Applied Surface Science 303 (2014) 1422

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Applied Surface Science

journal homepage: www.elsevier.com/locate/apsusc

Hydrothermally modied y ash for heavy metals and dyes removal

in advanced wastewater treatment
Maria Visa , Andreea-Maria Chelaru
Transilvania University of Brasov, Renewable Energy Systems and Recycling R&D Department, Eroilor 29, 500036 Brasov, Romania

a r t i c l e

i n f o

Article history:
Received 9 October 2013
Received in revised form 7 February 2014
Accepted 7 February 2014
Available online 26 February 2014
Keywords:
Fly ash
Hydrothermal synthesis
Heavy metal
Dye
Cationic surfactant

a b s t r a c t
Fly ash resulted from coal burning is a waste that can be used in wastewater treatment for removal of
dyes and heavy metals by adsorption.
Class F y ash (FA), collected from the Central Heat and Power (CHP) Plant Brasov (Romania), with
oxides composition SiO2 /Al2 O3 over 2.4 was used for obtaining a new substrate with good adsorption
capacity for dyes and heavy metals from wastewater. A new material was obtained from modied y ash
with NaOH and hexadecyltrimethylammonium bromide (HTAB) a cationic surfactant. Contact time, optimum amount of substrate and the pH corresponding to 50 mL solution of pollutants were the parameters
optimized for obtaining the maximum efciency in the adsorption process. The optimized adsorption
parameters were further used in thermodynamic and kinetic studies of the adsorption processes.
The adsorption kinetic mechanisms, and the substrate capacities are further discussed correlated with
the surface structure (XRD), composition (EDS, FTIR), and morphology (SEM, AFM).
The results indicate that the novel nano-substrate composite with y ash modied can be used as an
efcient and low cost adsorbent for simultaneous removal of dyes and heavy metals, the resulted water
respects the discharge regulations.
2014 Elsevier B.V. All rights reserved.

1. Introduction
Textile industry is among the most polluting industries
regarding the fact that it uses a large amount of water during the
dyeing process [1] and because of this the discharged efuents are
loaded with numerous pollutants like dyes, toxic metals, suspended
solids, microbial pathogens and parasites, biodegradable, volatile
and recalcitrant organic compounds [2,3]. The efuents from textile
industry change the biological life of rivers and lakes [4,5].
Wastewaters with a load like this cause damages to the environment by creating problems to the groundwater resources [6]. These
wastewaters are highly colored, have a uctuating pH, high temperature and chemical oxygen demand, large amounts of suspended
oils. The main problem related to the dyes (which are stable to light
and are not biodegradable [2]) in wastewater is the color which
decreases the light permeability thus causing a negative effect on
photosynthesis [7]. Decreasing permeability of light, the amount
of oxygen decomposed lead to extinction of some living beings
and to restriction of the reuse of water. The heavy metals from the

Corresponding author. Tel.: +40 729109355.

E-mail addresses: maria.visa@unitbv.ro (M. Visa), andreea.chelaru1@yahoo.com
(A.-M. Chelaru).
http://dx.doi.org/10.1016/j.apsusc.2014.02.025
0169-4332/ 2014 Elsevier B.V. All rights reserved.

dyes structure represent also a problem. Metals are present in dyes

because they are used as catalysts during the manufacture of some
dyes and can be present as impurities or exist into dye molecule,
forming an integral structural element [1].
The presence of heavy metals in wastewater is unwanted due to
their solubility in water thus can be absorbed by living organisms
and like this they enter in the food chain and start to accumulate in
the human body. Ingestion of heavy metals beyond the permitted
concentration can cause serious health disorders [8].
Because of the problems caused by the presence of dyes and
heavy metals in wastewater their removal started to become
important and for this several methods like: adsorption, coagulation, occulation, precipitation, reverse osmosis, biological process,
ionizing, gamma radiations, photocatalysis are being used. But
many of these methods are expensive and when they are applied
for treating large amounts of waters, from all of them the adsorption techniques are preferred because of their advantages: low
cost, ease of operation, efciency, simplicity of the equipment and
mostly because the adsorbent can be chosen from a wide variety of
materials, natural, synthetic and wastes, for example y ash [9].
Fly ash is one of the most known waste and it is being used as raw
material in many industries such as cement industry, but its negative effect on the environment cannot be completely neutralized
by doing this, so reusing it as an adsorbent in removal of different

