Wastewater Engineering: Advanced Wastewater Treatment Systems

IJSR Publications
Wastewater Engineering: Advanced

Wastewater Treatment Systems

ii

Wastewater Engineering: Advanced Wastewater
Treatment Systems

ISSN: 2322-4657
DOI 10.12983/1-2014-03-01
IJSR Publications, Penang, Malaysia,

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iii
PREFACE

As the global population grows and many developing countries modernize, the importance of
water supply and wastewater treatment becomes a much greater factor in the welfare of nations.
Clearly, in todays world the competition for water resources coupled with the unfortunate
commingling of wastewater discharges with freshwater supplies creates additional pressure on
treatment systems. Recently, researchers focus on wastewater treatment by difference methods
with minimal cost and maximum efficiency.
This volume of the Wastewater Engineering: Advanced Wastewater Treatment Systems is a
selection of topics related to physical-chemical and biological processes with an emphasis on
their industrial applications. It gives an overview of various aspects in wastewater treatments
methods including topics such as biological, bioremediation, electrochemical, membrane and
physical-chemical applications. Experts in the area of environmental sciences from diverse
institutions worldwide have contributed to this book, which should prove to be useful to
students, teachers, and researchers in the disciplines of wastewater engineering, chemical
engineering, environmental engineering, and biotechnology. We gratefully acknowledge the
cooperation and support of all the contributing authors.

Hamidi Abdul Aziz

Amin Mojiri
Professor, School of Civil Engineering,
Engineering Campus, Universiti Sains Malaysia,
cehamidi@usm.my
Research Assistant, School of Civil Engineering,
Engineering Campus, Universiti Sains Malaysia,
amin.mojiri@gmail.com

iv
TABLE OF CONTENTS

PREFACE ............................................................................................................................... iii
TABLE OF CONTENTS ........................................................................................................ iv
CHAPTER 1: INTRODUCTION OF PRELIMINARY AND SECONDARY
TREATMENTS ...................................................................................................................... 1
1.1 Introduction of preliminary and Secondary Treatments; Z. Amirossadat .............. 2
CHAPTER 2: WASTEWATER BY TREATMENT BY PHYSICAL-CHEMICAL
TECHNOLOGIES ............................................................................................................... 05
2.1 Recent Development in Landfill Leachate Treatment Using Low Cost Adsorbent
Prepared From Waste Material; N. Azmi, J.K. Bashir, S. Sethupathi, C.A. Ng ......... 06
2.2 Removal of Colour from Synthetic Dye Wastewater Using Adsorbent Prepared from
Psyllium Husk; I. Dahlana and S.M.O. Tayeh ............................................................. 15
2.3 COD and BOD Removal from Textile Wastewater Using Naturally Prepared
Adsorbents and Their Activation forms Using Sulphuric Acid; Patel and Vashi ........ 31
2.4 Fenton oxidation for the Treatment of Liquid Waste with High COD and
Anionic/Non-ionic Surfactants; M. Collivignarelli, S. Sorlini, A. Abb, M. Sordi ..... 41
2.5 Ultrasound Irradiation on the Treatment of Aromatic Compounds in Wastewater
W.L. Peng, G. Xinxin, M.J.K. Bashir .......................................................................... 48
CHAPTER 3: WASTEWATER TREATMENT BY BIOLOGICAL METHODS ........ 62
3.1 Wastewater Treatment by Biological Methods; A. Dadrasnia, N. Shahsavari and
C.U. Emenike ............................................................................................................... 63
3.2 Biological Treatment of Recycled Paper Mill Wastewater Using Modified Anaerobic
Inclining-Baffled (MAIB) Bioreactor; H.M. Zwaina and I. Dahlan ............................ 71
3.3 Augmentation of Biological Nitrogen Removal via Optimization of Support Media
Size and Aeration Strategy in Moving Bed Sequencing Batch Reactor; J.Wei Lim, M.J.K.
Bashir, S.L. Ng, S. Sethupathi, L.P. Wong. ................................................................. 87

v
CHAPTER 4: ELECTROCHEMICAL METHODS ........................................................ 96
4.1 Electrochemical Oxidation Process Contribution in Remediating Complicated
Wastewaters; M.J. K. Bashir, J.W. Lim, S.Q. Aziz, S.S.A. Amr ................................ 97
CHAPTER 5: WASTEWATER TREATMENT BY BIOREMEDIATION
TECHNOLOGIES ............................................................................................................. 107
5.1 Wastewater Treatment by Bioremediation Methods; A.N. Amenaghawon and K.O.
Obahiagbon ................................................................................................................ 108
5.2 Supplementation of Novel Solid Carbon Source Prepared from Dried Attached-
Growth Biomass for Bioremediation of Wastewater Containing Nitrogen; J.W. Lim,
M.J.K. Bashir, C.A. Ng, X. Guo. ............................................................................... 125
CHAPTER 6: WASTEWATER TREATMENT BY MEMBRANE TECHNIQUES . 136
6.1 Supported Liquid Membrane in wastewater Treatment; T.T. Teng, A. Talebi, and G.
Muthuraman ............................................................................................................... 137
6.2 Role of Emulsion Liquid Membrane (ELM) in Separation Processes; T.T. Teng, M.
Soniya, G. Muthuraman and A. Talebi ...................................................................... 149
6.3 Bulk Liquid Membrane and its Applications in Wastewater Treatment; T.T. Teng, S.
Elumalai, G. Muthuraman and A. Talebi ................................................................... 158
6.4 Challenges in Fabricating Suitable Membrane for Water Treatment Application;
L.Y. Wong, C.A. Ng, MJ.K. Bashir, T.L. Chew ....................................................... 171
6.5 Removal of Copper from Aqueous Solution by Using Thermo-responsive Polymer
Hydrogel as Copper Chelator via Polymer-enhanced Ultrafiltration (PEUF); J.J. Chen,
A.L. Ahmad and B.S. Ooi .......................................................................................... 183
CHAPTER 7: WASTEWATER TREATMENT BY PHYTOREMEDIATION
TECHNOLOGIES ............................................................................................................. 193
7.1 Wastewater Treatment by Phytoremediation Methods; H. Farraji ..................... 194
CHAPTER 8: LANDFILL LECHATE TREATMENT TECHNIQUES...................... 207
8.1 Municipal Landfill Leachate Treatment Techniques: An Overview; S.Q. Aziz, H.A.
Aziz, M.J.K. Bashir, A. Mojiri .................................................................................. 208

vi
CHAPTER 9: APPLICATION OF OPTIMIZATION IN TREATMENT ................... 225
9.1 Application of Optimization in Wastewater Treatment; Y.L. Lim, Y.C. Ho, A.F.M.
Alkarkhi ..................................................................................................................... 226
Wastewater Engineering: Advanced Wastewater Treatment Systems
Available online at http://www.ijsrpub.com/books
2014 IJ SRPUB
1

Treatment Systems

Chapter 1: Introduction of preliminary and
Secondary Treatments
2014 IJ SRPUB
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Introduction of preliminary and Secondary Treatment

Zahra Amirossadat

Isfahan (Khorasgan) Branch, Islamic Azad University, Isfahan, Iran

Abstract. Recently, the amounts of wastewater are sharply increasing and the kinds of pollutants are also varied as the world
wide industry is being developed incessantly. With respect to both the quantity and composition, the textile processing
wastewater is recorded as the most polluted source among all industrial sectors. This chapter explained the preliminary and
secondary treatment of wastewater.

Keywords: Preliminary treatment, Secondary treatment, Wastewater

1. INTRODUCTION

Recently, the amounts of wastewater are sharply
increasing and the kinds of pollutants are also varied
as the world wide industry is being developed
incessantly. With respect to both the quantity and
composition, the textile processing wastewater is
recorded as the most polluted source among all
industrial sectors (Chang et al., 2009). At wastewater
treatment plants, wastewater is treated before it is
allowed to be returned to the environment, lakes, or
streams.
Discharge criteria required the installation of
facilities that performed what is now called primary
treatment of wastewater. This involved using screens
and sedimentation tanks to remove most of the
materials in the wastewater that float or settle. As
subsequent discharge criteria were tightened,
secondary treatment became necessary. Secondary
treatment is accomplished by bringing together waste,
bacteria and oxygen in trickling filters or the activated
sludge process. Bacteria are used to consume the
organic parts of the wastewater. Facilities and their
designers are now considering and installing tertiary
treatment facilities to comply with the latest
regulatory and permit parameters. These advanced
treatment processes go beyond conventional
secondary treatment and include the removal of
recalcitrant organic compounds, as well as excess
nutrients such as nitrogen and phosphorus (Coppen,
2004). Conventional wastewater treatment consists of
a combination of physical, chemical, and biological
processes and operations to remove solids, organic
matter and, sometimes, nutrients from wastewater.
General terms used to describe different degrees of
treatment, in order of increasing treatment level, are
preliminary, primary, secondary, and tertiary and/or
advanced wastewater treatment. In some countries,
disinfection to remove pathogens sometimes follows
the last treatment step.

2. Primary treatment

The objective of primary treatment is the removal of
settleable organic and inorganic solids by
sedimentation, and the removal of materials that will
float (scum) by skimming. Approximately 25 to 50%
of the incoming biochemical oxygen demand (BOD
5
),
50 to 70% of the total suspended solids (SS), and 65%
of the oil and grease are removed during primary
treatment. Some organic nitrogen, organic
phosphorus, and heavy metals associated with solids
are also removed during primary sedimentation but
colloidal and dissolved constituents are not affected.
The effluent from primary sedimentation units is
referred to as primary effluent. In many industrialized
countries, primary treatment is the minimum level of
reapplication treatment required for wastewater
irrigation. It may be considered sufficient treatment if
the wastewater is used to irrigate crops that are not
consumed by humans or to irrigate orchards,
vineyards, and some processed food crops. However,
to prevent potential nuisance conditions in storage or
flow-equalizing reservoirs, some form of secondary
treatment is normally required in these countries, even
in the case of non-food crop irrigation. It may be
possible to use at least a portion of primary effluent
for irrigation if off-line storage is provided. Primary
sedimentation tanks or clarifiers may be round or
rectangular basins, typically 3 to 5 m deep, with
hydraulic retention time between 2 and 3 hours.
Settled solids (primary sludge) are normally removed
from the bottom of tanks by sludge rakes that scrape
the sludge to a central well from which it is pumped to
sludge processing units. Scum is swept across the tank
surface by water jets or mechanical means from which
it is also pumped to sludge processing units.
(http://www.fao.org/docrep/t0551e/t0551e05.htm).
Primary treatment involves:
Amirossadat
Advanced Wastewater Treatment
3
1. Screening- to remove large objects, such as
stones or sticks that could plug lines or block tank
inlets.
2. Grit chamber- slows down the flow to allow grit
to fall out
3. Sedimentation tank (settling tank or clarifier)-
settleable solids settle out and are pumped away,
while oils float to the top and are skimmed off
(http://www.sd1.org/resourcehandler.aspx?id=28).

2. Secondary treatment

Secondary wastewater treatment is the second stage of
wastewater treatment that takes place after the
primary treatment process. The process consists of
removing or reducing contaminants or growths that
are left in the wastewater from the primary treatment
process. Usually biological treatment is used to treat
wastewater in this step because it is the most effective
type of treatment on bacteria, or contaminant, growth.
Secondary treatment processes can remove up to 90
percent of the organic matter in wastewater by using
biological treatment processes. The two most common
conventional methods used to achieve secondary
treatment are attached growth processes and
suspended growth processes
(http://www.water.siemens.com/en/applications/waste
water_treatment/secondary-treatment).
Secondary treatment typically utilizes biological
treatment processes, in which microorganisms convert
nonsettleable solids to settleable solids. Sedimentation
typically follows, allowing the settleable solids to
settle out. Three options include:
1. Activated Sludge- The most common option
uses microorganisms in the treatment process to break
down organic material with aeration and agitation,
then allows solids to settle out. Bacteria-containing
activated sludge is continually recirculated back to
the aeration basin to increase the rate of organic
decomposition.
2. Trickling Filters- These are beds of coarse
media (often stones or plastic) 3-10 ft. deep.
Wastewater is sprayed into the air (aeration), then
allowed to trickle through the media. Microorganisms
attached to and growing on the media, break down
organic material in the wastewater. Trickling filters
drain at the bottom; the wastewater is collected and
then undergoes sedimentation.
3. Lagoons- These are slow, cheap, and relatively
inefficient, but can be used for various types of
wastewater. They rely on the interaction of sunlight,
algae, microorganisms, and oxygen (sometimes
aerated).
After primary and secondary treatment, municipal
wastewater is usually disinfected using chlorine (or
other disinfecting compounds, or occasionally ozone
or ultraviolet light). An increasing number of
wastewater facilities also employ tertiary treatment,
often using advanced treatment methods.
Tertiary treatment may include processes to
remove nutrients such as nitrogen and phosphorus,
and carbon adsorption to remove chemicals. These
processes can be physical, biological, or chemical.
Settled solids (sludge) from primary treatment and
secondary treatment settling tanks are given further
treatment and undergo several options for disposal
(http://www.sd1.org/resourcehandler.aspx?id=28).
The objective of secondary treatment is the further
treatment of the effluent from primary treatment to
remove the residual organics and suspended solids. In
most cases, secondary treatment follows primary
treatment and involves the removal of biodegradable
dissolved and colloidal organic matter using aerobic
biological treatment processes. Aerobic biological
treatment (see Box) is performed in the presence of
oxygen by aerobic microorganisms (principally
bacteria) that metabolize the organic matter in the
wastewater, thereby producing more microorganisms
and inorganic end-products (principally CO2, NH3,
and H2O). Several aerobic biological processes are
used for secondary treatment differing primarily in the
manner in which oxygen is supplied to the
microorganisms and in the rate at which organisms
metabolize the organic matter.
High-rate biological processes are characterized by
relatively small reactor volumes and high
concentrations of microorganisms compared with low
rate processes. Consequently, the growth rate of new
organisms is much greater in high-rate systems
because of the well-controlled environment. The
microorganisms must be separated from the treated
wastewater by sedimentation to produce clarified
secondary effluent. The sedimentation tanks used in
secondary treatment, often referred to as secondary
clarifiers, operate in the same basic manner as the
primary clarifiers described previously. The biological
solids removed during secondary sedimentation,
called secondary or biological sludge, are normally
combined with primary sludge for sludge processing.
Common high-rate processes include the activated
sludge processes, trickling filters or biofilters,
oxidation ditches, and rotating biological contactors
(RBC). A combination of two of these processes in
series (e.g., biofilter followed by activated sludge) is
sometimes used to treat municipal wastewater
containing a high concentration of organic material
from industrial sources.

(a) Activated Sludge

In the activated sludge process, the dispersed-growth
reactor is an aeration tank or basin containing a
Chapter 1: Introduction of preliminary and Secondary Treatments
4
suspension of the wastewater and microorganisms, the
mixed liquor. The contents of the aeration tank are
mixed vigorously by aeration devices which also
supply oxygen to the biological suspension. Aeration
devices commonly used include submerged diffusers
that release compressed air and mechanical surface
aerators that introduce air by agitating the liquid
surface. Hydraulic retention time in the aeration tanks
usually ranges from 3 to 8 hours but can be higher
with high BOD
5
wastewaters. Following the aeration
step, the microorganisms are separated from the liquid
by sedimentation and the clarified liquid is secondary
effluent. A portion of the biological sludge is recycled
to the aeration basin to maintain a high mixed-liquor
suspended solids (MLSS) level. The remainder is
removed from the process and sent to sludge
processing to maintain a relatively constant
concentration of microorganisms in the system.
Several variations of the basic activated sludge
process, such as extended aeration and oxidation
ditches, are in common use, but the principles are
similar.

(b) Trickling Filters

A trickling filter or biofilter consists of a basin or
tower filled with support media such as stones, plastic
shapes, or wooden slats. Wastewater is applied
intermittently, or sometimes continuously, over the
media. Microorganisms become attached to the media
and form a biological layer or fixed film. Organic
matter in the wastewater diffuses into the film, where
it is metabolized. Oxygen is normally supplied to the
film by the natural flow of air either up or down
through the media, depending on the relative
temperatures of the wastewater and ambient air.
Forced air can also be supplied by blowers but this is
rarely necessary. The thickness of the biofilm
increases as new organisms grow. Periodically,
portions of the film 'slough off the media. The
sloughed material is separated from the liquid in a
secondary clarifier and discharged to sludge
processing. Clarified liquid from the secondary
clarifier is the secondary effluent and a portion is
often recycled to the biofilter to improve hydraulic
distribution of the wastewater over the filter.

(c) Rotating Biological Contactors

Rotating biological contactors (RBCs) are fixed-film
reactors similar to biofilters in that organisms are
attached to support media. In the case of the RBC, the
support media are slowly rotating discs that are
partially submerged in flowing wastewater in the
reactor. Oxygen is supplied to the attached biofilm
from the air when the film is out of the water and from
the liquid when submerged, since oxygen is
transferred to the wastewater by surface turbulence
created by the discs' rotation. Sloughed pieces of
biofilm are removed in the same manner described for
biofilters
(http://www.fao.org/docrep/t0551e/t0551e05.htm).

REFERENCES

Chang W, Tran H, Park D, Zhang R, Ahn D (2009).
Ammonium nitrogen removal characteristics
of zeolite media in a Biological Aerated Filter
(BAF) for the treatment of textile wastewater.
Journal of Industrial and Engineering
Chemistry, 15: 524-528.
Cppen J (2004) Advanced Wastewater Treatment
Systems. Courses ENG4111 and 4112
Research Project, University of Southern
Queensland, Faculty of Engineering and
Surveyin.

2014 IJ SRPUB
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Treatment Systems

Chapter 2: Wastewater Treatment by Physical-
Chemical Technologies

2014 IJ SRPUB
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Recent Development in Landfill Leachate Treatment Using Low Cost Adsorbent
Prepared From Waste Material

Nurshazwani Binti Azmi, Mohammed J.K. Bashir*, Sumathi Sethupathi, Choon-Aun Ng

Department of Environmental Engineering, Faculty of Engineering and Green Technology (FEGT), University Tunku Abdul
Rahman, 31900 Kampar, Perak, Malaysia
*Corresponding Author: jkbashir@utar.edu.my; Tel: 605-4688888 ext: 4559; Fax: 605-4667449

Abstract. Landfill leachate has become the subject of recent research interest as it is a strongly polluted wastewater. The
produced leachate is one of the most important drawbacks of municipal solid waste disposal (MSW) in sanitary landfill.
Adsorption by activated carbon (AC) appears to have considerable potential in landfill leachate treatment due to the simplicity
design, superior removal of organic compound and less land area required. However, the high demand for AC is a major
problem due to limited carbon based substances such as coal, wood and lignite. Therefore, waste material seems to be a good
option as an alternatives source of AC. Consequently, this paper focuses on effectiveness of using AC in landfill leachate
treatment and highlighted the recent development treating landfill leachate using adsorbent prepared from waste material.

Keywords: Landfill Leachate, Treatment, Adsorbent

1. INTRODUCTION

As the exponential population and social civilization
growth, together with the developments of industries
and technologies, rapid generation of MSW has
becomes a global environmental problem (Saeed et
al., 2009). There are many options available for MSW
disposal such as sanitary landfill, open dump,
incineration, composting, grinding, hog feeding,
milling, and anaerobic digestion (Aziz et al., 2010).
Sanitary landfill is the most common MSW disposal
method due to such advantages as the simple disposal
procedure, low cost, and landscape-restoring effect on
holes from mineral workings (Bashir et al., 2010).
However, the production of highly contaminated
leachate is a major drawback of this method (Aziz et
al., 2010).
Landfill leachate is defined as any contaminated
liquid effluent percolating through deposited waste
and emitted within a landfill or dump site through
external sources (Taulis, 2005). In a more precise
definition, it is a soluble organic and mineral
compound formed when water infiltrates into the
refuse layers, which extracts a series of contaminants
and instigates a complex interplay between the
hydrological and biogeochemical reactions that acts as
a mass transfer mechanisms for producing of moisture
content sufficiently high to start the liquid flow (Aziz
et al., 2004). As shown in Figure 1, leachate
generation induced by the gravity force, precipitation,
irrigation, surface runoff, rainfall, snowmelt,
recirculation, liquid waste co-disposal, refuse
decomposition, groundwater intrusion and initial
moisture content present within the landfills
(Achankeng, 2004). As the consequences, leachate
may contain high concentration of organic matter
(biodegradable and non-biodegradable), ammonia
nitrogen, heavy metals, chlorinated organic and
inorganic salts (Renou et al., 2008). Without an
appropriate treatment, landfill leachate could be a
potential source of surface and groundwater
contamination, as it could seep into soils and subsoil,
causing severe pollutions to receiving water body
(Oman and Junestedt, 2008).
Typically, leachate characteristics and
compositions depends on various factors such as
waste composition, age of landfill, site hydrogeology,
specific climate conditions, moisture routing through
the landfill, and the landfill design and operation
(Ghafari et al., 2010). Age of landfill site is one of the
main variables that affect the leachate characteristics
(Bashir et al., 2012), where the concentration of
leachates parameters changes with the age of the
leachate. Young acidogenic landfill leachate
commonly characterized by high biochemical oxygen
demands(BOD) and chemical oxygen demands(COD)
, high concentration of ammonium nitrogen followed
by low pH value as low as pH 4 (Wu et al., 2001). The
degradation of biological matter by microorganism
lead to generation of Volatile Fatty Acid(VFA) that
lead to low ph value and high BOD/COD ratio. On
the contrary, aged landfill (i.e. >10 years old)
produces mature (stabilized) leachate that contains
bio-refractory compounds such as humic acid (HA)
and fulvic acids (FA), with BOD
5
/COD ratio less than
0.1 (Alvariz-Vazqurez et al., 2004) as illustrated in
Table 1.
Biological treatment of landfill leachates have been
shown to be very effective in removing organic matter
in early stages (Berruetta and Castrillon, 1992) with
high BOD/COD ratio. As the BOD/COD ratio
decrease with the passage of time (Rodriguez et al.,
2000), the biodegradable organic content of leachate
reduced where biological treatment no longer
effective due to the presence of refractory organic
matter and physico-chemical processes may become
Azmi et al.
Recent Development in Landfill Leachate Treatment Using Low Cost Adsorbent Prepared From Waste Material
7
one of the appropriate options for stabilized landfill
leachate. Various physico-chemical process have been
practiced for old landfill leachate treatments such as
adsorption (Halim et al., 2012), ion-exchange (Bashir
et al., 2012), Fenton reaction (Mohajeri et al., 2011),
coagulation/flocculation (Ghafari et al., 2010),
electrochemical oxidation process (Marco et al., 2013)
ozonation (Salem et al., 2013), and air stripping
(Bloor and Banks, 2005). Among all process,
adsorption technology is one of the most applicable
and simple methods.
Adsorption is defined as a mass transfer process by
which a substance is transferred from liquid or gas
phases to the solid surface of adsorbent and form
attachment via physical or chemical interactions. The
material providing the solid surface is called the
adsorbent and material removed from the liquid phase
is called as adsorbate. AC demonstrated significant
adsorption efficiency in gas and liquid phases due to
its high micropore volume, large specific surface area,
favorable pore size distribution, thermal stability, and
capability for rapid adsorption and low acid/base
reactivity (Li et al., 2009). The unique adsorptive
properties of AC, makes it as one of the best filtration
media in the world. However, high manufacturing
cost and expensive carbonaceous material for
producing high quality AC (Mohan and Pittman,
2006) lead to limitation of this application for landfill
leachate treatment especially in developing countries.
Thus, the use of non-conventional material such as
agriculture waste and industrial by-product that are
locally available can be chemically modified and
utilized as a low carbon adsorbent (Babel and
Kurniawan, 2003). Several studies have been
conducted by using AC for various types of waste
water. Consequently, the present work reviews and
evaluates the recent published works focuses on
landfill leachate treatment using adsorbent prepared
from the waste materials.

