CPPM 2015 0046

Chem. Prod. Process Model.
2016; aop
M. Aminul Haque*
A Statistical Comparison of Mathematical Models

for Heavy Metal Leaching Phenomena from
Solidified Landfill Waste Mortar
DOI 10.1515/cppm-2015-0046
Received October 28, 2015; revised December 30, 2015;
accepted December 30, 2015
Abstract: In this research, landfill solid waste was solidified

as cement-waste matrix to protect the environment from
excessive intrusive contaminants like Fe, Cu and Ni and
minimize the waste load. Within this context, ingredients
of cement-waste mortar were characterized to determine
their physical properties. Long-term feasibility study was
conducted to examine the metal contents stabilization by
employing the standard mass transfer-leaching test. The
cumulative leaching concentration of Fe, Cu and Ni were
found to be 1.29 mg/l, 0.18 mg/l and 0.63 mg/l respectively
up to 180 days static leaching test period that satisfied the
surface water quality standard. Mechanical strength test
was also conducted to characterize the solidification
technique. Five well-established non-linear mathematical
Models were conducted to evaluate the mechanisms of Fe,
Cu and Ni migration. Goodness of fit statistical parameter
analysis and visual examination indicated that polynomial
equation Model is better for explaining the experimentally
generated data. Moreover, parameter of polynomial equation was extended from five to nine for examining the best
calibration profile to the observations. In context of slopeintercept and visual observation analysis resulted that polynomial equation based Model bearing five parameters with
0.5 power interval of each parameter describes the leaching
phenomena quite similar with the experimental observations whereas goodness of fit parameters and information
criterion shows reverse. It was found that the studied immobilized landfill waste mortar have acceptable mechanical
performance that confirms to be used as construction
material.
Keywords: landfill waste mortar, leaching phenomena,
fitted models, statistical analysis, visual examination
*Corresponding author: M. Aminul Haque, Department of Civil

Engineering, Leading University, 5th Floor, Rangmahal, Bandar
bazar, Sylhet-3100, Bangladesh, E-mail: mahaque@lus.ac.bd
1 Introduction
Landfill leachate is a significant source of ground water
pollution [1] that formed by decomposition of municipal
solid waste [2, 3] and excess rainwater percolating through
the waste layers [1, 2]. Leachates are highly concentrated
complex effluents which contain dissolved organic matters;
inorganic compounds, such as ammonium, calcium, magnesium, sodium, potassium, iron, sulphates, chlorides and
heavy metals such as cadmium, chromium, copper, lead,
nickel, zinc etc.; and xenobiotic organic substances [1, 46].
Especially presence of heavy metals in leachate have potential impact on human health and the quality of environment
having the greater possibility of surface and ground water
pollution [7].
The long-term safe landing of the solidified hazardous
waste is an important request for keeping the surrounding
environment more secure for the coming generations [8].
Therefore, solidification/stabilization (S/S) techniques
are used to minimize the immense pressure of waste load
in landfill sites and leachate production by reducing the
mobility as well as solubility of contaminants in wastes
and converts them into chemically inert form [9]. In S/S
process, the immobilization of the contaminants is achieved
by formation of chemical bonds and/or by physical encapsulation. This ensures the reduction of the quantity and
release speed of contaminants to the environment to a
large extent [10] and avoids a back release of contaminants
from the matrix during aggressive conditions of storage and
disposal [11]. Macroencapsulation works in S/S by physically
entrapping contaminants within a large structural matrix
whereas microencapsulation entraps contaminants within
the crystalline structure of solidified matrix at a microscopic
level [12] and incapable of chemical interactions [9].
Cementitious materials are widely used in waste management systems with different aims and requirements for
long-term performance. Both conventional and novel
cementitious materials are used to create reliable immobilizing elements for safe storage and disposal of wastes.
Conventional cementitious materials such as Portland
cement and composite cements with supplementary cementitious materials in the form of fly ash, iron blast furnace
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M. A. Haque: Statistical Comparison of Mathematical Models
slag, silica fume, natural pozzolans as well as novel cement

systems such as geopolymers, high alumina (calcium sulfoaluminate), MgO-based or phosphate (acidic) cements are
used to encapsulate the contaminants whereas the aluminosilicate polymers e. g. geopolymers, metakaolinite, blast furnace slag, pulverized fuel ash etc. are used as novel materials
to develop structural strength of waste matrices and immobilize both cations and anions. The barrier elements as well
as interactions envisaged between various components are
important to ultimately ensure the overall safety of a storage
and disposal system. The behavior and performance of
cementitious materials including waste package components, waste form and backfilling are analyzed within the
International Atomic Energy Agency (IAEA) Coordinated
Research Project (CRP) which is involved by 26 research
organizations from 21 Member States (MS) [13]. The IAEA
CRP on Behavior of Cementitious Materials gathered together
researchers from 21 Member States which cover a large number of topics related to use of cementitious materials are
shown in Table 1 [13].
Various studies have been performed on leaching
phenomena on cementitious material over the last four
decades. Figure 1 shows a simple figure of contaminants
leaching pattern from waste matrix to the immersion
leachant. In the presence of leachant, contaminants
transport from the surface and inside of the waste material that can be depicted by a conceptual leaching Model
[9, 14] (Figure 2) of contaminants transport from the S/Streated waste. Transport of the mobilized contaminants
occurs by bulk advective flow or diffusion. If water flows
within the S/S-treated waste advective transport causes
contaminants that have been mobilized by reactions in
the pores to flow through the waste. Figure 2 illustrates
the several transport mechanisms and chemical reactions
that would be part of a comprehensive mechanistic leaching Model.
Curing beaker
Aqueous solution or leachant
Waste block
Cd
2+
Cu2+
Fe2+
Interface of leachant and waste block
Metal release from waste

mortar to leachant
Fe2+, Cu2+,
Ni2+, Cd2+, Cr6+
Ni2+
Cr6+
Figure 1: Diffusion based static leaching test.
Aqueous solution
Interface
Waste matrix
Leachate rate
Interface of leachant
and waste
block
Leachant
renewal
Surface
phenomena
Bulk Diffusion
Diffusion
Convection
Figure 2: Conceptual model of contaminants leaching mechanisms

