Journal of Hazardous Materials 244245 (2013) 773779

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Journal of Hazardous Materials

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Methyl-orange and cadmium simultaneous removal using y ash and

photo-Fenton systems
Maria Visa , Anca Duta
Transilvania University of Brasov, Department of Renewable Energy Systems and Recycling, Eroilor 29, 500036 Brasov, Romania

h i g h l i g h t s

g r a p h i c a l

a b s t r a c t

 The mixed substrates of FA-M + TiO2

proved to be highly efcient in
adsorption.
 FA-M + photo-Fenton are a low-cost
material for advanced treatment of
wastewater.
 The adsorbed MO may act as a complexion agent, increasing the afnity
for metals.
 Dye removal by photodegradation
is the favourable mechanism compared to adsorption.

a r t i c l e

i n f o

Article history:
Received 18 April 2012
Received in revised form 8 November 2012
Accepted 8 November 2012
Available online 16 November 2012
Keywords:
Wastewater
Adsorption
Photocatalysis
Fenton-system
Fly ash

a b s t r a c t
Wastewaters resulting from the textile and dye nishing industries need complex treatment for efcient
removal of colour and other compounds existent in the dyeing and rising baths (heavy metals, surfactants, equalizers, etc.). Modied y ash (FA) mixed with TiO2 photocatalyst represent a viable option
for simultaneous removal of dyes and heavy metals, and the optimized conditions are discussed in this
paper for synthetic wastewaters containing methyl-orange (MO) and cadmium. For a cost-effective dye
removal process, further tests were done, replacing the photocatalyst with a (photo)Fenton system. The
optimized technological parameters (contact time, amount of y ash and amount of Fe2+ /H2 O2 ) allow
to reach removal efciencies up to 88% for the heavy metal and up to 70% for the dye. The adsorption
mechanisms and the process kinetic are discussed, also considering the possibility of in situ generation
of the Fenton system, due to the y ash composition.
2012 Elsevier B.V. All rights reserved.

1. Introduction
Economic growth brings transformation, with a focus on
high-tech products and domestic goods, including the dyes manufacturing and the textile nishing industries; an immediate
consequence is the increase in water consumption and in wastewaters discharged into efuents. There are more than 10,000 dyes
currently used in the textile industry and over 280,000 tonnes of

Corresponding author. Tel.: +40 729109355; fax: +40 268410525.

E-mail addresses: visamro2000@yahoo.com, maria.visa@unitbv.ro (M. Visa),
a.duta@unitbv.ro (A. Duta).
0304-3894/$ see front matter 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.jhazmat.2012.11.013

the textile dyes are discharged every year worldwide [1]. Dyes
and heavy metals are hazardous pollutants which can modify the
physical and chemical properties of any ecosystem. Wastewaters
resulted in the dye nishing industry have high BOD to COD values
(>2000 mgO2 L1 ) while the discharge limits [2,3] are much lower
(BOD < 40 mgO2 L1 ; COD < 120 mgO2 L1 ), indicating the need for
wastewater treatment, because most of the dyes are slowly or nonbiodegradable.
Most of the wastewaters resulted in the dye nishing industry
are also containing additives (solubility and anti-foaming agents,
pH conditioners, whitening agents, etc.) and heavy metals, making the wastewater treatment complex and difcult. Toxicological
studies show that the most bio-toxic heavy metal is cadmium (also

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M. Visa, A. Duta / Journal of Hazardous Materials 244245 (2013) 773779

Table 1
Fly ash composition.
Major oxides (wt.%)
SiO2

Al2 O3

Fe2 O3

CaO

MgO

K2 O

Na2 O

TiO2

MnO

LOIa

53.32

22.05

8.97

5.24

2.44

2.66

0.63

1.07

0.08

1.58

Trace elements (mg g1 )

Ba

Cu

Zr

Sn

Pb

As

Ni

Zn

Ti

Cr

Co

700

60

100

35

100

55

160

6414

100

115

12

Loss of ignition.