Fig. 1: Leachate Formation (Agamuthu, 2001)

Chapter 2: Wastewater Treatment by Physical-Chemical Technologies
8
Table 1: Classification of landfill leachate (Alvarez-Vazquez et al., 2004)
Parameters Young Intermediate Stabilized
Age (years) <5 5-10 >10
pH <6-5 6-5-7-5 >7.5
COD (mg L
-1
) >10 000 4000-10 000 <4000
BOD
5
/COD 0.5-1 0.1-0.5 <0.1
TOC/COD <0.3 0.3-0.5 >0.5
NH-N <400 NA >400
Heavy metal (mg L
-1
) Low to
medium
Low Low
Organic compound 80%
VFA
5-30%
VFA+ HA+ FA
HA+FA

Biodegradability Important Medium Low
Kjeldahl Nitrogen (g L
-1
) 0.1-0.2 NA NA

2. PREPARATION OF ACTIVATED CARBON

In general, the process for manufacturing of AC
involves two steps, carbonization of the raw material
followed by the activation of the carbonized product.
The activation process can be carried out in two ways,
either by physical activation (PhA) or chemical
activation (Cha). Pretreatment of the raw material
normally conducted before carbonization process.
Few preliminary stages involves such as crushing,
milling and sieving for appropriate particle size are
important for subsequent handling of the raw material
(Alslaibi et al., 2013). During carbonization, the raw
material will undergo thermal decomposition in inert
atmosphere through gasification by Nitrogen gas.
Carbonization process can be carried out using tubular
furnaces, reactors, muffle furnace and more recently
in a glass reactor placed in a modified microwave
oven (Foo and Hameed, 2011). This process known as
pyrolysis where the non-carbon elements such
hydrogen, nitrogen and oxygen will be released
leaving a rigid carbon skeleton with a rudimentary
pore structure. Based on previous studies, pyrolysis of
lignocellulosic material such as olive stones, coconut
shells or olive shells will remove most of non-carbon
elements in the form of char, tar (oil) and gas where
the proportion depends on the parameter during
pyrolysis such as temperature of pyrolysis, nitrogen
flow rate and heating rate. According to Mohammed
et al., (2010), flash pyrolysis will give high liquid
production, while slow heating rate recommended for
high yields of the char residue.
Physical activation is normally made by
carbonization followed by activation in partial or
control gasification at high temperature (Rodriguez-
Reiniso and Molina-Sabio, 1992). Activation
completed through gasification using oxidizing agent
(Table 2) or mixture of it at temperature ranging from
700-1100
o
C to develop the porosity (micropores and
mesopores) of the carbonized material (Rodrigues-
Reinoso and Molina-Sabio, 1992). CO
2
can develop
narrow micropores, while steam will widen the initial
micropores. Accordingly, CO
2
produced larger
volume and narrower micropores (Mohamed et al.,
2010) while steam created a larger volume of
mesopores and micropores.
Meanwhile in ch(A), carbonization and activation
can be run simultaneously, where the raw material
will be impregnated with chemical agent (Table 2)
followed by conventional heating at moderate
temperature between 400-800
o
C (Demiral and
Gunduzoglu, 2010). The chemical agent acts as
deactivating agent where it inhibits formation of tar
and develops AC porosity via dehydration and
degradation. The pore distribution and surface area is
determined by the impregnation ratio between the
mass of precursor and the chemical agent chosen. The
resulting AC produced is then washed with distilled
water or mild acid in order to remove residual
chemicals from the material. Nowadays, chemical
activation is widely applied for the activation because
of its lower activation temperature and higher product
yield compared with the physical one (Guo and
Rockstraw, 2007). Based on the literature reviewed, it
was found that alkaline hydroxides (KOH and NaOH)
(Lillo-Rodenas et al., 2007) can be used to prepare the
activated carbon, which gave high specific surface
area in the range of 23183500 m
2
/g (Tseng, 2006).

Azmi et al.
9
Table 2: Common activating agent for different activation method in preparation of AC (Alslaibi et al., 2013)

Some additional studies combine the physical
activation with chemical activation where it is known
as physicochemical activation. In general,
physicochemical activation is performed by changing
the activation atmosphere of the chemical activation
by a gasification atmosphere (steam, CO
2
) at higher
temperatures or the chemical activation is carried out
directly under the presence of a gasifying agent. The
combination of both types of carbon activation makes
ACs with textural and chemical properties which are
different from those obtained by any of the activations
alone. For example, steam reduces the occurrence of
heteroatoms into the carbon structures. Also, the
combination of oxidizing reagents in the liquid phase
(nitric or sulfuric acids) with gasification agents
improves the development of porosity on the final
carbons. In addition, continued development of
activated carbon lead to the new application of
microwave heating in preparing activated carbons.
Recently, the usage of microwave heating as an
alternative to conventional heating in ch(A) receives
considerable attention in many research works.
Microwave synthesis is an alternative technique that
overcomes the problems of conventional fast firing
because microwave synthesis is a non-contact
technique where the heat is transferred to the product
via electromagnetic waves, and large amounts of heat
can be transferred to the interior of the material,
minimizing the effects of differential synthesis (Jones
et al., 2002). This leads to uniform heating, rapid
temperature rise and saving energy (Zhang et al.,
2011). In addition, the short period of treatment time,
reduced extra processing cost by reduction in energy
consumption (Xin-Hui et al., 2011) and gas
consumption within the process (Foo and Hameed,
2009). Besides, previous study illustrate relatively
higher surface areas developed during AC preparation
by microwave heating compared to conventional
heating for the same precursor (Alsalibi et al., 2013).
Since carbonaceous materials are a good microwave
absorber, microwave assisted thermal process turned
to interesting alternative approach in preparation of
AC. The experimental apparatus used in ch(A) by
microwave heating in the laboratory scale is shown in
Figure 2.

3. PERFORMANCE OF AC

Performance of AC is largely depends on two
parameters e.g. the surface area and the pore structure
(Figueiredo et al., 1999). The larger surface area will
contribute to higher adsorption capacity. Although a
microporous AC is generally desired for adsorption
purposes, the presence of mesopores is also valuable
for the adsorption of large molecules or where a faster
adsorption rate is required (Huang et al., 2011).
Meanwhile, the macropores have larger pore volume
and act as access pores that provide a passageway to
the particles. The pore volume limits the size of
particles that can be access while the surface area
limits the amount of material that can be adsorbed.
According to the International Union of Pure and
Applied Chemistry (IUPAC), porosity within the
adsorbent has been categorized according to width.
The largest macropores (access pores) generally have
width between 50nm-100nm, the mesopores (transport
pores), between 2-50nm wide and the smallest pores,
micropores (high adsorption properties) have width <
2nm. Figure 3 shows the three types of AC pore
structure: micropores,mesopores and macropores.

10
Fig. 2: A schematic diagram of the experimental apparatus used in activation process (Deng et al., 2009)

4. RECENT DEVELOPMENTS IN LANDFILL
LEACHATE TREATMENT VIA ADSORBENTS
FROM WASTE MATERIALS

In the recent years, adsorption technology has been
applied in landfill leachate treatment by using low
cost adsorbents prepared from waste materials,
particularly agricultural waste, as precursors for AC
production. As adsorption by AC offer number of
advantages such as not getting affected by toxic
compound, superior removal of organic contaminants
(Weber, 1978), high degree of porosity and very well
developed surface area (Sevilla et al., 2011), it has
turned to a powerful standard technique for removing
toxic and non-biodegrable metal ion (Foo and
Hameed, 2011). The effectiveness of adsorption
process by physical and chemical activation method is
presented in Table 3.
Study conducted by Foo et al., (2013a) showed
good removal of NH
3
-N

and orthophosphate by
79.63% and 85.06% via adsorption, where
adsorptive removal increased as adsorbent dosage
increased from 0.5g/200ml to 5.0g/200ml. The
experimental data revealed the feasibility of sugarcane
bagasse as developed adsorbent for leachate treatment
with micropore volume 0.515cm
3
/g and micropore
surface area 659.25 mg/cm
2
. In another study
conducted by Foo et al., (2013b), the potential of the
banana front as the precursor in AC production was
attempted. The experimental data showed that, with
increasing of adsorbent dosage, from 0.5g/200ml to
3.5g/200ml and from 0.5g/200ml to 4.0mg/200ml at
30
o
C, the adsorptive removal of Boron and Iron
increased. The greatest adsorptive removal of boron
and total Iron is by 97.45% and 95.14% with
maximum monolayer adsorption capacity at 11.09 and
26.15 mg/g. Meanwhile, tamarind fruit seed derived
granular activated carbon showed higher adsorptive
removal of colour (91.22%) while COD (79.93%).
The optimum adsorbent dosage in this experiment is
6.0g/200ml at temperature 30
o
C. The adsorption of
COD and color onto TSAC was best described by the
Langmuir isotherm model, with a monolayer
adsorption capacity of 64.93 mg/g and 168.57 Pt
Co/g, respectively. The results indicated that the
tamarind fruit seed derived granular activated carbon
adsorption process was sufficient for removing these
targeted contaminants, to reach to the industrial
discharge limit of COD (500 mg/L) permitted by the
World Health Organization (WHO).Kamarudin et al.,
(2012) presented the physical activation of durian
peels for AC preparation, with 41.98% and 39.86%
removal of color and COD with optimum activation
temperature at 800
o
C, activation time 2.1H and CO
2

flow rate 68.68 mg/L. In another study conducted by
Ching et al., (2011), impregnated coffee ground with
Azmi et al.
11
H
2
SO
4
by chemical activation via microwave heating,
they found that the optimum impregnation ratio was
0.5 and 2.5 with a 10g AC dosage at pH 8.1, with
removal of iron by 77% and PO
4
-P by 84%. In the
case of rice husk, Kalderis et al., (2008) observed that
the micropore volume of Rice Husk Activated Carbon
produced was 0.42cm
3
/g with chemical activation by
ZnCl
2
via microwave heating. The percentage removal
of COD was by 60% and colour by 70% with
optimum AC dosage at 30g/L.

Fig. 3: Diagram of Activated Carbon (Source: Sushrut Chemicals, 2013)

Table 3: Application of adsorbent prepared from various waste materials in treating landfill leachate

12
Based on the previous experimental works, waste
material especially agriculture waste has high
potential to be converted to AC and then utilized in
treating hazardous landfill leachate. The percentage of
COD, colour, and heavy metals such as Iron,
orthophosphate and Boron reduced and meet the
requirement set by the officially authorized prior
discharge to the surface water. However, only small
numbers of research works conducted for landfill
leachate treatment by using waste material as
adsorbent. Thus, more studies should be conducted to
understand the process of low-cost landfill leachate
treatment through adsorption process by AC.

5. OPPORTUNITIES AND CHALLENGES

Recently, many research works have been done to
highlight the potential use of waste material as a
precursor for landfill leachate treatment. Higher
availability with lower cost makes waste material such
as agriculture waste and industrial waste as an
alternative choice of precursor. Furthermore, with
favorable characteristic as an adsorbent (high porosity
and large surface area), waste materials are
comparable with the typical precursor (coal, wood,
lignite).
Although the precursor selection depends on their
availability, cost and purity, but the manufacturing
process and the application of the product are also
important considerations (Yavuz et al., 2010). In
addition, low social acceptability and lack of
economical affordability, especially in the
management of the treatment such as treatment
facilities, chemical, labor, energy consumption,
transportation, collection and maintenance are among
the main key drivers deciding its flexibility, reliability
and suitable manner.
Thus, corrective and transparent policies, mandates
and standards which governing the collection,
transportation, disposal prevention, recycling, reuse,
monitoring, designing and supervision of solid waste
management should to be pointed out and well-
planned. Besides, the sound of professional in order to
creates environmental awareness for public
participation, adequate financial provisions,
engineering and operating standards, responsibilities
sharing, product stewardship, staff capacities
upgrading formal procedures redressing, regular
opinion survey, site rehabilitation and aftercare
maintenance need to be properly assigned and
counteracted (Bernache, 2003).

6. CONCLUSION

Landfill leachate treatment by adsorption process
using AC has a potential to be practice in sanitary
landfill. Together with simplicity design, less land
area required, alongside with the recycling of waste
material as a low- cost precursor reduces the numbers
of MSW and resolves the landfill leachate problem.
However, full cooperation between communities,
private sectors, local government and states are
required in order to apply this valuable technology
towards sustainable environment.

ACKNOWLEDGEMENTS

The authors are grateful for the financial support
provided by the Universiti Tunku Abdul Rahman
(UTAR) through grant No:
IPSR/RMC/UTARRF/2012-C2/M03 and
IPSR/RMC/UTARRF/2013-C2/T02.

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2014 IJ SRPUB
15
Removal of Colour from Synthetic Dye Wastewater Using Adsorbent Prepared from
Psyllium Husk

Irvan Dahlan
1*
, Somaia M.O. Tayeh
2

1
School of Chemical Engineering, Universiti Sains Malaysia, Engineering Campus, Seri Ampangan, 14300 Nibong Tebal,
Pulau Pinang, Malaysia.
2
School of Civil Engineering, Universiti Sains Malaysia, Engineering Campus, Seri Ampangan, 14300 Nibong Tebal, Pulau
Pinang, Malaysia.
*Corresponding Author: chirvan@eng.usm.my

Abstract. Color removal from textile effluents has been given much attention in the last few years by the adsorption process
using low cost adsorbents. In this study, four different adsorbents were prepared from psyllium husk (i.e. PH/CFO-Al,
PH/CFO-Ac, QPH and NPH) for removal of direct blue dye (DB71) from synthetic wastewater. From the preliminary study,
PH/CFO-Ac adsorbent gave the highest color removal efficiency. PH/CFO-Ac adsorbent was prepared from psyllium husk and
CoFe
2
O
4
by a facile refluxing route in acidic solution. PH/CFO-Ac adsorbent was selected to be used for further batch studies
to examine the effect of various experimental parameters, i.e. contact time, adsorbent amount, shaking rate, initial dye
concentration, pH and temperature. The best conditions for dye removal using PH/CFO-Ac adsorbent were obtained at pH 9.0,
temperature of 30
C, shaking rate of 150 rpm and contact time of 2 hours. The adsorption kinetics was found to follow pseudo-
second-order kinetic model. The experimental data fitted well with the Langmuir model with a monolayer adsorption capacity
of 188.7mg/g. It was also found that prepared and spent PH/CFO-Ac adsorbents have a homogenous particle size distribution.
In addition, the surface morphology of the spent PH/CFO-Ac adsorbents had more compact structures with small granular
particles attached on the surface.

Keywords: Colour removal, Synthetic Dye Wastewater, Psyllium Husk

1. INTRODUCTION

Due to the increase in the world population and
development of industrial applications, environmental
pollution problem became very important, especially
wastewater pollution problem. Communities produce
both liquid and solid wastes. The liquid waste, i.e.
wastewater, is essentially the water supply of the
community after it has been used in a variety of
applications. Wastewater handling, disposal &
treatment are serious worldwide problem. Many
industrial and agricultural activities use water in an
excessive way. However, it is now well known that
the fresh water resources are limited and fragile, so
they must be protected. Discharge of sanitary
wastewater, industrial effluent and agricultural fields
runoff can be the main source of freshwater pollution.
This causes many diseases for human, and it is known
that 70-80% of illness in developing countries is
related to water contamination, particularly for
children and women (WHO/UNICEF, 2000).
Textile industries consume large volumes of water
and chemicals for wet processing of textiles. The
chemical reagents used are very diverse in chemical
composition, ranging from inorganic compound to
polymers and organic compound (Correia et al.,
1994). The color is an evident indicator of water
pollution by the dyes. Industrial dye effluents are
visible even at concentrations lower than 1 mg/l.
Moreover, some dyes and their degradation products
are carcinogenic (Ahn et al., 1999). Also, some dyes
are harmful to aquatic life in rivers where they are
discharged. Since, dye can reduce light penetration
into the water thereby decreasing the efficiency of
photosynthesis in aquatic plants and hence having
adverse impact on their growth (Che Ani, 2004).
Textile wastewater is generally high in both color
and organic content. Effluents discharged from dyeing
industries are highly colored and they can be toxic to
aquatic life in receiving waters (Lee et al., 1999,
Kadirvelu et al., 2003). Color removal from textile
effluents has been given much attention in the last few
years, not only because of its potential toxicity, but
mainly due to its visibility problems (Morais et al.,
1999). The total dye consumption of the textile
industry worldwide is in excess of 10
7
kg/year, and an
estimated 90% of this ends up on fabrics.
Consequently, 1000 tonnes/year or more of dyes are
discharged into waste streams by the textile industry
worldwide (Ahmad et al., 2007).
Development of the appropriate techniques for
treatment of dye wastewater is important for the
protection of natural water. To eliminate dyes from
aqueous colored effluents and reduce their ecological
consequences, several biological and chemical
techniques have been proposed: anaerobic/aerobic
degradation (Ahmed et al., 2007),
coagulation/flocculation (Papi et al., 2000) and also
oxidative/reductive chemical and photochemical
processes (Lucas and Peres, 2006). Due to relatively
high operating costs and low removal efficiencies
using the above-mentioned processes, textile, pulp and
Dahlan and Tayeh
Removal of Colour from Synthetic Dye Wastewater Using Adsorbent Prepared from Psyllium Husk
16
paper industries seldom apply these to treat their
effluents.
Among several chemical and physical methods, the
adsorption has been found to be superior to other
techniques in water reuse methodology because of its
capability for adsorbing a broad range of different
types of adsorbates efficiently, and simplicity of
design. Many researchers researched for cheaper
substitutes, which are relatively inexpensive, and are
at the same time endowed with reasonable adsorptive
capacity. These studies include the use of coal, fly
ash, activated clay, palm-fruit bunch, Bagasse pith,
cellulose-based waste, peat, bentonite, slag and fly
ash, rice husk, activated sludge, etc (Ahmad et al.,
2007).
Psyllium husk has not been investigated as
adsorbent for color removal from dye solutions. This
research studied the adsorption for color removal from
synthetic dye wastewater using an adsorbent prepared
from an inexpensive and readily available material,
i.e. psyllium husk. Also, the study aims to achieve the
following measureable objectives:
1- To prepare and characterize adsorbent from
psyllium husk using quaternized and magnetic
methods.
2- To investigate the ability of the best psyllium
husk adsorbent for removal of color from synthetic
dye under various operating conditions (initial dye
concentration, amount of sorbent, shaking rate,
contact time, pH, and temperature).
3- To determine the kinetic behavior and
isotherms for the adsorption process of color onto
psyllium husk adsorbent.

2. MATERIALS AND METHODS

2.1. Materials

The raw psyllium husk (Fig. 1) was obtained directly
from a store in Parit Buntar, Penang, and used in the
preparation of the adsorbent for this study. Direct blue
dye (DB71) was provided by Sigma Aldrich, Co.,
and used without further purification. The dye was
used as the adsorbate in the batch experimental study.
The chemicals used in this study are Na
2
CO
3
and
Ferric nitrate [Fe(NO
3
)
3
9H
2
O] which is provided by
Bendosen Laboratory Chemicals, whereas NaOH,
H
2
SO
4
and Cobalt nitrate [Co(NO
3
)
2
6H
2
O] are
provided by Qrc, Bright Chem. Sdn Bhd. In addition,
N-(3-chloro-2-hydroxy-propyl)-trimethylammonium
chloride was provided by Aldrich Chemistry. All
chemicals were used without any purification process.

Fig. 1: Raw psyllium husk (PH).

2.2. Preparation of Adsorbent

2.2.1. Preparation of raw psyllium husk

The raw psyllium husk was dried in the oven at 100
o
C
for 24 hours, and then ground by using domestic
blender to pass through a 1mm-sieve (Laboratory Test
Sieve). The husk obtained was kept in a closed plastic
and labeled as raw psyllium husk (RPH).

2.2.2. Preparation of Quaternized Adsorbent

About 20g of the raw psyllium husk was treated with
250 ml of 1% w/v Na
2
CO
3
solution (Fig. 2a). The
mixture was shaken for 45 min at room temperature
(Fig. 2b). It was subsequently rinsed several times
with distilled water (Fig. 2c) and dried at 60C (Fig.
2d). The husk obtained was labeled as natural
psyllium husk (NPH). A portion of NPH was
quaternized according to the method reported by Low
and Lee (1997). The natural psyllium husk (10g) in
12.5 ml of 5 M NaOH solution was left at room
temperature for 30 min (Fig. 2e). At the end of
incubation period 10 ml of 4 M N - (3-chloro-2-
hydroxy-propyl) - trimethylammonium chloride was
added to the mixture (Fig. 2f). It was thoroughly left
in the oven at 60-70C for 4 hours (Fig. 2g) with
intermittent stirring. The reaction mixture was then
rinsed several times with water and finally with
17
distilled water (Fig. 2h). The product after drying was
labeled as quaternized psyllium husk (QPH).

2.2.3. Preparation of psyllium husk/CoFe
2
O
4

adsorbent (PH/CFO)

Psyllium husk/CoFe
2
O
4
adsorbent was synthesized by
a facile refluxing route in alkaline solution as reported
by Ai et al., (2010) with some modifications. In a
typical procedure, 8g of raw psyllium husk was added
into a 150mL alkaline solution containing 3.4g NaOH,
and stirred at room temperature for 30 minutes (Fig.
3a) to get the psyllium husk suspension. The
suspension was then maintained at 100C to keep
boiling state (Fig. 3b). A 50mL metal nitrate aqueous
solution was prepared by dissolving Fe(NO
3
)
3
9H2O
(5.4944 g) and Co(NO
3
)
2
6H2O (1.9790 g) in distilled
water (Fig. 3c). The solution was poured as quickly as
possible into the above boiling suspension (Fig. 3d).
The mixture solution was then refluxed at 100C for 2
h (Fig. 3e). By a simple magnetic procedure, the
resulting product was separated from water, dried at
80C for 12 h (Fig. 3f), and the product was labeled as
PH/CFO-Al. This preparation method was repeated
twice, the second time was by replacing the 150 mL
alkaline solution NaOH by 150ml acidic solution
H
2
SO
4
(2N

) to obtain PH/CFO-Ac.