from S/S treated waste [9].
The leaching behavior of the waste matrix is as a combination of the two processes [15, 16]: (i) surface washoff and (ii) diffusion stage mechanism. The maximum
leaching of the contaminant is seen at the initial period
because of the washout of loosely bounded surficial
compounds of the waste form. In this process, a rapid
equilibrium is established between ionic species present
in the surface pores of the waste matrix and ions in
the leachant solution. When each ion has been leached
out from the surface of the block, it migrates by longer
pathways from the bulk through diffusion-controlled
stage, which determines the long-term leaching
behavior of the waste matrix block. Rahman et al. [17]
Table 1: Member states(MS), organisations, researchers and research topics of IAEA CRP on Cementitious Materials [13].
MS, Organization, Researchers
Research topics
Switzerland, PSI, A. Wallisch

Belgium, SCKCEN, W. Bastiaens, E. Martens,
P. Van Iseghem
Long-term mechanical stability and leaching behaviour of a solidified radioactive sludge.

Behaviour of cementitious materials in long term storage and disposal of radioactive
waste. Behaviour of cementitious materials and interactions with host environment in
radioactive waste disposal.
The immobilisation of radioactively contaminated soil in cementitious materials.
Evaluation of the use of synthetic zeolite as a backfill material in radioactive waste
disposal facility.
Long term behaviour of cementitious materials in the Korean repository environment.
Behaviours of cementitious materials in long term storage and Disposal.
Behaviour of cementitious materials in multipurpose packaging for transportation, long
term storage and disposal
China, NUDT, S. Bai, S. Yang

Egypt, AEAE, A. El-Kamash
Korea, KHNP/NETEC, J.H. Yoon, J. Wan Park
Serbia, Vinca INS, I. Plecac, D. Kievi
South Africa, NECSA, W. Meyer

added an additional conception of leaching phenomena.

The last stage of contaminant leaching mechanism
from waste matrix is the slow portion of dissolution
control the leaching phenomena. Moreover, the dissolution of materials from the surface proceeds faster that
the diffusion through the pores. Both the rapid and
slow portion of dissolution will result in the release of
highly soluble materials but it will not cause depletion
of material.
For interpreting the contaminants leaching mechanism from waste matrix, some researchers have been used
different non-linear Models. To identify the long term
leaching phenomena, some researchers [1720] provided
a Fickian diffusion based equation that is,
Pan
f=
a0
p
2S Detn
p
V
(1)
Where f = Cumulative fraction leached of heavy metals. De

can be calculated from the slope of an/A0 versus tn1/2,
according to the following relationship:
De =
m2
V2
(2)
Similarly, Plecas and Dimovic [25] and Plecas and

Dimovic [26] used same Model up to its fifth terms for
characterizing the immobilization of industrial waste within
cement-bentonite clay matrix and transport phenomena of
60
Co from radioactive material respectively,
f = A0 + A1 t1=2 + A2 t + A3 t3=2 + A4 t2
(7)
In the current study, concentration of five heavy

metals like Fe, Cu, Ni, Cr and Cd were examined in landfill decomposed solid waste and effluent leachate. It was
observed that concentration of Fe, Cu and Ni exceeded
the Bangladesh standard [27]. Therefore, the aims of
present work is oriented to characterize the leaching
phenomena of Fe, Cu and Ni from waste matrices with
controlling leaching mechanism and predict the longterm leaching phenomena by applying various non-linear
mathematical Models such as diffusion, polynomial,
logarithmic, exponential and power based equations.
The performance of the prediction Models were measured
based on some statistical goodness of fit indicators with
the accuracy of 95 % confidence interval of the estimated
Model parameters.
Pan
Where, m = pa0
tn
From eqs (1) and (2),
2 Materials and methods
p
f = m tn
(3)
2.1 Experimental approach
To generalize the Model equation (3) can be expressed as,

1=2
f = A0 + A1 t
(4)
As the diffusion rate gradually slow down with the

leaching period elapsed. Therefore, if the diffusion
path becomes longer, diffusion rate is not a controlling
factor in any of the leaching intervals. Some researchers
[2123] adopted polynomial equation based a semiempirical method to overcome this problem because
polynomial equation describes the long-term leaching
characteristics of a waste component. In this Model,
the cumulative amount of contaminant leached is
expressed by:
f = A0 + A1 t1=2 + A2 t
(5)
Plecas [24] applied polynomial equation based Model up

to its fourth terms of this Model to observe the leaching
behavior of 137Cs from radioactive waste formation,
f = A0 + A1 t1=2 + A2 t + A3 t3=2
(6)
In the current study, solidified waste mortar (SWM) specimen was prepared using stabilizing binding materials
like Ordinary Portland cement (OPC) and fine aggregate
such as sand and landfill decomposed solid waste
(LDSW). OPC and sand were collected from locally available areas. LDSW was collected from Matuail Sanitary
Landfill Site (MSLS), Dhaka, Bangladesh and prepared
through air drying, blending and sieving at room
temperature (25 1 C). Concentration of selected heavy
metals in LDSW and effluent leachate samples were
determined using flame emission atomic absorption spectrophotometer (AAS) (Spectra AA Varian). Physical characteristics of specimen ingredients were measured
following the ASTM standard methods that are mentioned in Figure 3. Cubical specimen having the mold
dimensions of 5 cm 5 cm 5 cm was prepared whereas
in each specimen 30 % of the total volume of fine aggregate was replaced by LDSW [28]. Standard leaching
test method ANS 16.1 was used to observe the Fe, Cu
and Ni leaching phenomena from solidified waste form.

