Journal of Environmental Chemical Engineering 1 (2013) 581588

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Journal of Environmental Chemical Engineering

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Adsorption of nickel(II) and copper(II) ions from aqueous solution by

coal y ash
Eleonora Soco *, Jan Kalembkiewicz
Department of Inorganic and Analytical Chemistry, Faculty of Chemistry, Rzeszow University of Technology, Powstancow Warszawy Ave. 6, PL-959 Rzeszow, Poland

A R T I C L E I N F O

A B S T R A C T

Article history:
Received 13 March 2013
Received in revised form 3 June 2013
Accepted 26 June 2013

The research on adsorptive properties of coal y ash was carried out. The results obtained on the
adsorption of copper and nickel were analyzed by the well known models given by Langmuir and
Freundlich. For the sorption isotherms, initial metal ion concentration varied while the pH of solution
and adsorbent weight in each sample held constant. The sorption isotherms were researched with
copper and nickel. The inuence of pH (310), blend time (0.54 h) and the initial concentration of Cu(II)
and Ni(II) ions (5100 mg L1) was researched on adsorption/desorption of analyses elements from/to
the aqueous solutions by using coal y ash. Optimum conditions of adsorption/desorption of Cu(II) and
Ni(II) ions in studied systems were established. The coefcient of adsorption/desorption on the basis of
Freundlich and Langmuir equation was found.
2013 Elsevier Ltd All rights reserved.

Keywords:
Coal y ash
Nickel(II)
Copper(II)
Adsorption
Freundlich and Langmuir isotherms

Introduction
Coal y ash is a particulate material produced from the
combustion of coal in thermoelectric power plants. According to
the World Energy Council, as of 2009, China held an estimated
103.8 Gt of recoverable coal reserves, the third-largest in the world
behind the United States and Russia and about 14% of the worlds total
reserves. In recent years, coal made up about 74% of Chinas total
primary energy consumption and about 60% of the chemical
materials derived from coal products [13]. The amount of coal y
ash generated in Poland was 4.2 Gt per year, of which 52% (2.2 Gt)
was recycled while the rest was land-lled [4]. Ash contamination
poses a serious threat to environment. The conrmed presence of
heavy metals in y ash their bioactivity and biotoxicology, rst of all,
their mobility can cause signicant environmental problems.
Contamination during disposal of y ash, as well as interaction of
y ash and heavy metals in the environment is very limited. A lot of
investigations have revealed that leachable coal ash contaminants
[5], particularly arsenate, chromium [68], selenium, boron, strontium, and barium, have different effects on the quality of impacted
environments. Trace elements in coal can provide useful information
from an environmental point of view for possible pollution control of
toxic trace elements during coal combustion and utilization [3]. Some
valuable trace elements (e.g., Au, Ge, Ga, Nb, Zr, U, Re, REE, and PGE)
are enriched in some coals or coal-bearing strata, and, thus are being
or can be potentially recovered from coal ashes [3,9].

* Corresponding author. Tel.: +48 178651508.

E-mail address: eleonora@prz.edu.pl (E. Soco).
2213-3437/$ see front matter 2013 Elsevier Ltd All rights reserved.
http://dx.doi.org/10.1016/j.jece.2013.06.029

Coal y ash, the inorganic residue from the combustion of

powdered coal has, for many years, been considered a waste
material, the production of which has continued to increase, hence,
the motivation to look for possible industrial applications [10,11].
In the present study, efforts have been made to investigate the use
of coal y ash as an economical adsorbent [12,13] for removing
heavy metals from aqueous solutions due to its abundance and
easy availability. Processes for metal removal like adsorption have
been suggested as being cheaper and more effective than the other
technologies, such as chemical precipitation, solvent extraction,
electrolytic processes, membrane separation, ion-exchange, reverse osmosis or biological systems [14,15]. Coal y ash has
potential use in wastewater treatment because of its major
chemical components, which are alumina, silica, ferric oxide,
calcium oxide, magnesium oxide, and carbon, and its physical
properties, such as porosity, particle size distribution, and surface
area [6]. Several studies reported that signicant amounts of heavy
metals were removed from solution by adsorption on coal y ash, a
byproduct of thermal power units. Srivastava et al. [13] have
recently shown the feasibility of using coal y ash as an adsorbent
for the individual and simultaneous removal of Cd(II) and Ni(II)
ions from single metal solutions. For each single metal, batch
experiments were designed for the sorption process and batch
kinetics and isotherm studies were conducted to determine the
adsorption capacity of coal y ash. Nascimento et al. [16], present
study, the adsorption properties of synthetic zeolite produced from
Brazilian coal y ash were investigated for some heavy metal
cations (Zn, Cu, Mn and Pb). Gupta and Ali [12] and Bayat [17], the
bagasse coal y ash, a byproduct of sugar industries, has been
converted into an inexpensive and effective adsorbent for the

