Wastewater Engineering: Advanced

Wastewater Treatment Systems

IJSR Publications
 Wastewater Engineering: Advanced Wastewater
Treatment Systems

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

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

iii
 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

iv
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

v
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

vi
Wastewater Engineering: Advanced Wastewater Treatment Systems
Available online at http://www.ijsrpub.com/books
2014 IJSRPUB

Wastewater Engineering: Advanced Wastewater

Treatment Systems

Chapter 1: Introduction of preliminary and

Secondary Treatments

1
Wastewater Engineering: Advanced Wastewater Treatment Systems
Available online at http://www.ijsrpub.com/books
2014 IJSRPUB

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 2. Primary treatment

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.
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 (BOD5),
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:

2
 Amirossadat
Advanced Wastewater Treatment
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
3
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
 Wastewater Engineering: Advanced Wastewater Treatment Systems
Chapter 1: Introduction of preliminary and Secondary Treatments
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 BOD5 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
4
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.
Wastewater Engineering: Advanced Wastewater Treatment Systems
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2014 IJSRPUB

Wastewater Engineering: Advanced Wastewater

Treatment Systems

Chapter 2: Wastewater Treatment by Physical-

Chemical Technologies

5
Wastewater Engineering: Advanced Wastewater Treatment Systems
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2014 IJSRPUB

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 inorganic salts (Renou et al., 2008). Without an

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
6
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 BOD5/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

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)

7
 Wastewater Engineering: Advanced Wastewater Treatment Systems
Chapter 2: Wastewater Treatment by Physical-Chemical Technologies
Table 1: Classification of landfill leachate (Alvarez-Vazquez et al., 2004)
Parameters Young
Age (years) <5
pH <6-5
COD (mg L-1) >10 000
BOD5/COD 0.5-1
TOC/COD <0.3
NH-N <400
Heavy metal (mg L-1) Low to
medium
Organic compound 80%
VFA
Biodegradability Important
Kjeldahl Nitrogen (g L-1) 0.1-0.2
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
8
Intermediate Stabilized
5-10 >10
6-5-7-5 >7.5
4000-10 000 <4000
0.1-0.5 <0.1
0.3-0.5 >0.5
NA >400
Low Low
5-30% HA+FA
VFA+ HA+ FA
Medium Low
NA NA
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 oC to develop the porosity (micropores and
mesopores) of the carbonized material (Rodrigues-
Reinoso and Molina-Sabio, 1992). CO2 can develop
narrow micropores, while steam will widen the initial
micropores. Accordingly, CO2 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 400-800oC (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 m2/g (Tseng, 2006).
 Azmi et al.
Recent Development in Landfill Leachate Treatment Using Low Cost Adsorbent Prepared From Waste Material
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, CO2) 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,
9
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.
 Wastewater Engineering: Advanced Wastewater Treatment Systems
Chapter 2: Wastewater Treatment by Physical-Chemical Technologies
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 NH3-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 0.515cm3/g and micropore
surface area 659.25 mg/cm2. In another study
conducted by Foo et al., (2013b), the potential of the
10
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
30oC, 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 30oC. 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 800oC, activation time 2.1H and CO2
flow rate 68.68 mg/L. In another study conducted by
Ching et al., (2011), impregnated coffee ground with
 Azmi et al.
Recent Development in Landfill Leachate Treatment Using Low Cost Adsorbent Prepared From Waste Material

H2SO4 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 PO4-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 0.42cm3/g with chemical activation by
ZnCl2 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

11
 Wastewater Engineering: Advanced Wastewater Treatment Systems
Chapter 2: Wastewater Treatment by Physical-Chemical Technologies
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
12
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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Wastewater Engineering: Advanced Wastewater Treatment Systems
Available online at http://www.ijsrpub.com/books
2014 IJSRPUB

Removal of Colour from Synthetic Dye Wastewater Using Adsorbent Prepared from
Psyllium Husk
Irvan Dahlan1*, Somaia M.O. Tayeh2
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
CoFe2O4 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 30C, 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 are harmful to aquatic life in rivers where they are

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
15
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 107 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
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
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 100oC
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 Na2CO3 solution (Fig. 2a). The
mixture was shaken for 45 min at room temperature
16
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 Na2CO3 and
Ferric nitrate [Fe(NO3)39H2O] which is provided by
Bendosen Laboratory Chemicals, whereas NaOH,
H2SO4 and Cobalt nitrate [Co(NO3)26H2O] 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. 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
 Wastewater Engineering: Advanced Wastewater Treatment Systems
Chapter 2: Wastewater Treatment by Physical-Chemical Technologies
distilled water (Fig. 2h). The product after drying was
labeled as quaternized psyllium husk (QPH).
2.2.3. Preparation of psyllium husk/CoFe2O4
adsorbent (PH/CFO)
Psyllium husk/CoFe2O4 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
Table 1: Summary of batch studies
Preliminary 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)
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, qe (mg/g)
was calculated using Equation
where Co and Ce (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 Ct 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
boiling state (Fig. 3b). A 50mL metal nitrate aqueous
solution was prepared by dissolving Fe(NO3)39H2O
(5.4944 g) and Co(NO3)26H2O (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
H2SO4 (2N ) to obtain PH/CFO-Ac.
Main Batch study
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 60oC
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 Qo signifies the adsorption
capacity (mg/g) and b is related with the energy of the
adsorption (L/mg), KF 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 k1 is the pseudo-rst-order rate constant
(min1), qe and qt 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):
17
 Dahlan and Tayeh
Removal of Colour from Synthetic Dye Wastewater Using Adsorbent Prepared from Psyllium Husk

concentration, while the other kinds of adsorbent

(PH/CFO-Al, QPH and NPH), gave negative
efficiency due to the color of dye became more
where k2 (g mg1 min1 ) is the rate constant of the
darker.
pseudo-second-order adsorption.
It was noticed also from Figure 4 (b) that the
PH/CFO-Ac, has the best removal efficiency, with
2.5. Analysis and Characterization
88.6%% color removal when 1g adsorbent was used
and 73% color removal when 3g adsorbent was used,
The initial concentration of dye (direct blue 71 dye
while the other three kinds of adsorbent gave negative
solution) and samples after sorption treatment were
efficiency due to the color of dye became more
measured using DR 2800 spectrophotometer
darker. Based on the results of the preliminary study,
according to the Platinum Cobalt Standard Method
PH/CFO-Ac was selected to be used for the main
(Adopted from Standard Methods for the Examination
study.
of Water and wastewater and NCASI, Technical
Bulletin No. 253, Dec. 1971). All the concentrations
3.2. Batch Experiments for Synthetic Wastewater
of sample analysis were conducted in triplicate to
increase the precision of the results, and only the
3.2.1. Effect of contact time
average value was reported throughout this analysis.
Selected magnetic sorbents, before and after the
One of the most important parameters affecting the
adsorption process, were characterized using
adsorption process is the contact time. It is supposed
Mastersizer 2000 in order to study the particle size
that the color removal efficiency will increase by the
distribution for the adsorbent. To obtain the surface
increasing of the contact time, until reaching a time at
morphologies of the selected adsorbent, before and
which no significant amount of dye is removed; this
after the adsorption process, the scanning electron
time is called the equilibrium time. Figure 5 shows the
microscopy (SEM) examinations were performed with
effect of contact time on the adsorption of DB71 using
5 kV of accelerating voltage using Leo Supra 35VP-
PH/CFO-Ac adsorbent
24-58 microscope.
It was shown in Figure 5 that the removal
efficiency of PH/CFO-Ac increased rapidly from
3. RESULTS AND DISCUSSIONS
90.8% to 94.03 % when the contact time was
increased from 1 to 2 hours. After that, no significant
3.1. Preliminary Batch Study
increase was noticed in the removal efficiency with
increasing the contact time. This is probably due to
As described before, four types of adsorbents were
larger surface area of the PH/CFO-Ac adsorbent being
prepared to select the best adsorbent for the main
available at the beginning of the adsorption process,
batch experimental studies. Figure 4(a) shows the
so the adsorption rate was fast. As the surface
results for the adsorbent selection based on dye
adsorption sites become exhausted, the uptake rate is
concentration, and Figure 4(b) shows the results for
controlled by the rate at which the adsorbate is
the adsorbent selection based on adsorbent amount. It
transported from the exterior to the interior sites of the
was noticed from Figure 4(a) that the PH/CFO-Ac
adsorbent particles (Ai et al., 2010, Kumar et al.,
which is the magnetic adsorbent prepared from
2010).
psyllium husk treated with acidic solution (H2SO4) 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

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 Wastewater Engineering: Advanced Wastewater Treatment Systems
Chapter 2: Wastewater Treatment by Physical-Chemical Technologies

Fig. 2: Preparation of quaternized adsorbent

19
 Dahlan and Tayeh
Removal of Colour from Synthetic Dye Wastewater Using Adsorbent Prepared from Psyllium Husk

Fig. 3: Preparation of psyllium husk/CoFe2O4 adsorbent (PH/CFO)

20
 Wastewater Engineering: Advanced Wastewater Treatment Systems
Chapter 2: Wastewater Treatment by Physical-Chemical Technologies

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

21
 Dahlan and Tayeh
Removal of Colour from Synthetic Dye Wastewater Using Adsorbent Prepared from Psyllium Husk

with increasing adsorbent amount, the amount of dye removal efficiency with increasing adsorbent amount
adsorbed onto unit weight of adsorbent gets reduced, (Vadivelan and Kumar, 2005).
thus causing a decrease in adsorption capacity and

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.

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 Wastewater Engineering: Advanced Wastewater Treatment Systems
Chapter 2: Wastewater Treatment by Physical-Chemical Technologies

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

3.2.5. Effect of pH up from 87.8% to 91.5% when pH was increased from

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
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 temperature was increased to 60oC. Similar results

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 -
60oC. Figure 10 shows that the highest removal
efficiency (92.04%) was obtained at temperature
30oC, and decreased slowly until temperature 50oC,
after that it decreased rapidly to 76.36% when the
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).

23
 Dahlan and Tayeh
Removal of Colour from Synthetic Dye Wastewater Using Adsorbent Prepared from Psyllium Husk

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 (R2 = 0.85), however, the
calculated qe (qe,cal ) obtained from this equation does
not give reasonable value (Table 2), which is much
lower compared with qe obtained from the
experimental data (qe,exp ).

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 Wastewater Engineering: Advanced Wastewater Treatment Systems
Chapter 2: Wastewater Treatment by Physical-Chemical Technologies

Y= -0.013X + 0.545
R2 = 0.85

Fig.12: Pseudo-first-order kinetic plot for adsorption of DB71 onto PH/CFO-Ac (C0 = 200mg/L, pH 9)

Y = 0.00509 X + 0.00083
R2 = 0.997

Fig. 13: Pseudo-second-order kinetic plot for adsorption of DB71 onto PH/CFO-Ac (C0 = 200mg/L, pH 9)

Table 2: Kinetic parameters for adsorption of DB71 onto PH/CFO-Ac

q e,exp Pseudo-rst-order Pseudo-second-order
(mg g -1)
K1 (min-1) q e,cal R2 K2 q e,cal R2
(mg g -1) (g mg-1 min-1) (mg g -1)

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 R2 value is
0.997 and the (qe,cal =196mg/g) agrees very well with
the (qe,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

25
 Dahlan and Tayeh
Removal of Colour from Synthetic Dye Wastewater Using Adsorbent Prepared from Psyllium Husk

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
Ce/qe versus Ce (Fig. 14) yields a straight line with
slope 1/Q0 and intercepts 1/Q0b. The essential
characteristics of the Langmuir isotherm can be
expressed in terms of dimensionless constant
separation factor RL given by (Mahmoodi et al., 2011)
(7)
where b is the Langmuir constant and Co 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 RL value (Mahmoodi et al., 2011)

Value of RL Type of adsorption
RL > 1.0 Unfavourable
RL = 1.0 Linear
0 < RL < 1.0 Favourable
RL = 0 Irreversible

The value of RL calculated (0.00066) was in the studied. Table 4 summarizes Langmuir constants and
range between 0 and 1 which indicate that the computed maximum adsorption capacity Q0 of DB71
adsorption is favorable at operation conditions onto the PH/CFO-Ac.

Table 4: Langmuir and Freundlich isotherm model constants and correlation coefficients for adsorption of DB71 onto
PH/CFO-Ac
2
Langmuir b (L/mg) Q (mg/g) R R
o L
isotherm
7.57 188.7 0.00066 0.997

2
Freundlich isotherm KF Q (mg/g) n R
o
203 177.7 40 0.991

In addition, the Freundlich isotherm is an empirical
equation based on a heterogeneous surface. A plot of
ln qe versus ln Ce (Fig. 15) enables the constant KF
and exponent n to be determined. KF 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
26
of adsorption intensity or surface heterogeneity. These
values together with the correlation coefficient are
presented in Table 3.3. Based on the values of
2
correlation coefficients (R ) and Qo 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.
 Wastewater Engineering: Advanced Wastewater Treatment Systems
Chapter 2: Wastewater Treatment by Physical-Chemical Technologies

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 m2/g)
than that of the spent adsorbent with low removal and
spent adsorbent with high removal (0.0158 and 0.0112
m2/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.

27
 Dahlan and Tayeh
Removal of Colour from Synthetic Dye Wastewater Using Adsorbent Prepared from Psyllium Husk

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) 4. CONCLUSIONS

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
CoFe2O4 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.
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.

28
 Wastewater Engineering: Advanced Wastewater Treatment Systems
Chapter 2: Wastewater Treatment by Physical-Chemical Technologies

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

ACKNOWLEDGMENT synthesis, magnetic performance and their

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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Wastewater Engineering: Advanced Wastewater Treatment Systems
Available online at http://www.ijsrpub.com/books
2014 IJSRPUB

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 adsorption. The relative advantages of adsorption over

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
31
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
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
Table 1: Experimental Details for treatment of wastewater using adsorbents
Effect of System Adsorption Dose (g/l)
1, 2, 4, 6, 8, 10, 12, 14,
Effect of adsorption dose
16, 18 and 20
Effect of contact duration 5.0
298, 303, 308, 313, 318,
Effect of temperature 5.0
Effect of pH 5.0
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
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.
Temperature (K) Contact Duration (min) pH
300 180 7
30, 60, 90, 120, 150,
300 7
180, 210 and 240
180 7
323 and 328
300 180 3, 5, 7, 9 and 11
effectively on multilayer and is expressed by the
following equation.
qe = KFCe1/n or log qe = log KF + 1/n log Ce
Where, qe and Ce is the amount of adsorbed
adsorbate per unit weight of adsorbent and
unadsorbed adsorbate concentration in solution at
equilibrium, respectively and KF (L/mg) and n are
Freundlich constant characteristics of the system,
which are determined from the log qe vs. log Ce. 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:
32
 Wastewater Engineering: Advanced Wastewater Treatment Systems
Chapter 2: Wastewater Treatment by Physical-Chemical Technologies
qe = kLCe / (1 + aLCe) or (Ce/qe) = (1/ KL) + (aL/KL)
Ce
The constant KL (L/g) is the Langmuir equilibrium
constant and the KL/aL gives the theoretical monolayer
saturation capacity, Qmax (mg/g). These Langmuir
parameters were obtained from the linear correlations
between the values of Ce/qe and Ce. 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:
qe = qme-2 or In qe = In qm - 2
Where qm (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/Ce)
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/Ce) = ln(KFH) + aFH ln(1- qe)
Where q is the surface coverage of the adsorbent
by adsorbate. KFH (mg/g) and aFH are the Flory-
Huggins constants. These constants can be obtained
from the plot of log (q/Ce) versus log (I-qe)
Furthermore the equilibrium constant KFH,
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:
33
G0 = - RT/ In KFH
Where R is universal gas constant 8.314 J/K/mol,
T is absolute temperature (K) and KFH 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[(KRPCe /qe) 1] = RP ln(Ce) + ln(aRP)
Where, qe (mg/g), is the solid-phase adsorbate
concentration at equilibrium, Ce (mg/l) is the liquid-
phase adsorbate concentration at equilibrium, KRP
(1/mg) and aRP (Lmg), 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(Ce) = - ln(Ks/qe) + ln(as)
Where Ks 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
COD and BOD Removal from Textile Wastewater Using Naturally Prepared Adsorbents and Their Activation Forms
Using Sulphuric Acid
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
qe = (qm bT Ce) / [1 + (bTCe) 1/nT] nT
Where, qm (mg/g) is the Khan adsorption capacity,
and bT (1/mg) is the Toth model constant and nT 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
Fig. 1: Effect of adsorbent dose for percentage COD and BOD removal using NLPs
34
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.
 Wastewater Engineering: Advanced Wastewater Treatment Systems
Chapter 2: Wastewater Treatment by Physical-Chemical Technologies

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
35
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
COD and BOD Removal from Textile Wastewater Using Naturally Prepared Adsorbents and Their Activation Forms
Using Sulphuric Acid

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

36
 Wastewater Engineering: Advanced Wastewater Treatment Systems
Chapter 2: Wastewater Treatment by Physical-Chemical Technologies

Table 3: Effect of temperature for percentage COD and BOD removal using naturally prepared adsorbents
Adsorbent Temperature (K)
% Removal
298 303 308 313 318 328 328
COD 39.1 48.6 56.0 62.2 70.1 75.6 76.0
a-NLP
BOD 34.7 41.4 48.0 52.6 60.1 63.0 63.2
COD 20.1 32.2 45.5 50.5 61.2 65.6 65.6
NLP
BOD 20.2 32.2 35.6 42.5 51.2 55.5 55.5
COD 30.3 39.1 54.6 62.2 68.3 72.3 73.0
a-GLP
BOD 29.0 35.0 45.4 52.1 61.6 67.6 68.0
COD 20.0 28.5 44.2 52.1 57.2 61.2 61.2
GLP
BOD 18.2 25.5 34.4 41.1 54.2 60.0 60.0
COD 15.2 20.2 26.5 37.3 44.5 47.5 47.5
a-TSP
BOD 7.8 12.5 25.5 35.8 43.6 47.7 47.7
COD 24.3 37.9 44.9 52.2 56.5 62.5 63.0
TSP
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
pH
Adsorbent % Removal
3 5 7 9 11
COD 14.8 23.6 39.0 56.5 64.8
a-NLP
BOD 9.7 17.6 32.1 50.1 60.0
COD 10.0 15.5 27.4 45.5 55.5
NLP
BOD 5.2 10.5 20.5 41.4 54.2
COD 7.5 14.8 26.5 42.1 57.4
a-GLP
BOD 3.2 10.2 20.2 34.7 48.7
COD 5.5 10.2 15.5 30.2 47.5
GLP
BOD 1.2 5.5 11.1 25.5 40.2
COD 4.5 12.5 24.5 41.5 50.2
a-TSP
BOD 3.5 15.2 20.5 31.5 41.4
COD 8.0 24.2 34.8 50.4 56.5
TSP
BOD 5.7 21.7 31.7 40.0 44.7

3.6. Adsorption Model adsorbent then other investigated adsorbents.

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, KF 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, Qmax 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
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 H2SO4 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
parameters for COD and BOD removal using
naturally prepared adsorbents were depicted in Table
6. Maximum DubininRadushkevich monolayer
capacity, qm 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

37
 Patel and Vashi
COD and BOD Removal from Textile Wastewater Using Naturally Prepared Adsorbents and Their Activation Forms
Using Sulphuric Acid

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, kFM
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
G0 for this study was computed in the range of -
9.1909 to -13.8271 kJ/mol. The negative value of G0
indicates that the sorption process is spontaneous in
nature.

Table 5: Freundlich and Langmuir parameters for COD and BOD removal using naturally prepared adsorbents
Freundlich Parameters Langmuir Parameters
Adsorbent Removal
KF (L/mg) n Qmax (mg/g) KL (L/mg)
COD 79.39 0.1377 87.58 0.049
a-NLP
BOD 41.64 0.2262 84.51 0.037
COD 45.12 0.1379 80.45 0.045
NLP
BOD 40.25 0.1919 79.58 0.012
COD 28.69 0.4065 85.65 0.12
a-GLP
BOD 12.13 0.1447 81.45 0.14
COD 20.45 0.3175 82.41 0.21
GLP
BOD 15.18 0.2809 78.57 0.54
COD 17.4 0.2353 75.14 0.14
a-TSP
BOD 7.45 0.1212 70.45 0.024
COD 23.07 0.1570 81.25 0.17
TSP
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
Dubinin-Radushkevich Parameters Flory-Huggins Parameters
Adsorbent Particular
qm (mg/g) (mmol2/J2) E (kJ/mol) nFH kFH (mg/g) G0 (kJ/mol)
COD 18.45 4.613 1.2412 -0.699 0.0552 -6.9707
a-NLP
BOD 13.27 10.332 0.9574 -0.657 0.0452 -7.2395
COD 15.21 15.485 0.8747 -0.547 0.0212 -6.1091
NLP
BOD 8.27 22.258 0.8547 -0.512 0.0392 -6.7909
COD 15.27 0.3547 0.8258 -0.431 0.0450 -10.2111
a-GLP
BOD 12.17 0.3948 0.6847 -0.379 0.0402 -11.2551
COD 12.41 0.5158 0.5258 -0.3954 0.0166 -9.1909
GLP
BOD 7.55 0.7414 0.6868 -0.354 0.0305 -10.7929
COD 8.65 0.3470 0.7265 -0.407 0.0185 -9.4405
a-TSP
BOD 5.87 0.5081 0.8584 -0.317 0.0205 -12.6157
COD 10.65 0.6587 0.7457 -0.375 0.0252 -10.2332
TSP
BOD 8.54 0.8714 0.6585 -0.298 0.0301 -13.8271

Table 7 depicted Redlish-Peterson and Sips
parameters for COD and BOD removal using
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, qm 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
parameters for COD and BOD removal using
naturally prepared adsorbents. Maximum Toth
adsorption capacity, qm 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, nT = 1, this
isotherm reduces to the Langmuir sorption isotherm
equation. Maximum Khan adsorption capacity, qm 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.

38
 Wastewater Engineering: Advanced Wastewater Treatment Systems
Chapter 2: Wastewater Treatment by Physical-Chemical Technologies

Table 7: Redlish-Peterson and Sips parameters for COD and BOD removal using naturally prepared adsorbents
Redlish-Peterson Parameters Sips Parameters
Adsorbent Particular KRP
aRP (Lmg) RP qm (mg/g) Ks (L/mg) n
(1/mg)
COD 2.40 0.234 0.874 19.7 1030.2 0.734
a-NLP
BOD 3.18 7.489 0.907 18.5 9217.4 0.847
COD 1.25 45.12 0.915 14.4 9845.5 0.745
NLP
BOD 1.02 0.245 0.995 10.8 5545.5 0.824
COD 1.23 61.67 0.940 17.9 8462.5 0.885
a-GLP
BOD 0.31 0.032 1.007 15.2 1251.4 0.755
COD 0.915 75.45 0.954 10.5 4578.5 0.705
GLP
BOD 0.29 0.025 0.54 7.4 1020.2 0.821
COD 0.83 149.8 0.991 12.1 1656.5 0.927
a-TSP
BOD 0.24 0.004 0.96 7.2 768.5 0.835
COD 0.71 158.5 0.542 15.5 754.5 0.812
TSP
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
Adsorbent Particular
qm (mg/g) bT (1/mg) nT qm (mg/g) bK (L/mg) aK
COD 14.25 0.025 0.854 17.34 0.245 0.057
a-NLP
BOD 7.87 0.058 0.754 15.82 0.547 0.047
COD 11.24 0.047 0.687 14.14 0.657 0.068
NLP
BOD 4.58 0.052 0.847 10.25 0.847 0.084
COD 10.47 0.047 0.856 11.44 0.574 0.064
a-GLP
BOD 5.84 0.065 0.884 10.78 0.632 0.057
COD 8.66 0.043 0.785 7.45 0.478 0.068
GLP
BOD 4.58 0.045 0.847 15.45 0.558 0.062
COD 5.58 0.042 0.748 8.45 0.874 0.041
a-TSP
BOD 3.85 0.028 0.789 7.45 0.658 0.038
COD 6.58 0.045 0.840 11.14 0.782 0.057
TSP
BOD 4.58 0.036 0.705 10.47 0.687 0.047

4. CONCLUSION data for removal of COD and BOD using naturally

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
39
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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Wastewater Engineering: Advanced Wastewater Treatment Systems
Available online at http://www.ijsrpub.com/books
2014 IJSRPUB

Fenton Oxidation for the Treatment of Liquid Waste with High COD and
Anionic/Non-ionic Surfactants
M.C. Collivignarelli1, S. Sorlini2*, A. Abb1, M. Sordi1
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 (Fe2+ e H2O2) and contact time. In particular, Fe2+/H2O2 ratio varied from 0.25
to 0.50, H2O2/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
Fe2+/H2O2 ratio equal to 0.25, a H2O2/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 wastes containing surfactants involve chemical and

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
41
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

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 FeSO47H2O 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: H2O2
and Fe2+ 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
BOD5 mg/L 8000 6000 - -
BOD20 mg/L - - - -
TN mg/L 307 < 0.5 - -
N-NH4+ mg/L 37.4 < 0.5 8.8 65
N-NO3- mg/L 17.3 < 0.5 - -
N-NO2- 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

42
 Wastewater Engineering: Advanced Wastewater Treatment Systems
Chapter 2: Wastewater Treatment by Physical-Chemical Technologies

2.3. Experimental tests reaction time and temperature in order to determine

the optimal process conditions. The detailed
The tests were carried out with different dosages of experimental conditions are reported in Table 2.
reagents (expressed as H2O2/COD and Fe2+/H2O2),

Table 2: Experimental conditions applied during Fenton oxidation

Operative conditions
Tests Liquid Waste (LW)
Contact time [minutes] (H2O2/COD)0 Fe2+/H2O2
F1 30 0.36 1/2
F2 30 0.36 1/5
I
F3 30 0.72 1/4
(mix 1)
F4 60 1 1/2
F5 60 0.72 1/2
F6 60 0.72 1/2
I
F7 60 1.17 1/2
(mix 2)
F8 60 2 1/4
F 11 60 0.72 1/4
F 12 60 1 1/4
F 13 60 0.72 1/2
II
F 14 30 0.72 1/4
F 15 60 1.5 1/4
F 16 120 0.72 1/4
F 17 60 0.72 1/4
F 18 60 1 1/4
F 19 60 1.5 1/4
III
F 20 30 0.72 1/4
F 21 60 1 1/2
F 22 120 1 1/4
F 23 60 0.72 1/4
F 24 60 1 1/4
F 25 60 1.5 1/4
IV
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-
NH4+, N-NO2-, N-NO3-, 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. BOD5 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 Fe2+ dosage
0.25 and 0.5 respectively. The removal yields of COD
and surfactants (MBAS and TAS) versus Fe2+/H2O2
and with different contact time and H2O2/COD ratio
are reported in Figures 2 and 3 respectively. As
concerns COD the optimal dosage of iron seems to be
Fe2+/H2O = 0.25, for which most of the processed LW
showed better removal yields for reaction times of 30
and 60 minutes and for H2O2/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%.

In order to assess the optimal dosage of iron, each

liquid waste was tested with two ratios of Fe2+/H2O2:

43
 Collivignarelli et al.
Fenton Oxidation for the Treatment of Liquid Waste with High COD and Anionic/Non-ionic Surfactants

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 Fe2+/H2O2 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 H2O2 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 H2O2/COD ratios were 0.72,
1, 1.5 and only for LWI - mix 2 the 1.17 ratio was
44
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%.
 Wastewater Engineering: Advanced Wastewater Treatment Systems
Chapter 2: Wastewater Treatment by Physical-Chemical Technologies

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 H2O2/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).

45
 Collivignarelli et al.
Fenton Oxidation for the Treatment of Liquid Waste with High COD and Anionic/Non-ionic Surfactants

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 30 minutes. These process conditions allow obtaining

The results showed that the optimal treatment
conditions for surfactant removal from liquid wastes
can be obtained with a Fe2+/H2O2 ratio equal to 0.25
and a H2O2/COD ratio of 1 and a reaction duration of
46
an average removal yield of 70% for TAS and COD
95% for MBAS. In fact, the experimental data
obtained show that higher dosages of Fe2 + produce for
almost all tested liquid wastes a lower removal yield
of both the surfactants. Instead, regarding H2O2 the
 Wastewater Engineering: Advanced Wastewater Treatment Systems
Chapter 2: Wastewater Treatment by Physical-Chemical Technologies
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, 21st
edition. American Public Health Association,
Washington DC, USA.
CESIO - European Committee of Organic Surfactants
and their Intermediates (2012). CESIO
surfactants statistics for Western Europe.
47
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.
Wastewater Engineering: Advanced Wastewater Treatment Systems
Available online at http://www.ijsrpub.com/books
2014 IJSRPUB

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 organic pollutants and also used as pretreatment to

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
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

48
 Peng et al.
Ultrasound Irradiation on the Treatment of Aromatic Compounds in Wastewater
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).
49
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
 Wastewater Engineering: Advanced Wastewater Treatment Systems
Chapter 2: Wastewater Treatment by Physical-Chemical Technologies
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 (H2O2) and hydrogen
molecules (H2) 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)
H2O + ultrasound H + OH (1)
OH + H H2O (2)
H + O2 HO2 (3)
2OH H2O2 (4)
2HO2 H2O2 + O2 (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 H2O2 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
50
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.
Ultrasound Irradiation on the Treatment of Aromatic Compounds in Wastewater
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
51
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 (C2H2),
methane (CH4) and carbon dioxide (CO2) 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
(4.1107 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 (C0=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 (C0 = 100 mg/L; time=300 min) and by
Mahamuni and Pandit (2005) who reported 17%
degradation (C0=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.
 Wastewater Engineering: Advanced Wastewater Treatment Systems
Chapter 2: Wastewater Treatment by Physical-Chemical Technologies

Table 1: Sonochemical degradation of aromatic compounds

No. Aromatic compounds
1 Chlorobenzene (ClBz)
Sonochemical conditions Results Reference
At concentration above 1000 M, Dewulf et al., 2001
Ulrasonic power: 9.4 W pyrolysis was the dominant mechanisms,
Ultrasonic frequency: 520 kHz at concentration 1-5M, radical
Undatim reactor mechanisms played a crucial role.

Product: Oxalic acid, Peller et al., 2001

Intermediate: 2,4-dichlorophenol,
2,4- hydroquinone, catechol were detected
Ultrasonic power: 50 W
2 dichlorophenoacetic OH radicals were primary reactive
Ultrasonic frequency: 640 kHz
acid species. With argon, 90% degradation
was achieved in less than 100 minutes

Ultrasonic power: 400 W He et al., 2007

The degradation increased with an
3 p-amino phenol (PAP) Ultrasonic frequency: 20 kHz
increased in the ultrasonic density
Ultrasonic probe
Ultrasonic power: 250 W
Song et al., 2009
4 C.I. direct blue 168 88.3% decolorization
Ultrasonic frequency: 40 kHz
Ultrasonic bath

OH is the major process for complete Sponza and
Ultrasonic power: 650 W sonodegradation of less hydrophobic Oztekin, 2010
Polycyclic aromatic
5 Ultrasonic frequency: 35 kHz PAHs while pyrolysis is the major
hydrocarbons (PAH)
Ultrasonic probe process for complete degradation of more
hydrophobic PAHs.

Aromatic intermediates: 2-(4- Inoue et al., 2008

Ultrasonic frequency: 400 kHz
6 Bisphenol A (BPA)
Piezoelectric ceramic transducer
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.

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
52
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.
Ultrasound Irradiation on the Treatment of Aromatic Compounds in Wastewater
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 H2O2)
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
53
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 H2O2.
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 (C6H5) 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
 Wastewater Engineering: Advanced Wastewater Treatment Systems
Chapter 2: Wastewater Treatment by Physical-Chemical Technologies
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 H2O2 (6)
C6H5-OH + OH C6H5(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 CCl4
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 H2O2. 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
54
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 (O3), the
thermal decomposition of ozone in the cavitation
bubbles enhanced OH and H2O2 yields. Xu et al.
(2005) studied on synergetic effect of ozonation with
ultrasonic treatment for p-nitrophenol degradation. In
O3/ultrasonic system produced more OH and H2O2
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/O3
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.
Ultrasound Irradiation on the Treatment of Aromatic Compounds in Wastewater
excess hydroxyl radical generation, and iii)formation
of secondary oxidation species (O2- and O2H). 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 CO32- , SO42-and PO43- (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
55
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 H2O2, 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.
 Wastewater Engineering: Advanced Wastewater Treatment Systems
Chapter 2: Wastewater Treatment by Physical-Chemical Technologies
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.
56
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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60
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Wastewater Engineering: Advanced Wastewater Treatment Systems
Available online at http://www.ijsrpub.com/books
2014 IJSRPUB

Wastewater Engineering: Advanced Wastewater

Treatment Systems

Chapter 3: Wastewater Treatment by Biological

Methods

62
Wastewater Engineering: Advanced Wastewater Treatment Systems
Available online at http://www.ijsrpub.com/books
2014 IJSRPUB

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 into chemical, physical, biological and energetic

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
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:

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 Dadrasnia et al.
Wastewater Treatment by Biological Methods
(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 CO2,
water, and energy for their own reproduction and
growth. The biological method is then followed by
inclusion more sedimentation tanks to adequately
64
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
 Wastewater Engineering: Advanced Wastewater Treatment Systems
Chapter 3: Wastewater Treatment by Biological Methods
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 (BOD5).
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.
65
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.
Wastewater Treatment by Biological Methods
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
66
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).
 Wastewater Engineering: Advanced Wastewater Treatment Systems
Chapter 3: Wastewater Treatment by Biological Methods
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
67
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.
Wastewater Treatment by Biological Methods
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
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
68
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).
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 reintroduced into the aeration tank(s)
before depletion of the dissolved oxygen present. By
so doing, there is replenishment of the biological
 Wastewater Engineering: Advanced Wastewater Treatment Systems
Chapter 3: Wastewater Treatment by Biological Methods
community required to metabolize influent organic or
inorganic matter in the wastewater stream.
-ASP 5
Here, the activated sludge which is characterized of
high microbial load must be removed or discarded
(referred to as waste activated sludge or WAS) from
the treatment process. It is done using pumps and
carried out in parts so as to regulate the food-to-
microorganism ratio (F:M) inside the aeration tank.
5.2. ASP Process Requirements
A standard activated sludge process will require the
following for effective operation;
(a) Formation of flocs as it ensures effective
separation of the microbial biomass.
(b) The mean cell residence time (MCRT) should
be increased alongside adequate aeration in order to
enhance settling ability of the microbial biomass.
(c) Oxygen level needs to be properly regulated.
(d) Microorganisms constitute the biological
component of activated sludge system. The microbes
can contain about 70 90% organic matter. In fact,
the wastewater composition and the specific
characteristics of microbes in the biological
community determine the cell makeup.
(e) Most commonly found organisms within the
biological component of activated sludge are bacteria,
fungi, protozoa and rotifiers. In some cases, nematode
worms which are from metazoan can be present.
However, the growth of higher microbes can be
impaired by the constant agitation in the aeration
tanks in addition to recirculation connected with
sludge.
In 1990s when ASP was developed, it was
characterized of fill and draw reactors (batch process).
The continuous flow reactors were developed in order
to tackle the problem of regulating a number of batch
reactors that always have varied influent flow rate.
Interestingly, over the years, sequential batch reactor
(SBR) has replaced the old system and aeration
process is the significant energy consumption
operation of the system, whereas operations on RAS
and clarifiers are insignificant. Yet, the major
expenses can arise from the sludge processing and
disposal.
6. CONCLUSION
Previously, water was regarded as the most abundant
natural resource based on its global distribution, and
as such less caution was taken to on securing its
natural quality. Unfortunately, it has turned out to be
the scarcest resource now and no thanks to some
socio-economic developments that do not take into
69
account environmental impact assessment. Therefore,
wastewater treatment has been adopted as a mitigation
agent that will prevent aquatic pollution. Hence many
treatment options abound; physical, chemical and
biological. Adoption of biological method ahead of
others is being canvassed for due to its greener nature
and relatively reduced cost. Yet, the time consumed
when using biological methods of wastewater
treatment is a recurring factor that is a drawback, and
the broad spectrum of pathogens in wastewater often
rise concerns on the use of microbes in treatments.
Acknowledgement
We wish to express our deepest gratitude to all the
researchers whose valuable data as reported in their
respective publications and cited in this chapter have
been of considerable significance in adding substance.
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Wastewater Engineering: Advanced Wastewater Treatment Systems
Available online at http://www.ijsrpub.com/books
2014 IJSRPUB

Biological Treatment of Recycled Paper Mill Wastewater Using Modified Anaerobic

Inclining-Baffled Bioreactor (MAIB-R)
Haider M. Zwain1, Irvan Dahlan2*
1
School of Civil Engineering, Universiti Sains Malaysia, Engineering Campus, Seri Ampangan, 14300 Nibong Tebal,
Pulau Pinang, Malaysia.
2
School of Chemical Engineering, Universiti Sains Malaysia, Engineering Campus, Seri Ampangan, 14300 Nibong Tebal,
Pulau Pinang, Malaysia.
*Corresponding Author: chirvan@eng.usm.my

Abstract. Industrial wastewater treatment has gained importance due to the insistence of the environmental groups,
environmental regulation and public awareness. Wastewater from pulp and paper industry is among the most harmful
wastewater that needs to be treated since it contains high organic substances. Although the raw materials of this kind of
industry has been replaced by recycled materials in order to reduce wastes, however effluent from this recycled paper mill is
still highly polluted that need to be treated. In this study, the start-up performance of treating recycled paper mill wastewater
using a modified anaerobic inclining-baffled bioreactor (MAIB-R) has been studied. The MAIB-R was started with a hydraulic
retention time (HRT) of 5 days at 37C. The start-up process took 14 days before it reached steady state on day 15. The MAIB-
R, after successful start-up, can achieve relatively high average COD removal of 92% with pH level of effluent relatively
stable at 6.63. In addition, the biogas production reached 0.77L/d with methane content up to 57% on day 15. The result shows
that during the start-up period, MAIB-R was successfully operated in treating recycled paper mill wastewater.

Keywords: Anaerobic Inclining-Baffled, Biological Treatment, Paper Mill Wastewater

1. INTRODUCTION France. In Malaysia, recycled paper and boards are

1.1. Recycled Paper Mills
Paper and pulp industry together with recycled paper
mill ranked among the largest industries in the world.
There are mills found in more than 100 countries in
every region of the world. The major pulp and paper
producing nations include the United States, China,
Japan, Canada, Germany, Brazil, Sweden, Finland and
important sources for pulp and paper industry. Of 20
paper mills in the country, only Sabah Forest
Industries Sdn. Bhd. is an integrated pulp and paper
mill. All of the 19 others utilize 95% waste papers as
their main raw material except for Kimberly Clark
(M) Sdn. Bhd. which uses 80% imported virgin pulp.
Table 1 shows the existing pulp and paper companies
in Malaysia (Roda and Rathi, 2006).

Table 1: Pulp and Paper Industry in Malaysia.

Company Total Capacity Per Annum (mt)
Cita Peuchoon 30,000
Johmewah 35,000
Genting Sanyen 300,000
Muda Paper (Kajang) 170,000
Muda Paper (S. Prai) 130,000
Malaysia Newsprint 250,000
Nibong Tebal 60,000
Pascorp Paper 140,000
Pembuatan Kertas (Perak) 3,000
Sabah Forest 165,000
See Hua Paper 12,000
Taiping Paper 2,400
Theen Seng Paper 15,000
Trio Paper 30,000
Union Paper 12,400
United Paper Board 80,000
Yeong Chaur S 3,600

1.2. Recycled Paper Mill Wastewater and Its
Environmental Hazards
Recycled paper mills (RPM) are using recovered
paper as their feedstock, unlike paper and pulp mills
which are using wood pulp, mixture of cellulose fibers
and water as the basis of all paper products. The
72
recovered paper is used to produce new paper
products. This is an effort emphasize on the present
green awareness which can help to reduce the cutting
of trees. However, RPM is one of the industries that
have caused concerns about hazardous water
pollutants being continuously discharged into streams
and other water bodies without clean-up treatment.
 Zwain and Dahlan
Biological Treatment of Recycled Paper Mill Wastewater Using Modified Anaerobic Inclining-Baffled (MAIB)
Bioreactor

The RPM wastewater characteristics is shown in wastewater contain heavy metal is given in Table 3
Table 2 (arkovi et al., 2011). Furthermore, the RPM (Hassan et al., 2014).

Table 2: Typical Physico-chemical characterization of RPM wastewater

Parameter (in mg/L, except pH value) Range Mean S.D.
pH 7.0-7.7 7.30.22
Chemical oxygen demand, COD 3770-9330 5539412
Biochemical oxygen demand, BOD 816-2495 1372108
Ammonia, as NH4 1.4-3.8 2.360.8
Total solids, TS 2051-11161 4654276
Total dissolved solids, TDS 200-892 59550
Total suspended solids, TSS 603-8495 3993216
Settleable solids, SS 40-850 48058

Table 3: Heavy metals present in RPM wastewater

Heavy metals Concentration (mg/L) Standard B*(DOE, 2009)
As 1.06 0.1
Be 0.01
Ca 398.78
Cd 0.39 0.02
Co 0.64
Cr 0.51 0.05
Cu 1.10 1.00
Fe 2.39 1.00
Li 0.65
Mg 12.19
Mn 0.85 0.20
Mo 0.92
Ni 0.72 0.20
Pb 1.11 0.50
Sb 1.47
Se 1.63
Ti 0.99
Tl 0.82
V 0.86
Zn 1.39 1.00
*Acceptable conditions for discharge of industrial effluent or mixed effluent of standards B.