1. Analysis of
oxides
2. Compressive
strength test at 3
and 7-day.
OPC (Type I and 52.5 grade)
Sand
DSW
Grinding
Collection of SWMBs
ingredients.
Selection of mixing
proportion for SWM
specimen ingredients.
Preparation of
waste mortar
specimen.
Demoulded after 24
hours.
Static
leaching test
OPC:
1. Fineness (ASTM C184-94)
2. Consistancy limit (ASTM C187)
3. Initial settting time (ASTM C150)
4. Final setting time (ASTM C150)
5. Specific gravity (IS -2720)
Physical
property
analysis
Sieve < 2mm dia.
Collection
Measurement of heavy
metal concentration in
effluent leachate using
AAS.
Collection of
effluent leachate
from landfill
leachate pond.
Digestion by
Aqua-regia
Solution (1:3).
Collection of
DSW
MSLS
Sand and LDSW:

1. pH (Hevi-sand-TP283)
2. Dry density (ASTM-D2937-00)
3. Bulk density (ASTM C29)
4. Specific gravity (ASTM 128-15)
5. Porosity (Bowels, 1997)
6. Water content (ASTM D2216-80)
7. WAC (ASTM C 128-88)
8. FM (ASTM C136 96a)
Comparison of results
with the inland surface
water quality standard
[27].
Measurement of heavy
metal concentration in
LDSW sample using AAS.
Physical characteristics of waste mortar:

Parameters (Per specimen)
Dimension
Mixing proportion (OPC:FA)
Unit weight of specimen
Unit weight of cement
Unit weight of sand
Unit weight of waste
Unit weight of water
Replacement of sand by waste
Water to cement ratio
Compressive strength test
Values
5cmx5cmx5cm
1: 2 [28]
2080 5 kg/m3
690.39 kg/m3
976.66 kg/m3
414.01 kg/m3
334.84 kg/m3
30% of the sand volume
0.485
Curing characteristics:
1. ANS 16.1 leaching test method
2. Distill water (pH=7.0)
3. Solid to liquid ratio =4
4. Average temperature 25010 C
5. Average humidity 93% 2%
Compressive strength test at 3, 7, 14, 21, 28, 56, 90 and 180 days
curing period using concrete compression machine (B-ELE, MADR 2000KN)
Mortar specimen cured for compressive strength

and heavy metal leaching test.
Leaching water collection at 1-7, 14, 21, 28, 56, 90

and 180 days curing period.
Take Decision. Is it satisfy the metal release standard of BECR

1997 in inland surface water discharge and compressive strength
requirement of PWDB (2011) for paving block?
Measurement of heavy metals concentration in curing

leachant using AAS.
Comparison of heavy metal leaching concentration

with the inland surface water quality standard [27].
If not satisfied, then change the mixing
proportion of ingredients for solidified waste
mortar block.
Compare the compressive strength value of solidified waste mortar

block with the PWDB (2011) standard for paving block (15 MPa at
28th day period).
If satisfied, then simulate mathematical models for

demonstrating the heavy metal leaching behavioral pattern
from SBMB during the curing period.
Use goodness of fit indicator parameters to select the best

demonstrating calibration model.
Figure 3: The overall experimental working methodology of heavy metal leaching behavior of SWM.
Leaching tests were performed for 17, 14, 21, 28, 56, 90
and 180 days immersion period and results were recorded
in terms of cumulative release in the curing leachant
versus curing ages. The compressive strength test, given
as applied maximum load divided by the cross-sectional
area of a specimen, was performed to confirm the structural integrity of solidified waste matrix. All tests were
performed three times to ensure the statistical significance of the experimental data. Average value of each
test was presented in this study along with the standard
deviation. The overall experimental and analytical working steps are briefly depicted in Figure 3.
2.2 Fitting of the leachate Models

Five different well-known non-linear mathematical equation based Models were fitted as leachate Model to calibrate for demonstrating the leaching mechanism and
justify against the experimental observations showing

heavy metal migration phenomena from SLWM. Fitted

non-linear Models are presented below:
1. Diffusion equation based Model (Generalize form):
f = A0 + A1 t1=2
2.
(4)
Polynomial equation based Model:

f = A0 + A1 t1=2 + A2 t
3.
(5)
2.4 Evaluation of fitted leachate Models

calibration
Well calibration between the simulated data from fitted
Models and experimentally generated data from leaching
(Fe, Cu and Ni) test were evaluated using the most commonly
used statistical parameters like goodness of fit indicators and
information criteria. These are presented in Table 2.
Logarithmic equation based Model:

f = a + b lnt
(8)
3 Results and discussions
4. Exponential equation based Model:

f = aebt
5.
(9)
Power equation based Model:

f = atb
(10)
2.3 Parameter extension of well-fitted

leachate Model
In this study, parameter of polynomial equation based
Model was extended in different longer terms with 0.5
and 0.25 intervals as trial basis using the least squares
procedure for demonstrating the best fit Model of
metal leaching mechanism in a better way with high
accuracy. The study adopted the following fitted Model
options such as Polynomial extended model one (PEMO),
Polynomial extended model two (PEMT), Polynomial
extended model three (PEMTh), Polynomial extended
model four (PEMF), Polynomial extended model five
(PEMFv) and Polynomial extended model six (PEMS) as
trial basis to well calibrate with the experimental observations of Fe, Cu and Ni releasing data from SWM with
curing ages:
f = A0 + A1 t1=2 + A2 t
5 PEMO
f = A0 + A1 t1=2 + A2 t + A3 t3=2
6 PEMT
f = A0 + A1 t1=2 + A2 t + A3 t3=2 + A4 t2
7 PEMTh
f = A0 + A1 t1=4 + A2 t1=2 + A3 t3=4 + A4 t1
11 PEMF
f = A0 + A1 t1=4 + A2 t1=2 + A3 t3=4 + A4 t1 + A5 t5=4 + A6 t3=2
3.1 Heavy metal concentration in DSW

