (RL). The RL value varied in between
0 and 1 denoting the process of adsorption of COD and Hg on the chitosan beads was
favorable. Freundlich isotherm constants n and KF were determined by plotting logarithm
of qe versus logarithm of Ce . The process of adsorption is favorable as 1n lie between 0 and 1
and demonstrate Langmuir isotherm since 1n is below 1. Temkin isotherm constants A and B
were obtained by plotting qe versus ln Ce . In order to better optimize the adsorption
isotherm models, Chi-square analysis have been adopted. The Chi-square values of the
isotherm models indicated COD and Hg adsorption on the chitosan beads obeyed Lang-
muir isotherm as the value of Chi-square for Langmuir isotherm is smaller in comparison
with other isotherm models.

3.7 Adsorption kinetics

Adsorption kinetics help to identify the mechanism underlying the adsorption process
providing an insight of adsorbate uptake, adsorption rate and residence time (Foo et al.
2013). Thus, in this study, adsorption kinetics were studied using pseudo-first-order,
pseudo-second-order, and intra-particle diffusion models.
The pseudo-first-order rate equation as observed by Lagergren can be illustrated by the
following equation: (Lagergren 1898)
 
k1
logðqe  qt Þ ¼ log qe  t ð12Þ
2:303
where qt (mg/g) denotes adsorption capacity at any time t and k1 denotes pseudo-first-order
rate constant (1/min).
The pseudo-second-order rate equation as observed by Ho and McKay can be repre-
sented by the following equation: (Ho and McKay 1999)
t 1 t
¼ þ ð13Þ
qt k2 q2e qe
where k2 denotes pseudo-second-order rate constant (g/mg min).
The intra-particle diffusion model as observed by Weber and Morris can be represented
as follows: (Weber and Morris 1963)
qt ¼ kid t0:5 þ C ð14Þ
0.5
where kid denotes intra-particle diffusion rate constant (mg/g min ) and C is a constant.

Table 7 Kinetic parameters for the adsorption of Hg on chitosan beads


Adsorbate qe, exp Pseudo-first order Pseudo-second order Intra-particle diffusion
(mg/g)
k1 (1/ qe, R2 k2 (g/ qe, R2 kid (mg/ C R2
min) calc mg min) calc g min0.5)

COD 477.1 0.03 223.5 0.988 2.1 9 10-4 526.3 0.997 27.7 231.2 0.886
Hg 1.9 0.04 1.5 0.985 0.03 2.2 0.994 0.1 0.6 0.913

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S. De et al.

The results of all the kinetic models are given in Table 7. Adsorption rate of COD and
Hg was fast in the first 30 min and gradually slowed down reaching a constant value at the
adsorption equilibrium. This can be explained by two phenomenon: Firstly, adsorbate was
removed rapidly by forming a monolayer on the exterior of the adsorbent. Then it was
removed slowly by pore diffusion through the adsorbate monolayer reaching the interior of
the adsorbent (Chowdhury et al. 2009). The rate-determining step of any process is based
on its slowest step. For comparing the different kinetic models, coefficient of determination
(R2) is used to indicate the divergence of the calculated values from the experimental
values. The results indicated COD and Hg adsorption by chitosan obeyed pseudo-second-
order kinetic model with maximum R2 of 0.995 and 0.994, respectively. Moreover, the
calculated qe value from pseudo-second-order kinetic model was more in agreement with
the experimental qe value. Thus pseudo-second-order kinetic model can successfully
describe the adsorption process and the rate-determining step was assumed to be
chemisorption.

3.8 Desorption study

Equilibrated chitosan beads were air-dried and then observed for desorption study. Various
concentrations of EDTA were used for recovering the adsorbed Hg ions from chitosan
beads. The Hg recovery percentage increases with the increasing concentration of EDTA
(Table 8). However, percentage of recovered Hg remained more or less constant beyond
0.005 (M) of EDTA. Thus 0.005 (M) of EDTA was considered as the optimum concen-
tration for regenerating chitosan. Further, different S/L ratio was also used which is the
ratio of amount of desorbent present in the volume of desorbing medium. Percentage of
recovered Hg beyond S/L ratio of 1 was similar, and thus the optimum S/L ratio was
considered to be 1 which can recover about 77.2% of adsorbed Hg at the optimum EDTA
concentration (Table 8).