Untreated recycled paper mill effluent (RPME) can
cause disastrous environmental consequences,
including the destruction of fisheries and the
contamination of drinking and irrigation water.
Studies have showed that pulp and paper industry is
considered as the third largest polluter in the United
States (Sinclair, 1991). The effluent generated by pulp
and paper industry contains a considerable amount of
pollutants characterized by biochemical oxygen
demand (BOD), chemical oxygen demand (COD),
suspended solids (SS), toxicity, and colour when
untreated or poorly treated effluents are discharged to
receiving waters (Pokhrel and Viraraghavan, 2004).
Black liquor, an aqueous solution of lignin
residues, hemicelluloses and inorganic chemicals used
in the paper manufacturing process is by-product of
many paper pulp mill and recycled paper industries. It
comprises 15% solids by weight of which 10% are
inorganic and 5% are organic. Black liquor released
by paper mills constitutes only 10-15% of total
wastewater, but contributes approximately 95% of the
total pollution load of pulp and paper mill effluents
(Grover et al., 1999). The black liquor has
characteristically contained high biochemical oxygen
73
demand (BOD), chemical oxygen demand (COD), and
total solids (TS) along with slowly degradable lignin
compounds, which make it significantly toxic to the
environment. Thus pulp and paper mill effluent
treatment has to be taken seriously as it can cause
serious environmental pollution and threat to human
health.
1.3. Biological Treatment
Many new wastewater treatment methods are being
developed and designed from recent research findings
to create more efficient and cost effective wastewater
treatment systems. Wastewater is treated by removing
or reducing certain harmful constituents found in
wastewater. These constituents are removed by
physical, chemical and biological methods. Table 4
listed the processes involve for each method (United
Nations, 2003).
Almost all wastewater contains biodegradable
constituents, therefore it can be treated biologically
with proper analysis and understanding of biological
treatment processes. Biological unit operations shown
in Table 1.4 are used to transform (i.e. oxidize)
 Wastewater Engineering: Advanced Wastewater Treatment Systems
Chapter 3: Wastewater Treatment by Biological Methods
dissolved and particulate biodegradable constituents
into desired end products (i.e. biogas and cell tissues).
Besides that, these unit operations are used to remove
or reduce the concentration of organic content which
measured as BOD, TOC or COD and nutrient content
(mainly nitrogen and phosphorus) that are relatively
high and above allowable limit in regulations.
Physical and chemical methods, although quite
effective in reducing the constituents of wastewater
Table 4: Wastewater treatment unit operations and processes
Methods
Physical unit operation
Chemical unit operation
Biological unit operation
1.4. Anaerobic Process
Since the early 1980s, anaerobic process for
wastewater treatment has attracted a lot of attention.
This process has advantages as design simplicity, use
of non-sophisticated equipment, high treatment
efficiency, low excess sludge production and low
operating and capital cost (Saktaywin et al., 2005).
There are three basic steps are involved in the overall
anaerobic oxidation of a waste: (1) hydrolysis, (2)
fermentation (also referred to as acidogenesis) and (3)
methanogenesis. The first step for most fermentation
processes, in which particulate material is converted
to soluble compounds that can then be hydrolyzed
further to simple monomers that are used by bacteria
that perform fermentation, is termed hydrolysis.
The second step is fermentation (also referred to as
acidogenesis). In the fermentation process, amino
acids, sugars, and some fatty acids are degraded
further. Organic substrates serve as both the electron
donors and acceptors. The principal products of
fermentation are acetate, hydrogen, CO2, and
propionate and butyrate. The propionate and butyrate
are fermented further to produce hydrogen, CO2, and
acetate. Thus, the final products of fermentation
(acetate, hydrogen, and CO2) are the precursors of
methane formation (methanogenesis) (Wang, 2012).
which are harmful, are unattractive for industrial
applications because of the high costs involved.
However, biological methods of effluent treatment
have the advantage of being cost-effective and they
can also reduce both the biological oxygen demand
(BOD) and chemical oxygen demand (COD) of the
wastewater. Biological treatment can be divided to
aerobic process, anaerobic process, and anoxic
process.
Unit operations
Screening
Comminution
Flow equalization
Sedimentation
Floatation
Granular-medium filtration
Chemical precipitation
Adsorption
Disinfection
Dechlorination
Other chemical applications
Activated sludge process
Aerated lagoon
Trickling filters
Rotating biological contractors
Pond stabilization
Anaerobic digestion
Biological nutrient removal
The third step, methanogenesis, is carried out by a
group of organisms known collectively as
methanogens. Two groups of methanogenic organisms
are involved in methane production. One group,
termed aceticlastic methanogens, split acetate into
methane and carbon dioxide. The second group,
termed hydrogen-utilizing methanogens, uses
hydrogen as the electron donor and CO2 as the
electron acceptor to produce methane. Bacteria within
anaerobic processes, termed acetogens, are also able
to use CO2 to oxidize hydrogen and form acetic acid.
However, the acetic acid will be converted to
methane, so the impact of this reaction is minor
(Wang, 2012).
1.5. Methane Gas Production
The microorganisms responsible for methane
production, classified as archaea, are strict obligate
anaerobes. Many of the methanogenic organisms
identified in anaerobic digesters are similar to those
found in the stomachs of ruminant animals and in
organic sediment taken from lakes and rivers. In
methanogenesis, methanogens consume the acids
produced by the acidogens, generating biogas
(methane gas) as byproduct. Instead of oxygen
accounting for the change in COD, the COD loss in
74
 Zwain and Dahlan
Biological Treatment of Recycled Paper Mill Wastewater Using Modified Anaerobic Inclining-Baffled (MAIB)
Bioreactor
the anaerobic reactor is accounted for by the methane
production (Ngre and Jonsson, 2010). By
stoichiometry the COD equivalent of methane can be
determined as shown in equation 1.1.
(1.1)
1.6. Anaerobic Baffled Reactor
Nowadays, many researchers have focused on
anaerobic reactors for the treatment of wastewater. As
one of the high-rate anaerobic reactors, ABR was
extensively used in treating wastewater (Liu et al.,
Fig. 1: Schematic diagram of anaerobic baffled reactor.
Each gas chamber was separated permitting the
measurement of gas composition and production from
each compartment. The separation of the gas can also
enhance the reactor stability by shielding syntrophic
bacteria from the elevated levels of hydrogen which
are found in the front compartments of the baffled
reactor (Barber and Stuckey, 1999).
The performance of the ABR in treating a variety
of wastewaters, in particular, low and high strength
wastewater and other refractory wastewaters has been
well reviewed in the literature (Liu et al., 2010).
Table 5 shows low strength wastewater treated by
ABR. Dilute wastewaters inherently provide a low
mass transfer driving force between biomass and
substrate, and subsequently biomass activities will be
greatly reduced according to Monod kinetic. Thus,
ABR is effective in treating low strength wastewater
with no substantial change occurred in the population
of acid producing bacteria down the length of the
reactor. Lower gas production rates can help to
overcome the problem of sludge washout with low
75
2010). The reactor design has been developed since
the early 1980s. ABR comprises a series of vertical
baffles to force the wastewater to flow under and over
them and therefore, the wastewater comes into contact
with a large active biological mass (Grover et al.,
1999). Bacteria within the reactor gently rise and
settle due to flow characteristics and gas production,
but move down the reactor at a slow rate. Figure 1
shows a schematic diagram of anaerobic baffled
reactor (Zwain et al., 2013).
HRTs (6-2 days) in which can increase hydraulic
turbulence, which can lower apparent KS values, thus
enhance treatment efficiency. When treating dilute
wastewater, baffled reactors should be started-up with
higher biomass concentrations in order to obtain a
sufficiently high sludge blanket (and better mixing) in
as short time as possible to counteract the problem of
low sludge blankets caused after long periods of
biomass settling (Kato et al., 1997).
In addition, ABR is also applied for the treatment
of high strength wastewaters. A brief summary of the
literatures on high strength treatment is shown in
Table 6. In high strength wastewater treatment, longer
retention times are necessary due to the high gas
mixing caused by improved mass transfer between the
biomass and substrate. Longer retention time
enhances biomass settling ability. According to
kinetic consideration, high substrate concentrations
will encourage to increase the rate of bacteria growth
and gas production.
 Wastewater Engineering: Advanced Wastewater Treatment Systems
Chapter 3: Wastewater Treatment by Biological Methods

Table 5: Selected low strength performance data (Liu et al., 2010).

Wastewater HRT Influent COD COD Removal OLR Gas Produced Reference
(h) (mg/L) (%) (kg/m3d) (LCH4/g COD d)
Synthetic 10 501 90.7 1.2 0.36 (Gopala Krishna and
wastewater Kumar, 2007)
Domestic 48 305.1836.22 745 - - (Feng et al., 2008)
wastewater1
Municipal 6 350 86 2.62 0.34 (Bodkhe, 2009)
wastewater
Complex 8 500 88 2 0.31 (Gopala Krishna et al.,
wastewater 2008)

Diluted wastewater 10 500 95 0.13 0.3 (Langenhoff and

Stuckey, 2000)

Domestic 22 71654.4 723 - - (Foxon et al., 2004)

wastewater2
Low strength 12 550 89 1.69 - (Shen Y.L., 2004)
wastewater
Low strength 3 850 90 6.9 - (Shen Y.L., 2004)
wastewater
1= at 281C; 2= on pilot scale; others carried out on laboratory scale.

Table 6: Selected high strength performance data (Liu et al., 2010)

Wastewater HRT Influent COD COD Removal OLR Gas Produced (LCH4/g Reference
(h) (mg/L) (%) (kg/m3d) COD d)
Palm oil mill wastewater 72 16000 77.3 5.33 0.33 (Faisal and Unno,
2001)
Whisky distillery 96 9500 96.1 2.38 - (Akunna and Clark,
wastewater 2000)

Brewery wastewater 19.23 10720 93 13.38 - (Baloch et al.,

2007)

Soybean protein processing 39.5 1000 97 6.0 - (Zhu et al., 2008)

wastewater

ABR shows a promise for industrial wastewater
treatment due to its ability to withstand severe
hydraulic and organic shock loads, intermittent
feeding, temperature changes, and tolerant certain
toxic materials. The successful application of
anaerobic technology in the treatment of industrial
wastewater critically dependent on the development
and use of high rate anaerobic bioreactors (Barber and
Stuckey, 1999). Table 7 shows the recommendations
based on literature findings on anaerobic baffled
reactor.
1.7. Advantages of Anaerobic Baffled Bioreactor
The most significant advantage of the ABR is its
ability to separate acidogenesis and methanogenesis
longitudinally down the reactor, allowing the reactor
to behave as a two-phase system without the
associated control problems and high costs (Hassan et
al., 2013). Barber and Stuckey (1999) study showed
that ABR is capable of treating a variety of
wastewaters of varying strength, over a large range of
loading rates, and with high solids concentrations.
Table 8 shows the advantages associated with
anaerobic baffled reactor.
2. CASE STUDY
The development of effective and simple methods for
treatment recycled paper mills (RPM) wastewater is a
challenging task to environmental engineers and
scientists. Therefore, in this study, a novel modified
anaerobic inclining-baffled bioreactor (MAIB-R) was
developed and tested for RPM wastewater treatment.
The aims of this study are to characterize the RPM
wastewater and to perform the start-up of MAIB-R.

76
 Zwain and Dahlan
Biological Treatment of Recycled Paper Mill Wastewater Using Modified Anaerobic Inclining-Baffled (MAIB)
Bioreactor

Table 7: Recommendations based on literature findings (Barber and Stuckey, 1999)

Recommendations
Start-up Low initial loading rates will encourage granule/ floc growth.
Pulses of methane precursors (e.g. acetate) have been successfully used to encourage
methanogenic growth and dampen the effects of increases in loading rate.
Start-up with long retention times reduces solids loss due to low liquid upflow
velocities and promotes higher methanogenic populations in every compartment.

Recycle Recycle is beneficial with respect to diluting toxicants in feed stream, increasing front
pH and reducing production of foam and SMPs.

Low strength wastewater Low retention time enables better mass transport due to improved hydraulic mixing
and reduces biomass starvation in latter Compartments.
methane production will originate from scavenging bacteria (Methanosaeta).

High strength wastewater Long retention times reduce solids washout caused by high gas production, otherwise
the reactor may be modified (by adding packing) to decrease biomass loss.
Methane production will be mainly due to Methanosarcina, and hydrogen scavenging
methanogens.

High solids wastewater A larger front compartment has proved to be effective in treating wastewater with high
solids content.

Temperature Reducing temperature to 25C from 35C has no effect on easily degradable waste,
further decreases in temperature are detrimental on reactor performance, this may be
due to potential toxicity, nutrient bioavailability and slower kinetic rates.
Reactors started-up and kept at lower temperatures perform consistently well

2.1. Reactor Design and Fabrication
MAIB-R used in this study was rectangular, consisted
of five compartments and constructed by using plexi-
glass with a dimension of 80cm long, 15cm wide and
30cm in height, having a total effective volume of 35
L as shown in Figure 2. Each compartment composed
of upflow and downflow sections by using modified
inclining baffles in series in which this bioreactor is
called as modified anaerobic inclining-baffled
bioreactor (MAIB-R). It was a modification from
ABR. Feed tank was equipped with a mixer to mix the
RPM wastewater well before it was pumped into
MAIB-R. Peristaltic pump was used to adjust the flow
rate of incoming RPM wastewater into the MAIB-R.
The biogas generated from each compartment was
collected by using biogas bag. The volume of the
biogas was measured according to the volume of
biogas bag. Each compartment was equipped with
liquid sampling ports for the convenient of grabbing
liquid sample to be analyzed for its characteristic. The
MAIB-R was maintained at 37 C in a water bath. The
treated RPM wastewater was collected in effluent
collection tank to be analyzed for its characteristic.
2.2. Seeding and Acclimatization
Mill Effluent (POME) (Malpom Palm Industries Bhd,
Penang, Malaysia). While the RPM wastewater
samples were taken from Muda Paper Mill Penang,
Malaysia. The sludge and RPM wastewater samples
were kept in refrigerator at 4C before they were used
for seeding process to avoid biological contamination
at different temperature.
Initially, the MAIB-R was inoculated with mixture
of POME sludge (about 10% of total volume of
MAIB-R) and fresh RPM wastewater taken from
Muda Paper Mills Penang (about 10% of total sludge
mixture). Then, the MAIB-R was sealed tightly so that
no air could enter the MAIB-R. Besides that, the
MAIB-R was flushed with nitrogen gas to displace
any air inside the bioreactor and purge out to remove
oxygen content before feeding with RPM wastewater.
Then, the MAIB-R was daily batch-fed with fresh
RPM wastewater which was diluted to 1000 mg
COD/L as much as 10% of total volume of bioreactor
(3.5 liter) every day until the MAIB-R reach its
capacity. Then, continuous phase was started. The
acclimatization of sludge with RPM wastewater
during start-up period was monitored by daily
measurement of physico-chemical parameters (pH,
temperature, COD and biogas production) until steady
state is achieved.

The inoculum for seeding the MAIB-R was

anaerobically digested sludge taken from Palm Oil

77
 Wastewater Engineering: Advanced Wastewater Treatment Systems
Chapter 3: Wastewater Treatment by Biological Methods

Table 8: Advantage associated with the anaerobic baffled reactor (Barber and Stuckey, 1999)
Advantage
Construction 1. Simple design
2. No moving parts
3. No mechanical mixing
4. Inexpensive to construct
5. High void volume
6. Reduced clogging
7. Reduced sludge bed expansion
8. Low capital and operating costs

1. No requirement for biomass with unusual settling properties

Biomass 2. Low sludge generation
3. High solids retention times
4. Retention of biomass without fixed media or a solid-settling chamber
5. No special gas or sludge separation required

1. Low HRT
2. Intermittent operation possible
3. Extremely stable to hydraulic shock loads
Operation 4. Protection from toxic materials in influent
5. Long operation times without sludge wasting
6. High stability to organic shocks

Fig. 2: Schematic diagram of the MAIB bioreactor experimental set-up.

2.3. Experimental Analysis procedure analyzed using specialized equipments, such as

The RPM wastewater collected from Muda Paper Mill
Penang were subjected to the analysis of the following
parameters, i.e. pH, chemical oxygen demand (COD),
biochemical oxygen demand (BOD), total dissolved
solids (TDS), total suspended solids (TSS), total
solids (TS), volatile suspended solids (VSS) and
biogas methane concentration. These parameters
analyses were performed according to American
Public Health Association (APHA, 1995). They were
78
Spectrophotometer DR-2800, Shimadzu Gas
Chromatography-FID (GC) with FID column and
COD reactor digest.
The MAIB-R was operated continuously until
steady-state condition achieved. The MAIB-R
samples were monitored each two days for pH,
temperature, COD and biogas. During the steady state,
the influent, each compartment and effluent samples
were collected. Samples were collected starting from
the last compartment towards the first compartment to
 Zwain and Dahlan
Biological Treatment of Recycled Paper Mill Wastewater Using Modified Anaerobic Inclining-Baffled (MAIB)
Bioreactor

prevent air intrusion and maintain anaerobic 3. RESULTS AND DISCUSSION

condition. All the parameters were determined
according to APHA Standard Method (APHA, 1995)
Biogas generated (methane gas) in each
compartment of MAIB bioreactor was collected from
the upper part of each compartment using biogas bag.
Volume of biogas was measured daily by using biogas
bag with a volume of 1 L per bag and pipette bulb
with 40 ml per pump. Shimadzu Gas
Chromatography-FID (GC) with propack N column
equipped with Flame ionization detector (FID) and
data acquisition system with computer software was
used to determine methane concentration in biogas
collected. Nitrogen gas was used as carrier gas. The
temperature of detector was set to 100C and injector
temperature at 90C. Methane concentration was
analyzed by injecting 1.0 ml of biogas sample in
column of GC using airtight glass syringe. Then, the
methane concentration was taken.
3.1 Characteristic of Recycled Paper Mill
Wastewater
The characteristic of the RPM wastewater generated
depends on the type of processes, process technology
applied, management practices internal recirculation
of the effluent for recovery, and the amount of water
to be used in the particular process (Pokhrel and
Viraraghavan, 2004). Table 9 shows the characteristic
of RPM wastewater generated by Muda Paper Mill
Penang, Malaysia. The RPM wastewater generated
contained a considerable high amount of pollutants
characterized by various physico-chemical
constituents. If the untreated RPM wastewater
discharges into streams and other water bodies, it can
cause disastrous environmental consequences,
including the destruction of fisheries and the
contamination of drinking and irrigation water.

Table 9: Characterization of RPM wastewater

pH - 6.2-7.8
Temperature C 35-45
Biological oxygen demand (BOD) mg/L 1650-2565
Chemical oxygen demand (COD) mg/L 3380-4930
BOD5/ COD - 0.488-0.52
Total Solids (TS) mg/L 3530-6163
Total dissolved solids (TDS) mg/L 1630-3025
Total suspended solids (TSS) mg/L 1900-3138
Total volatile solids (VSS) mg/L 840-2920

These physico-chemical constituents were
relatively high compared to Malaysian Standard of
parameter limits of effluent discharge in Fifth and
Seventh Schedules of Environmental Quality
(Industrial Effluent) Regulations as shown in Table 10
and Table 11, respectively. There are two standards
stipulated in EQA 1974, namely Standard A and
Standard B. Standard A is for effluent discharges
upstream of a raw water intake and is more stringent.
On the other hand, Standard B is for effluent
discharges downstream of raw water intake. These
standards are interpreted as absolute standards, which
sewage and industrial effluent must comply before
being discharged; in this study is RPM wastewater.
This wastewater standard is established for the main
purpose of regulating the disposal pollutants into a
receiving water course to protect aquatic ecosystems,
public health and welfare.

Table 10: Environmental Quality Act 1974 and Regulations. Environmental Quality (Industrial Effluent) Regulations (PU (A)
434), Fifth Schedule
Standard
Parameters Units
A B
Temperature C 40 40
pH value - 6.0-9.0 5.5-9.0
Suspended solids mg/l 50 100

Table 11: Acceptable conditions for discharge of industrial effluent containing chemical oxygen demand (COD) for specific
trade or industry sector
Trade/Industry Unit Standard A Standard B
(a) Pulp and paper industry
(i) pulp mill mg/L 80 350
(ii) paper mill (recycled) mg/L 80 250
(iii) pulp and paper mill mg/L 80 300

79
 Wastewater Engineering: Advanced Wastewater Treatment Systems
Chapter 3: Wastewater Treatment by Biological Methods
By comparing Table 9 with Table 10 and 11, the
characterization of RPM wastewater was far from the
allowable limit set by EQA 1974 for discharge
industrial effluent, therefore a proper and systematic
wastewater treatment is required to treat the RPM
wastewater to make sure the parameters are in
allowable range before it is discharged.
From Table 9, the RPM wastewater generated had
relatively neutral pH with the range of pH 6.2 to 7.8.
Thus, the wastewater does not require alkaline
adjustment because the pH is within the allowable
discharge range by EQA 1974. The BOD5/COD
relationship of 0.5 showed that the wastewater is of
high strength organic type and has a potential to
increase in strength with time, hence its suitable to be
treated anaerobically (Nyanchaga and Elkanzi, 2002).
The BOD5/COD was found comparable to the
average BOD5/COD ratio of 0.59 reported by
Nyanchaga and Elkanzi (2002).
The ratio of BOD5/COD of a wastewater is a good
indication of amount of the total organic load (or
oxygen demand) is available for degradation.
Indirectly, BOD5/COD ratio is a measure of food
value. If the ratio is higher, it has higher food and less
toxicity. However, researchers used to describe
BOD5/COD ratio as biodegradability level of
materials by which organic matter containing
wastewater is readily broken down in the
environment. BOD5/COD ratio can be categorized
into toxic, biodegradable and acceptable or stable
zones (Samudro and Mangkoedihardjo, 2010).
3.2 Start-up at Continuous Feeding
The start-up was the most crucial and important part
of overall MAIB-R processes, it requires a long period
of time to reach steady state due to slow growth rates
of the anaerobic microorganisms inside the MAIB-R,
especially methanogens. The adaptation during this
period is very important for the bacterial population to
develop the microbial culture for treating wastewater
in an anaerobic environment in the MAIB-R.
The anaerobic digestion process was begun in the
absence of oxygen. During this stage, MAIB-R was
under close monitoring to ensure that the anaerobic
active sludge is well grown by monitoring the
temperature of the bioreactor, pH, COD. The
continuous operation of MAIB-R was started at
hydraulic retention time (HRT) of 5 days. To obtain a
good start-up, low initial organic loading rate was
80
being carried out to provide good condition for the
growth of anaerobic active sludge as well as to
prevent slow growing microorganisms from
overloaded in MAIB-R.
Later, COD removal efficiency and the varying of
pH curve of RPM wastewater were closely monitored
and studied to determine the performance efficiency
of MAIB-R during start-up. These parameters were
analyzed using the standard methods by American
Public Health Association (APHA, 1995).
3.2.1. pH Level at Continuous Feeding
The obtained result for pH of MAIB-R in each
compartment during continuous feeding period for 15
days is shown in Figure 3. The pH level of RPM
wastewater in influent was relatively stable at about
7.90. However, in first compartment, the pH level was
decreased drastically with the range from 6.70 to 6.21.
On day 2 to day 6, the pH in compartment 2 to 4 were
increased, but the pH level was decreased in
compartment 5 and slightly increased again to 7.20,
7.10 and 7.03 for the effluent pH on day 2, day 4 and
6, respectively.
The decreasing of the pH in first compartment
(acidification zone) is due to the presence of large
population of acidogenic bacteria. The optimum pH of
acidogenic bacteria was recorded in the range
between 5.8 and 6.2 (Zoetemeyer et al., 1982) which
has shown on day 15 in first compartment. The
substrate level was high thus contributing to the fast
growing bacteria. According to Hu and Li (2008), the
pH level of each compartment increased towards the
end of the reactor from compartment 2 to 5 which has
been proven through this study.
On day 11 to day 15, pH in compartment 2 to 4 is
relatively stable and not much of fluctuation. On day
11, pH of MAIB-R from compartment 1 to 5 showed
a smooth increase which is the same as predicted by
Hu and Li (2008) in their study. If the first
compartment has higher pH compared to other
compartment, it could be due to the substrate level
was insufficient to feed the fast growing bacteria and
some of them starved thus died. This shows that pH
has an important effect on the selection, survival, and
growth of microorganism. On day 15, the pH in every
compartment showed a smooth increase and had
almost negligible fluctuation, hence steady state was
reached.
 Zwain and Dahlan
Biological Treatment of Recycled Paper Mill Wastewater Using Modified Anaerobic Inclining-Baffled (MAIB)
Bioreactor

Fig. 3: pH profiles for each compartment of MAIB bioreactor during continuous feeding period

3.2.2. COD Removal at Continuous Feeding
As shown in Figure 4, the influent COD concentration
was ranging from 717-752mg/L with an average of
737mg/L. It was greatly reduced with the COD
concentration in effluent was varied in the range of
264 to 60 mg/L. On day 2, the COD removal
efficiency was 63% with influent and effluent COD at
720mg/L and 264mg/L, respectively. COD removal
efficiency was slightly increased to 74% on day 4.
Then, the COD removal rate was further increased
steadily with the influent COD relatively constant at
737mg/L. It increased gradually from 63% to 92%
from day 2 to 15. On day 11 to 15, the COD removal
efficiency of MAIB-R showed relatively stable with
the range from 91% to 92%.
On day 15, the influent COD concentration
reduced from 750mg/L to 60mg/L with COD removal
efficiency at 92%. This could be the beginning day of
steady state in MAIB-R. Steady state of COD removal
of more than 80% is considered acceptable for
anaerobic bioreactor start-up and acclimatization
(Buitron G., 2003; Enright A.M., 2005). As for other
type of wastewater, ABR can remove up to 77% of
COD for treatment of textile dye effluent with HRT
of 4 days (Goel, 2010). The average COD removal
efficiency of ABR was constantly maintained at
around 65% and the total COD removal rate of the
system in treating chemical synthesis-based
pharmaceutical wastewater was as high as 95% to
98% (Lili et al., 2009).

Fig. 4: COD concentration and removal efficiencies in the MAIB bioreactor during continuous feeding

81
 Wastewater Engineering: Advanced Wastewater Treatment Systems
Chapter 3: Wastewater Treatment by Biological Methods
3.2.3. Methane Gas Production at Continuous
Feeding
Table 12 shows the result of methane concentration in
biogas analyzed by GC. The methane gas production
rate during continuous feeding and at steady state was
monitored and analyzed from day 2 to 15. Methane
gas was produced along with degradation of organic
matter in MAIB-R. Methane concentration in biogas
was varied in the range of 46 to 70%. The average
methane concentration from day 2 to 15 was 67% to
57%. On day 2 to 6, the methane content was in the
range of 59 to 67% with 0.65L/d, 0.44L/day and
0.57L/day of biogas for day 2, 4 and 6, respectively.
The biogas yield was obtained by measuring the
volume of biogas produced within 24hours. Then, on
day 11 to 15, the methane content in biogas was
slightly higher than previous days in the range of 47 to
57% with varied amount of biogas by 0.67L/day,
0.77L/day and 0.77L/day for day 11, 13 and 15,
respectively.
Table 12: Methanogenesis of RPM wastewater using MAIB bioreactor at different time
Day Methane content (% v/v)
1 2
2 70 65
4 69 64
6 52 60
11 46 50
13 58 53
15 55 57
3.3. Steady State Performance
3.3.1. pH Level
Steady state was achieved on day 15 of continuous
feeding. As shown in Figure 5, on day 15, influent pH
of RPM wastewater was 7.94 while effluent pH of
RPM wastewater dropped to 6.63 after anaerobic
digestion in MAIB-R. The pH level decreased
drastically to 6.21 in first compartment. However, the
pH level from compartment 2 to 5 increased smoothly
towards the end of the MAIB-R with pH of 6.39, 6.47,
6.59 and 6.60, respectively.
In the anaerobic digestion process, there are three
types of bacteria exist in anaerobic digestion process,
namely acid producing fermentation bacteria,
hydrogen-producing acetogenic bacteria and
methanogens. However, the pH demanded by the
three bacterial communities was different. The best
pH for the growth of methanogen ranged from 6.6 to
7.8. If the pH falls below 6, methanogenic bacteria
cannot survive. Hydrogen-producing acetogenic
bacteria and methanogen generate together. The pH
for hydrogen-producing acetogenic bacteria was
82
Organic matter which is broken down by bacteria
without oxygen will produce significant quantities of
methane gas (CH4) with sufficient supply of nutrients
like nitrogen and phosphorus. The lack of nutrients or
substrate will limit biogas production. Having more
organic content in sludge will generate more methane
gas. Biogas mainly composed of methane and carbon
dioxide is a byproduct of anaerobic decomposition of
organic waste. Increase in biogas production and
methane content may be due to greater activity of
methanogenic bacteria in MAIB-R (Goel, 2010).
However, the quality of biogas and methane content
generated by organic waste materials does not remain
constant but varies with the period of digestion in
MAIB-R (Mahdi, 1986).
As for textile dye effluent, ABR generated up to
83% of methane content in biogas (Goel, 2010).
Meanwhile, methane content in biogas generated by
ABR in treating palm oil mill effluent was up to
67.4% (Setiadi et al., 1996).
Biogas yield
3 Average (L/d)
66 67 0.65
62 65 0.44
65 59 0.57
46 47 0.67
59 57 0.77
59 57 0.77
similar to that of methanogen, whose pH ranged from
6.0 to 8.0 (Guochen et al., 2009).
The pH level in the first compartment of MAIB-R
(acidification zone) has lower pH of 6.21. In the
acidogenesis process, acidogenic bacteria converts the
product of hydrolysis (amino acids, fatty acids, simple
sugars and glucose) into simple organic compounds,
mostly short chain acids, volatile acids (Metcalf &
Eddy, 2004). The transition of the high substrate
(carbon and energy source) level from organic
material to organic acids in the acid forming stages
causes the pH of the first compartment to drop
drastically and increase the growth rate of the
bacteria. This is beneficial for the acidogenic and
acetagenic bacteria that prefer a slightly acidic
environment and are less sensitive to changes in the
incoming feed stream.
The growth rate of scavenging bacteria becomes
slower towards the end of the reactor (methanogenic
zone) at higher pH (Hu and Li, 2008). In
methanogenesis, methane-producing bacteria,
methanogens are very sensitive towards changes and
prefer a neutral to slightly alkaline environment (Gas
Technology Inc, 2003). If the pH falls below 6,
 Zwain and Dahlan
Biological Treatment of Recycled Paper Mill Wastewater Using Modified Anaerobic Inclining-Baffled (MAIB)
Bioreactor

methanogenic bacteria cannot survive. Thus, the
change in pH can be both an indicator to determine
the performance efficiency and the cause of process
imbalance in MAIB-R. At steady state, effluent pH of
RPM wastewater produced using MAIB-R was 6.63.
If compared with the regulations in EQA 1974 shown
in Table 10 and it was found to be complying and
within the limit of both Standard A (pH6.0-9.0) and
Standard B (pH5.5-9.0).

Fig. 5: pH profiles for each compartment of the MAIB bioreactor at steady state on day 15

3.3.2. COD Removal in RPM wastewater, and a better adaptation of the

Figure 6 shows the COD concentration in each
compartment at the steady state performance. The
removal efficiency of COD on day 15 was 92% when
the pH was recorded above 6. These results proved
that MAIB-R reactor has showed good bioreactor
performance. The COD concentration was further
decreased towards the end of the MAIB-R from
compartment 1 to 5. In compartment 1 of MAIB
bioreactor, the COD concentration was dropped
drastically to 328mg/L from initial 988mg/L of
influent COD concentration. As for compartment 2,
the COD concentration measured was 322 mg/L while
in compartment 3 was 316 mg/L. The COD
concentration for compartment 4 and 5 of MAIB-R
was 298 mg/L and 294 mg/L, respectively.
From this result clearly indicates that MAIB-R led to
a higher biological degradation of the organic matter
biomass for the degradation of the substrates. Similar
observation was reported by Guochen et al (2009)
using ABR bioreactor, where the COD removal
efficiency up to 89%. Guochen et al. (2009) reported
that during stable stage, average COD removal rate of
ABR treating high-concentration sugar producing
wastewater was 85.5%. COD removal of ABR in
treating wheat flour starch industry wastewater was up
to 67% (Movahedyan et al., 2007).
At steady state, effluent COD concentration of MAIB-
R was 60mg/L. From Table 11, it showed that it
complied to EQA 1974 Standard B with COD limit of
100mg/L. However it failed to comply with Standard
A with COD limit of 50mg/L with a slight difference
by 10mg/L. Further studies need to be done for better
COD removal efficiency so that the effluent (RPM
wastewater) can be reached below 50mg/L.

83
 Wastewater Engineering: Advanced Wastewater Treatment Systems
Chapter 3: Wastewater Treatment by Biological Methods
Fig. 6: COD concentration in the MAIB bioreactor at steady state on day 15
4. CONCLUSIONS AND RECOMMENDATIONS
Recycled paper mill wastewater contained a
considerable high amount of COD with the range of
3380mg/L to 4930mg/L; BOD with the range of
1650mg/L to 2565mg/L. The BOD5/COD relationship
(0.488-0.52) showed that RPM wastewater was of
high strength wastewater. In addition, RPM
wastewater also contained relatively high total solids,
total suspended solids and total dissolved solids. The
start-up process of MAIB-R in this study has been
shortly achieved and the steady state was obtained on
day 15. The MAIB-R after successful start-up can
achieve relatively high average COD removal of 92%.
The pH showed a smooth increased from
compartment 1 towards the end of the MAIB-R,
compartment 5. Influent pH of RPM wastewater was
7.94 and dropped to 6.63 (effluent pH). On the other
hand, the COD concentration in each compartment
was slightly decreased from compartment 1 to
compartment 5. The removal efficiency of COD on
day 15 was 92%. Methane content in biogas generated
by MAIB-R was up to 57% with biogas yield of
0.77L/d on day 15. Although, this MAIB-R start-up
was successfully carried out, however further study is
needed to enhance the performance of the MAIB-R at
wide range of OLR, HRT and temperature. It is also
suggested that effort should be made to investigate the
microbial growth kinetic of the MAIB-R.
ACKNOWLEDGMENT
The authors wish to acknowledge the financial
support from the Universiti Sains Malaysia (RU-I
Grant A/C. 1001/PJKIMIA/814148).
84
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Wastewater Engineering: Advanced Wastewater Treatment Systems
Available online at http://www.ijsrpub.com/books
2014 IJSRPUB

Augmentation of Biological Nitrogen Removal via Optimization of Support Media

Size and Aeration Strategy in Moving Bed Sequencing Batch Reactor
Jun-Wei Lim1, Mohammed J.K. Bashir1,*, Si-Ling Ng2, Sumathi Sethupathi1, Lai-Peng Wong1
1
Department of Environmental Engineering, Faculty of Engineering and Green Technology (FEGT), University Tunku Abdul
Rahman, 31900 Kampar, Perak, Malaysia
2
School of Science, Monash University Sunway Campus, 46150 Petaling Jaya, Selangor, Malaysia
*Corresponding Author: jkbashir@utar.edu.my; Tel: 605-4688888 ext: 4559; Fax: 605-4667449

Abstract. As the discharge of wastewater containing nitrogen is in soaring trend, the objectives of this research aim to
optimize the size of support media and aeration strategy in moving bed sequencing batch reactor (MBSBR) for the biological
nitrogen removal enhancement. In accordance with these objectives, MBSBRs packed with polyurethane (PU) foam cubes of
sizes 8 to 125-mL as the support media and operated with continuous aeration (CA) strategy was initially experimented to
determine the optimum size of support media, reflected by the highest total nitrogen (TN) removal. Subsequently, the
operation of MBSBR packed with optimum size of support media was converted to intermittent aeration (IA) strategy and its
performance in terms of TN removal was investigated again. The results of these two steps experiments vindicated that the
MBSBR packed with 8-mL PU foam cube and operated with IA strategy removed the highest TN removal, signifying the
optimum condition. This optimum condition had eventually resulted the MBSBR procured the highest total weight of attached-
growth biomass that was associated to the maximum amount of internally stored carbon source in which favorable the
simultaneous nitrification and denitrification (SND) process.

