Degradation of mono azo dye in aqueous solution using

IJRET: International Journal of Research in Engineering and Technology eISSN: 2319-1163 | pISSN: 2321-7308
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Volume: 02 Issue: 09 | Sep-2013, Available @ http://www.ijret.org 227
DEGRADATION OF MONO-AZO DYE IN AQUEOUS SOLUTION USING
CAST IRON FILINGS
Raja Kumar1
, Alok Sinha2
1
Research Scholar, 2
Assistant Professor, Department of Environmental Science and Engineering, Indian School of
Mines,Dhaanbad,aloksinha11@yahoo.com
Abstract
The mono-azo dye, Orange II, solution was substantially degraded with cast iron particles under varied conditions of experimental
variables such as pH, initial dye concentration and cast iron dosage.At all solution pH studied, the degradation efficiency achieved
was > 90%. With an initial dye concentration of 100 mg/L and optimum cast iron load of 28.56 g/L, the optimum degradation
efficiency of 97.63% was achieved at pH 3. With same cast iron load and solution pH, more than 95% dye degradation efficiency was
achieved at different initial Orange II concentrations ranging from 50-500 mg/L. The efficiency of cast iron particles in degrading
Orange II dye was compared with that of pure elemental iron used in other study. Cast iron particles showed better degradation
efficiencies than elemental iron that too at relatively lower dosages. Ultimately, from the results it can be inferred that cast iron
fillings can be successfully applied to treat textile effluents containing high dye concentration and treatment efficiency can be
enhanced by optimizing the reaction conditions.
Index Terms: azo dyes, Orange II, degradation efficiency, cast iron fillings
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1. INTRODUCTION
Textile dyeing industries have long been one of the most
important industries in the world. According to an estimate,
around 0.7 million tons of dye are used every year of which
50% are azo dyes [1]. Of the total dye produced, 15% is lost
during the dyeing process [2]. Dyes being tinctorially stronger
are visible in water at concentrations as low as 1 ppm [3].
Available literatures points that dye containing effluent are
more mutagenic and toxic when compared to other industrial
discharges [4]. Researchers have shown that azo dyes released
into ground and surface waters from textile discharges
contribute to mutagenic activity [5,6]. Besides, the release of
coloured wastewater in the ecosystem is a remarkable source
of aesthetic pollution, eutrophication, and perturbations in
aquatic life [2].Several chemicals found in dye-bath effluent
are toxic, carcinogenic, mutagenic, or teratogenic to various
life forms. The human health impact of dyes, especially azo
dyes and their degradation products have caused concern for a
number of years, with legislation controlling their use, being
developed in a variety of countries [7]. Increasingly, the
environment and subsequent health effects of azo dyes
released in textile industry wastewater are becoming subject to
scientific scrutiny. It is hence not surprising that removal of
these compounds has now-a-days become a major
environmental concern.
Many physical and chemical treatment processes have been
developed in scientific laboratory but their practical
applicability is restricted either by cost or efficiency and
cannot be adopted as an exclusive method.Conventional
biological treatment methods alone generally are ineffective
insofar as complete azo dye degradation is concerned[8].
Since biological treatment methods are still the cheapest
option available, efforts should be made to develop an
effective pretreatment technology that could transform the azo
dyes into easily bio-decomposable compounds.
Reductive transformation of pollutants using cast iron filings
is widely gaining attention for environmental remediation.
Cast iron filings are cheap and easily available strong reducing
agent. The literature substantially reports the applicability of
cast iron filings in treating wastewater contaminated with
chlorinated compounds [9], nitroaromatic compounds [10],
heavy metals [11], explosives[12] and dyes[13], etc. Among
these pollutants azo dyes are considered as most susceptible to
metallic reduction [14], thus, if the treatment conditions are
optimized cast iron filings can serve as an effective
pretreatment alternative. In this study, treatment of synthetic
wastewater containing mono-azo dye Orange II has been
carried out using cast iron filings. This study intends to
optimize the key reaction parameters that could affect the
applicability of cast iron filings for treating azo dye-containing
wastewater in large scale.
2. MATERIALS AND METHODS
2.1. Dye
Commercially available mono-azo dye Orange II (M.W.-
350.32)which is a widely used anionic monoazo-dye [15] was

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chosen as a model of the hydro soluble phenylazonaphthol
dyes due to its resistance to biological degradation.AO7 was
purchased from Atul Ltd. (India) and was used as received.
The dye solutions in a 1cm quartz cuvette were scanned over
the wavelength range 200–800nm using a UV–visible
spectrophotometer (UV-1800 series, Shimadzu, Japan) for
determination of the wavelength of maximum absorbance (λ
max).