part of some metal-complex dyes), while dyes and pigments are

affecting water transparency, reducing light penetration and gas
solubility in water [4], also being mutagenic to human. The conventional removal processes mostly used are: chemical precipitation
[5], occulation/coagulation, membrane separation (ultraltration,
reverse osmosis), adsorption (mainly using activated carbon), catalytic oxidation [6], and ozonation. But full colour removal has
limited efciency when both pollutants (dyes and heavy metals)
are present. Supplementary, colour removal does not necessarily end up with complete de-pollution (mineralization); bleaching
without demineralisation can lead to by-products more harmful
(un-saturated hydrocarbons, carbonyl and carboxyl products, etc.)
and fullling the discharge regulations [3] might be questionable.
Modied y ash proved to be an efcient heavy metal adsorbent
(Cd, Cu and Ni) [7,8], and dyes removal (methylene blue) with over
60% efciency [9]. Mixtures of y ash and activated carbon powder were already investigated with good results for heavy metals;
average results were also obtained on these substrates for methylorange [8,10].
Combined substrates for a single-step process able to simultaneously remove pollutants from different classes represent a study
initiated in the past years, aiming at developing up-scalable and
low-cost advanced wastewater treatment processes. The efciency
of the pollutants removal process especially methyl-orange from
wastewaters loaded with dyes and heavy metals can be improved
by using y ash and TiO2 [11] or WO3 [12], by combining adsorption
and photocatalysis.
The photocatalysis efciency is improved by adding oxidation agents as H2 O2 and/or Fenton systems, usually based on
Fe2+/3+ + H2 O2 [13]. In this case, three mechanisms can be expected
in the system containing both, y ash and TiO2 : adsorption, heterogeneous photocatalysis and homogeneous (photo) catalysis.
This paper investigates a combined treatment process of
wastewaters with complex pollution load (heavy metals and dyes);
the process includes simultaneous adsorption (FA), along with
homogeneous (Fenton) and heterogeneous (TiO2 and FA) photocatalysis. Methyl-orange (MO) was used in the experimental test
because it has a remarkable stability to photo-degradation (due to
the extended -electrons delocalisation on the two aromatic rings
and the adjacent groups), being therefore used as standard in many
studies, while cadmium was chosen as one of the most toxic heavy
metal.
2. Experimental
2.1. The substrates
Raw y ash (FA) was collected from the electro-lters. The coal
burned in power plant CHP Brasov from Romania is a mixture of
coals (bituminous and pit coal). The main oxides and trace elements
in the raw y ash were identied by atomic absorption spectrometry with graphite furnace and are presented in Table 1, as given by
the CHP plant.

Table 2
The surface characteristics of FA-M with TiO2 .
Component

Surface area
(m2 /g)

Total pore
volume (cm3 /g)

Average pore
diameter (nm)

FA-M
TiO2

11.33
50.02

0.06
0.25

20.33
30.08

The main oxides in the y ash composition are SiO2 (53.7%),

Al2 O3 (21.60%) and Fe2 O3 (9.56%); according to the ASTM standards
[14], the y ash is of F type, and it hardens or modies only in contact
with water and lime, otherwise it does not aggregate during long
contact with water. Other oxides in the y ash composition (TiO2
1.07% and Mn2 O3 0.08%) are important as possible participants in
dyes photodegradation; the y ash also contains unburned carbon
(1.58%) representing efcient adsorption sites for dyes and heavy
metals [15].
Raw y ash was washed with ultra-pure water, by mechanical
agitation (100 rpm) using Nahita GJ-1 stirrer, at room temperature
(23 C), for 48 h, to remove the soluble compounds. The ratio raw y
ash (g):ultra-pure water (mL) was 1:10. After 48 h the suspension
was subject of ltration and dried at 105 C.
Modied y ash (FA-M): adsorption experiments on waterwashed FA proved very low efciencies in heavy metals and dyes
removal as result of a low surface charge and a low specic surface. Based on previous studies [16], optimized conditions were
applied to modify the y ash surface (area and charge), by mechanical stirring (100 rpm) using Nahita GJ-1 stirrer washed FA for 48 h,
at room temperature (23 C) in NaOH 2 mol L1 solution, followed
by ltration, washing with ultra pure water, drying at 105115 C
and selecting the 40100 m fraction by mechanical sieving (Analysette 3 Spartan); this fraction represents 37.35 wt.% of the total
FA and the rest of the ash could be further valorized in obtaining
geo-polymers, in manufacturing concrete, bricks and ceramic tiles,
or as ller in plastics and paints.
This fraction was selected because of two main reasons: (a)
as adsorbent, a large specic surface is required (corresponding
to low dimensional grains) and (b) these values still make possible up-scalable separation processes in designing the wastewater
treatment process. The last reason also made us not to further mill
this fraction.
This y ash was further used in the experiments.
Mixed substrates FA-M with TiO2 was obtained using TiO2
Degussa P25. Degussa P25 is a mixture of anatase and rutile in a 3:1
ratio, delivered as 30 nm nano-sized particles, with a high specic
surface area.
The surface characteristics, both for FA-M and TiO2 were evaluated using a BET surface analyser (Tri Star II 3020 Micromeritics)
and are presented in Table 2.
All the experiments on mixed substrates used the previously
optimized ratio FA:TiO2 = 3:1 [11].
The FA crystalline structure was evaluated by XRD (Bruker D8
Discover Diffractometer) and AFM images (Ntegra Spectra, NT-MDT