Keywords: Nitrogen Removal, Sequencing Batch Reactor, Biological Method

1. INTRODUCTION step mediated by Nitrosomonas sp. and Nitrobacter

The increasingly discharge of nitrogen wastes from
industrial, livestock and agricultural wastewaters
without prior channeling to a proper treatment can
adversely contaminate the quality of receiving waters.
Serious concern related to the adverse impacts of
nitrogen wastes particularly ammonium-nitrogen
(NH4+-N) includes dissolved oxygen (DO) depletion,
toxicity and eutrophication (Gerardi, 2002; Magri et
al., 2013). Therefore, the necessity to remove NH4+-N
in wastewaters before the disposal is utmost crucial to
comply with the stringent discharged limits for
wastewaters containing nitrogen.
Biological nitrogen removal has been widely
recognized to offer a more economical and
environmentally friendly approach in removing NH4+-
N via nitrification and denitrification processes
(Gerardi, 2002; Jokela et al., 2002; Leta, 2004;
Dempsey et al., 2005; Aslan et al., 2009; Yao et al.,
2013). Over the decades, various operational
parameters had been studied with intention to
optimize the biological nitrogen removal (Deguchi
and Kawashiwaya, 1994; Pochana and Keller, 1999;
Katsogiannis et al., 2003; Daniel et al., 2009; Chu and
Wang, 2011).
1.1. Nitrification Process
The nitrification process is a two steps aerobic
process. The first step involves the oxidation of NH4+-
N to nitrite-nitrogen (NO2--N) which is subsequently
oxidized to nitrate-nitrogen (NO3--N) in the second
sp., respectively (Kotlar et al., 1996; Qiao et al.,
2008). The oxidation of NH4+-N to NO2--N is
conventionally known as nitritation process, whereas
the oxidation of NO2--N to NO3--N is typically
identified as nitratation process (Zeng et al., 2009;
Fukumoto et al., 2011).
Nitritation process performed by Nitrosomonas sp.:
NH4+ + 1.5O2 NO2- + 2H+ + H2O (1)
Nitratation process performed by Nitrobacter sp.:
NO2- + 0.5O2 NO3- (2)
Overall nitrification process:
NH4+ + 2O2 NO3- + H2O + 2H+ (3)
The nitrifying bacteria of Nitrosomonas spp. and
Nitrobacter spp. are categorized as
chemolithoautotrophs, indicating that the nitrifying
bacteria obtain carbon from the inorganic carbon, i.e.,
carbon dioxide, and energy from the chemical
reactions (Eqs. 1 and 2, respectively) for growth and
multiplication. Carbon dioxide is accessible to
nitrifying bacteria in the form of bicarbonate in the
wastewaters (Gerardi, 2002; Liao et al., 2008). As
more energy can be reaped from the oxidation of
NH4+-N to NO2--N than NO2--N to NO3--N, the
population size of Nitrosomonas spp. is always greater
than Nitrobacter spp. Besides, Nitrosomonas spp. also
has a shorter generation time which enables its
numbers to faster than Nitrobacter spp. (Gerardi,
2002). Therefore, in the activated sludge system, the

87
 Lim et al.
Augmentation of Biological Nitrogen Removal via Optimization of Support Media Size and Aeration Strategy in
Moving Bed Sequencing Batch Reactor
ability of being oxidized for NH4+-N is always higher
than for NO2--N, causing a transient accumulation of
NO2--N which is removed when NH4+-N is completely
oxidized. However, during unfavourable operational
conditions such as low DO concentration, excessive
sludge washout, extreme change in temperature, etc.,
significant accumulation of NO2--N concentration can
be detected in the mixed liquor of the bioreactors
(Ruiz et al., 2006; Jubany et al., 2009; Lim et al.,
2010; Gu et al., 2012).
Although the activated sludge system is commonly
used to treat wastewaters containing NH4+-N in many
treatment plants, it is actually not an ideal system for
the nitrification process. As demonstrated by Gerardi
(2002), the typical population size of nitrifying
bacteria in the activated sludge system is merely in the
range of 3% to 10% with the remaining consisting of
organotrophs. This is due to the nitrifying bacteria has
a very low reproductive rate as large amounts of
NH4+-N and NO2--N are required during the
assimilation process.
1.2. Denitrification Process
The sole nitrification process is only partially
fulfilling the objective of biological nitrogen removal
as the NH4+-N is merely bio-transformed to the
oxidized nitrogen, viz., NO3--N and NO2--N, by the
nitrifying bacteria. These oxidized nitrogen species
must be later reduced to nitrogen gas (N2) and
released to the atmosphere in order to remove nitrogen
from wastewaters. The reduction process is known as
denitrification process which reduces the oxidized
nitrogen to N2 with the sequence shown hereafter
(Gerardi, 2002):
Nitrate ion (NO3-) Nitrite ion (NO2-) Nitric
oxide (NO) Nitrous oxide (N2O) Ntrogen gas
(N2)
The process of denitrification can be achieved by a
broad range of facultative anaerobes which make up
an approximately 80% of the bacteria in the activated
sludge system. The largest numbers of facultative
anaerobes that can perform the denitrification process
are from genera of Alcaligenes, Bacillus and
Pseudomonas (Gerardi, 2002). More so, the
facultative anaerobes that denitrify are also termed by
several names including denitrifying bacteria,
organotrophs, denitrifiers and heterotrophs.
In assuring the feasibility of denitrification
process, the carbon source must be made available to
the denitrifying bacteria under an anoxic environment
with DO concentrations of lower than 1.0 mg/L or 2%
saturation in the mixed liquor of the bioreactors (Goh,
2007; Lim et al., 2012). As the denitrifying bacteria
can reap more energy through the aerobic respiration,
88
the denitrification process has to be strictly
commenced in the anoxic environment to enable the
added carbon source is primarily utilized to reduce the
oxidized nitrogen instead of being aerobically
degraded (Gerardi, 2002). According to Gerardi
(2002), the reduction of NO3- ion in the presence of
carbon source under the anoxic environment can be
expressed in two simplified biochemical reactions
shown hereafter:
NO3- + Carbon Source NO2- + CO2 + H2O (4)
NO2- + Carbon Source N2 + CO2 + OH- (5)
1.3. Moving Bed Sequencing Batch Reactor -
Support Media Size and Aeration Strategy
Sequencing Batch Reactor (SBR) system has been
extensively manipulated for the treatment of domestic,
municipal and industrial wastewaters and also offers
an attractive option in the biological wastewater
treatment systems with the advantages as below
(Irvine and Ketchum, 1989; Wobus et al., 1995;
Louzeiro et al., 2002; Goh, 2007):
(a) Resistant to influent loading fluctuation;
(b) Simplicity and cost effective;
(c) Flexibility in terms of sequence and cycle time;
(d) Ideal quiescent settling condition;
(e) Ability of combining aerobic and anoxic phases in
a single reactor.
Incorporated with an activated sludge system, SBR
is primarily running on the fill and draw principle.
The operation of the SBR is usually achieved by five
sequential periods, namely FILL, REACT, SETTLE,
DRAW and IDLE in a single tank instead of
simultaneously in the separate tanks as typically
observed in the conventional activated sludge system
(Arora et al., 1985). Thus, permits the construction of
smaller treatment plant which is suitable in the area
with limited land availability. Nevertheless, a
conventional SBR system is generally incapable of
executing an effective biological nitrogen removal
(Goh, 2007; Li et al., 2011). As a result, an
improvement of SBR system is deemed essential
when the bio-treatment of wastewater containing
nitrogen is to be addressed.
For years, numerous attempts have been
committed to modify the SBR system in order to
enhance the performance. Among others, the moving
bed sequencing batch reactor (MBSBR) which is
developed by retrofitting support media into the SBR
has attracted much interest among the researchers in
the field of biological wastewater treatment (Garzon-
Zuniga and Gonzalez-Martinez, 1996;
Sirianuntapiboon and Yommee, 2006; Goh et al.,
2009; Hosseini Koupaie et al., 2012). In general, three
 Wastewater Engineering: Advanced Wastewater Treatment Systems
Chapter 3: Wastewater Treatment by Biological Methods
categories of support media, namely Kaldnes
(polyethylene media), Liapor (ceramic media) and
Linpor (plastic media with high porosity) are used to
pack the MBSBR (Valdivia et al., 2007). The mobility
of the support media in MBSBR is usually conserved
by the aeration or mechanical mixing systems
(Odegaard et al., 1994). Once the attached-growth
biomass (biofilm) has grown on the surfaces of
support media, the MBSBR which contains both
suspended-growth and attached-growth biomasses are
anticipated to outperform the SBR which consists of
only suspended-growth biomass.
Among of these three types of support media used,
Valdivia et al. (2007) reported that the MBSBR
packed with Linpor performed better than either
Kaldnes or Liapor in removing chemical oxygen
demand (COD) and NH4+-N at the organic loading
rate higher than 3.0 g COD/m3 day. The polyurethane
(PU) foam which belongs to the Linpor type of
support media has a high porosity and is an ideal
medium for biomass immobilization through
attachment. In addition, PU foam also has a good
mechanical strength and is relatively low cost (Golla
et al., 1994; Chu and Wang, 2011).
Nitrogen removal via simultaneous nitrification
and denitrification (SND) process had been
investigated in previous studies (Kotlar et al., 1996;
Daniel et al., 2009; Chu and Wang, 2011). The SND
process is potentially reducing the operational period
which ultimately results in the reduction of operation
cost. The oxygen concentration and the availability of
the carbon source for denitrification were found to be
the important parameters for the commencement of
SND process (Pochana and Keller, 1999). By using
the PU foam cubes as a support media for biofilm
formation, studies had demonstrated the occurrence of
decreasing dissolved oxygen (DO) gradient within the
inner layer of biofilm and also deep inside the PU
foam which leads to the creation of an anoxic zone
(Morper, 1994; Guo et al., 2010). Furthermore, as the
carbon source is also an important constituent to
ensure the viability of the denitrification process, the
SND process is frequently inhibited in treating
wastewaters containing low COD/N ratio.
Nevertheless, in the study of Guo et al. (2010), the
SND process was still detected in the anoxic zone of
the PU foam. The occurrence of the SND process
without the addition of the external carbon source in
their study could be explained by the possibility of
carbon storage in the deeper biofilm layers which was
also reported by several researchers (Morgenroth and
Wilderer, 1999; Pastorelli et al., 1999; Gieseke et al.,
2002). The presence of carbon storage together with
anoxic zone within the biofilm and deep inside the PU
foam could be used to kindle the denitrification
process which eventually stimulated the SND process.
89
Based on the results of previous studies, PU foam
was found to be a good support media in the MBSBR
system. Its porous structure will allow the formation
of attached-growth biomass, the establishment of
anoxic zone and the storage of carbon which enhance
the nitrogen removal via SND process. However, to
date, relatively little is documented on the effect of
different sizes of the PU foam cubes on the nitrogen
removal in the MBSBR system. In addition, the
biomass growth onto the surfaces and into the interior
porous structure of the various sizes of PU foam cubes
along with the role of these various sizes of PU foam
cubes in the SND process in treating low COD/N ratio
wastewaters have not been thoroughly investigated.
The main advantage of intermittent aeration (IA)
strategy application in treating wastewater containing
nitrogen includes the reduction of the operational cost
due to a decrease of continuous aeration (CA) supply
and the amount of external carbon source required for
the subsequent denitrification phase (Li et al., 2008).
In the IA system, the high DO concentration during
the aeration period enables the aerobic nitrifiers to
oxidize NH4+-N to NO2--N and then to NO3--N.
During the subsequent non-aeration period, the DO
concentration will decrease to such a low level that
the NO2--N and NO3--N species are reduced to N2
mediated by the denitrifiers (Li et al., 2008).
Nonetheless, the feasibility of IA strategy
application in removing nitrogen from low COD/N
ratio wastewaters is still questionable due to
inadequate supply of carbon source which results in
an incompetency of denitrification process. In view of
the carbon storage in the deeper layers of biofilm
within the support media which can serve as the
carbon source, the integration of IA strategy in
MBSBR (IA-MBSBR) packed with PU foam cubes is
not expected to face the aforesaid problem. The
carbon storage is not only found in the biofilm on the
external surfaces which is typically exhibited by most
of the support media but is also located within the
interior porous structure of the PU foam cubes which
is being occupied by the attached-growth biomass.
However, to date, the available information to sustain
the viability of IA-MBSBR in the enhancement of
nitrogen removal is still lacking. The availability of
the carbon storage located onto and into the
acclimated PU foam cubes with attached-growth
biomass also needed to be further substantiated.
In light of relatively little information on the
potential of MBSBR in the removal of nitrogen, the
objectives of this study are to optimize the size of
support media, i.e., PU foam cubes, and aeration
strategy in MBSBR system for biological nitrogen
removal via SND process.
 Lim et al.
Augmentation of Biological Nitrogen Removal via Optimization of Support Media Size and Aeration Strategy in
Moving Bed Sequencing Batch Reactor

2. METHODOLOGY to reduce the oxidized nitrogen to N2. At the end of

To achieve the aforementioned objectives, two major
experiments were carried out with the first experiment
aimed to determine the optimum size of support media
used to pack the MBSBR and the subsequent
experiment targeted to investigate the optimum
aeration strategy; both emphasized on the
enhancement of biological nitrogen removal via SND
process.
2.1. Determination of Optimum Support Media
Size Packed in MBSBR
Five plexiglass reactors were inoculated with the
activated sludge collected from municipal sewage
treatment plant and fed with synthetic wastewater
simulating the municipal wastewater composition
with NH4+-N and COD concentrations of
approximately 48 and 200 mg/L, respectively. The
reactors were operated with a cycle time of 24 h in the
following sequencing periods: instantaneous FILL, 0
h; aerobic REACT, 10 h; anoxic REACT, 2 h;
SETTLE, 1.5 h; DRAW, 1 h and IDLE, 9.5 h.
Adequate amount of ethanol solution was
instantaneously added into the reactor as a carbon
source at the beginning of the anoxic REACT period
the REACT period, mixed liquor was wasted to
maintain the sludge age of suspended-growth biomass
at 40 days. During the DRAW period, the supernatant
or treated effluent was drawn out with an exchange
volume of the reactor being retained at 70.3%. The
residual settled solids in the reactor were left to rest
throughout the IDLE period in preparation for the next
cycle.
After achieving the quasi-steady state, four rectors
were transformed to the MBSBR by introducing PU
foam cubes into its mixed liquor for the development
of attached-growth biomass. The packing volume of
the PU foam cubes in each MBSBR was fixed at 8%
(v/v) of the working volume. The performance of
MBSBRs were investigated using four different sizes
of PU foam cubes, namely 8-, 27-, 64- and 125-mL
cubes which were labeled as R2 - R5, respectively.
One of the reactors was continuously operated without
the addition of support media to serve as the SBR
system (R1) for comparison. The schematic diagram
of the MBSBR is shown in Figure 1. The
performances of all reactors were monitored in terms
of nitrogen removal consisting of NH4+-N, NO2--N
and NO3--N species.

Fig. 1: Schematic diagram of the MBSBR: (a) plexiglass reactor; (b) aquarium air pumps; (c) addition of feed solution by the
peristaltic pump; (d) addition of ethanol solution by the peristaltic pump; (e) draw out tubing to remove treated effluent
containing unsettled suspended solids by the peristaltic pump; (f) support media of PU foam cubes; (g) ejector; (h) air
diffusers; (i) aeration tubing; (j) working volume of 12.8 L; (k) residual volume of 3.8 L.

90
 Wastewater Engineering: Advanced Wastewater Treatment Systems
Chapter 3: Wastewater Treatment by Biological Methods
2.2. Determination of Optimum Aeration Strategy
in MBSBR
The selected MBSBR with optimum size of PU foam
cubes from the experiment as outlined in Section 2.1
was then converted to IA-MBSBR in which the
REACT period was converted to begin with 1 h of
aeration period followed by 1 h of non-aeration period
and the pattern was repeated throughout the 12 h
REACT period. The instantaneous addition of
adequate amount of ethanol solution to serve as a
carbon source was only implemented at the beginning
of the last non-aeration period in every cycle to reduce
the oxidized nitrogen to N2. The performance of IA-
MBSBR in terms of nitrogen removal was compared
with its former stage of aeration strategy, i.e., CA
strategy.
Figure 2: SEM image of PU foam cube with 40X magnification and captured at WD of 7 mm using EHT and
signal of 5.00 kV and SE2, respectively.
3.1. Optimization of Support Media Size Packed in
MBSBR
The concentration profiles of nitrogen species during
the REACT period for SBR and MBSBRs are shown
in Fig. 3. For SBR, a small NO2--N concentration peak
was observed during the initial stage of the aerobic
REACT period and a constant NO3--N concentration
was attained when the nitrification process was
completed. In contrast, for MBSBRs, the formation of
NO2--N was barely observed in the aerobic REACT
period. Figure 3 shows that the NO3--N concentrations
in R2 to R5 decreased gradually after the completion
of nitrification, with the most obvious reduction seen
in R2. The percentages of total nitrogen (TN) removal
during the aerobic REACT period for R1 to R5 were
15%, 37%, 31%, 24% and 19%, respectively. If only
nitrification process was involved, the TN should
remain constant during the aerobic REACT period.
91
3. RESULTS AND DISCUSSIONS
The comparative study of MBSBRs packed with
various sizes of PU foam cubes each and with SBR
was initially discussed in this section. Optimum size
of PU foam cubes used to pack the MBSBR was
culled based on the highest nitrogen removal
efficiency via SND process. Subsequently, the
MBSBR packed with optimum size of PU foam cubes
was operated with IA strategy during the REACT
period and the results obtained were compared with its
former stage, i.e., CA strategy, to determine the
optimum aeration strategy for the enhancement of
biological nitrogen removal.
The image of Scanning Electron Microscope of
support media, i.e., PU foam cube, added into the
MBSBR is presented in Figure 2. There are many
pores on and into the surfaces of PU foam cubes; thus,
permitting the growth and attachment of biomass.
Instead, an increasing percentage of TN removal was
observed in the order of R1 < R5 < R4 < R3 < R2.
The removal of nitrogen can be plausibly
explained by the assimilation and SND processes
(Valdivia et al., 2007). Several studies have reported
the aeration condition and carbon source as the
parameters affecting the yield of the SND process
(Pochana and Keller, 1999; Third et al., 2003; Walters
et al., 2009; Khor et al., 2011). The percentage of TN
removal was found to be the lowest in R1. The
occurrence of SND process was not favored in R1 due
to the high DO and low COD concentrations in the
mixed liquor (Pochana and Keller, 1999; Chu and
Wang, 2011; Seifi and Fazaelipoor, 2012). Therefore,
the TN removal in R1 was deemed to be caused by
only assimilation process in which the lost TN was
used to build cell mass. In MBSBRs, aerobic
condition was kept on the surface of the acclimated
PU foam cubes whereas, distinctive DO gradient
 Lim et al.
Augmentation of Biological Nitrogen Removal via Optimization of Support Media Size and Aeration Strategy in
Moving Bed Sequencing Batch Reactor

occurred along the acclimated PU foam cubes inward
depth (Uemura et al., 2002; Guo et al., 2010).
Moreover, the carbon source required for
denitrification process could be obtained from the
storage inside the deep layer of acclimated PU foam
cubes (Pastorelli et al., 1999; Gieseke et al., 2002).
According to Gray (2004), the denitrification process
is dependent on the size of microorganism population.
The total weight of attached-growth biomass of all
MBSBRs were measured and found to be 49, 35, 33
and 30 g for R2 to R5, respectively, which was in
accordance with the decreasing trend of TN removal
from R2 to R5 as abovementioned. The lower weight
of attached growth biomass measured in larger PU
foam cubes was due to the failure of biomass to
diffuse into the internal surface of cubes to form
attachment viz--viz the smaller cubes as shown by
the SEM images in Figure 4. Hence, among the
MBSBRs, R2 packed with 8-mL acclimated PU foam
cubes was the most optimum reactor due to the
highest achievable of TN removal.

Fig. 3: Profiles of nitrogen species concentrations during the REACT period for (a) R1, (b) R2, (c) R3, (d) R4 and (e) R5.

(a) (b) (c) (d)

Fig. 4: SEM images of (a) internal surface of acclimated 8-mL PU foam cube, (b) internal surface of acclimated 27-mL PU
foam cube, (c) internal surface of acclimated 64-mL PU foam cube and (d) internal surface of acclimated 125-mL PU foam
cube all with 40X magnification and captured at WD of 7 mm using EHT and signal of 5.00 kV and SE2, respectively. The
internal surface of each size of the PU foam cube is referring to the surface of the cube cross sectional area.

3.2. Optimization of Aeration Strategy in MBSBR
The study in Section 3.1 had underscored the
advantages of using 8-mL PU foam cubes as the
support media in MBSBR for the removal of nitrogen
from low COD/N ratio wastewater as opposed to
92
larger PU foam cubes. The highest growth of
attached-growth biomass was achieved in the MBSBR
packed with this size of PU foam cubes which led to
the highest TN removal mainly via SND process.
However, the application of continuous aeration (CA)
strategy in MBSBR (CA-MBSBR) during the 10 h of
 Wastewater Engineering: Advanced Wastewater Treatment Systems
Chapter 3: Wastewater Treatment by Biological Methods
aerobic REACT period increases the operation cost
especially when the nitrification process has
completed. Besides, the CA strategy would also
deplete the carbon storage in the acclimated PU foam
cubes which plausibly led to the slowing down of
SND process. Thus, the potential of integrating IA
strategy in MBSBR (IA-MBSBR) packed with 8-mL
PU foam cubes as the support media for nitrogen
removal enhancement was investigated.
Figure 5 shows that the NH4+-N was completely
removed only at the third aeration period. During the
first and second non-aeration periods, the oxidation of
NH4+-N was impeded due to the exhausted supply of
DO in the mixed liquor, resulting in a relatively flat
region of the NH4+-N concentration profile. The NO3--
N concentration, however, decreased gradually during
the non-aeration period due to the denitrification
process. Figure 5 also shows that the NH4+-N was
swiftly oxidized to NO3--N during the nitrification
process with negligible accumulation of NO2--N.
Based on Figure 5, the calculated percentage of TN
removal in IA-MBSBR during the REACT period
prior to the addition of ethanol solution was 57%. The
TN removal could be explained by the occurrence of
the SND process within the anoxic zone in the
acclimated PU foam cubes. The percentage of TN
removal in the IA-MBSBR was also found to be
higher than the CA-MBSRB of R2, which was
Fig. 5: Profiles of nitrogen species concentrations during the REACT period for IA-MBSBR.
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Wastewater Engineering: Advanced Wastewater Treatment Systems
Available online at http://www.ijsrpub.com/books
2014 IJSRPUB

Wastewater Engineering: Advanced Wastewater

Treatment Systems

Chapter 4: Electrochemical Methods

96
Wastewater Engineering: Advanced Wastewater Treatment Systems
Available online at http://www.ijsrpub.com/books
2014 IJSRPUB

Electrochemical Oxidation Process Contribution in Remediating Complicated

Wastewaters
Mohammed J. K. Bashir1,*, Jun-Wei Lim1, Shuokr Qarani Aziz2, Salem S. Abu Amr3
1,*
Department of Environmental Engineering, Faculty of Engineering and Green Technology, Universiti Tunku Abdul Rahman,
31900 Kampar, Perak, Malaysia
3
Department of Civil Engineering, College of Engineering, University of SalahaddinErbil, Iraq
2
School of Civil Engineering, Engineering Campus, Universiti Sains Malaysia,14300 Nibong Tebal, Penang, Malaysia
*Corresponding Author: jkbashir@utar.edu.my; Tel: 605-4688888 ext: 4559; Fax: 605-4667449

Abstract. In recent years, electrochemical oxidation process has gained increasing interest due to its exceptional technical
features to eliminate a wide range of pollutants exist in various types of wastewaters, e.g., refractory organic matter, nitrogen
species, microorganisms, etc. Serve as a clean, adaptable and powerful tool in removing pollutants, this review paper focuses
on the fundamental mechanisms of electrochemical oxidation process and provides discussions on the possible applications in
wastewater treatment. To top it off, special attention on the most recent developments and challenges are as well highlighted in
this review.

Keywords: Electrochemical, Wastewater, Oxidation Process

1. INTRODUCTION pollutants in wastewater. Furthermore,

Basically, wastewater treatment aims to improve the
quality of wastewater before discharging to the
receiving water bodies by using reliable technology.
The conventional sequence of wastewater treatment
starts with draining the wastewater in a central,
separated location and subjecting the wastewater to
several treatment processes. Wastewater treatment can
be generally categorized by the character of the
treatment process operation being used such as
biological, chemical or physical methods. Wastewater
treatment via biological technology is the most
economical means of treatment and normally utilizes
for the removal of biodegradable organic pollutants
presented in the wastewater. Nevertheless, the
presence of toxic and refractory substrates in the
wastewater would virtually foil the biological
treatment process as these substrates are potentially
inhibiting the bioactivity of microorganism (Grimm et
al., 1998). Among the various techniques, the use of
electro-chemical oxidation process in the wastewater
treatment has engrossed many researchers attention,
particularly in remediating industrial wastewater. To
date, electrochemical oxidation processes have been
shown to be a valuable option for the elimination of
refractory organic compounds from various types of
wastewaters (Bashir et al., 2013). Electrochemical
oxidation is highly capable and efficient in reducing
the organic compounds from various types of
wastewater as compared with other types of physio-
chemical technologies which only bring about phase
transfer of the contaminants in question with no
chemical destruction is taking place.
Similarly, Kapalka et al. (2009) stated that the
electrochemical oxidation process is a clean, versatile
and powerful tool for the destruction of organic
97
electrochemical method presents many significant
gains since it does not require any ancillary chemical,
appropriate for large range of pollutants removal and
does not require high pressures and temperatures for
the reaction to commence. However, the efficiency of
the electro-oxidation techniques depends strongly on
the operation conditions and on the nature of the
electrode materials (Wang et al., 2008). Recently, the
strict wastewater discharge limits with health quality
standards obligation set by legislation may be met by
applying electrochemical oxidation. Wastewaters
generated from municipal landfill and a wide diversity
of industries including the food, textile, and tannery
productions have been successfully treated by this
process. Thus, due to its high competence together
with its disinfection capabilities, electro-oxidation is a
suitable technique for water reuse programs. On the
other hand, treatment costs have to be cut down prior
to full-scale application of this technology.
Accordingly, the employment of electrochemical
oxidation together with other technologies and the use
of renewable energy sources to operate this process
are two significant steps required to reduce the overall
operational cost (Anglada et al., 2009).
2. ELECTROCHEMICAL OXIDATION
PROCESS
Electrochemical oxidation process has been
recognized as one of the most effective techniques in
degrading pollutants present in textile wastewater,
landfill leachate, simulated wastewater, olive mill
wastewater, paper mill effluents, and industrial paint
wastewater (Krbahti and Tanyola 2003; Un et al.,
2008; Bashir et al., 2009 ). The electrochemical
reactor in the laboratory experiments is shown in
 Bashir et al.
Electrochemical Oxidation Process Contribution in Remediating Complicated Wastewaters

Figure 1. Figure 2 shows the conceptual diagram of provides the ion transport mechanism between the
electrochemical reactor for wastewater treatment, anode and the cathode necessary to maintain the
which includes a direct current (DC) power supply, a electrochemical process).
cathode, an anode, and the electrolyte (a medium that

Fig. 1: The electrochemical reactor in the laboratory experiments. (1) DC power supply, (2) magnetic stirrer, (3) cover, (4)
electrodes, (5) magnetic bar-stirrer, (6) wastewater and (7) electric wire (Source: Bouhezila et al., 2011).

Fig. 2: Conceptual diagram of an electrochemical reactor (Source: Anglada et al., 2009)

Electrochemical oxidation of impurities in It should be clear that during electro-oxidation of

wastewater is accomplished through two different
mechanisms as demonstrated in Figure 3: (1) direct
anodic oxidation, where the pollutants are destroyed at
the anode surface and (2) indirect oxidation where
mediators (NaCL, HClO, H2S2O8, etc) are
electrochemically produced to achieve the oxidation.
aqueous effluents, both oxidation mechanisms may
coexist (Chiang et al., 1995). Generally, the
mechanism of electrochemical degradation of
wastewater is a complex phenomenon involving
coupling of electron transfer reaction with a dissociate
chemisorptions step.

98
 Wastewater Engineering: Advanced Wastewater Treatment Systems
Chapter 4: Electrochemical Methods
Fig. 3: Schemes for direct and indirect electrolytic treatment of pollutants (Chiang et al., 1995).
2.1. Direct oxidation
Direct oxidation of pollutants takes place in two steps:
(i) diffusion of pollutants from the bulk solution to the
anode surface and (ii) oxidation of pollutants at the
anode surface. As a result, the effectiveness of the
electrochemical oxidation will depend on the
correlation between mass transfer of the substrate and
electron transfer at the electrode surface. The rate of
electron transfer is determined by the electrode
activity and current density. In general, there are two
different pathways of anodic oxidation of organic
substances as shown henceforth (Drogui et al., 2007):
Electrochemical conversion. Organic
substances (R) are partially oxidized as presented in
Eq. 1. Thus, a following treatment is needed to
completely destroy the oxidized substrates.
R RO + e (1)
Electrochemical incineration (combustion).
Organic substances are transformed into water, carbon
dioxide and other inorganic constituents as presented
in Eq. 2.
R CO2 + H2O + Salts + e (2)
2.1. Indirect oxidation
During indirect electrochemical oxidation, a strong
oxidizing agent is electro-generated at the anode
surface and subsequently destroys the organic
compounds in the bulk solution. The most widespread
electrochemical oxidant is chlorine which is produced
via the oxidation of chloride at the anode. Throughout
indirect oxidation, the agents produced on the anode
that are responsible for oxidation of inorganic and
organic matters could be chlorine and hypochlorite,
99
hydrogen peroxide, peroxodisulfuric acid, and ozone
(Li et al., 2010; Scialdone et al., 2009). Accordingly,
throughout the electrochemical oxidation of
wastewater, the impurities removal principally
occurred due to indirect oxidation, utilizing
chlorine/hypochlorite produced by anodic oxidation of
chlorine that existing or being added in the aqueous. A
chain of reactions that involve chlorine/hypochlorite
indirect oxidation are presented in Eqs. 3-9.
Anodic reactions:
2Cl Cl2 + 2e (3)
6HOCl + 3H2O 2ClO3 + 4Cl + 12H+ + 1.5O2 +
6e (4)
2H2O O2 + 4H+ + 4e (5)
Bulk reactions:
Cl2 +H2O HOCl + H+ + Cl (6)
HOCl H+ + OCl (7)
Cathodic reactions:
2H2O + 2e- 2OH + H (8)
OCl + H2O + 2e Cl + 2OH (9)
The hypochlorite (OCl) generated in bulk solution
(Eqs. 6 and 7) is a strong oxidizing agent that can
oxidize aqueous organic substances (Scialdone et al.,
2009). In addition to the common oxidants that can be
electrochemically produced, metal catalytic mediators
(Ag+2, Co+3, Fe+3, etc.) are also employed for the
generation of hydroxyl radicals, as seen in the electro-
Fenton system. Nevertheless, the use of metal ions
may result in the treated effluent to be more toxic than
that its initial state. Therefore, the system of this kind
needs a separation step to recover the metallic species
 Bashir et al.
Electrochemical Oxidation Process Contribution in Remediating Complicated Wastewaters
(Anglada et al., 2009), leading to the unfavorable
intricate treatment process.
2.3. Process Design Issues
Electrode materials, cell design (configuration),
working conditions and energy consumption have to
be taken into the consideration when it comes to the
building up of the electrochemical oxidation system.
2.3.1. Electrode material
The choice of electrode materials is very important
since it affects the selectivity and the efficiency of the
process. The complexity of electrode performances
and lack of adequate information insights make it
unfeasible to choose the optimum electrode for a
given process on a theoretical basis. The preliminary
selection is depending on process experience and this
is then tested and refined during an extensive
development program. In fact, it is complicated to
expect the achievement of an electrode material or to
characterize its lifetime without extended studies
under realistic operation conditions (Klamklang et al.,
2012).
Essentially, the electrode materials must have the
following properties (Anglada et al., 2009; Klamklang
et al., 2012):
(a) High physical stability; the electrode material
must have good mechanical strength, good resistance
to erosion and must be resistant to cracking.
Table 1: Potential of oxygen evolution of different anodes, V versus normal hydrogen electrode (Chen, 2004)
Anode Potential (V)
Pt 1.3
Pt 1.6
IrO2 1.6
Graphite 1.7
PbO2 1.9
SnO2 1.9
TiO2 2.2
Si/BDD 2.3
Ti/BDD 2.7
There are some general guidelines to assist the
choice of an electrode material. In general, low O2
overvoltage anodes are distinguished by a high
electrochemical activity toward oxygen evolution and
low chemical reactivity toward oxidation of organic
compounds. Efficient pollutants oxidation at these
anodes may take place at low current densities. A
significant reduction of the current efficiency is
expected at high current densities due to the
production of oxygen. Conversely, at high O2
overvoltage anodes, higher current densities may be
used with minimal involvement from the oxygen
evolution side reaction. Thus, high O2 overvoltage
100
(b) High chemical stability; the electrode material
must be resistant to corrosion, unwanted oxide or
hydride formation and the deposition of inhibiting
organic films under all conditions.
(c) Suitable physical shape; it should be feasible to
make the material into the required shape, to assist
sound electrical connections and also to allow simple
fixing and replacement at a variety of scales.
(d) Electrical conductivity; conductivity must be
practically high throughout the electrode system
including the current feeder, electrode connections
and the entire electrode surface exposed to the
electrolyte.
(e) Catalytic activity and selectivity; the electrode
material must sustain the desired reaction and in some
cases, significant electro-catalytic properties are vital.
The electrode material must encourage the desired
chemical change while inhibiting all competing
chemical changes.
(f) Low cost/life ratio; the use of reasonably priced
and durable electrode materials must be favored.
Competition between organics oxidation at the
anode and the side reaction of oxygen evolution
should be considered to assess the choice of an anode
material. The oxidation of water to oxygen (Eq. 5)
happens at about 1.2 V versus normal hydrogen
electrode. Yet, a higher voltage is required for
electrochemical oxidation of water to take place at the
anode. The oxygen evolution over potential of a
number of electrode materials is illustrated in Table 1
(Chen, 2004).
Conditions
0.5 mol L1 H2SO4
0.5 mol L1 H2SO4
0.5 mol L1 H2SO4
0.5 mol L1 H2SO4
1.0 mol L1 H2SO4
0.5 mol L1 H2SO4
1.0 mol L1 H2SO4
0.5 mol L1 H2SO4
0.5 mol L1 H2SO4
anodes are generally preferred. For example, boron-
doped diamond (BDD) anodes have been confirmed
to yield higher organic oxidation rates and superior
current efficiencies than other commonly used metal
oxides including PbO2 and Ti/SnO2-Sb2O5 (Anglada et
al., 2009).
2.3.2. Cell design
Maintaining high mass transfer rates as the main
reactions that occur in electrochemical process
transpire on electrode surfaces are the most important
issue in cell design. To improve mass transfer,
 Wastewater Engineering: Advanced Wastewater Treatment Systems
Chapter 4: Electrochemical Methods

techniques such as gas sparging, high fluid velocity,
use of baffles and incorporation of several types of
turbulence promoters are frequently employed. In
obtaining a high mass transfer rate, the cell
construction should account for simple access to and
exchange of cell parts (Wendt and Kreysa, 1999).
Figure 4 summaries the various features that should be
considered in the design of an electrochemical reactor
(Anglada et al., 2009).

Fig. 4: Categorization of electrochemical reactors in regards to cell configuration, electrode geometry and flow type (Anglada
et al., 2009).

Two types of electrodes, principally of 2-
dimensional and 3-dimensional construction subsist.
The 3-dimensional assures a high value of electrode
surface to cell volume ratio. Both types can be
classified into static and moving electrodes as shown
in Figure 4. Accordingly, the utilization of moving
electrodes increases the mass-transport coefficient
owing to the turbulence promotion. However, among
the 2-dimensional electrodes, static parallel and
cylindrical electrode cells are used in the major
reactor designs in the latest studies. Cell designs using
the parallel plate geometry in a filter press
arrangement are generally used because of the
simplicity of scale-up to a larger electrode size by
merely adding electrodes or increasing number of cell
stacks (Rajeshwar and Ibanez, 1997). Furthermore,
cell configuration (divided and undivided) needs to be
considered. In divided cells, the anolyte and catholyte
are separated via a porous diaphragm or an ion
conducting membrane. The selection of the separating
diaphragm or membrane in divided cells is equally
vital as the selection of electrode materials. In general,
divided cells choice should be avoided whenever
possible, as separators are expensive and tightening of
a divided cell (reduction of electrode gap) is difficult
and encounters a host of mechanical and corrosion
problems (Wendt and Kreysa, 1999).
2.3.3. Operation conditions
(a) The current density (CD) is among the most
important factors that usually control electrochemical
oxidation processes through the reaction rate. It
should be clear that an increase in CD does not
necessarily result in the increase of oxidation
efficiency; the effect of current density on the
treatment level depends on the features of the effluent
to be treated. On the other hand, the use of higher CD
generally results in higher operating costs due to the
increase of energy use.
(b) An increase in the temperature leads to more
efficient processes by global oxidation. While direct
oxidation processes remain almost unaffected by
temperature, this fact may be explained in terms of the
presence of inorganic electro-generated reagents. An
enhancement with rising temperature of the mediated

101
 Bashir et al.
Electrochemical Oxidation Process Contribution in Remediating Complicated Wastewaters
oxidation processes by inorganic electro generated
reagents (active chlorine, peroxodisulfate) has been
reported. But, operation at ambient temperature is
preferred as it offers electrochemical processes with
less temperature requirements than those of the
equivalent non-electrochemical counterparts (i.e.,
incineration, supercritical oxidation) (Canizares et al.,
2006).
(c) The physicochemical features of the wastewater
(e.g., electrolyte nature and amount, pH value and
initial concentration of pollutants) also affect the
electrochemical oxidation process. The higher the
concentration of electrolyte is used, the higher the
conductivity and the lower cell voltage for a given
current density are recorded. Thus, treatment by
electrochemical oxidation is more suitable and cost
efficient when the wastewaters contain high salinity.
The effect of pH value is similar temperature, affects
mostly indirect oxidation processes (Anglada et al.,
2009). In chloride mediated reactions, the pH value
may influence the oxidation rate. During indirect
oxidation, chlorine evolution occurs at the anode (Eq.
3). At pH values < 3.3, the primary active chloro
species is Cl2 while at higher pH values its diffusion
away from the anode is coupled to its
disproportionation reaction to form HClO at pH<7.5
(Eq. 6) and ClO at pH>7.5 (Eq. 7). Theoretically,
operation at acidic conditions could be the finest
option as chlorine is the strongest oxidant followed by
HClO. Accordingly, higher pH values would improve
the electro-oxidation of pollutants, as HClO and ClO
are almost unaffected by desorption of gases and they
can act as oxidizing reagents in the total volume of
wastewater (Canizares et al., 2006).
2.3.4 Energy Consumption
The energy expenditure should be reduced to
minimize the power costs. The total power
requirement has contributions for both electrolysis and
movement of either the solution or the electrode. The
design of both electrodes and cell has a chief role in
reducing power needed. Therefore, a very open flow-
through porous electrode will have a low pressure
drop linked with it, giving rise to modest pumping
costs and facilitating reactor sealing. A high surface
area electrode which itself a turbulence promoter in
bed electrode, will give rise to a moderately high mass
transfer coefficient and active area without the need
for high flow rates through the cell; the pumping cost
will again be moderately low (Klamklang et al.,
2012). The maintenance of a low cell voltage requires
awareness to electrodes and cell design. The following
aspects should be considered:
102
(a) The counter electrode reaction should be
selected to reduce the reversible cell voltage. Thus, a
suitable and stable electrode material is required.
(b) The over-potentials at both electrodes should
be minimized through using electro catalysts.
(c) The electrodes, current feeders, and connectors
should be prepared from greatly conducting materials.
(d) Electrode and cell design should allow a small
inter-electrode or electrode membrane gap. The
electrode may touch the membrane as in zero-gap or
solid polymer electrolyte cells.
(e) A separator should be avoided by suitable
selection of the counter electrode chemistry or a thin
conductive membrane should be applied.
3. APPLICATIONS OF ELECTROCHEMICAL
OXIDATION IN WASTEWATER TREATMENT
Being touted as an effective treatment process, the
performance of electrochemical oxidation process in
treating various types of complicated wastewater
containing various pollutants has been studied. Also,
considerable efforts have been contributed recently to
elimination micro-contaminants using electrochemical
oxidation process. In general, microorganisms can be
deactivated via direct electrochemical process or by
the creation of killer agents, for example OH
(Lazarova and Spendlingwimmer 2008; Polcaro et al.,
2007). The combination of pollutants removal with
disinfection of wastewaters in a single treatment step
poses an attractive option, mainly in water recovery
and reuse where effectual removal of pathogens is
critical to protect public health. Table 2 presents the
effectiveness of electrochemical oxidation process in
treating variety of wastewaters.
Post-treatment of slaughterhouse wastewater via
electrochemical oxidation process was studied by
Awang et al. (2011). The most favorable conditions
were determined as 220 mg/L influent COD, 30
mA/cm2 current density and 55 min reaction time.
This resulted in 96.8% of color removal, 81.3% of
BOD removal and 85.0% of COD removal. Under the
optimal operation conditions (initial pH 6.9, current
density of 10 mA/cm2, conductivity of 3,990 micro
S/cm, and electrolysis time of 10 min), the removal
efficiencies of the textile wastewater by
electrochemical oxidation were 78% of COD and 92%
of turbidity. The energy and electrode consumptions
at the optimum conditions were calculated to be 0.7
kWh/kg COD (1.7 kWh/m3) and 0.2 kg Fe/kg COD
(0.5 kg Fe/m3), respectively (Kobya et al., 2009).
Landfill leachate treated electrochemically using
graphite carbon electrodes by Bashir et al. (2009), the
highest COD removal of 68% was achieved under the
operational conditions of 4 h reaction time and 79.9
mA/cm2 current density, while the initial COD was
 Wastewater Engineering: Advanced Wastewater Treatment Systems
Chapter 4: Electrochemical Methods
1414 mg/L. In another study conducted by Moraes
and Bertazzoli (2005), about 73% of COD, 57% of
TOC, 86% of color removals at a current density of
116.0 mA/cm2 and 180 min of reaction were attained.
They used oxide-coated titanium as an anode
electrode. The electrochemical treatment of industrial
water-based paint wastewater was examined in a
continuous tubular reactor. The effects of reaction
time on COD, color and turbidity removals was
investigated at 30 C, 35 g/L electrolyte and
7496 mg/L of initial COD concentrations with
66.8 mA/cm2 current density. The optimum residence
time in the reactor was fixed at 6 h for a cost driven
approach, enabling COD, color and turbidity removal
of 44.3%, 86.2% and 87.1%, respectively (Krbahti
and Tanyola, 2009).
Electrochemical treatment of organic pollutants
from paper mill effluent was investigated by El-
Ashtoukhy et al. (2009). The results showed that the
percentage of COD and color removals were 97% to
100%, respectively. Energy consumption calculation
shows that energy consumption ranges from 4 to
29 kWh/m3 of effluent depending on the operating
conditions. In another study, the electrochemical
oxidation of paper mill effluents was investigated via
a dimensionally stable anode of composition Ti/RuPb
(40%) Ox. The results indicated that about 99% of
COD and 95% of color and polyphenols were
removed after 15 min of electrolysis. The UV-Vis
spectrum illustration confirmed the formation of
hypochlorite ions (ClO-) during the electrolysis
process, indicating that the electrochemical oxidation
proceeds via an indirect mechanism with the
participation of hypochlorite ions (Zayas et al., 2011).
In the case of olive oil mill wastewater, the removal
rates of organics increased with the increase of
applied current density, sodium chloride level,
recirculation rate and temperature. The original COD
concentration of 41,000 mg/L was reduced to 167
mg/L, 99.85% of turbidity removal, 99.54% of oil-
grease removal were achieved after 7 h electrolysis at
the conditions of 135mA/cm2, 2M NaCl, 7.9 cm3 /s,
and 40C (Un et al., 2008). The effect of current
density (40-120A/m2) and initial pH (3-11) on the
Pharmaceutical wastewater treatment efficiency by
electro oxidation process was investigated
(Deshpande et al., 2012).Under optimum operating
conditions (CD 80A/m 2; pH 7.2), the process used
aluminum electrodes resulted in 24% of COD
removal after 25 min, whereas the process used
carbon electrode achieved 35.6% of COD removal
after 90 min of treatment (Deshpande et al., 2012). An
investigation of tannery wastewater treatment using
graphite cathodes and Ti/SnO2/PdO2/RuO2 anode,
with a current density of 2.1 A/dm2 was carried out.
After 55 min of the process the catholyte was
103
transferred into the anodic space and the process was
continued. After 55 min of electro-Fenton process, the
COD was reduced by 52.0%. Electrooxidation
continued by the anodic process resulted in
elimination of ammonia in 55 min and a total
reduction of COD by 72.9% (Naumczyk and
Kucharska, 2011).
Due to its unique performance in treating various
types of wastewater especially industrial wastewater
and landfill leachate which contain large amount of
the toxic and non-biodegradable pollutants as
aforementioned, it can be concluded that
electrochemical oxidation process represents a useful
solution when the existence of refractory and toxic
pollutants prevents the use of conventional biological
treatments. Under suitable operation conditions, a
total removal of COD, color, ammonia and
microorganisms can be achieved.
4. OPORTUNITIES AND CHALLENGES
The appearance of pollutants that are unmanageable
by conventional biological and chemical treatments
together the means of stricter restrictions enforced by
new legislation have resulted in much research work
focus on wastewater treatment via electro-oxidation
processes. Electrochemical oxidation has been found
to be an environmentally caring technology with
capability to remove completely non-biodegradable
organic compounds and eliminate nitrogen species.
Recently, the researchers in this field directed their
work towards two lines: (i) replacement of
conventional processes by electrochemical oxidation
and (ii) integration of electrochemical oxidation into a
treatment plant. As electrical energy is mainly
consumed in electrochemical oxidation process, the
use of photovoltaic (PV) modules as a power supply is
also expected to reduce the operating costs
(Klamklang et al., 2012; Anglada et al., 2009).
Indeed, high energy consumption is generally
required, limiting the further full-scale marketable
application. Two steps have been taken to reduce
treatment costs; (i) the use of this technology in
combination with other techniques as either a pre-
treatment or as a polishing step and (ii) the use of
renewable energy sources to power electrochemical
oxidation (Anglada et al., 2009). In addition to the
energy consumption, during the process design some
critical issues are important to be considered
especially in the design of electrodes and cells. These
include cost, safety, simplicity of maintenance, and
ease to use. It is also necessary that the performance
of the electrodes is maintained during the expected
operating life of the cells (Klamklang et al., 2012).
Although it has been confirmed that
electrochemical oxidation is a technically practicable
 Bashir et al.
Electrochemical Oxidation Process Contribution in Remediating Complicated Wastewaters

option to eliminate organic pollutants, the partial
oxidation of ammonia to nitrate ions has been
reported. The deployment of electrochemical
oxidation in combination with other process such as
ion exchange (Cabeza et al. 2007) as a post treatment
step could be a plausible solution to this issue.
Consequently, Comninellis et al. (2008) had
demonstrated the promising results obtained from the
treatment of industrial wastewaters via combined
methods involving electrochemical oxidation have
built up foundation for upcoming works. Contriving a
sustainable process based on the combination of
efficient technologies is one of the key obstructions
that need to be overcome before full-scale
implementation of electrochemical oxidation.