E. Soco, J. Kalembkiewicz / Journal of Environmental Chemical Engineering 1 (2013) 581588

582

Nomenclature
A
C0
ads
Caq

Csads
V0
mads
KFads
KLads
n
D
KFdes
KLdes
Csdes
des
Caq
ads
C1
des
C1

VT
tads
tdes
t
LOI
I
FAAS
CRM
RSD
REE
PGE

adsorption percentage (%)

initial concentration of adsorbate in solution
(mg L1)
unadsorbed concentration of component in aqueous solution at adsorption equilibrium (mg L1) or
(ppm)
content of adsorbate in coal y ash at adsorption
equilibrium (mg mg1)
initial volume of aqueous phase under adsorption
(mL) or (L)
mass of adsorbent (coal y ash) (g)
Freundlich adsorption coefcient (L mg1)
Langmuir adsorption coefcient (L mg1)
Freundlich heterogeneity factor of each component
desorption percentage (%)
Freundlich desorption coefcient (L mg1)
Langmuir desorption coefcient (L mg1)
content of adsorbate in ash at desorption equilibrium (mg mg1)
content of adsorbate in aqueous solution at
desorption equilibrium (mg L1) or (ppm)
maximum content of adsorbate in ash at adsorption equilibrium (mg g1)
maximum content of adsorbate in ash at desorption equilibrium (mg g1)
total volume of aqueous phase under desorption
(mL) or (L)
adsorption time (h)
desorption time (h)
temperature (8C)
loss on ignition
ionic strength
ame atomic absorption spectrometry
certied reference material
relative standard deviation
rare earth element
platinum group elements

removal of copper, nickel and zinc from wastewater. Various

parameters such as pH, contact time, adsorbent dose, initial metal
ions concentrations, temperature, and particle size were optimized. The adsorption was found to be endothermic in nature and
follows both the Langmuir and Freundlich models. Taking into
account the dominating metal species, which are Ni2+, NiOH+,
Cu2+, Cu(OH)+, Cu(OH)2, Zn2+ and ZnOH+ according to the simple
species diagrams constructed by Panday et al. [18] and Hsu et al.
[19] for Ni(II), Cu(II) and Zn(II), respectively, at the pH values
where the maximum adsorption of the metal took place, the
maximum Ni(II) and Zn(II) adsorption capacity of the coal y
ashes can be attributed to the electrostatic interaction of the
adsorbate with surface silica and iron sites. Ricou-Hoeffer et al.
[20] have reported that aluminosilicate compounds in the y
ashes may also be involved in the adsorption phenomena through
a SiO bond with ve metallic ions (Cu2+, Ni2+, Zn2+, Cd2+, Pb2+).
Similarly Zhu et al. [21] adsorption of copper(II) ions from aqueous
solution by means of coal y ash and bentonite complex were
studied. Adsorption of nickel(II) ions in research systems is
described in the paper of Kalyani et al. [22]. Toxic heavy metals, i.e.
copper(II), lead(II) and cadmium(II), can be removed from water

by metallurgical solid wastes, i.e. bauxite waste red muds and coal
y ashes acting as sorbents [23]. The distribution ratios of metals
between the solid sorbent and aqueous solution have been found
as a function of sorbent type, equilibrium aqueous concentration
of metal and temperature. Wang et al. [24] the removal of copper
and nickel ions on the treated coal y ash have researched. The
pseudo second-order kinetics would be better for tting the
dynamic adsorption of Cu and Ni ions. Similarly Papandreou et al.
[25], the application of y ash porous pellets as adsorbent of
lead(II), zinc(II) and chromium(III) ions from aqueous solution
was studied. Adsorption isotherms of lead, zinc and chromium
were determined for agglomerated material using the Langmuir
equation. Cho et al. [10] the purpose of this study was to
investigate the possibility of the utilization of coal y ash as a
cheap adsorbent for the removal of heavy metals in aqueous
solutions if not strongly acidic. Kinetic experiments were also
performed and the zeta-potentials of the coal y ash particles
were measured at various pHs. Li et al. [26] the experiments to
determine the adsorption of calcium lignosulfonate (CLS) onto
Shand and Boundary Dam (BD) coal y ashes were performed.
Gangoli et al. [27] reported that the surface of silica (SiO2) might
exhibit considerable afnity toward metal ions. The central ion of
silicates (Si4+) has a very strong afnity for electrons; therefore,
the oxygen atoms that are bound to the silicon ions have a low
basicity, making the silica surface act as a weak acid. Visa et al. [28]
proved that the Class F y ash (FA), with oxides composition
SiO2/Al2O3 over 2.4 proved good adsorbent properties. The FA was
used for removing the Pb2+, Cd2+ and Zn2+ cations from mixed
solutions. The optimized adsorption parameters were further
used in thermodynamic and kinetic studies of the adsorption
processes. Sarbak and Kramer-Wachowiak [29] described if it is
assumed that adsorption takes place mainly on the surface of
2CaOSiO2, the interaction of the hydrolysis metal forms with the
surface in an idealized manner may occur as follows:
In acid solutions dealumination of coal y ash:

Si
Si

OH

4H

Si O Al O Si

HO Si

Si OH

+ Al

3+

OH

Si

Si
2+

Si OH + M(H2O)n

Si

O(H O)M + (n - 1)H2O + H

2

In order described model adsorption of M2+ ion in aqueous solution

and in alkaline solutions, where M represents the bivalent metal ions,
bound with hydroxyl group in the form of M(OH)2. However structure
of coal y ash surface was shown as aluminosilicate model:

HO

OH
OH

HO

Si

Si
O

(a)

HO

OH

OO

M
OH

OH

OH

Al

Si

Si

(b)

OO

OO

HO

OH
OH
+
Al H Si

OO

(c)

In the model was shown adsorptive interaction [29]. In the

model (a) assumed interaction with isolate hydroxyl group locate

E. Soco, J. Kalembkiewicz / Journal of Environmental Chemical Engineering 1 (2013) 581588

on the silicate ions, as a result of that, two particle dehydration.

Interaction of hydroxyl group bounded with M2+ can be with acid
centers of Lewis (three-coordinated aluminum ions) (b) or acid
centers of Bronsted assist interaction with hydroxyl group AlOH
(c). As a result of that interaction, two particle dehydration.
Materials and methods

Table 1
Composition and characteristic of coal y ash.
No.

Determination

Value

1.
2.
3.
4.

pH
Bulk density, kg m3
Moisture content, % (m/m)
Loss on ignition (LOI)

9.1
618.3
1.08
7.50%

5.

Size distribution, % (m/m):

0.320.2 mm
<0.2 mm

3.1
96.9

6.

Content of combustible part, % (m/m)

9.9

7.

Content of nonmetals, % (m/m):

Carbon
Nitrogen
Sulfur
Hydrogen

5.76
0.00
0.00
0.00

Content of metals oxide, % (m/m):

SiO2
Al2O3
Fe2O3
CaO
MgO
K2O
Na2O

51
20
12.5
4
2
0.8
0.7

Content of metals, mg kg1:

Lead
Cadmium
Chromium
Copper
Nickel
Zinc
Manganese
Cobalt

141
4
71
73
39
98
956
29

Sampling and sample pretreatment

The coal y ash obtained from coal combustion in the Heat
and Power Plant (Rzeszow, Poland) was used in the experiment. Coal y ash from boiler with dry away of y ash and
uidized combustion of coal. Five samples were collected by
multiple sampling according to the BN-81/0623-01 norm (by
Polish Standards). All of them were collected at a depth of
about 10 cm. The ash samples were put into polyethylene bags
and transported to the laboratory. The wet weight of each
sample was about 5 kg. Air-dry ash subsamples weighing 0.5 kg
were prepared from the 5 kg sample. In the laboratory the
ashes were air-dried at ambient-temperature for two weeks.
The dried material was sieved at w  0.06 mm sieve. The
obtained material was homogenized by shaking and placed in
the dark. Then, the ash samples were kept in polyethylene
containers until adsorption. The containers were rinsed with
acetonitrile.
The loss on ignition (LOI) was determined by heating a preweighed dry sample (left at 110 8C in an oven and then cooled in
desiccators) to 600 8C over a period of 2 h. Composition and
characteristic of coal y ash are shown in Table 1.

583

8.

9.

Adsorption and desorption

For solidliquid system, adsorption isotherm is important in
description of adsorption behavior. To nd out the mechanistic
parameters associated with nickel and copper adsorption, the
results obtained by the adsorption experiments were analyzed by
Freundlich [3032] and Langmuir [33] models.
The Freundlich isotherm is an empirical equation employed to
describe heterogeneous systems. The Freundlich equation (1) is
expressed:
n

ads
Csads KFads Caq

(1)

where n is the Freundlich constant, KFads is the adsorption

coefcient, Csads is the mass (amount) adsorbed per unit mass of
ads
adsorbent (mg g1), and Caq
is the equilibrium concentration of
the adsorbate in uid (mg L1).
The logarithmic form of the Freundlich model is given by the
following equation:
ads
log Csads log KFads n log Caq

(2)

The Langmuir isotherm [27] has been used by various workers

for the sorption study of a variety of compounds. The model
assumes uniform energies of adsorption onto a surface and no
transmigration of adsorbate in the plane of the surface. The
Langmuir isotherm takes an assumption that the adsorption
occurs at specic homogeneous sites within the adsorbent. The
linear form of the Langmuir isotherm is given by the following
equation:
Csads

ads
C1

ads
KLads Caq
ads
1 KLads Caq

(3)