Table 1: Summary of batch studies
Preliminary Batch study Main Batch study
Using four types of adsorbent prepared from
psyllium husk, to select the best adsorbent with the
highest efficiency to be used in the main study, the
effect of two parameters were studied:

a- Effect of adsorbent amount (using 1g
and 3g adsorbent)

b- Effect of initial dye concentration (using
5mg/ L, 15mg/L)

Main experiments for synthetic wastewater
a. Effect of contact time using 1hr, 2hr, 3hr, 4hr and 5hr
b. Effect of adsorbent amount using 0.1g, 0.3g, 0.6g, 1g
and 1.5g
c. Effect of shaking rate using 100rpm, 150rpm,
200rpm, 250rpm and 350rpm.
d. Effect of initial dye concentration using 15, 30, 60,
100 and 200mg/L
e. Effect of pH using pH 3, 4.5, 6, 7.5, 9 and10.5
f. Effect of temperature using 30, 40, 50 and 60
o
C

2.4. Isotherm and Kinetic studies

For the isotherm and kinetic studies, one batch
experiment was conducted using 1000ml of synthetic
wastewater with initial dye concentration of 200mg/L
and pH 9. About 1.0g of adsorbent was added to the
sample, it was agitated at the agitation rate of 150
rpm. Samples were taken at different time intervals (0
60 min), and the final concentration of the dye was
measured at each time t. At time t = 0 and
equilibrium, the dye concentration was measured and
the amount of adsorption at equilibrium, q
e
(mg/g)
was calculated using Equation

where C
o
and C
e
(mg/L) are the liquid-phase
concentrations of sample at initial and equilibrium,
respectively. W (g) is the mass of sorbent used and V
(L) is the volume of the solution. The removal
efficiency of dye can be calculated from Equation 2

where C
t
is the dye concentration at time t.
Adsorption isotherm is fundamentally essential to
explain how solutes interact with sorbents, and is
critical in optimizing the use of sorbents. In the
present study, the equilibrium isotherms were
analyzed using the Langmuir and Freundlich,
isotherms. The linear form of Langmuir isotherm is
given in Equation 3 (Keleolu, 2007) and Freundlich
isotherm is given in Equation 4 (Schwarzenbach et
al., 2003),

where the constant Q
o
signifies the adsorption
capacity (mg/g) and b is related with the energy of the
adsorption (L/mg), K
F
and n are Freundlich constants.
To investigate the adsorption mechanism, pseudo-
rst-order and pseudo-second-order kinetic models
were tested to nd the best tted model for the
experimental data. The pseudo-rst-order equation is
given by Equation 5.

where k
1
is the pseudo-rst-order rate constant
(min
1
), q
e
and q
t
are the amounts of dye adsorbed
(mg/g ) at equilibrium and at time t (min). The
pseudo-second-order model can be expressed in
Equation 6 (Ho and McKay, 1998):
Dahlan and Tayeh
18

where k
2
(g mg
1
min
1
) is the rate constant of the
pseudo-second-order adsorption.

2.5. Analysis and Characterization

The initial concentration of dye (direct blue 71 dye
solution) and samples after sorption treatment were
measured using DR 2800 spectrophotometer
according to the Platinum Cobalt Standard Method
(Adopted from Standard Methods for the Examination
of Water and wastewater and NCASI, Technical
Bulletin No. 253, Dec. 1971). All the concentrations
of sample analysis were conducted in triplicate to
increase the precision of the results, and only the
average value was reported throughout this analysis.
Selected magnetic sorbents, before and after the
adsorption process, were characterized using
Mastersizer 2000 in order to study the particle size
distribution for the adsorbent. To obtain the surface
morphologies of the selected adsorbent, before and
after the adsorption process, the scanning electron
microscopy (SEM) examinations were performed with
5 kV of accelerating voltage using Leo Supra 35VP-
24-58 microscope.

3. RESULTS AND DISCUSSIONS

3.1. Preliminary Batch Study

As described before, four types of adsorbents were
prepared to select the best adsorbent for the main
batch experimental studies. Figure 4(a) shows the
results for the adsorbent selection based on dye
concentration, and Figure 4(b) shows the results for
the adsorbent selection based on adsorbent amount. It
was noticed from Figure 4(a) that the PH/CFO-Ac
which is the magnetic adsorbent prepared from
psyllium husk treated with acidic solution (H
2
SO
4
) has
the best removal efficiency with 79% color removal
from the 5mg/L initial DB71 dye concentration, and
88% color removal from the 15mg/L initial dye
concentration, while the other kinds of adsorbent
(PH/CFO-Al, QPH and NPH), gave negative
efficiency due to the color of dye became more
darker.
It was noticed also from Figure 4 (b) that the
PH/CFO-Ac, has the best removal efficiency, with
88.6%% color removal when 1g adsorbent was used
and 73% color removal when 3g adsorbent was used,
while the other three kinds of adsorbent gave negative
efficiency due to the color of dye became more
darker. Based on the results of the preliminary study,
PH/CFO-Ac was selected to be used for the main
study.

3.2. Batch Experiments for Synthetic Wastewater

3.2.1. Effect of contact time

One of the most important parameters affecting the
adsorption process is the contact time. It is supposed
that the color removal efficiency will increase by the
increasing of the contact time, until reaching a time at
which no significant amount of dye is removed; this
time is called the equilibrium time. Figure 5 shows the
effect of contact time on the adsorption of DB71 using
PH/CFO-Ac adsorbent
It was shown in Figure 5 that the removal
efficiency of PH/CFO-Ac increased rapidly from
90.8% to 94.03 % when the contact time was
increased from 1 to 2 hours. After that, no significant
increase was noticed in the removal efficiency with
increasing the contact time. This is probably due to
larger surface area of the PH/CFO-Ac adsorbent being
available at the beginning of the adsorption process,
so the adsorption rate was fast. As the surface
adsorption sites become exhausted, the uptake rate is
controlled by the rate at which the adsorbate is
transported from the exterior to the interior sites of the
adsorbent particles (Ai et al., 2010, Kumar et al.,
2010).

19

Fig. 2: Preparation of quaternized adsorbent

Dahlan and Tayeh
20

Fig. 3: Preparation of psyllium husk/CoFe
2
O
4
adsorbent (PH/CFO)

21

Fig. 4: (a) Adorbent selection based on dye concentration, and (b) adsorbent selection based on adsorbent amount.

Fig. 5: Effect of contact time on the adsorption of DB71 from synthetic wastewater

3.2.2. Effect of adsorbent amount

Figure 6 shows the plot of amount of PH/CFO-Ac
adsorbent against percentage removal efficiency of
DB71. It was observed that the removal efficiency is
varied with varying amount of adsorbent and it
decreased with increasing the amount of adsorbent.
The removal efficiency decreased from 94.78% to
81.1% for an increase in adsorbent amount from
0.1g/100ml to 1.5g/100ml. The decrease in removal
efficiency with increasing adsorbent amount may be
due to the concentration gradient between solute
concentration in the solution and the solute
concentration in the surface of the adsorbent. Thus
Dahlan and Tayeh
22
with increasing adsorbent amount, the amount of dye
adsorbed onto unit weight of adsorbent gets reduced,
thus causing a decrease in adsorption capacity and
removal efficiency with increasing adsorbent amount
(Vadivelan and Kumar, 2005).

Fig. 6: Effect of adsorbent amount on the adsorption of DB71 from synthetic wastewater

3.2.3. Effect of shaking rate

Figure 7 shows the effect of shaking rate on the
adsorption of DB71. The removal efficiency of DB71
was 98.74% at low shaking rate (100 rpm) and rose to
99.36% as the shaking rate was increased to 150 rpm.
This effect can be attributed to the decrease in
boundary layer thickness around the adsorbent
particles being a result of increasing the degree of
mixing (Gupta et al., 2011). The removal efficiency
decreased again when the shaking rate was increased
to 350 rpm. This might be due to higher boundary
layer resistance to mass transfer in the bulk (Dahlan
and Razali, 2011).

Fig. 7: Effect of shaking rate on the adsorption of DB71 from synthetic wastewater

3.2.4. Effect of initial dye concentration

The effect of initial dye concentration in the range of
15 to 200 mg/l on adsorption was investigated and the
results are shown in Figure 8. It is evident from figure
that the percentage dye removal increased with the
increasing in initial concentration of dye. The increase
in initial dye concentration enhances the reaction
between dye and PH/CFO-Ac. The percentage dye
removal was found to be 95.11% for 15 mg/l of initial
concentration, and it increased to 99.54% when the
initial dye concentration was increased to 200mg/l.

23

Fig. 8: Effect of initial dye concentration on the adsorption of DB71 from synthetic wastewater

3.2.5. Effect of pH

The pH of the solution plays an important role in the
whole adsorption process. To determine the optimum
pH for the adsorption of DB71 using PH/CFO-Ac, the
effect of solution pH was investigated in the range of
310.5 and the results are shown in Figure 9. The
removal efficiency of DB71 at pH less than 7 is
relatively lower than at pH more than 7. It increased
up from 87.8% to 91.5% when pH was increased from
3 to 9. Solution pH may affect both aqueous chemistry
and surface binding-sites of the adsorbent. The
decrease of adsorption at pH less than 7 can be
explained by the fact that at this acidic pH, H
+
may
compete with dye ions for the adsorption sites of
adsorbent, thereby inhibiting the adsorption of dye
(Hameed and El-Khaiary, 2008).

Fig. 9: Effect of pH on the adsorption of DB71 from synthetic wastewater

3.2.6. Effect of temperature

The effect of temperature on the adsorption process
was investigated by carrying out the adsorption
experiments using PROTECH Shaker Incubator with
different degrees of temperature ranging from 30 -
60
o
C. Figure 10 shows that the highest removal
efficiency (92.04%) was obtained at temperature
30
o
C, and decreased slowly until temperature 50
o
C,
after that it decreased rapidly to 76.36% when the
temperature was increased to 60
o
C. Similar results
were obtained by various authors for the adsorption of
dyes on various adsorbents (Ho and McKay, 1998;
Chern and Wu, 2001; Chiou and Li, 2002; Hamdaoui,
2006). This can be explained by the exothermic
spontaneity of the adsorption process and by the
weakening of bonds between dye molecules and
active sites of adsorbents at high temperatures (Amin,
2009).

Dahlan and Tayeh
24

Fig. 10: Effect of temperature on the adsorption of DB71 from synthetic wastewater

3.3. Adsorption kinetics

Figure 11 shows that the adsorption capacity of
PH/CFO-Ac increased rapidly in the initial stages of
the experiment and it reached equilibrium at 40
minutes although the data were measured for 2 hours.
The results indicate that, at the beginning the dye ions
were adsorbed by the exterior surface of PH/CFO-Ac,
so the adsorption rate was fast. When the adsorptions
of the exterior surface reached saturation, the dye
exerted onto the pores and was adsorbed by the
interior surface of the adsorbent. The time profile of
dye uptake is a single, smooth and continuous curve
leading to saturation, suggesting also the possible
monolayer coverage of dye on the surface of the
PH/CFO-Ac A similar phenomenon was observed
from previous study for the adsorption of direct blue
71 dye on palm ash adsorbent and the equilibrium
time was 1 hour (Sengil, 2003).

Fig. 11: The variation of adsorption capacity of DB71 onto PH/CFO-Ac with adsorption time, 1L solution, 1g adsorbent,
200mg/L dye concentrations, pH 9, at 30 C

To investigate the adsorption kinetic of DB71 on
the surface of PH/CFO-Ac, pseudo-rst-order and
pseudo-second-order kinetic models were tested. The
plots of pseudo-rst-order and pseudo-second-order
kinetic models are shown in Figure 12 and Figure 13,
respectively. Kinetic constants obtained by linear
regression for the two models are listed in Table 2.
The correlation coefficient for the pseudo-rst-order
model is relatively good (R
2
= 0.85), however, the
calculated q
e
(q
e
,
cal
) obtained from this equation does
not give reasonable value (Table 2), which is much
lower compared with q
e
obtained from the
experimental data (q
e,exp
).

25

Fig.12: Pseudo-first-order kinetic plot for adsorption of DB71 onto PH/CFO-Ac (C
0
= 200mg/L, pH 9)

Fig. 13: Pseudo-second-order kinetic plot for adsorption of DB71 onto PH/CFO-Ac (C
0
= 200mg/L, pH 9)

Table 2: Kinetic parameters for adsorption of DB71 onto PH/CFO-Ac
q
e,exp

(mg g
-1
)
Pseudo-rst-order Pseudo-second-order
K
1
(min
-1
) q
e,cal

(mg g
-1
)
R
2
K
2

(g mg
-1
min
-1
)
q
e,cal

(mg g
-1
)
R
2

196.48 0.032 3.0 0.85 0.031 196 0.997

This result suggests that the adsorption process
does not follow the pseudo-rst-order kinetic model,
which is similar to the result reported for adsorption
of direct blue 71 onto palm ash adsorbent (Ahmad et
al., 2007). In many cases the pseudo-rst-order
equation of Lagergren does not t well to the whole
range of contact time and is generally applicable over
the initial stage of the adsorption processes (Ho and
McKay, 1999, Hameed and Hakimi, 2008). For the
pseudo-second-order kinetic model, the R
2
value is
0.997 and the (q
e,cal
=196mg/g) agrees very well with
the (q
e,exp
=196.48mg/g) value, which indicates that
the adsorption of DB71 onto PH/CFO-Ac follows a
pseudo-second-order kinetic model.

3.4. Adsorption isotherm

The adsorption isotherm is the most important
information which indicates how the adsorbate
molecules distribute between the liquid phase and the
Y= -0.013X + 0.545
R
2
= 0.85
Y = 0.00509 X + 0.00083
R
2
= 0.997

Dahlan and Tayeh
26
solid phase when the adsorption process reaches an
equilibrium state. To optimize the design of an
adsorption system for the adsorption of adsorbates, it
is important to establish the most appropriate
correlation for the equilibrium curves. In this study,
the equilibrium isotherms were examined using the
Langmuir and Freundlich isotherms.
In the linear form of Langmuir isotherm, a plot of
C
e
/q
e
versus C
e
(Fig. 14) yields a straight line with
slope 1/Q
0
and intercepts 1/Q
0
b. The essential
characteristics of the Langmuir isotherm can be
expressed in terms of dimensionless constant
separation factor R
L
given by (Mahmoodi et al., 2011)
(7)
where b is the Langmuir constant and C
o
is the
highest initial dye concentration (mg/L). According to
the value of RL the isotherm shape may be interpreted
as shown in Table 3.

Fig. 14: Linearized Langmuir isotherm

Table 3: Adsorption Types based on R
L
value (Mahmoodi et al., 2011)
Value of R
L
Type of adsorption
R
L
> 1.0
R
L
= 1.0
0 < R
L
< 1.0
R
L
= 0
Unfavourable
Linear
Favourable
Irreversible

The value of R
L
calculated (0.00066) was in the
range between 0 and 1 which indicate that the
adsorption is favorable at operation conditions
studied. Table 4 summarizes Langmuir constants and
computed maximum adsorption capacity Q
0
of DB71
onto the PH/CFO-Ac.

Table 4: Langmuir and Freundlich isotherm model constants and correlation coefficients for adsorption of DB71 onto
PH/CFO-Ac
Langmuir
isotherm
b (L/mg) Q
o
(mg/g) R
L

R
2

7.57 188.7 0.00066 0.997

Freundlich isotherm K
F
Q
o
(mg/g) n
R
2

203 177.7 40 0.991

In addition, the Freundlich isotherm is an empirical
equation based on a heterogeneous surface. A plot of
ln q
e
versus ln C
e
(Fig. 15) enables the constant K
F

and exponent n to be determined. K
F
can be defined as
adsorption of distribution coefficient and represents
the quantity of dye adsorbed onto adsorbent for an
equilibrium concentration. The slope 1/n is a measure
of adsorption intensity or surface heterogeneity. These
values together with the correlation coefficient are
presented in Table 3.3. Based on the values of
correlation coefficients (R
2
) and Q
o
shown in Table
3.3, the adsorption isotherm with PH/CFO-Ac can be
described by Langmuir equation. The Langmuir
equation yields a better fit of the experimental data
than Freundlich equation.
27

Fig. 15: Linearized Freundlich isotherm

3.5. Characterization of magnetic PH/CFO-Ac
adsorbent

3.5.1. Particle Size Distribution analysis

Figure 16 shows the particle size distribution of
prepared adsorbent, spent adsorbent with high
removal efficiency and spent adsorbent with low
removal efficiency, respectively. The maximum
volume percentage corresponds to the particle size of
approximately 1000m, 900m and 600m for
prepared adsorbent, spent adsorbent with low removal
and spent adsorbent with high removal, respectively.
The average volume of the particle size distribution
range of spent PH/CFO-Ac adsorbents is higher than
the prepared PH/CFO-Ac adsorbent, which means that
higher particle size distributions range are formed
after DB71 adsorption onto PH/CFO-Ac adsorbent. It
was also found that the specific surface area of the
prepared adsorbent was much higher (0.034 m
2
/g)
than that of the spent adsorbent with low removal and
spent adsorbent with high removal (0.0158 and 0.0112
m
2
/g, respectively). The lower specific surface area of
spent PH/CFO-Ac adsorbents could be due to the
agglomerating of smaller particles (which is most
probably the dye particles that cover the surface of the
adsorbent) during the adsorption process. It was also
shown from the figure that prepared and spent
PH/CFO-Ac adsorbents have a unimodal particle size
distribution, which indicates a homogeneous particle
size for the prepared and the spent adsorbents.

Dahlan and Tayeh
28

Fig. 16: Particle size distribution of prepared PH/CFO-Ac adsorbent, spent adsorbent with high removal efficiency, and spent
adsorbent with low removal efficiency.

3.6.2. Surface morphology analysis (SEM)

The morphology of the raw psyllium husk, prepared
and spent PH/CFO-Ac adsorbent is shown in Figure
17. Surface analysis indicated that the surface
morphology of the raw psyllium husk (Figure 17a)
consists of lumps of uneven shapes particles. After the
preparation of PH/CFO-Ac adsorbent, it can be
observed from Figure 17b that the prepared adsorbent
consists of irregular rough particles that were
unevenly scattered together which might be due to the
CoFe
2
O
4
particles deposited on the surface of raw
psyllium husk. After the adsorption of DB71, the
surface of the PH/CFO-Ac adsorbents was found to
have more compact structures with small granular
particles attached on the surface (Figure 17c) which is
most probably the dye particles that covered the
external surface of PH/CFO-Ac adsorbents.

4. CONCLUSIONS

This study showed that PH/CFO-Ac adsorbent was
successfully synthesized by a facile one-step refluxing
route could be used as an effective adsorbent for the
removal of direct blue dye (DB71) from synthetic
wastewater. All experimental parameters such as
contact time, adsorbent amount, shaking rate, initial
dye concentration, pH and temperature affected the
adsorption of dye from synthetic wastewater. The
equilibrium of adsorption of dye onto PH/CFO-Ac
adsorbent was suitably described by the Langmuir
models. The process of adsorption was relatively rapid
and was best described by the pseudo-second-order
kinetic model. The results obtained in this study
shows that PH/CFO-Ac adsorbent could be used as an
effective adsorbent for the removal of direct blue dye
from synthetic wastewater and this has never been
reported in the literature.

29

Fig. 17: SEM micrographs of (a) raw psyllium husk, (b) prepared PH/CFO-Ac adsorbent and (c) spent PH/CFO-Ac adsorbent

ACKNOWLEDGMENT

The authors wish to acknowledge the financial
support from the Universiti Sains Malaysia (Short
Term Grant A/C. 60310014 and Incentive Grant).

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2014 IJ SRPUB
31
COD and BOD Removal from Textile Wastewater Using Naturally Prepared
Adsorbents and Their Activation Forms Using Sulphuric Acid

Himanshu Patel*, R.T. Vashi

Department of Chemistry, Navyug Science College, Rander Road, Surat 395009, Gujarat, INDIA
*Corresponding Author: hjpatel123@yahoo.co.in

Abstract. Comparative adsorption studies of naturally prepared adsorbents (Neem leaf powder, Gauva leaf powder and
Tamarind seed powder) and their activation forms using sulphuric acid were conducted for removal COD and BOD from
textile wastewater. Process parameters like adsorbent dose, conduct duration, temperature and pH were examined in this study.
The adsorption data were analyzed using Freundlich, Langmuir, Dubinin-Raduskevich, Flory-Huggins, Redlich-Peterson, Sips,
Toth and Khan model to understand adsorption mechanism. Activated Neem leaf powder was most suitable than investigated
adsorbents. The maximum adsorption capacities were found to be 87.58, 85.65 and 81.25 mg/g for NLPs, GLPs and TSPs
respectively for COD and 84.51, 81.45 and 75.54 mg/g for NLPs, GLPs and TSPs respectively for BOD.