Table 2: Application of electrochemical oxidation process in waste water treatment

Type of wastewater Electrode material Performance references

Slaughterhouse aluminum 96.8% color, 81.3% BOD, and 85.0% Awang et al.(2011)
Wastewater COD removals.

Textile Wastewater iron electrode 78% COD, and 92% turbidity removals Kobya et al. (2009)

Textile Wastewater graphite electrodes 100% dye removal Kariyajjanavar et al.

(2011)
Landfill leachate graphite Carbone 68%COD, 84% color, and 70% BOD Bashir et al. (2009)
removals.

Landfill leachate 30% RuO2 and 70% TiO2 73% COD, 57% TOC, 86% color Moraes and
coated titanium removals Bertazzoli, (2005)

Industrial paint stainless steel 44.3% COD, 86.2% color, and 87.1% (Krbahti and
wastewater turbidity removals Tanyola, 2009)

paper -A cylindrical lead sheet as 97% COD, and 100% color removals El-Ashtoukhy et al.
mill effluents anode (2009)
- a cylindrical stainless steel
sheet as cathode

paper -Ti/RuPb(40%)Ox as anode 99% COD and 95% of color and

mill effluents -Ti/PtPd(10%)Ox as polyphenols removals Zayas et al. (2011)
cathode.

Olive oil mill RuO2 coated Ti 99.6% COD, 99.85% turbidity, and Un et al.(2008)
Effluents 99.54% oil-grease removals

Pharmaceutical Carbon electrode 35.6% COD removal Deshpande et al.

Wastewater (2012)

Tannery -graphite cathodes 72.9 % COD removal Naumczyk and

Wastewater -Ti/SnO2/PdO2/RuO2 anode Kucharska (2011)

5. CONCLUSION ACKNOWLEDGEMENTS

Wastewater treatment by electrochemical oxidation The authors are grateful for the financial support
process was established in a laboratory scale for many provided by the Universiti Tunku Abdul Rahman
years. However, electrochemical oxidation (UTAR) through grant No:
technologies have not reached real application IPSR/RMC/UTARRF/2012-C2/M03.
maturity in commercial scale perhaps due to the
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Wastewater Engineering: Advanced Wastewater Treatment Systems
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2014 IJSRPUB

Wastewater Engineering: Advanced Wastewater

Treatment Systems

Chapter 5: Wastewater Treatment by Bioremediation

Technologies

107
Wastewater Engineering: Advanced Wastewater Treatment Systems
Available online at http://www.ijsrpub.com/books
2014 IJSRPUB

Wastewater Treatment by Bioremediation Methods

Andrew N. Amenaghawon*, Kessington O. Obahiagbon

Department of Chemical Engineering, Faculty of Engineering, University of Benin, PMB 1154, Benin City, Nigeria
*Corresponding Author: E mail: andrew.amenaghawon@uniben.edu

Abstract. Increasing global population and the attendant increase in the level of industrialisation has resulted in the generation
of large amounts of effluents with wastewater chief amongst them. The deleterious effect the improper discharge of untreated
wastewater has on the environment and living things has prompted many nations of the world to take this problem very
seriously. This has resulted in the promulgation of stiffer environmental laws and regulations. This in turn has led to the search
for more efficient ways of treating wastewater. Because of the inherent limitations of the conventional wastewater treatment
methods, bioremediation has jumped to the fore front as a sustainable, acceptable, effective, low cost and environmentally
friendly wastewater treatment strategy. Bioremediation is a wastewater treatment process that utilises microorganisms either
autochthonous or exogenous to degrade numerous organic pollutants as a result of their metabolic activity and their capability
to adapt to extreme and often inhospitable environments. Bioremediation as a treatment strategy involves natural attenuation
which involves the use of indigenous microbial population without any interference, biostimulation which is the process of
stimulating viable indigenous microbial population, bioaugmentation which is the introduction of exogenous microbial
population to the remediation medium, bioaccumulation which is the use of live cells, biosorption which is the use of dead
microbial biomass, phytoremediation (the use of plants) and rhizoremediation which involves plant and microbe interaction.
This chapter explores the special features of bioremediation, its principles, strategies and forms of operation. It also takes a
look at the application of bioremediation to selected pollutants like petroleum hydrocarbons and derivatives, polycyclic
aromatic hydrocarbons and heavy metals as well as factors that affect bioremediation and the role of microorganisms in
bioremediation.

Keywords: Bioremediation, Wastewater, Treatment

1. INTRODUCTION and Muchie, 2010; Otokunefor and Obiukwu, 2010).

The population explosion currently experienced in the
world today especially in the urban centres of the
world poses a considerable threat to the environment
as a result of the generation of huge amounts of
wastewater (Amenaghawon et al., 2013; Akpor and
Muchie, 2010). The increasing population has resulted
in a corresponding increase in industrial and
agricultural activities from which these wastewaters
are produced (Godos et al., 2009; Morill et al., 2009).
The discharge of untreated wastewater generated from
these operations into natural water bodies represents a
huge environmental burden such as the accumulation
of hazardous and toxic chemicals in the receiving
water bodies with potentially deleterious
consequences on the immediate ecological
environment. This has necessitated the need to
monitor the quality and quantity of wastewater
generated and discharged into natural water bodies
(Amenaghawon et al., 2013; Kshirsagar, 2013). This
has also led to the development of wastewater
treatment strategies that focus on effective removal of
pollutants from water rather than disposal.
Wastewater treatment is presently carried out
mainly through chemical and biological means.
Irrespective of the advantages of chemical treatment
methods which include the mineralisation of
otherwise non-biodegradable substances and the use
of a smaller reactor size, the disadvantages of this
method are still significant (Agarry et al., 2008; Akpor
108
As a result of the limitations of the chemical treatment
methods, biological methods have been encouraged.
Recently, a lot of attention has been given to
bioremediation as a suitable and sustainable biological
method for wastewater treatment. It is touted to be an
effective, environmentally friendly and economic
treatment option for wastewater (Crawford and
Crawford, 2005; Otokunefor and Obiukwu, 2010).
Bioremediation involves the use of naturally
occurring microorganisms to breakdown complex
pollutant molecules into simpler substances such as
carbon dioxide and water (Obahiagbon and Aluyor,
2009). It can be accomplished on its own, a process
known as natural attenuation or intrinsic
bioremediation or it can be stimulated through
nutrient supplementation to increase bioavailability
within the remediation medium, a process known as
biostimulation (Sharma, 2012). In order to be a
successful treatment strategy, bioremediation must
take into account, the multiphase and complex nature
of the remediation environment; thus resulting in the
need to incorporate other subjects such as chemistry,
microbiology, engineering etc. Recently, a lot of
attention is being given to the state and condition of
the environment culminating in the formulation of
new environmental laws and regulations. These
regulations advocates better protection for the
environment and mandates cleanup of polluted sites.
This has had a positive boomerang effect on
bioremediation. Bioremediation is now gaining more
 Amenaghawon and Obahiagbon
Wastewater Treatment by Bioremediation Methods
acceptance as a suitable treatment method, it is
becoming a choice treatment scheme for the cleanup
of polluted sites particularly sites contaminated with
petroleum hydrocarbons, it is attracting funding from
agencies in governments and private corporations and
a lot of advancement is being made in improving on
the effectiveness of the technology (Crawford and
Crawford, 2005; Vidali, 2001).
1.1. Natural Attenuation
Natural attenuation also called intrinsic
bioremediation refers to the combination of natural
processes that occur, without human involvement, to
decrease or attenuate contaminant concentrations
and toxicity in wastewater, and thereby reduce the
hazards posed by the contaminants. The
Environmental Protection Agency (EPA) defines
natural attenuation to include biodegradation,
biosorption and biological stabilisation or destruction
of contaminants (EPA, 1999). Natural attenuation is
usually employed at the site of contamination and the
appropriate conditions must be put in place for the
process to function effectively. This is why the
process is typically monitored in which case the
process is referred to as monitored natural attenuation.
Cleanup of contaminants from wastewater by
natural attenuation occurs in various forms:
(a) Biodegradation: this occurs when
microorganisms metabolise pollutants in
wastewater leading to the mineralisation of these
pollutants into simpler and harmless substances
such as carbon dioxide and water. The wastewater
typically contains indigenous microorganisms that
effect the mineralisation of the pollutants through
the natural attenuation process (Adekunle and
Adebambo, 2007; Amenaghawon et al., 2013).
(b) Dilution: the concentration of pollutants
reduces as they move through the bulk of the
receiving water body and mix with it.
(c) Evaporation: some volatile compounds in
wastewater such as petroleum hydrocarbons and
their derivatives typically referred to as volatile
organic compounds (VOCs) can be mobilised into
the vapour phase thereby reducing their
concentration in the liquid phase. These gases
released are typically diluted by mixing with air
when they are mobilised into the vapour phase.
(d) Chemical reactions: pollutants in wastewater
may be converted to less harmful forms when they
react with other components in the wastewater.
A lot of studies have been done on the use of
natural attenuation for the remediation of polluted
wastewater. Most of the early work done in this area
was focused on remediation of benzene, toluene,
ethylbenzene, and xylene (BTEX) using natural
109
means. These are hydrocarbons that are commonly
found in refinery effluents (Hidayat and Tachibana
2012). Fono et al. (2006) investigated the application
of natural attenuation to the remediation of
wastewater derived chemical contaminants in an
effluent dominated river. The results they reported
indicate that natural attenuation can result in a
substantial reduction in the concentrations of the
wastewater derived contaminants. Yu et al. (2005)
investigated the bioremediation of a mixture of PAHs,
namely fluorene (Fl), phenanthrene (Phe) and pyrene
(Pyr) in mangrove sediment slurry using natural
attenuation. They reported that the indigenous
microorganism degraded over 99% Fl and Phe but
only around 30% of Pyr through natural attenuation
within a one month period suggesting that natural
attenuation may be a more appropriate method for
remediation of Fluorene and Phenanthrene
contaminated mangrove sediments.
Monitored natural attenuation is a low cost process
involving only the cost of monitoring and the time
required for the process to occur. It also does not lead
to the destruction of the immediate ecological
environment (Yu et al., 2005). This has made it an
acceptable choice for the cleanup of low risk oil
contaminated waters (Margesin and Schinner, 2001).
However, the process usually takes a long time to
effect satisfactory cleanup as a result of the small
population of indigenous microorganisms present
(Forsyth et al., 1995; Yu et al., 2005).
1.2. Biostimulation
The indigenous microbial population present in
wastewater implies that there is possibility for
remediation through natural attenuation. Nevertheless,
the remediation of wastewater through natural means
is still limited by several factors which might inhibit
microbial growth and activity. Some contaminated
wastewater might contain complex synthetic and
recalcitrant pollutants which are not readily amenable
to biodegradation. Also, there might be deficiency of
electron acceptors or donors and low availability of
nutrient sources such as nitrogen and phosphorus
(Nyyssnen et al., 2009; Qin et al., 2013). In
situations like these, it becomes imperative to improve
the conditions of remediation in the form of external
nutrient supplementation to improve bioavailability,
supplying air or adding electron acceptors or donors to
the substrate analogue (Cosgrove et al., 2010; El
Fantroussi and Agathos, 2005). The process of
externally stimulating microbial growth and activity
for the remediation of contaminants is referred to as
biostimulation. Biostimulation enhances the rate of
bioremediation since the addition of rate limiting
nutrients to the remediation medium promotes the
 Wastewater Engineering: Advanced Wastewater Treatment Systems
Chapter 5: Wastewater Treatment by Bioremediation Technologies
decontamination capacity of the indigenous microbial
population (Nikolopoulou and Kalogerakis, 2009).
Previous studies on bioremediation of contaminated
wastewater have investigated the role of
biostimulation during bioremediation. Roling et al.
(2002) investigated the effect of nutrient
supplementation on the bioremediation of oil spills.
They observed that nutrient supplementation
substantially enhanced the degradation of oil over a
wide range of concentrations. They further noted that
the addition of nutrients rather than the quantity of
nutrient added was the determining factor. Yu et al.
(2005) reported that biostimulation in the form of the
addition of mineral salt medium resulted in the
degradation of over 97% of fluorene (Fl),
phenanthrene (Phe) and pyrene (Pyr), in mangrove
sediment slurry. This was an improvement over the
results obtained for the case of natural attenuation.
Kim et al. (2005) reported that the addition of
inorganic nutrients stimulated the CO2 evolution rate
which was used as an indication of the performance of
the bioremediation treatment. They also observed that
the addition of surfactants enhanced the degradation
of oil though the effect was not very significant.
Obahiagbon and Aluyor, (2009) investigated the
potential use of sodium nitrate and sodium nitrite as
inorganic nutrient supplements for the biostimulation
of Aspergilllus niger for the bioremediation of
petroleum hydrocarbon polluted water. They recorded
over 97 and 98% reduction levels respectively in total
hydrocarbon content and biochemical oxygen demand
which are key indicators of biodegradation efficiency.
Otokunefor and Obiukwu, (2010) investigated the
treatment of phenol laden refinery effluent using
inorganic fertilisers as biostimulants. They noted that
the inorganic nutrients stimulated rapid growth of the
microbial population present in the remediation
medium. They further observed that the degree of
phenol degradation was dependent on the
concentration of fertilisers used. Amenaghawon et al.
(2013) studied the role of urea and NPK 15:15:15
fertilisers as biostimulants of microbes in the
bioremediation of domestic wastewater. By
monitoring bioremediation indicating parameters such
as pH, biochemical oxygen demand, and dissolved
oxygen over a period of 5 weeks, they were able to
obtain treated wastewater that met the requirements of
environmental regulatory agencies such as the Federal
Environmental Protection Agency (FEPA) and the
department of petroleum resources (DPR) (FEPA,
1999).
For marine environments, it is important to
monitor the use of biostimulants for the following
reason. Firstly, the stimulants should be directed at the
microbial population close to the point of
contamination. Secondly, they should be dispensed in
110
such a way that they don't get diluted or washed away
by the on rushing waves. Lastly, the concentration of
nutrients especially those containing nitrogen and
phosphorus should be closely monitored as too low a
concentration will not have the desired effect while
too high a concentration can result in eutrophication
which subsequently leads to algal bloom which in turn
can cause a reduction in the dissolved oxygen
concentration in the water body (Gonzalez, 2011).
1.3. Bioaugmentation
The major limitation of natural attenuation processes
for bioremediation of contaminants is that the
population of indigenous microorganisms is low. In
some cases, the indigenous microorganisms might not
even be able to utilize the pollutants for metabolic
activities possibly because they do not possess the
metabolic pathways for the mineralisation of the
pollutants into smaller and harmless compounds like
carbon dioxide and water (El Fantroussi and Agathos,
2005). It is also possible that the pollutants to be
removed can only be biodegraded by a particular
consortium of microorganisms. This observation is
typical of recalcitrant pollutants like polycyclic
aromatic hydrocarbons (PAHs), aromatic and aliphatic
halogenated hydrocarbons, pesticides and nitrated
compounds like 2,4,6-trinitrotoluene (TNT). For
instances like this, it becomes necessary to inoculate
the contaminated site with specific microbial
populations that can perform the desired
bioremediation functions. The process of introducing
external microbial populations into the remediation
medium is referred to as bioaugmentation (Yu et al.,
2005). Bioaugmentation can therefore be defined as
the process of introducing specific microorganisms
with the desired degradation capability for the purpose
of enhancing the removal of pollutants from
wastewater or any other contaminated site (Vogel,
1996).
Bioaugmentation has been the subject of much
research. Gentry et al. (2004) reviewed recent trends
and approaches in bioaugmentation strategies. They
highlighted the techniques and tools advanced in
recent times to improve the activity of externally
introduced microorganisms after their introduction
into the site of remediation. Mrozik and Piotrowska-
Seget, (2010) did a survey on bioaugmentation as a
strategy for the degradation of aromatic compounds.
They argued that a successful bioaugmentation
strategy requires knowledge on the type and
concentration of pollutants and suitable strains of
microorganism with the required degradation
capability. They further mentioned that certain
features of the microorganisms should determine their
selection. These features include the ability for grow
 Amenaghawon and Obahiagbon
Wastewater Treatment by Bioremediation Methods
fast, ability to tolerate high concentrations of the
target pollutants and survive in a wide range of
environmental conditions. Lendvay et al. (2003) did a
side by side comparison of bioaugmentation and
biostimulation for the cleanup of a chloroethene
contaminated aquifer. Their results indicated that the
deployment of the bioaugmentation strategy yielded a
near stoichiometric dechlorination of the chloroethene
to ethane within six weeks. Smith et al. (2005) also
did a comparison study of biostimulation and
bioaugmentation with a bacterial strain for the
remediation of methyl tertiary butyl ether (MTBE)
contaminated groundwater. They reported a
substantial decrease in the concentration of MTBE in
the contaminated water after a treatment period of six
months. Obahiagbon and Owabor, (2009) utilised a
mixed microbial consortium for the remediation of
crude oil contaminated water. By monitoring key
indicators of bioremediation such as biochemical
oxygen demand and total hydrocarbon content, they
observed that almost 100% degradation was achieved
over a treatment duration of nine weeks. Obahiagbon
and Akhabue, (2009) investigated the effect of
microbial count of Pseudomonas aeruginosa bacteria
amended with NPK 15:15:15 fertiliser on the
biodegradation of crude oil-contaminated water. At
the end of nine weeks of bioremediation, they
obtained satisfactorily treated wastewater that met the
requirements of environmental regulatory agencies
such as the Federal Environmental Protection Agency
(FEPA) and the department of petroleum resources
(DPR) (FEPA, 1999).
Despite the results reported in the literature, there
is still some debate regarding the implementation of
bioaugmentation strategies particularly in relation to
the use of biostimulation. Gonzalez, (2011) reported
that the prevailing conditions at the site of
contamination should determine the choice of strategy
to be deployed.
Bento et al. (2005) did a comparative study on the
degradation of diesel oil by natural attenuation,
biostimulation and bioaugmentation. They noted that
the best option was bioaugmentation. They further
observed that to obtain best performance,
bioaugmentation should be implemented in such a
way that microorganisms chosen for bioaugmentation
should be isolated from the site of contamination. The
reasoning behind this is that the indigenous
microorganisms are more likely to survive and grow
when introduced into the site of contamination
compared with microorganisms foreign to that site
(Thompson et al., 2005).
Some contradictory reports have shown that the
introduction of enriched external cultures of
microorganisms did not affect the degradation
capacity of the microorganisms but biostimulation
111
enhanced the degradation of the pollutants
(Thomassin-Lacroix et al., 2002). When implemented
with bioaugmentation, biostimulation can provide the
nutrient requirement and the enabling environment for
both indigenous and externally introduced
microorganisms. In the light of this and the inherent
limitations of both methods, it is instructive to deploy
both as complementary strategies rather than
competing ones (Gonzalez, 2011).
2. PRINCIPLES AND OPERATION OF
BIOREMEDIATION
Perhaps the most significant principle of
bioremediation is that microorganisms possess the
ability to degrade contaminants in wastewater.
Wastewater contains biodegradable contaminants that
can be degraded by microorganisms such as bacteria,
fungi and even protists. These organisms are either
indigenous to the contaminated water or are added
exogenously to perform specific remediation
functions. Conventional wastewater treatment is
accomplished in three steps namely primary,
secondary and tertiary. The primary treatment step is
designed to remove suspended and coarse solids from
the wastewater stream. It typically involves the use of
screens and sedimentation vessels to remove solids
from wastewater by the action of gravity. It has been
reported that the primary treatment step can reduce the
total suspended solid particles by as much as 60%.
The secondary step is a biological treatment step
which removes dissolved organic materials. The
tertiary step is often optional. It can remove more than
99% of all contaminants in wastewater resulting in
treated wastewater of almost drinking quality.
Bioremediation finds its place during the
secondary treatment stage. The principles and
technologies applied here typically includes the basic
activated sludge process, trickling filters, rotating
biological contactors and other forms of treatment that
involves the use of biological means to degrade
pollutants.
2.1. The Activated Sludge Process
The activated sludge process developed by Ardern
and Lockett, (1914) represented the highpoint of
major advances in the application of aeration
technology to wastewater treatment. In its
conventional form, it consists of a multi chamber
reactor which makes use of an activated population of
aerobic microorganisms (bacteria, fungi, yeast,
protozoa etc) with the capability to degrade organic
pollutants in wastewater (EPA, 1997). Despite the fact
that a lot of configurations of the process currently
exists, the essential features has remained the same as
 Wastewater Engineering: Advanced Wastewater Treatment Systems
Chapter 5: Wastewater Treatment by Bioremediation Technologies
shown in Figure 3.1. Typically, the set up consists of
an aeration tank and a secondary settling tank or
clarifier. Wastewater that has gone through primary
treatment is charged into the aeration tank along with
the microorganisms to form what is referred to as an
activated sludge or mixed liquor. The aeration in the
tank is accomplished by using submerged diffused or
surface mechanical aeration or a combination of both
to keep the activated sludge as a suspension
(Amenaghawon and Aisien, 2011; EPA, 1997). The
compressed air used for aeration is constantly
transported through the wastewater as it flows through
the aeration tank. The compressed air serves to
provide a source of oxygen for the aerobic microbial
population floc that forms in the tank and the
turbulence and agitation required to bring the
wastewater and the microorganisms into proper
contact. During the process of aeration, the microbial
population will aggregate together to form small
Fig. 1: Conventional activated sludge process configuration with aeration and settling tanks
Over the years, different configurations of the
conventional activated sludge process have surfaced.
These adaptations have been made to meet acceptable
effluent standards for biochemical oxygen demand,
nitrogen and phosphorus. By properly calibrating the
aerobic condition, providing microorganisms capable
of degrading the target pollutants, proper nutrient
supplementation, recycle design etc, the activated
sludge process can achieve significantly high
treatment efficiencies.
2.2. Trickling Filter Systems
A trickling filter is a fixed packed bed, biological
filter that operates under aerobic conditions. The fixed
bed is packed with high specific surface area solid
materials like rocks, gravel, shredded PVC materials
or more conventional filter materials (Guyer, 2011).
Typically, materials to be used in designing trickling
filters should have a specific surface area in the range
of 30 to 900 m2/m3. The filter usually has a depth of
12 m however filters packed with lighter synthetic
plastic materials can have depths as high as 12 m. The
112
clumps or flocs. After a sufficient time of aeration, the
activated sludge which would have become flocculent
is separated from the wastewater in the secondary
settling tank or clarifier where the flocs settle out. The
clarified wastewater is then sent for further
processing. A part of the effluent sludge from the
clarifier is returned to the aeration tank to maintain the
required microbiological balance in the tank and the
process is repeated. The concentration of sludge
returned to the aeration tank is specified by the ratio
of mixed liquor volatile suspended solids (MLVSS) to
the biochemical oxygen demand of the influent
wastewater that will result in the degradation of the
most amounts of organics from the influent
wastewater. The excess sludge due to microbiological
growth is wasted for further handling. The value of
this ratio affects the efficiency of the treatment
process (Amenaghawon and Aisien, 2011; Guyer,
2011).
use of deeper filters can enhance nitrification potential
and can serve as a second stage in a two-stage
biological system design for nitrification (Guyer,
2011). Wastewater that has gone through primary
treatment is trickled or sprayed over the filter set up
using a rotating sprinkler. The filter arrangement
provides support for the growth of microorganisms
and the wastewater flowing downward through the
filter provides nutrients for the microorganisms. It is
important to first take the wastewater through the
primary treatment step to prevent clogging and ensure
an efficient treatment process. As the wastewater
trickles through the filter, the organic pollutants in it
are degraded by the microorganisms growing on the
filter to simple and non toxic compounds like carbon
dioxide and water and in the process more microbial
cells are produced. A secondary clarifier is typically
needed to clarify the effluent from the trickling filter.
For a completely functional trickling filter system,
reduction levels in biochemical oxygen demand in the
range of 80 to 90 percent have been obtained.
The primary justification of trickling filter systems
has been their low start up, operating and maintenance
 Amenaghawon and Obahiagbon
Wastewater Treatment by Bioremediation Methods
cost as well as their ease of operation. With modern
designs, the performance of trickling filter systems is
comparable to that of conventional activated sludge
processes. However, trickling filter systems holds the
advantage of providing good performance with little
operational and energy requirements.
2.3. Rotating Biological Contactors
The rotating biological contactor (RBC) is a fixed film
equipment used for secondary wastewater treatment
and operates similar to the trickling filter system
(Guyer, 2011). In its basic form, it consists of a series
of circular disks arranged side by side on a shaft
which is rotated through the wastewater stream. The
surface of the disks is usually covered with
populations of microorganisms such as bacteria and
protists. As the disks slowly rotate on the shaft, it
extracts a film of wastewater into the air which
trickles down and absorbs oxygen. During this
process, the aerobic microorganisms degrade the
organic pollutants in the wastewater to simpler and
less toxic products (Amenaghawon et al., 2013). Any
excess solid and waste product are sloughed off and
transported with the wastewater into the secondary
clarifier for separation. This is usually done to prevent
clogging of the media and to maintain the population
of the microorganisms (Grady et al., 2011). For
operational purposes, a group of contactors are usually
used in series as a single contactor cannot achieve the
desired level of treatment. The speed of rotation of the
RBC is typically in the range of 1 to 2 rpm. This is
enough to provide a reasonable level of degradation.
Some advantages of the RBC system include: high
level of nitrification, short contact times as a result of
the large surface available, ability to handle a wide
range of flows, the excess solids are readily separated,
low operating cost and power requirement. However,
there are some limitations to the use of the RBCs
which include the fact that the RBC units must be
covered in temperate regions to prevent freezing. Also
there is need for frequent maintenance of the moving
parts of the unit which include the shaft bearings and
mechanical drive units.
2.4. Waste Stabilization Ponds
Waste stabilisation ponds are a sustainable and
economic means of treating a wide range of
wastewater with a reasonably clean effluent. The
ponds are usually 0.8 to 1.2m in depth and can be
used after primary treatment as standalone treatments
facilities, in series or parallel. The degree of treatment
obtainable is dependent on the type and number of
ponds used. Wastewater treatment is effected by the
indigenous microorganisms in the pond which
113
metabolise the organic substances in the wastewater to
simpler and less toxic products (Amenaghawon et al.,
2013).The exposure of the surface of the pond to the
atmosphere creates the aerobic environment need for
the microorganisms to function hence they are
typically referred to as oxidation ponds. This method
of treatment has an advantage over other aeration
treatment methods in that there is no need to install an
aerator to add oxygen to the water as the aeration is
accomplished naturally (Grady et al., 2011). However,
aeration by the natural method is much slower
compared to when an aerator is used. The
consequence of this is that stabilisation ponds treat
wastewater slower than other conventional treatment
plants.
3. FORMS AND STRATEGIES OF
BIOREMEDIATION
3.1. In situ bioremediation
In situ bioremediation is a biological treatment
process where microorganisms metabolise organic
contaminants to stable and less toxic substances such
as carbon dioxide, methane, water and inorganic salts,
either in natural or engineered conditions (Farhadian
et al., 2008). This technique for the cleanup of
contaminants is applied at the site of contamination.
In making the decision to implement in situ
bioremediation for the cleanup of pollutants, it is
important to carry out a bioremediation feasibility
study. Answers to the following questions must be
provided: biodegradability of the contaminants,
distribution of the contaminants in the wastewater
stream, chemical reactivity of the contaminants, extent
of contamination, presence or absence of substances
that inhibit the growth of microorganisms and the
ability of the microorganisms to degrade the target
contaminants. Answers to these questions will
determine the suitability of in situ bioremediation for
a given contaminated site (Cauwenberghe and Roote,
1998; Farhadian et al., 2008).
In situ bioremediation is usually adopted when
economic considerations are of paramount importance
and since the wastewater is treated at the site of
contamination, there is no further environmental
burden posed as a result of transportation and disposal
of the wastewater. However, this strategy may not
succeed in sites that are saturated with contaminants
as a result of the inadequate mass transfer of electron
acceptors typically oxygen. This limitation is also
evident in sites with limited nutrient availability
particularly nitrogen and phosphorus. In situ
bioremediation processes include phytoremediation,
bioventing, biosparging etc (Sharma, 2012).
 Wastewater Engineering: Advanced Wastewater Treatment Systems
Chapter 5: Wastewater Treatment by Bioremediation Technologies
Phytoremediation: this is a bioremediation
strategy that involves the use of plants and vegetation
in the cleanup of contaminated water and soil. It is an
emerging treatment strategy which has been receiving
a lot of attention in terms of research, innovation, and
funding. It has been reported to be a more cost
effective alternative to more conventional treatment
methods (Sharma, 2012). This is the main advantage
of phytoremediation. Phytoremediation techniques
include the following:
(a) Phytoextraction is a phytoremediation process
that involves the use of plants to remove contaminants
particularly metals from the environment. The
contaminants are accumulated in the roots, shoots and
leaves of the plants. This is a cost effective method for
the remediation of low concentrations of contaminants
(Macek et al., 2000; Zhuang et al., 2007).
(b) Phytotransformation is a phytoremediation
process that involves the uptake of contaminants from
wastewater and soil and the subsequent transformation
of these contaminants to more stable and less toxic
forms (Subramanian et al., 2006).
(c) Phytodegradation is a phytoremediation process
that involves the degradation of contaminants by
taking advantage of the symbiotic relationship
between plants and microorganisms. The plants
provide the nutrients needed by the microorganisms to
survive while the microorganisms in turn provide the
necessary soil environment for the plants (Garrison et
al., 2000; Newman and Reynolds, 2004).
(d) Rhizofiltration is similar to phytoextraction in
that it is mainly used for the removal of heavy metals
from the environment. The plant to be used for
phytoremediation is grown on clean water initially
and after the development of a large root system, the
plant is transferred and planted in the polluted site
where the roots take up the polluted water and the
contaminants along with it. When the roots become
saturated with contaminants, they are harvested and
disposed off safely (Dushenkov et al., 1995; Verma et
al., 2006).
In situ bioremediation has been applied with some
success to the remediation of ground water
contaminated with various organic pollutants such as
carbon tetrachloride, trichloroethylene,
tetrachloroethylene, pentachlorophenol, gasoline,
diesel, methyl tert-butyl ether (MTBE), petroleum
hydrocarbons, xenobiotics, mono aromatic
hydrocarbons, benzene, toluene, ethylbenzene and
xylenes isomers (BTEX) and so on (Bradley and
Landmeyer, 2006; Cunningham et al., 2001; Curtis
and Lammey, 1998; Da Silva et al., 2005; Ferguson
and Pietari, 2000; Kao et al., 2006; Schmidt et al.,
1999; Widdowson, 2004; Yerushalmi et al., 1999).
Biosparging:
114
Biosparging is an in situ bioremediation strategy
that utilises indigenous microorganisms to degrade
contaminants. For contaminated sites that suffer from
inadequate mass transfer of oxygen, biosparging
becomes a useful strategy to adopt. It involves the
injection of air under pressure and nutrients (if
necessary) to stimulate the microorganisms and
increase the microbial activity of the indigenous
microorganisms. It can be applied in the remediation
of groundwater contaminated with petroleum
hydrocarbons as well as contaminated soil. The ease
and low cost of installing small-diameter air injection
points allows significant flexibility in the
implementation of this strategy.
3.2. Ex situ bioremediation
This is a bioremediation strategy in which the
contaminated material is removed from the site of
contamination and treated in another location. It is
most suited for the decontamination of polluted soil.
The techniques that can be used include land farming,
composting, biopiles and bioreactors (Sharma, 2012).
4. BIOREMEDIATION OF PETROLEUM AND
CRUDE OIL POLLUTED WASTEWATER
Crude oil is a complex biodegradable substance
containing a large variety of hydrocarbons (Hidayat
and Tachibana, 2012; Obahiagbon et al., 2009). It is
the major pollutant in marine environments as a result
of its release from activities such as offshore drilling,
natural oil seepage, washing of oil tankers as well as,
transportation and ruptured pipeline accidents
(Elshafie et al., 2007; Hasanuzzaman et al., 2007).
The effect of petroleum pollution on the environment
depends on the type and quantity of crude oil
involved. The water soluble fraction of the oil has
been reported to reduce the growth of biomass in the
affected environment as a result of the reduction in
dissolved oxygen, increase in turbidity, and the
toxicity of the crude oil components (Edema, 2012).
Bioremediation has been identified as the most
rational choice in the decontamination of water
polluted with hydrocarbon derivatives. It involves
treating the petroleum pollutants with hydrocarbon
degrading microorganisms possessing the kind of
enzymes required for such a process. Many
microorganisms (Pseudomonas, Escherichia coli,
clostridium, Candida, Aspergillus niger, Yeasts,
Penicillium etc) are known to grow on and utilize
petroleum and its derivatives for metabolic activities.
These organisms are able to actively degrade fractions
of petroleum oil to less toxic and stable product
(Adekunle and Adebambo, 2007; Chaillana et al.,
2004; Obahiagbon and Owabor, 2008). Khan et al.
 Amenaghawon and Obahiagbon
Wastewater Treatment by Bioremediation Methods
(2006) isolated, identified and characterised efficient
oil degrading bacterial strains to study the effect of
crude oil loading on the growth of the bacterial
strains. They observed that Bacillus sp. showed
promise for the biodegradation of crude oil and
consequently, its application for the cleanup of oil
spills. Obahiagbon and Owabor, (2009) investigated
the bioremediation of crude oil polluted water using a
mixed microbial culture. Using biochemical oxygen
demand and total hydrocarbon content as indicators of
bioremediation, they recorded almost 100%
degradation over a treatment period of nine weeks.
Thavasi et al. (2006) investigated the potential use of
Azotobacter chroococcum a marine nitrogen fixing
hydrocarbon degrading bacterium and its
biosurfactants for the bioremediation of crude oil
polluted marine environment. Obahiagbon and
Akhabue, (2009) studied the effect of microbial count
of Pseudomonas aeruginosa stimulated with NPK
fertiliser on the biodegradation of crude oil-
contaminated water. The effluent water obtained at the
end of nine weeks of bioremediation satisfied the
treatment requirements of environmental regulatory
agencies such as the Federal Environmental Protection
Agency (FEPA) and the department of petroleum
resources (DPR) (FEPA, 1999).
Mukred et al. (2008) examined the growth of
microbial populations and effectiveness of
bioremediation of crude oil polluted water. They
reported up to 98% reduction in total hydrocarbon
content with a bacteria consortium of Acinetobacter
faecalis, Staphylococcus sp. and Neisseria elongate.
Bioremediation by natural attenuation was a major
part of the cleanup effort of the Exxon Valdez oil spill
in Prince William Sound, Alaska (Samanta et al.,
2002). Arotiowa et al. (2007) studied the
bioremediation of petroleum diesel polluted water
using an ex situ strategy. They investigated the
potential of Bacillus subtilis, Pseudomonas
aeruginosa and Penicillium funiculosum isolated from
refinery wastewater for the degradation of diesel in
water. They reported that of the three microorganisms,
Penicillium funiculosum had the highest degradation
ability. Otokunefor and Obiukwu, (2010) investigated
the treatment of refinery wastewater using a microbial
consortium consisting of Bacillus sp, Pseudomonas
sp, Staphylococcus sp, Klebsiella sp., and Citrobacter
sp. stimulated with inorganic fertilisers. They
observed that inorganic nutrient supplementation
enhanced the growth of the microbial population.
They further observed that the degree of degradation
of the target pollutant was dependent on the
concentration of fertilisers used. Gargouri et al. (2011)
applied a continuous stirred tank bioreactor for the
bioremediation of hydrocarbon laden industrial
wastewater. They developed a successful
115
bioremediation strategy using an efficient
acclimatised microbial consortium. After a treatment
period of 225 days, they observed that the process was
highly efficient in remediating the wastewater as seen
in the performance of the bioaugmented reactor
demonstrated by the reduction levels of up to 95 and
97.5% respectively for chemical oxygen demand
(COD) and total hydrocarbon content. They further
reported that the use of the mixed cultures resulted in
a high degradation performance for hydrocarbons
range of n-alkanes (C10C35). Li et al. (2005) treated
wastewater produced from an oil field using Bacillus
sp. immobilised on polyvinyl alcohol (PVA). They
reported over 90% reduction in chemical oxygen
demand for continuous wastewater treatment using
immobilised bacteria cells. They further reported that
the efficiency of COD removal was improved when
the remediation medium was supplemented with a
nitrogen source such as (NH4)2SO4.
The effectiveness of the application of
bioremediation technology to contaminated sites
varies from site to site and it requires information on
the characteristics of the site, the type of contaminant
and the factors that affect the growth of pollutant
degrading microorganisms (Obahiagbon and Aluyor,
2009). Okoh, (2006) reported that a number of factors
such as the composition of crude oil contaminant,
availability of nutrients especially nitrogen and
phosphorus, and the nature of the contaminated
environment could affect the biodegradation of
petroleum hydrocarbons.
5. BIOREMEDIATION OF POLYCYCLIC
AROMATIC HYDROCARBON POLLUTED
WASTEWATER
Polycyclic aromatic hydrocarbons (PAHs) are a group
of compounds that consists of two or more benzene
rings fused together in various configurations (Woo et
al., 2009). These compounds enter the environment
through two major avenues which are natural and
anthropogenic. Natural sources of PAHs include
volcanic eruptions and forest fires (Bamforth and
Singleton, 2005). They also enter the environment
through a host of anthropogenic activities such as
incomplete combustion of gasoline and diesel in
internal combustion engines, combustion of coal and
oil for power generation, wood burning, tobacco
smoking, fumigants, and many other sources (Jia and
Batterman, 2010; Li et al. 2010; Wilson et al. 2003).
They are typically hydrophobic and have low
solubility in water; however they can be mobilised
into the aqueous phase through discharges from
industrial and domestic effluents, leaks of PAHs
containing materials, runoff from paved roads,
parking lots among other sources (Alamo-Nole et al.
 Wastewater Engineering: Advanced Wastewater Treatment Systems
Chapter 5: Wastewater Treatment by Bioremediation Technologies
2011; Yu et al., 2005). PAHs are highly recalcitrant
and resistant to degradation and typically persist in the
environment (Bamforth and Singleton, 2005).
Exposure to these compounds can cause serious
deleterious effects to humans such as central nervous
system and respiratory diseases as well as damage to
the kidneys and liver hence they are classified to as
priority pollutants by many countries (ATSDR 2005;
NPT 2004; Owabor and Aluyor, 2008).
The vast amounts of evidences and results reported
in literature have identified bioremediation as one of
the major ways of treating PAH contaminated
wastewater (Owabor and Aluyor, 2008). The principle
behind the use of this method is the degradation of the
pollutants into less harmful products by the
indigenous microorganisms in the wastewater. This
process is referred to as natural attenuation or intrinsic
bioremediation (Amenaghawon et al., 2013; Yu et al.,
2005). Reports have also shown that biostimulation
which is the addition of nutrients and provision of
enabling environment for biodegradation as well as
bioaugmentation which is the introduction of
exogenous microorganisms with specific
bioremediation capabilities to the remediation
medium have enhanced the efficiency of
bioremediation (Obahiagbon and Akhabue, 2009;
Cosgrove et al., 2010; Yu et al., 2005). To this end,
bioremediation has become successful over the years
in harnessing the natural activity of microorganisms.
Bioremediation of PAH contaminated wastewater can
be effected by in situ and ex situ methods. Though
more expensive than in situ methods, PAH
contaminated can also be treated using bioreactors
(Bamforth and Singleton, 2005).
The first stage in the biodegradation of PAHs
involves the incorporation of oxygen at two carbon
atoms of a benzene ring of the PAH molecule by
dioxygenase resulting in the formation of cis
dihydrodiol. This intermediate compound undergoes
rearomatisation in the presence of dehydrogenase to
form dihydroxylated intermediates which
subsequently undergo ring cleavage (Samanta et al.,
2002). An appreciable number of PAH degrading
microorganisms including Alcaligenes denitrificans,
Mycobacterium sp., Pseudomonas putida, P.
fluorescens, P. paucimobilis, P. vesicularis, P.
cepacia, P. testosteroni, Rhodococcus sp.,
Corynebacterium venale, Bacillus cereus, Moraxella
sp., Streptomyces sp., Vibrio sp. and Cyclotrophicus
sp. have been isolated and tested for mineralisation
(Hedlund and Staley, 2001).
Yu et al. (2005) compared the efficiency of
degrading a PAH mixture by three bioremediation
strategies, namely natural attenuation,
bioaugmentation and biostimulation, in a mangrove
microcosm. The study evaluated the population sizes
116
of PAH degraders, the fate and mass balance of PAH
compounds under these three strategies. They reported
that natural attenuation may be a more suitable
remediation strategy for the degradation of Fluorene
and Phenanthrene while biostimulation was more
suited to the degradation of pyrene. They further
suggested that the nature of the target pollutant should
be considered when choosing a suitable remediation
strategy. Owabor and Aluyor, (2008) applied a
combination of adsorption and biodegradation in the
abatement of a PAH, anthracene. They reported
significant reductions in the concentration of
anthracene in the course of treatment. They further
observed that the percentage reduction in the
concentration of anthracene was proportional to the
temperature of activation of the adsorbent with almost
100% reduction recorded at a temperature of 900oC.
San Miguel et al. (2009) investigated the
bioremediation of naphthalene in water by bacterial
populations of Sphingomonas paucimobilis using a
new biodegradable surafactant based on poly ( -
caprolactone). They reported up to 90% reduction in
the concentration of naphthalene in solution after 140
hours of incubation time. Furthermore, they observed
that the addition of poly caprolactone based surfactant
did not interfere with the mineralisation of
naphthalene in solution. Ting et al. (2011) studied the
biodegradation of two polycyclic aromatic
hydrocarbons, phenanthrene and pyrene by a white rot
fungus, Ganoderma lucidum. They reported that over
90 and 85 % of phenanthrene and pyrene respectively
were degraded. They further noted that the addition of
copper sulphate (CuSO4,) citric acid, gallic acid,
tartaric acid, veratryl alcohol, guaiacol, 2,2-azino-bis-
(3- ethylbenzothazoline-6-sulfonate) (ABTS)
enhanced the degradation of both PAHs and laccase
activities; whereas the supplement of oxalate, di-n-
butyl phthalate (DBP), and nonylphenol (NP)
decreased the degradation of both PAHs and inhibited
laccase production. Janbandhu andJanbandh, (2011)
isolated and characterised a high efficiency PAH
degrading microbial consortium from a 3 decade old
petrochemical refinery field. Results of
biodegradation studies revealed 100, 56.9 and 25.8%
degradation at concentrations of 100, 250 and 500
mg/L respectively within 14 days. They further
indicated that the microbial consortium holds great
promise for the bioremediation of petrochemical
contaminated environments. Lin et al. (2010) studied
the biodegradation of naphthalene in cultured medium
using bacterial strains isolated from oil refining
sludge. They recorded a degradation efficiency of
more than 99% during a treatment period of 96 hours
under optimum conditions reported as initial
naphthalene concentration of 50 mg/L, temperature of
30 C, pH of 7.0, 0.2% inoculum size and C/N ratio of
 Amenaghawon and Obahiagbon
Wastewater Treatment by Bioremediation Methods
1.0. Bamforth and Singleton, (2005) reported that
several environmental factors including pH and
temperature of the medium, nutrient and oxygen
availability and the bioavailability of the contaminant
can affect the bioremediation process by inhibiting the
growth of PAH degrading microorganisms.
6. BIOREMEDIATION OF HEAVY METALS
POLLUTED WASTEWATER
Heavy metals are elements such as cobalt, nickel,
chromium, copper, iron, lead, manganese, arsenic,
molybdenum, vanadium, strontium, and zinc having
atomic weights between 63.5 and 200.6. They are
referred to as heavy because the metal ions have
specific gravity greater than 5 g/L (Chen and Wang,
2008; Srivastava and Majumder, 2008). Living
organisms require trace amounts of some of these
metals such as cobalt, copper, iron, manganese,
molybdenum, zinc etc for specific metabolic
activities. However, some of these metals particularly,
lead; arsenic, chromium, nickel, cadmium, mercury,
antimony etc are very toxic and carcinogenic to living
organism (Srivastava and Majumder, 2008).
Increased use of metals and chemicals in process
industries has led to the generation of large quantities
of wastewater containing high concentrations of these
toxic heavy metals. The most common sources of
heavy metal polluted wastewater include
electroplating and metal finishing plants, mining,
nuclear and electronics industries (Ahluwalia and
Goyal, 2007; Costley and Wallis, 2001). Heavy metals
contamination has become a serious environmental
problem today because of the health risks posed to
humans and animals from exposure as a result of their
toxicity. This problem is heightened by the fact that
the toxicity of these metals can last for a long time in
the environment. Some of the metals can undergo
transformation from relatively less toxic forms to
more toxic forms. The concentration of some of the
metals can increase in the environment over the
course of time through bioaccumulation and
bioaugmentation and more importantly some of the
metals are toxic even in low concentrations (Chen and
Wang, 2008).
Environmental scientists and researchers are
therefore faced with the task of developing suitable
and sustainable strategies for treating heavy metals
contaminated effluents. Conventional methods for
treating heavy metals contaminated effluents include
ion exchange, precipitation, reverse osmosis,
adsorption, electro dialysis, ultra filtration, chemical
oxidation or reduction (Adebayo et al., 2012;
Ahluwalia and Goyal, 2007; Congeevaram et al.,
2007; Kadirvelu et al., 2002; Zouboulish et al., 2004).
The application of these methods is limited on
117
economic grounds as they are expensive when used
for the treatment of low concentration heavy metal
solutions. In addition, these methods are not very
effective and they often lead to the production of toxic
sludge and its disposal becomes another challenge
both environmentally and economically (Adebayo et
al., 2012; Chen and Wang, 2008; Schiewer and Patil,
2008). This has led to the search for effective,
economically viable and sustainable alternatives.
Over the last two decades, biological approaches to
the decontamination of heavy metals polluted sites
have been examined. Biosorption involves the use of
biological materials of microbial and plant origin to
remove heavy metals from contaminated water. These
materials are able to effectively interact with heavy
metals in solution and as a result of their unique
chemical composition; they are able to remove these
metals from solution. Biosorption is a cost effective
strategy for the treatment of high volume wastewaters
contaminated with low concentrations of heavy metals
(Chen and Wang, 2008; Costley and Wallis, 2001). In
addition, the biomaterials are usually readily available
and cheap and the process does not lead to the
generation of further waste products like conventional
physicochemical methods. Varieties of
microorganisms like bacteria, algae, yeasts, and fungi
have been used as biosorbent and studied extensively
(Chen and Wang, 2008). In the same vein, a lot of
agricultural materials have been examined for their
potential to remove heavy metals from solutions
(Babarinde et al., 2008).
Davis et al. (2003) and Wang and Chen. (2006)
reviewed the biosorption of heavy metals by algae and
Saccharomyces cerevisiae respectively. Whitehead et
al. (2005) investigated the potential of natural
attenuation for the bioremediation of acid mine
drainage. They reported iron oxidation and removal of
other important toxic metals using the indigenous
microbial populations. Costley and Wallis, (2001)
utilised a rotating biological contactor for the
bioremediation of heavy metals in a synthetic
wastewater. They used immobilised microorganisms
to treat heavy metal contaminated waters using
multiple sorption-desorption cycles. The results they
obtained suggested that the rotating biological
contactor can be used for the successful treatment of
high strength contaminated wastewaters.
Congeevaram et al. (2007) investigated the
biosorption of chromium and nickel using heavy
metal resistant fungal and bacterial populations
isolated from soil samples in an electroplating
industry environment. The isolated microorganisms
were characterised to evaluate their applicability for
heavy metal removal from industrial wastewater.
Their results indicated that extended residence times
in the stationary phase can be recommended while
 Wastewater Engineering: Advanced Wastewater Treatment Systems
Chapter 5: Wastewater Treatment by Bioremediation Technologies
using the fungal and bacterial chromium resistant
isolates for removing chromium. In the case of Nickel
resistant bacterial isolate, a non-extended residence
time was recommended for designing continuous-flow
completely stirred (CFCS) bioreactor so that a mid-
log phase of cellular growth can be kept during the
bioaccumulation process.
Li et al., (2004) studied uranium biosorption using
powdered biomass of lake harvested water bloom
cyanobacterium Microcystis aeruginosa. They
reported batch equilibrium time of 1 hour and an
optimum biosorption pH of 4-8. The biosorption
process was well described by the Freunlich isotherm
model. The study showed that the abundant otherwise
nuisance constituting biomass show a great promise
for application in removal of uranium from
wastewaters. Padilha et al. (2005) used waste biomass
of Sargassum sp. for the removal of copper from
simulated semiconductor wastewater using a
continuous system made up of four biomass filled
column reactors. Starting with different volumes of
different copper solutions with the same copper
concentration of 500mg/L, they reported that the
adopted treatment method resulted in an effluent
containing less than 0.5g/L of copper. Adebayo et al.
(2012) investigated the batch biosorption of lead from
aqueous solution using Streblus asper leaves. They
determined the optimum conditions of biosorption in
terms of initial lead concentration, contact time,
temperature, biosorbent dose, and pH. Results of
thermodynamic studies indicated that the biosorption
process was spontaneous, endothermic and there was
increased entropy at the solid-solution interface.
Results of isotherm studies indicated that the process
was well described by the Langmuir, Tempkin, and
DubininRadushkevich isotherms. Kinetic studies
revealed that the process was well described by the
pseudo second-order, intra-particle diffusion and
Elovich kinetic models. Babarinde et al. (2012)
reported the biosorption of nickel, chromium and
cobalt on cocoyam leaves. They observed that the
biosorption process was pH dependent. The process
was well described by the pseudo-second order kinetic
model. Thermodynamically, the biosorption of each of
nickel and chromium was found to be endothermic
while that of cobalt was determined to be exothermic.
The biosorption of each metal ion was also
determined to be spontaneous and the order of
spontaneity of the biosorption process was
cobalt>nickel>chromium. They further reported
positive change in entropy for each metal and the
order of disorder was nickel>cobalt >chromium.
Lodeiro et al. (2005) investigated the potential use
of five different brown seaweeds, Bifurcaria
bifurcata, Saccorhiza polyschides, Ascophyllum
nodosum, Laminaria ochroleuca and Pelvetia
118
caniculata for the removal of cadmium from aqueous
solutions. They observed that the biosorption process
was relatively fast with about 90% removal of
cadmium occurring within 1 hour. Chen and Wang,
(2008) investigated the removal of lead, silver,
caesium and strontium from aqueous solution using
brewery's waste biomass. Their results revealed that
the biosorption process was rapid and was well
described by the pseudo second order kinetic and
Langmuir isotherm models. Ho, (2005) investigated
the biosorption of lead using tree fern in a baffled
agitated system. The optimum pH for lead removal
was determined to be 4.9. The pseudo second order
kinetic model sufficiently described the kinetics of the
biosorption process. Bishnoi et al. (2004) studied the
removal of chromium from aqueous solutions using
activated rice husk and activated alumina while Garg
et al. (2004) studied the removal of chromium from
aqueous solution using formaldehyde treated saw dust
and saw dust carbon activated with sulphuric acid. In
both studies, results obtained indicated that the degree
of chromium removal was proportional to the dosage
of the adsorbent used and their contact time. All the
works done by these researchers show that biosorption
utilizing microorganism and agricultural materials
offer an ideal alternative for the treatment of heavy
metal polluted water.
7. MICROORGANISMS IN BIOREMEDIATION
The ability of microorganisms to utilise natural and
synthetic pollutants as substrate for growth is a very
important quality upon which bioremediation is based.
A lot of work is still ongoing in the area of isolation,
identification and characterisation of microorganisms
and their potential for bioremediation. Reports
suggests that more work still needs to be done to
explore microbial diversity with a view to identifying
microorganisms with specific and unique qualities
vital to bioremediation.
Microorganisms indigenous to the site of
contamination have been utilised in various
bioremediation processes. Information on microbial
populations relevant to bioremediation is building up
at a fast pace as a result of recent advances in
molecular microbial ecology (Watanabe, 2001). This
has made available new tools that makes it possible to
carry out molecular analyses of microbial populations
at contaminated and bioiremediation sites.
Microorganisms can be isolated from virtually any
environmental condition as they are able to adapt even
in very extreme conditions of temperature, oxygen,
water, pH etc. The major requirement for growth is an
energy and a carbon source. The ability of
microorganisms to adapt is what makes them very
versatile in the bioremediation of contaminated sites
 Amenaghawon and Obahiagbon
Wastewater Treatment by Bioremediation Methods
(Sharma, 2012). These microorganisms can be divided
into the following groups:
(a) Aerobic microorganisms or aerobes carry out
metabolic activities in the presence of oxygen. They
require oxygen to oxidise susbtrates through cellular
respiration. Examples of aerobic microorganisms with
the capacity for biodegradation include Pseudomonas,
Alcaligenes, Sphingomonas, Rhodococcus, and
Mycobacterium (Giavasis et al., 2006). These
microorganism have been reported to possess the
capacity to degrade organic pollutants such as
aliphatic hydrocarbons, polycyclic aromatic
hydrocarbons, pesticides etc. (Vidali, 2001).
(b) Anaerobic microorganisms can carry out
metabolic activities in the absence of oxygen. They
are not as common in use compared to aerobic
microorganisms. However, there is an increasing
interest in the use of anaerobic microorganisms for the
biodegradation of polychlorinated biphenyls (PCBs)
in river sediments and the dechlorination of the
solvent like trichloroethylene (TCE), and chloroform
(Sharma, 2012).
(c) Ligninolytic fungi such as white rot fungus like
Phanaerochaete chrysosporium have been reported to
have the ability to degrade an extremely diverse range
of recalcitrant and toxic contaminants. (Adenipekun
and Fasidi, 2005).
(d) Methylotrophs are aerobic bacteria that utilise
methane for metabolic activities. They have the ability
to degrade a wide range of organic contaminants such
as chlorinated aliphatic trichloroethylene and 1,2-
dichloroethane.
For efficient biodegradation, it is important that the
microorganism and the target contaminant be in
intimate contact. . This can be enhanced by making
use of some surfactants such as sodium dodecyl
sulphate (SDS).
8. FACTORS OF BIOREMEDIATION
A host of factors can affect the extent and
effectiveness of bioremediation. These factors are
environmental in consideration and include the
availability of nutrients and oxygen. These can be
readily manipulated using effective biostimulation
strategies. Other factors include temperature and pH
of the remediation medium. These however are not
easily controllable.
8.1. Nutrients
Microorganisms need nutrients to survive. These
nutrients are the basic building blocks of living things
and enable microorganisms to carry out metabolic
activities needed for the breakdown of contaminants
during bioremediation. All microorganisms need
119
carbon, nitrogen and phosphorus and some others in
lesser amounts but carbon is needed in greater
proportions than the others. These nutrients are often
present in wastewater stream but not in the proportion
required by the cells for optimum metabolic activities.
The lack of nitrogen and phosphorus limits the rate of
biodegradation. In the light of this, it becomes
important to ensure adequate supply of these
important nutrients to enhance biodegradation rates.
This is usually accomplished through biostimulation
which involves the addition of limiting nutrient such
as nitrogen and phosphorus to the wastewater stream.
Biostimulation has been reported to enhance the
biodegradation of organic pollutants (Obahiagbon et
al., 2009; Otokunefor and Obiukwu, 2010)
8.2. Oxygen
This is one of the most important requirements for
microbial degradation. Most wastewater treatment
facilities adopt aeration based treatment strategies. In
such cases, the availability of oxygen becomes a
critical factor. Oxygen is generally necessary for the
initial degradation of oil, and subsequent reactions
may also require direct incorporation of oxygen.
Typically, 3 to 4 parts of dissolved oxygen are
necessary to completely oxidize 1 part of oil into
carbon dioxide and water (Giavasis et al., 2006).
Though anaerobic degradation of oil in wastewater
can occur, it is however in very small degrees. For oil
spills on the ocean surface, oxygen is not usually a
factor that limits the rate of biodegradation as there is
plentiful supply of oxygen close to the surface of the
ocean. However, inadequate supply of oxygen limits
the extent of biodegradation. This is the reason why it
takes longer to degrade oil that has sunk below the
surface of the water.
8.3. Temperature
Temperature is another important environmental
factor that affects the rate of bioremediation. In the
same way that chemical reactions are affected by
temperature, biochemical reactions upon which the
process of bioremediation is based are also
temperature dependent. A temperature increase results
in a decrease in viscosity of liquid organic pollutants,
consequently affecting the degree of distribution and
increasing diffusion rates of the compounds.
Typically, an increase in temperature favours the
biodegradation reaction. However, above a certain
optimum temperature which is organism specific, the
activity of the microorganism begins to slow and they
subsequently die. Hence it is important to identify this
optimum and ensure that bioremediation operations
are maintained at that temperature.
 Wastewater Engineering: Advanced Wastewater Treatment Systems
Chapter 5: Wastewater Treatment by Bioremediation Technologies
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Wastewater Engineering: Advanced Wastewater Treatment Systems
Available online at http://www.ijsrpub.com/books
2014 IJSRPUB