M. Visa, A.-M. Chelaru / Applied Surface Science 303 (2014) 1422

types of pollutants from wastewater solves two problems: water

quality and waste management [10].
This paper reports the synthesis, characterization and
adsorption behavior of mesoporous material obtained by
hydrothermal method using alkali y ash and hexadecyltrimethylammonium bromide (98% purity, SigmaAldrich) (HTAB)
[CH3 (CH2 )15 N+ (CH3 )3 ]Br as template.
2. Experimental

15

randomly at a scanning grate of 1 Hz. Further surface investigations

were done using scanning electron microscopy (SEM, S-3400N
Hitachi) at an accelerating voltage of 20 kV. Surface compositions were measured using energy dispersive X-ray spectroscopy
(EDS Thermo Scientic Ultra Dry). Surface characterization was
completed by porosity analysis and BET surface (Autosorb-IQ-MP,
Quantachrome Instruments). The FT-IR spectroscopy (PerkinElmer
BX II 75548) was employed for complementary investigations on
the surface chemistry, before and after removal of the MB dye and
Cu2+ or Cd2+ cations from systems.

2.1. Substrate preparation

2.3. Adsorption experiments
The cheap starting material in producing the adsorbent materials is y ash (FA) obtained from a mixture lignite and bituminous
coal burned in the CPH plant Brasov, Romania. The major constituents of this y ash are oxides: SiO2 , Al2 O3 , Fe2 O3 , CaO, MgO,
Na2 O, K2 O, TiO2 MnO and small amounts of metals (Ba, Cu, Sn, Pb,
Cr, Ni, V, Zn) identied by atomic spectroscopy. According to the
ASTM standards [11] the FA collected from the electro-lters of the
plant is of F type (the sum of the major compounds, oxides SiO2
(53.32%), Al2 O3 (22.05) and Fe2 O3 (8.97) is over 70%).
The pH value of the raw y ash was evaluated by mixing FA
with ultra pure water (1 g:10 mL), then mechanical stirring, at room
temperature (2022 C) till constant pH = 10.2 and conductivity values = 1710 mS). This type of y ash is not aggregate in water. The
initial TDS value of the batch is 600 mg/L and after 24 h increases
to 840 mg/L and after 48 h the value is 890 mg/L. The soluble compounds: K2 O, Na2 O, MgO, CaO, were thus removed in solution and
can be available by further separation and purication [12]. After ltration, washing, drying at 105120 C over night till constant mass,
the dried substrate (FAw) was sieved and the 2040 m fraction
was selected for experiments. The fractions of FAw up to 200 m
size can be used in cement industry.
One half of FAw was mixed with NaOH 2 N solution and HTAB
[CH3 (CH2 )15 N+ (CH3 )3 ]Br (98% purity, SigmaAldrich) cationic
surfactant in 1000 ml volumetric ask with reux condenser further stirred (300 rpm) 24 h at atmospheric pressure and 100 C, and
other half was stirred 48 h in the same conditions on a thermoset
heating and notated (FAA-CS24) respectively (FAA-CS48).
The amount of HTAB added was lower than the critical micelle
concentrations (CMCHTAB = 298 mg/L), evaluated based on conductivity measurements [13]. The crystallinity and the energy surface
of FAw materials can be modied adding natural materials, clay
diatomite [14] and bentonite in alkali solutions [15]. The surface
area and pore size of mesoporous silica materials can be tailored
by different hydrothermal treatments [16].
The pore size of adsorbent material increases with the chain
length of the surfactant, composition mixture, the pH value and
temperature post synthesis [1719].
The colloidal suspension was vacuum ltrated, washed repeatedly using ultra pure water and dried at 115125 C till constant
mass; the novel micro-nano material substrate was used in adsorption experiments of Cu2+ , Cd2+ cations and methylene blue (MB)
from the bicomponent system.
2.2. Characterization of the new materials
The FAA-CS crystalline structure was evaluated by XRD (Bruker
D8 Discover Diffractometer), over the 2 range 1070 . Morphology studies (roughness and macro-pore size distribution) were
done using AFM (Ntegra Spectra, NT-MDT model BL222RNTE);
images were taken in semi-contact mode with Golden silicon
cantilever (NCSG10), with constant force 0.15 N/m, having the tip
radius of 10 nm. Scanning was conducted on three or more different
places with a certain area of 5 m 5 m for each position, chosen