Csads is the mass (amount) adsorbed per unit weight of adsorbent

ads
(mg g1), and Caq
is the equilibrium concentration of the

adsorbate in uid (mg L1), KLads (L mg1) is the afnity

parameter or the Langmuir constant related to energy of
ads
adsorption, and C1
(mg g1) is the capacity parameter related
to maximum adsorption capacity.
The adsorption/desorption of Cu(II) and Ni(II) ions was studied
in the system: coal y ash  water (ions of Cu(II) and Ni(II))
mads = 5 g; w < 0.06 mm; V0 = 250 mL; mads:V0 = 1:50 and I = 0.1
(NaNO3)). There was analyzed the inuence of: pH of system after
adding coal y ash (3, 4, 5, 7, 8 and 10), initial concentration of
Cu(II) and Ni(II) ions (5, 10, 25, 40, 70 and 100 mg L1) to
adsorption coefcient found, and time (0.5, 1, 1.5, 2, 3 and 4 h) on
adsorption of Cu(II) and Ni(II) ions. The research was carried out by
using: magnetic mixer, pH-meter, shaker, centrifuge and ltrating
set. Determined of Cu(II) and Ni(II) ions simultaneously in aqueous
phase after desorption. The desorption of Cu(II) and Ni(II) ions from
coal y ash was carried out by aqueous solution at pH = 3 (HNO3)
by 3 h.
The research was carried out on three parallel samples (n = 3).
The reagent blank was simultaneously run. The results of Cu and Ni
concentrations for reagent blank were corrected. Blank extractions
were carried out for each set of analysis using the same reagent as
described above. All analytical determinations were carried out in
triplicate.
Evaluation of Cu and Ni mobility
Evaluation of Cu and Ni mobility from coal y ash to solution
inuence on pH water phase was performed in order to check pass
through of studied metals from coal y ash to solution. Desorption
of Cu(II) and Ni(II) ions was carried out in the system: coal y
ash  water, mads = 5 g; w < 0.06 mm; V0 = 250 mL; mads:V0 = 1:50
and I = 0.1 (NaNO3), pH (111), and desorption time 3 h.

584

E. Soco, J. Kalembkiewicz / Journal of Environmental Chemical Engineering 1 (2013) 581588

Pseudototal coal y ash and CRM digestion

The total contents of Cu and Ni have been studied as content
close total in the coal y ash by means of pseudototal coal y ash
digestion in the mixture of conc. acids HNO3 and HCl (1:3) (aqua
regia) in mineralizing set with reux condenser and splash head.
The air-dried ash samples of 2.50 g and a diameter of ash grains
w  0.06 mm were wetted with deionized water. 5 mL of
concentrated HNO3 acid and 15 mL of concentrated HCl acid were
added to the samples, put on a mineralizer and heated for an 2 h at
200 8C. After that the test tubes content was hot-ltered by a
medium quantitative lter paper (cellulose acetate lters; retention 10 mm), decanting sediment traces with the help of the hot 1%
HCl. The obtained supernatant was analyzed for Cu and Ni. The
reagent blank was simultaneously run.
Content of metals, metal oxides and nonmetals determination
Concentrations of Cu and Ni in solutions (after adsorption and
desorption) were determined by ame atomic adsorption spectrometry FAAS method (for conditions see section Reagents and
instrumentation). All analytical determinations were carried out
in triplicate. The calibrant solutions containing 0.0, 2.0, 4.0,
5.0 mg L1 Cu and 0.0, 6.0, 10.0, 12.0, 20.0 mg L1 Ni were
prepared. The results of Cu and Ni concentrations for reagent
blank were corrected. The obtained results were calculated per dry
mass of ash. Concentrations of metals and metal oxides in solutions
after mineralization were determined by FAAS method. Concentrations of nonmetals were determined by elemental analysis.
Concentrations of nonmetals were determined by elemental
analysis. The statistical analysis of the results was performed for
the total metal content in the ash. The obtained results have the
following value of standard deviation sR = 2.5%. The standard
deviation (sR) value was estimated according to the literature. The
relative standard deviation (RSD)% and Student correlation
coefcient were calculated, signicance was set at P = 95% and
n = 3.
Reagents and instrumentation
The chemicals used for the experiments were: sodium
hydroxide, nitric acid, hydrochloric acid, sodium nitrate, copper(II)
nitrate trihydrate, nickel(II) nitrate hexahydrate, standard copper
and nickel solution (1000 mg L1) were used, as well as the
certied reference material CTA-FFA-1 (Institute of Nuclear
Chemistry and Technology, Warsaw, Poland). All reagents were
Fluka or Aldrich analytical grade or suprapur grade. Metal
determination in the extracts was carried out by means of a
PERKIN-ELMER Model 3100 atomic absorption spectrometer.
Nonmetal (C, N, S, H) determination in the coal y ash was carried
out by means of Elemental Analyser EA 1108 (Carbo Erba, Italy).
The spectrum determination of coal y ash sample was by means
of Fourier transform infrared spectrometer FT-IR model ALPHA of
the BRUKER Company. The heating digester with programmable
increase of temperature from 25 to 450 8C Model DK6 with
mineralization groups nalized to heavy metals trace determinations Model TMD6 of the VELP Company (Italy) was used.