and leachate samples
In the current study, concentration of five heavy metals like
Fe, Cu, Cd, Ni and Cr in LDSW and effluent (Outflowing to
the surface water body) leachate samples collected from
MSLS were examined. The average concentration of tested
heavy metals are presented in Table 3. In DSW, the study
observed that Fe was the highest concentration about
11,233.35 mg/kg at MSLS. Similar results of Fe concentration
was observed in landfill waste by Oluyemi et al. [42],
Mamtaz and Chowdhury [43] and Esakku et al. [44] about
4,130.02 mg/kg, 9,600 mg/kg and 20,485 mg/kg respectively. Cu content was found greater about 260.675 mg/kg
than the observation of Esakku et al. [44], almost 169.9 mg/
kg. Moreover, the study revealed the significant level of rest
of the three tested metals such as Ni, Cr and Cd contents in
DSW as compared to the observations of Adjia et al. [45],
Mamtaz and Chowdhury [43] and Esakku et al. [44].
Though the average concentration of Cd and Cr in
outflowing treated leachate samples were observed to be
safety limit (Table 3) according to the BECR [27], the
contents of Fe, Cu and Ni were found not safe for disposal
to the near surface water body at landfill site, since they
exceed the Bangladesh standards that may be pointed
out a potential risk of metals entrance into food chain
through overflow of landfill site due to heavy rainfall
and leachate disposal to the surrounding environment.
Therefore, solidification/stabilization of landfill waste
may be a promising solution to prevent the metal intrusion and contamination into the environmental cycle.
12 PEMFv
f = A0 + A1 t1=4 + A2 t1=2 + A3 t3=4 + A4 t1 + A5 t5=4
+ A6 t3=2 + A7 t7=4 + A8 t2
13 PEMS
The estimation of Model parameters was done following

non-linear techniques using MATLAB (R2015a).
3.2 Characteristics of SWM ingredients

As the LDSW was used as the partial replacement of sand in
the mortar specimen, physical properties of sand and LDSW

Table 2: Goodness of fit indicators for the selection of fitted model.

Parameter
Expression
Reference
Correlation coefficient (r)
P
P P
xy
x
y
r = q
P 2 P 2 q
P 2 P 2
n
x
x
n
y
y
Coefficient of determination (R-squared)
12
Pn
Oi O pi p
i=0
@
q
R =
A; oi
pP
Pn
2
n
2
pi p
Oi O
i=0
i=0
Adjusted R-squared
R2 = nn k1SSE
SST ; Here, n = Nos. of observations, k = Nos. parameter in model,
SSE = Sum of squares error; SST = Total sum of squares.
[]
Observed data pi = Predicted data
PN
oi pi 2
NSE = 1 PNi = 1
2 ; = Mean of observed data
Oi O
i=1
PN
oi pi 2
cp = 1 PN i =1 2
2
Oi + 1 O
i=1
PN
Oi pi 2
d = 1 PN i = 1
2
p
j
i Oj + jOi Oj
i=1
NashSutcliffe efficiency (NSE)

Coefficient of persistence (cp)
Index of Agreement (d)
KGE = 1 ED
q
ED = s1 r 12 + s2 vr 12 + s3 12
Kling-Gupta Efficiency (KGE)
[,]
[]
[,]
[]
[,]
[]
r = Person product moment correlation coefficient

= s =o

, method = 2009
vr =
, method =2012
= s = 0
=
Root mean square error (RMSE)
CVs
CV0
= 0s =s
0
s
N
P
rmse = N1
Oi pi 2
[]
PN
o pi
i=1 i
PBIAS = 100* P
N
[]
i=1
Percent bias (PBIAS)
i=1
Weighted coefficient of determination (wr)
Oi
wr2 = |b|R2, |b| 1; br2 = jRbj, b>1; b = Slope of the regression

line between observed and predicted data
[,]
Schwarz Bayesian Information Criteria (SBIC)
K + 1
AICC = 2 lnL + 2K + 2K
n K 1 ; ln(L) = Likelihood function for the model,
n = Number of observations, K = Number of estimated parameters
of the model.
SBIC = 2 lnL + K lnn
HannanQuinn information criterion (HQC)
HQC = 2 lnL + 2K lnlnn
[]
Mallows Cp
Cp = RSS
2 n 2k; RSS = Residual sum of squares,
2 = Residual mean square error.
[]
Akaike Information Criteria (AICc) (Second

order). Generally used when n/k < .
Table 3: Concentration of heavy metals in DSW and effluent leachate

of MSLS.
Heavy
Metal
Fe
Cu
Ni
Cr
Cd
DSW (mg/kg)
,.
.
,.
.
.
.
.
.
.
.
Effluent
leachate
(mg/l)
.
.
.
.
.
.
.
.
.
.
Inland surface water

quality standard
(mg/l) []
.
.
.
.
.
[,]
[,]
were analyzed in mix condition to measure the values with

quality parameters and the level of effectiveness and efficiency for using waste as fine aggregate in constructional
purposes. The study revealed that water absorption capacity and moisture content in mix condition of study sample
were slightly higher due to the presence of LDSW. Waste
sample was organic matter which generally absorbs higher
water amount than inert material like sand. Otherwise, rest
of the examined parameters showed quite similar results
with the reported studies. Experimental results of SWM
ingredients characteristics are represented in Table 4.

Table 4: Physical characteristics of mixed MLSW and sand as fine

aggregate.
Parameters
Dry density (gm/cm)

Bulk density (gm/cm)
Specific gravity
Water absorption capacity (%)
Moisture content (%)
Porosity (%)
Fineness modulus
pH
Experimental
values
.
.
.
.
.
.
.
.
.
.
.
.
.
.
References
. []
. []
. [, ]
. [, ]
. []
[]
.. []
In the study OPC was used as stabilizing agent. The

chemical compositions and different properties of OPC
are given in Table 5, which were analyzed in the laboratory. The examined results showed the quite well as
compared with the standard and reported studies that
ensured as a binding material to be used for the solidified
waste mortar.
3.3 Leaching characteristics of Fe, Cu

and Ni ions
Leaching is generally considered as the basic criterion to
evaluate the safety, acceptability and the chemical behavior of the final waste forms in the disposal site [52]. The
cumulative migration characteristics of Fe, Cu and Ni
from Solidified waste mortar block (SWMB) to curing
leachant with the increases of curing ages are shown in
Figure 4. It could be noticed clearly from Figure 4 that the
rate of Fe, Cu and Ni release contents were high at early
ages of leaching and then decreased with the increases in
leaching duration. The cumulative releasing behavioral
curves of Fe, Cu and Ni can be characterized by three
distinct regions. 1st region from 1 to 7 days, observed
highest leaching trend ranges from 0.483 mg/l to 0.951
mg/l, 0.039 mg/l to 0.108 mg/l and 0.166 mg/l to 0.416
mg/l for Fe, Cu and Ni respectively. 2nd region from 7 to
56 days, slightly lower releasing content was found than
1st region whereas drastic reduction of metal releasing
Table 5: Properties and chemical analysis of OPC.