The pollutant systems were synthetically prepared using bidistilled water and CdCl2 2.5H2 O (Scharlau Chemie S.A., c < 98%),
CuCl2 2H2 O (Scharlau Chemie S.A., c < 98%) and MB (C16 H18 N3 S)
(Fluka AG, reagent grade). The experiments were done using heavy
metal solutions in the concentration range of cCd = 0, . . ., 515 mg/L
and cCu = 0, . . ., 350 mg/L, respectively; methylene blue (MB) initial
concentrations were: cMB = 0.0625 mmol/L.
The behavior of the new adsorbents materials (FAA-CS24)
respectively (FAA-CS48) were tested to decide which one is the
most efcient adsorbent for the next adsorption processes.
Two series of experimental tests of adsorption were done using
the bicomponent pollutant systems:
(a) Adsorption on FAA-CS24 substrate in solutions containing two
pollutants:
- Cd2+ and MB, under mechanical stirring;
- Cu2+ and MB, under mechanical stirring;
(b) Adsorption on FAA-CS48 substrate in solutions containing two
pollutants:
- Cd2+ and MB, under mechanical stirring;
- Cu2+ and MB, under mechanical stirring.
The solutions were used at their natural pH; the initial pH of
the solutions containing dyes and heavy metals in contact with
FAA-CS24 substrate was 8.22, respectively 9.57 with FAA-CS48 substrate, which are higher than the new material point of zero charge
(PZC = 7.44).
Preliminary experiments proved that heavy metals and dyes
losses due to adsorption to the container walls are negligible.
The kinetic and thermodynamic adsorption parameters of the
heavy metals and MB from bi-pollutant systems were evaluated
from batch experiments; in each experiment, 0.1 g of FAA-CS24 or
0.1 g of FAA-CS48 substrate was stirred (200 rpm) at room temperature (2023 C), with 50 mL solution, at initial concentrations
(CiCd = 515 mg/L, CiCu = 350 mg/L) set according to the experimental
study; for the kinetic studies, aliquots were taken each at 15, 30,
60, 90, 120, 150, 180, 240, 300 min, when stirring was briey interrupted and the substrate was removed by centrifugation (GL-20G,
Shanghai).
The supernatant was further analyzed by AAS (Analytic Jena,
ZEEnit 700), at: Cd = 228.8 nm and Cu = 324.75 nm and UVvis
absorbance measurements (PerkinElmer UVVIS spectrophotometer, Lambada-950) were done at the maximum absorption
wavelength (665 nm) for MB.
3. Results and discussion
3.1. Characterization of the substrates
The siliconalumininous composition in the y ash is conrmed by XRD spectra, Fig. 1. The major crystalline components
of washed y ash are: SiO2 (quartz), mullite (3Al2 O3 2SiO5 ),

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M. Visa, A.-M. Chelaru / Applied Surface Science 303 (2014) 1422

The XRD data show that the new substrates, FAA-CS24 and FAACS48, have well embedded the new phase of alumino-silicates with
area picks more high. The crystallite sizes were calculated using the
Scherrer equation. (1) [20].