3.9 Treatment efficiency

The present process of leachate treatment through the sequential application of air strip-
ping, CF, and adsorption results in cumulative percent of removal of 96.3% for NH3–N,
91.8% for color, 95.8% for BOD5, 90% for COD, and 95.8% for Hg (Table 9). The results
demonstrated that combined effect of air stripping, CF, and adsorption may be a conve-
nient option to remove heavy metals especially mercury and other pollutants from leachate
sample.

Table 8 Desorption study of Hg


Desorbent Concentration (M) Recovered Hg (%)
with different concentrations of
EDTA and S/L ratios
EDTA (S/L ratio 0.5) 0.001 46.6 ± 1.3
0.003 54.1 ± 0.8
0.005 62.5 ± 1.1
0.01 65.7 ± 2.2
S/L ratio (0.005 M EDTA) 0.3 58.2 ± 0.7
0.5 62.5 ± 1.4
1 77.2 ± 2.1
1.5 80.2 ± 1.6

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Treatment of landfill leachate by integrated sequence of…

Table 9 Removal percentage of the pollutants in leachate through different treatment processes
Methods of treatment Removal percentage

NH3–N Color BOD5 COD Hg

Air stripping 96.3 ± 1.8 – 74.1 ± 2.1 49.3 ± 1.7 8.4 ± 0.2
CF – 91.8 ± 2.4 84.0 ± 3.5 55.3 ± 2.4 42.2 ± 2.1
Adsorption – – – 56.1 ± 0.8 89.2 ± 1.9
Cumulative removal percentage 96.3 ± 1.8 91.8 ± 2.4 95.8 ± 3.2 90.0 ± 3.3 95.8 ± 2.6

4 Conclusion

In the present study, treatment of landfill leachate was undertaken by the processes of air
stripping followed by a sequence of CF and adsorption. Initial treatment of air stripping
within an optimum retention period of 36 h was managed to remove up to 49.3% of COD,
74.1% of BOD5, 96.3% of NH3–N, and 8.4% of Hg. After air stripping, CF followed by
adsorption was applied for the removal of targeted leachate pollutants. Statistical opti-
mization of CF and adsorption was accomplished using RSM based on CCD. The optimum
conditions for CF were pH 5.2 and FeCl3 3.1 g/L. At the optimum conditions, the
experimental response values were 55.3% for COD, 83.9% for BOD5, 91.8% for color, and
42.2% for Hg removal, whereas at the optimum conditions of adsorption (pH 7, chitosan
beads 0.6 g/L and contact time 66.4 min), COD and Hg removal was 56.1 and 89.2%,
respectively. COD and Hg adsorption followed Langmuir isotherm and the kinetic studies
demonstrated that pseudo-second-order kinetics were followed by the adsorption processes
and the rate-determining step was assumed to be chemisorption. Desorption study indi-
cated that 0.005 (M) of EDTA and S/L ratio of 1 was optimum to recover about 77.2% of
adsorbed Hg from chitosan beads. The results indicated that the integrated sequence of air
stripping, CF and adsorption, showed an effective reduction of 96.3% for NH3–N, 91.8%
for color, 95.8% for BOD5, 90.0% for COD, and 95.8% for Hg. However, still landfill
leachate required further treatment to enhance the removal of Hg before discharging it in
reference to Indian leachate discharge standards.

Acknowledgements The first author would like to express her gratitude toward University Grants Com-
mission (UGC), New Delhi, India, for granting the research fellowship and all the authors thank Kolkata
Municipal Corporation (KMC) for assisting in the field work.

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