Parameters
Physical property
Fineness (%)
Consistency Limit (%)
Initial setting time (min.)
Final setting time (min.)
Specific Gravity
Mechanical property
Compressive strength (MPa)
days
days
days
Experimental values
. .
. .

. .
. .
. .
. .
References
not less than % (ASTM standard)

% % by weight (ASTM standard)
not less than minutes (ASTM standard)
not more than minutes (ASTM standard)
. [IS: (Part -)]
Minimum . (ASTM standard)

Chemical composition (%)

Oxides
CaO
SiO
AlO
FeO
SO
MgO
Loss on Ignition (LOI)
Insoluble Residue (IR)
NaO + . KO
Free Lime (FCaO)
.
.
.
.
.
.
.
.
.
.
[]
[]
. []
. []
Maximum
Maximum
Maximum
Maximum
Maximum
Mineral composition (%)

CS
CS
CA
CAF
LSF
.
.
.
.
.
(Test results by ASTM C )

% []

. (ASTM standard)
. (ASTM standard)
. (ASTM standard)
. (ASTM standard)
. (ASTM standard)
Leaching of Heavy metal (mg/l)
1.4
1.2
Fe (mg/l)
Cu (mg/l)
0.8
Ni (mg/l)
0.6
0.4
0.2
0
0
20
40
60
80
100
120
140
160
180
200
Curing age (Day)
Figure 4: Cumulative leaching characteristics of Fe, Cu and Ni from SWMB.
from 56 to 180 days curing ages. Similar results were

observed in some reported studies in the literature [15, 53].
Moreover, a major reason of metal ion release rate
reduction is that compressive strength of waste mortar
block increases over the curing age due to the hydration
of binding material like OPC (Figure 5). Compressive
strength and structural integrity bond develops for the
hydration of OPC with the presence of water. The metal
ion species are strongly captured and pore spaces in
waste forms decreased day by day. Therefore, migration
rate of metal ion contents are impeded from SWMB
through diffusion.
3.4 Controlling leaching phenomena

of Fe, Cu and Ni
In some reported studies [1517, 54] the contaminant
content releasing phenomena from waste forms are characterized by three distinct parts such as surface-wash off,
diffusion and dissolution. But under the which region
contaminants leachates from the waste matrices in the
duration of leaching, to determine it, some researchers
[53, 55, 56] indicated that controlling leaching mechanism
could be conducted based on the slope of the linear
30
0.27
0.24
0.21
0.18
0.15
0.12
0.09
0.06
0.03
0
25
20
15
10
5
0
20
40
60
80
100
120
140
160
180
CS of SWMB (MPa)
Incremental rate (mg/d)
tendency or quite steady state condition observed in 3rd

region from 56 to 180 days curing ages.
The study revealed the cumulative leaching concentration of Fe, Cu and Ni were about 1.29 mg/l, 0.18 mg/l and
0.63 mg/l respectively up to 180 days static leaching test
period that satisfied the surface water quality standard [27]
by using the mixing proportion of 1:2. These leaching results
ensured the potentiality of waste product as reusable with
environmental safety. The leach incremental rate of Fe, Cu
and Ni with the development of waste mortars compressive
strength over the examined period are graphically depicted
in Figure 5. Before the immersion of waste mortar block in
curing leachant, ionic species contents are fully encapsulated or entrapped within the waste matrix. At the initial
contact time of curing, incremental rate of each ion release
was high. This trend could be attributed to the washout
of the loosely bounded surficial compounds of the waste
block [52]. When each ion has been leached out from the
surface of the block [16] incremental rate dramatically
reduced in release from 1st region to 2nd region that is
maintained over a longer period of curing time (Up to 180
days) by longer pathways from the bulk through diffusioncontrolled stage, which determines the long term leaching
behavior of the block [15, 16]. Even the study observed
that the rate is reduced to about zero in the 3rd region
Fe
Cu
Ni
CS
0
200
Curing age (Day)
Figure 5: Leaching incremental rate of Fe, Cu and Ni with CS development and curing age.

regression of the logarithm of CLF versus the logarithm of

time. If the slope is less than 0.35 the controlling leaching
mechanism will be the surface wash-off, for the slope
values ranging from 0.35 to 0.65 the controlling mechanism will be the diffusion, and higher slope values represent the dissolution mechanism [10, 53, 57]. The plots of
the log(Fe, Cu and Ni concentration) versus log(Curing
duration) are shown in Figure 6. From the result of the
linear regression for Fe, Cu and Ni leaching content using
logarithm, it can be clearly concluded that the values of
the correlation factor (R2) have high values for three
tested metal ions leaching. The values of the slopes for
Fe, Cu and Ni are less than 0.35 (Figure 6) which indicate
that surface wash-off govern the leaching phenomena.
That means Fe, Cu and Ni contents only migrated from
the surface of studied waste mortar during the whole
curing period that confirms the studied waste mortar

can be catalogued as sustainable potential re-usable
material in the construction field.
3.5 Calibration of fitted leachate Model