Keywords: Textile wastewater, Naturally prepared adsorbents and their activated form, Process Parameters, Adsorption
equilibrium isotherms

1. INTRODUCTION

Increasing public pressure and administrative concern
to arrest further deterioration of the environment may
result in more stringent standards. The objective of
wastewater treatment has expanded considerably from
simple nuisance control to include public health,
environmental, aesthetic and ecological
considerations. The day is not far off when industries
will have to acquire a nonpolluting or zero polluting
status to meet future environmental regulations. The
problem is more severe for the textile industry
because of its dynamic nature. Constantly changing
process lines result in diverse and complex wastes that
are ever changing in constitution and color (Venkata
Mohan et al., 1999). The textile industry is very
chemical-intensive; wastewater from textile-
processing contains huge residues from different
textile dyeing and finishing operations. Of particular
concern are dyestuffs, which are often major sources
of heavy metals, salt, adsorbable organic halogens and
color in dyehouse effluent, sizing agents, which have
high BOD and COD levels; and anionic/non-ionic
surfactants, most of which are still of poorly
biodegradable nature (Alaton et al., 2006).
There are many methods for the removal of
contaminations from wastewater, such as membrane
process, ion exchange, biological degradation and
adsorption using various kinds of adsorbent.
Adsorption process is proven to be an effective
process for the removal of various pollutants from its
aqueous solutions because adsorption process can
remove pollutant in wide range of concentrations
(Budyanto et al., 2008). The adsorption process has
not been used extensively in wastewater treatment, but
demands for a better quality of treated wastewater
effluent, including toxicity reduction, have led to an
intensive examination and use of the process of
adsorption. The relative advantages of adsorption over
other conventional advanced treatment methods are:
(1) it can remove both organic as well as inorganic
constituents even at very low concentrations, (2) it is
relatively easy and safe to operate, (3) both batch and
continuous equipment can be used, (4) no sludge
formation, and (5) the adsorbent can be regenerated
and used again. Moreover the process is economical
because it requires low capital cost and there are
abundant low-cost materials available which can be
used as adsorbents (Mohanty, et al., 2006). Low cost
adsorbents especially made from natural sources like
plant root, leaf, seed, peel, etc are being investigated.
Ulmus leaves and their ash, rubber (Hevea
brasiliensis) seed shell, Platanus orientalis leaves,
Rich husk, Sunflower stalks and Neem leaf powder
have been used for wastewater treatment and
adsorption has emerged as a cost-effective and
efficient alternative for the removal of hazardous
contaminations including dyes from low strength
wastewaters. Also, some acids were also utilized for
activation of adsorbents (Patel and Vashi, 2011).
Previously we had utilized activated neem leaf
powder (Patel and Vashi, 2012), activated guava leaf
powder (Patel and Vashi, 2011) and tamarind seed
powder (Patel and Vashi, 2010) for removal of dyes
from its aqueous solution and provided outstanding
results. There are very few research literatures
available for removal of COD and BOD from real
wastewater as per authors best knowledge. Present
investigation involved the preparation of naturally
prepared adsorbents (and its activation form) and
treatment of textile wastewater using these adsorbents
for removal of COD and BOD. Effect of adsorbent
dose, contact duration, temperature and pH were
studied. Freundlich, Langmuir, Dubinin-Raduskevich,
Flory-Huggins, Redlich-Peterson, Sips, Toth and
Khan models were tested for their applicability.
Patel and Vashi
COD and BOD Removal from Textile Wastewater Using Naturally Prepared Adsorbents and Their Activation Forms
Using Sulphuric Acid
32
2. METHODS AND MATERIALS

2.1. Adsorbent

The Neem (scientific name: Azadirachta indica)
belongs to the meliaceae family and is native to Indian
sub-continent. The Guava (Psidium Guajava; Family:
Myrtaceae) tree are easily available in Indian region.
The mature leaves of plant (Neem and Guava) used in
the present investigation are collected from the
available trees near Navyug Science College, Gujarat.
The mature leaves of plant washed thrice with water
to remove dust and water soluble impurities and were
dried until the leaves become crisp. The dried leaves
were crushed and powdered and further washed with
distilled water till the washings were free from color
and turbidity. Then this powder was dried in an oven
at 60 2 C and placed in desiccator for the
adsorption studies, thus natural adsorbent prepared.
The Tamarind (Tamarindus indica), a family of
Fabaceae, has used for preparation of medicines for
internal and external applications and as condiment in
many dishes. Tamarind fruit seed, collected from
nearby Navyug Science College, Gujarat, a waste
product of tamarind pulp, are washed, dried and
pulverized. This powder was washed with distilled
water till the washings were free from color and
turbidity and thereafter, dried in the oven at 60 C. For
activation of adsorbent, each adsorbent was stirred
with excess amount of 0.1 N sulphuric acid.
Thereafter, it washed with de-ionized water to remove
untreated acid dried in an oven at 60 2 C.

2.2. Experimental Details

The textile wastewater samples were withdrawn from
Pandesara, GIDC, Gujarat, India. Combine
wastewater samples were collected bimonthly for
three times in sampling bottles and placed in ice box
to preserve the characteristics of wastewater and were
analyzed as per standard method (APHA, 1992). For
removal of COD and BOD, batch experiments of
textile wastewater were carried out as per table 1.
Briefly, each adsorbent i.e. NLP and a-NLP (NLPs),
GLP and a-GLP (GLPs) and TSP and a-TSP (a-TSP)
was added to wastewater samples and the mixture was
stirred at 400 rpm. Each adsorbent was kept in contact
till equilibrium state was attained. The required pH of
system was maintained by using 0.1 N HCl or 0.1 N
NaOH during experiment. All chemicals used were of
analytical reagent grade and purchased from
Qualigens, India. The important physico-chemical
characteristics i.e. COD and BOD were determined
before and after treatment using standard methods.

Table 1: Experimental Details for treatment of wastewater using adsorbents
Effect of System Adsorption Dose (g/l) Temperature (K) Contact Duration (min) pH
Effect of adsorption dose
1, 2, 4, 6, 8, 10, 12, 14,
16, 18 and 20
300 180 7
Effect of contact duration 5.0 300
30, 60, 90, 120, 150,
180, 210 and 240
7
Effect of temperature 5.0
298, 303, 308, 313, 318,
323 and 328
180 7
Effect of pH 5.0 300 180 3, 5, 7, 9 and 11

2.3. Batch adsorption model

The equilibrium sorption isotherm is fundamentally
important in the design of sorption systems.
Equilibrium studies in sorption give the capacity of
the sorbent. It is described by sorption isotherm
characterized by certain constants whose values
express the surface properties and affinity of the
sorbent. (samsun clone). Different equilibrium models
were available to predict the sorption behavior. The
most commonly available models are Freundlich,
Langmuir, Dubinin-Raduskevich, Flory-Huggins,
Redlich-Peterson, Sips, Toth and Khan models.

2.3.1. Freundlich Isotherm

The Freundlich expression is an empirical equation
based on sorption on a heterogeneous surface and
effectively on multilayer and is expressed by the
following equation.
q
e
= K
F
C
e
1/n
or log q
e
= log K
F
+ 1/n log C
e

Where, q
e
and C
e
is the amount of adsorbed
adsorbate per unit weight of adsorbent and
unadsorbed adsorbate concentration in solution at
equilibrium, respectively and K
F
(L/mg) and n are
Freundlich constant characteristics of the system,
which are determined from the log q
e
vs. log C
e
. If the
value of exponent n was greater than 1 (n >1) then the
adsorption represent favorable adsorption

2.3.2. Langmuir Isotherm

This monolayer adsorption isotherm is very useful for
predicting adsorption capacities and also interpreting
into mass transfer relationship. The isotherm can be
written as follows:

33
q
e
= k
L
C
e
/ (1 + a
L
C
e
) or (C
e
/q
e
) = (1/ K
L
) + (a
L
/K
L
)
C
e

The constant K
L
(L/g) is the Langmuir equilibrium
constant and the K
L
/a
L
gives the theoretical monolayer
saturation capacity, Q
max
(mg/g). These Langmuir
parameters were obtained from the linear correlations
between the values of C
e
/q
e
and C
e
. Generally, the
Langmuir equation, applies to the cases of adsorption
on completely homogeneous surfaces where
interactions between adsorbed molecules are
negligible (Ozacar and Sengil, 2005).

2.3.3. Dubinin-Raduskevich Isotherm

This isotherm can be used to describe adsorption on
both homogenous and heterogeneous surfaces. The
DubininRadushkevich equation has the following
form:
q
e
= q
m
e
-2
or In q
e
= In q
m
-
2

Where q
m
(mg/g) is the DubininRadushkevich
monolayer capacity a constant related to sorption
energy, and is the Polanyi potential which is related
to the equilibrium concentration as follows:

= RT In (1 + 1/C
e
)
Where R is the gas constant (8.314 J/mol K) and T
is the absolute temperature. The constant gives the
mean free energy, E, of adsorption per molecule of the
adsorbate when it is transferred to the surface of the
solid from infinity in the solution and can be
computed using the relationship.
E = 1/ (2)

The magnitude of E is useful for estimating the
mechanism of the adsorption reaction. In the case of E
< 8 kJ/mol, physical forces may affect the adsorption.
If E is in the range of 816 kJ/mol, adsorption is
governed by ion exchange mechanism, while for the
values of E > 16 kJ/mol, adsorption may be dominated
by particle diffusion.

2.3.4. Flory-Huggins Isotherm

The Flory-Huggins model accounts for the degree of
surface coverage characteristics of adsorbate on the
adsorbent and the linear form of the Flory-Huggins
equation is expressed as:
ln (q/C
e
) = ln(K
FH
) + a
FH
ln(1- q
e
)
Where q is the surface coverage of the adsorbent
by adsorbate. K
FH
(mg/g) and a
FH
are the Flory-
Huggins constants. These constants can be obtained
from the plot of log (q/C
e
) versus log (I-q
e
)
Furthermore the equilibrium constant K
FH
,
obtained from the Flory-Huggins isotherm model is
used to compute the Gibbs free energy for the
adsorption process. The Gibbs free energy is related to
equilibrium constant as follows:
G
0
= - RT/ In K
FH

Where R is universal gas constant 8.314 J/K/mol,
T is absolute temperature (K) and K
FH
is equilibrium
constant from Flory-Huggins isotherm equation
(Israel et al., 2010).

2.3.5. Redlich-Peterson Isotherm

The Redlich-Peterson isotherm model is widely used
as a compromise between the Langmuir and
Freundlich systems, since it combines elements from
both the Langmuir and Freundlich equations, where
the mechanism of adsorption is a hybrid one and does
not follow ideal monolayer adsorption. The Redlich-
Peterson isotherm has a linear dependence on
concentration in the numerator and an exponential
function in the denominator. It approaches the
Freundlich model at high concentration and is in
accordance with the low concentration limit of the
Langmuir equation. It can be applied either in
homogenous or heterogeneous systems due to the high
versatility of the equation. This model incorporates
three parameters into an empirical isotherm. It can be
described as follows,

ln[(K
RP
C
e
/q
e
) 1] =
RP
ln(C
e
) + ln(a
RP
)
Where, q
e
(mg/g), is the solid-phase adsorbate
concentration at equilibrium, C
e
(mg/l) is the liquid-
phase adsorbate concentration at equilibrium, K
RP
(1/mg) and a
RP
(L
mg
), are the Redlich-Peterson

isotherm constants and
RP
is an exponent, which lies
between 1 and 0. If
RP
is equal to one, the equation
modifies to Langmuir model, and if
RP
is equal to
zero then the equation changes to Henrys law
equation (Quintelas et al., 2008).

2.3.6. Sip Isotherm

Sips isotherm is a combined form of Langmuir and
Freundlich expressions deduced for predicting the
heterogeneous adsorption systems and circumventing
the limitation of the rising adsorbate concentration
associated with Freundlich isotherm model. At low
adsorbate concentrations, it reduces to Freundlich
isotherm; while at high concentrations, it predicts a
monolayer adsorption capacity characteristic of the
Langmuir isotherm. As a general rule, the equation
parameters are governed mainly by the operating
conditions such as the alteration of pH, temperature
and concentration. The linear form of Sip isotherm
model is represented as

s
ln(C
e
) = - ln(K
s
/q
e
) + ln(a
s
)
Where K
s
is the total number of binding sites
(mg/g), as the median association constant (L/mg) and
1/n is the heterogeneity factor. If the value for
s
is
Patel and Vashi
34
less than one, it indicates that it is heterogeneous
adsorbents, while values closer to or even one
indicates that the adsorbent has relatively more
homogeneous binding sites.

2.3.7. Toth Isotherm

Toth isotherm model, is another empirical equation
developed to improve Langmuir isotherm fittings
(experimental data), and useful in describing
heterogeneous adsorption systems, which satisfying
both low and high-end boundary of the concentration.
Its correlation presupposes an asymmetrical quasi-
Gaussian energy distribution, with most of its sites has
adsorption energy lower than the peak (maximum) or
means value

q
e
= (q
m
b
T
C
e
) / [1 + (b
T
C
e
)
1/nT
]
nT

Where, q
m
(mg/g) is the Khan adsorption capacity,
and b
T
(1/mg) is the Toth model constant and n
T
the
Toth model exponent (Foo and Hameed, 2010).

3. RESULTS AND DISCUSSION

3.1. Characterization of Textile Wastewater

It was reported that water requirement vary from 61 to
646 liters per kg of cloth processed with an average
value of 235 liters per kg. These values correspond to
12 - 130 liter per meter of cloth with an average value
of 47 liters per kg. The pH of the investigated textile
mill effluent ranges from 9.24 to 7.64 having average
value of 8.2. The color of the wastewater is brownish
yellow having color unit 291.3 Hazen. The average
value of COD, BOD, Total Dissolved Solid (TDS),
Hardness, Alkalinity, Fluoride, Chloride and Sulphate
were 1556.2, 924.1, 6845.3, 1086.7, 670.7, 874.3,
475.3 and 877.1 ppm respectively. Also, average
value of Electrical Conductivity and Sulphate were
found to be 7417.0 s/cm. High value of
contaminations are presented due to usage of
chemicals such as starches, dextrin, gums, glucose,
waxes, pectin, alcohol, fatty acids, acetic acid, soap,
detergents, sodium hydroxide, carbonates, sulfides,
sulfites, chlorides, dyes, pigments, carboxymethyl
cellulose, gelatin, peroxides, silicones, flourcarbons,
resins, etc. in wet processes of textile mill. Same types
of contaminations were found, while investigating
textile wastewater (Fanchiang et al., 2006, Pathe et al.,
2005, Martins et al., 2006).

3.2. Effect of Adsorbent Dose

Figure 1, 2 and 3 shows the effect of different doses
(Ceq vs. Adsorbent dose) of naturally prepared
adsorbents i.e. NLPs, GLPs and TSPs respectively
maintaining temperature of 300 K, contact duration of
180 and pH 7. It can be seen that there is a large
reduction in the COD content when NLPs was used,
from an initial value of 1625.8 ppm to zero and 110.2
ppm at a dosage of 20 g/L of a-NLP and NLP
respectively. BOD had an initial value of 1002.4 to
11.2 and 51.5 ppm by 20 g/L of a-NLP and NLP
respectively. It can be also seen that there is a large
reduction in the COD content when GLPs is used,
from an initial value of 1625.8 to 258.4 and 411.2
ppm at a dosage of 20 g/L of a-GLP and GLP
respectively. BOD had an initial value of 1002.4 to
201.2 and 212.2 ppm when 20 g/L of a-GLP and GLP
was used respectively. It can be seen that there is a
large reduction in the COD content using TSPs, from
an initial value of 1625.8 to 411.2 and 312.2 ppm at a
dosage of 20 g/L of TSP and a-TSP respectively.
BOD had an initial value of 1002.4 to 280.5 and 251.2
ppm by 20 g/L of TSP and a-TSP respectively.

Fig. 1: Effect of adsorbent dose for percentage COD and BOD removal using NLPs

35

Fig. 2: Effect of adsorbent dose for percentage COD and BOD removal using GLPs

Fig. 3: Effect of adsorbent dose for percentage COD and BOD removal using TSPs

From all the adsorbents, a-NLP was found to be
more effective than all investigated adsorbents for
removal of COD and BOD. Also, it was easily
appeared that value of Ceq was continuously
decreasing with increasing adsorbent dose upto 18.0
g/L. The increase in adsorption with increase in
adsorbent may be attributed due to the reason of
increased adsorbent surface and availability of more
adsorption sites. The reason behind the phenomenon
may be speculated to be due to the interference
between binding sites at higher concentrations in
solution with respect to available binding sites. Then
after straight line indicated the equilibrium was
attained at dose of 18.0 g/l for all adsorbents
investigated. It can explain that further increase in the
dose of adsorbent did not affect the uptake capacity
because of the unavailability of adsorbate sites due to
saturation (Li et al., 2008).

3.3. Effect of Contact Duration

Table 2 reveals effect of different contact durations
(30 to 240 minutes) on the COD, BOD and color
removal using 5.0 g/L dosage of NLPs, GLPs and
TSPs at constant temperature (300 K), pH (7) and
agitator speed (400 rpm). Percentage removal of COD
was found to be 30.3 to 63.6, 19.6 to 63.4 and 9.5 to
41.5 using a-NLP, a-GLP and a-TSP respectively.
Also, percentage removal of COD was found to be
20.1 to 57.2, 11.2 to 47.5 and 13.4 to 56.2 using NLP,
GLP and TSP respectively. Percentage removal of
BOD was found to be 26.1 to 57.4, 14.6 to 49.7 and
5.2 to 32.1 using a-NLP, a-GLP and a-TSP
respectively. Also, percentage removal of BOD was
found to be 15.2 to 46.2, 9.2 to 42.1 and 10.1 to 40.1
using NLP, GLP and TSP respectively. These
removals were found at contact duration of 30 to 240
min respectively.
In adsorption process, a knowledge regarding the
contact time required to achieve the equilibrium is
highly important. Table 2 clearly indicates a rapid
increase in the amount of adsorption with increase in
time initially, gradually leading to equilibrium.
Although at higher contact time, the rate of adsorption
decreased and a saturation stage was attained due to
the accumulation of the adsorption sites. This decline
is due to decrease in total adsorbent surface area and
increased diffusion pathway. It can also elucidate that
Patel and Vashi
36
mechanism of solute transfer to the solid includes
diffusion through the fluid film around the adsorbent
particle and diffusion through the pores to the internal
adsorption sites. Initially the concentration gradient
between the film and the solid surface is large, and
hence the transfer of solute onto the solid surface is
faster. That is why it takes lesser time to attain
percentage removal of COD and BOD. As time
increases, intraparticle diffusion becomes
predominant. Hence solute takes more time to transfer
from solid surface to internal adsorption sites through
the pores (Hameed et al., 2008, Gulipalli et al., 2011).

Table 2: Effect of contact duration for percentage COD and BOD removal using naturally prepared adsorbents
Adsorbent % Removal
Contact Duration (min)
30 60 90 120 150 180 210 240
a-NLP
COD 30.3 39.9 50.4 54.1 57.2 60.1 63.6 63.6
BOD 26.1 31.2 39.0 49.5 53.6 55.7 57.4 57.4
NLP
COD 20.1 30.2 41.2 45.2 51.0 55.2 57.2 57.2
BOD 15.2 20.5 28.5 40.5 44.2 45.5 46.2 46.2
a-GLP
COD 19.6 32.3 44.3 48.9 56.5 58.5 63.4 63.4
BOD 14.6 28.6 34.5 40.1 45.1 48.1 49.7 49.7
GLP
COD 11.2 20.2 30.2 35.5 41.2 45.5 47.4 47.4
BOD 9.2 15.4 20.4 30.2 34.5 40.1 42.1 42.1
a-TSP
COD 9.5 14.5 19.5 28.9 33.3 39.5 41.5 41.5
BOD 5.2 10.2 16.5 20.5 27.5 30.2 32.1 32.1
TSP
COD 13.4 20.9 30.5 39.7 50.4 53.1 56.2 56.2
BOD 10.1 18.8 24.7 31.2 36.7 38.0 40.1 40.1

3.4. Effect of Temperature

The effect of variation in temperature i.e. 298, 303,
308, 313, 318, 323 and 328 K on the adsorption by a-
NLP, a-GLP and TSP at constant contact duration,
with respect to COD, BOD and color of wastewater is
depicted in Table 3. It can be seen that the increase in
temperature leads to linear decrease in percent
removal in three cases. Also, straight line after
temperature of 323 K indicating equilibrium
accomplished at temperature of 323 K. The values of
percent removal of COD were seen to increase from
39.1 to 75.6 % by a-NLP, 20.15 to 65.6 by NLP
whereas from 30.3 to 72.3 % by a-GLP, 20.1 to 61.2
% using GLP and from 15.2 to 47.7 % by a-TSP and
also, 24.3 and 63.0 % by TSP at temperature of 298 to
328 K respectively. The values of percent removal of
BOD were seen to increase from 34.7 to 63.2 % by a-
NLP, 20.25 to 55.5 by NLP whereas from 29.0 to 68.0
% by a-GLP, 18.2 to 60.0 % using GLP and from 7.2
to 47.7 % by a-TSP and also, 18.7 and 58.1 % by TSP
at temperature of 298 to 328 K respectively. The
adsorption capacity increases with the increasing
temperature, indicating that the adsorption is an
endothermic process. This may be a result of an
increase in the mobility of chemicals (contributing
COD and BOD) with increasing temperature. An
increasing number of molecules may also acquire
sufficient energy to undergo an interaction with active
sites at the surface. Furthermore, the increasing
temperature may produce a swelling effect within the
internal structure of adsorbents (NLPs, GLPs and
TSPs), enabling to penetrate further (Malkoc et al.,
2007).

3.5. Effect of pH

The effect of pH (3 to 11) is represented in Table 4
using NLPs, GLPs and TSPs (dose: 5.0 g/L) for
removal of COD, BOD and color from textile
wastewater at constant contact duration of 180 min,
temperature of 300 K and agitator speed of 400 rpm.
The percentage removal was increasing, as pH of
system increases. The highest percentage removal of
COD was found to be 64.8, 55.5, 57.4, 47.5, 50.2 and
56.5 by a-NLP, NLP, a-GLP, GLP, a-TSP and TSP
respectively at pH 11. The highest percentage removal
of BOD was found to be 60.0, 54.2, 48.7, 40.2, 41.2
and 44.7 by a-NLP, NLP, a-GLP, GLP, a-TSP and
TSP respectively at pH 11. Though, the factor pH is
an important parameter in adsorption studies, but due
to presence of various elements in dyeing mill
wastewater such as starches, dextrin, gums, glucose,
waxes, pectin, alcohol, fatty acids, acetic acid, soap,
detergents, sodium hydroxide, carbonates, sulfides,
sulfites, chlorides, dyes, pigments, carboxymethyl
cellulose, gelatin, peroxides, silicones, flourcarbons,
resins; the moderate removal of COD, BOD and color
was found with change of factor, pH (ONeill et al.,
1999).