M. Visa, A. Duta / Journal of Hazardous Materials 244245 (2013) 773779

775

model BL222RNTE) were used for morphology studies, before and

after MO adsorption and/or photodegradation).
2.2. Adsorption experiments
Batch adsorption experiments were done at room temperature, under mechanical stirring (100 rpm). In all the experiments
a constant ratio substrate mass:solution volume was set at 4 g
(FA:TiO2 = 3:1):100 mL.
The pollutant systems were synthetically prepared using cadmium from solid salts CdCl2 2.5H2 O (Scharlau Chemie S.A., <98%
purity) and reagent grade methyl-orange (C14 H14 N3 NaO3 S, sodium
4-[(4-dimethylamino) phenyldiazenyl] benzenesulphonate (E.
Merck 99.98% purity) dissolved in ultra-pure water.
The adsorption mechanisms and the kinetic data were evaluated
on three types of suspensions:
(1) substrate: FA-M + TiO2; pollutant systems: mono-component
solution of (a) MO (C1 = 104 mol L1 ; C2 = 5 105 mol L1 ) and
(b) cadmium (Ci = 5 103 mol L1 ); these concentrations were
chosen as they represent a usual upper limit of the industrial
wastewaters subject of investigations.
(2) substrate: FA-M + TiO2 ; pollutants system: bi-component solutions of MO (C1 = 104 mol L1 ) + Cd2+ (Ci = 5 103 mol L1 );
(3) substrate: FA-M; pollutants system: bi-component solutions
of MO (C1 = 104 mol L1 ) + Cd2+ (Ci = 5 103 mol L1 ); Fenton
system: FeSO4 + H2 O2 . The iron salt (FeSO4 7H2 O (Scharlau
Chemia S.A., 98.99% purity)) were added to reach nal concentrations in the tested systems in the range of 5 104 to
3 103 mol L1 . The volume of H2 O2 (Scharlau Chemia S.A.
30%, purity, d = 1.11 g/cm3 , M = 34.01) was kept constant at
50 L resulting in a concentration of 4.45 103 mol L1 in the
pollutants solutions.
In the kinetic studies, aliquots were taken at preset moments
(up to 360 min), when stirring was briey interrupted and, after
ltration on a 1.5 m lter, the supernatant was analysed. Preliminary experiments allowed optimizing the lter type, considering
three conditions: (1) no retention of the soluble species, especially
methyl-orange and Cd, to avoid results denaturation; (2) full retention of the substrates; (3) ltering rate as fast as possible, having in
view the possible up-scaling.
2.3. Homogeneous and heterogeneous photo-catalysis
Parallel photodegradation studies were done on FA-M and
FA-M:TiO2 suspensions with identical overall concentration of
the dispersed phase, with/without Fenton reactive and hydrogen peroxide (30%), under UV irradiation, using quartz beakers.
The experiments were developed in a home-made reactor,
equipped with three F18W/T8 black light tubes (Philips, UVA range
340400 nm, with max,emission = 365.29 nm) placed annular to the
photoreactor [17]. The mean value of the radiation ux intensity, reaching the middle of the reacting suspension was 3 Lx
(Mavolux5032B/USM) and the irradiance is 846 W m2 . During the
adsorption studies the radiation ux intensity was in the range of
0.71.6 Lx, with an average irradiation of 215 W m2 .
All the adsorption results are denoted with (A), while the results
obtained under UV irradiation have the (F) symbol.
In all experiments the solutions were tested at their natural pH.
The pH value of the MO solutions in contact with FA-M was 8.6
and in contact with the mixed system FA-M + TiO2 , the pH value
was 8.1, and these values are below those indicated in the Pourbaix
diagram for Cd(OH)+ (pH = 9.2) or Cd(OH)2 (pH > 9.5) formation at
the working temperature [18].

Fig. 1. XRD of raw FA, washed with water (1) and of FA-M (2).