and parameter estimation
The prediction of Fe, Cu and Ni transport phenomena trend
(Figure 4) from the studied SWMB, the experimental leachate data of Fe, Cu and Cu were fitted to the five nonlinear equation based Models such as diffusion equation
(DE), polynomial equation (PE), logarithmic equation (LE),
exponential equation (EE) and power equation (Power E) as
illustrated in Figures 79. From the visual observation of
Figures 79, it could be concluded that for the studied
Log (Heavy metal content)
0.3
0.1
y = 0.1807x 0.2118
R2 = 0.8504
0.1
0.3
Fe
y = 0.2601x 0.6794
R2 = 0.8742
0.5
Cu
0.7
Ni
0.9
y = 0.299x 1.305
R2 = 0.8862
1.1
1.3
1.5
0
0.25
0.5
0.75
1.25
1.5
1.75
2.25
2.5
Log (Curing age)
Figure 6: Controlling leaching phenomena identification of Fe, Cu and Ni.
Leaching of Fe (mg/l)
2
Fe
DE
PE
LE
EE
Power E
1.5
1
0.5
0
0
20
40
60
80
100
120
140
160
180
200
Curing age (day)
Figure 7: Calibration of non-linear models with the Fe leaching concentration.
Leaching of Cu (mg/l)
0.3
0.25
Cu
DE
PE
LE
EE
Power E
0.2
0.15
0.1
0.05
0
0
20
40
60
80
100
120
140
160
180
200
Curing age (day)
Figure 8: Calibration of non-linear models with the Cu leaching concentration.

10
Leaching of Ni (mg/l)
1
0.8
Ni
DE
PE
LE
EE
Power E
0.6
0.4
0.2
0
0
20
40
60
80
100
120
140
160
180
200
Curing age (Day)
Figure 9: Calibration of non-linear models with the Ni leaching concentration.
waste matrix, the DE, LE, EE and power E Model cannot

represent the experimental observations adequately during
the whole examined curing period. In every cases, the
polynomial equation based Model were found to be successful and quite good for demonstrating the experimental
releasing behavior of metal ion contents from the waste
matrix. Although metal ion species releasing phenomena
associated with the matter of diffusion based, diffusion rate
is not a controlling factor because the diffusion path was
longer. The reason is that diffusion rate rapidly occur at the
initial period but gradually slow down with the leaching
time elapsed. Moreover, LE, EE and power E Model underestimates the releasing profile of Fe, Cu and Ni that shows
unrealistic leaching pattern (Figures 79). In order to assess
the better calibration statistically of the leachate Models to
the experimental observations, goodness of fit indicators
like R2 and RMSE values were calculated which are shown
in Table 6. Statistical analysis shows that polynomial equation Model have ability to explain each data point for that
matter R2 was found greater and RMSE also lower as compared to the other fitted Models.
Table 6: Statistical evaluation of fitted leachate models for Fe, Cu
and Ni.
Heavy
metal
Parameter
Fe
R
RMSE
R
RMSE
R
RMSE
Cu
Ni
DE
PE
LE
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
EE Power E
.
.
.
.
.
.
.
.
.
.
.
.
3.6 Statistical comparison of fitted PE

Models for well calibration
Several techniques have been used by the previous
researchers to provide a comparison between the simulated
and measured data. In the study, quantitative and graphical

technique were used to evaluate the better demonstrating
leachate Model of Fe, Cu and Ni from the SWMB. Graphical
technique provide a visual comparison and a first overview
of Model performance [33, 58] and are essential to appropriate Model evaluation [29, 31].
3.6.1 Goodness of fit indicators

The number parameters of the fitted PE Model were
extended in different terms as trial basis for the well calibration to the experimentally generated leaching data of Fe,
Cu and Ni (Figure 4). From the visual examination of
Figures 1012, it is clearly seen that PE Models shows
comparatively better calibration with the increases of parameter from 3 to 5 (From PEMO to PEMTh). But reverse result
is seen for further extension of parameters. PE Model with 7
and 9 parameters (PEMTFv and PEMS) are shown deviated
profile with the experimental metal release contents. The
visual analysis revealed that PEMTh and PEMF with 5 parameters shows well calibration by comparison whereas
PEMTS with 9 parameters cannot represent the experimental data adequately (Figures 1012) that describes the most
unrealistic predicted pattern. For the selection of PE based
well calibrate leachate Model among the six fitted, the
statistical analysis using goodness of fit parameters are
shown in Table 6 that measure the how well the experimental data points fit the PE based regression Models. In
the study, goodness of fit parameters are calculated using
the simulated data predicted from PEMO to PEMTS and
experimental observed data. The analysis shows a specific
trend that is, fitting the experimental leaching data of Fe, Cu
and Ni to the fitted PE Models resulting in a high accuracy of
each statistical parameter with the increases of parameters
from PEMO to PEMTS, which confirm that PEMTS is better
than other Models to represent the leaching data (Table 7).
However, it is quite reverse result than visual examination.
The reason behind that if the parameter of PE based Model

Concentration of Fe (mg/l)
11
1.5
Fe
PEMO
PEMT
PEMTh
PEMF
PEMFv
PEMS
1.3
1.1
0.9
0.7
0.5
20
40
60
80
100
120
140
160
180
200
Curing age (Day)
Figure 10: Calibration of PE Models for demonstrating the Fe migration phenomena.
Concentration of Cu (mg/l)
0.4
0.35
0.3
Cu
PEMO
PEMT
PEMTh
PEMF
PEMFv
PEMS
0.25
0.2
0.15
0.1
0.05
0
20
40
60
80
100
120
140
160
180
200
Curing age (Day)
Figure 11: Calibration of PE Models for demonstrating the Cu migration phenomena.
Concentration of Ni (mg/l)
0.9
0.8
Ni
0.7
PEMO
PEMT
0.6
PEMTh
0.5
PEMF
0.4
PEMFv
0.3
PEMS
0.2
0.1
20
40
60
80
100
120
Curing age (Day)
140
160
180
200
Figure 12: Calibration of PE Models for demonstrating the Ni migration phenomena.
increases, it explains or touch the each data point in a better

way but deviates from the original smooth curve line of
experimental data. As the simulated data predicted by
PEMTS are almost near to experimental observations, therefore goodness fit parameters of PEMTS shows better results
than other fitted Models.
3.6.2 Model selection based on information criteria