37
Table 3: Effect of temperature for percentage COD and BOD removal using naturally prepared adsorbents
Adsorbent

% Removal
Temperature (K)
298 303 308 313 318 328 328
a-NLP
COD 39.1 48.6 56.0 62.2 70.1 75.6 76.0
BOD 34.7 41.4 48.0 52.6 60.1 63.0 63.2
NLP
COD 20.1 32.2 45.5 50.5 61.2 65.6 65.6
BOD 20.2 32.2 35.6 42.5 51.2 55.5 55.5
a-GLP
COD 30.3 39.1 54.6 62.2 68.3 72.3 73.0
BOD 29.0 35.0 45.4 52.1 61.6 67.6 68.0
GLP
COD 20.0 28.5 44.2 52.1 57.2 61.2 61.2
BOD 18.2 25.5 34.4 41.1 54.2 60.0 60.0
a-TSP
COD 15.2 20.2 26.5 37.3 44.5 47.5 47.5
BOD 7.8 12.5 25.5 35.8 43.6 47.7 47.7
TSP
COD 24.3 37.9 44.9 52.2 56.5 62.5 63.0
BOD 18.7 25.9 38.6 45.9 51.6 58.1 58.1

Table 4: Effect of temperature for percentage COD and BOD removal using naturally prepared adsorbents
Adsorbent % Removal
pH
3 5 7 9 11
a-NLP
COD 14.8 23.6 39.0 56.5 64.8
BOD 9.7 17.6 32.1 50.1 60.0
NLP
COD 10.0 15.5 27.4 45.5 55.5
BOD 5.2 10.5 20.5 41.4 54.2
a-GLP
COD 7.5 14.8 26.5 42.1 57.4
BOD 3.2 10.2 20.2 34.7 48.7
GLP
COD 5.5 10.2 15.5 30.2 47.5
BOD 1.2 5.5 11.1 25.5 40.2
a-TSP
COD 4.5 12.5 24.5 41.5 50.2
BOD 3.5 15.2 20.5 31.5 41.4
TSP
COD 8.0 24.2 34.8 50.4 56.5
BOD 5.7 21.7 31.7 40.0 44.7

3.6. Adsorption Model

Table 5 described Freundlich and Langmuir
parameters for COD and BOD removal using
naturally prepared adsorbents i.e. NLPs, GLPs and
TSPs. Freundlich adsorption capacity, K
F
was found
to be 79.39 and 41.64 L/mg using a-NLP and 45.12
and 40.25 L/mg using NLP for COD and BOD
respectively. Freundlich adsorption capacity was
found to be 28.69 and 12.13 L/mg using a-GLP and
20.45 and 15.18 L/mg using GLP for COD and BOD
respectively. Freundlich adsorption capacity was
found to be 20.45 and 15.18 L/mg using a-TSP and
23.07 and 11.71 L/mg using TSP for COD and BOD
respectively. Langmuir adsorption capacity, Q
max
for
COD and BOD was obtained 87.58 and 84.51 mg/g
respectively using a-NLP and 80.45 and 79.58 mg/g
respectively using NLP. Langmuir adsorption capacity
for COD and BOD was obtained 85.65 and 81.45
mg/g respectively using a-GLP and 82.41 and 78.57
mg/g respectively using GLP. Langmuir adsorption
capacity for COD and BOD was obtained 75.14 and
70.45 mg/g respectively using a-TSP and 81.25 and
75.54 mg/g respectively using TSP. Freundlich and
Langmuir adsorption capacities indicate the good
sorbing capacity of the naturally prepared adsorbents.
Also, it shows that a-NLP is more preferable
adsorbent then other investigated adsorbents.
Activation of Neem Leaf Powder and Guava Leaf
Powder using sulphuric acid were found more
proficient than regular NLP and GLP. Regular
Tamarind Seed Powder (TSP) was found to be more
efficient than activated TSP using sulphuric acid. This
shows that H
2
SO
4
is effective in creating well-
developed pores on the surface of NLP and GLP with
large surface area and porous structure. But in the case
of TSP, there was no change in surface of TSP while
activation using sulphuric acid. Further, value of
exponent n was greater than 1 (n > 1), so, the
adsorption represents favorable adsorption.
DubininRadushkevich and FloryHuggins
naturally prepared adsorbents were depicted in Table
6. Maximum DubininRadushkevich monolayer
capacity, q
m
was found to be 18.45, 15.27 and 10.65
mg/g for NLPs, GLPs and TSPs respectively for COD
and 13.27, 12.17 and 8.54 mg/g for NLPs, GLPs and
TSPs respectively for BOD. All these value are close
to that obtained from the Langmuir isotherm model.
The calculate energy was found to be in the range of
1.2412 - 0.5258 KJ/mol, which confirm physical
adsorption reaction. Physisorption processes have
adsorption energies less than 8 KJ/mol and the energy
in the range of 1.2412 - 0.5258 KJ/mol for removal of
Patel and Vashi
38
COD and BOD using naturally prepared adsorbents
indicates that the sorption process is physisorption and
the positive value of energy (E), of sorption indicates
that the sorption process is endothermic and that
higher solution temperature will favor the sorption
process. The FloryHuggins adsorption capacity, k
FM

was calculated and found to be 0.0555, 0.0450 and
0.0252 mg/g for NLPs, GLPs and TSPs respectively
for COD and 0.0452, 0.0402 and 0.0301 mg/g for
NLPs, GLPs and TSPs respectively for BOD. The
G
0
for this study was computed in the range of -
9.1909 to -13.8271 kJ/mol. The negative value of G
0

indicates that the sorption process is spontaneous in
nature.

Table 5: Freundlich and Langmuir parameters for COD and BOD removal using naturally prepared adsorbents
Adsorbent Removal
Freundlich Parameters Langmuir Parameters
K
F
(L/mg) n Q
max
(mg/g) K
L
(L/mg)
a-NLP
COD 79.39 0.1377 87.58 0.049
BOD 41.64 0.2262 84.51 0.037
NLP
COD 45.12 0.1379 80.45 0.045
BOD 40.25 0.1919 79.58 0.012
a-GLP
COD 28.69 0.4065 85.65 0.12
BOD 12.13 0.1447 81.45 0.14
GLP
COD 20.45 0.3175 82.41 0.21
BOD 15.18 0.2809 78.57 0.54
a-TSP
COD 17.4 0.2353 75.14 0.14
BOD 7.45 0.1212 70.45 0.024
TSP
COD 23.07 0.1570 81.25 0.17
BOD 11.71 0.1350 75.54 0.016

Table 6: DubininRadushkevich and Flory-Huggins parameters for COD and BOD removal using naturally prepared
adsorbents
Adsorbent Particular
Dubinin-Radushkevich Parameters Flory-Huggins Parameters
q
m
(mg/g) (mmol
2
/J
2
)

E (kJ/mol) n
FH
k
FH
(mg/g) G
0
(kJ/mol)

a-NLP
COD 18.45 4.613 1.2412 -0.699 0.0552 -6.9707
BOD 13.27 10.332 0.9574 -0.657 0.0452 -7.2395
NLP
COD 15.21 15.485 0.8747 -0.547 0.0212 -6.1091
BOD 8.27 22.258 0.8547 -0.512 0.0392 -6.7909
a-GLP
COD 15.27 0.3547 0.8258 -0.431 0.0450 -10.2111
BOD 12.17 0.3948 0.6847 -0.379 0.0402 -11.2551
GLP
COD 12.41 0.5158 0.5258 -0.3954 0.0166 -9.1909
BOD 7.55 0.7414 0.6868 -0.354 0.0305 -10.7929
a-TSP
COD 8.65 0.3470 0.7265 -0.407 0.0185 -9.4405
BOD 5.87 0.5081 0.8584 -0.317 0.0205 -12.6157
TSP
COD 10.65 0.6587 0.7457 -0.375 0.0252 -10.2332
BOD 8.54 0.8714 0.6585 -0.298 0.0301 -13.8271

Table 7 depicted Redlish-Peterson and Sips
naturally prepared adsorbents, in which an exponent
of Redlish-Peterson,
RP
not far from 1, indicate that
the Langmuir isotherm best-fits the isotherm data for
removal of COD and BOD using naturally prepared
adsorbents. The Sips adsorption capacity, q
m
was
calculated and found to be 19.7, 17.9 and 15.5 mg/g
for NLPs, GLPs and TSPs respectively for COD and
18.5, 17.9 and 10.0 mg/g for NLPs, GLPs and TSPs
respectively for BOD. Similar to the RedlichPeterson
model constants, the same trends were observed for
the Sips model constants. The exponent, n values were
close to unity. This means that sorption data obtained
in this study is more suited to Langmuir form than
Freundlich.
Table 8 described the Toth and Khan Isotherm
naturally prepared adsorbents. Maximum Toth
adsorption capacity, q
m
was found to be 14.25, 10.47
and 6.58 mg/g for NLPs, GLPs and TSPs respectively
for COD and 7.87, 5.84 and 4.58 mg/g for NLPs,
GLPs and TSPs respectively for BOD. Further, It is
obvious that for Toth model exponent, n
T
= 1, this
isotherm reduces to the Langmuir sorption isotherm
equation. Maximum Khan adsorption capacity, q
m
was
found to be 17.34, 11.44 and 11.14 mg/g for NLPs,
GLPs and TSPs respectively for COD and 15.82,
10.78 and 10.47 mg/g for NLPs, GLPs and TSPs
respectively for BOD.

39
Table 7: Redlish-Peterson and Sips parameters for COD and BOD removal using naturally prepared adsorbents
Redlish-Peterson Parameters Sips Parameters
KRP
(1/mg)
aRP (Lmg) RP qm (mg/g) Ks (L/mg) n
a-NLP
COD 2.40 0.234 0.874 19.7 1030.2 0.734
BOD 3.18 7.489 0.907 18.5 9217.4 0.847
NLP
COD 1.25 45.12 0.915 14.4 9845.5 0.745
BOD 1.02 0.245 0.995 10.8 5545.5 0.824
a-GLP
COD 1.23 61.67 0.940 17.9 8462.5 0.885
BOD 0.31 0.032 1.007 15.2 1251.4 0.755
GLP
COD 0.915 75.45 0.954 10.5 4578.5 0.705
BOD 0.29 0.025 0.54 7.4 1020.2 0.821
a-TSP
COD 0.83 149.8 0.991 12.1 1656.5 0.927
BOD 0.24 0.004 0.96 7.2 768.5 0.835
TSP
COD 0.71 158.5 0.542 15.5 754.5 0.812
BOD 0.12 0.0011 0.547 10.0 625.5 0.714

Table 8: Toth and Khan parameters for COD and BOD removal using naturally prepared adsorbents
Toth Isotherm Khan Isotherm
q
m
(mg/g) b
T
(1/mg) n
T
q
m
(mg/g) b
K
(L/mg) a
K

a-NLP
COD 14.25 0.025 0.854 17.34 0.245 0.057
BOD 7.87 0.058 0.754 15.82 0.547 0.047
NLP
COD 11.24 0.047 0.687 14.14 0.657 0.068
BOD 4.58 0.052 0.847 10.25 0.847 0.084
a-GLP
COD 10.47 0.047 0.856 11.44 0.574 0.064
BOD 5.84 0.065 0.884 10.78 0.632 0.057
GLP
COD 8.66 0.043 0.785 7.45 0.478 0.068
BOD 4.58 0.045 0.847 15.45 0.558 0.062
a-TSP
COD 5.58 0.042 0.748 8.45 0.874 0.041
BOD 3.85 0.028 0.789 7.45 0.658 0.038
TSP
COD 6.58 0.045 0.840 11.14 0.782 0.057
BOD 4.58 0.036 0.705 10.47 0.687 0.047

4. CONCLUSION

This study provides characterization of textile
wastewater and, simple and effective adsorption
process for COD and BOD removal using naturally
prepared adsorbents (NLP, GLP and TSP) and their
activation forms using sulfuric acid. It is observed
from the present investigation that the textile
wastewater contains various types of pollutants, which
are not easily removed. Batch adsorptive treatment
was carried out using various parameters like
adsorbent dose, conduct duration, temperature and
pH, in whixch activation of Neem Leaf Powder and
Guava Leaf Powder using sulphuric acid was found
more proficient than investigated regular NLPs and
GLPs. Regular Tamarind Seed Powder (TSP) was
found to be more efficient than activated TSP using
sulphuric acid. The adsorption equilibrium isotherms,
viz. Freundlich, Langmuir, Dubinin-Raduskevich,
Flory-Huggins, Redlich-Peterson, Sips, Toth and
Khan isotherm ware analyzed, in which maximum
adsorption capacities of linear equation Langmuir
isotherm was calculated and found to be 87.58, 85.65
and 81.25 mg/g for NLPs, GLPs and TSPs
respectively for COD and 84.51, 81.45 and 75.54
mg/g for NLPs, GLPs and TSPs respectively for
BOD. Also, Langmuir isotherm best-fits the isotherm
data for removal of COD and BOD using naturally
prepared adsorbents. This sorption process is
physisorption and endothermic and that higher
solution temperature will favor the sorption process,
derived from calculated free energy, E. The negative
value of G0 indicates that the sorption process is
spontaneous in nature.

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154.

2014 IJ SRPUB
41
Fenton Oxidation for the Treatment of Liquid Waste with High COD and
Anionic/Non-ionic Surfactants

M.C. Collivignarelli
1
, S. Sorlini
2*
, A. Abb
1
, M. Sordi
1

1
Department of Civil Engineering and Architecture, University of Pavia, via Ferrata 1, 27100, Pavia, Italy
2
Department of Civil Engineering, Architecture, Land, Environment and Mathematics, University of Brescia, via Branze 43,
25123, Brescia, Italy
*Corresponding Author: Email: sabrina.sorlini@ing.unibs.it

Abstract. In the present work, liquid wastes from different kinds of industrial plants, characterized by high COD (up to
100,000 mg/L) and surfactants (up to 16,000 and 3,800 mg/L for non-ionic and anionic respectively) concentrations were
treated by means of Fenton oxidation. During the experimental research 28 tests at laboratory scale were performed. Each test
was characterized by specific dosage of reagents (Fe
2+
e H
2
O
2
) and contact time. In particular, Fe
2+
/H
2
O
2
ratio varied from 0.25
to 0.50, H
2
O
2
/COD ratio from 0.72 to 1.5 while the contact time increased from 30 to 120 minutes. The main objective of this
work was to define the dosage of reagents and the reaction contact time able to optimize the process performance in terms of
removal yields of COD and surfactants. The results showed that the optimal treatment conditions could be obtained with a
Fe
2+
/H
2
O
2
ratio equal to 0.25, a H
2
O
2
/COD ratio of 1 and a reaction time of 30 minutes. An average removal yield of 70% for
AS (non-ionic surfactants) and COD and 95% for MBAS (anionic surfactants) respectively was obtained.

Keywords: Surfactants, Fenton Oxidation, High COD

1. INTRODUCTION

Surfactants are a group of compounds used daily in
huge amounts mainly in household applications and as
industrial cleaning agents (Gonzalez et al., 2007;
Hosseinnia et al., 2006). As is known, the surfactants
can be classified in different groups depending on the
electrostatic charge of its hydrophilic groups: anionic
(MBAS), non-ionic (TAS), cationic and amphoteric
surfactants (the last compounds behave as acids or
bases, depending on the solution acidity). The first
two groups are the most common and account for over
80% of the total usage in detergents. Cationic
surfactants are used mainly in fabric conditioners to
give a pleasant soft feel to the product while
amphoteric surfactants are used mainly for their skin
mildness properties (AISE, 2012). The new European
Detergent Regulation (Regulation 648/2004, that
entered in force on 2005) requires that the surfactants
used in household detergents must be biodegradable,
while derogation may be accepted for surfactants in
detergents used in special industrial or institutional
sectors. In Western Europe each year over 2.5 million
tonnes of surfactants are produced (45% anionic, 43%
non-ionic, 8% cationic, 4% amphoteric) (CESIO,
2012).
In the past, some types of surfactants (non-ionic)
resulted to be dangerous for the humans and the
environment also after biological treatment. In fact,
although they were easily removable in well operating
treatment plants with removal yields of about 90-95%,
the last oxidation step was much slower due to the
formation of by-products that are toxic and refractory
to biological treatment (Gonzalez et al., 2007). The
main methods for the treatment of sewage and liquid
wastes containing surfactants involve chemical and
physical processes such as coagulation, foaming,
advanced chemical oxidation, adsorption on different
types of active carbon and polyelectrolytes (Kowalska
et al., 2006). Liquid wastes produced in personal care
product manufacturing are primarily treated by
aerobic activated sludge systems coupled with
physico-chemical methods, although biological
methods are generally favoured because they produce
more tractable solids residuals (Ahammad et al.,
2013). Anaerobic biological processes typically are
not used for high color waster because of the presence
of compounds that inhibit anaerobic microorganisms
(Ahammad et al., 2013). Often liquid wastes
containing surfactants (such as those arising from
industries for the production of personal care
products) are characterized by high COD
concentrations and by poorly biodegradable
compounds that may be toxic (Dias de Melo et al.,
2013). Also liquid waste from tannery industries
belong to the same typology, so conventional
treatments produce effluents still do not meet the
required limits, at least for some parameters such as
COD, salinity, ammonia and surfactants (Kurt et al.,
2007). Hence chemical oxidation systems appear to be
more suitable in treating liquid wastes characterized
by poorly biodegradable and toxic compounds and
high concentrations contents in COD and surfactants.
In the present study Fenton oxidation was
experimented at laboratory scale in order to evaluate
the treatment of colored liquid wastes with high
concentrations of COD and surfactants.

Collivignarelli et al.
Fenton Oxidation for the Treatment of Liquid Waste with High COD and Anionic/Non-ionic Surfactants
42
2. MATERIALS AND METHODS

2.1. Equipment used for Fenton oxidation

Fenton experimental tests were carried out at lab scale
with a 2 liter-glass beaker placed over a magnetic
stirrer (Figure 1 a). A probe for the measurement of
pH was placed inside the beaker (Figure 1 b).
Each experimental test was carried out according
to the following procedure:
(1) Addition of 1 L- volume of liquid waste into
the beaker;
(2) pH adjustment of the liquid waste through the
gradual addition of 1 N sulfuric acid until the desired
pH test;
(3) Dosage of reagents (hydrogen peroxide 40%
w/v solution and FeSO
4
7H
2
O ferrous salt in solid
form) and start of the reaction; both the two reagents
were dosed gradually inside the beaker in order to
allow a better distribution within the mixture;
(4) Monitoring of the reaction, at regular intervals,
maintaining the sample in stirring conditions: H
2
O
2

and Fe
2+
concentrations, temperature and pH were
measured;
(5) pH increasing up to 8.5-9 by gradual dosage of
lime milk (Ca(OH)
2
) in solution at 5%;
(6) settling of the mixture for 2 hours by means of
an Imhoff cone in order to observe the sedimentation
characteristics of the treated liquid waste (Figure 1c);
the level of the solid/liquid interface was recorded
every 30 minutes;
(7) Samples extraction by 0.45 m (paper filter)
filtration of the supernatant obtained from step 6.

Fig. 1: Equipment used for Fenton oxidation tests 1 a - pH measurement 1 b - settling of the mixture 1 c

2.2. Characteristics of liquid wastes

Table 1 shows the qualitative characteristics of the
liquid wastes (LW) treated during the experimental
tests: raw LW II - III - IV and LW I, previously
mixed with an acid liquid waste (characterized by
COD concentration of 30000 mg/L and pH < 1.5) that
allowed to reach the optimal pH without the addition
of sulfuric acid (LW I - mix 1 and mix 2 contained
83% and 17% of LW I respectively).

Table 1: Qualitative characteristics of the liquid wastes
PARAMETER U.M. LW I LW II LW III LW IV
COD mg/L 17800 56680 50450 101900
TAS mg/L 24.7 1033 845 16000
MBAS mg/L 102 1490 13100 3870
BOD
5
mg/L 8000 6000 - -
BOD
20
mg/L - - - -
TN mg/L 307 < 0.5 - -
N-NH
4
+
mg/L 37.4 < 0.5 8.8 65
N-NO
3
-
mg/L 17.3 < 0.5 - -
N-NO
2
-
mg/L 0.2 < 0.1 - -
TP mg/L 393 < 0.5 - -
pH - 6.7 5.8 5.5 8.6
color/appearance - green/limpid white/mushy gray/mushy brown/limpid

43
2.3. Experimental tests

The tests were carried out with different dosages of
reagents (expressed as H
2
O
2
/COD and Fe
2+
/H
2
O
2
),
reaction time and temperature in order to determine
the optimal process conditions. The detailed
experimental conditions are reported in Table 2.

Table 2: Experimental conditions applied during Fenton oxidation
Tests Liquid Waste (LW)
Operative conditions
Contact time [minutes] (H
2
O
2
/COD)
0
Fe
2+
/H
2
O
2

F 1
I
(mix 1)
30 0.36 1/2
F 2 30 0.36 1/5
F 3 30 0.72 1/4
F 4 60 1 1/2
F 5 60 0.72 1/2
F 6
I
(mix 2)
60 0.72 1/2
F 7 60 1.17 1/2
F 8 60 2 1/4
F 11
II
60 0.72 1/4
F 12 60 1 1/4
F 13 60 0.72 1/2
F 14 30 0.72 1/4
F 15 60 1.5 1/4
F 16 120 0.72 1/4
F 17
III
60 0.72 1/4
F 18 60 1 1/4
F 19 60 1.5 1/4
F 20 30 0.72 1/4
F 21 60 1 1/2
F 22 120 1 1/4
F 23
IV
60 0.72 1/4
F 24 60 1 1/4
F 25 60 1.5 1/4
F 26 30 0.72 1/4
F 27 60 1 1/2
F 28 120 1 1/4

2.4. Analytical methods

The physical-chemical parameters such as COD, N-
NH
4
+
, N-NO
2
-
, N-NO
3
-
, TN (total nitrogen), MBAS
(anionic surfactants), TAS (non-ionic surfactants), pH
were measured according to the standard methods for
water and wastewater (APHA et al., 2001). TP (total
phosphorus) was analyzed by ICP-MS. BOD
5
was
determined at 20 C by inoculation of active biomass
collected from an activated sludge wastewater
treatment plant (WWTP).

3. RESULTS AND DISCUSSIONS

3.1. Effect of the Fe
2+
dosage

In order to assess the optimal dosage of iron, each
liquid waste was tested with two ratios of Fe
2+
/H
2
O
2
:
0.25 and 0.5 respectively. The removal yields of COD
and surfactants (MBAS and TAS) versus Fe
2+
/H
2
O
2

and with different contact time and H
2
O
2
/COD ratio
are reported in Figures 2 and 3 respectively. As
concerns COD the optimal dosage of iron seems to be
Fe
2+
/H
2
O = 0.25, for which most of the processed LW
showed better removal yields for reaction times of 30
and 60 minutes and for H
2
O
2
/COD ratio equal to 0.36,
0.72 and 1 (LW I - mix1, LW II, LW III). The tests
performed on the LW II and LW IV show a decrease
of COD removal yields with increasing the iron
dosage. The best removal yields were achieved in the
treatment of liquid waste LW III with values slightly
below 90%.

44

Fig. 2: Effect of the iron dosage on COD removal

The removal yields of surfactants as a function of
the iron dosage are shown in Figure 3. In this case
doubling the iron dosage a reduction in the removal
yields of surfactants occurred (LW - mix 2, LW II,
LW IV), in particular for TAS that showed a higher
reduction than MBAS (LW I - mix 2, LW II).
Doubling Fe
2+
/H
2
O
2
ratio an improvement of
surfactant removal yields was observed only for LW I
- mix 1 and LW III. Moreover, the anionic surfactants
are the most easily removed, as shown by the average
yield obtained for all the tests equal to about 90%and
60% respectively for anionic and non-ionic
surfactants.