Adding cadmium cations in the MO solutions did not alter these

pH values and there was no evidence of hydroxide precipitation (as
result of the low heavy metal concentrations).
2.4. Pollutants analysis
The initial and residual metal concentration in the aqueous
solution was analysed by AAS (Analytic Jena, ZEEnit 700, at
Cd = 228.8 nm) and the MO was analysed by UVvis spectrometry (Perkin Elmer Lambda 25), on the calibration curve registered
at  = 460 nm.
The removal efciency was estimated by the following equation:
 (%) =

c0 ct
100
c0

(1)

where c0 represents the initial concentration and ct the concentration at moment t for the pollutant species (heavy metal or dye).
Preliminary experiments proved that heavy metal and MO
losses due to adsorption on the beakers walls and on the lter
paper were negligible. Blank tests done with the alkali conditioned
FA showed that during the experiments duration (up to 360 min) no
leaching occurred. Experiments also showed that there was no shift
in the absorption peak (in the initial solution and after the removing processes); supplementary interference with the Degussa P25
powder was investigated by analysing the spectra of ultra-pure
water and the supernatant resulted after ltering a Degussa P25
suspension in ultra-pure water and there were no differences.
3. Results and discussion
3.1. The substrates
The XRD spectra, Fig. 1, show that y ash contains crystalline compounds such as carbon (graphite), SiO2 (tetragonal
and orthorombic) combined with Al2 O3 as rhomb H, -Al2 O3 and
mullite (3Al2 O3 2SiO5 ), aluminosilicates with ions of Na+ or Ca2+ .
During the initial FA washing, the alkali and alkali-ferrous oxides
are likely to be removed; the further NaOH treatment can end up
in silica re-precipitating, as previously outlined [19,20].
The XRD data also show that FA contains small amounts of
crystalline titanium oxide (as brookite and as non-stoichiometric
Ti4 O7 ) thus indicating a possible photocatalyitic activity. Other
crystalline oxides are also part of y ash, as bixbyite (Mn2 O3 ) commonly found with hematite that can be responsible for in situ
oxidation/reduction systems of Fenton type. The unburned carbon,
as micro-sized crystallites is part of the FA and can explain the

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M. Visa, A. Duta / Journal of Hazardous Materials 244245 (2013) 773779

Fig. 2. The AFM topography and average macro-pore size distribution in (a) FA-M before adsorption, (b) TiO2 before adsorption, (c) FA + TiO2 after MO interaction, and (d)
FA-M after MO adsorption.

versatility of this material in various adsorption processes. These

components are characterizing the raw y ash and can be found also
in the modied FA. The alkali treatment (FA-M) is responsible for
the partial dissolution/re-precipitation processes of the major components (alumina and silica) but the unburned carbon, the titanium,
manganese and iron oxides content have no signicant variation
during the FA conditioning.
Based on the method proposed by Otero et al. [21], the AFM data,
Fig. 2, were used to get supplementary information about the FA
macro-pores resulted from particles associations. Large pores are
developed as result of particle aggregation. It is interesting to notice
that MO adsorption uniformly lls the FA-M voids, thus shifting
the distribution maxima to lower values, while the dye adsorption
on the mixed substrate results in higher maxima for TiO2 , proving
preferential adsorption.
The interactions between the ash and sodium hydroxide
develop new active sites ( SiO ) and ( AlO ), allowing metals to
form complexes on the surface (Eqs. (2) and (3)) [22]:
2( SiO ) + M2+ ( Si O)2 M

2( AlO ) + M

2+

( Al O)2 M

(2)

Protolytic equilibria
Ti OH + H
Ti OH

Ti O + H

(4)
(5)

Alkaline pH values will therefore support heavy metal adsorption:

Ti OH + M2+

(7)

TiO2 (h+ ) + H2 O OH + H+ + TiO2

(8)

TiO2 (h+ ) + HO OH + TiO2

(9)

The TiO2 based compounds on the FA-M surface are expected to

host similar processes.
On the FA-M:TiO2 mixture, simultaneous processes of adsorption and photocatalysis will be developed. A competition is
expected on the active sites, but dyes adsorption is less favoured
considering the working pH (pKaMO = 3.7) when the ionized form
has a negatively charged head. These processes can be: (1) cadmium adsorption on FA-M; (2) cadmium adsorption on TiO2 ; (3)
dyes adsorption on the heterogeneous mixture FA-M:TiO2 surface,
according to Eqs. (10) and (11).