Supplementation of Novel Solid Carbon Source Prepared from Dried Attached-

Growth Biomass for Bioremediation of Wastewater Containing Nitrogen
Jun-Wei Lim, Mohammed J.K. Bashir*, Choon-Aun Ng, Xinxin Guo

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. The main objective of this study is to validate the feasibility of using dried attached-growth biomass from the
polyurethane (PU) foam cubes as a solid carbon source for the enhancement of denitrification process in the intermittently
aerated moving bed sequencing batch reactor (IA-MBSBR). The IA-MBSBR packed with PU foam cubes coated with dried
attached-growth biomass could maintain approximately 80% of total nitrogen (TN) removal efficiency for 8 consecutive cycles
of operation. Subsequently, the exhausted stored carbon source within the PU foam cubes could be replenished by merely
drying the fresh attached-growth biomass formed when the cubes were used as a carbon source. Thus, the reuse/recycle of
biomass-coated PU foam cubes is possible, making it a sustainable solid carbon source for the enhancement of denitrification
process in bioremediating wastewater containing nitrogen-cum-low COD/N via IA-MBSBR.

Keywords: Bioremediation, Wastewater, Solid Carbon Source

1. INTRODUCTION improper sewage treatment and disposal. In some

It is undeniable that water is an indispensable element
for survival of all living creatures. Although the
Earth's surface is virtually covered with 70% of water,
its presence is not limitless. Of all the water, 97%
consist of salt water which is unacceptable for the
direct human consumption. To top it off, of the
remaining 3% of potable water, only about 15% is
easily accessible, e.g., rivers, streams, creeks, ponds,
etc., and about 85% is found in ice floes and glaciers,
neither of which are readily accessible (Sills, 2003).
Owing to the tremendous increase of human growth in
recent decades, water scarcity has emerged as one of
the dire issue for communities across the country. In
United States, almost all the region of the country has
experienced water shortages in the last five years
(USEPA, 2008). As per United Nations, every day
approximately 4400 children under the age of five die
because of diseases cause by contaminated water
ingestion and sanitation (Ghaitidak and Yadav, 2013).
In a third worlds population, one in every six persons
has no access to clean water within a kilometer of
reach (Ghaitidak and Yadav, 2013). In parts of Asia
and Africa, it was estimated that the people under a
threshold of water stress, i.e., accessible of renewable
water resources <1700 m3/person/year, would surge to
three billion by 2025 (FAO, 2012; WHO, 2012;
Ghaitidak and Yadav, 2013).
Globally, although the storage of potable water is
getting lesser due to the excessive consumption, the
problem of potable water contamination particularly
the groundwater and surface water with nitrate is
inevitable. The nitrate pollution is mainly caused by
the intensive use of nitrogen-based fertilizers in
agriculture and irrigation with ammonia-rich effluents
discharged by wastewater treatment plants and
125
industrial activities such as fossil fuels combustion
and fertilizers, explosive, glass, plastics and foods
productions also can contribute to nitrate pollution
(Robinson-Lora and Brennan, 2009; Wang et al.,
2013). In nature, the concentrations of nitrate in
groundwater are usually less than 2 mg/L (Mueller et
al., 1995). However, in contaminated areas, nitrate
concentrations can exceed 200 mg/L (ITRC, 2002).
The Water Quality Assessment program of the US
Geological Survey reports that nitrate is the pollutant
that most frequently exceeds its standard limits
(Squillace et al., 2002). The main health effect
associates to the ingestion of water contaminated with
high concentration of nitrate are the occurrence of
methemoglobinemia notably in infants or blue-baby
syndrome. Some studies have demonstrated that
nitrate can be endogenously reduced to nitrite, which
can then undergo nitrosation reactions in the stomach
with amines and amides to form various N-nitroso
compounds, most of which are extremely
carcinogenic (WHO, 2004; Yang et al., 2007). On that
account, appropriate standards have been set by
various agencies. The USEPA (2000) has set the
maximum contaminant levels of 10 and 1 mg/L for
nitrate-nitrogen (NO3--N) and nitrite-nitrogen (NO2--
N), respectively, in drinking water. The World Health
Organization and European Economic Community
have set the standards of 11.3 mg/L for NO3--N which
are later adopted as national standard for drinking
water by most of the countries in the world (Wang,
2013). Therefore, for the sake of fulfilling the
standards requirement, the discharge wastewater
containing nitrate must be stringently treated before
releasing to the environment in order to minimize the
possibilities of contamination of potable water with
nitrate.
 Lim et al.
Supplementation of Novel Solid Carbon Source Prepared from Dried Attached-Growth Biomass for Bioremediation of
Wastewater Containing Nitrogen
Various technologies have been used to treat
wastewater containing nitrate. These include ion-
exchange, electrodialysis, photocatalytic reduction of
nitrate, reverse osmosis, etc (Kesore et al., 1997;
Schoeman and Steyn, 2003; Kim and Benjamin, 2004;
Yang et al., 2013). Of these, biological denitrification
has been proven to be the most cost effective and
environmentally sound technique by many researchers
particularly in treating large quantity of wastewater
containing nitrate (Robinson-Lora and Brennan, 2009;
Wang and Wang, 2009). Biological denitrification is a
natural process that is part of the nitrogen cycle, and is
commonly exploited in the wastewater treatment plant
for the removal of nitrate. The term denitrification
was first used in France in 1886 to describe the use of
nitrate and nitrite (oxidized nitrogen) to biodegrade
substrate (Gerardi, 2002). The process of
denitrification can be accomplished by a wide range
of facultative anaerobes which make up an
approximately 80% of the bacteria in the activated
sludge system. The largest numbers of facultative
anaerobes that are capable of performing the
denitrification process are from Alcaligenes, Bacillus
and Pseudomonas genera (Gerardi, 2002). Besides,
the facultative anaerobes that denitrify are also termed
by several names including denitrifying bacteria,
denitrifiers, heterotrophs and organotrophs. During
the denitrification process, nitrate is reduced to nitrite
and subsequently to nitrogen gas by means of the
action of denitrifying bacteria in accordance with the
following sequence (Gerardi, 2002):
Nitrate ion (NO3-) Nitrite ion (NO2-) Nitric
oxide (NO) Nitrous oxide (N2O) Ntrogen gas
(N2)
Each step of the denitrification process is
fundamentally regulated by the specialized reductase
enzymes of the denitrifying bacteria. The nitrate is
initially reduced to nitrite by the nitrate reductase
enzyme. This enzyme is a highly soluble membrane-
bound molybdoprotein which is only produced in the
presence of nitrate and its concentration synthesized is
directly proportional to the concentration of nitrate
(Downey, 1966; Bryan, 1981; Payne, 1985; Gerardi,
2002; Gardner, 2008). In the second step of
denitrification process, the nitrite is further reduced to
nitric oxide which is regulated by nitrite reductase
enzyme found in the periplasm of the denitrifying
bacteria (Gerardi, 2002; Kumar and Lin, 2010). The
nitric oxide is then swiftly reduced to nitrous oxide by
the nitric oxide reductase enzyme, a membrane bound
protein (Bryan, 1981; Payne, 1985; Gerardi, 2002;
Kumar and Lin, 2010). In the final step of
denitrification process, the nitrous oxide reductase
enzyme, a periplasmic copper-containing protein,
reduces the nitrous oxide to nitrogen gas before it is
126
being released to the atmosphere (Payne, 1985;
Gerardi, 2002; Kumar and Lin, 2010).
The prerequisite for the commencement of
denitrification process is the availability of strictly
anoxic environment. This is because the energy
harvested through the aerobic respiration of substrate
is greater than the energy obtained through anoxic
respiration for the growth of denitrifying bacteria. The
examples of quantity of energy produced via the
aerobic and anoxic oxidations of glucose are shown in
Eqs. 1 and 2, respectively (Gerardi, 2002):
C6H12O6 +6O2 6CO2 + 6H2O + 686 kcal (1)
C6H12O6 + 4.8NO3- + 4.8H+ 6CO2 + 2.4N2 +
8.4H2O + 636kcal (2)
In terms of energy point of view, i.e., more
negative Gibbs free-energy value, oxygen is a more
favorable electron acceptor than either nitrate or
nitrite during the respiration of similar substrate
(Lens, 2005), vindicating the dominant selection of
oxygen species over the oxidized nitrogen. In
addition, the synthesis and activity of all
denitrification enzymes are also adversely affected in
the presence of oxygen with nitrous oxide reductase
being the most sensitive denitrification enzymes and it
is inhibited by the dissolved oxygen (DO)
concentrations of less than 0.2 mg/L (Kumar and Lin,
2010). Thus, it is important to ensure the anoxic
environment exists with the redox potential of less
than +50 mv (negligible detection of DO
concentration in the measured environment) so as to
kindle the denitrification process (Gerardi, 2002). This
obligation is crucial since the presence of oxygen has
a direct impact on the usage of substrate in which the
oxygen is selected as an electron acceptor during the
substrate respiration instead of nitrate, leading to the
wastage of the added substrate for the enhancement of
denitrification process. Also, the objective of
removing nitrate from the wastewater remains
unfulfilled as the denitrification process is retarded in
the aerobic environment.
Another factor which is also playing an important
role during the denitrification process is the substrate
used as the reducing agent in reducing nitrate to
nitrogen gas. In this case, organic carbon source is
commonly used as an electron donor and its
characteristic has an imperative effect on denitrifying
bacteria performing the denitrification process. In
general, the denitrifying bacteria will use organic
carbon source found in the wastewater in performing
the denitrification process. This category of carbon
source is termed as internal carbon source. However,
in treating wastewaters containing low COD/N ratio,
e.g., supernatants from sludge digesters and
stabilization ponds as well as pretreated industrial
 Wastewater Engineering: Advanced Wastewater Treatment Systems
Chapter 5: Wastewater Treatment by Bioremediation Technologies
wastewaters by anaerobic fermentation, carbon source
is frequently added in order to stimulate the
denitrifiation process; and this category of carbon
source is termed as external carbon source. The
external carbon source can be further subdivided
depending on their physical phases, namely liquid
carbon source and solid carbon source. In recent
Fig. 1: Tree diagram presenting category of carbon sources used for denitrification process
1.1. Solid Carbon Source for Denitification Process
Liquid carbon sources such as ethanol, methanol,
acetate or glucose are normally added during the
denitrification process. However, the disadvantages of
this approach are the risk of overdosing which would
deteriorate the effluent quality, leading to the
requirement of using a sophisticated and costly
process control (Hiraishi and Khan, 2003; Zhou et al.,
2009; Shen and Wang, 2011). In recent years, the use
of solid carbon sources as an alternative to liquid
carbon sources has gained increasing momentum of
interests among the researchers (Robinson-Lora and
Brennan, 2009; Wang and Wang, 2009; Zhou et al.,
2009; Zhou et al., 2009a; Shen and Wang, 2011; Fan
et al., 2012). The solid carbon sources packed in the
bioreactors perform two important tasks, namely to
serve as a reducing agent in denitrification process
and to act as a support media for biofilm formation
(Wang and Wang, 2009; Zhou et al., 2009a). The
presence of constant carbon sources and anoxic zones
within the deeper layers of the biofilm as well as in
the porous structure of the solid carbon sources would
ensure a stable reduction of the oxidized nitrogen
(Walters et al., 2009; Wang and Wang, 2009; Zhou et
al., 2009a). Hence, the use of an expensive and
sophisticated system control can be avoided as the
addition of liquid carbon sources is no longer
127
years, the research on the solid carbon source used for
the denitrification process has gained increasing
momentum among the researchers and this carbon
source can be classified based on their origin, namely
synthetic and natural polymer carbon sources. Figure
1 shows all the organic carbon source categories as
above-mentioned in a tree diagram.
necessary. Generally, two types of solid carbon
sources, namely synthetic and natural polymers have
been studied. Synthetic polymers include
polycaprolactone (PCL) (Boley et al., 2000; Honda
and Osawa, 2002; Zhou et al., 2009), polylactic acid
(PLA) (Fan et al., 2012), polyhydroxyalkanoates
(PHA) (Boley et al., 2000; Hiraishi and Khan, 2003)
and bionolle (Boley et al., 2000) whereas, natural
polymers include wheat straw (Soares and Abeliovich,
1998; Fan et al., 2012), cotton (Rocca et al., 2005),
biodegradable meal box (Wang and Wang, 2009) and
crab-shell chitin (Robinson-Lora and Brennan, 2009).
Since the rate of denitrification is closely related to
the biodegradability of the solid carbon source
(Hiraishi and Khan, 2003), the use of natural polymers
which are more likely to be biodegraded than
synthetic polymers is expected to attain higher
denitrification rates than synthetic polymers. In fact,
Wang and Wang (2009) had proved that the rate of
denitrification by using biodegradable meal box was
higher than PCL.
Fan et al. (2012) had also revealed that faster
biofilm development and higher denitrification rate
could be achieved when wheat straw was utilized as a
solid carbon source as compared to PLA. From an
economic point of view, the relatively high cost of
using synthetic polymers such as PCL and bionolle
limits its extensive application especially in treating
 Lim et al.
Supplementation of Novel Solid Carbon Source Prepared from Dried Attached-Growth Biomass for Bioremediation of
Wastewater Containing Nitrogen
large quantity of wastewater (Walters et al., 2009;
Chu and Wang, 2011). Zhou et al. (2009) estimated
that a denitrification system using
polyhydroxybutyrate (PHB) costs almost ten times
higher than a traditional system using methanol. As
natural polymers such as cotton and wheat straw are
easily available and they can achieved higher
denitrification rate than synthetic polymers, the
application of solid carbon source using natural
polymers have gained priority over that of synthetic
polymers.
Nevertheless, in order to maintain the efficiency of
denitrification, the addition of fresh natural polymers
after certain period of operation is necessary. Soares
and Abeliovich (1998) reported that a weekly addition
of fresh wheat straw could be seen preventing the
deterioration of denitrification performance.
Moreover, for some natural polymers such as crab-
shell chitin, the content of soluble components such as
volatile fatty acids and chloride, sulphate and
ammonium ions are very high. Robinson-Lora and
Brennan (2009) illustrated that an initial flushing
period of 3 days was needed before the crab-shell
chitin could be used as a solid carbon source to reduce
the concentrations of soluble components in the
treated effluent. Consequently, as a result of frequent
addition or replacement of such solid carbon sources,
more time is required to be spent on flushing. In
addition, post-treatment system such as trickling sand
filter or powdered activated carbon adsorption have to
be installed to remove colour and organic matter
released particularly from fresh natural polymers
(Soares and Abeliovich, 1998; Rocca et al., 2005).
Thus, it is essential to find an alternative natural
material which can serve as a solid carbon source
without releasing soluble components.
Qiao et al. (2008) reported that the potential of
attached-growth biomass in oxidizing NH4+-N was
lower than the suspended-growth biomass as the
Ammonium Oxidizing Bacteria (AOB)s mobility was
more restricted in the attached state, leading to
lessened contact possibility between AOB and NH4+-
N. For this reason, the attached-growth biomass
formed onto and into the support media in the
bioreactor could be utilized to serve as a solid carbon
source for the denitrification process. These days, the
research activities have only focused on the reuse of
suspended-growth biomass or sludge as a carbon
source (Ra et al., 2000; Kampas et al., 2007; Soares et
al., 2010). The use of dried attached-growth biomass
as a solid carbon source has not been thoroughly
reported in the literature. Therefore, the possibility of
using dried attached-growth biomass formed onto and
into the support media as a solid carbon source for the
denitrification process in the bioreactor deserves more
128
research attentions. On that account, the main
objective of this study is to investigate the feasibility
of using this dried attached-growth biomass as a solid
carbon source for the denitrification process
enhancement in an intermittently aerated moving bed
sequencing batch reactor (IA-MBSBR).
2. METHODOLOGY
2.1. Set-up of Bioreactor and Operation
A sequencing batch reactor (SBR) was initially set-up
and operated with a cycle time of 24 h in the
following sequencing periods: instantaneous FILL, 0
h; REACT, 12 h; SETTLE, 1.5 h; DRAW, 1 h and
IDLE, 9.5 h. The REACT phase was operated with
cyclical intermittent aeration (IA) strategy which
began with 1 h of aeration period followed by 1 h of
non-aeration period. The activated sludge collected
from municipal sewage treatment plant was cultured
in this SBR and fed with synthetic wastewater
simulating the municipal wastewater composition
with NH4+-N and COD concentrations of
approximately 48 and 200 mg/L, respectively. The
instantaneous addition of adequate amount of ethanol
solution to serve as a carbon source was carried out at
the beginning of the last non-aeration period in every
cycle to reduce the oxidized nitrogen to N2. At the end
of the REACT period, mixed liquor was wasted to
maintain the sludge age of suspended-growth biomass
at 40 days. During the DRAW period, the supernatant
or treated effluent was drawn out with an exchange
volume of the reactor being retained at 70.3%. The
residual settled solids in the reactor were left to rest
throughout the IDLE period in preparation for the next
cycle.
Upon achieving the quasi-steady state, the SBR
with integrated IA strategy was converted to IA-
MBSBR by packing with 8% (v/v) of 8-mL
polyurethane (PU) foam cubes as the support media.
Figure 2 shows the laboratory set-up of IA-MBSBR
packed with PU foam cubes. After the PU foam cubes
were cultured for 4 consecutive cycles in the IA-
MBSBR, they were taken out of the reactor and
replaced by a new batch of 8% (v/v) of 8-mL PU
foam cubes. The PU foam cubes with the attached-
growth biomass was dried in the oven at 60 oC and
weighed. The dried foam cubes were then introduced
back into the reactor whilst the batch in the reactor
was taken out for drying and weighing. This process
was repeated until the weight of the PU foam cubes
with dried attached-growth biomass reached a
constant value and this cubes with dried attached-
growth biomass were later used in the studies
hereafter this section.
 Wastewater Engineering: Advanced Wastewater Treatment Systems
Chapter 5: Wastewater Treatment by Bioremediation Technologies
Fig. 2: Laboratory set-up of IA-MBSBR packed with PU foam cubes, (a) side view and (b) top view of the bioreactor.
2.2. Assessment of IA-MBSBR Performance Using
PU foam Cubes with Attached-Growth Biomass
The evaluation of IA-MBSBR using PU foam cubes
with dried attached-growth biomass involved 4-cycle,
6-cycle, 8-cycle, 10-cycle and 12-cycle operational
modes and every mode was repeated twice. In the 4-
cycle mode, the batch of PU foam cubes which had
achieved a constant dried weight was put back into the
IA-MBSBR for 4 cycles. At the end of the operational
mode, the foam cubes were taken out for drying at 60
o
C and could be reused again as recycled PU foam
cubes with dried attached-growth biomass to complete
another 4-cycle operational mode. During the first and
fourth cycles of this operational mode, time courses of
nitrogen species (NH4+-N, NO2--N and NO3--N)
concentrations during the REACT period were
analyzed. Similarly, for the 6-, 8-, 10- and 12-cycle
modes, the PU foam cubes with dried attached-growth
biomass of constant dried weight were also replaced
by the recycled PU foam cubes with dried attached-
growth biomass at the end of the respective mode. The
performance data were collected for the first and last
cycles of each operational mode.
129
2.3. Investigation of the Optimum IA Strategy and
Selection of the Optimum Operational Mode
The study as described in Section 2.2 allows the
optimum operational mode to be ascertained based on
the IA strategy of consecutive 1 h of aeration period
followed by 1 h of non-aeration period (1:1 IA
strategy). This operational mode was adopted for the
determination of the optimum IA strategy in the
experiment conducted in this section. The time
courses of the concentrations of nitrogen species
during the REACT period of the IA-MBSBR without
the instantaneous addition of ethanol solution were
determined using the 1:1, 1:2 and 1:3 IA strategies.
3. RESULTS AND DISCUSSIONS
The total weight of attached-growth biomass in the
PU foam cubes saturated with attached-growth
biomass was found to be 58 g (constant dried weight
of total attached-growth biomass). The Scanning
Electron Microscope (SEM) images show that the
attached-growth biomass shrank and adhered closely
to the surface of PU foam cubes when it was dried to
constant weight as shown in Figure 3 (c). Figure 3 (b)
shows that the fresh attached-growth biomass could
be instantly formed on the surface of dried biomass-
coated PU foam cubes after only one cycle in the IA-
MBSBR.
 Lim et al.
Supplementation of Novel Solid Carbon Source Prepared from Dried Attached-Growth Biomass for Bioremediation of
Wastewater Containing Nitrogen

Fig. 3: SEM images of (a) fresh PU foam cube, (b) fresh attached-growth biomass formed on the surface of dried biomass-
coated PU foam cubes after one cycle in the IA-MBSBR and (c) dried biomass-coated PU foam cubes all with 150X
magnification and captured at WD of 7 mm using EHT and signal of 5.00 kV and SE2, respectively.

3.1. Optimum Operational Mode Based on 1:1 IA
Strategy
The selection was based on the performance of IA-
MBSBR packed with dried biomass-coated PU foam
cubes during the REACT period under different
operational modes based on 1:1 IA strategy. The
concentration profiles of the nitrogen species during
the REACT period of the IA-MBSBR operating at 8-
cycle, 10-cycle and 12-cycle modes and using the 1:1
IA strategy with the addition of ethanol solution for
complete denitrification are shown in Figure 4.

Fig. 4: Profiles of nitrogen species concentrations during the REACT period for (a) first cycle of the 8-cycle operational mode,
(b) last cycle of the 8-cycle operational mode, (c) last cycle of the 10-cycle operational mode and (d) last cycle of the 12-cycle
operational mode under 1:1 IA strategy.