=

Fig. 1. XRD data of (1) FAw, (2) FAA-CS48 and (3) FAA-CS24.

identied by the sharp peaks in the range of at 2 = 42.5 ,

along with -Al2 O3 , hematite (Fe2 O3 ) and maghemite, bixbyite
(Mn2 O3 ), brookite (TiO2 ), with coexistence of an amorphous
phase.

K
cos 

(1)

where  is the size of crystallites, K is the shape factor with a typical

is the line broadvalue 0.94,  is the X-ray wavelength (1.5406 A),
ening at half the maximum intensity (of a peak), and  is diffraction
angle.
An increased crystallinity is identied in the both substrates:
quartz syn (with 135.9 A crystallite size), sodium aluminum silicate
(Na6 Al6 Si10 O32 with 359.6 A crystallite size), Kyanite (Al2 SiO5 with
207.5 A crystallite size) conrming that chemical restructuring
occurs within FAw when hydro-thermally processed. The unburned
carbon graphite, and carbon hexagonal (chaoite or white), along
with compounds as micro-sized crystallites represents a signicant
part of the substrate and can explain the versatility of this material in adsorption processes of heavy metals, organic pollutants,
including dyes [21]. The overall crystallinity degree of FAA-CS24
is estimated at 53.9% and of FAA-CS48 is 66.66%, the rest being
represented by amorphous phases.
The crystallinity modications are accompanied by a signicant
increase in the BET surface, from 6.14 m2 /g in FAw at 62.57 m2 /g.

Fig. 2. AFM images for (a) FAw; (b) FAA-CS24; (c) FAA-CS48.

Fig. 3. SEM images of (a) FAA-CS24 and (b) FAA-CS48 substrate.

M. Visa, A.-M. Chelaru / Applied Surface Science 303 (2014) 1422

17

Table 1
Surface composition, in atomic %, of the FAA-CS surface before and after adsorption the (Cd2+ + MB) solution.
Element

FAA-CS24

N
O
Na
K
Al
Si
S
Ca
Ti
Br
Cd

FAA-CS48

Before adsorption

After adsorption

Before adsorption

After adsorption

16.40
39.50
2.53

1.58
1.22
10.08
28.53
1.92

1.49
7.68
27.00

39.48
4.64

9.09
72.23
1.71

5.56
8.93
0.19
0.17
0.16
0.00
1.96

3.16
5.45

1.67
0.12

3.23
8.93

0.19
0.17

During long time washing under stirring in ultra pure water,

the soluble alkaline oxides, (K2 O, Na2 O, MgO, CaO) were removed
from the raw y ash surface into the solution, with a corresponding increase in the pH value (10.2), conductivity (1710 mS) and
TDS, leading to grains with average roughness of 90.79 nm. The
hydrothermal process of FAw and HTAB in the alkaline solution
further promotes surface interactions, including dissolution, recrystallization of the FAw components and new aluminosilicates
had been developed by reaction of NaOH with silica from quartz
[21]. The result is a much rougher surface (123.61 nm). Increasing
the value roughness signies increasing defects in the surface and a
possible increase in the number of high energy active site, Fig. 2(b).
As the images in Fig. 3 shows, the FAA-CS grains are signicantly larger (3.37, . . ., 90.5 m) than the individual particles, or
agglomerations developed on spherical grains of y ash particles.
3.2. Characterization of the substrates after adsorption of
(Cd2+ /Cu2+ + MB)
In alkaline environment on FA surface new active sites ( SiO )
and ( AlO ) can develop, allowing metals to form new compounds,
Eqs. (2) and (3) [22].

2( SiO ) + M

2+

( Si O)2 M

(2)

2( AlO ) + M2+ ( Al O)2 M

(3)

These processes are conrmed by the XRD data of FAA-CS24

registered before and after adsorption of (Cu2+ + MB), Fig. 4, which
shows new peaks, corresponding to Dioptase (Cu(SO3 )(H2 O) and
CuSO4 (H2 O), indicating a possible formation of chemical bonds
between the adsorbed species and the activated sites indicated in
Eqs. (2) or (3).