appropriate of stretching vibrations nOH. The spectrums were in

air atmosphere recorded that is why clear-cut interpretation of this
band was difculty because it could derive from OH groups,
chemically bounded with surface of y ash, and also from
stretching vibrations HOH of water molecule adsorbed on ash
surface. Interpretation of next band (1636 cm1), for the sake of
structure complexity is not clear but it was found that band was
from oxide compounds of y ash derived. These compounds
inuence on symmetry of condensed aromatic rings system,
therefore C5
5C bond is active bond in infrared, shows absorbance in
the eld of 1600 cm1. Thus the band in the eld of 1636 cm1 is
ascribed carboxylic-carbonate structures. The most intensity of
band in spectrum of coal y ash is in the eld of 1050 cm1 (with
inexion at 1200 cm1 and 1100 cm1) can be described of
stretching vibrations of bounds in CO (nCO) carboxylic, phenolic,
etheral groups. The bands in dactyloscopic range of 800450 cm1
derive from CH group.
Adsorption
The removal of pollutants from wastewaters by adsorption is
highly dependent on the pH of the solution, which affects the
surface charge of the adsorbent, and the degree of ionization and
speciation of the adsorbate. It is shown in Fig. 2 that the amount of
metal removal by adsorption increased with an increase of pH level
up to about pH 8.0 for Ni(II) and Cu(II). These results correspond to
the pH values at which the maximum removal was observed under
equilibrium conditions. To avoid precipitation of the metal ions, all
the experiments were conducted at pH values less than 10. The
maximum degree of metal removal was in the ranges of 98.0
98.4% at pH 8.010.0 in the case of Cu(II) and 97.7% at pH 8.0 in the
case of Ni(II).
The metal concentrations were determined at varying time
intervals. The results are shown for Cu(II) and Ni(II) in Fig. 3. As
shown, the removal of Cu(II) and Ni(II) from coal y ash increased
with extending time to 2 h for Cu(II) and 1 h for Ni(II). Further
removal was not signicant, indicating that the minimum contact
time necessary for an efcient heavy metal removal was 2 h for
copper and 1 h for nickel. It can be seen in Fig. 3 that the metal
removal in the rst 0.5 h was 39.6% and 95.5% of the maximum
removal in the case of Cu(II) and Ni(II), respectively. The maximum
removal efciencies of 90.9% Cu(II) and 99.6% Ni(II) were also
attained with the coal y ash, respectively, in the initial 2 and 1 h.
Therefore, the equilibrium time was xed at 2 and 1 h in the case of
Cu(II) and Ni(II) in all the further tests.

Results and discussion

Spectroscopic measurements (IR)
In coal y ash was observed absorption broadband in the range
of 3444 cm1, band in range of 1636 cm1 and absorption
broadband at about 1050 cm1 (Fig. 1). This last band had weak
two inexion at 1200 cm1 and 1100 cm1. Band at 3444 cm1

Fig. 1. FT-IR spectrum of coal y ash.

E. Soco, J. Kalembkiewicz / Journal of Environmental Chemical Engineering 1 (2013) 581588

Fig. 2. pH dependence of Cu(II) and Ni(II) adsorption (A) and desorption (D) on/from
coal y ash, C0 = 25 mg L1.

The removal of Cu(II) increased with an increase of initial ion

concentration in the solution while the removal of Ni(II) decreased
slightly for coal y ash. With the increase of the initial
concentration of Cu(II) and Ni(II) from 5 to 100 mg L1, respectively, the percentage removal increased from 96 to 97.6% for
Cu(II), while it decreased from 100 to 98% for Ni(II) when coal y
ash was used under equilibrium conditions. The studied coal y
ash is the good adsorbent at higher soluble Cu(II) and Ni(II)
concentrations as a result of its higher soluble lime content. It is
also known from the experimental data that in the solutions of
higher initial Cu(II) and Ni(II) ions concentrations the removal
efciencies of coal y ash are sufcient for permissible levels in
mixed industrial efuent discharge for Cu(II) and Ni(II)
(100 mg L1). Equilibrium data are basic requirements for the
design of adsorption systems. Adsorption models are used for the
mathematical description of the adsorption equilibrium of the
metal ion on to the adsorbent. The results obtained on the
adsorption of copper and nickel were analyzed by the well known
models given by Langmuir and Freundlich. The experimental
equilibrium data for the adsorption of Cu(II) and Ni(II) by coal y
ash at 20  2 8C using Cu(II) and Ni(II) concentrations of
25  2 mg L1 in the pH range of 3.010.0 were correlated using
the linear forms of the Langmuir and Freundlich equations. The
Freundlich and Langmuir isotherm parameter was determined by
least-squares t of the sorption data in Figs. 4 and 5. The Freundlich
model was more applicable than the Langmuir model, since the