It should be noted that the results were the same
irrespective of whether dried biomass-coated PU foam
cubes of constant dried weight in the first run or
recycled dried biomass-coated PU foam cubes in
subsequent runs were used. Figure 4 (a) shows the
concentration profiles of nitrogen species for the first
cycle of the 8-cycle operational mode and it was
found that those of all the studied operational modes
of first cycle were the same. Figure 4 (b) to Figure 4
(d) show the concentration profiles of the monitored
parameters for the last cycles of the 8-cycle, 10-cycle
and 12-cycle operational modes, respectively. The
results for the last cycles of the 4-cycle and 6-cycle
operational modes were basically the same as those of
the 8-cycle mode. Figure 4 shows that, irrespective of
the first or last cycle of the operational modes, NH4+-

130
 Wastewater Engineering: Advanced Wastewater Treatment Systems
Chapter 5: Wastewater Treatment by Bioremediation Technologies
N was only completely removed in the fourth aeration
period. During the first three non-aeration periods, the
oxidation of NH4+-N was hindered due to the limited
supply of DO in the mixed liquor resulting in a
relatively flat region of the NH4+-N concentration
profile. In all cases, after the complete removal of
NH4+-N, the concentration of NO3--N was seen
decreasing gradually until the last non-aeration period
due to the occurrence of the denitrification process.
The NO3--N was then removed rapidly when the
ethanol solution was added during the last non-
aeration period to accelerate the denitrification
process. However, the rate of decrease of NO3--N
concentration was less for the last cycles of the 10-
cycle and 12-cycle modes [Figures. 4-c and 4-d)
compared to that of the 8-cycle mode (Figure 4-b).
Figure 5 shows the calculated total nitrogen (TN)
removal percentages in the REACT period prior to the
addition of ethanol solution for various operational
modes. It was observed that the TN removal
efficiency was fairly constant up to the 8-cycle
Fig. 5: TN removal efficiency for different operational modes under 1:1 IA strategy. Error bars indicate standard deviations.
3.2. Optimum IA Strategy Based on 8-Cycle
Operational Mode
Figure 6- a to 6-c show the concentration profiles of
nitrogen species during the REACT period of the IA-
MBSBR operating under 1:1, 1:2 and 1:3 IA
strategies, respectively. For all the three IA strategies,
the results of the monitored parameters concentration
profiles in the first cycle were basically similar to
those in the last cycle of the 8-cycle operational mode
Figure. 6. It was observed that the solid carbon source
in the prepared biomass-coated PU foam cubes was
insufficient to completely reduce the oxidized
nitrogen in cases involving 1:1 and 1:2 IA strategies.
As a result, the NO3--N was detected in the treated
effluents of these cases (Table 1). In the IA-MBSBR
operated with 1:1 IA strategy, two aeration periods
after the complete removal of NH4+-N (Figure. 6-a)
was unnecessary. In addition, the application of
131
operational mode but decreased sharply after that.
This indicates that the stored carbon source in the
prepared biomass-coated PU foam cubes had been
depleted to the level which could not sustain the same
TN removal efficiency after 8 consecutive cycles of
operation. Thus, replacement with new batch of
biomass-coated PU foam cubes after every 8
consecutive cycles in the IA-MBSBR was necessary
to avoid the deterioration of the denitrification
process. The depleted stored carbon source in the
biomass-coated PU foam cubes could be replenished
and reused again by drying the attached-growth
biomass formed when these cubes were used in the
IA-MBSBR. Of all the solid carbon sources reported
in the literature which were used to improve the
denitrification process (Soares and Abeliovich, 1998;
Walters et al., 2009; Fan et al., 2012), it was not
possible to reuse the solid carbon sources as these
biodegradable materials would be eventually
consumed by the microorganisms in long term
operation period.
excess aeration period would bring a negative impact
on the reduction of NO3--N as the NO2--N formed was
likely to be oxidized to NO3--N again rather than
being reduced to N2. As a consequence, the highest
effluent NO3--N concentration was detected with this
IA strategy resulting in the lowest percentage of TN
removal as compared to the other IA strategies (Table
1). Although the percentage of TN removal was the
highest in the IA-MBSBR operated with 1:3 IA
strategy (Table 1), the removal of NH4+-N was
incomplete due to inadequate aeration period Figure
6-c). In comparison, NH4+-N was completely removed
during the last aeration period in the IA-MBSBR with
1:2 IA strategy Figure -b; thus, avoiding the
subsequent unnecessary aeration period. In this case,
the NO3--N formed could be easily removed by adding
adequate ethanol solution during the last non-aeration
period. Therefore, the IA-MBSBR under 1:2 IA
strategy appears to be the optimum alternative.
 Lim et al.
Supplementation of Novel Solid Carbon Source Prepared from Dried Attached-Growth Biomass for Bioremediation of
Wastewater Containing Nitrogen

Fig. 6: Profiles of nitrogen species concentrations during the REACT period for the last cycle of the 8-cycle operational mode
under (a) 1:1, (b) 1:2 and (c) 1:3 IA strategies.

Table 1: Concentrations of NH4+-N and NO3--N in the treated effluent and percentages of TN removal in the IA-MBSBR
operated with 8-cycle mode.
Parameter IA strategy
1:1 1:2 1:3
Effluent NH4+-N concentration 0.0 0.0 6.4
(mg/L)
Effluent NO3--N concentration 10.7 7.1 0.0
(mg/L)
TN removal (%) 71 79 83

3.3. Proposed Methodology for Real Wastewater
Treatment Plant
This study has shown the potential of utilizing the
dried attached-growth biomass from the PU foam
cubes as a novel solid carbon source in enhancing the
denitrification process. When the PU foam cubes with
dried attached biomass was introduced into the reactor
to serve as the solid carbon source, the attached-
growth biomass would start forming on the surface of
the biomass-coated PU foam cubes; which slowly
limited the penetration of suspended-growth biomass
containing denitrifiers as well as oxidized nitrogen
into the interior layers of the cubes. Consequently, the
solid carbon source located in deeper layers of the
biomass-coated PU foam cubes was foreseen to be not
completely exploited due to the limitation of
132
denitrification process. Thus, in a practical scale, the
procedure for the preparation of the dried attached-
growth biomass can be simplified by air drying or
drying under the sunlight rather than oven drying
which will reduce the cost of treatment. This is
because only the surface of the wet biomass-coated
PU foam cubes is needed to be dried as merely the
superficial portion of the dried biomass is
predominantly used as a solid carbon source during
the denitrification process. In addition, the application
of air drying or drying under the sunlight also permits
the real scale reactor to be packed with higher
percentage of PU foam cubes as the drying process of
large quantity of wet biomass-coated PU foam cubes
can be easily carried out in an open space instead of
limited space when it is performed in the oven. The
presence of higher percentage of packing volume of
 Wastewater Engineering: Advanced Wastewater Treatment Systems
Chapter 5: Wastewater Treatment by Bioremediation Technologies
biomass-coated PU foam cubes is more preferable as
it can further enhance the denitrification process due
to the availability of more solid carbon source.
Furthermore, as merely the superficial portion of the
PU foam cubes with dried attached biomass is
predominantly used as a solid carbon source during
the denitrification process, attaining a constant weight
of the dried biomass-coated PU foam cubes is
unnecessary in the real application. In fact, once the
surface of the fresh PU foam cubes is covered by the
attached-growth biomass, which takes about a week of
culturing, these PU foam cubes could be dried and are
ready to serve as a solid carbon source. Therefore,
only a short start-up period is required which added its
advantages of using PU foam cubes with dried
attached biomass as a solid carbon source for the
denitrification process enhancement.
Generally, low DO concentration and accessibility
of carbon source are found to be the crucial factors
affecting the denitrification process. Since the IA
strategy was applied in this study, the denitrification
process was deemed more preferable to take place
during the non-aeration period as the high DO
concentration in aeration period would inhibit the
reduction of oxidized nitrogen. When the dried
biomass-coated PU foam cubes were introduced into
reactor, it would serve as the solid carbon source to
facilitate the denitrification process. The freshly
formed attached-growth biomass was as well capable
of harvesting the carbon source from these biomass-
coated PU foam cubes to ensure the commencement
of the denitrification process. Once the supplied of
carbon source was exhausted, the formed attached-
growth biomass onto and into the biomass-coated PU
foam cubes could be dried to replenish the depleted
carbon source and subsequently reused/recycle in the
IA-MBSBR. Thus, lesser amount of external carbon
source was required to completely remove the
oxidized nitrogen as large portion of this oxidized
nitrogen was already being reduced using the carbon
source from the prepared dried biomass-coated PU
foam cubes which served as a supplementary solid
carbon source for the denitrification process.
4. CONCLUSIONS
The dried attached-growth biomass from the PU foam
cubes could be exploited as a novel solid carbon
source to enhance the denitrification process in the
IA-MBSBR. With the packing volume of 8% (v/v) of
prepared dried biomass-coated PU foam cubes, the
TN removal efficiency of approximately 80% could
be achieved up to 8 consecutive cycles of operation
when 1:2 IA strategy during the REACT period was
adopted during the treatment of low COD/N
containing wastewater. Once the stored carbon source
133
within the prepared biomass-coated PU foam cubes
was exhausted due to the continuously used in every
cycle to maintain the denitrification process, the
formed attached-growth biomass could be dried again
to enable the reuse/recycle of biomass-coated PU
foam cubes.
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(2009). Simultaneous
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Biodenitrification Reactor Packed with
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Wastewater Engineering: Advanced Wastewater Treatment Systems
Available online at http://www.ijsrpub.com/books
2014 IJSRPUB

Wastewater Engineering: Advanced Wastewater

Treatment Systems

Chapter 6: Wastewater Treatment by Membrane

Techniques

136
Wastewater Engineering: Advanced Wastewater Treatment Systems
Available online at http://www.ijsrpub.com/books
2014 IJSRPUB

Supported Liquid Membrane in Wastewater Treatment

Tjoon Tow Teng1*, Amir Talebi1 and Govindaraju Muthuraman2
1
School of Industrial Technology, Universiti Sains Malaysia, 11800 Penang, Malaysia
2
Department of Chemistry, University of Madras, Presidency College, Chennai 600 005, India
*Corresponding Author: ttteng@usm.my

Abstract. Supported liquid membrane (SLM) has been investigated by many researchers recently. The application of SLM in
wastewater treatment, pharmaceutical purposes, metallurgy, biological process and medical science has made it an interesting
topic for researchers globally. Different methods of SLM systems such as simple, facilitated and active transport have been
described and discussed, as well as solute transport mechanism from the aqueous feed phase through the polymeric
microporous support into the aqueous stripping phase. SLM stability, selectivity, recovery and reuse are the other topics which
in this chapter have been discussed and described. For future trend, green supported liquid membrane and the application of
ionic liquids in SLM system have been suggested.

Keywords: Supported Liquid Membrane, Wastewater Treatment

1. INTRODUCTION
Liquid membrane (LM) is water insoluble
(immiscible) liquid with the feed and stripping phases.
Once a specific solute of a mixture moves through the
liquid membrane from feed phase towards the
stripping phase, extraction can be achieved.
Liquid membrane systems are being investigated
widely in various fields such as chemistry (organic,
inorganic and analytical), biotechnology, biomedical
technology, wastewater treatment, etc. (Muthuraman
et al., 2009; Talebi et al., 2013). LM can be applied
for different purposes such as selective removal and
recovery of heavy metals, separation of aromatics
from hydrocarbons, antibiotics purification,
purification of aromatics such as benzene, xylene and
toluene, protein extraction using aqueous two-phase
systems, dyes and pigments removal, metallurgical
purifications, etc. (Chang et al., 2011).
The term solvent extraction refers to the
distribution of a solute between two immiscible liquid
phases, which are somehow in contact with each
other. For this process, the International Union of Pure
and Applied Chemistry (IUPAC) recommends the
term liquid-liquid extraction (LLE) (Rydberg et al.,
2004). The mechanism of the contact of two
immiscible liquid phases with each other makes three
different liquid membrane types: Bulk Liquid
Membrane (BLM), Supported Liquid Membrane
(SLM) and Emulsion Liquid Membrane (ELM).
1.1. Bulk Liquid Membrane
Bulk liquid membrane (BLM) contains two bulk
aqueous phases (feed and stripping) separated by a
bulk organic and water immiscible liquid phase. In its
simplest type, the extraction and partition take place in
U-tube (high density solvent, Figure. 1A) or H-tube
(low density solvent, Figure 1B.) configuration
1.2. Supported Liquid Membrane
In supported liquid membrane (SLM) a thin
micropourous filter is installed as a support between
feed and receiving (stripping) phases. The support is
impregnated by an organic carrier (mobilizer) or ionic
liquid to modify the extraction process. Fig.2. shows a
schematic of an SLM reactor in which the LM is
sandwiched between feed and stripping phase.
1.3. Emulsion Liquid Membrane
In 1968, Li invented a different type of liquid
membrane in which the stripping phase was
emulsified in an immiscible liquid membrane (Li,
1968). ELM may be in water-organic-water (W/O/W)
or organic-water-organic (O/W/O). In emulsion liquid
membrane (ELM) mass transfer takes place by
dispersion of emulsion in the feed solution. Fig. 3
shows a configuration of ELM.

137
 Teng et al.
Supported Liquid Membrane in Wastewater Treatment
2. LIQUID-LIQUID EXTRACTION
Liquid-Liquid Extraction (LLE) is considered as the
principal and first step for liquid membrane
application. Recently, separation techniques such as
solvent extraction or liquid-liquid extraction (LLE),
liquid membrane, etc. have been widely used in the
separation of heavy metals from aqueous solutions
(Cox, 2004; Talebi et al. 2012). The principle of
liquid-liquid extraction (LLE) is based on distribution
of a solute between an aqueous phase and an organic
phase (Thornton, 1992). LLE is a process where a
138
solute can distribute itself in a certain ratio between
immiscible solvents and extraction process depends
on its mass transfer rate (Lee et al., 2000).
LLE is considered as the preliminary investigation
of LM application in order to find the best and
optimum condition for various parameters affecting
the extraction efficiency, such as equilibrium pH
(pHeq), mixing time, extractant concentration, salt
concentration, and organic-to-aqueous phase ratio
(O/A).
 Wastewater Engineering: Advanced Wastewater Treatment Systems
Chapter 6: Wastewater Treatment by Membrane Techniques
If for example solute A dissolved in aqueous phase
distributes into the organic phase in a way to reach
equilibrium, the distribution coefficient is
D = [A]org/[A]aq (1)
where [A]org is the solute concentration in organic
phase and [A]aq is the solute concentration in aqueous
phase at equilibrium stage.
The percentage of extraction (%E) is given by:
%E= [D/(1+D)]*100 (2)
3. Diffusion and Transport Mechanism
Considering LLE as a liquid membrane basic
principle, diffusion transport plays a major role in
liquid membrane technique. Diffusion flux J (M,
g/cm2/s) for a particular species (S) is basically the
amount of that particular species diffuses through unit
area per unit time.
Based on Ficks first law:
J = D (3)
where D is diffusion coefficient and d is membrane
thickness. For steady state diffusion across a thin
membrane, only one dimension can be considered. By
applying the mass transfer coefficient k
k = D/d (4)
Equation (3) can be simplified and integrated to give
J = k ([Ss] [Sf]) = k ([Sf] [Ss]) (5)
where [Sf] and [Ss] are the concentrations of the
species in feed phase and stripping phase, respectively
(Kislic, 2010).
Fig. 4 shows a schematic of solute transfer from
the aqueous feed phase, through the LM and extracted
in the aqueous stripping phase in BLM system. The
basic concept of liquid membrane can be described as
follows:
Feed phase and receiving (stripping) phases are
divided by an immiscible organic solution either with
or without carrier (modifier). Different types of LM
139
are based on this organic phase installation and
position: if it is a thin layer of emulsion sphere
(globule), then it is called ELM, while in BLM the
organic phase is an independent bulk layer and in
SLM, the impregnated microporous membrane
support is considered as the organic phase.
The diffusion of a solute from the feed phase, into
the LM and consequently the extraction of it in
stripping phase, is the main direction of liquid
membrane extraction process. There is not any routine
and unique model for all different types of LM
diffusions (Kislic, 2010); however, the basic
diffusion-chemical reactions in LM can be described
based on diffusion, partition and interdiffusion of the
solute in different stages of LM process, as shown in
Fig. 5.
First the diffusion inside the aqueous feed phase:
Jf = kf ([Sf] [Sfm1]) (6)
This is the first step of all three LM configurations
(BLM, SLM and ELM). [Sf] is solute concentration at
feed phase and [Sfm1] is solute concentration at the
feed phase-LM interface.
After this step, solute partition takes place due to
thermodynamic conditions and the solute
concentration changes from [Sfm1] to [Sfm2].
The second step is after solute partition and
complexations, which is solute diffusion through the
liquid membrane (interdiffusion):
Jm = km ([Sfm2] [Sms1]) (7)
where [Sfm2] is solute concentration at feed phase-LM
interface and [Sms1] is the solute concentration at
LMstripping phase interface.
Similar to the first step, after this step the solute
concentration changes from [Sms1] to [Sms2] as a result
of different thermodynamic conditions.
The third step is diffusion through the stripping phase:
Js = ks ([Sms2] [Ss]) (8)
where [Ss] is the solute concentration at the stripping
phase.
 Teng et al.
Supported Liquid Membrane in Wastewater Treatment

Fig. 4: Solute transport configuration from aqueous feed phase to aqueous stripping phase through BLM

3.1. Liquid Membrane Types Based on Transport
Mechanism
Three different types of liquid membranes (BLM,
SLM and ELM) can be divided by three different
types based on transport mechanism:
3.1.1. Simple Transport
The solubility of the solute in the liquid membrane
plays an important role. Because the LM is not
impregnated with any modifier then no chemical
reaction occurs between the solute and the LM and
hence it is in the same form in stripping phase as it has
been in feed phase and LM. The permeation stops at
equilibrium level (Schlosser et al., 1993; Schlosser
and Sabolova, 1999; Wodzki and Nowaczyk, 2002).
Fig.6. shows the mechanism of solute transport
through the LM; [Sf] is solute concentration in the
feed phase, [Sm] is the solute concentration in the
liquid membrane and [Ss] is the solute concentration
in the stripping phase. In simple transport mechanism,
the solute permeation stops when concentration
equilibrium is reached.

140
 Wastewater Engineering: Advanced Wastewater Treatment Systems
Chapter 6: Wastewater Treatment by Membrane Techniques

Fig. 5: Solute concentration [S] Vs distance (H) profile from the aqueous feed phase through the LM to the aqueous stripping
phase

Fig. 6: Simple transports of Species (S) from Feed phase (F), through LM (M) to Stripping phase (S)

3.1.2. Facilitated Transport LM interface due to chemical potential, then a

The most important transport mechanism in LM
technique is based on carrier facilitated transport.
Partitioning, complexations and diffusion are the
major parts of facilitated transport mechanism. This
type of LM accelerates the flux rate and extraction
process. However, subsequent mechanisms like
coupled counter transport or coupled co-transport can
be derived from the facilitated transport mechanism.
Fig.7. shows the schematic of the solute facilitated
transport through LM. The first stage is the solute (S)
partitioning in LM, diffusing from feed phase to feed-
chemical reaction between the solute and the carrier
(C) at the interface occurs to form solute-carrier
complex (S=C) and the complex moves through the
LM (due to the solubility of the solute) towards the
LM-stripping interface (reverse reaction and
partitioning the solute in stripping phase and
decomplexation) and stripping in the stripping phase
due to different thermodynamic conditions at LM-
stripping phase interface and diffusion to the stripping
phase (SA formation due to chemical reaction with
anion (A) in stripping phase (Kislic, 2010).

141
 Teng et al.
Supported Liquid Membrane in Wastewater Treatment
Fig. 7: Facilitated transport of species S through LM
3.1.3. Active Transport
Active transport is based on oxidation-reduction
process and is recommended for the time that only one
and no other species is transported and is suitable for
selectivity. Catalytic reactions and also biochemical
Fig. 8: Active transport of species S through LM
4. SUPPORTED LIQUID MEMBRANE (SLM)
In SLM a thin microporous hydrophobic (or
hydrophilic) support is impregnated by an organic
solvent (mixed with an extractant or suitable carrier)
and is placed between aqueous feed and stripping
phases. For laboratory purpose, the most common
design is flat sheet geometry but due to low surface
area to volume ratio this design is not suitable for
industrial application.
Usually hydrophobic organic solvents like
hydrophobic ethers and esters, long chain alcohols etc,
are the most common immobilizers in separating the
feed and stripping phases. Although this will lead to
instability of the SLM system, using ionic liquids can
be a solution to this matter. Ionic liquids (IL) are
eutectic molten salts which consist of organic cation
or anion. Large distribution coefficients in metal ion
extraction for example are the advantage of using IL
as an alternative for common organic solvents in LM
technique (Lertlawasin et al., 2010).
The advantages of SLM can be summarized as
being energy saving and low cost, and also due to
142
conversions at the LM interface are the other major
parameters in active transport mechanism. Fig.8.
shows the active transport process where S2+ S+
reduction takes place in the feed phase, S=C=A2
complexation in LM (with the carrier C) and S+S2+
oxidation in the stripping phase.
small scale of operation the possibility of using
expensive materials.
In SLM the overall driving force for solute
diffusion is concentration difference of the solute in
both feed and stripping phases.
For the solid support, hydrophobic microfilters are
most recommended. Choosing a right polymeric
support can improve the SLM stability which is the
main disadvantage of using SLM in practice.
The driving force for a solute to be dissolved in the
organic phase (the impregnated hydrophobic
membrane) is chemical potential across the
membrane. For the solute i the chemical potential is:
Di = RT d ln ci + RT d ln i (9)
where i is chemical potential of the species
(solute) i, R is universal gas constant, T is absolute
temperature and Ci is the concentration of the species
i, i is activity coefficient of the species i.
The solute transport from the feed phase to the
stripping phase can be simplified into the five
sequential steps as follows:
 Wastewater Engineering: Advanced Wastewater Treatment Systems
Chapter 6: Wastewater Treatment by Membrane Techniques
1. Solute diffusion across the feed phase
2. Solute extraction on the Feed-LM phase
interface
3. Diffusion across the LM
4. Re-extraction on the LM-Stripping phase
interface
5. Diffusion across the stripping phase
The membrane flux can be calculated by Ficks first
law:
J = km S/d (10)
where km is mass transfer coefficient, S the
solute concentration difference between stripping
phase and feed phase.
For an SLM, considering that mass transfer
coefficient is equal to diffusion coefficient multiple by
partition coefficient, the flux can be given by:
J = DSLM Kf S/d
where DSLM is the SLM diffusion coefficient and
Kf is the partition coefficient, S the concentration
difference between stripping phase and feed phase of
the solute (Reid et al., 1977).
Diffusion coefficient itself is derived by Stokes-
Einstein (kinetic theory) equation:
D = kT/(6 r) (11)
where D is diffusion coefficient (cm2/s), k is
Boltzmann constant, T is absolute temperature
(Kelvin), is the organic phase viscosity and r is the
pore radius of the solute.
4.1. Permeation in SLM
Permeation is the process in which a solute dissolves
in the organic phase and diffuses towards the stripping
phase. Substance solubility plays the major role in
simple transport permeation and equilibrium level is
the final step of permeation. In other words, the
transported compound is in the same condition either
in feed phase or stripping phase (Cussler et al., 1989).
The advantage of SLM system is that by using
facilitated organic phase, the transport of solute
through the LM and as a consequence solute
permeability and selectivity can be enhanced
drastically. In this method, the reaction between solute
and the selected carrier only takes place at the
membrane or in better words at the interface of feed
phase and membrane (Juang et al., 1998).
If C is the carrier in the LM which is able to form a
complex with the solute S:
S + C S=C (12)
then the dissociation constant is:
Ka = [S=C]/[S][C] (13)
From the Ficks first law, the flux is:
143
J = Ds=c Ss=c/d (14)
where Ds=c is diffusion coefficient of carrier-solute
complex, Ss=c, is the concentration gradient of the
carrier-substance complex and is equal to the initial
concentration of the transported substance multiple by
the extraction constant:
Ss=c, = Ss Kext (15)
and Kext (extraction constant) can be written as:
Kext = Kf Ka (16)
where Kf is partition coefficient between organic
phase and feed phase, and Ka is dissociation constant
(Park et al., 2006).
4.2. Ionic Liquids Application in SLM
Application of ionic liquids (IL) either as carrier or as
organic solvent in SLM is considered as a new
approach. IL consists of two parts: cationic organic
part and anionic part. IL mostly remain in liquid form
between 0 and 400 C and shows very high thermal
stability (Han and Armstrong, 2007).
Ionic liquids are capable of amino acids and their
derivatives transportation through liquid membranes.
The needed driving force for this transportation is
counter ions gradient from the stripping (receiving)
phase to the feed (source) phase. Dzygiel et al. (1998)
used Aliquat 336 as a carrier to transport amino acids
by supported liquid membrane in which the extraction
process performed from an aqueous donor phase with
pH > 11, a gradient of chloride ions from the strip to
the feed phase provides a driving force for the mass
transport. According to Wieczorek et al. (1997), on
their investigation on concentration of amino acids
using supported liquid membranes with di-2-
ethylhexyl phosphoric acid as a carrier, the extractions
are made from an aqueous donor phase with pH 3 to a
more acidic acceptor phase and the mass transfer is
driven by the proton gradient between these phases.
4.3. Organic Solvents Selection in SLM
Hydrophobicity is the main characteristic for an
organic solvent to be used in SLM to ensure
immiscibility with aqueous feed and stripping phases.
Low viscosity of an organic solvent also plays a major
role in mass transfer of solute through the LM but at
the same time it has a negative effect on SLM
stability. Low volatility, low interfacial tension
between aqueous and organic phases in the support
pores which lead to the higher mass transfer can be
considered as important parameters for organic
solvent selection in SLM. Table 1 Shows selected
parameters of the commonly used organic solvents in
SLM (Rydberg et al., 2004).
 Teng et al.
Supported Liquid Membrane in Wastewater Treatment
Table 1: selected parameters of the commonly used organic solvents in SLM (Rydberg et al., 2004)
Organic Solvent Density x 10-3 Viscosity x 103 (Pa s)
(kg/m3)
Dodecane 0.75
Heptane 0.68
Toluene 0.78
Kerosene 0.79
Diphenyl methane 1.00
Diheyl ether 0.79
1-octanol 0.83
4.4. SLM and Species Recovery
One of the most important issues in extraction and
separation process is substance recovery which is
directly related to pertraction efficiency and/or
recovery.
The solute concentration difference S over the
membrane can be expressed as:
S = fSf - sSsKs/Kfm (17)
where f and s as are the fractions of the
transported substance, which are pertractable from the
feed to the strip phases, respectively. Ksm is the
partition coefficient for the solute between the strip
and membrane phase, and Kfm is the partition
coefficient for the solute between the feed and
membrane phase. While the feed and strip phases are
mostly aqueous, both partition coefficients are similar
(Kislic 2010).
Other parameters like diffusion coefficients in feed
and membrane phases, partition coefficients or
membrane thickness can also affect the extraction
rate. According to Jonsson and Mathiasson (1999),
there are two possibilities for pertraction controlling:
(i). Membrane controlled pertraction, when there is
a limiting step for diffusion of the transported solute
through the liquid membrane.
(ii). Feed controlled pertraction, when the diffusion
through the feed phase to the feed-membrane interface
appears as the limiting step.
4.5. SLM and Selective Extraction
The selective extraction in SLM is the ability to
transfer the desired compounds only and not the
interfering or unwanted compounds. The selectivity
depends mostly on the species capture method and
also the used transport mechanism (Thornton, 1992).
When the simple permeation is applied, the selectivity
is not high and is governed by solubility differences
between the solutes in the membrane phase; however,
when carrier is used the transport efficiency and
consequently the selectivity increases. Various carrier
molecules or ions can be incorporated in the
membrane phase to enhance the selectivity and mass
transfer (Dzygiel and Wieczorek, 2010).
Surface tension x 10 - Solubility in water x
3
(N/m) 10-3 (kg/m3)
1.50 24.9 0.07
0.38 19.6 -
0.54 27.9 -
1.24 25.3 -
2.96 38.4 6.51
1.87 - -
7.47 27.1 -
A good carrier that can be used to enhance the
selectivity should have the following characteristics:
(i). Formation and decomposition of the complex
on membrane interfaces should be fast and rapid.
(ii). Side reactions can decrease the selectivity and
extraction process.
(iii). Irreversible reaction and degradation are
considered as limiting parameters in selectivity.
(iv). Low solubility in the aqueous feed and strip
phases of the carrier has a key role for choosing a
suitable carrier.
(v). Should not be hazardous or toxic to the
environment and should be cost effective specially in
industrial applications.
As the ionic carriers, mostly amines or carboxylic
and phosphoric acids for metals, organic acids and
amines are typically used. For metal extraction, the
addition of thiocyanate ions to the donor is needed to
form a negatively charged metal thiocyanate complex,
which can give an ion pair with the carrier (Papantoni
et al., 1995).
The other parameter that can affect the selectivity
is the diffusion coefficient which depends on the
molecular radius of the solute. Changing pH in feed
and stripping phases for the purpose of activating and
deactivating the compounds in these phases can
increase the selectivity as well. For example, the basic
feed phase and acidic strip phase is useful for selective
amines extraction (Dzygiel and Wieczorek, 2010). If
the pH of the feed (donor) phase is adjusted to a
sufficiently high value, the transported amines are
uncharged and are transported over the organic liquid
that is used as a membrane phase. The strip (acceptor)
phase on the other side of the membrane is an acidic
solution or buffer with low pH.
4.6. SLM Unit Design
Pertraction, extraction and transport processes in SLM
like all LM types, highly depend on the membrane
design and constructor.
Microporous polymeric membrane is typically
used for the membrane phase in SLM design and
modification. The type of polymeric microporous
membrane has a direct impact on the membrane
lifetime, stability, performance and efficiency.
Nowadays, the new generation of developed inorganic
144
 Wastewater Engineering: Advanced Wastewater Treatment Systems
Chapter 6: Wastewater Treatment by Membrane Techniques
membranes like ceramics, porous metals and zeolites
are used in SLM reactor modification and design and
have shown a range of advantages like thermal and
mechanical stability, being resistant to chemical and
organic solvents and being recyclable.
The utilization of advanced inorganic membrane
materials is nowadays very important. Cot et al.
(2000) worked on preparation of inorganic membrane
materials innovative concepts like templating effect,
nanophase materials, growing of continuous zeolite
layers, and hybrid organicinorganic materials with
permselective properties for gas separation and
facilitated transport of solutes in liquid media which
have been successfully adapted to membrane
applications. Resina et al. (2008) used hybrid and
activated composite membranes containing Aliquat
336 for the transport of Pt(IV) and McCleskey et al.
(2002) used a thin layer of gold (700 ) and have
reported high selectivity of U over Eu until [U] is
<0.84 mM in the feed solution on manufactured
alumina pourous supports to yield nanopores with
openings of <7 nm.
To choose an effective and practical organic
solvent for the membrane, it should be taken into
account that the organic liquid should be hydrophobic
enough to ensure immiscibility with aqueous phases.
Moreover, the low viscosity of the solvent can
decrease the SLM stability but increase the mass
transfer through the membrane.
4.7. SLM Stability and Reuse
One of the disadvantages of SLM in industrial
application is the low stability of this kind of liquid
membrane. Leaching carrier and emulsification in
liquid membrane phase reduce the SLM lifetime
(Neplenbroek, 1992). The other factor affecting SLM
stability is the operating temperature. According to
Saito (1992), the increasing operating temperature has
shown a direct effect on the solubility of both
membrane solvent and carrier in the aqueous phases
and has reduced membrane lifetime; but due to the
lower viscosity of the membrane phase, flux rate has
increased. Increasing viscosity leads to lifetime
increase but this will badly affect the flux rate and
deduce it drastically (Deblay et al., 1991).
Physicochemical characteristics and molecular
structure of the carriers are very important in SLM
stability. According to Chiarizia (1991), the more the
surface-active compound carrier usage, the less the
SLM stability would become.
The microporous polymeric membrane with
smaller pore size is more stable than larger pore size
type; although the surface porosity should not be
lower than certain levels that can decrease the flux.
145
The SLM could be reused by reloading the
membrane supports with fresh liquid membrane
solution after they have been used or continuous re-
impregnated which provides the same extraction
efficiency as a newly prepared SLM (Dzygiel et al.,
1998; Kocherginsky and Yang, 2007).
Membrane emulsification is considered as an
important degradation parameter of SLM stability.
Membrane emulsification occurs due to the lateral
shear forces and can be prevented by barrier formation
on the membrane interface or interfacial
polymerization (Wijers et al., 1998; Wang et al., 1998;
Wang et al., 1999).
Yang et al., (2000) worked on SLM stability by
applying polymerization surface coating, using
hexamethyldisiloxane and heptylamine as monomers
and hydrophobic microporous microfiltration
membranes with pore sizes of 0.050.2 m were used
as substrate.
5. SUPPRTED LIQUID MEMBRANE and
WASTEWATER TREATMENT
SLM has been used widely in researches and
investigation, in various fields of environmental
technologies, pharmaceutical, food technology,
biotechnology and environmental science and sample
preparation in related fields. Metal ions such as Cu,
Cd, Co, Ni and Zn have been enriched in SLM for
sample preparation by a simple diffusion and pH
adjustment (Papantoni et al., 1995).
A counter coupled transport using D2EHPA as
carrier has been investigated for Pb sample
preparation and lead determination in urine (Djane et
al., 1997). Selective separation and pre-concentration
application of SLM for Cr (VI) removal from
wastewater (Ashraf and Mian, 2006) or Cu recovery
from spent ammoniacal electronic industry using
kerosene as solvent, can be mentioned as reference
(Kocherginsky and Grishchenko, 2003). Kedari et al.
(2013) reported uranium(VI) and thorium(IV)
transport across SLM containing
trioctylphosphineoxide as carrier. Ros et al. (2013)
worked on the selective separation of metal ions using
supported ionic liquid membranes. Raut et al. (2012)
worked on selective strontium separation and Azzoug
et al. (2014) on metallic ions extraction.
6. FUTURE TREND: GREEN SUPPORTED
LIQUID MEMBRANE and IONIC LIQUIDS
The conventional solid membranes and related
separation processes have disadvantages such as low
flux rate, low selectivity (because of polymeric
membrane characteristic) and fouling. On the other
hand, liquid membrane separation methods use
 Teng et al.
Supported Liquid Membrane in Wastewater Treatment
conventional petroleum-based organic solvents and
carriers which are hazardous to the environment.
According to Teng and Talebi (2012), liquid
membrane can be modified to green liquid
membrane by using environmentally friendly
materials. Vegetable oils (such as coconut or palm oil)
as non-toxic and clean solvents can be used instead of
regular organic solvents and are capable of reducing
the amount of common toxic and hazardous chemicals
using in liquid membrane methods.
Ionic liquids also can be considered as promising
materials that recently researchers have been working
on in order to enhance the ability of solute
transportation in liquid membrane technology
(Meinderisma et al., 2005; Sun et al., 2011 and
Gonzlez et al., 2012).
Ionic liquids are basically salts that are liquid
below 100C and consist entirely of ions. The unique
characteristics of ionic liquids such as an extremely
low vapour pressure, high thermal stability and certain
physico-chemical properties can be used in modifying
of organic phase in liquid membrane basicl structure
(Fischer et al., 2011) despite the fact that using a large
amount of ionic liquids as solvent in liquidliquid
extraction process might not be cost effective due to
the high cost of ionic liquids compared to
conventional organic carriers (Matsumoto et al.,
2007).
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acid pertraction through a multimembrane
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207-220.
Wieczorek P, Jonsson JA , Mathiasson L (1997).
Concentration of amino acids using supported
liquid membranes with di-2-ethylhexyl
phosphoric acid as a carrier. Analytica Chimica
Acta, 346: 191-97.
Wijers MC, Jin M, Wessling M, Strathmann H (1998).
Supported liquid membranes modification with
sulphonated poly (ether ether ketone),
Permeability, selectivity and stability. Journal
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Wastewater Engineering: Advanced Wastewater Treatment Systems
Available online at http://www.ijsrpub.com/books
2014 IJSRPUB

Role of Emulsion Liquid Membrane (ELM) in Separation Processes

Tjoon Tow Teng1*, Munisamy Soniya2, Govindaraju Muthuraman2 and Amir Talebi1

1
School of Industrial Technology, Universiti Sains Malaysia, 11800 Penang, Malaysia
2
Department of Chemistry, University of Madras, Presidency College, Chennai 600 005, India
*Corresponding Author: ttteng@usm.my

Abstract. Liquid membranes (LM) have received much attention over the last decades. In recent years, a remarkable increase
of the applications of emulsion liquid membranes in separation processes is observed. Emulsion liquid membrane (ELM) is
reputed to be a standout amongst the most guaranteeing detachment techniques for extraction of metal contaminants. Emulsion
liquid membrane systems in which two immiscible phases are separated by a third phase which is immiscible with the other
two phases, are divided into two types: (1) facilitated mass transfer, (2) mass transfer without any reaction involved.