Fig. 3: Effect of the iron dosage on TAS and MBAS removal

3.2. Effect of the H
2
O
2
dosage

After determining optimal dosages of iron, different
laboratory tests were carried out on the same liquid
wastes in order to evaluate the optimal dosage of
hydrogen peroxide. The H
2
O
2
/COD ratios were 0.72,
1, 1.5 and only for LWI - mix 2 the 1.17 ratio was
added. Figure 4 shows the removal yields of COD
obtained during these tests. All liquid wastes showed
an increase of COD removal yields with increasing
the dosage of hydrogen peroxide with the exception of
the LW III for which the removal yield was constantly
about 85%.
45

Fig. 4: Effect of the hydrogen peroxide dosage on COD removal

The anionic surfactants showed a similar behavior
to COD. Instead, for the non-ionic surfactants (TAS)
the yield of removal (Figure 5) significantly increased
with increasing the dosage of hydrogen peroxide with
respect to the initial COD from 0.72 to 1. A further
increase of the dosage of hydrogen peroxide (from 1
to 1.5 H
2
O
2
/COD ratio), does not lead to any
improvement in TAS removal yields (as concerns LW
II, LW III LW IV).

Fig. 5: Effect of the hydrogen peroxide dosage on TAS and MBAS removal

3.3. Effect of contact time

Finally, the effect of the contact time on the removal
of COD (Figure 6) and surfactants (Figure 7) was
evaluated. The results obtained showed that the
optimal contact time was equal to 30 minutes for each
liquid waste. Indeed, the low increase of removal
yields is observed for COD increasing the contact
time from 30 to 60 minutes may be partially caused by
an increase of the dosage of hydrogen peroxide (LW
III, LW IV) or iron (LW I - mix 2).

46

Fig. 6: Effect of reaction time on COD removal

The effect of contact time on surfactants removal is
shown in Figure 7. The optimal contact time for
anionic surfactants for all the tested liquid wastes is 30
minutes. Going into detail, for LW II a removal yield
of 90% was obtained after a 30 minutes contact time;
moreover, the slight increase of the removal efficiency
observed for the LW I - mix 2 at 60 minutes may be
due to the use of a higher dosage of iron. Regarding
TAS, as observed for COD, all tested liquid wastes
(LW - mix 2, LW III, LW IV) show the best removal
condition at 30 minute contact time, with the
exception of LW II for which the removal yield
increased from 40% to 60% and 80% with increasing
the test duration from 30 minutes to 60 and 120
minutes respectively.

Fig. 7: Effect of reaction time on TAS and MBAS removal

4. CONCLUSION

The results showed that the optimal treatment
conditions for surfactant removal from liquid wastes
can be obtained with a Fe
2+
/H
2
O
2
ratio equal to 0.25
and a H
2
O
2
/COD ratio of 1 and a reaction duration of
30 minutes. These process conditions allow obtaining
an average removal yield of 70% for TAS and COD
95% for MBAS. In fact, the experimental data
obtained show that higher dosages of Fe
2 +
produce for
almost all tested liquid wastes a lower removal yield
of both the surfactants. Instead, regarding H
2
O
2
the
47
used of dosages lower than the optimal one reduces
the removal yields of both TAS and MBAS, while
higher dosages do not significantly improve the
process efficiency). Finally, an increase of contact
time over 30 minutes does not generally improve the
removal of surfactants.

ACKNOWLEDGEMENT

The authors would like to give a special thanks to the
company ASMortara spa for the financial support to
the experimental research; moreover we want to thank
l'Eng. Chiara Clemente for the assistance in carrying
out the tests.

REFERENCES

Ahammad SZ, Zealand A, Dolfing J, Mota C,
Armstrong DV, Graham DW (2013). Low-
energy treatment of colourant wastes using
sponge biofilters for the personal care product
industry. Bioresource Technology, 129: 634
638
AISE (2012). The new detergents regulation: fact
sheet on aerobic biodegradation of surfactants.
http://www.aise.eu/downloads/05_Fact%20shee
t%20biodegradability-
updated%2027082012.pdf
APHA, AWWA, WEF (2001). Standard methods for
the examination of water and wastewater, 21
st

edition. American Public Health Association,
Washington DC, USA.
CESIO - European Committee of Organic Surfactants
and their Intermediates (2012). CESIO
surfactants statistics for Western Europe.
http://www.cefic.org/Documents/About-
Us/Industry%20sectors/CESIO/CESIO-
Statistics-2012.pdf
Dias de Melo E, Mounteer A H, Henrique de Souza
Leo L, Cibele Barros Bahia R, Ferreira
Campos IM (2013). Toxicity identification
evaluation of cosmetics industry wastewater.
Journal of Hazardous Materials, 244245: 329
334.
European Commission (2004). Regulation (EC) No
648/2004 of the European Parliament and of the
Council of 31 March 2004 on detergents.
Official Journal of the European Union.
http://eur-
lex.europa.eu/LexUriServ/LexUriServ.do?uri=
OJ:L:2004:104:0001:0035:en:PDF
Gonzalez S, Petrovic M, Barcelo D (2007). Removal
of a broad range of surfactants from municipal
wastewater Comparison between membrane
bioreactor and conventional activated sludge
treatment. Chemosphere, 67: 335 343.
Hosseinnia A, Hashtroudi M S, Pazouki M,
Banifatemi M (2006). Removal of surfactants
from wastewater by Rice Husk. Iranian Journal
of Chemical Engineering, 3(3).
Kowalska I, Majewska-Nowak K, Kabsch-
Korbutowicz M (2006). Ultrafiltration
treatment of detergent solutions. Desalination
200: 274276.
Kurt U, Apaydin O, Gonullu MT, (2007). Reduction
of COD in wastewater from an organized
tannery industrial region by electro-fenton
process. Journal of Hazardous Materials, 143:
3340.

2014 IJ SRPUB
48
Ultrasound Irradiation on the Treatment of Aromatic Compounds in Wastewater

Wong Lai Peng, Guo Xinxin, Mohammed J. K. Bashir
*

Department of Environmental Engineering, Faculty of Engineering and Green Technology, Universiti Tunku Abdul Rahman,
31900 Kampar, Perak, Malaysia
*Corresponding Author: jkbashir@utar.edu.my; Tel: 605-4688888 ext: 4559; Fax: 605-4667449

Abstract. The presence of aromatic compounds such as, chlorinated aromatic compounds, phenolic compounds and dyes can
contaminate aquatic environment. Owing to the toxic, mutagenic and carcinogenic properties of some of aromatic pollutants,
their levels need to be controlled strictly in treated wastewater. Nevertheless, most of the conventional treatments methods are
not able to remove the toxicity of these pollutants completely. Ultrasonication treatment has been employed for the treatment
of hazardous materials in wastewater. Thus, the aim of this study is to investigate the characteristics, influencing factors and
applications of ultrasonic irradiation method. Also, review the current situation of applying cavitation process individually and
combined with other AOPs treatment methods for treatment of aromatic pollutants. In addition, the possible degradation
mechanism of aromatic compound is discussed and the configuration of ultrasonic equipment is suggested.

Keywords: Ultrasound Irradiation, Wastewater, Aromatic Compounds

1. INTRODUCTION

Recalcitrant aromatic compounds have been
extensively used in many industrial processes like
textile industry for dying leather, silk wool and paper.
Consequently, these industrial wastewater streams
always contain high concentration of aromatic
compounds which is harmful to human due to their
carcinogenicity and genotoxicity by accumulating in
fat tissue (Berberidou et al., 2007; Gogate and Pandit,
2004a; Gregory, 2009; Ju et al., 2008). Therefore it is
necessary and important to remove aromatic
compounds from wastewater before discharge and
keep the concentration of chemicals in the effluent
stream at a certain minimum level (Gogate and Pandit,
2004a; Zhou et al., 2012). Due to the stringent
environmental laws and regulations against hazardous
pollutants, the technologies for wastewater treatment
have been extensively developed in the last decades
(Pera-Titus et al, 2004). However, aromatic
compounds are resistant to conventional biological
wastewater treatment process due to high toxicity and
carcinogenicity of the pollutants. So, it is necessary to
develop novel and efficient methods degrade
biorefractory aromatic compounds into smaller
molecules, which can be complete minimized by
conventional biological or photochemical
technologies.
Researchers have tested various methods with
advanced oxidation processes (AOPs) for the
degradation of biorefractory aromatic compounds,
such as ozone oxidation, hydrogen peroxide oxidation,
Fenton with UV light or catalysts and cavitation
generated by ultrasonic irradiation (Ai et al., 2010;
Berberidou et al.,2007; Guinea et al., 2009; Meric et
al., 2005; Zhang and Zheng, 2009). Cavitation have
been found to be the most attractive and suitable
system in degradation or decolorization of recalcitrant
organic pollutants and also used as pretreatment to
convert pollutants into shorter chain compounds that
can be treated by conventional or biological methods
(Anjaneyulu et al., 2005; Gogate and Pandit, 2004a;
Gogate and Pandit, 2004b). This method is based on
the producing of highly reactive hydroxyl radicals
(OH) with high oxidation potential compared to the
conventional oxidants like potassium permanganate
and hydrogen peroxide (Gogate and Pandit, 2004a).
The combination of different AOPs has been found to
be more efficient for the treatment of aromatic
compounds as compared to individual oxidation
process due to the high energy efficiency and
production of higher amount of free radicals
(Chakinala et al., 2008; Ioan et al., 2007; Namkung et
al., 2008; Papadaki et al., 2004; Sun et al., 2007).
The aim of this study is to consider the principles,
characteristics, influencing factors and applications of
ultrasonic irradiation method and takes an overview of
the current situation on applying cavitation process
individually and combined with other AOPs treatment
methods for treatment of aromatic pollutants including
chlorinated aromatic pollutants, phenolic pollutants,
dyes etc. In addition, the possible degradation
mechanism of aromatic compound is discussed and
the configuration of ultrasonic equipment is
suggested.

2. BASIC PRINCIPLES OF ULTRAONIC
CAVITATION AND SONOCHEMISTRY

Ultrasound is the term given to sound waves above 20
kHz which is the frequency above the range audible to
human being. Depending on the application and
frequency, ultrasonication is broadly divided into
three areas: i) low frequency or conventional power
ultrasound (20-100 kHz), (ii) medium frequency or
sonochemical effects ultrasound (300-1000 kHz) and
Peng et al.
49
iii) high frequency or diagnostic ultrasound (2-10
MHz) (Mason and Lorimer, 1988; Show and Wong,
2012). The effect of ultrasound in liquid medium was
first recognized by Alfred L. Loonis in 1927, however
the major developments in sonochemistry took place
in 1980s after the arrival of inexpensive high-intensity
ultrasound generators (Suslick, 1989). Recently, the
majority utilization of ultrasound in chemical reaction
included synthesis (organic, organometallic and
inorganic), polymer chemistry (degradation, initiation,
and copolymerization) and nanomaterial preparation
and some aspects of catalysis (Mason and Lorimer,
1988). In addition, ultrasound show great potential in
environmental engineering and protection, thus since
1990 there has been an increased interest in the use of
ultrasound to destroy organic contaminants present in
water and/or wastewater (Hao et al., 2003;
Chowdhury and Viraraghavan, 2009; Eden, 2012).
Environmental sonochemistry is a rapidly growing
area, and cavitation is an effective tool for degrading
different organic pollutants, including aromatic
compound (Hamdaoui et al., 2008; Minero et al.,
2008; Sonawane et al., 2009; Suslick, 1990).
Ultrasonic irradiation is generated by directly
introducing the source, i.e. a probe in the reactor or
immersing the reactor in an ultrasonic bath (Hong et
al., 1999; Vinodgopal and Peller; 2003). Ultrasonic
bath is the most widely used and cheapest source of
ultrasound however it does not produce better
sonochemical effects compare to the probe-type
ultrasonic irradiation (Goel et al., 2004).

2.1. Cavitation

The diffuse energy of sound is enhanced through
cavitation (Suslick, 1990). The process is principally
based on the phenomenon of acoustic cavitation,
which includes the formation, growth, and implosive
collapse of micro-bubbles in a liquid. When a liquid is
sonicated, positive and negative pressures are exerted
on a liquid by compression and expansion cycles
respectively of ultrasound waves (Suslick, 1989). The
dissolved gas molecules are entrapped by micro-
bubbles that grow and expand upon rarefaction of the
acoustic cycle; when a sufficiently large negative
pressure is applied to the liquid, the average distance
between the molecules would exceed the critical
molecular distance necessary to hold the liquid intact,
and the liquid will break down and voids or cavities
will be created; cavitation bubbles will then be formed
(Mason and Lorimer, 1988). These cavities, voids or
bubbles may grow in size until the maximum of the
negative pressure then extreme temperature release
upon adiabatic collapse (Mason and Lorimer, 1988;
Lin et al., 2008; Wang et al., 2007).
There are three possible reaction sites in
ultrasonically irradiated homogeneous liquids: i) the
gaseous interiors of collapsing cavities; ii) the
interfacial liquid region between cavitation bubbles
and the bulk solution, where high temperature and
high temperature gradients exist; and, iii) the bulk
solution at ambient temperature, where small amounts
of hydroxyl radicals (
OH) diffuse from the interface

(Ghodbane and Hamdaoui, 2009; Ozen et al., 2005).
The high temperatures (5000 K) and pressures (1000
atm) induced by cavitation in collapsing gas bubbles
in aqueous solution lead to the thermal dissociation of
water molecules into hydrogen radicals (
H) and
hydroxyl radicals (
OH) (Crum et al., 1999; Shimizu

et al., 2007).
The sonochemical effect takes place at the gas-
liquid interface due to the oxidation of organic
molecules to lesser extent by
OH in the bulk solution

or the pyrolytic decomposition inside the bubbles
(Goel et al., 2004; Li et al., 2008). Acoustic cavitation
generates hydro-mechanical forces and pyrolytic
reactions, in many cases, there are dominant factors in
the pollutant degradation.
However, it has been demonstrated that the
reaction mechanisms depending on the different
physico-chemical characteristics of the pollutant.
Hydrophobic pollutant degradation mainly happened
in the hydrophobic boundary where pyrolysis and
radical reactions contribute to the degradation. While
hydrophilic pollutants in the bulk liquid degradation
mainly contributed by free radicals or hydrogen
peroxide reactions in the cavitation bubbles
(Behnajady et al., 2008; Tezcanli-Guyer and Ince,
2003; Vajnhandl and Le Marechal, 2007). In brief the
cavitational collapse creates an unusual environment
for a chemical reaction in terms of enormous local
temperature and pressure (Suslick, 1990).

2.2. Basic Theories of Sonochemistry

The wide range of oxidations and reductions that
occurs with aqueous sonochemistry is often a
consequence of secondary reactions of the high
energy intermediates. The locally high pressure,
temperature and the formation of highly reactive
radicals could facilitate and accelerate the chemical
reactions inside the reactors. There are three popular
theories of reactivity have been proposed in applying
ultrasound on wastewater treatment: i) hot-spot
theory, ii) electrical theory, and iii) plasma discharge
theory. The localized short-lived (<10 s) hot spots
in an irradiated liquid generated by the rapid collapse
of acoustic cavities implying the existence of
extremely high heating and cooling rates in the
vicinities of 1010 K/s (Ince et al., 2001). The reported
temperature inside the bubble is around 5000 K. The
50
collapse and the implosion of these cavitation bubbles
would result in light emission (sonoluminescence) of
more than 107 photons per flash (Flint and Suslick,
1991; Lohse, 2005).
According to Marguls (1992), during bubble
formation and collapse, large electrical field gradients
are produced. This would lead to sonochemical
reactions and sonoluminescence phenomena. Lepoint
and Mullie (1994) observed the analogies between
sonochemistry and coronachemistry, thus introduced
plasma theory to explain cavitation. They assumed it
as a fragmentation process due to an intense electrical
field rather than a true implosion. However, in the
environmental field, the hot-spot theory is widely
accepted in explaining sonochemical reactions
(Adewuyi, 2001).

2.3. Sonochemistry of Water

As reported by Neis (2000), the ultrasound induced
splitting of water molecules into extremely reactive
hydroxide radicals and hydrogen radicals. During the
quick cooling phase, these radicals recombined again
to form hydrogen peroxide (H
2
O
2
) and hydrogen
molecules (H
2
) as shows in equation in Eqs. 1-5 (Ai et
al., 2007; Ghodbane and Hamdaoui, 2009; Ince and
Tezcanli, 2004; Inoue et al., 2006; Minero et al., 2008;
Suslick, 1989; Wang et al., 2008)

H
2
O + ultrasound
H +
OH (1)
OH +
H H
2
O (2)
H + O
2

HO
2
(3)
2
OH H
2
O
2
(4)
2
HO
2
H
2
O
2
+ O
2
(5)

Violent and fast collapse of the bubbles
compresses adiabatically gas and entrapped vapour,
which conducts to short and local hot spots (Crum,
1995). At the final step of the collapse, temperature
inside the residual bubble is thought to be above 2000
K. Under these conditions, entrapped molecules of
dissolved gases, vaporised water and solutes can be
brought to an excited state and dissociate. The local
concentration of
OH is at its maximum, and a large

majority of
OH are recombined at the gas-liquid

interface before being ejected into the bulk solution.
There is only a small fraction of
OH escapes from the

interfacial region and diffuse into the bulk solution
(Gultekin et al., 2009). In absence of any organic
compound,
OH radicals combine to produce H

2
O
2
in
the bulk solution.

2.4. Cavitation on liquid-solid systems

The most important effects of ultrasound on liquid-
solid systems are mechanical and attributed to
asymmetric cavitation. When a bubble is collapsing in
a spherically asymmetric environment, the collapse
changes in a remarkable way: a flat solid surface
nearby caused the bubble to involutes from the surface
below the top and developed a micro-jet liquid with
speed up to 200 ms
-1
. This resulting in newly
developed high reactive surface as well as corrosion
and erosion at the surface. In addition, the implosion
of cavitation bubbles also produced high energy
shockwaves within interfacial films surrounding
nearby solid particles that have the potential to create
microscopic turbulence (Hamdaoui et al., 2008).
These cavitation effects increase the rate of mass
transfer near the catalyst surface and enhance the
reaction rate (Song et al., 2009).

3. INFLUENCING FACTORS IN
SONOCHEMICAL REACTIONS

Under proper condition, there are at least three
successive stages in acoustic cavitation, i) nucleation,
ii) bubble growth and iii) implosive collapse (Suslick,
1990). The effect of cavitation is influenced by a
number of factors, namely ultrasonic frequency,
ultrasonic intensity, ultrasonic density, quid
temperature, type of pollutant, present of gas, external
pressure, viscosity and surface tension.
A few authors explained the cavitation theory with
the help of resonance frequency of bubble (Mason and
Lorimer, 1988). The resonant radius of a bubble is
inversely proportional to the ultrasonic frequency
(Hua and Hoffmann, 1997; Hung and Hoffmann,
1999). The important cavity effects were reported to
occur when the frequency of the wave was equal to
the resonating frequency of the bubbles (Mason and
Lorimer, 1988). Higher frequency was energetically
more favorable, It was also suggested that mass
transfer from liquid to vapor phase and
OH radical
formation were enhanced with high frequency
ultrasonication (Petrier et al., 1994; Hung and
Hoffmann, 1999).
Reaction temperature also influences sonochemical
reactions as it is directly related to solvent vapor
pressure. Higher temperature lowers the threshold
intensity required to produce cavitation. This could be
due to rising of vapour pressure or lowering of
viscosity or surface tension. The maximum
sonochemical benefit is achieved at as low
temperature as is feasible (Mason and Lorimer, 1988).
Cavitation is favored by the liquid of high vapor
pressure and low density. This was supported by the
results of Petrier et al. (1998) for sonochemical
degradation of chlorobenzene and 4-chlorophenol.
Chlorobenzene degradation was much faster than 4-
chlorophenol because of its higher vapor pressure.
Again solvents with higher viscosity, surface tension
Peng et al.
51
and density showed poor cavitation efficiency
(Adewuyi, 2001). The lower the vapour pressure for a
given external pressure, the larger the acoustic
pressure, thus the type of solvent in the systems plays
an important factor.
In general, it is assumed that the bubbles collapse
is an adiabatic process. A higher temperature and
pressure are expected with gases of higher heat
capacity ratio () values. Lower thermal conductivity
and higher solubility provides better cavitation in the
system (Price, 1992).
Cavitation threshold is the minimum amount of
energy required to intitiate cavitation. Only the energy
applied above the threshold will contribute to the
formation of cavitation bubbles. The higher the
intensity level, the higher the acoustic amplitude and
the collapse pressure. Thus, the collapse is faster and
more violent. However, at frequencies greater than 1
MHz, the acoustic wave impacts on the liquid and
creates micro-currents together with stable and
oscillating gas bubbles which will not collapse but
occasionally rise to the surface of the water body
(Neis et al., 2000).

4.1. Sonochemical Degradation of Aromatic
Pollutants

A large variety of aromatic contaminants detected in
water bodies which included chlorinated aromatic
compounds, phenolic compounds and dyes. The
presence of these compounds even in low
concentration can contaminate aquatic environment.
Besides, due to the toxic, mutagenic and carcinogenic
properties of some of these pollutants, their
concentrations need to be controlled strictly in treated
wastewater. Some of these compounds are listed as
US-EPA and EU priority pollutants (Adewuyi, 2001,
2005). However, as consequences of the
characteristics of the aromatic compounds, most of the
conventional treatments methods are not able to
remove the toxicity of these pollutants completely.
Ultrasonication treatment have been proposed and
employed for the treatment of hazardous materials in
wastewater. Table 1 presented some studies conducted
of aromatic pollutant degradation by ultrasound
treatment.

4.2. Degradation of Chlorinated Aromatic
Pollutants

The application of high intensity ultrasound to a liquid
system may lead to physical and chemical reactions
that can significantly modify the structure and
materials present in the system. Ultrasonic
degradation of chlorobenzene (ClBz) takes place
predominantly within both the bubbles where it
undergoes pyrolysis and within the liquid gas
interface of bubble. Jiang et al. (2002) concluded that
during ClBz degradation by ultrasonication, more than
90% of the chlorine was recovered as chloride ions
along with carbon monoxide (CO), acetylene (C
2
H
2
),
methane (CH
4
) and carbon dioxide (CO
2
) as gaseous
products. Some hydroxylated intermediates, namely
4-chlorophenol, hydroquinone and 4-chlorocatechol
were also detected in a low yield (less than 2 M),
however these compounds disappeared on extended
ultrasonic irradiation.
Petrier et al. (1998) examined preferential thermal
degradation of chlorobenzene inside the cavitation
bubble. In this study, the degradation rate increased at
a higher frequency which may be due to a lower
resonance radius of the cavitation bubble.
Peller et al. (2001) investigated high frequency
sonolysis of 2,4-dichlorophenoxyacetic acid (2,4-D)
in oxygen and argon saturated aqueous medium. The
study shown that the degradation rate was faster in
argon medium compared to oxygen medium due to
argon has a higher heat capacity ratio () value than
oxygen.