Fig. 4. XRD of FAA-CS24 (1) before and (2) after adsorption the (Cu2+ + MB) solution.

Based on the high content functional groups as (SiO4 ) , (AlO4 ) ,

the FAA-CS24 and FAA-CS48 substrates could develop electrostatic
bonds with the cadmium, copper cations or MB.
The elemental EDS analysis of FAA-CS24 is being shown in Fig. 5.
The elemental EDS analysis of and FAA-CS24 and FAA-CS48 samples show high intensity signals for Si, Al, Na, O, and conrm the Cd,
N and S atoms on the surface of substrate scanned after adsorption
Table 1, Figs. 6 and 7.
The high percentage of nitrogen atoms (9.09%), Table 1, may
involve coordination of several molecules (2) or (4) of methylene
blue at cadmium or copper cations.

Fig. 5. EDS spectra of FAA-CS24 before adsorption.

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M. Visa, A.-M. Chelaru / Applied Surface Science 303 (2014) 1422

Fig. 6. EDS spectra of FAA-CS24. Intensity of Si, Al, Cd on surface scanned after contact with the (Cd2+ + MB) solution.

Fig. 7. EDS spectra of FAA-CS48. Intensity of Si, Al, Cd on surface scanned after contact with the (Cd2+ + MB) solution.

Fig. 8. AFM images after adsorption process.

M. Visa, A.-M. Chelaru / Applied Surface Science 303 (2014) 1422

19

Table 2
Characteristics of IR bands associated with zeolites (common for all zeolites).
Type of IR band vibrational

Frequency [cm1 ]

Internal tetrahedral
Pore opening vibrations
T O bending vibration
Symmetric stretch of T O bond

300420
420500
660

External tetrahedral
Double ring vibration
Symmetric stretch
Asymmetric stretch of TO bond
Asymmetric stretch

500670
750820
9501500
10501150

T = Si or Al.

The SEM and AFM images, Fig. 8(a) and (b), shows modied surfaces due to adsorption processes of the MB and the Cd2+ , Cu2+ ions,
conrmed by roughness modication.
These AFM images were used to characterize the surface morphology: the uniformity, grain size and pore size distribution [23]
of the samples Fig. 9.
Supplementary information was obtained using the FTIR spectra. The y-ash based substrate has a composition close to a zeolite
(SiO2 /Al2 O3 over 2.4); therefore the frequency regions corresponding to different types of vibrations in zeolites, presented in Table 2
were considered as reference [24] in investigating the experimental
results.
T = SiorAl
Fig. 10 Illustrates the FTIR spectra of the substrates before and
after adsorption. The asymmetric stretching modes of Si O Si or
Si Al O in all samples analysis was suggested by the absorption band at 954.21 cm1 for all with sharp peaks, indicating the
links between the framework units in the structure of FAA-CS.
In this type of material, water molecules are associated with the
cations that are in some extent hydrogen bonded to the oxygen
ions of the framework, explaining the peak with less intensity,
recorded at 16351644 cm1 which is characteristic to the bended
mode in the water molecules. The absorption band observed
from 3200 to 3600 cm1 was attributed to the hydroxyl group
stretching/vibration in Si OH, Al OH Al, Si OH Al units [25]. I
R spectroscopic studies conducted by Rayalu et al. [26] showed
that there was good agreement between IR and the XRD analysis.
3.3. Adsorption
In aqueous solutions hydrated heavy metal cations can be
subject of (for) hydrolysis, according to reaction (4), written for
divalent heavy metals [14]:
M2+ (aq) + nH2 O M(OH)2n + nH+

(4)

This is a strongly pH dependent reaction; based on the

Pourbaix diagrams [27], it may be concluded that cadmium
cations are not signicantly hydrolysed in the working conditions
(pHCd, hydrolisys > 9).
The copper ion could be found as Cu(OH)+ , at pH values above
6.8, but not as neutral hydroxide, which is formed at pH values
above 7.5. For both cations, the anionic combinations require pH
values above 10 and are not likely to be formed in the working
conditions.
Considering the experimental conditions (working pH
=8.22, pHPZC1 FAA-CS24 = 7.80 and pHPZC2 FAA-CS24 = 5.72) on
the FAA-CS24, (working pH = 9.56, pHPZC1 FAA-CS48 = 8.34 and
pHPZC2 FAA-CS48 = 5.27) on the FAA-CS48 substrates the component
will be slightly negatively charged, while the FA matrix preserves
an overall negative surface charge.