Keywords: Emulsion Liquid Membrane, Separation Process

1. INTRODUCTION proposed by Li (1968) ELM engineering has been

Liquid membranes (LM) have received much
attention over the last decades: liquid membrane
applications having different configurations and have
recently become of substantial practical
consequentiality in separation technology,
macromolecular chemistry and membrane technology.
The benefits of utilizing LM are high selectivity,
utilizing carriers for the transport mechanism, and
concrete molecular recognition. Therefore, the
synthesizing of incipient type of carriers having high
selectivity for categorical applications becomes very
consequential and a number of researchers have been
working in the area (Muthuraman et al., 2009; Chang
et al., 2011; Talebi et al., 2012).
LM in general plays a paramount role in disunion
science. Their efficiency and economic advantages
distinguish them as a solution for some vital
environmental quandaries such as metals recovery,
hazardous species elimination (metals, organic
molecules) from wastewaters or selective applications.
LM can be modified as bulk liquid membranes
(BLM), supported liquid membranes (SLM), emulsion
liquid membranes (ELM), polymer inclusion
membranes (PIM) and activated composite
membranes (ACM).
In this deference, emulsion liquid membranes have
shown great potential, especially in cases where solute
concentrations are relatively low and other techniques
cannot be applied efficiently, since they cumulate the
process of extraction and divesting in a single unit
operation. The extraction chemistry is rudimentally
identical tantamount to that found in solvent
extraction, but the transport is supported by kinetic
rather than equilibrium parameters, that is, it is
governed by a non-equilibrium mass transfer (Len
and Guzmn, 2004; Teng et al., 2013).
Since emulsion liquid membrane (ELM) as an
enhanced solvent extraction method was at first
improved quickly. It has been used in dye removal
(Das and Hamdaoui, 2010; Kumar and Das, 2010;
Othman et al., 2011), phenols extraction (Park et al.,
2006; Ng et al., 2010) and metal ions removal and
recovery (Park et al., 2010; Nosrati et al., 2011) from
aqueous solutions. Typically, under best conditions,
dye removal can achieve up to 9099% (Othman et
al., 2011). The reported extraction rate for phenol was
9899% (Park et al., 2006; Ng et al., 2010) while for
aniline removal, the recovery rate was 99.5%
(Devulapalli and Jones, 1999) and for chromium
extraction, the most noteworthy recovery rate could be
97.599.6% (Rajasimman et al., 2009; Nosrati et al.,
2011). The emulsion is made by scattering the inner
phase in the membrane stage under high
emulsification speed in the vicinity of a surfactant,
which enhances the emulsion stability by averting the
droplets of inside stage from merging. Regularly, the
size circulation of the scattered internal phase droplets
is in the vicinity of 1 to 100 m (Devulapalli and
Jones, 1999).
In contrast to liquidliquid extraction, ELM holds
a lot of researchers preferences, for example,
effortlessness, enhanced kinetics and high selectivity.
Also, ELM method of action permits exceptionally
high mass transfer rate because of its expansive
surface range inside the emulsion globules and inner
droplets (Rajasimman et al., 2009) and permits both
extraction and stripping synchronously in one and
only step. Along these lines it is picking up more
vitality in the fields like metallurgy, solution, organic
chemistry and environmental industries.
2. DEFINITION and CLASSIFICATION
Emulsion liquid membrane (ELM) is reputed to be a
standout amongst the most guaranteeing detachment
techniques for extraction of metal contaminants
(Chakraborty et al., 2003; Ortiz et al., 2003;

149
 Teng et al.
Role of Emulsion Liquid Membrane (ELM) in Separation Processes
Kumbasar and Sahin, 2008) and hydrocarbons
(Correia et al., 2003; Park et al., 2006) due to the high
mass exchange rate, high specificalilty, low solvent
stock and low cost. Frankenfeld et al. (1981) reported
that the ELM could be dependent upon 40% shabbier
than other solvent extraction techniques. This process
consolidates both extraction and stripping stages to
perform a synchronous purification and concentration.
Be that as it may, this strategy has been constrained
by the emulsion unsteadiness (Florence and Whitehill,
1981; Li et al., 1988; Xuan-cai and Fu-quan, 1991;
Hou and Papadopoulos, 1996; Zihao et al., 1996;
Bandyopadhyaya et al., 1998; Wan and Zhang, 2002).
The absence of emulsion stability reduces extraction
efficiency. In the ELM process, three steps are
emulated incorporating an emulsification ready by
blending the layer and the internal phase, extraction,
and demulsification. In the first step, water is scattered
into the oil phase as fine globules. The second stage
takes after by penetration of solutes from the feed
phase, through the LM, to the receiving phase. In the
third stage, the emulsions are settled and demulsified
to discharge the internal phase within the loaded
solutes. This step is connected with the recuperation
and recovery of the LM.
ELM removes the limitation of solvent extraction
equilibrium by consolidating extraction and stripping
in a solitary operation, consequently accomplishing
decrease of metal concentration in the feed stream to
quite low levels. Besides, it diminishes the stock of
the organic solvent and metal extractant significantly.
ELM has been utilized to treat aqueous phases with
metals like copper, zinc, cadmium, chromium, and so
on. (Frankenfeld and Li, 1977; Marr and Kopp, 1982;
Gu et al., 1992; Winston and Li, 1996) ELM for metal
extraction is made by structuring a water in oil (W/O)
emulsion, stabilized by a surfactant, the W/O
emulsion holds the metal extractant (carrier) in the oil
phase and the stripping acid in the interior aqueous
receiving phase. This emulsion is then scattered by
mellow unsettling into a feed phase containing the
metal to be extracted. After extraction, the
concentrated emulsion is differentiated from the feed
phase, demulsification yields an oil phase that could
be reused.
Emulsion liquid membrane (ELM), also called
surfactant liquid membranes or "Double Emulsion
Membrane (DEM)", is basically twofold emulsions,
i.e., water/oil/water (W/O/W) systems or oil/water/oil
(O/W/O) systems. For the W/O/W frameworks, the oil
stage differentiating the two fluid stages is the liquid
membrane. For the O/W/O systems, the liquid
membrane is the water phase that is between the two
oil stages. Since their disclosure over two decades
prior, emulsion liquid membranes have shown
extensive potential as successful apparatuses for wide
separation applications.
2.1. Classification
Emulsion liquid membrane systems in which two
immiscible phases are separated by a third phase
which is immiscible with the other two phases, are
divided into two types: (1) facilitated mass transfer,
(2) mass transfer without any reaction involved. The
basic idea of mass transfer mechanism in emulsion
liquid membrane (ELM) systems can be described as:
solute transfer from the bulk external phase to the
external phase-membrane interface, followed by an
equilibrium reaction between the solute and the carrier
to form the solute carrier complex at the interface;
then, diffusion of the solute-carrier complex in the
membrane phase to the membrane-internal phase
interface; consequently, second equilibrium reaction
of the solute-carrier complex to strip the solute at the
membrane-internal phase interface into the internal
phase.
3. TRANSPORT MECHANISM
Emulsion liquid membrane (ELM) has been widely
used to investigate the ion transport against its
concentration gradient by the coupled transport
mechanism (uphill transport). The ion transport
through an ELM plays an important role in separation
technologies because of high transport efficiency,
excellent selectivity and economic advantage. Liquid
membrane extraction is the use of a carrier species
incorporated in the organic solvent to increase the
solute solubility: by introducing a 'carrier' molecule
into the membrane phase, the solute solubility is
increased by the reversible formation of a membrane-
soluble carrier-solute complex as shown in Fig 1
(Das and Hamdaoui, 2010).
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 Wastewater Engineering: Advanced Wastewater Treatment Systems
Chapter 6: Wastewater Treatment by Membrane Techniques
Fig.1: Emulsion Liquid Membrane
The use of a carrier enhances selectivity by the
formation of a reversible complex between the carrier
and the solute, which is only soluble in the organic
solvent. This is particularly effective for the recovery
of charged solutes which may be poorly soluble in the
organic solvent. Many of the carriers so far employed
in liquid membrane processes are extractants used in
conventional liquid-liquid extraction, e.g. secondary
and tertiary amines, and phosphorus-containing
extractants.
The efficacy of emulsion liquid membrane (ELM)
process is a result of the facilitated mechanism that
maximizes both the extraction rate, i.e., the flux
through the membrane phase, and the capacity of the
receiving phase (the internal phase in the case with an
external feed phase) for the diffusing species. There
are fundamentally, however, two types of facilitated
transport in emulsion liquid membrane system, i.e.,
Type I and Type II facilitation. In the first type, the
concentration gradient of the membrane soluble
solute/permeate is maximized by irreversibly reacting
the solute with the reagent into an impermeable form
in the receiving phase thereby maintaining the
permeate concentration at efficaciously zero in this
phase. The diffusing species first dissolve in the layer
stage, which is made out of some organic solvents and
after that diffuse through the membrane and respond
with the interior stage (Ho et al., 1982; Fales and
Strove, 1984).
One approach in W/O/W systems for instance, is to
transport the solute from the outside fluid stage over
the oil medium of the globule (membrane), and
afterward in this manner react it with a reagent in the
internal water drops. This is regarded as type I. In
Type II category, a carrier (complexing executor or
extractant) is consolidated in the membrane phase and
it transports the diffusing solute over the membrane to
the stripping phase, a mechanism ordinarily reputed to
be "carrier mediated" facilitated transport. In this kind
of facilitation, the reaction in the internal phase
upholds a solute centralization of adequately zero. The
reaction of diffusing species with the chemical reagent
in the stripping phase structures an item that cannot
diffuse back again through the membrane (Stroeve
151
and Varanasi, 1982; Teramotoet al., 1983a). Reaction
happens both at the external interface between the
internal and membrane phase, and at the inner
interface between the membrane and internal phase.
This transporter (carrier) may be recovered after it
reacts with the inner reagent at the interface between
the films. Then again, for solutes insoluble in oil (e.g.
metal particles), an extractant must be utilized within
the interceding membrane phase, which ties and
discharges the solute at the outside and inward
interfaces progressively, permitting dispersion of the
solute-extractant complex through the liquid
membrane. This approach constitutes type
II(Teramotoet al., 1983b; Burge and Noble, 1984;
Chan and Lee, 1987).
4. MODELING of LIQUID MEMBRANES
Emulsion liquid membrane (ELM) is one of the
potential methods for treatment of industrial
wastewater aiming at recovery of various organic and
inorganic solutes (Borwankaret al., 1988; Kataokaet
al., 1989; Yan et al., 1992; Yan, 1993; Bhowal and
Datta, 1998; Kargariet al., 2006).Numerous
mathematical models have been developed. These
models can be categorized into two generic groups,
namely, carrier mediated transport models for type II
facilitation and diffusion-type mass transfer models
for type I facilitation. Applications of these models in
carrier mediated type II emulsion liquid membrane are
tested for extraction of various metal ions, namely,
silver (Lee et al., 1998), chromium (El-Said et al.,
2003)cesium (Chakraborty et al., 2003), nickel (Reis
and Carvalho, 2004), zinc, gold (Teramotoet al.,
1983b). Advancing front model is a much cited and
useful model for both types of transport models.
Therefore, it may be noted that in the modeling study,
concerted research efforts are directed to obtain the
closed form analytical solution. It may be worth
mentioning that all the modeling works in ELM are
based on single component system.
 Teng et al.
Role of Emulsion Liquid Membrane (ELM) in Separation Processes
4.1. Advancing Front Model
In this model the solute reacts at the same time and
irreversibly with the internal receiving reagent at a
reaction surface which transfers into the globules as
the reagent reacts. This model leads to nonlinear
partial differential equations which can be solved by a
perturbation method the zero-order solution generally
provides reasonable prediction for the diffusion
process. According to Yan et al. (1992) diffusion
controlled mass transfer model for type I facilitation
overcomes the shortcomings associated with
advancing front model. The model considers mass
transfer inside and outside of the globule as well as
the reaction between solute and internal phase reagent.
Yans model assumes that this reaction is not
instantaneous but irreversible. When Biot number and
Damkohler number approach infinity, Yans model
converges with the advancing front model (Kargariet
al., 2006).Lorbach and Marr (1987) developed a
model for type II facilitation that takes into account
the diffusion of the carrier and the carriersolute
complex in emulsion globules and reversible reactions
at the externaland internal interfaces (Lorbach and
Marr, 1987). Some recent studies on ELM models
include: Bhowal and Datta (1998); Lee et al. (1998);
El-Said et al. (2003); Chakraborty et al. (2003) and
Reisand Carvalho (2004).
4.2. Carrier Facilitated Transport Model
Six major stages for the carrier facilitated transport
model for type II can be described as:(1) external
phase mass transfer resistance from external phase to
the externalmembrane interface, (2) mass fluxes at
the externalmembrane interface, (3) chemical
equilibrium of extraction reaction on the external
membrane interface, (4)simultaneous diffusion of the
solutecarrier complex inside the emulsion globule
phase, (5) stripping of the complex at the membrane
internal interface, and (6) chemical equilibrium of the
stripping reaction at the membraneinternal interface.
The advantage of carrier facilitated transport model is
capability of predicting theoretically the effects of
individual parameters on overall extraction rate. This
model not only predicts the concentration of the solute
in the external phase but gives the concentration
profile inside the membrane phase and the interfacial
concentration at the external phasemembrane
interface as well (Ho and Sirkar, 2001).
4.3. Mass Transport Model of ELM Systems
The model describes diffusion of the solute in the
external phase, mass transfer of the solute across the
film between the external phase and membrane phase,
152
chemical equilibrium of the extraction reaction on the
external-membrane interface, simultaneous diffusion
of solute-carrier complex inside the globule
membrane phase, and chemical equilibrium of the
stripping reaction on the membrane-internal interface.
Simultaneous partial differential equations can be
solved analytically by the Laplace transform method.
Some dimensionless groups are found with special
physical meanings to characterize the emulsion liquid
membrane system. The analytical solutions of the
model give concentration profiles of solute in the
external phase, concentration profile of the metal-
carrier complex in the membrane phase and surface
concentration of solute on the external membrane
interface (Ho and Sirkar, 2001).
4.4. Reversible Reaction Model
Extraction models for type-I facilitation clearly
demonstrate the superiority of the reversible reaction
model of Bunge and Noble (1984) in comparison to
the advancing front treatment of Ho et al., (1982)
which assumes irreversible reactions, especially
towards the end of batch extraction. Both these
models are based on diffusion of solute through the
membrane. However, the approach in reversible
model of depicting the reaction between solute and
internal reagent to be reversible is more realistic (Kim
et al., 1983; Stroeve and Varanasi, 1984; Chan and
Lee, 1987). A convenient method towards description
of interactions in the dispersed phase is the framework
of population balance equations (PBE). However, the
reversible model itself requires computation of the
solute concentration profile in a globule, typically of
around 0.1-0.2 mm in diameter that cannot be
regarded as well mixed because of slow membrane
phase diffusion of solute. A population balance
approach therefore has to incorporate both the size
distribution of globules as also the existing
concentration profile in each of them. Solution of such
a multivariate PBE would be too difficult to attempt.
Consequently, recourse to Monte Carlo simulation is
taken to describe interaction in a system of globules,
and in conjunction, the reversible model is solved for
each individual globule. A further aspect of
importance in membrane extraction is leakage of
internal droplets into the external phase, resulting in
decreased extraction efficiency. The leakage
phenomenon has been incorporated in existing
diffusion reaction models as a continuous flux of
internal droplets from a single globule (Borwankaret
al., 1963; Chan and Lee, 1987). However, in a model
of a single, stable globule, this should be accounted
for only during intermittent globule break-up.
Therefore, the task of the model is to include the
effect of globule interaction by combining membrane
 Wastewater Engineering: Advanced Wastewater Treatment Systems
Chapter 6: Wastewater Treatment by Membrane Techniques
phase mixing and exchange of globule contents along
with leakage of internal droplets, in order to interpret
batch extraction data in an ELM system.12
1.
5. ELM DESIGN CONSIDERATIONS
5.1. Emulsification
Ultrasound has been proved to be suitable for
emulsification (Higgins et al., 1972; Ensminger, 1973;
Alegria et al., 1989; Price, 1996; Chanamai et al.,
1998; Abismail et al., 1999; Asano and Sotoyama
1999; Ooi and Biggs, 2000; Behrend et al., 2000;
Sivakumar et al., 2002). However, these studies dealt
with oil-in-water (O/W) emulsions that are applied in
food, cosmetic, and pharmaceutical industries as well
as in polymerization processes. Little work has been
reported on the utilization of ultrasound for the
production of water-in-oil (W/O) emulsions used in
ELM processes. Juang and Lin (2004) have examined
the production of W/O emulsions in LM processes
using the model system of
water/kerosene/D2EHPA/Span 80 using a low
frequency ultrasound (20 kHz).
5.2. Membrane Stability
Figure 2 shows an emulsion liquid membrane process.
Some problems remain to be solved in order to apply
the ELM to a practical process. The major problem
associated with emulsion liquid membranes is
emulsion stability. The stability of the emulsion
globules (due to membrane rupture) is known as one
of the most serious problems in the application of the
liquid surfactant membrane to industrial separation.
The main factors affecting the emulsion stability
encompass membrane formulation, method of
emulsion preparation, and the condition under which
the emulsion is contacted with a reactant phase.
Stability of W/O/W emulsions is generally understood
as the resistance of the individual globules against
coalescence (Hou and Papadopoulos, 1996). The
breakdown of w/o/w type dispersions is described
through several possible mechanisms (Florence and
Whitehill, 1981), which include: (i) coalescence of the
internal aqueous droplets into larger internal droplets;
153
(ii) coalescence of the oil droplets suspended in the
aqueous phase; (iii) the expulsion of the internal
droplets following rupture of the thin oil films during
the interaction of the internal and external aqueous
phases (Li et al., 1988; Bandyopadhyaya et al., 1998)
and (iv) swelling or contraction due to water
permeation through the oil membrane by diffusion
(Ding and Xie, 1991; Wang et al., 1996; Wan and
Zhang, 2002).
5.3. Demulsification
Generally, an emulsion prepared with a high energy
density input (such as by an electrostatic method) will
have very small droplets. This will enhance membrane
stability if the surfactant concentration is high enough.
Meanwhile, the small droplet size gives a very large
interfacial area for mass transfer, but an ultra-stable
emulsion should be avoided because of possible
difficulties later during the demulsification step. Two
principal approaches for the demulsification of the
loaded emulsion are chemical and physical treatments.
Chemical treatment involves the addition of a
demulsifier to the emulsion. This method seems to be
very effective. However, the added demulsifier will
change the properties of the membrane phase and thus
inhibits its reuse. In addition, the recovery of the
demulsifier by distillation is rather expensive.
Therefore, chemical treatment is usually not suitable
for breaking emulsion liquid membrane, although few
examples of chemical demulsification have been
reported for certain liquid membrane systems (Zhang
et al., 1988). Physical treatment methods include
heating, centrifugation, ultrasonics, solvent
dissolution, high shear, and use of high voltage
electrostatic fields. The method of demulsification by
high shear includes the use of centrifugation as the
first step, followed by pumping the half-broken
emulsion through a high shear device (Kato and
Kawasaki, 1988). Demulsification with electrostatic
fields appears to be the most effective and economic
way for breaking W/O emulsion in ELM processes
(Lu et al., 1997). Since this type of technique is
strictly a physical process, it is most suitable for
breaking emulsion in liquid membranes to recover the
membrane phase for reuse.
 Teng et al.
Role of Emulsion Liquid Membrane (ELM) in Separation Processes

Fig. 2: The emulsion liquid membrane process

6. SUMMARY 1. Anything effecting emulsion stability must be

6.1. Applications
In recent years, a remarkable increase of the
applications of emulsion liquid membranes in
separation processes is observed. The main
advantages of the ELM system are: (a) high interfacial
area for mass transfer, especially at the inner
membranewater interface, due to the small size of
the aqueous phase droplets; (b) high diffusion rate of
metal ions through the membrane; (c) simultaneous
performance of extraction (at the outer interface) and
stripping (at the inner interface) in the same system,
and (d) capability of treating a variety of elements and
compounds in industrial setting at a greater speed and
with a high degree of effectiveness, with varying
contaminant concentrations and volume requirements.
6.2. Disadvantages
This system has several disadvantages, all having to
do with the formation of the emulsion.
154
controlled. i.e. ionic strengths, pH, etc.
2. If, for any reason, the membrane does not
remain intact during operation, the separation
achieved to that point is destroyed.
3. In order to recover the receiving phase, and in
order to replenish the carrier phase, one has to break
down the emulsion. This is a difficult task, since in
order to make the emulsion stable; one has to work
against the ease of breaking it back down.
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Wastewater Engineering: Advanced Wastewater Treatment Systems
Available online at http://www.ijsrpub.com/books
2014 IJSRPUB

Bulk Liquid Membrane and Its Applications in Wastewater Treatment

Tjoon Tow Teng1*, Sampath Elumalai2, Govindaraju Muthuraman2, Amir Talebi1
1
School of Industrial Technology, Universiti Sains Malaysia, 11800 Penang, Malaysia
2
Department of Chemistry, University of Madras, Presidency College, Chennai 600 005, India
*Corresponding Author: ttteng@usm.my

Abstract. Liquid membrane separation is a process which is depending on rate process and chemical potential gradient. The
theory of membrane-based solvent extraction suggests that overall mass transfer of solute consists of several steps: diffusion of
the solute through the aqueous layer from the bulk source aqueous solution to the phases interface (nonequilibrium process),
interaction of the solute with extractant and formation of the solute-extractant complex (as a rule, the process is rapid and
reaches equilibrium at the interface), diffusion of the solute-extractant complex through the membrane support itself
(nonequilibrium process), and diffusion of the solute-extractant complex through the organic layer to the bulk organic solution
(nonequilibrium process).

Keywords: Bulk Liquid Membrane, Wastewater Treatment

1. INTRODUCTION Schlosser and Sabolova, 2002; Teramoto et al., 2002;

After the novel study in liquid membrane (LM)
extraction method by Li (1968), LM technology was
further investigated by various researchers for the
recovery of metal ions (Gyves and Rodriquez, 1999;
Chang et al., 2011) and organic compounds
(Muthuraman et al., 2009). LM process combines
extraction and stripping into one single stage and thus
involves non-equilibrium mass transfer characteristic
where the separation is not limited by the conditions
of equilibrium. Membrane can be defined as selective
barrier between two phases with mass transfer taking
place from the feed phase to the stripping phase.
There are mainly three types of liquid membrane
(LM) namely bulk liquid membrane (BLM),
supported liquid membrane (SLM) and emulsion
liquid membrane (ELM). BLM consists of three
phases, namely an organic phase that is sandwiched
between an aqueous feed phase and an aqueous
stripping phase. The organic solvent contains a carrier
that is insoluble in both aqueous solutions. The
samples diffuse from the aqueous feed solution
through the organic liquid membrane into the aqueous
receiving solution (Yang et al., 2009).
The BLM term includes several similar LM
systems, developed by different research groups such
as hybrid liquid membrane (HLM) (Majumdar and
Sirkar, 1992; Kislik et al., 1996 a&b; Gega et al.,
2001), hollow-fiber contained liquid membrane
(HFCLM) (Boyadzhiev, 1987; Bovadzhiev and
Lazarova, 1987; Sengupta et al., 1988; Bovadzhiev,
1990; Boyadzhiev and Alexandrova, 1992; Lazarova
and Bovadzhiev, 1992; Lazarova and Bovadzhiev,
1993; Schlosser et al., 1993; Boyadzhiev and
Dimitrov, 1994; Schlosser and Rothova, 1994;
Kawasaki et al., 1996; Qin and Cabral, 1998;
Schlosser et al., 1999; Dai et al., 2000; Cara et al.,
2001; Cichy et al., 2001a; Dimitrov et al., 2002;
158
Wodzki and Szczepanski, 2002; Wodzki et al., 2002;
Boyadzhiev et al., 2003; Bhaumik et al., 2004;
Wodzki et al., 2004; Zhivkova et al., 2004), flowing
liquid membranes (FLMs) (Teramoto et al., 1987;
1989; Matsuyama et al. 1990; Teramoto et al., 1990;
Prasad and Sirkar 1992; Teramoto et al., 1994; 2001),
membrane based solvent extraction and stripping
(Baniel et al., 1992; Bromberg et al., 1992; Kedem et
al., 1992; Eyal and Bressler, 1993; Kedem and
Bromberg, 1993; Vajda et al, 2003; Kubisova et al.,
2004) and multimembrane hybrid system (Wodzki
and Sionkowski, 1996 a&b; Wodzki et al., 1999;
2000; Wodzki and Nowaczyk, 2001; 2002).
In this chapter, BLM principles such as
interaction mechanisms and theories of transport,
solvent used in the membrane phase, carrier in
membrane phase and kinetics studies are analyzed by
comparison of the modifications by different research
groups.
2. THEORY and MECHANISMS
Recovery and concentration of solutes, as well as
separation of samples, have attracted interest of
researchers, especially in connection with their
recovery from fermentation broths, reaction mixtures
and waste solutions. Several reviews including
membrane based solvent extraction (MBSE),
pertraction, solvent extraction and extractive
fermentations or bioconversions have been published
(Daugulis, 1988; Mattiasson and Holst, 1991; Roffler
et al., 1991; Schugerl, 1994; Schlosser, 2000 a&b;
Schugerl, 2000; Malinowski, 2001). The solvent can
be regenerated by membrane based solvent stripping
(MBSS) where the solute is re-extracted into the
stripping solution.
Several mechanisms have been proposed to
achieve transport of solute(s) through the L/L
 Teng et al.
Bulk Liquid Membrane and Its Applications in Wastewater Treatment
interface or through a liquid membrane. The
separation mechanism could be based on differences
in physical solubility of the solutes or their
solubilisation into the solvent or reverse micelles or
on the chemistry and rate of chemical or biochemical
reactions occurring on L/L interface(s). The
complexing or solubilisation agent extractant (carrier
in the liquid membrane) forms by reversible reaction
complex(es) or aggregate(s) with the solute, which are
soluble in the solvent or membrane. The chemistry of
reactive extraction and stripping in MBSE and MBSS,
as well as in PT, is identical with the classical solvent
extraction or stripping and is presented in several
books (e.g. Lo 1983; Schugerl et al., 1994; Bart,
2001).
To avoid direct contact of biomass with the liquid
membrane, whose components are not seldom toxic, a
multi-membrane hybrid system (MHS) with both
extraction and stripping L/L interfaces immobilised in
ion-exchange polymer membranes was suggested
(Kedem et al., 1992; Eyal and Bressler, 1993. MHS
Fig. 1: Hollow fiber contactor with cross-flow of phases (Schlosser et al., 2005)
4. KINETICS of TRANSPORT
In a liquid membrane setup, variation of solute
concentration versus time can be directly measured in
both feed solution (feed phase, [Sf]), stripping solution
(stripping phase, [Ss]) and the solute concentration in
the membrane phase is established from the material
balance.
The transport of solute can be expressed by the
following equations.
d[Sf]/dt = -k1 Sf* = Jf
d[SLM]/dt = k1 SLM* - k1 SLM* (2)
d[Ss]/dt = k1 Ss* = Js
where and are volume ratio of the feed phase to
the liquid membrane phase and the stripping phase to
the liquid membrane phase, respectively. ( ==2).
Sf*, SLM* and Ss* are the dimensionless concentration
was studied for the separation of carboxylic acids by
Wodzki and Nowaczyk, 1997; Wodzki et al., 2000).
3. MEMBRANE CONTACTORS
There are two main types of hollow fiber (HF)
contactors, those with parallel flow or cross-flow of
phases. Cylindrical HF contactor with cross-flow of
phases is shown in Fig. 1.
HF contactors have a large interfacial area per unit
volume of the contactor without requirement of
desperation of one phase that can be advantageous in
systems sensitive to emulation (Tong et al., 1999;
Cichy et al., 2001b). The volume ratio of phases could
be varied practically without limitations. The
disadvantage of HF contactors is connected with
additional mass-transfer resistance introduced by
porous wall(s) immobilizing L/L inter-face(s). Some
problems with swelling of HF and especially of
potting material of HF in solvents may occur.
of solute in feed, liquid membrane and stripping
phase, respectively. They are defined as,
Sf* = [Sf]/[Sf,0]
SLM* = [SLM]/[Sf,0]
Ss* = [Ss]/[Sf,0]
where [Sf,0] is the initial concentration of solute in
the feed phase.
If the differential Equations (1) to (3) are
integrated, the following equations are obtained
(Gyves and Miguel, 1999).
(1)
Sf* = exp(-k1t) (4)
(3) SLM* = 2k1/2(k2-k1) [exp(-k1t) exp (-2k2t)] (5)
Ss* = 1- 1/2k2-k1 [2k2 exp(-k1t) k1 exp(2k2t)] (6)
According to Equation (5) SLM has a maximum
value (dSLM*/dt) =0, and the corresponding maximum
time is:
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 Wastewater Engineering: Advanced Wastewater Treatment Systems
Chapter 6: Wastewater Treatment by Membrane Techniques
SLMmax = (k1/k2)-k2/(k1-k2) (7)
tmax = ln(2k1/k2)/2k1-k2 (8)
Combining Equation (7) and (8) gives
k2 = ln (1/SLMmax)/tmax (9)
First order time differentiation of Equation (4) to
(6) leads to the final form of flux Equation
dSf*/dt = -k1 exp( k1t) (10)
dSLM*/dt = k1/k2-k1[-k2exp(-k2t)-k1exp(k1t)] (11)
dSs*/dt=k1 k2/ k2-k1 [exp(-k1 exp(-k1t)-exp-k2t)] (12)
The complexity of these equations prevents simple
comparison of kinetics observed for different
membrane materials. Therefore, it is useful to
examine and compare maximum release rates which
can be attained in a given experimental condition.
dSf/dt|max = -k1 (k1/k2)-k1/(k1-k2) =Jfmax (13)
dSLM/dt|max = 0 (14)
dSs/dt|max = k2 (k1/k2)-k2/(k1-k2) =Jsmax (15)
5. SOLVENTS and EXTRACTANTS used in LM
The nature of solvent in liquid membranes has also
great influence on the efficiency of solute transport
through membrane to received phase. Some
commonly used solvents are listed in Table 1. The
solvents chosen belong to different solvent classes
(Kislik and Eyal, 1996a). Class I: open-chain and
160
cyclic hydrocarbons (methylcyclohexane, n-octane, n-
decane, n-dodecane, n-tetradecane, n-hexadecane and
kerosenes of & different origine); class II: -donor
molecules (isopropylbenzene (cumene) and
1,3,Strimethylbenzene (mesitylene) ); class III:
halogenated molecules (2-chlorobutane); class IV, -
donor molecules (ethylcarbonate); protic solvents (2-
ethylhexanol). The solvents selection is based on the
fact that they ought to have lower density than water
and a vanishingly small mutual solubility in the latter.
The paraffins used as membrane were chosen for
physicochemical and technological reasons. They are
structurally related (homologous series) and lighter
than water, they have low volatility, high flash point
and low melting point (all liquids at T= 25 C). Their
viscosity varies considerably in the series and their
mutual solubility in water is practically zero.
The solvents generally used for liquid membrane
processes are typically flammable, volatile, toxic and
their use leads to environmental and safety risks. The
room temperature ionic liquids (RTIL) are considered
green solvent due to non-flammable nature and
negligible vapour pressure. However, their toxicity
data are not available (Swatloski et al., 2003).
Nevertheless, the choice of a solvent also depends on
economic considerations, which has not been
evaluated in laboratory scale studies. Vegetable oils
are considered to be the non-hazardous, cheap
chemicals, which can be used in BLM, as the novel
and greener LM. These vegetable oils are naturally
occurring, easily available, non-toxic, low cost and
renewable sources (Muthuraman and Palanivelu,
2006; Chang et al., 2010; Talebi et al., 2012).
 Teng et al.
Bulk Liquid Membrane and Its Applications in Wastewater Treatment

Table 1: Some commonly used solvents for liquid membrane

Extracted Material Solvent (extractant/diluent) Reference
Acetic acid TOA/(MIBK; octanol; n -alkanes) Lee et al., 2001
Amines/n alkanes Solichien et al., 1995
(TOA; TOPO; TBP)/hexane Eyal and Bressler, 1993; Wodzki and
Nowaczyk , 2002
(Aliquat 336; TBP; TOPO; Alamine Juang and Wu, 1999
Tertiary amines/diluents Senol, 1999
Propionic acid Amines/n alkanes Solichien et al., 1995
TOA/xylene Juang et al., 1993
(TOA; TOPO; TBP)/hexane Wodzki et al., 2000; Wodzki and
Nowaczyk, 2002
Butyric acid TOA/n alkanes Sabolova and Schlosser, 2000, 2001,
Kertesz and , Schlosser, 2005)
Amines/(corn oil, oleyl alcohol) Wu and Yang, 2003
TOA/n alkanes Sabolova and Schlosser, 1998; 2000
TOA/n alkanes Sabolova and Schlosser, 1999
Valeric acid Amberlite LA-2/toluene Rodriguez et al., 1997; Viegas et al.,
1997; Coelhoso et al., 2000; Gonzalez
et al., 2001
(Amines; Aliquat 336; TBP)/(kerosene; n - heptane; Luque et al., 1995
toluene)
Dimethylcyclopropan- TOA/n alkanes Schlosser et al., 2001
carboxylic acid (DMCCA)
TOA/n alkanes Schlosser et al., 2001; Sabolova et al.,
1999; Schlosser and Sabolova, 2002
5-Methyl-2-pyrazinecarboxylic TOA/xylene Sabolova et al., 2001; Kubisova et al.,
acid (MPCA) 2002a, 2004
TOA/xylene Kubisova et al., 2002b
Succinic acid n Butanol Prasad et al., 1988
Aconitic, oxalic, malic acids TBP/Shellsol 2046 McMurray et al., 2002
Lactic acid Tertiary amines/(n -alkanes, isodecanol, isotridecanol) Kubisova and Schlosser, 1996
Aliquat 336/Shellsol A Coelhoso et al., 1997; Coelhoso et al., 2000
TOPO/kerosene Scheler et al., 1999
(TOA; TOPO)/(oleyl alcohol, n -hexane) Hano et al., 1996
Alamine 336/(kerosene, oleyl alcohol) Chen and Lee, 1997
Alamine 336/2-octanol Huang et al.,2004
(Amines; Aliquat 336)/(n -alkanes; oleyl alcohol) Giorno et al., 1996
TOA/xylene Juang et al., 2000
TOMAC/oleyl alcohol Tong et al., 1998
TOMAC/oleyl alcohol Tong et al., 1999
TOMAC/1-decanol Gonzalez et al., 2004
TOPO, TOA, TBP Kondo et al., 2004
Tertiary amines/(n -alkanes, isodecanol, isotridecanol) Kubisova and Schlosser, 1996; Gonzalez-
Munoz et al., 2004
TBP/(isooctane, SPAN80) Demirci et al., 2007
Amines/n alkanes Scholler et al., 1993
TOA/xylene Juang et al., 1998
(Amines; TOA; TOPO; TOMAC; TBP)/(kerosene; hex- Hano et al., 1993
ane; toluene; oleyl alcohol)
(Amines; trialkylphosphinoxides)/(kerosene; oleyl alco -hol) Siebold et al., 1995

Alamine 336/oleyl alcohol Tik et al., 2001

Citric acid TOA/xylene Juang et al., 2000; Juang and Chen, 2000
TOA/MIBK Basu and Sirkar, 1991
Amines/(hydrocarbons, alcohols) Juang et al., 1998; Friesen et al., 1991
Alamine 336/(n -alkanes and chloroform) Yordanov and Boyadzhiev, 2004
Phenylalanine Aliquat 336/(kerosene, isodecanol) Escalante et al., 1998; Escalante and
Irabien, 2001
L-Isoleucine D2EHPA/kerosene Ma et al., 2002
Phenylalanine, L-isoleucine Reversed micelles with polyoyalkylene Wang et al., 2004
L-Lysine D2EHPA/n alkanes Boyadzhiev and Atanassova, 1991
Tryptophan, dipeptide AOT/oleyl alcohol Hossain, 2000
Tryptophan Aliquat 336/Shellsol A Coelhoso et al., 2000
N -(Benzyloxycarbonyl)-L- tert Amylalcohol Rindfleisch et al., 1997; Lazarova et al.,

161
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Chapter 6: Wastewater Treatment by Membrane Techniques

2002
Antibiotics: Penicillin G Amberlite LA2/(kerosene, isodecanol) Kedem and Bromberg, 1993; Isono et
al.,1997
Cephalosporine Aliquat 336/n heptanes Sahoo et al., 1999
Erythromycin Decanol Kawasaki et al. 1996
Tylosin Isodecanol; octanol Boyadzhiev and Kirilova, 2000;
Boyadzhiev et al., 2003
Bacteriocins (nisin, variacin, Alkanes, toluene, decanol, butylacetate Kelly et al., 2000
Mevinolinic acid (MV-819) Isopropyl acetate Prasad and Sirkar, 1989
4-Methyltiazole, 4- Toluene; benzene Prasad and Sirkar, 1990
cyanothiazole
Diltiazem Decylalcohol Basu and Sirkar, 1992
7-Aminocephalosporanic acid Aliquat 336/butylacetate Sahoo et al., 1996
p -Aminobenzenesulfonic acid TOA/(kerosene, octanol) Wang et al., 2002
2-Aminoethanesulfonic acid Ionic liquids Gu et al., 2004
Nucleotides (adenosine Quaternary ammonium salt/isooctane Kubota et al., 2002
derivatives)
Oxygenates (aromas) from Cyclodextrine derivatives Brose DJ et al., 1995
citrus oil
Phenol Cyanex 923/kerosene Urtiaga et al., 1994
Phenol Cyanex 923/kerosene Urtiag et al., 1994
Nitrophenol 1-Octanol Tompkins et al., 1992

5.1. Hybrid Membrane System
From simple bulk liquid membranes (BLM) shown in
Fig. 2A, construction of multimembrane hybrid
systems (MHS) such as those shown in Fig.2B and
Fig. 2C have been proposed (Kedem and Bromberg,
1993; Wodzki and Sionkowski, 1995; Kislik and Eyal,
1996 a&b; Wodzki and Nowaczyk, 1997; Eyal and
Kislik, 1999, 2000 a&b; Wodzki et al., 2000; Gega et
al., 2001; Wodzki and Nowaczyk, 2002; Wodzki and
Nowaczyk, 2002; Wodzki et al., 2002a).

Fig. 2: Schemes of pertractors and their operation: (A) simple bulk liquid membrane pertractor (BLM), (B) multimembrane
hybrid system (MHS), (C) multimembrane hybrid system coupled to Donnan dialysis (DD-MHS). f: feed solution, s: stripping
solution, m: liquid membrane, CEM: cation-exchange membrane, ms: mediating solution. Specific subprocesses1: interfacial
extraction or back-extraction, 2: loaded (C2 M) and unloaded (CH) carrier diffusion, 3: ion-exchange sorption or desorption of
cations from/into aqueous solution, 4: cation-exchange dialysis, 5: interfacial cation-exchange between the carrier and CEM
functional groups, 6: Donnan dialysis between f and ms through CEM.

162
 Teng et al.
Bulk Liquid Membrane and Its Applications in Wastewater Treatment
The general idea of MHS is based on coupling the
operation of the BLM to the operation of other,
physically different, dense polymer membranes that
are able to support the properties of BLM and
maintain its stable functioning in time. A simple MHS
can be constructed in the form of a serial arrangement
of cation (CEM) or anion exchange polymer
membranes with a liquid membrane placed in between
(Fig. 2B). The MHS performances can be regulated
both by changing the properties of a liquid membrane
and the proper selection of polymer membranes
(Wodzki et al., 1999). Moreover, the sandwiching
of a liquid membrane between two reactive polymer
membranes allows an additional coupling of the
overall system with other membrane processes, e.g.
Donnan dialysis (DD) and pertraction in the MHS
(DD-MHS), Fig. 2C (Wodzki and Szczepanski, 2001),
or MHS pertraction with the process of water
pervaporation from the liquid membrane (Wodzki and
Szczepanski, 2000, 2002; Wodzki et al., 2002b). On
the other hand, a parallel arrangement of two different
MHS leads to a double multi membrane hybrid system
(d-MHS) presented schematically in Fig. 3A. A
general idea of pertraction (Zn2+ and Cu2+) throughout
two different supported liquid membranes arranged in
parallel was described in the pioneering paper by
Drioli and coworkers (Loiacono et al., 1986). A
similar system made of two different bulk liquid
membranes, with noncyclic polyether carriers, for
simultaneous separation of Li+ and K+ was reported by
Hiratani et al. (1987). The same idea was applied by
Sengupta and Sirkar (1988) for simultaneous
separation of two gases from ternary mixtures in a
system composed of two different polymer
membranes. The d-MHS was designed in order to
separate simultaneously two species of metal cations
from a multicomponent feed followed by their active
concentration in two separate receivers. The
163
pertraction process in each of the two MHS
subsystems involves such steps as:
cation-exchange between the feed and CEM,
cation-exchange dialysis throughout the
CEM,
cation-exchange between CEM and the ionic
carrier in a liquid membrane,
diffusion of the carrier in a loaded and
unloaded form,
back-cation-exchange between the carrier and
the CEM at the stripping side,
cation-exchange dialysis,
stripping-cation-exchange into one of the two
receiving solutions.
Depending on the carrier used for the liquid
membrane preparation, the selective separation of a
given cation from the feed can be achieved. On the
other hand, both the cation-exchange dialysis (CEM),
and pertraction (LM with ionic carrier) operate as
counter-transport processes which enable the up-hill
transport of cations (chemical pumping or secondary
active transport) to occur (Wodzki et al., 1999) . In
practice, liquid membrane systems operate slowly
when the concentration of the feed phase or the
concentration of the carrier in the membrane is very
low. To overcome this problem, the DD-d-MHS
integrated system (Fig. 3B) can be applied. In this
case, both MHS modules functioning is additionally
supported by preconcentration of cations by the DD
process. The respective membrane device (pertractor)
can be constructed by adding one additional CEM and
a mediating solution containing counter-transported
cations (usually H+) to d-MHS. According to the
scheme of operation in Fig. 3B, during Donnan
dialysis (Wodzki and Szczepanski, 2001), the cations
from the feed are continuously preconcentrated in the
mediating solution which is used simultaneously as
the feed solution for the MHS modules.
 Wastewater Engineering: Advanced Wastewater Treatment Systems
Chapter 6: Wastewater Treatment by Membrane Techniques

Fig. 3: Schemes of new pertractors and their operation: (A) double multimembrane hybrid system (d-MHS), (B) double
multimembrane hybrid system supported by Donnan dialysis unit (DD-d-MHS). Detailed description: the same as in Fig. 2.

6. CONCLUSION
Liquid membrane separation is a process which is
depending on rate process and chemical potential
gradient. This is important to take notice that
equilibrium between phases has not any effect on the
separation process.
The theory of membrane-based solvent extraction
suggests that overall mass transfer of solute consists
of several steps: diffusion of the solute through the
aqueous layer from the bulk source aqueous solution
to the phases interface (nonequilibrium process),
interaction of the solute with extractant and formation
of the solute-extractant complex (as a rule, the process
is rapid and reaches equilibrium at the interface),
diffusion of the solute-extractant complex through the
membrane support itself (nonequilibrium process),
and diffusion of the solute-extractant complex through
the organic layer to the bulk organic solution
(nonequilibrium process). Here, only one of the
components may be equilibrium based in two phases:
(1) if the kinetics of solute-extractant interaction is a
rate-controlling process, which is not true in the
majority of separations published in the literature, and
(2) if the overall mass transfer of the solute from the
bulk source solution to the bulk membrane solution
reaches equilibrium.
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Wastewater Engineering: Advanced Wastewater Treatment Systems
Available online at http://www.ijsrpub.com/books
2014 IJSRPUB

Challenges in Fabricating Suitable Membrane for Water Treatment Application

Ling-Yong Wong 1, Choon-Aun Ng1, Mohammed J. K. Bashir 1,*, Thiam-Leng Chew 2
1
Department of Environmental Engineering, Faculty of Engineering and Green Technology (FEGT), University Tunku Abdul
Rahman, 31900 Kampar, Perak, Malaysia
2
Department of Petrochemical 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. In this study, a multi component dope solutions with the range of polymer concentration 13 wt.% to 17 wt.% were
prepared using polyethersulfone, 1-methyl-2-pyrrolidinone and water. The PES-UF membranes were prepared based on a
dry/wet phase inversion technique. Membrane performances in terms of pure water permeability, salt water permeation, salt
water rejection and bacteria removal had been evaluated using low operating pressure (100 kPa to 500 kPa). The results
showed that membrane with polymer concentration of 13.60 wt.% had the best performance in terms of flux production and
salt water rejection. High salt water permeation from 1027.4 L/m2.h to 4109.6 L/m2.h and also 99.7% of salt water rejection
were achieved. In addition, a total rejection for E. coli and E. faecalis with flux rate of 320 L/m2.h and 400 L/m2 were obtained,
respectively. SEM image obtained also showed a fine asymmetrical membranes structures.

Keywords: Membrane, Water, Treatment

1. INTRODUCTION Studies showed that membrane technology has the

Water is an important essence for every living
creature throughout the world. We hardly separate our
daily life with the water. As water is so important to
us, various water treatment plants had been built up in
order to make sure the water we use is safe and free
from any threats. Water that passes through all the
treatments such as coagulation, flocculation,
sedimentation, filtration, and disinfection had been
guaranteed to be clean enough for us to drink, but
there is doubt about the safety to drink the water.
Since cases of waterborne breakout caused by
pathogens had been detected in many countries all
over the world, it indicates that water treatment plants
had face difficulties in providing water that is
perfectly safe for us (Drinking Water Contamination,
2006). One of the reasons is the water treatment plant
involves complicated and complex system in treating
process (Xia et al., 2004). With many systems
involved, some avoidable technical error will occur
causing severe effect to the users. In addition, the
disinfection product, usually chlorine had been long
time ago proven to cause side effects to the users
(Rook et al., 1974; Monarca et al., 2004). Over the
last decades, the tightening of water quality
regulations and the increased attention given to trace
contaminants in surface water and drinking water has
been urging of alternative treatment technologies in
order to improve conventional water treatment
processes (Hassan et. al., 2013). In order to serve the
purpose, membrane technology has become an
alternative since it can provide clean water and
rejecting all threats during the treatment process.
Moreover, the technology also has easier handling
system than the commercial water treatment plant.
171
potential to remove all pathogens in the water as well
as guaranteed a satisfactory safety level for the users
(Lo et al., 1996 and Cheryan, 1998). It has been the
most promising water treatment technique as it
provides good quality of treated water (Gupta and Ali,
2013).
In order to serve the application, membrane has to
be fabricated accordingly. There are generally several
important factors which will influence the
performance of produced membranes. Those factors
are materials selection (polymer, solvent, non-solvent
and additive), casting condition (shear rate and
surrounding temperature), and system components
(binary, ternary, and quaternary). Since there are too
many factors to be concerned, this study will mainly
focus on the polymer concentration which found to be
affecting the UF membrane performance most.
2. MEMBRANE TECHNOLOGY
Generally a membrane is defined as a selective barrier
between two phases; the term selective being
inherent to a membrane or a membrane process
(Mulder, 1996). There are several types of membrane,
such as microfiltration membrane (MF), ultrafiltration
membrane (UF), nanofiltration membrane (NF), and
reverse osmosis (RO). These membranes are listed in
Table 1 below according to their type, pore radius,
material, pressure, and application.
Membrane processes including microfiltration,
ultrafiltration, and nanofiltration experienced rapid
growth in drinking water purification applications in
past two decades (Liu, 2014). The low pressure
membrane processes, which are microfiltration (MF)
and ultrafiltration (UF) play an important role in the
 Wong et al.
Challenges in Fabricating Suitable Membrane for Water Treatment Application

water cycle. They are used in surface water treatment
to remove turbidity, pathogens and natural organic
matter (NOM). Often in these cases a chemical
coagulant is applied to generate a fine flocculants to
aid removal before membrane filtration. The low
pressure processes are also being used for
pretreatment of sea water or secondary treated effluent
(used water) prior to the high pressure of reverse
osmosis membranes (Fane et al., 2005). The low
pressure membranes also potentially simplify
treatment process trains by eliminating coagulation,
flocculation and sedimentation processes, and have
been considered as a substitute for conventional
drinking water treatment. Since membrane technology
has been applied for water and wastewater treatment,
it has grown steadily coincident with public demand
for high water quality and strict regulations (Lee et al.,
2004), until membrane considered as a promising
process to provide better drinking water quality for
water supply.