4.3. Degradation of Phenolic Pollutants

Petrier et al. (1994) observed that ultrasonic
degradation of phenol was favored at a higher
frequency. At 20 kHz, only 2% of carbon was
recovered in gaseous phase after 300 min, however at
487 kHz, 15% of the carbon was recovered. Besides,
they found that the resonant radius of cavitation
bubble (6.6 m) as well as the life of the bubble
(4.110
7
s) was lower in the case of 487 kHz
frequency. These factors enhanced the release of
OH
radical at a high frequency. Entezari et al. (2003)
reported only 20% degradation of phenol under
sonolysis (C
0
=60 mg/L; time=150 min). This study is
similar to the study conducted by Maleki et al. (2005)
who reported only 13% degradation of phenol under
sonolysis (C
0
= 100 mg/L; time=300 min) and by
Mahamuni and Pandit (2005) who reported 17%
degradation (C
0
=85 mg/L; time=60 min). Phenol is
hydrophilic moderately soluble compound with a
relatively low vapor pressure. These characteristics
prevent the diffusion of phenol molecule into
cavitation bubble, so it remains in the bulk of the
solution during cavitation.

52
Table 1: Sonochemical degradation of aromatic compounds
No. Aromatic compounds Sonochemical conditions Results Reference
1 Chlorobenzene (ClBz)
Ulrasonic power: 9.4 W
Ultrasonic frequency: 520 kHz
Undatim reactor
At concentration above 1000 M,
pyrolysis was the dominant mechanisms,
at concentration 1-5M, radical
mechanisms played a crucial role.

Dewulf et al., 2001
2
2,4-
dichlorophenoacetic
acid
Ultrasonic power: 50 W
Product: Oxalic acid,
Intermediate: 2,4-dichlorophenol,
hydroquinone, catechol were detected
OH radicals were primary reactive

species. With argon, 90% degradation
was achieved in less than 100 minutes

Peller et al., 2001
3 p-amino phenol (PAP)
Ultrasonic probe
The degradation increased with an
increased in the ultrasonic density
He et al., 2007
4 C.I. direct blue 168

Ultrasonic bath
88.3% decolorization

Song et al., 2009
5
Polycyclic aromatic
hydrocarbons (PAH)
Ultrasonic probe
OH is the major process for complete

sonodegradation of less hydrophobic
PAHs while pyrolysis is the major
process for complete degradation of more
hydrophobic PAHs.
Sponza and
Oztekin, 2010
6 Bisphenol A (BPA)
Piezoelectric ceramic transducer

Aromatic intermediates: 2-(4-
hydroxyphenyl)-2-(3,4-
dihydroxyphenyl)propane, commonly
known as 3-hydroxybisphenol A were
detected.
Bisphenol A (0.50mM) was completely
degraded after 10, 3 and 2 h of ultrasonic
irradiation at a frequency of 404 kHz, and
intensities of 3.5, 9.0 and 12.9kW/m2
respectively.

Inoue et al., 2008

In another study, Jiang et al. (2006) observed the
sonolysis of 4-ClPh in oxygen saturated aqueous
solution. Results showed that above 40 C the
degradation rate and temperature were inversely
proportional whereas below 40C a reverse relation
was observed. Nagata et al. (2000) compared the
degradation rate of 3-ClPh to 2-, 4-chlorophenol and
pentachlorophenol under air or argon atmosphere.
Faster degradation rate was observed in argon
medium. Argon medium was more favourable for
degradation because of high heat capacity ratio ().
Kotronarou et al. (1991) carried out the
degradation of 4-nitrophenol (4-NP) at low frequency
(20 kHz). They reported primary products after
degradation were nitrate, nitrite and hydrogen ions.
This study also found that the degradation rate was
greatly affected by the initial solute concentration.
Studies have shown AOPs can be applied for the
elimination of Bisphenol A (BPA) in industrial
wastewater (Chiang et al., 2004; Horikoshi, 2004).
Ultrasonic treatment shows some similarity to AOP
has been found efficient in BPA decomposition (Ioan
et al., 2007; Kitajima et al., 2006). Torres et al.
(2007) proved ultrasonic process could transforms
BPA in biodegradable aliphatic acids that could be
eliminated in a subsequent biological treatment.
Therefore, ultrasound systems represent a very
interesting AOP for the treatment of water
contaminated with phenolic pollutants.

4.4. Degradation of Dyes

In the past few years, synthetic dyes are used
extensively, especially in textile industries. It was
estimated that more than 100,000 different
commercial dyes and pigments and over 70,000 tons
of dyestuff were produced annually (Ghodbane and
Hamdaoui, 2009). Out of this figure, an estimated 10-
15% of dyestuff was lost in the effluent during the
dyeing process (Inoue et al., 2006). Synthetic dyes
containing one or more benzene rings that do not
easily decompose (Wang et al., 2005). In addition,
textile effluent is considered as high strength
wastewater which is highly variable in composition
with intense color, high concentration of chemical
oxygen demand, relatively low concentration of
biological oxygen demand, and high concentration of
suspended and dissolved salts that could hinder the
Peng et al.
53
penetration of oxygen into the water body (Entezari et
al., 2008; Song et al., 2009; Tezcanli Tezcanli-Guyer
and Ince, 2003). Conventional treatment processes for
textile wastewater usually involve coagulation,
flocculation, adsorption, and biological treatment.
However the treated water from these treatment most
of the time could not meet the standard discharged
regulations especially decolorization. Furthermore,
these processes not able to destroy or degrade dyes,
only remove the dye physically from the effluent and
disposal the sludge in landfill eventually (Destaillats
et al., 2000; Inoue et al., 2006; Ozen et al., 2005;
Tezcanli-Guyer and Ince, 2003; Velegraki et al., 2006;
Vinodgopal et al., 1998). In view of that, the
management of textile wastewater requires the
development of suitable treatments that could remove
or reduce the harmful pollutant from the effluents and
be able to recyclable the water for use. Recently,
several studies have promoted sonolysis as a feasible
method for the decolorization and mineralization of
dyes (Hong et al., 1999; Vinodgopal et al., 1998;
Voncina and Majcen-Le-Marechal, 2003).
Vajnhandl and LeMarechal (2007) used two
different types of ultrasonic devices to evaluate the
efficiency of degradation of reactive dye by
monitoring the oxidative species (
OH and H
2
O
2
)
during ultrasonic degradation. They found the radical
formation rate was 20-25 folds higher in plate type
system compare to probe type system at same acoustic
power. Tauber et al. (2005) reported that ultrasound
treatment successfully degraded six azobenzene dyes
(Acid Orange 5, Acid Orange 52, Direct Blue 71,
Reactive Black 5, Reactive Orange 16, Reactive
Orange 107) whereas enzyme treatment was unable to
degrade. In another study, Byun and Kwak (2005)
achieved the multi bubble sonoluminescence (MBSL)
condition by adjusting the ultrasound intensity, liquid
temperature and the distance between horn tip and the
bottom of the cell. At MBSL condition the
degradation efficiency of methylene blue was much
better than conventional photolytic degradation (TiO2
dispersion/UV). pH is interior optimization factor for
ultrasonic dye degradation. Acidic pH accelerates the
dye degradation by protonation of negatively charged
SO
-
3
sites, thus providing hydrophobic enrichment of
the molecules (Behnajady et al., 2008). Acidic
conditions enhance the probability of the dyes
approaching to the negatively charged cavity bubbles
where
OH are most abundant and undergo additional

oxidation/pyrolysis reactions at the gas-liquid
interface (Ozen et al., 2005; Wang et al., 2007).
In another study, Inoue et al. (2006) investigated
the effects of power input and frequency to the
degradation rate for Rhodmine B and Orange II. They
concluded that rate constant increased with increased
input power and at higher frequency. This degradation
mechanism can be explained with the production of
OH radicals. At lower frequency, the degradation rate

was lower due to the
OH radical production rate was

slow.

5. REACTIONS AND MECHANISMS OF
AROMATIC COMPOUND DURING
SONOCHEMICAL DEGRADATION

The reaction occurs in the solution bulk for highly
water-soluble dyes are largely hydrophilic. The
OH
radicals ejected into the solution bulk cause oxidative
dye destruction, whereas hydrophobic and volatile
species degrade thermally to the gas phase or gas-
liquid interface (Ince and Tezcanli- Gyer, 2004;
Vajnhandl and Le Marechal, 2007). However, for
hydrophilic compounds with high concentration, an
additional degradation mechanism occurs quickly via
reactions with
OH radicals or pyrolysis in the

interface region of the collapsing bubbles (Ince and
Tezcanli-Gyer, 2001; Okitsu et al., 2005). For dye
degradation and mineralization, hydrodynamic
cavitation had been reported to be more energy
effective compared to acoustic cavitation (Chakinala
et al., 2008; Wang et al., 2009). Decolorization with
hydrodynamic cavitation increased by increasing the
inlet pressure and it is substantially enhanced with the
addition of H
2
O
2
.
Petrier et al. (1998) have proposed a preferential
thermal degradation in terms of pseudo first order
kinetic law of ClBz by conducting a comparative
study with 4-ClPh and ClBz as models for hydrophilic
and hydrophobic substrates respectively. They found
degradation of 4-ClPh was governed by
OH
formation whereas ClBz degradation was basically a
thermal degradation inside the cavitation bubble. In
the similar study by Stavarache et al. (2002) showed
the decomposition of ClBz took place inside
cavitation bubbles forming phenyl (C
6
H
5
) and
chlorine (Cl
) radicals. According to the authors, at

micromolar concentrations the degradation induced by
the
HO radical is significant compare to the pyrolytic

process.
As reported by Jiang et al. (2002) the sonolysis of
ClBz solution was following the pseudo-first-order
rate constant. Similar trends were observed for 1,4-
dichlorobenzene (1,4-DClBz) and 1-
chloronaphthalene (ClNt) degradation where the rate
constants of ultrasonic degradation for 1,4-DClBz and
ClNt solutions also increased with ultrasonic intensity.
The authors proposed two possible schemes of ClBz
degradation as, i) the degradation followed by
chlorine removal by high temperature combustion and
ii) degradation with reactive
OH radicals. However,
the second reaction scheme was recognized as a minor
54
pathway as the hydroxylated intermediate production
was too low.
The degradation of phenol compound can be
proved by the formation of hydroxylated
intermediates (hydroquinone, catechol and resorcinol).
According to Petrier et al. (1994), phenol degradation
in terms of free radical reaction was following two
possible reactions as presented in Eqs 6-7:

OH +
OH H
2
O
2
(6)
C
6
H
5
-OH +

OH C
6
H
5
(OH)
2
(7)

However, the degradation of phenol by ultrasound
was comparable low due to the hydrophilic nature of
phenol which made it unavailable for free radical
reaction with
OH radicals (Maleki et al., 2005).

Zheng et al. (2005) conducted a study to enhance the
sonochemical degradation of phenol by applying the
hydrogen atom scavenger. The additional of CCl
4

traps the hydrogen atoms and prevents their
recombination with OH radicals. This increased
availability of
OH radical that ultimately accelerated

the sonochemical degradation of phenol.
To understand the degradation mechanisms of 4-
ClPh during sonolysis, Hao et al. (2003) have
performed an oxidation experiment between 4-ClPh
and H
2
O
2.
The experiment result showed that high
temperature pyrolysis was the dominant degradation
for 4-ClPh. On the other hand, Jiang et al. (2006)
reported that the 4-ClPh degradation mechanism was
strongly dependent on solute concentration. Teo et al.
(2001) used ion selective electrode to measure the
produced Cl
ions during 4-ClPh degradation. The

results precisely showed the presence of Cl

from the
cleavage of CCl bond of the 4ClPh due to ultrasonic
irradiation. The Cl
balance in the system suggested

the formation of chlorinated intermediates.
Kotronarou et al. (1991) expressed the degradation
of p-nitrophenol (PNP) as a first order reaction. This
was because PNP did not diffuse into the imploding
cavities at a low vapor pressure, but collected at the
liquid/gas interface where it was pyrolyzed and/or
attacked by the solvent radicals. The decomposition
mechanism of PNP was based on a combination of
both pyrolysis and radical reaction (Colarusso and
Serpone, 1996). In another study, Tauber et al. (2000)
found that the reaction mechanism was pH dependent.
At acidic pH (4.0) oxidative pyrolytic decomposition
was predominant whereas at alkaline pH (10.0) free
radical mechanism mainly occurred.
The ultrasonic degradation of hydrophobic
organics such as PAHs can occur when they penetrate
to the surrounding of the hot heart of the cavitation
bubble being pyrolyzed, burnt and/or ionized in the
plasma core (Flannigan and Suslick, 2005). According
to Sponza and Oztekin (2011), sonication alone had a
potential for use in the decomposition of PAHs from
petrochemical industry wastewater. Radical attack
was an important degradation mechanism of less
hydrophobic PAHs while pyrolysis was an important
destruction pathway for more hydrophobic PAHs
In the homogenous sonochemical reactor for
aromatic pollutants degradation, most of the
hydrophobic compounds reacted inside the cavitation
bubble whereas hydrophilic substances reacted at bulk
phase (Adewuyi, 2001; Liang et al., 2007). The
heterogeneous systems also follow the same physical
mechanism but differ in terms of cavitational
threshold, high speed liquid jet and other related
physical effects from acoustic cavitation (Liang et al.,
2007).

6. COMBINATION OF ULTRASONICATION
AND OTHER DEGRADATION
TECHNOLOGIES

Although sonochemical reactions were quite efficient
for degradation of organic compounds, however,
complete mineralization was not achieved sometimes.
This might be due to higher polarity of the organic
compound, low availability of
OH radical or lack of
dissipated power. Therefore, to overcome these
disadvantages in the sonochemical process, ultrasound
has been widely used as an auxiliary process with
other treatment techniques mostly biochemical,
electrochemical, ozonation, photolysis, photocatalysis
and Fenton processes.
Studies of the combined process involving
ultrasound and ozone had shown faster degradation
rates for a range of chemical contaminants than either
method applied alone (Mason and Petrier, 2004). As
the mass transfer rate of ozone in the solution was the
limiting parameter, thus the combined operation of
sonolysis and ozonation renders synergistic effected in
degradation and accelerateed the mass transfer of
ozone in the solution due to ultrasonic effects. When a
liquid was sonicated in the presence of ozone (O
3
), the
thermal decomposition of ozone in the cavitation
bubbles enhanced
OH and H
2
O
2
yields. Xu et al.
(2005) studied on synergetic effect of ozonation with
ultrasonic treatment for p-nitrophenol degradation. In
O
3
/ultrasonic system produced more
OH and H
2
O
2

than the sonolysis system alone. This combined
sonolysis/ozonolysis process showed 116%
enhancement in removal rate for p-nitrophenol.
Gultekin and Ince (2006) investigated the
degradation of aryl-azo-naphthol dyes with
ultrasound, ozone and combination of the two
processes at optimized condition. The US/O
3

combination was the best option for the degradation of
these dyes. The synergetic effect incorporated three
main factors, i) increased mass transfer of ozone, ii)
Peng et al.
55
excess hydroxyl radical generation, and iii)formation
of secondary oxidation species (
O
2
-
and
O
2
H). The
major part of the dissolved ozone was therefore
efficiently decomposed by ultrasonic irradiation
because of the additional pathways involving the
production of these secondary oxidation species. The
combination of these two processes provided three
sources of
OH which are from (i) sonochemical

decomposition of water,ii) the normal chemical
degradation of ozone, and iii) the thermolytic
decomposition of ozone in the acoustic cavitation
bubble. (Mason and Petrier, 2004).
The degradation and mineralization study showed
that dye degradation rate under high frequency
ultrasound (300 kHz) and ozone combined reactor is
higher than the sum of the individual processes
(Gultekin and Ince, 2006). Ozone concentration was
an important parameter in the sonolytic ozonation
process. An increase in ozone dose could improve the
mass transfer of ozone due to an increase in ozone
concentration in the liquid phase (Song et al., 2007).
The pH value in the dye solution was an important
factor in determining the rate constants (Ince and
Tezcanli, 2001). The dye degradation rate increased
when the pH value increased to 8-10. However,
further pH increase would result in reducing dye
degradation due to the existence of the radical
scavengers such as CO
3
2-
, SO
4
2-
and PO
4
3-
(He et
al.,2007; Song et al., 2007; Zhang et al., 2006; Zhang
et al., 2008a,b;Zhang et al., 2009).
Tauber et al. (2005) incorporated ultrasound
treatment followed by enzyme treatment for azo dyes
(Acid Orange 5, Acid Orange 52, Direct Blue 71,
Reactive Black 5, Reactive Orange 16 and Reactive
Orange 107). It was predicted that the intermediates
created during the ultrasonication had acted as the
internal mediator for the subsequent enzyme (laccase)
treatment. Thus, the degradation rate was higher and
showed better efficiency in these dyes removal.
Another study of ultrasonic as pre-treatment for
Congo red solution followed by a biological treatment
presented that sonolysis reduced the biological
treatment time from 23-29 h to 6-8 h, thus reduced the
power consumption and cost (Basto et al., 2007). The
effects of ultrasonic irradiation on biological treatment
can be evaluated by following justification: (i) the
facilitation of substrate diffusion and (ii) the
enhancement of cell enzyme secretion. In addition, the
formation of ultrasonic cavitation could promote
particle movement in reaction solution thus
accelerated mass transfer in the reactor and enhanced
the permeability of cell membrane and wall around
cavitation bubbles (Liu et al., 2005).
The first-order rate constant of the sonophotolytic
process in the presence of hydrogen peroxide is 17.87
times greater than that of the sonophotolytic process
alone for Malachite oxalate green degradation
(Behnajady et al., 2008). In general, the utilization
efficiency of photocatalysis was low because of the
screening effect of catalysts; this disadvantage could
be overcome with the combined use of ultrasonic
irradiation. Ultrasonic irradiation might increase the
photocatalytic reaction rate by increasing the catalytic
activity and reducing the size of photocatalyst
particles following particle disaggregation, which
increased the surface area (Stock et al., 2000). Peller
et al. (2003) study showed the complete
mineralization of chlorinated organic compounds was
achieved with no toxic intermediate build up in low
calatyst loading from the combination of
ultrasound/photocatalysis treatment system. The
beneficial effect of photocatalysis coupled with
ultrasonic irradiation could also be attributed to: (i)
the increased production of
OH by ultrasound, (ii) the

enhanced mass transfer of dye between the liquid
phase and the catalyst surface (Stock et al.,2000; Yuan
et al., 2009), (iii) the excitation of catalyst by
ultrasonically induced wavelength (<375 nm) i.e.
sonoluminescence and (iv) the constantly refreshed
catalyst surface due to acoustic micro-streaming
cleaning and sweeping, which allowd more active
catalyst sites to be available for dye degradation
(Kritikos et al.,2007).
As showed in Eqs (4) and (6), when an aqueous
solution was irradiated with ultrasound, hydrogen
peroxide would be produced. If ferrous ions were
added to this solution, they react with ultrasonically
generated H
2
O
2
, thus enhanced the production of
OH
which could be readily used for dye degradation. The
pseudo first-order rate constant of dye by sono-Fenton
oxidation was three fold greater than that of its
sonolysis alone in the presence of Fe (II) in the
concentration range of 0.1 mM to 0.5 mM. The
increment was due to the formation of more
OH
radical via Fenton reaction (Joseph et al. (2000). In
ultrasonic assisted Fenton process, the highest
decolorization efficiency of dye is achieved at pH 3
(Song et al., 2009). This process was pH dependent
when pH was below 3, hydrogen radicals could be
consumed by the scavenging effects of H
+
and
hydrogen peroxide would formed ozonium ion which
could enhanced the stability and reduced the reactivity
between hydrogen peroxide and ferrous ions (Sun et
al., 2007; Wang et al., 2008a). Another similar study
by Zhang et al. (2009) evaluated the decolorization of
C.I. Acid Orange 7 with the combination of
ultrasound and advanced Fenton process. The
decolorization fit the modified pseudo-first order
kinetic model where the decolorization rate increased
with hydrogen peroxide concentration and power
density but decreased with the increased of initial pH
value.
56
From the studies can concluded that the
combination of ultrasound with relevant treatment
were more economically attractive than the use of
ultrasound alone for aromatic pollutants treatment.

7. CONFIGURATION OF ULTRASONIC
EQUIPMENT

In sonochemical treatment the electrical energy was
basically converted to vibration via a transducer
(Price, 1992). Depending upon the application or the
reaction to be achieved, one can choose different
generators and design appropriate transducers as
required (Ashokkumar and Grieser, 1999).
In general there were four types of laboratory
ultrasonic equipments that were widely used namely,
i) whistle, ii) bath, iii) probe (horn) and iv) cup-horn
system (Mason and Lorimer, 1988). The whistle
reactors were primarily applicable for emulsification,
polymerization and phase transfer reactions.
Ultrasonic bath system was the low intensity load
system with a power density of 12 W/cm2 (Mason
and Lorimer, 1988). The main advantages of bath
system were simplicity and economy. While the
disadvantages were the limitation in temperature
control and ultrasonic intensity control. The ultrasonic
probe system was a high intensity system with better
temperature control. However, horn configuration
became a major limiting factor when dealing with
high amplitudes. Sometimes there were some
chemical interference issues due to the cavitational
erosion of the horn tip metal. The horn design could
essentially limit its ability to achieve greater
cavitation levels and power output. The cup-horn
system was a combination of bath and horn (probe)
system with a better temperature control device. It
allows much higher intensity without any
contamination by the horn tip material (Price, 1992).
Most of the studies describing the degradation of
organic dyes (Rehorek et al., 2004; Vajnhandl and
LeMarechal, 2007 , phenolic compounds (Petrier et
al., 1994; Nagata et al., 2000; Maleki et al., 2005; Xu
et al., 2005) and chlorinated organic compounds
(Drijvers et al., 1998; Gaddam and Cheung, 2001)
used probe (horn) type systems because of its high
power output and optimum performance at different
amplitudes. In the case of a low intensity irradiation a
batch reactor with a submersible transducer was
shown to be the best option (Mason and Tiehm,
2001). Gogate and co-researches (2004) suggested a
few important points on large scale sonochemical
reactors:
(i) multiple frequencies gave higher intensities of
cavitation compared to a single frequency operation.
(ii) Hexagonal geometry was more efficient in
terms of better distribution of cavitational activity.
Bhirud et al. (2004) used ultrasonic bath having
longitudinally vibrating transducer for formic acid
degradation. The longitudinally vibrating reactor
provided 45 times more cavitational yield than
multiple frequency flow cells. The design of the
reactor and the reactor performance also greatly
affected by the ultrasonic poser and free volumetric
flow rate (Gondrexon et al. (1999). According to
Asakura et al. (2008) the sonochemical reactor
volume for pilot scale and industrial scale should be
more than 100 L and 1000 L, respectively. The
observed sonochemical efficiency of the large reactor
was comparable with the laboratory scale reactors. It
was found that the sonochemical efficiency was
dependent on frequency and liquid height in the
frequency range of 45490 kHz.