(10)

(11)

Ti OH2

2TiO2 + h TiO2 (h+ ) + TiO2 (e )

(3)

On the amphoteric TiO2 , the protolytic equilibrium can lead to

various surface charges, according to the solution pH and the point
of zero charge (pHpzc, DegussaTiO2 = 6.2) [23]. For pH values higher
than pHpzc , the surface is negatively charged and it is the opposite
for pH < pHpzc , according to the following equilibrium:

Photocatalysis, based on HO . Active species is also expected

on/near the TiO2 surface:

(Ti O )2 M + 2H+

(6)

Supplementary, the adsorbed MO may increase the substrates

afnity for heavy metals; the two aromatic rings in the almost planar structure and the amine head can act as electron donors in the
interaction with the cadmium cations [9]. In the working conditions
cadmium exists as hydrated cation [18].

M. Visa, A. Duta / Journal of Hazardous Materials 244245 (2013) 773779

777

Fig. 3. Cadmium removal efciency on FA-M:TiO2 substrate from mono-component

pollutant systems (C = 0.005 mol L1 ).

3.2. Heavy metals and dye removal from mono-component

pollutant suspensions of FA and TiO2
Adsorption experiments were done (A), in parallel with photocatalysis under UV irradiation (F).
For cadmium removal the results are presented in Fig. 3. As
expected, there is no inuence of the irradiation (vis or UV), and
very good efciencies are recorded after 30 min. On the substrate
FA-M:TiO2 = 3:1.
The results presented in Fig. 4a prove that, without H2 O2 addition a change in the mechanisms is registered after 180 min; this
can be possible the result of a slow, in situ Fenton type process,
caused by the Fe2+ and Mn3+ , on/near the surface of the y ash.
Under UV irradiation, the effect of H2 O2 is much stronger and the
efciency strongly increases, although the changes in the slopes
may indicate various mechanisms or various pore sizes/reaction
sites opened to adsorption/photo-degradation.
The concentration of the dye represents another parameter of
interest. According to the data presented in Fig. 4b, higher removal
efciencies correspond to the lower concentration (C2 ), both in
adsorption and in photodegradation. The slopes variation indicates
that initial processes are followed by concurrent reactions, as result
of new species generated in the H2 O2 reaction with the oxides from
the y ash. Considering these results the optimized MO removal
conditions from single component solutions are: a dye concentration of 5 105 mol L1 , using a mixed FA-M:TiO2 substrate, with a
contact time of 300 min, when H2 O2 is added, under UV irradiation
when efciencies over 90% can be reached. Efciencies up to 70%
can be reached in similar conditions in environmental conditions
(natural light).

3.3. Heavy metals and dye removal from multi-component

pollutant suspensions
The use of TiO2 mixed with FA proved to be efcient but
TiO2 nanoparticles have quite high costs and raise technological
problems in removing the photocatalyst in industrial processes.
Therefore, further investigations were done to test an alternative
process, based on FA and photo-Fenton system.
Photocatalysis is enhanced by a larger amount of hydroxyl
radicals. One way to produce them is using Fenton systems
(H2 O2 /Fe2+ /Fe3+ ), when the oxidation-reduction process is
H2 O2 + Fe2+ Fe3+ + HO + HO

(12)

Fig. 4. Methyl-orange removal efciency on FA-M:TiO2 substrates from monocomponent pollutant systems in adsorption (A) and photocatalytic (F) experiments:
(a) inuence of H2 O2 addition and (b) inuence of the MO concentration
(C1 = 104 mol L1 and C2 = 5 105 mol L1 ).

Under UV irradiation, in the photo-Fenton system, supplementary amounts of HO are produced from the fast hydrogen peroxide
decomposition:
H2 O2 + UV HO + HO

(13)

Fe3+ + H2 O + UV+ Fe2+ + HO + H+

(14)

Fe2+ + HO Fe3+ + HO

(15)

Besides these reactions, since FA also contains about 1% of TiO2 ,

photocatalysis may also be expected. Experiments targeted the
optimization of the Fe2+ concentration in the system containing
MO and cadmium (Fig. 5).
As the results show, by adding Fe2+ /H2 O2 , after 90 min the equilibrium is reached for most of the samples. The sample obtained
with 2 103 mol L1 Fe2+ has a particular behaviour and the mechanism(s) that reect these results will be analysed in the future.
Considering that 90 min is a technologically feasible contact
time, the optimal amount of Fe2+ solution (3 103 mol L1 ) was
further investigated; it was found that the iron cation directly inuences the MO removal efciency, as Fig. 6 shows.
In similar conditions, cadmium removal has lower efciencies comparing to the mono-component solution (Fig. 3), proving
competitive adsorption of the dye and heavy metal and/or the
development of CdMO structures which have a lower diffusion
rate and an increased stability also blocking a larger amount of