2.2 Preparation of Cast Iron Fillings
Commercially available cast iron rod was chipped on a lathe
machine and then ground into iron filings in a dough-size ball
mill. The filings were sieved and those between 40 (425 μm)
and 80 (212 μm) mesh sizes were retained for use. Cast iron
fillings, thus produced, was washed 5-6 times with N2-sparged
1N HCl with periodic shaking. Then it was rinsed 10-12 times
with N2-sparged deionised (Milli Q) water. The washed
fillings were rinsed twice with acetone to remove moisture.
Again it was rinsed twice with 95% pure ethanol and dried for
1 hour. This treatment yielded black metallic filings with no
visible rust on the surface. Fillings were stored in a vacuum
desiccator until use in various experiments.Surface area of the
treated filings was determined by BET (N2) analysis using a
BET surface area analyzer (NOVA 4000e, Quanta chrome
Instruments, USA) to be 1.4 m2/ g.
2.3 Experimental Procedure
Time series batch experiments were carried out in 35 ml
capacity glass vials with screw caps (Borosil, India). All dye
solutions were prepared using deionized (Milli Q) water and
all reagents utilized were of analytical purity. The solution pH
was adjusted to the desired levels using HCl (0.5M) or NaOH
(0.1 M) with a pH meter (Digital pH meter 111, EI, India). For
proper mixing, the vials were placed on a test tube rotator
(Rotospin, Tarsons, India), at 30 rpm, keeping the axis of vials
horizontal. Temperature was 25 ± 2○C for all experiments.
Vials were removed from the rotator in duplicate (along with a
control) at specified times for sampling and analysis and were
put on a magnet to allow iron particles to settle down quickly.
Supernatant samples were taken out from vials and filtered
through GF/C filter paper (1.2 µm nominal pore size, What
man, Springfield Mill, England).
2.4 Analytical Procedure
Efficiency of cast iron fillings for the degradation of Orange II
was assessed in terms of decolorization efficiency (%) as
follows:
Degradation efficiency (%) = 1 A A⁄ ] 100% (1)
Where At = absorbance of solution at time‘t’ of treatment,
A0 = absorbance of untreated solution.
3.0 RESULTS & DISCUSSION
3.1 UV-Vis Scan
The UV-vis spectra of Orange II scanned over wavelength
range of 200 to 800 nm is shown in Fig.1. Different
absorbance peaks exhibit different structural units and groups
of the dye molecule.Orange II is characterized by one main
band in visible region, with its maximum absorption at 484
nm, and two bands in ultraviolet region located at 229 nm
and 310.5 nm. These observed peaks correspond to
chromophore containing azo linkage, benzene ring and
naphthalene ring, respectively [16].
Fig.1: UV-Vis spectra of Orange II azo dye
3.2 Effect of Solution pH
Solution pH has been considered as one of the important
factors in governing the reduction of contaminants by
elemental iron, therefore the effect of initial solution pH on the
decolorization of Orange II was studied, and the results are
shown in Fig.2. The degradation efficiency crossed more than
90% within 5 min of treatment.Final Orange II degradation
efficiency after 60 min of treatment was 97.63%,97.11%,
96.97%, 95.14%, 93.95%,for pH 3, pH 4, pH 5, pH 6 and pH
7, respectively. As the solution pH increased decolorization
efficiency decreased.When dye molecule collides with
elemental iron, elemental iron, as an electron donor, loses
electrons, the dye molecule, as an electron acceptor, accepts
electrons, and combines with H+to form a transitional product.
This product receives electrons from elemental iron and
combines with H+ again, finally turning into terminal
products. With more H+ in acid solution than that in alkaline
solution, the reaction in acid solution is easier [17].
nm.
200.00 400.00 600.00 800.00
Abs.
2.500
2.000
1.500
1.000
0.500
0.000
229 nm
310.5 nm
484 nm
Wavelength

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pH
3 4 5 6 7
Degradationefficiency(%)
90
91
92
93
94
95
96
97
98
5 min
40 min
60 min
Fig.2: Effect of different pH values on degradation of Orange
II dye solution (Initial conditions:cast iron dose=
28.56g/Ll;Orange II conc.=100 mg/L; mixing speed-30 rpm)
3.3 Effect of Initial Dye Concentration
The effect of initial concentrations of Orange II on its
degradation efficiency were evaluated at a concentration range
of 50 mg/L to 500 mg/L using 28.56 mg/L cast iron dosage at
pH 3. As shown in Fig. 3, the degradation efficiencies
achieved after 5 min was decreasing with increasing initial
Orange II concentration, i.e., 97.21, 94.81, 92.48,75.18, 57.07
and 47.63% for initial dye concentrations of 50 mg/L, 100
mg/L, 200 mg/L, 300 mg/L, 400 mg/L and 500 mg/L,
respectively. This suggests that the decolorization is
adsorption controlled process [18]. The final efficiencies were
greater than 95% after 60 min of treatment for all
concentrations of Orange II studied.