Fig. 9. The interparticle voids distribution.

According with the working concentration (CiCd = 515 mg/L,

CiCu = 350 mg/L) for heavy metals at working pH for both substrates
the effect of ionic strength is JCu2+ > JCd2+ . The ionic strength and
hydrated ionic radius (copper 0.295 nm < cadmium 0.426 nm) [28]
explain faster adsorption of copper cations.
Under these conditions, cationic species (heavy metals and S+
from MB) are supposed to be adsorbed, in concurrent processes
based on electrostatic attractive forces, between substrates and
cationic species, and the volume of the species.
The adsorption efciency, , was evaluated based on the initial
i
i
cHM/MB
and equilibrium momentary cM/MB
concentrations of the
heavy metal (M) or methylene blue:
=

i
e
(cHM/MB
cHM/MB
)
i
cHM/MB

100

(5)

Good removal efciencies are obtained after 120 min for heavy
metals and earlier for MB, Fig. 11(a) and (b). For further thermodynamic studies the contact time optimized used for Cd2+ and Cu2+
cations, when equilibrium adsorption process was reached.
Increased efciencies over 90% for MB, 60% for cadmium and
71% for copper in adsorption processes are mainly related to the
morphology of substrates Fig. 2.
The average roughness in case of FAA-CS24 (123.61 nm) is bigger
than the average roughness of FAA-CS48 (56.441 nm). The value of
surface roughness provides information about the effective surface
area of the material, increasing surface roughness value signies
the increasing defects in the surface area and a possible increase
in the number of active sites, that is why the removal efciency
of MB and Cd2+ in case of using FAA-CS24 as substrate is bigger
than in case of FAA-CS48, Fig. 12(b). Both substrates are effective
in removing the pollutants by adsorption process but considering
the consumption of energy in substrate preparation the substrate
notated FAA-CS24 can be recommended.
The dates from Fig. 11(a), Fig. 13, indicate removal of hydrated
copper cations and MB cations by the same mechanism.
These dates correlated with the elemental EDS analysis of substrates Figs. 6 and 7 indicate that both substrates are effective
in removing the pollutants by adsorption process but considering
the consumption of energy in substrate preparation the substrate
notated FAA-CS24 can be recommended.
The removal efciency of heavy metals from solution with two
pollutants (HM cations and MB) is much higher for all pollutants
(Cu2+ , Cd2+ cations and MB) Fig. 13, as result of increasing the substrate dosage implicit of the active sites.

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M. Visa, A.-M. Chelaru / Applied Surface Science 303 (2014) 1422

The pseudo-second order kinetics, Ho and McKay [30], could

well model the processes:
t
1
t
=
+
qt
qe
k2 q2e

(11)

where k2 is the pseudo second-order rate constant of adsorption

(g mg1 min1 ).
Another possible kinetic model which can be applied in the
adsorption on highly porous materials is the interparticle diffusion. In this case, the amount of adsorbed heavy metals ions can
be calculated with the Eq. (12) [31]:
q = kid t 1/2 + C

Fig. 10. IR spectrum (1) FAA-CS48, (2) FAA-CS24, (3) FAA-CS48/MB + Cu2+ , (4) FAACS24/MB + Cu2+ after adsorption with the (Cu2+ + MB) solution.