The Model selection problem can be tackled using a traditional approach in which parameter learning is repeated on
a set of candidate Model scales among which one is selected
by a Model selection criterion [39] like AIC, SBIC, HQC and
Mallows cp. AIC means the Akaike Information Criterion

that is useful in selecting the best Model in the set [36]. In
addition, AIC is designed to select the Model that will predict best and is less concerned with having a few too many
parameters. Schwarz Bayesian Information Criterion (SBIC)
is designed to select the true values of parameters exactly
like AIC. SBIC can be used to compare in sample or out
of sample predicting performance of a Model. The
Hannan-Quinn Criterion (HQC) for identifying an autoregressive Model denoted by HQ (p) was introduced by
Hannan and Quinn (1979). The best Model is the Model
that corresponds to minimum HQC [59]. These criteria
attempt to select a Model with small generalization error,
by trading off between the likelihood-based goodness of fit

12
Table 7: Model evaluation based on goodness of fit parameters.

Parameter
Heavy metal
PEMO
PEMT
PEMTh
Fe
Cu
Ni
.
.
.
.
.
.
.
.
.
R-squared
Fe
Cu
Ni
.
.
.
.
.
.
Adjusted R-squared
Fe
Cu
Ni
.
.
.
NSE
Fe
Cu
Ni
cp
PEMFv
PEMS
Standard range
.
.
.
.
.
.
.
.
.
[, + ]
.
.
.
.
.
.
.
.
.
.
.
.
to
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
to
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
and .
Fe
Cu
Ni
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
to
Fe
Cu
Ni
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
to
KGE
Fe
Cu
Ni
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
and .
rmse
Fe
Cu
Ni
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
Minimum value is taken.
pbias
Fe
Cu
Ni
br
Fe
Cu
Ni
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
and Model complexity subject to noise and uncertainty in a

finite number of observations [39]. In the current study,
statistical analysis using information criterion including
AIC, SBIC, HQC and Mallows cp for Model selection
shows the similar results with the goodness of fit parameters and contrast with visual observation. In addition,
the study found a trend for PE Models that is, the lower
number of parameters the lower value of AIC, SBIC, HQC
and Mallows cp. Generally, the Model bear the comparatively lower value of AIC, SBIC, HQC and Mallows cp is
selected as the better Model. The calculated values from the
analysis of AIC, SBIC, HQC and Mallows cp (Table 8), it is
clearly seen that PEMO shows the lowest values. Therefore,
according to the principle, PEMO is better Model to represent the Fe, Cu and Ni leaching data than other fitted
Models that is opposite result of visual examination.
PEMF
.
.
.
Optimal value is
Maximum value is
3.6.3 Slope and y-intercept

The slope and y-intercept of the best-fit regression line can
indicate how well simulated data match with measured data.
The slope indicates the relative relationship between the
simulated and measured data. The y-intercept indicates the
presence of a lag or lead between Model predictions and
measured data, or that the data sets are not perfectly aligned
[29, 60]. The current study compared the well calibration
between the simulated PE Models curves to the experimentally measured data of Fe, Cu and Ni ion leaching curves
(Figures 1012) using slope and y-intercept of the best-fit
regression line which are shown in Table 9. The slope and
y-intercept of the simulated curves were calculated by three
distinct parts based on the three regions which is already
mentioned in Section 3.3. The comparative analysis shows

13
Table 8: Model selection based on statistical information criteria.

Parameter
Heavy metal
AIC
Fe
Cu
Ni
Fe
Cu
Ni
Fe
Cu
Ni
Fe
Cu
Ni
SBIC
HQC
Mallows cp
PEMO
PEMT
PEMTh
PEMF
PEMFv
PEMS
Standard value
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
Minimum value is taken
Table 9: Comparison of slope and intercept between the experimental observations and fitted PE models.
Parameter
Heavy metal
Slope
Intercept
Curing days
Experimental observation
PEMO
PEMT
PEMTh
PEMF
PEMFv
PEMS
Fe
to
to
to
.
.
.
.
.
.
.
.
.
.
.
.
.
.

.
.
.
.
.
.
Cu
to
to
to
.
.

.
.

.
.

.
.

.
.

.
.

.
.
.
Ni
to
to
to
.
.
.
.
.
.
.
.

.
.
.
.
.
.
.
.

.
.
.
Fe
to
to
to
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
Cu
to
to
to
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
Ni
to
to
to
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
that slope and y-intercept values of simulated curve by

PEMTh are quite similar with the Fe, Cu and Ni ion leaching
curves (Table 8). Moreover, it can be concluded that PEMTh
can demonstrate the experimental metal ion leaching contents profile with curing ages quite well than other five fitted
PE Models. Although PEMTF can explain approximately
the phenomena but PEMTh can better that result shows
similar with the visual examination of the figures whereas
the goodness of fit parameters and information criterion
measures opposite results. So, the study suggests based on
the visual examination and comparison results using slope
and y-intercept, PEMTh can be used to represent the leaching
phenomena.
The accuracy of the PE Models calibration result was

justified through statistical comparison. Goodness of fit
parameters and information criterion were calculated
using the statistical software R.
3.7 Statistical significance test of

well-calibrated PE Model parameters
The parameter estimation outcomes of well-calibrated
PEMTh for Fe, Cu and Ni are presented in the Table 10.
Parameters were calculated with their 95 % confidence

14
Table 10: Estimated parameters of model 03 with statistical significant test.

t-stat
p-value
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
Heavy metal
Parameter
Estimate
Fe
A
A
A
A
A
.
.
.
.
.
Cu
A
A
A
A
A
Ni
A
A
A
A
A
Std. Error
interval. The study tested the statistical significance level

of each parameter using t and p-value statistics. The tvalue measures the ratio between the coefficient and its
standard error whereas p-value quantify the statistical
significance level of parameter. If the p-value of each
parameter is less than the significance level (e. g., p <
0.05), then it can be conclude that the parameter reflects
the characteristics of the Model. Otherwise, parameter
will be rejected [61, 62]. In this study, the significant
test analysis shows that p-value of all the parameters in
prediction PEMTh are in significance level that indicates
their strength of the evidence against the null hypothesis
(Table 10). The analysis also revealed that parameter A2
gives the very strong evidence against the null hypothesis
because of the lowest p-value. That means A2 has greater
level of statistical significance on PEMTh than the rest of
four parameters to predict the three tested metal ion
species. Depends on the p-value, the significance level
Range of p-value
Significance level if p < .
and
Insignificance level if p > .
of five parameters on PEMTh can be ranked as A2 > A3 >