8. CONCLUSION

Ultrasound technologies have been widely used for
the degradation of aromatic compounds at laboratory
scale and the combination of ultrasound with other
relevant treatments can prove to achieve complete
mineralization and be more economically attractive
than the use of individual techniques due to the
generation of higher quantum of free radicals and high
degree of energy efficiency. It has been observed that
the efficacy of sonochemical reactions in cavitation
process is influenced by many important operating
parameters such as resonance frequency of bubbles,
reaction temperature and energy intensity. An
optimised reactor configuration should be able to
maximize the expected output. Thus, the
configurations of the sono-reactor may significantly
affect the efficacy of ultrasonic system for
sonochemical degradation.

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2014 IJ SRPUB
62

Treatment Systems

Chapter 3: Wastewater Treatment by Biological
Methods
2014 IJ SRPUB
63
Wastewater Treatment by Biological Methods

Dadrasnia A.
1,*
, Shahsavari N.
2
, Emenike C.U.
1

1
Institute of Biological Sciences, Faculty of Science, University of Malaya, 50603 Kuala Lumpur, Malaysia
2
Science and Research Branch, Islamic Azad University, Sirjan, Iran
*Corresponding Author: are.dadrasnia@gmail.com

Abstract. Wastewater generation is just inevitable but discharging it into the environment in a sustainable way is the subject of
concern. Hence, treatments adopted have the common goal of conforming to water quality standards to ensure environmental
protection. Different sources that range from industrial productions to domestic use of water has continued to generate
wastewater and various treatment methods are employed, which includes biological methods. For effective treatment,
considerations are paid to wastewater characteristics, requirement of treated wastewater quality, treatment alternatives and
associated sampling techniques with analysis. Most biological treatments often take care of the removal of biochemical oxygen
demand, chemical oxygen demand, suspended solids, ammonia and even other inorganic compounds that includes heavy
metals. This chapter evaluated the use of oxidation, anaerobic, aerobic ponds, and activated sludge process as biological
treatment methods for wastewater. Common to the options is the utilization of microorganisms to degrade pollutants of
interest, but varied on certain conditions that border on design and oxygen utilization and limitation. Biological treatments can
be achieved under reduced cost when compared to physical and chemical methods, yet time consumption appear to be its
drawback.

Keywords: Wastewater, Treatment, Biological Methods

1. INTRODUCTION

Wastewater emanates from many sources which
includes industrial production and domestic use of
water. Hence, wastewater characteristics are highly
dependent on the source, and when it is not properly
treated before discharge, it can significantly pollute
watercourses. Regardless of the treatment option
adopted for any form of wastewater, the end
expectation is to relate to discharge/effluent standards
and quality. With high level of varied forms of
production and changing lifestyle, chemical
composition and loading of most wastewater are of
significant interest world over, excess organic
Chemical pollution from heavy metals, dyes,
solvents and pesticides is one of the major threats to
water quality. Chemicals enter the aquatic
environment through different ways, among which are
via wastewater treatment plants (WWTP) that do not
fulfill their obligations (Oller et al., 2011), and direct
discharge of industrial effluents. Similarly, indirect
chemical pollution of water arises from the use of
plant health products, such as biocides and, fertilizers
in agriculture (Oller et al., 2011). Considering the fact
that water soluble substances can be distributed and
transported more easily in the water cycle, treatment
of wastewater by discharge becomes paramount.
Wastewater treatment refers to the process of
removing pollutants from water, especially those
associated with agricultural, industrial and municipal
activities. This process is designed to achieve the
expectation and/or standard level in the quality of the
wastewater. Current methods used for removing
pollutants present in the wastewater can be divided
into chemical, physical, biological and energetic
methods.
The aim of applying various treatment processes
are to reduce:
(a) Biodegradable organic parts [chemical oxygen
demand (COD) and Biochemical oxygen demand
(BOD)] serve as food for bacteria. Microorganisms
combine oxygen with organic part of the wastewater
to yield the energy they need to multiply and thrive; in
addition, fish and other organisms in the river need
this oxygen as well. Heavy organic pollution of the
environment may result in dead zones and simply
imply that no fish is found; sudden releases of heavy
organic may result in dramatic Fishkill.
(b) Suspended solid part (including those particles
that can block channels or rivers)
(c) Pathogenic bacteria/disease organisms. These
are most appropriate where the water is necessary for
drinking, or where people would otherwise have close
contact by using it; and
(d) Nutrients, which includes nitrates as well as
phosphates. These nutrients can bring about excessive
levels of algal distribution, which can significantly
contribute to higher loading of biodegradable organic
matter. Treatment techniques could also remove or
neutralize industrial wastes and dangerous chemicals.
Such remedy goal should be practiced in-situ
industrial plant, before final effluent discharge,
especially to watercourses.

1.1. Levels of wastewater treatment

In order to be able to bring about effective treatment
of the effluent, it is necessary to know more about:
Dadrasnia et al.
64
(a) Characteristics of wastewater to be treated
(b) Requirement of treated wastewater quality
(c) Types of treatment alternatives available
(d) Techniques of wastewater sampling and analysis
These are the additions to the preventive and
corrective maintenance of the treatment machinery,
knowledge of repairs to and replacement of various
parts of equipment, record keeping, report
preparation, and aspects of safety in treatment plants.
The characterization involves determination of
biological, physical and chemical characteristics of
the samples of wastewater using laboratory techniques
such as gravimetry, colorimetry and titrimetry.
Knowledge of the characteristics helps the plant
operators to provide the information on:
(a) The strength of the raw and treated wastewater
(b) The efficiency of the plant operation as a whole
and each of the treatment processes
(c) The nature of treatment required in the case of the
given wastewater to meet the quality standard.

1.1.1. Primary treatment (mechanical)

Primary treatment (mechanical) is a preliminary
treatment used to protect and facilitate other
equipment in the treatment processes. It is designed to
cut up or remove the large suspended, gross and
floating solids, and heavy organic solids or amount of
oil from raw sewage. However, this stage is called
mechanical treatment, while chemical substances
can be used to increase the actual sedimentation
procedure. It includes screening or sieving to trap and
remove sediments and solid parts based on principle
of gravity. By this way, the BOD of the incoming
wastewater can be reduced by 20-30% alongside 50-
60% of total suspended solids. Primary treatment is
usually done at the initial period of wastewater
treatment. Many devices are employed for preliminary
treatment, including screens bar, rack, pre-aeration
tanks, as well as grit chambers. These devices require
careful operation and design. Several advanced
wastewater treatment facilities in industrialized places
started with primary treatment, and have after that
included other treatment phases as wastewater load
has grown, and there is requirement for
comprehensive treatment.

1.1.2. Secondary treatment

Secondary treatment method eliminates the dissolved
organic matter which escapes preceding treatment
method. This is realized by microbes consuming the
organic matter as meal, and converting it to CO
2
,
water, and energy for their own reproduction and
growth. The biological method is then followed by
inclusion more sedimentation tanks to adequately
remove remaining suspended solids. In relation to
removal of 85% of the suspended solids, BOD may be
taken off by a well designed plant with secondary
treatment part. Secondary treatment method
technologies are classified as the necessary stimulated
sludge procedure, the variants of pond and constructed
wetland systems, trickling filtration and other forms of
treatment method designed to use biological activity
in order to break down organic matter.

1.1.3. Tertiary treatment

Tertiary treatment is simply an added treatment option
that is more advanced than the secondary treatment.
Tertiary treatment can certainly take away
approximately 99% of all the impurities from sewage,
producing great effluent associated with practically
drinking-water top quality. This associated technology
are often very expensive, requiring a high level of
technical know-how as well as expert plant operators,
a steady energy supply, chemicals and specific
products which in turn may not be easily obtainable.
An example of a typical tertiary treatment action will
be the change of a secondary treatment method to take
out more phosphorus as well as nitrogen.
Disinfection, usually together with chlorine, could
possibly be the last move ahead before discharge of
the effluent. Even so, a few environmental authorities
are concerned which chlorine residuals in the effluent
can be a problem. Disinfection is often that are part of
treatment plant design, although not properly used, as
a result of the higher price of chlorine, as well as
decreased efficiency of ultraviolet radiation where the
normal water is not completely clear, and without any
contaminants.

2. BASICS OF BIOLOGICAL TREATMENTS

2.1. BOD, COD and suspended solids

Biochemical oxygen demand (BOD) is similar in
function to chemical oxygen demand (COD), Organic
waste and natural organic detritus from wastewater
treatment plants, failing septic methods, and farm and
downtown runoff, functions as a food source for
water-borne microorganisms. Bacteria decompose
these natural components employing dissolved
oxygen, thus reducing the DO present for fish or even
marine organisms. Biochemical oxygen demand
(BOD) is usually a way of measuring how much
oxygen bacteria utilize while decomposing organic
matter under aerobic conditions. Biochemical oxygen
need is dependent upon incubating a sealed sample of
water for several times and also measuring the loss of
oxygen from the beginning to the end of the test.
Samples must be diluted prior to incubation; else the
Chapter 3: Wastewater Treatment by Biological Methods
65
bacteria will drastically reduce the available oxygen
inside the container prior to end of the test. The main
focus of all wastewater treatment facilities is to reduce
the BOD in the effluent discharged to natural waters.
Wastewater treatment plants are created to function as
bacteria farms, where bacteria are usually given
oxygen and organic waste. The excess bacteria grown
in the system are usually taken away as sludge, and
disposed of on land as solid waste.
Chemical oxygen demand (COD) does not
basically differentiate between organic matter that is
biologically available and the inert one. However, it is
a measure of the total amount of oxygen required to
oxidization of all organic materials to carbon dioxide
and water. When values are compared, BOD is often
less than COD, though COD measurements can be
produced in some hours though BOD measurements
take five days (BOD
5
).

3. BIOLOGICAL WASTEWATER TREATMENT

3.1. Oxidation Ponds

Before the discharge of wastewater into an aquatic
ecosystem, oxidation ponds are often used for
effective reduction of BOD considering its relatively
low cost and simple technology. It is involves ring
channel that is equipped with mechanical ventilation
apparatuses. Monitored wastewater penetrating the
pool is ventilated by mechanical apparatuses which
circulate at about 0.250.35 m/s. Oxidation pools
normally operate in an expanded aeration mode with
long confinement and solids retention times (Sperling,
et al., 2005). Kotsou et al (2004) had studied an
aerobic biological method by utilizing an Aspergillus
niger strain in a bubble column bio-reactor that was
combined with chemical oxidation treatment of
process wastewater from table olive. Authors reported
that a relatively significant decline of chemical
oxygen require (COD) was found 2 days after
biological treatment, just as the simple and total
phenolic complexes were also reduced by 41 and
85%, respectively. The stage of chemical oxidation
principally influenced the clearance of constant
phenolic complexes during the biological treatment of
total phenolic compounds. Furthermore, coagulation
support from CaO considerably enhanced the
treatment efficiency.

3.2. Anaerobic Ponds

Anaerobic ponds (Figure 1) are planned in a manner
that such will enable effective pretreatment of high
resistance wastewaters. This is applied to the aerobic
treatment and is regularly very efficient and cost-
effective for eliminating BOD and COD high
concentrations (Dewil et al., 2006). These ponds have
more organic loading in comparison to the oxygen
content entering the pond for sustaining the anaerobic
state of the pond surface. Anaerobic bacteria which
occur naturally degrade the organic components in the
wastewater, releasing carbon dioxide and methane.
The ensuing sludge will settle at the bottom while a
crust may aggregate at the surface (Doorn et al.,
2006). Fu et al. (2011) demonstrated textiles
wastewater treatment with the application anoxic filter
bed (AFB) and (BWB-BAF). The study showed that
the AFB effluent COD content reduction upon
addition of new carriers and the average efficiency for
the COD removal was 20.2%.
Leal et al. (2010) studied the occurrence of
xenobiotics in gray water and the associated removal
via three different biological treatment systems. In this
study, 18-selected xenobiotics related to chemicals
from personal care and household products were
estimated in gray water from different houses (32) and
in effluents of three different biological treatment
systems (aerobic, anaerobic, and anaerobic-aerobic).
The authors pointed out that the degree of removal
was optimal was highest at aerobic condition than
when anaerobic situation was used.

3.3. Aerobic Ponds

Aerobic ponds contain suspensions, typically bacteria
and algae that sustain aerobic conditions throughout
their depth. Two types of aerobic wetlands namely,
aerated and shallow ponds are often used
(Vijayaraghavan, 2007). Souza et al., (2011)
investigated the treatment of refinery wastewater by
AOPs along with biological activated carbon (BAC)
with the objective to produce water intended for reuse.
BAC filtration were being observed to be effective,
attaining average efficiencies up to 65% in a
sufficiently long period (84 days), while granular
activated carbon filters were saturated after twenty-
eight days. Cao et al. (2011) suggested internal
electrolysis biological contact oxidation process for
the treatment wastewater containing linear
alkylbenzene sulfonate.

Dadrasnia et al.
66

Figure 1- Anaerobic pond

4. MODELING THE BIOLOGICAL
PROCEEDING

Biology aims to understand the mechanisms by which
organisms survive, grow, and reproduce. It collects
remarks, identifies returning phenomena, and using
existing knowledge attempts to explain these
phenomena, Like other scientific fields. However, this
attempt is a compound one, and biologists would
advantage from computational tools to support them
in construct and evaluate their models.
The achievement of apparatus learning and data
extraction in business areas has led to enhanced
interest in using comparable methods to find out
information in biology and other scientific
arrangements (Fayyad et al., 1996). However, in the
absence of background knowledge, the best-developed
techniques are designed to operate on large data sets.
Regardless the contrary of rhetoric, biology stay puts
a data-sparse field, but it has significant knowledge
available to limit the study for models.
The construction descriptive models are another
disadvantage of standard induction methods. These
can construct precise forecasts on new assessment
cases, which may be adequate for commercial uses,
but biologists naturally desire descriptive models of
behavior. A reason of some occurrence is cast in terms
of other knowledge, such as constructions or courses
that are well-known to field specialists.
Finally, customary instruction techniques create
models that are articulated in documents designed by
computer scientists, few of which biologists discover
intelligible. Even effort on inducing causal models,
which often have an instructive taste, spotlights on
summary formalisms that compose little contact with
implications from biomedical science. Information
that supports the integration of area impressions more
directly would most probably be easier to recognize
and make available additional controls on model
mechanism (Langley et al., 2006).
Biologists require computational methods for data
analysis and organization, with the increasing volume
of genomic data available. We first require a
knowledge model that can indicate biological systems,
to develop computer applications that aid in this task.
Such a model should demonstrate the advanced
physiological processes and attach them to molecular-
level applications. The appearance of structural
reforms, such as the Gene Ontology (The Gene
Ontology Consortium, 2000) is an important first step
in making the communications requisite for a
biological knowledge model (Peleg et al., 2001).
A model of biological process can (1) constantly
indicate the dynamic knowledge about advanced
biological processes, in the framework of their part
molecular-level sub-processes, and (2) be agreeable to
deduction, validation of dynamic (control-flow)
characteristics, and qualitative simulation.
There are a set of desirable requirements for a
model of biological process. First, the model has to
show the following three cases of a biological system.
(1) The Static-structural outlook of bio-molecular
compounds, chemical, and biopolymers that
contribute in the system, their characteristics, and the
relationships between them;
(2) The Dynamic view that indicates how methods
are arranged over time (control flow) and how a
course is recursively decomposed to component
processes and reactions (atomic processes). The
dynamic model have to carry parallel, consecutive,
restrictive and iterative processes; and
(3) The practical view that demonstrates the
performers (e.g., enzyme) that carries out each
purpose, the substrates (input) of each function, and
the results of the function (outputs). The cellular
position of the substrates and products has to be
particular (Peleg et al., 2001).
Chapter 3: Wastewater Treatment by Biological Methods
67
Second, the model has to comprise a biological
ontology that will characterize biological thoughts and
organize them in classification hierarchies. Ontologies
make available constant definitions and explanations
of biological concepts, and make possible software
applications to share and reprocess the knowledge
constantly (Gruber, 1995). Ontologies can be used to
make logical conclusion over the set of impressions to
provide for simplification and clarification facilities
(Schulze- Kremer, 1998).
Third, the demonstration should be sensitive.
Biologists have to find it easy to make and realize a
system that is demonstrated using the model.
Fourth, the model has to be hierarchical to handle the
density of the represented system.
Fifth, the model has to be mathematically based to
permit verification of characteristics that are
advantageous in biological systems, and simulation of
system activities. For example, we were able to
validate that there is no toxic aggregation of
metabolites in pathways (boundedness property).
For a high-level biological process consisting of
lower-level processes, could validate that all the
component processes can contribute (liveness
property). We are able to also investigate to processes
that are constantly in use (violate the fairness
property) and may consequently be good objectives
for affecting system manners. A formal model have to
also make possible us to ensure whether we are able to
move from one system state (e.g., parasite inside host
liver cell) to another status (e.g., parasite cleared).
And sixth, the model should permit important
deduction abilities. For example, proposing the
consequences of knockout experiments substrates
that may accumulate, other reactions that might
procedure these substrates, etc. Other examples
contain recognizing processes that are operated in
response to environmental effects (e.g., heat shock),
or discovery procedures that are active during a
determined developmental stage. The argument
mechanism should apply the biological concept model
to structure abstract concepts (e.g., tight-junction
formation is a kind of adhesion process) (Peleg et al.,
2001).

4.1. TAMBIS model

Clear Access to numerous Biological Information
resources (TAMBIS) (Baker et al., 1999) is ontology
for a description of data to be fined from
bioinformatics resources. TAMBIS goes beyond
taxonomic models. It demonstrates biological
concepts and appearances a semantic template of
concept relations that can be used to create deductions
from biological data. TAMBIS is defined as a logic-
based knowledge representation formalism using
explanation Logic (Bordiga, 1995) that defines
concepts using argument to sort the concepts based on
those descriptions in terms of their properties.

4.2. The Workflow model of the Workflow
Management Coalition

The Workflow Management Coalition is defined as a
Workflow model for business procedures (Workgroup
Management Coalition, 1999). Definition of the
Workflow model is a representation of a business
(high-level biological) process in an automated
manipulation form. The process definition presents a
functional and dynamic model that includes of a
network of activities (logical steps in the process) and
their relationships, criteria to demonstrate the start and
ending of the process, and information about the
participants of individual activities.

4.3. Petri Nets model

A Petri Net (Peterson, 1981) which is used to model
concurrent systems defined a formal model. A Petri
Net is represented by a directed, bipartite graph in
which nodes are either locations or transmissions,
where locations indicate conditions (e.g., parasite in
blood stream) and transitions demonstrate activities
(e.g., invasion of host erythrocytes).

5. ACTIVATED SLUDGE PROCESS

The activated-sludge process (ASP) is one of the
forms of wastewater treatment via biological method.
It is principally based on the utilization of different
but mixed community of microbes within an aerobic
aquatic environment. The carbonaceous organic
matter in the aerated wastewater serve as the source of
energy for the microbes which they use for generation
of new cells via biosynthesis, while undergoing
respiration simultaneously by giving out energy when
the organic matter is converted into compounds of
lower energy, especially carbon dioxide and water.
Similarly, some of the microbes in this system
generate energy through nitrification process;
ammonia nitrogen is converted to nitrate nitrogen.
Therefore, activated sludge refers to the consortium of
microbes with the associated biological component of
the process.

5.1. Principles of Activated Sludge Process (ASP)

Dadrasnia et al.
68

Storage of the wastewater in aeration tank
Bacteria growth is enhanced by supplying
oxygen, food (BOD), time and optimal temperature.
The consortium of BOD substrate enhances bacteria
growth and increased population.
Secondary clarifiers receive the treated
wastewater, and the bacteria cells that settle are
collected from the clarifiers as sludge.
A portion of the sludge is returned back to the
activated sludge tank (partial recycling) to ensure that
certain bacteria population is maintained in the
system.
Remaining sludge is totally removed as waste.
-ASP 1
The ASP comprised of interrelated equipment (5) and
components. Aeration tanks(s) are the first
components which serve as an aerobic environment
when air or oxygen is injected/supplied to the system.
Such environment basically satisfies the requirement
of the biological community and thoroughly ensures
proper mixing of the activated sludge (Figure 2).

Fig. 2: Schematic presentation of aeration reactors in Activated Sludge Process

-ASP 2
An aeration source is the second vital component
which supplies sufficient oxygen to the tanks and
ensures adequate mixing within the system. The
oxygen supply can be in form of mechanical aeration
or introduction of pure compressed oxygen.
Equipment for the supply of oxygen to this system can
vary in design and operation due to the number and
modifications in shape of aeration tanks used.

-ASP 3
Third in the line of ASP equipment are the secondary
clarifiers. Here, separation of activated sludge solids
from water occurs. This is based on the principle of
flocculation (aggregation of large particles or flocs
due to adherence of floc-forming organisms to
filamentous organisms) and gravity sedimentation,
where flocs settle at the base of the clarifier sluggish
environment. Subsequently, a secondary effluent
(wastewater characterized of low-level activated-
sludge solids that are in suspension) is formed from
the separation at the upper segment of the clarifier.
However, at the base of the clarifier is a thickened
sludge characterized of flocs and referred to as return
activated sludge (RAS).

-ASP 4
The RAS generated must be removed from the
clarifiers and rei

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Wastewater Engineering: Advanced

), are the Redlich-Peterson

OH) diffuse from the interface

OH) (Crum et al., 1999; Shimizu

OH in the bulk solution

OH is at its maximum, and a large

OH are recombined at the gas-liquid

OH escapes from the

OH radicals combine to produce H

OH radicals were primary reactive

OH is the major process for complete

OH are most abundant and undergo additional

OH radicals. At lower frequency, the degradation rate

OH radical production rate was

OH radicals or pyrolysis in the

) radicals. According to the authors, at

HO radical is significant compare to the pyrolytic

OH radicals (Maleki et al., 2005).

OH radical that ultimately accelerated

ions during 4-ClPh degradation. The

balance in the system suggested

OH which are from (i) sonochemical

OH by ultrasound, (ii) the