Initial dye conc. (mg/L)
0 100 200 300 400 500
40
50
60
70
80
90
100
5 min
40 min
60 min
Fig. 3: Effect of different initial dye concentration on
degradation of Orange II dye solution (Initial conditions: cast
iron dose= 28.56g/L; pH- 3.00; mixing speed-30 rpm)
3.4 Effect of Cast Iron Load
The effect of the cast iron dosage on on Orange II removal
efficiency,shown in Fig. 4, indicates that Orange II
degradation efficiency increased with the increase of the cast
iron load. From the experimental data 54.93%, 75.13%,
96.25%, 96.79% and 96.91% degradation efficiencies within
first 5 min, and96.36, 97.63, 99.42, 99.21 and 99.21%after 60
min by cast iron doses of 7.14g/l, 14.28g/l, 28.56g/l, 42.84g/l
and 57.12g/l, respectively. Increasing the load of cast iron
provided substantially more active surface sites to accelerate
the initial reaction, resulting in more iron surface collision
with more azo dye molecules to enhance Orange II
degradation. However, highest degradation efficiency was
achieved at cast iron dosage of 28.56 g/L. This unusual
precept can be attributed to the fact that the presence of
excessive iron in the acidic solution system could be
detrimental since the final pH of the system could reach higher
values thereby decreasing the degradation rate [19].
Cast iron dose (g/L)
7.14 14.28 21.42 28.56 35.70 42.84 49.98 57.12
50
60
70
80
90
100
5 min
40 min
60 min
Fig. 4: Effect of different cast iron dosage on degradation of
Orange II dye solution (Initial conditions: solution pH -3;
Orange II conc.= 100 mg/L; mixing speed-30 rpm)
3.5 Comparison of Efficiencies of Cast Iron Fillings
and Pure Iron
Table 1 shows the comparative degradation efficiencies of
Orange II using pure elemental iron as reported by Mu et
al.[18], and cast iron fillings reported in this work. Mu et
al.[18] have reported highest degradation efficiency of 90-95%
for 101.5 mg/L Orange II adding 66.6g/L of pure iron after 80
min of reaction time. Whereas in this study greater than 99%

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degradation efficiency could be achieved for 100mg/L Orange
II using fairly low cast iron loading of 28.56 g/L within 60
min of reaction time. Also, the mixing speed was kept 4 times
lower at 30 rpm in this study compared to 120 rpm reported by
Mu et al.[18]. In addition, cast iron fillings showed
significantly higher degradation efficiencies at all pH ranges
studied. This greater ability of cast iron to degrade Orange II
could be attributed to the presence of graphite inclusions
embedded in the iron matrix which serves as anon-reactive
adsorption site[9,20,21]. Thus, adsorption and reduction takes
place simultaneously on cast iron surface.
Table 1: Comparison of degradation efficiency of cast iron and zero valent iron studies
Author Iron type
Dosage
(g/L)
Dye
Mixing
rate
(rpm)
Temp (◦
C)
Reaction
time
(min)
Conc.
(mg/L)
pH Efficiency (%)
Mu et
al.[18]
Micro-ZVI 66.6 Orange II 120 30 80
49
101.5
199.5
101.5
101.5
101.5
101.5
4
4
4
3
5
6
7
< 90
~75
75
90-95
70
60-70
60
This
work
Micron
sized Cast
Iron
28.56
Orange II 30 25±2 60
50
100
200
100
100
100
100
3
3
3
4
5
6
7
>99
>99
>99
97
~97
95
~94
CONCLUSIONS
In this work, the parameters affecting the reductive
degradation of Orange II dye were investigated. Although cast
iron particles were found to be capable of degrading more than
90 % of Orange II at all pH examined within 5 min of
treatment time, optimum degradation efficiency of 97.63%
was achieved at pH 3 after 60 min. More than 50% dye
degradation was achieved at all cast iron dosages within 5 min
and the efficiencies exceeded 90% at all dosages after 40 min.
At all the initial Orange II dye concentration studied, more
than 95% degradation efficiencies could be achieved using
cast iron dosage of 28.56 g/L. This indicates that cast iron can
be effective even at the wide range of dye concentration in
textile effluent. Comparative assessment of degradation
efficiencies of cast iron and pure elemental iron reveals greater
capability of cast iron to treat dye containing wastewater.Apart
from the experimental results, the fact that cast iron is
available at a fraction of the cost of the high purity iron makes
it a more ideal cost effective alternative for practical treatment
applications.
ACKNOWLEDGEMENTS
The authors heartily acknowledge Technical Education
Quality Improvement Programme Phase II (TEQIP II), ISM,
Dhanbad, for providing all necessary assistance for completion
of this research work.
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