Fig. 3. Mixing time dependence on Cu(II) and Ni(II) adsorption (A) and desorption
(D) on/from coal y ash; C0 = 25 mg L1; pH = 8.

585

correlation coefcients for the former were higher for the adsorption
of nickel ion on the coal y ash. The Freundlich model is valid for a
multilayer sorption model on a surface containing a nite number of
sites with mutual interactions between sorbed metal cations. As seen
Freundlich models are corrected for the simulation of experimental
data. The correlation coefcients for the Freundlich model and the
Langmuir model are not similar for all cases. The plot of log Csads
ads
against Caq
for the adsorption data of nickel shows that the data ts
well to the Freundlich model. The Freundlich equation predicts that
the metal ion concentration on the sorbent will increase as long as
there is an increase in the metal ion concentration while experimental
results showed a plateau indicating a limiting value of the sorption.
The coefcients KF and n can be estimated from the slopes. As shown
in Fig. 5, the Freundlich isotherm equation provided an excellent t to
the equilibrium sorption data, giving correlation coefcients R2 of
0.99 on the coal y ash for nickel. If R2 is a large number, one can
conclude that the independent variables (experimental data)
contribute to the prediction of the dependent variables (modeling
data). Hence, the linear model is well correlated. Detailed analysis of
the variance also showed that the Freundlich model described the
adsorption data better. The P value is the probability of being wrong in
concluding that there is an association between the dependent and
independent variables. Traditionally, the independent variable can be
used to predict the dependent variable when P < 0.05.
The adsorption data of Ni(II) were found to t well with the
Freundlich and 2nd Langmuir equation (Table 2). The linear plots of
ads
ads
Caq
=Csads versus Caq
at constant pH value suggest the applicability
of the 2nd Langmuir isotherm for Ni(II) adsorption by the coal y
ash, showing the formation of monolayer coverage of the
adsorbate at the outer surface of adsorbent.
The model parameters from Langmuir isotherms obtained from
linear regression are presented in Fig. 5. The corresponding
correlation coefcients are, respectively, between the ranges 0.976
ads
and 0.998. C1
and KLads were determined from the slope and
intercept of the Langmuir plot and are presented in Table 2. Ions of
Cu(II) at pH = 8 and tads = 2 h in all range of researched
concentrations from 5 to 100 mg L1 were total adsorbed from
aqueous solution, the maximum degree of metal removal was
100%.
Langmuir type model presupposes homogeneity of the sorbing
surface and no interactions, involving uniform energies of sorption
on the surface and no transmigration of metal cations in the plane
of the surface. The difference in adsorption capacities of two
sorbents is believed to be largely due to the physicalchemical
properties of them or the chemistry of the metal containing
solutions. These studies point at physisorption and monolayer
adsorption. The removal of copper and nickel using coal y ash

Fig. 4. Freundlich isotherm for Ni(II) adsorption; pH = 8, logarithmic form.

E. Soco, J. Kalembkiewicz / Journal of Environmental Chemical Engineering 1 (2013) 581588

586

Fig. 5. 2nd Langmuir isotherm for Ni(II) adsorption, pH = 8.