The amount of FAA-CS24 in the removal processes was optimized considering the highest risk of cadmium and copper cations.
Based on the experimental results, this amount was set at 0.15 g
FAA-CS24 in 50 mL pollutant solution, Fig. 13.
The same rate of curve (for copper, cadmium cations and for MB)
Fig. 11, can indicate the next interactions:
The Cd2+ and Cu2+ cations can also be adsorbed by the silanol
group (Si OH) of the layers, (Eqs. (7) and (8)) and MB will be protonated by electrophilic attack giving in solution the new species
MBH+ , Fig. 14.
Si OH + Cu2+ (H2 O)n Si OCu+ (H2 O)nx + H+ (H2 O)x

(7)

Si OH + Cu2+ (H2 O) (Si O)2 Cu(H2 O)nx + 2H+ (H2 O)x

(8)

The presence of electron donated NH2 groups and  conjugated electrons in complex may enhance the electron density
on S atom developing stable complexes with the heavy metals,
conrmed by dates from Table 1.
3.4. Uptake kinetics of heavy metals on FATiO2
In all cases after a rapid adsorption of cadmium, copper cations
and methylene blue (Fig. 10), adsorption slowly reached equilibrium at 120 min.
The adsorption capacity qt , in a V solution volume (50 mL), on
an ms amount of substrate (0.1 g), was evaluated using Eq. (9):
qt =

i
t
(cHM/MB
cHM/MB
)V

ms

(9)

In literature are reported three well-known kinetics models

for evaluating the experimental kinetics data: pseudo-rst-order,
pseudo-second-order and interparticle diffusion.
The pseudo rst-order equation Lagergren [29]:
log(qe qt ) = log(qe )

KL
t,
2.303

(10)

KL is the Lagergren constant, qe is the equilibrium uptake value and

qt the current pollutants uptake.

(12)

Using the linear form of Eqs. (10)(12), the kinetic parameters

were calculated and they are listed in Table 3.
Comparing the correlation coefcient (R2 ) value, the adsorption processes were best described by the pseudo-second-order
model for all pollutants from the system. The data also shows that
are developed parallel mechanisms: pseudo-second order kinetic,
pseudo-rst-order and interparticle diffusion for copper cations on
both substrates. The reason may be the higher mobility and lower
volume of the hydrated complexes of the cations in aqueous solution (hexa-complexes for Cd and tetra-coordination for Cu) [32] and
other processes at working pH = 8.22.
Considering the adsorption processes, the data indicate that the
large volume of MB allows the rapid adsorption of the cations,
leading to higher rate constants, as compared to cadmium cations.
3.5. Heavy metals adsorption isotherms
The adsorption isotherm data were experimentally obtained
based on the optimized contact duration (120 min) and substrate amount (0.15 g FAA-CS24 in 50 mL solution). The adsorption
parameters were calculated considering the Langmuir [33] and
Freundlich equations (13) and (14) [34].
- the Langmuir isotherm linearization:
ceq
ceq
1
=
+
qmax a
qeq
qmax

(13)

where qmax (mg/g) represents the maximum monolayer adsorption capacity, a is a constant related to the adsorption free energy,
qeq is the amount of metal ions adsorbed from the solution with
the equilibrium concentration, Ceq .
- the Freundlich isotherm linearization:
ln qeq = ln kf +

1
ln ceq
n

(14)

where kf is Freundlich constant, an indicator of the adsorption

capacity, and the 1/n dimensionless parameter is a measure of
the adsorption density.
To investigate the modication of the substrates capacities as
result of the interaction between y ash and cationic surfactant
adsorption in alkaline system, there were selected four systems for
which the adsorption parameters are given in Table 4, calculated
based on the linear form of the Langmuir and Freundlich equations.
Both mechanisms can model the adsorption process, supporting
the assumption of electrostatic attractions that govern the monolayer adsorption on the highly heterogeneous substrate.
The maximum adsorption capacities calculated from the
isotherms studies are in good agreement (slightly lower) with those
obtained from the kinetic data, indicating that most of the active
sites are involved in adsorption processes that can be described by
the pseudo-second order kinetics.