A4 > A1 > A5.
3.8 Statistical prediction bounds

of well-calibrated PE Model
Statistical prediction bounds of PEMTh with 95 % confidence intervals for Fe, Cu and Ni are presented in the
Figures 1315 respectively. Each figure contains the three
curves such as the fit, the lower confidence bounds, and the
upper confidence bounds. The confidence interval consists
of the space between the two curves (dotted lines).The fit
means fitted of PEMTh to the experimentally generated data
and the bounds reflect a 95 % confidence level. Confidence
interval with 95 % means there is a 95 % probability that the
fitted line of PEMTh for the Fe, Cu and Ni leaching data will
lie within the confidence interval.
Figure 13: Fitted prediction PEMTh for Fe leaching contents with 95 % prediction bounds.

15
Figure 14: Fitted prediction PEMTh for Cu leaching contents with 95 % prediction bounds.
Figure 15: Fitted prediction PEMTh for Ni leaching contents with 95 % prediction bounds.
4 Conclusion
Fe, Cu and Ni leaching phenomena from solidified landfill
waste matrices were evaluated by performing static leaching tests. The major conclusions pertaining to the findings
presented herein may be drawn from this research:
(1) The leaching contents of studied metal ions were
substantially reduced from waste matrices at
28 days curing age and similar result observed up
to 180 days that confirms the waste mortar block
to be used as an environmental friendly re-usable
product.
(2) Compressive strength test result was found quite satisfactory value 19.1 MPa at 28 days curing age that fulfill
the paving block standard (15 Mpa) in Bangladesh.
(3) The only surface wash off leaching phenomena was
found to control Fe, Cu and Ni leaching contents
that ensure the safe disposal of the product.
(4) By fitting the experimentally generated data to some
well-established non-linear models, it was revealed by
the visual examination and statistical analysis that the
migration phenomena of the studied metal ions from
(5)
(6)
(7)
landfill waste mortar block can be represented quite

well by semi-empirical Model PE for longer period.
From the statistical analysis, it was found that PE
Model bearing five parameters (PEMTh) with 0.5
power interval with each parameter can well explain
the leaching phenomena during the whole immersion
period in leachant that fails to prove using goodness of
fit indicators and information criteria like AIC, SBIC,
HQC and Mallows cp.
Experimental leaching behavior of Fe, Cu and Ni
versus curing age can quite describe using slope
and intercept of the fitted PEMTh curves.
It is recommended that the outcome of the study may
be a potential solution to recycle the landfill waste as
re-usable by product like paving blocks, road construction materials, etc. using S/S process.
Acknowledgements: The Author would like to acknowledge the authority of Dhaka City Corporations for the
permission to collect the decomposed solid waste and
leachate samples from Matuail Sanitary Landfill Site.

16
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Chem. Prod. Process Model.

A Statistical Comparison of Mathematical Models

Abstract: In this research, landfill solid waste was solidified

*Corresponding author: M. Aminul Haque, Department of Civil

Authenticated | mahaque@lus.ac.bd author's copy

M. A. Haque: Statistical Comparison of Mathematical Models

slag, silica fume, natural pozzolans as well as novel cement

Interface of leachant and waste block

Metal release from waste

Figure 1: Diffusion based static leaching test.

Figure 2: Conceptual model of contaminants leaching mechanisms

Switzerland, PSI, A. Wallisch

Long-term mechanical stability and leaching behaviour of a solidified radioactive sludge.

China, NUDT, S. Bai, S. Yang

Authenticated | mahaque@lus.ac.bd author's copy

M. A. Haque: Statistical Comparison of Mathematical Models

added an additional conception of leaching phenomena.

Where f = Cumulative fraction leached of heavy metals. De

Similarly, Plecas and Dimovic [25] and Plecas and

In the current study, concentration of five heavy

2 Materials and methods

2.1 Experimental approach

To generalize the Model equation (3) can be expressed as,

As the diffusion rate gradually slow down with the

Plecas [24] applied polynomial equation based Model up

Authenticated | mahaque@lus.ac.bd author's copy

M. A. Haque: Statistical Comparison of Mathematical Models

OPC (Type I and 52.5 grade)

Sieve < 2mm dia.

Sand and LDSW:

Physical characteristics of waste mortar:

Compressive strength test

Mortar specimen cured for compressive strength

Leaching water collection at 1-7, 14, 21, 28, 56, 90

Take Decision. Is it satisfy the metal release standard of BECR

Measurement of heavy metals concentration in curing

Comparison of heavy metal leaching concentration

Compare the compressive strength value of solidified waste mortar

If satisfied, then simulate mathematical models for

Use goodness of fit indicator parameters to select the best

2.2 Fitting of the leachate Models

Authenticated | mahaque@lus.ac.bd author's copy

M. A. Haque: Statistical Comparison of Mathematical Models

heavy metal migration phenomena from SLWM. Fitted

Polynomial equation based Model:

2.4 Evaluation of fitted leachate Models

Logarithmic equation based Model:

3 Results and discussions

4. Exponential equation based Model:

Power equation based Model:

2.3 Parameter extension of well-fitted

f = A0 + A1 t1=4 + A2 t1=2 + A3 t3=4 + A4 t1

f = A0 + A1 t1=4 + A2 t1=2 + A3 t3=4 + A4 t1 + A5 t5=4 + A6 t3=2

3.1 Heavy metal concentration in DSW

The estimation of Model parameters was done following

3.2 Characteristics of SWM ingredients

Authenticated | mahaque@lus.ac.bd author's copy

M. A. Haque: Statistical Comparison of Mathematical Models

Table 2: Goodness of fit indicators for the selection of fitted model.

Correlation coefficient (r)

Coefficient of determination (R-squared)

Observed data pi = Predicted data

NashSutcliffe efficiency (NSE)