takes place by a particle diffusion mechanism. Explain the t to

Freundlich and Langmuir isotherms. Researched multilayer
adsorption on the basis of BET isotherm. The results obtained on
the adsorption of copper and nickel were analyzed by the wellknown models given by Brunauer, Emmett and Teller. Obtained
calculations do not come guidelines of BET isotherm.
Coal y ash obtained from the local coal combustion in the Heat
and Power Plant is an effective and inexpensive adsorbent for the
removal of copper and nickel from aqueous solutions. The results
obtained may be useful for metal plating industry wastewaters
containing these metals since y ash is denitely inexpensive
compared to activated carbon.
Desorption
The inuence of pH on desorption of Cu(II) and Ni(II) ions from
coal y ash to aqueous solution in the range of 310 at mixing time
amount to 3 h was studied. It is readily apparent from Fig. 2 that
the amount of metal removal by desorption increased with an
decrease of pH level up to about pH 3.0 for Ni(II) and Cu(II). These
results correspond to the pH values at which the maximum
removal was observed under equilibrium conditions. The maximum degree of metal removal was in the ranges of 98.098.4 at pH
4.03.0 in the case of Cu(II) and 97.7 at pH 3.0 in the case of Ni(II).
The inuence of time on desorption of Cu(II) and Ni(II) ions from
coal y ash by means of aqueous solution was studied. The results
are shown for Cu(II) and Ni(II) in Fig. 3. As shown, the removal of
Cu(II) and Ni(II) by aqueous solution increased with increasing
time up to 3 h, and thereafter the removal was not signicant,
indicating that the minimum contact time necessary for a good
heavy metal removal was 3 h. As shown in Fig. 3 that the metal
removal in the rst 0.5 h was 31.5 and 27.9% of the maximum
removal in the case of Cu(II) and Ni(II), respectively. The maximum
removal efciencies of 93.0 Cu(II) and 95.0% Ni(II) were also
Table 2
ads
The values of adsorption coefcient and C1
for C0 = 5, 10, 25, 40, 70, and
100 mg L1.

attained with the aqueous solution, respectively, in the initial 3 h.

Therefore, the equilibrium time was xed at 3 h in the case of Cu(II)
and Ni(II) in all the further tests.
The inuence of initial concentration of ions on desorption of
Cu(II) and Ni(II) from coal y ash to aqueous solution (H+, NO3) at
pH = 3 and tdes = 3 h was studied.
The desorption data of Cu(II) and Ni(II) were found to t well
with the Langmuir equation (Table 3), while the Freundlich
equation did not t the desorption data well (Figs. 6 and 7). The
des
des
linear plots of Caq
=Csdes versus Caq
at constant pH value suggest
the applicability of the Langmuir isotherm (Fig. 6) for Cu(II) and
Ni(II) desorption from the coal y ash, showing the formation of
monolayer coverage of the adsorbate at the outer surface of
adsorbent.
des
The values of C1
and KLads at constant pH value were
determined from the slopes and intercepts of the respective plots.
ads
The data was shown in Table 3. Comparing the C1
values at a
constant pH value, changed in the order Ni(II) < Cu(II). This
classication could be explained with the rst hydrolysis product
of the metallic ions.
Evaluation of Cu and Ni mobility
In practice during Cu(II) and Ni(II) desorption studied essential
evaluate of Cu(II) and Ni(II) amount can be leached from coal y
ash to aqueous solutions in dependence on pH. Performed
researches indicate, that mobility fraction of metals in coal y
ash at pH = 1 is fraction of Cu(II). It was found, that independent on
pH of aqueous phase (1, 3, 5, 7, 9, 11) from coal y ash to solution
does not pass Ni(II) ions. Only Cu(II) ions undergo desorption to
aqueous solution at pH = 1 in quantity 6.8%. In order to
characterize Cu and Ni mobility in coal
P y ashes, the mobility
6
parameter was calculated as: a%
i1 Mi =Mtotal  100. a
parameter presents the percentage share of metal mobile forms in
relation to total contents in the ash. The results of the performed
research indicate that the mobility of Cu and Ni fractions at pH = 1
amount to [%]: 6.8 (Cu) and 0.0 (Ni), respectively.
Pseudototal content of Cu and Ni
Analysis of the total Cu and Ni was carried out in reference coal
y ash (certied reference material CTA-FFA-1) by the FAAS
method, obtaining accuracy h > 98%. In established conditions for
CTA-FFA-1 was carried out analysis of coal y ash and obtained
[Cu]total 158  9.0 and [Ni]total 99.0  5.8 mg kg1. Simultaneously
content of total Cu and Ni in ash was analyzed as sum of pseudototal
Cu and Ni (digestive part of ash with HNO3/HCl (1:3)) and content of
Cu and Ni in indigestive part of ash. The results of analysis are shown
in Fig. 9. It was found that the content of pseudototal Cu and Ni is
73.3  6.0 and 39.3  1.0 mg kg1 adequately moreover in indigestive part of ash is 2.5  1.1 and 4.4  1.5 mg kg1 (n = 4 and P = 95%).

Table 3
ads
The values of desorption coefcient and C1
for C0 = 5, 10, 25, 40, 70, and
100 mg L1.