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M. Visa, A. Duta / Journal of Hazardous Materials 244245 (2013) 773779

Table 3
Kinetic parameters of the MO removal in photo-Fenton + adsorption processes.
MO (MO + Cd2+ )

Parameter
1

5 104
0.358
27,228
0.952

CFe2+ (mol L )
qe (mg g1 )
k2 (g mg1 min1 )
R2

103
0.384
5319.2
0.998

2 103
0.708
19,261
0.964

3 103
0.617
4793.5
0.9795

Table 4
Kinetic parameters of the Cd2+ removal in photo-Fenton + adsorption processes.
Cd2+ (Cd2+ + MO)

Parameter

CFe2+ = 3 10

Fig. 5. Inuence of the Fe2+ on the photodegrdation efciency of methyl-orange.

qe (mg g1 )
k2 (g mg1 min1 )
R2

initial c i
metal
qt =

Fig. 6. Inuence of the Fe2+ amount on the MO removal efciency, at 90 min.

mol L

CFe2+ = 2 103 mol L

UV

Visible

UV

Visible

632.981
1.5751
0.978

727.517
2.8378
0.973

538.331
0.0019
1

540.355
0.0093
1

Cd2+ /MO

concentrations of the

dye (MO) using Eq. (16).

ct

Cd2+ /MO

ms

)V
(16)

According to the specic surface data, FA-M can be described

as a meso-porous substrate and TiO2 has rather large open pores,
easily accessible to adsorption, therefore, in the experimental condition (high substrate:volume ratio), inter-particle diffusion is not
likely to be the limiting factor. Different kinetic adsorption mechanisms were tested (pseudo-rst order, interparticle diffusion,
LangmuirHinshelwood) and the pseudo-second order kinetics (Ho
and McKay, 1999) was found to best model the general processes
[24]:
t
1
t
=
+
qt
qe
k2 q2e

Fig. 7. Cadmium adsorption efciency in the optimized Fenton systems.

Cd2+ (Cd2+ + MO)

1

and momentary c t

Cd2+ /MO
(Cd2+ ) and

(c i 2+
Cd /MO

(17)

where k2 is the pseudo second-order rate constant (g mg1 min1 ).

Based on the linear form of the equation, the kinetic parameters
were calculated and are presented in Table 3 for MO removal and
in Table 4 for cadmium adsorption, from bi-component solutions.
The data allow us to conclude that the amount of active sites
and the amount of reactive species are comparable, in terms of
adsorption.
The data show fast dye removal. The values of the maximum
adsorption capacity are apparent and correspond to the retained
dye on the substrate but the largest amount of dye is decomposed
as the data in Fig. 4 also conrm.
The cadmium adsorption kinetic is moderate but the maximum
capacity is high, recommending the substrate for industrial processes.
4. Conclusions

active sites. The data presented in Fig. 7 show a higher efciency

under UV irradiation, not as result of a direct inuence on the heavy
metal cation, but as a consequence of faster dye degradation, thus
leaving empty a larger amount of active sites for cadmium bonding
onto the substrate.
Further kinetic investigations on the FA-Mphoto-Fenton were
developed to elucidate the process mechanism(s).

3.4. Uptake kinetics of the heavy metals and dye

The adsorption capacity qt , for the given solution volume,
V, and amount of substrate, ms , were calculated based on the

Two low costs alternative processes were tested for the treatment of wastewaters containing dyes and heavy metals. The mixed
substrates of modied y ash and TiO2 proved to be highly efcient in cadmium adsorption, even after 30 min of contact, and
methyl-orange could be well removed, with efciencies above 75%
(after 300 min), when H2 O2 was added to systems with the dye
concentration of 0.05 mM.
Wastewaters containing mixed cadmiummethyl-orange can
be treated using modied y ash and photo-Fenton systems, under
UV irradiation. The results allow optimizing the Fe2+ amount for
reaching (after 90 min) methyl-orange removal efciencies close
to 70% while the cadmium adsorption was of 88%.

M. Visa, A. Duta / Journal of Hazardous Materials 244245 (2013) 773779

Acknowledgements
This paper is supported by the Sectoral Operational Programme
Human Resources Development (SOP HRD), nanced from the
European Social Fund and by the Romanian Government under the
contract number POSDRU ID 59323.
Appendix A. Supplementary data
Supplementary data associated with this article can be
found, in the online version, at http://dx.doi.org/10.1016/j.
jhazmat.2012.11.013.
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