M. Visa, A.-M. Chelaru / Applied Surface Science 303 (2014) 1422

21

Fig. 11. Removal efciency vs. contact time of (a) Cd2+ , (b) Cu2+ and MB from pollutant system in adsorption processes.

Fig. 12. The inuence of type of substrate in removing the Cd2+ , Cu2+ and MB from pollutant system by adsorption processes.

Table 3
Kinetic parameters of the heavy metal adsorption.
Substrate

Pseudo rst-order kinetics

Pseudo-second order kinetics

KL (min1 )

R2

k2 (g/mg min)

Cu (Cu + MB)
FAA-CS24
FAA-CS48

0.005
0.014

0.953
0.992

Cd2+ (Cd2+ + MB)

FAA-CS24
FAA-CS48

0.013

MB(MB + Cu2+ )
FAA-CS24
FAA-CS48
MB(MB + Cd2+ )
FAA-CS24
FAA-CS48

2+

Interparticle diffusion

qe (mg/g)

R2

Kid (mg/g min1/2 )

R2

0.446
0.231

119.058
138.889

0.969
0.996

5.754
5.330

0.888
0.696

0.097
0.055

156.25
126.582

0.995
0.993

2.989

0.017

0.987
0.312

21.754
0.089

1.7068
1.649

0.994
1

0.0861

0.2272

0.916
0.314

0.048

0.870
0.728

1.134
6.225

1.613
1.634

0.999
0.999

0.016
0.365

1.394
1.056

0.873
0.880

2+

11.554
42.240
101.0

0.939
0.951
0.929
0.613

Table 4
Adsorption isotherm parameters.
Solution system/substrate

2+

2+

Cu (Cu + MB)FAA-CS24
Cd2+ (Cd2+ + MB)FAA-CS24
MB (MB + Cu2+ ) FAA-CS24
MB (MB + Cd2+ ) FAA-CS24

Langmuir parameters

Freundlich parameters
2

qmax (mg/g)

a (L/mg)

KF

R2

56.497
87.719
0.3111
1.227

0.0016
0.0009
0.108
0.078

0.987
0.987
0.966
0.869

2.399
2.935

1.795

0.574
6.380

4.616E09

0.915
0.904
0.766
0.929

22

M. Visa, A.-M. Chelaru / Applied Surface Science 303 (2014) 1422

References

Fig. 13. Removal efciency of HM cations and MB vs. FAA-CS24 substrate dose in
adsorption process.

Fig. 14. The methlene blue protonated by electrophilic attack.

Supplementary, after adsorption and ltration the substrate loaded with pollutants was dried at 125 C and
subjected to desorption process. After 48 h, for ratio
mpFAA-CS/Cd+MB :Vbidistilled water = 0.3 g:100 mL there are no desorption of cadmium. Very small concentration of methylene blue was,
but not evaluated by spectrophotometer. These materials can be
reused for stufng in blocks of stone.
4. Conclusions
This results show that the y ash has potential to be used as
an alternative and cheap source of silica or alumino-silicates in the
production of adsorbents.
Micro-nano substrate was obtained in a hydrothermal process,
starting from y ash powder and HTAB cationic surfactant and was
tested for simultaneous removal of heavy metal cations and dyes,
in a single step process by adsorption.
The FAA-CS24 structural, morphology analysis and pore distribution showed that the substrate has a high crystallinity degree
and a surface with broad open pores, efcient in heavy metals (Cd2+
and/or Cu2+ ) removal from systems also containing methylene blue.
The kinetic and thermodynamic studies show that the substrate
has a good adsorption capacity mainly based on the electrostatic
attractions between the substrate and Cd2+ and/or Cu2+ cations.
Of the two substrates, FAA-CS24 substrate is effective in removing the pollutants by adsorption process and more economical in
terms of the process of obtaining, the energy consumption is lower.
Acknowledgment
This work was supported by the grant PNII-RU-TE-2012-30177/2013, nanced by Romanian National Authority for Scientic
Research, CNCS UEFISCDI.

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