Ni(II)
KFads
KFads
KLads
KLads
KLads
ads
C1
ads
C1
ads
C1

exp. f.
linear f.
(1)
(2)
(3)
(1)
(2)
(3)

1.2  103 L mg1

1.2  103 L mg1 (Fig. 4)
2.4  101 L mg1
4.2  101 L mg1 (Fig. 5)
2.8  101 L mg1
7.1 mg g1
4.5 mg g1 (Fig. 5)
6.3 mg g1

KFdes
KFdes
KLdes
KLdes
KLdes
des
C1
des
C1
des
C1

exp. f.
linear f.
(1)
(2)
(3)
(1)
(2)
(3)

Ni(II)

Cu(II)

2.0  107 L mg1

1.2  107 L mg1 (Fig. 6)

1.5  102 L mg1 (Fig. 7)

1.6  102 L mg1

8.6  102 mg g1 (Fig. 7)

1.1  101 mg g1

2.0  104 L mg1

1.9  104 L mg1 (Fig. 6)

1.3  102 L mg1 (Fig. 7)

1.4 mg g1 (Fig. 7)

E. Soco, J. Kalembkiewicz / Journal of Environmental Chemical Engineering 1 (2013) 581588

Fig. 6. Freundlich isotherm for Cu(II) and Ni(II) from coal y ash at pH 3; logarithmic
form; C0 = 5, 10, 25, 40, 70, and 100 mg L1.

587

Fig. 8. Initial concentrations dependence on Cu(II) and Ni(II) adsorption (A) and
desorption (D) on/from coal y ash.

The mass balance of Cu and Ni and verication of results

The evaluation of Cu and Ni ions contents in adsorption and
desorption process in industrial materials requires special control
of the analytical process and verication of the results.
So called analyte mass balance is, among others, an instrument
used to verify the correctness of the obtained analytical results
when the simultaneous adsorption and desorption are performed.
The mass balance of Cu and Ni in the ash was checked in the
investigated system by comparing the total contents of metals,
analyzed by adsorption with a Cu and Ni content obtained by
means of desorption. The range of results does not exceed
2 mg kg1. Evaluate of mass balance of Cu and Ni in investigated
coal
y
ash
indicates
that,
obtaining
accuracy
des
des
h 1  jC ads  Caq
j=Caq
j  100. It was found that coincidence factor of mass balance of metal mass balance corresponded
to: 98.9% Cu; 92.8% Ni.

Fig. 9. Content close total of Cu and Ni in coal y ash obtained by pseudototal

mineralization of coal y ash with mixture HNO3/HCl (1:3) and determination of
metals in solution by FAAS method.

Reversibility of adsorption
The aim of the experiment was studying the reversibility of
adsorption on coal y ash. This information is important because
desorption process matters on behavior of compound in coal y
ash in eld conditions. Moreover data of desorption can be

valuable for computer modeling of displacement phenomenon of

metal ions from coal y ash to soil prole.
In order to conrm the reversibility of adsorption process,
dependence of desorption percentage (%D) and adsorption
percentage (%A) on studied parameters (pH, time and initial
concentration of ions) in Figs. 2, 3 and 8 was shown.
On the basis of Figs. 2, 3 and 8 it was found, that adsorption is
depending on time and equilibrium state after 1.5 h however
desorption process after 3 h what is double time of adsorption. The
adsorption occurred in basis medium (pH from 8 to 10) with high
yield however desorption process occurred in acid medium (pH
about 3). The adsorption of Cu2+ and Ni2+ ions could be as oxide
forms of Cu(OH)2 and Ni(OH)2. Obtained results indicate, that
adsorption process of Cu(II) and Ni(II) ions by means of coal y ash
is reversible process.
The basis of aqua-complex formation and its subsequent acid
base dissociation at the solidsolution interface seems to be
responsible for the following results obtained at various pH values:

Fig. 7. 2nd Langmuir isotherm for Cu(II) and Ni(II) desorption from coal y ash at pH
3; C0 = 5, 10, 25, 40, 70, and 100 mg L1.

2+

OH

OH

OH

OH

M
OH

OH
H

O
M
OH

OH
H

O
M
O

where M represents Si, Al, Fe or Ca. In addition, the functional

oxidized group (SiO2, Al2O3 and Fe2O3) present on the surface of

588

E. Soco, J. Kalembkiewicz / Journal of Environmental Chemical Engineering 1 (2013) 581588

the coal y ash and pH of the system largely affect the adsorption of
the ionic species of Ni(II) and Cu(II), which are Ni2+, NiOH+,
Ni(OH)2, Cu2+, Cu(OH)+, Cu(OH)2, present in wastewater.
Conclusions
Coal y ash as a byproduct obtained from the coal-red Heat
and Power Plant is an effective and inexpensive adsorbent for the
removal of copper and nickel from aqueous solutions. This study
investigated the adsorption of nickel(II) and copper(II) ions by coal
y ash. Optimum conditions of adsorption/desorption of Cu(II) and
Ni(II) ions in studied systems were established. Adsorption follows
both Langmuir and Freundlich models. The removal of copper and
nickel using coal y ash takes place by a particle diffusion
mechanism. These studies point at physisorption and monolayer
adsorption. It is evident from the studies that coal y ash has
demonstrated good removal capabilities for Cu(II) and Ni(II) ions.
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