Table 1: Characterization of different membranes (Cheryan, 1998)

Membrane Type Membrane Process Diving
Process Applications
and Pore Radius Material Force

Cellulose nitrate or
Hydro-static
acetate,
Symmetric pressure
Polyvinylidene Sterile filtration,
Microfiltration microporous, 0.1- difference at
difluoride (PVDF), Clarification
10 microns approx.
Polyamides,
10-500 kPa
Polysulfone, etc.

Polysulfone, Hydrostatic
Asymmetric Polypropylene, pressure Separation of
Ultrafiltration microporous, Nylon 6, PTFE, difference at macromolecular
1-10 nm PVC, Acrylic approx. solutions
Copolymer 0.1-1.0 Mpa

Hydrostatic
Polymers,
Asymmetric skin- pressure Separation of salts
Reverse Cellulosic acetate,
type, difference at and microsolutes
Osmosis Aromatic
0.5-1.5 nm approx. from solutions
Polyamide
2-10 Mpa

Hydrostatic
Asymmetric
Polymers & pressure and Separation of gas
Gas Separation homogeneous
copolymers concentration mixtures
polymer
gradients
Cellulosic Acetate Removal of
Thin-film
Nanofiltration and Aromatic 9.3-15.9 bar hardness and
membranes
Polyamide desalting

Many researchers have suggested that the use of
low-pressure membrane filtrations that are MF and
UF have rapidly increased in the last decade due to
stricter regulations for finished water quality,
decreased cost, improved membrane materials and
modules, relative simplicity of installation, and
improved reliability compared to conventional
treatment processes such as sedimentation and rapid
filtration (Choi and Dempsey, 2004).
The rapid development of membrane technology in
recent years has boosted MF membrane to be an
alternative to overcome the problem. MF membranes
are widely utilized in the pharmaceutical industry, in
chemical engineering, biochemistry, and medicine as
well as in water and waste water engineering (Brock,
1983). It is more effective and safer compared with
the commercial treatment, but it brings about
drawback where microorganisms may pass through
the pores of microfiltration membranes. In certain
environment, during nutrient deprivation, bacteria
may become smaller than the previous size (Morita,
1993), with the diameter less than 0.3 m and pass
through 0.2 m membranes (Sadr Ghayeni et al.,
1999). In order to overcome this problem, UF
membrane which have relatively smaller pore size
than UF will be a need in the system.
2.1. Introduction to Asymmetric Membrane
An asymmetric membrane consists of very thin dense
top layer which has a thickness less than 0.5m. The
top layer is supported by porous layer where the
thickness is in a range of 50 to 200m (Mulder, 1996).
Its separation characteristics are determined by the

172
 Wastewater Engineering: Advanced Wastewater Treatment Systems
Chapter 6: Wastewater Treatment by Membrane Techniques
nature of membrane material or pore size, and skin
thickness mainly determines the mass transport rate.
Porous sub-layer acts as a support for the thin, fragile
skin and has little effect on the separation
characteristics (Hendricks, 2005). Asymmetric
membrane has been widely used for gas separation
and liquid separation. The thin top layer that plays a
role as a selective barrier film and the porous
sublayer, in which includes macrovoids, pores and
micropores, offers unique properties in terms of high
mass transfer rates and where good mechanical
stability can be best utilized (Ismail and Hassan,
2005). According to Ismail and Lai (2004),
asymmetric membrane consists of a skin of uniform
thickness supported on a porous sub layer whereby the
active skin layer acts as the actual separating barrier
while the sub layer serves only as a mechanical
support and do not involve in the separation process.
Mulder (1996) also stated that the transport rate is
determined by the top layer whereas sub-layer only
acts as a support. The permeation rate is inversely
proportional to the thickness of the actual barrier layer
and thus asymmetric membrane shows a much higher
permeation rate (water flux) than symmetric
membrane of comparable thickness. In addition to
high filtration rates, asymmetric membranes are most
fouling resistant. Asymmetric membranes are surface
filters and retain all rejection materials at the surface
where they can be removed by shear forces applied by
the feed solution moving parallel to the membrane
surface (Mark, 1988).
3. FABRICATION OF ASYMMETRIC
MEMBRANE
Asymmetric structure is usually prepared with dry/wet
phase inversion method. This method was preferred
since it was claimed to be the most versatile method to
produce high performance asymmetric membrane for
separation process (Ismail and Rahman, 2004). The
phase inversion process consists of the induction of
phase separation in a previously homogeneous
polymer solution either by changing the temperature,
by immersing the solution in a non-solvent bath (wet
process) or exposing it to a non-solvent atmosphere
(dry process) (Nunes and Peinemann, 2001). In the
formation process of a membrane, two types of phase
inversion can be distinguished. The dry phase
inversion takes place in the atmosphere by
evaporation of the volatile solvent during the casting
procedure forming a nascent membrane (more
obvious if induced with forced convection
evaporation). As for the wet phase inversion, it is
carried out by immersing the polymer solution into
coagulation bath of a non-solvent, where an exchange
of solvent and non-solvent occurred for membrane
173
mechanism formation or counter-diffusion of solvents
and non-solvent and extraction of the remaining
components occurs (Ismail and Hassan, 2005). The
dry/wet phase inversion normally involves multi-
component casting solution such as polymer, solvent,
non-solvent, and additive. In the research reported by
Ismail and Lai (2004), the solution was tailored to be
close to thermodynamic instability limit and
approaching phase separation. Binary system, ternary
system and quaternary system refer to casting solution
with respectively two, three and four components.
Figure 1 shows the framework for this study.
Membranes with ternary system were produced in
this study in order to differentiate the performance and
morphology among the membranes. For ternary
system, materials being used were polyethersulfone
(PES) as polymer, N-methyl-2-pyrrolidinone (NMP)
as solvent, and water as non-solvent. Water was also
used as coagulant bath, and methanol was used as post
treatment.
3.1. Binary System Solution
Binary system appears to be the fundamental solution
before it can be advanced to ternary and quaternary
system. To prepare a binary system, composition for
each chemical needed to be equipped as Equation 1.
Binary System Solution =
wt .% of component
x Volume of dope needed (1)
100%
3.2. Turbidimetric Titration Method
This is the method used to find out the real
composition of non-solvent additives which are
needed for preparing ternary or quaternary system
solution. Binary solution was poured into the burette
and the system was closed to minimize the
evaporation process. The solution was stirred with a
stirrer while non-solvent additives being added into it.
The speed for stirrer was set at 100rpm to minimize
the present of bubbles in the solution. 0.5ml of non-
solvent was added each time and waited until it was
totally dissolved by the solution before next 0.5ml
was added in. This process was continued until the
cloud point was reached, where the water
concentration in the polymer solution caused it to
remain turbid for more than 24 hours. This indicates
that phase inversion separation had occurred.
3.3. Ternary System Solution
The amount of non-solvent needed was determined
using turbidimetric titration method. The process for
ternary system preparation was similar to the process
 Wong et al.
Challenges in Fabricating Suitable Membrane for Water Treatment Application

to produce binary system. The only difference was the added into the solution together with solvent, and then
addition of non-solvent into the solution during the only polymer was added into it.
preparation for the ternary system. Non-solvent was

Fig. 1: Framework flowchart

3.4. Quaternary System Solution
The process for quaternary system preparation was
similar to the ternary system, with only addition of
additive into the ternary solution. In order to obtain
the amount of additive needed, titration method was
referred again. After polymer was totally dissolved in
solvent, additive was mixed into the solution little by
little until all of it was dissolved in the solution. The
solution was again kept agitated for at least 30
minutes to make sure that it was homogenized. After
that, casting solution was transfer into a glass bottle
and put into ultrasonic bath for about 2 hours in order
to remove the bubbles within the solution. Bottle
taken out from the ultrasonic bath was closed tightly
and placed at room temperature.
3.5. Membrane Casting
Membrane was prepared by casting solution with the
pre-determined composition. The membranes were
produced by dry/wet phase inversion technique using
casting machine. Firstly, solution was cast on a clean
smooth glass plate and supported with knife gap
setting of 150m. Ambient temperature was around
27C 30C. Time used in membrane casting was 10
174
seconds. After that, the glass plate with casting
solution was immersed into the coagulation bath
(water) immediately at ambient temperature for at
least 10 minutes where the phase inversion occurred
in the immersion. A thin polymeric film was form
immediately and after a few minutes it will separate
from the glass itself. This phase was responsible for
membrane formation by the diffusion exchange of
solvent and non-solvent across the interface between
casting solution and non-solvent (water). The formed
membranes were then overturned immersed with a
large amount of water for the next 24 hours (washing
bath). Finally, the membrane was put into methanol
for at least 8 hours for post treatment. This stage was
to remove excess solvent that was still left in the
membrane. Then the membrane was hanged for
drying at ambient temperature for 1 day.
4. Permeation Test
The membrane permeation tests were carried out with
Sterlitech stirred cell (Model HP4750) with volume
capacity of 300 ml. It has an active area of 14.6 cm2
for the membrane. Maximum operating pressure for
the cell is 69 bars. Membranes were characterized in
terms of membrane flux and salts rejection in the cell.
 Wastewater Engineering: Advanced Wastewater Treatment Systems
Chapter 6: Wastewater Treatment by Membrane Techniques
Prior to testing for inorganic electrolytes or salts
(NaCl, 0.01M), the pure water flux using distilled
water was measured to ensure the stability of the
membrane. The pure water flux was measured at
different pressure (1, 2, 3, 4, and 5 bar) with the
stirring speed fixed at 400 rpm to determine the water
permeability. The pressure was first increased then
decreased when testing the sample. Pure water flux
was calculated by taking the readings at a regular
interval by noting the time used to collect 5 ml of
permeate for each operating condition. Then,
experiments were carried out with salt (NaCl) to
obtain the rejection performance of the membrane.
The flux and rejection were measured using standard
0.01M NaCl for different feed solutions. The flux and
observed rejection were determined for each operating
condition. To reduce concentration polarization, the
stirring speed was fixed at 400 rpm or 41.881 rad/sec.
During the testing process, for example, when NaCl of
0.01M was passed through the membrane under
operating pressure of 1 bar, the rejection and flux was
measured after 10 ml of permeate had been collected
and the time to collect the mentioned volume was also
recorded.
Three sets of membrane samples were made from
the same casting condition specifies for this study and
the average flux and solute separation data was
reported. Under room temperature and different
operating pressure, the permeate flux was calculated
as Equation 2:
Volume permeationrate, (V )
Flux, Jv (2)
Membranearea, ( A) time(t )
Table 2: Casting solution formulation for ternary system
Before titration, in wt.%
(binary system)
Components
Casting Casting
Solution 1 Solution 2
PES 15 17
NMP 85 83
Water 0 0
5.1. Pure Water permeation (PWP) measurement
According to Figure 2 below, flux for produced
membranes increased when the pressure increased
from 1 bar to 5 bar. The flux increased linearly with
the increase in pressure. This is an important step to
shows that the produced membranes were stable in
producing flux and were suitable application. Figure 2
also shows the flux production increased as the
175
Where,Jv = the permeate flux of salt aqueous
solution or pure water flux (m3/m2 s); A = the effective
area of membrane (m2); t = the time (s); V = Volume
of permeate solution collected, (m3)
For pure water flux, the permeability of each
membrane was determined by the measurement of
water flux as a function of applied pressure, shown as
Equation 3.
Jv
Pm (3)
P
Where, Pm = Permeability (m3/m2 s Pa); Jv = Flux
(m3/m2 s); P = Applied Pressure (Pa)
5. RESULT AND DISCUSSION
Polyethersulfone UF membranes were formulated by
varying the polymer concentration in the range of 13
wt% to 17 wt%. This concentration range is usually
used for the preparation of ultrafiltration membranes.
High concentration of the polymer that is more than
19 wt.% may produce nanofiltration while polymer
concentration lower than 11 wt.% may produce
membranes in micofiltration. To achieve high
performance membrane (high rejection to solute with
acceptable flux rate), the membrane cannot be too
loose for the structure as it will decrease the rejection
ability, neither too tight which will decrease the flux
production. Range of polymer concentration used in
this study was in the middle of the UF range, which
means higher possibility to achieve the objectives. All
the compositions were obtained through turbidimetric
titration measurement. Composition for membrane
solution is presented in Table 2.
After titration, in wt.%
(ternary system)
Casting Casting Casting Casting
Solution 3 Solution 1 Solution 2 Solution 3
19 13.60 15.40 17.70
81 77.40 75.30 75.70
0 9.00 9.30 6.60
concentration of PES decreased in solution. Detail of
permeability coefficient of each membrane is as
shown in Table 3.
From Table 3, membrane with polymer
concentration of 17 wt.% produced the least flux if
compared to other membranes. It might cause by the
thickness of the membrane posts greater hindrance
effect on the permeate through the membrane. By
decreasing 2 wt.% of polymer, produced membrane
 Wong et al.
Challenges in Fabricating Suitable Membrane for Water Treatment Application

was showed a good result by increasing the flux rate
to around 100 times. This shows that membrane was
more porous and permeate could pass through it
faster. A deduction of polymer by 2 wt.% again
produced a membrane with a permeability coefficient
which was more than 4 times higher than the 15 wt.%
PES membrane, and 500 times than the 17 wt.% PES
membrane. It was found that PES 13 wt.% was the
best flux production membrane among the produced
membranes. Although having a great flux, there is
another important factor for membrane performance,
which is rejection. Produced membrane was tested
with 0.01 M NaCl and the result is explained in the
following section.

Fig. 2: PWP at different pressure

5.2. Electrolyte Rejection by ternary system
Based on Figure 3, once again the membrane with
PES concentration of 13 wt.% produced the highest
flux compared to other membranes. It was found that
flux produced has increased as the concentration of
PES in solution decreased. It shows a huge difference
in the amount of flux produced compared to the others
at the same pressure given (1 bar to 3 bar). Membrane
with 15 wt.% of PES produced second highest flux,
followed by membrane with 17 wt.% of PES which
produced the least flux at the same pressure provided.

Table 3: Permeability coefficient for membrane

176
 Wastewater Engineering: Advanced Wastewater Treatment Systems
Chapter 6: Wastewater Treatment by Membrane Techniques

4500

4200
PES 13 wt.%
3900
PES 15wt.%
3600
PES 17wt.%
3300

3000

2700
Flux [L/m 2 .h]

2400

2100

1800

1500

1200

900

600

300

0
0 1 2 3 4 5 6

P ressure (Bar)

Fig. 3: Fluxes of NaCl (0.01M) vs pressure for fabricated membrane with different polymer concentration

Detail for permeation produced by membranes in
salt water (NaCl 0.01 M) rejection is shown in Table 4
below. Membrane with the concentration of PES 17
wt.% showed a low flux rate of 5.5 21.1 L/m2.h
when 1-5 bar of pressure was provided. Decreasing 2
wt.% of polymer increased significantly the flux to
260-1120.8 L/m2.h, which is around 50 times higher
than the flux for membrane with 17 wt.% PES. By
decreasing 2 wt.% more of polymer concentration,
which brought it to 13 wt.%, the flux produced has
increased to a range of 1027.4 4109.6 L/m2.h when
low pressure (1-5 bar) was provided.

Table 4: Salt water flux produced by membranes at pressure given

It shows a great increase with more than 200% for
flux produced with decreasing PES concentration
from 17 wt.% to 13 wt.%. For 15 wt.% of PES
concentration, even it was showing better increase in
flux produced if compared to membrane with 17
wt.%, decrease of 2 wt.% more will provide the
membrane with greater performance in flux
production.
A high performance membrane should be able to
offer high flux and high solute rejection Salt rejection
(0.01 M NaCl) studies was tested on the membranes
and results are as shown in Figure 4.

177

Challenges in Fabricating Suitable Membrane for Water Treatment Application
120
100
80
Rejection (%)
60
40
20
0
0 1
Fig.4: Electrolyte rejection vs pressure for fabricated membrane with different polymer concentration
It was shown in Figure 4 that the membranes
performed differently in the solute rejection tests. The
lowest rejection range (40-60%) was provided by 17
wt.% membrane. Meanwhile, membrane with 15 wt.%
showed good rejection even at low pressure where the
performance increased with increasing pressure. For
membrane with 13 wt.% of polymer, it again achieved
Table 5: Rejection of NaCl (0.01M)
5.3. SEM Cross Section Analysis
Generally membrane with higher concentration of
polymer gives higher rejection, but in this study,
membrane with 17 wt.% PES performed poorly
compared to other membranes, which gave rejection
of 50% to 60%. By reducing the concentration of
polymer to 15 wt.%, the rejection increased to higher
range of 87% to 99%. When it came to membrane
with the PES concentration of 13 wt.%, again it gave
the total rejection ability to salt water, where it
Wong et al.
PES 13wt.%
PES 15wt.%
PES 17wt.%
2 3 4 5 6
Pressure (Bar)
highest rejection (100%) among the membranes even
only low pressure (1 and 2 bar) was provided. As
presented by Table 5, solute rejection for membranes
shows an increase in the sequence of membrane with
17 wt.%, 15 wt.% to 13 wt.%. This shows that the
concentration of PES had great effect on the rejection
performances.
achieved 99% rejection at low pressure (1-2 bar), and
even achieved 100% rejection when higher pressure
was applied (3-5 bar). The experimental data were
then confirmed by the cross sectional images taken by
scanning electron microscope (SEM) at magnification
of 700X. SEM images shown in Figure 5 revealed the
membranes cast at low polymer concentration tend to
posses thicker membrane layer, large pore radius and
larger macrovoids, thus exhibiting a highest rejection
and highest flux rate.
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 Wastewater Engineering: Advanced Wastewater Treatment Systems
Chapter 6: Wastewater Treatment by Membrane Techniques

A thick skin layer, nicely formed finger-like
structure, and large macrovoids was observed in the
cross section SEM view for membrane with 13 wt.%
PES. The structure provided a good condition to
produce high flux rate and high rejection. When 2
wt.% more polymer being added, macrovoid was
found to be absent and skin layer became thinner. This
situation explain the reduction in flux rate and
rejection ability of PES 15 wt.% compare to PES 13
wt.% membrane. SEM images of the membranes
sample showed that a finger-like structure provided
good membrane porosity and higher flux rate. As
polymer concentration increased, the larger macro
voids disappeared. This is a factor for the reduction of
flux rate. At 17% of polymer concentration, the
membrane pore size and membrane active layer were
reduced which resulted in the lowest flux rate.
However, the increasing number of membrane pores
did not influence the higher flux and rejection due to a
thinner active layer.
The result for the ternary system showed that
membrane with 13 wt.% of polymer concentration
was the best among the produced membranes. It not
only showed the outstanding performances in flux
produced, but also for the rejection of 0.01 M NaCl.
5.3. Bacteria Filtration Application
One of the important parameters in water treatment is
bacteria rejection for the system. If the system failed
to do so, then all the users are exposed to the bacteria
contaminated water, which will definitely jeopardize
their health. In this study, the bacteria removal studies
at low pressure (1-3 bar) were carried out for the
ternary system membrane with PES concentration of
13 wt.%, since it was found that the membrane with
13 wt.% PES gave the best performance. Pure cultures
for E. coli and E. Faecalis were applied in feeding
solution and result for flux production and removal
ability were shown as Table 6 and Table 7.

Table 6: Filtration result in log form for E. coli

179
 Wong et al.
Challenges in Fabricating Suitable Membrane for Water Treatment Application

Fig. 5: SEM cross-sections of novel AULP membranes at different composition; (a) 13 % polymer; (b) 15 % polymer and (c)
17 % polymer

180
 Wastewater Engineering: Advanced Wastewater Treatment Systems
Chapter 6: Wastewater Treatment by Membrane Techniques

Table 7: Filtration result in log form for E. faecalis

Feed Permeate
Pressure Flux BRI BRLI
Concentration, Concentration,
(Bar) (L/m2.h) (%) (log)
Cf (cfu/ml) Cp (cfu/ml)

7x106 1 342.47 100 >6

1
7x108 1 286.72 100 >6

7x106 1 616.44 100 >6

2
7x108 1 440.31 100 >6

7x106 1 725.22 100 >6

3
7x108 1 513.70 100 >6

According to the result obtained, removal of
bacteria which was higher than 6 logs (totally
removed) was achieved by the PES 13 wt.%
membrane even high concentration was used as feed
solution. Changing pressure did not post significant
effect on change of the removal ability of the
membrane. However, increasing pressure during
application enhance significantly the flux production.
As totally rejection obtained, it means that produced
UF membrane had a smaller pores size than the
bacteria. According to Tsummi et al. (1990), in the
cell separation by such porous membrane, molecular
size exclusion effect is dominant factor. When the size
of the solute is much larger than pore size of the
membrane, effective cutoff occurs. Once it achieved
totally rejection to the bacteria, it shows that produced
membrane was safe to be used for bacteria filtration
process as it was impossible for bacteria which have
bigger size than the membrane pores can pass through
it.
6. CHALLENGES IN FABRICATING
SUITABLE MEMBRANE FOR WATER
TREATMENT APPLICATION
There are several parameters must be considered in
order to produce high performance membranes, such
as dope formulation, casting condition, ambient
temperature during membrane casting, shear rate,
membrane thickness and so on. Changes on each
parameter, may affect membrane properties, and
hence changing the membrane performance in
different application. In order to reproduce a high
performance membrane, all the parameters involved
during membrane fabrication must be recorded in
detail.
Another challenge is to produce membranes which
give good fluxes and rejection. These always become
a limitation when it comes to the flux and selectivity
181
problems. Generally a membrane with bigger pore
size and loose structure will have higher flux, but
lower rejection ability. By increasing polymer
concentration in the solution, it will make the
membrane become denser and usually rejection ability
will be improved as well, but flux production will be
decreased. This is supported by Li (1993) where in his
study, he found out that as flux increase, membrane
selectivity will decrease and as the selectivity
increased, fluxes will be decreased.
Even though there is no perfect membrane, which
can serve all application with perfect rejection and
high flux production, but still there is optimum
membrane which can serve in specific application
with the acceptable range of removal ability and flux
production.
7. CONCLUSION
Based on the experimental data, this study had proven
that membrane with ternary system and concentration
of PES 13.60 wt.% was the best among the produced
membranes. It showed excellent performance in terms
of flux (2700 L/m2.h) and achieved 99.97% for salt
rejection (NaCl 0.01 M). In addition, the membrane
also achieved 100% rejection for the bacteria (E. coli
and E. faecalis) with an average flux of 320 L/m2.h
and 400 L/m2.h at low pressure provided (1 bar). SEM
cross sectional images clearly observed that this
asymmetric membrane provides great properties and
excellent separation performances. As the produced
membrane able to totally remove the bacteria in water,
this may help to provide a safe and clean drinking
water for those needed.
 Wong et al.
Challenges in Fabricating Suitable Membrane for Water Treatment Application
ACKNOWLEDGEMENTS
We would like to extend our gratitude to Ministry of
Science, Technology and Innovation (MOSTI) for
the fund with project No. 03-02-11-SF0161.
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Wastewater Engineering: Advanced Wastewater Treatment Systems
Available online at http://www.ijsrpub.com/books
2014 IJSRPUB

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, B.S. Ooi*

School of Chemical Engineering, Engineering Campus, Universiti Sains Malaysia, Seri Ampangan, Nibong Tebal 14300 Pulau
Pinang, Malaysia, Tel: +6045996418; Fax :+6045941013;
* Corresponding Author: chobs@eng.usm.my

Abstract. Membrane based separation is another efficient method for separating inorganic substances from aqueous effluents
due to its simplicity to scale-up and low energy consumption. Nevertheless, application of this method to remove heavy metals
from wastewaters is still a challenge to most researchers owing to the fact that heavy metals exist in aqueous solution as
hydrated ions with low molecular weights that can easily pass through most membranes except membranes for reverse osmosis
(RO) and nanofiltration (NF). However, RO and NF membranes with denser structures and narrower pores have very low
selectivity where nearly all types of solutes in the effluent are retained instead of separating only the targeted metal ions.
Furthermore, high energy is consumed and high operating pressure is required to achieve adequate permeation of solvent
through these types of membrane. Advanced materials combined with smart membrane systems could provide low energy and
highly sustainable metal recovery process. For example, polymer enhanced ultrafiltration combined with thermo-responsive
hydrogel could offer such attractive process. Compared to the conventional adsorbents, the adsorption capacity of the thermo-
responsive hydrogel is a function of solution pH, ligand density as well as temperature. The separation of hydrogel from the
waste stream can be realized through temperature induced agglomeration as well as steric retention by the membrane. The
separation process could be almost instantaneous with the metal recovery obtained even at very trace concentrations. Lower
temperature is more favorable due to the swollen hydrogel that exerts less diffusional resistance for metal to bind within the
interior marix. Low temperature is also favorable as it promises less membrane fouling phenomenon.

Keywords: Copper removal, Polymer-enhanced Ultrafiltration, Aqueous Solution

1. INTRODUCTION on metal removal is currently resolved by integration

Heavy metals are inorganic pollutants commonly
found in wastewaters discharged from industries like
metal-plating, tanneries, batteries, automobile and
fertilizer manufacturing. The pollution of natural
water-bodies especially rivers by the metal-
contaminated industrial effluents is becoming one of
the most serious environmental problems. Several
conventional methods had been widely adopted to
scavenge metal ions from aqueous solution including
ion exchange resins, electrodialysis, chemical
precipitation, adsorption and membrane separation.
However, the efficiency of these methods has been
constraint by some unsolved challenges such as
production of secondary sludge, low selectivity and
low metal-recovery efficiency (Lazaridis et al., 2004,
Dermentzis et al., 2009, Ghodbane et al., 2008).
In terms of low energy consumption and high
solute-rejection efficiency, ultrafiltration (UF) is
deemed as a promising membrane separation process
for the treatment of industrial wastewaters. The
average pore diameters of UF membranes fall within
the range of 10 1000 (1 100 nm). The pore
structures at this range of pore diameters allow
permeation of microsolutes with molecular weight
(MW) less than 300 g/mol. Nevertheless, copper
divalent ion (Cu2+) as a transition metal ion with
molar mass of merely 63.55 g is too low to be retained
by a UF membrane. The shortcoming of UF process
of both metal-polymer complexation and UF
(Micheals, 1990). This combination is known as
polymer-enhanced ultrafiltration (PEUF).
In PEUF operation, water-soluble polymer with
metal-chelating ability is used as chelating agent to
complex with a targeted metal ion. The metal ion is
chelated by functional ligands of the polymer such as
carboxylic (-COOH) and amide (-CONH) groups via
electrostatic interaction to form metal-polymer
complexes. The complex can then be retained by UF
membrane effectively (Almutairi and Lovitt, 2012,
Camarillo et al., 2012, Zerze et al., 2013).
Complexation of metal in aqueous solution is deemed
as a major type of metal ion adsorption by polymeric
substances through chelation process. Polymer with
metal-chelating ligands are known as chelating agent
(chelator) that bind with free metal ions in aqueous
solution to form complex molecules known as
chelates. A chelator contains one or more ligands
that are ionic or neutral such as SO3H, -COOH, -NH2,
-OPO3H and -C=O. Each ligand could possess mono-,
bi- or even polydentate enabling it to form ring
structure with a metal ion (Flora and Pachauri, 2010,
Butvin et al., 1988).

183
 Chen et al.
Removal of Copper from Aqueous Solution by Using Thermo-responsive Polymer Hydrogel as Copper Chelator via
Polymer-enhanced Ultrafiltration (PEUF)
1. COMPLEXATION OF COPPER IONS BY
POLYMER WITH METAL-CHELATING
LIGANDS
The metal-ligand complex formation between a metal
ion and ligands of a polymer can be described by the
following reaction:
(1.0)
where M refers to a free metal ion; L is a ligand of
polymer, and n is known as the number of ligands
involved in chelation with the metal ion.
The chelation of metal ion by acidic ligands of a
polymer involves dissociation of acidic functional
groups like carboxylic groups (-COOH) into both
anionic carboxylates (-COO-) and H+ protons at pH
higher than pKa of the acidic ligand involved, for
example, pKa of acrylic acid (AA) is around 4.3.
Hence, it is important to determine their dissociation
equilibrium prior to analyzing the copper binding
equilibrium. Camarillo et al. (2012) elucidated that the
dissociation equilibrium constant, Ka of protonated
ligands is expressed as:
(1.1)
where L- is the deprotonated ligands of polymers,
whereas HL refers to protonated ligands and
represents a constant depending on each polymer
ligand which accounts for nearest neighbouring
interaction (Camarillo et al., 2012, Porasso et al.,
2000). This expression is also applicable to other
polymers with acidic ligands in which their chelating
ability is mainly contributed by their acidic functional
groups.
Since the dissociation of carboxylic groups is
dependent on pH, therefore solution pH in the absence
of metallic ions is expressed as a function of Ka, and
the degree of protonation, . The expression is known
as modified Henderson-Hasselbach equation as shown
in Equation 1.2:
(1.2)
The protonation degree, is usually expressed as
molar ratio of added base (NaOH) to carboxylic acid
(-COOH) of AA moieties in a PNIPAM-co-AA
polymer hydrogel:
(1.3)
where [NaOH] represents molar concentration of
NaOH added into the reaction solution; CH is the total
molar concentration of carboxylic (-COOH) and
carboxylate (-COO-) of hydrogel (Camarillo et al.,
2012, Flora and Pachauri, 2010). Hence in the
presence of metal ions, the concentration balance of
184
protonated ligands, [LH], deprotonated ligands [L] and
chelated ligands [MLn] is expressed as:
(1.4)
where [L]total is the total ligand concentration in the
solution. In addition, the extent of metal-ligand
complexation is described by a complex formation
constant, Kf which is defined as: (1.5)
where: [MLn] = concentration of metal-ligand
complex formed; [M] = concentration of metal ion; [L]
= concentration of protonated ligand
The value of this formation constant is highly
dependent on solution pH, and it is also expected to be
influenced by temperature for thermo-responsive
PNIPAM-co-AA polymer hydrogels.
For ease of experimental measurements and
calculation, the chelating ability of a polymer is
usually quantified by its chelating capacity in
equilibrium state, which is always expressed as a
parameter known as equilibrium adsorption capacity,
qe in most of the metal adsorption studies as shown in
Equation 1.6:
(1.6)
where V (L) is the total volume of reaction solution,
M (g) is the dry mass of chelating polymer.
2. APPLICATION OF THERMO-RESPONSIVE
PNIPAM-co-AA POLYMER HYDROGEL AS
NOVEL CHELATING AGENT
Selection of a suitable chelating agent is important for
optimizing the efficiency of metal ions-complexing in
PEUF. Water-soluble polymers are usually chosen as
potential metal chelators due to the presence of
hydrophilic functional groups that act as ligands for
metal chelation such as amide (-CONH), carboxylate
(-COO-) and carbonyl (-C=O). These functional
ligands are Lewis acids or bases that donate electron
pair to fill the unoccupied d-orbital of a metal ion to
form a chelated complex (Flora and Pachauri, 2010,
Hancock and Martell, 1989).
There are numbers of studies reported on the use of
different water-soluble polymers as metal chelating
agents in PEUF processes. Among them,
polyethyleneimine (PEI), poly(vinyl sulfonic acid)
(PVSA) and poly(acrylic acid) (PAA) are the most
common chelators for the evaluation studies of PEUF.
Ca izares et al. (2002) applied water-soluble PEI
(MW = 25,000 g mol-1) and PAA (MW = 250,000 g
mol-1) for recovering Cu2+, Ni2+, Pb2+ and Cd2+ cations.
The affinity of these two types of polymer toward
metal ions are attributed to their metal-chelating
ligands like amines (-NH) groups in PEI and
carboxylic (-COOH) in PAA (Ca izares et al. 2002).
PEI also attracted interest from slamolu et al. (2006)
 Wastewater Engineering: Advanced Wastewater Treatment Systems
Chapter 6: Wastewater Treatment by Membrane Techniques
to study the effect of ionic strength on its
complexation with Cd2+ and Ni2+ in PEUF process.
They found that in the absence of NaNO3 salt, the
retention value of Cd2+ was higher than that for Ni2+.
In contrast, as 0.5 N NaNO3 was added to the binary
metal solution, the retention of Ni2+ became higher
instead (slamolu et al. 2006).
In 2008, Llanos and partners synthesized a novel
derivative of PEI known as partially ethoxylated
polyethylenimine (PEPEI) as chelator for Cu2+
recovery in PEUF. The results show a maximum
retention percentage over 97 % obtained with feed
loading ratio of 208 mg Cu per g. of PEPEI at pH 6
(Llanos et al., 2008). Labanda et al. (2009) compared
the ethoxylated PEI (EPEI) with polyvinyl alcohol
(PVA), polyacrylic acid-co-maleic acid (PACM) and
PEI on the recovery of Cr3+ in PEUF. They discovered
that among these four types of chelating agents,
PACM with carboxylic groups formed relatively
stable irreversible complex with Cr3+, whereas
alcoholic PVA with hydroxyl groups did not chelate
with Cr3+ at all. The amines of PEI and EPEI formed
hydroxo-complexes with Cr3+ ions under varying pH
(Labanda et al., 2009).
Since water-soluble polymers like PEI form highly
stable metal complex in aqueous solution, it is not
easy to be dissociated in low pH medium to achieve
objective of metal recovery. A type of intelligent
polymeric microgel with thermo-responsive property
known as poly(N-isopropylacrylamide-co-acrylic acid)
(PNIPAM-co-AA) polymer hydrogel is applied as a
novel chelating agent in PEUF for removal of divalent
copper ions (Cu2+) from aqueous solution. This
polymer hydrogel consists of a cross-linked network
structure with a shape of globule conformation which
makes each hydrogel structure a discrete nano-size gel
particle in aqueous phase. It undergoes a temperature-
induced volume phase transition (VPT) process
manifested as swelling-shrinking behaviour under
varying temperature (Yang et al., 2004, Burmistrova
et al., 2011, Chen et al., 2013, Zhang and Wang, 2009,
Yamashita et al., 2003).
3. THERMO-RESPONSIVENESS OF PNIPAM-
co-AA POLYMER HYDROGEL
Physically, the hydrogel swells below its volume
phase transition temperature (VPTT) (~32 C)
because its hydrophilic functional ligands like amides
(-CONH) and carboxylic (-COOH) and carbonyl (-
C=O) tend to form hydrogen bonds with water
185
molecules which leads to expansion of the hydrogel
network. As temperature increases above its VPTT,
the hydrophilic groups are hidden and forming strong
inner hydrogen bonds within hydrogel interior. The
formation of short-range hydrogen bonds among
ligands causes expulsion of water from hydrogel and
shrinkage of the entire hydrogel network
conformation. On the other hand, hydrophobic groups
like isopropyl and methyl groups are gradually
exposed to the exterior of hydrogel at temperature
above VPTT, and the shrinking mechanism causes
hydrogel to be separated from aqueous phase (Chen et
al., 2013, Zhang and Wang, 2009, Yamashita et al.,
2003).
The thermo-responsive behaviour of PNIPAM-co-
AA polymer hydrogel before and after copper
complexation is characterized by using dynamic light
scattering (DLS) technique. The change of
hydrodynamic diameter, Dh is plotted within
temperature range of 25 50 C. Figure 1(a) and (b)
show the temperature-induced Dh curves for PNIPAM
before and after complexing with copper ions,
respectively. The Dh of hydrogel before complexation
with copper decreases from 610 to 380 nm with
increasing temperature from 25 to 50 C. After
copper-hydrogel complexation, the sharp reduction in
Dh above VPTT had disappeared. This indicates that
the binding of Cu2+ with functional groups had
replaced the water-associated hydrogen bonds. The
ordinary trend of Dh change with temperature as in
Figure 1(a) is disturbed. The curve in Figure 1(b)
shows that the rate of Dh change is lowered for both
heating and cooling cycles. More pronounced
hysteresis effect is observed between heating and
cooling curves in Figure 1(b). This is because copper
chelation had reduced water-associated ligands and
chelation of Cu2+ ion by different ligands causes
certain extent of irreversible shrinkage (Chen et al.,
2013, Zhang and Wang, 2009, Yamashita et al., 2003,
Zhang et al., 2005, Sun et al., 2011).
4. FACTORS THAT AFFECT COMPLEXATION
OF COPPER BY PNIPAM-co-AA
The affinity of chelating ligands in PNIPAM-co-AA
toward copper ions in aqueous solution are sensitively
influenced by several factors including pH, density of
ligands (chelating functional groups) and temperature
(thermo-responsive polymers) (Flora and Pachauri,
2010, Hancock and Martell, 1989).
 Chen et al.
Removal of Copper from Aqueous Solution by Using Thermo-responsive Polymer Hydrogel as Copper Chelator via
Polymer-enhanced Ultrafiltration (PEUF)
(a)
Fig. 1: Thermo-responsiveness of hydrogels: (a) before and (b) after copper complexation
4.1. Effect of pH
pH is a critical parameter for influencing the rate,
efficiency and stability of metal-polymer complex
formation by altering the charges of ligands. Most of
the polymers bearing functional groups like NH
(amine) and -COOH (carboxylic acid) as chelating
ligands are inactive for chelating metal ions at low pH
(< pKa) due to protonation of the functional groups
and electron donors are not available for donating
electrons to metal ion. As pH increases above pKa of
the acidic ligand of polymer, the functional group
(ligand) is deprotonated and increases affinity of the
ligand toward metal ion. Nevertheless, at high pH (
pH 6), the formation of insoluble metal hydroxide
precipitates reduces free metal ions from being
chelated by polymer ligands leading to a decline in
metal-chelating efficiency of the polymer.
In the case of copper, it exists as a hydrated
tetracopper cationic complex, [Cu(H2O)4]2+ at pH 6
in aqueous solution. At pH range of 3 5,
mononuclear complexes of one ligand (LM+) or two
ligands (L2M) are formed. In condition where the
concentration ratio of ligands to copper cations is low
(<10), formation binuclear complexes (two central
copper ions) is induced at pH 4 8. Then at pH 6,
insoluble hydroxide species of copper, Cu(OH)2 is
precipitated. In the presence of high concentration of
carboxylate ligands, Cu(OH)2 tends have hydrophilic
interaction with the polymer ligands through hydrogen
bonds. The formation of binuclear, mononuclear
copper-ligand complexes and Cu(OH)2 species leads
to the increase in adsorption capacity of polymer
hydrogels with increasing solution pH at range of pH
4 7 (Yao et al., 2010, Powell et al., 2007, 2011).
Figure 2 shows the pH effect on copper removal
efficiency in percentage % in the presence of
PNIPAM-co-AA hydrogels. A sharp increase
186
(b)
observed from 26.6% to 53.4% when the solution pH
changed from 4.0 to 5.0. It is because increase in pH
value leads to increase in OH- hydroxyl ions from the
base added (NaOH) that consume H+ ions in the
solution. Consequently, lesser free H+ ions compete
with Cu2+ ions for the chelation sites of ligands. From
pH 6 to pH 9, copper removal was increased linearly
from 63.2% to 87.6% due to the fact that hydroxides
of copper started to form at pH 6 and it was increasing
at higher pH. The dominating species of copper at pH
3 5 is Cu2+ while at pH 6 and above, insoluble
Cu(OH)2 is dominating. At pH 6, Cu2+ is still
dominant in the solution, but the presence of
monohydroxo Cu(OH)+ which possess single charge
was adsorbed to a greater extent than divalent Cu2+
and slight Cu(OH)2 were also formed under this
condition. Thus, the increase in removal efficiency at
pH 5 is owed to deprotonation of AA ligands, whereas
at pH 6 and above, Cu(OH)+ and Cu(OH)2 species had
significant effect towards enhancement of copper
removal (Yao et al., 2010, Powell et al., 2007, 2011).
4.2. Effect of Ligand Density
The density of chelating functionalities (ligands)
indicates the amount of dentates present in a polymer
hydrogel. As previously discussed, a ligand could be
mono-, bi- or poly-dentate (electron pairs) which acts
as donor groups donating electron pairs to a metal ion.
The arrangement and spacing among chelating
functionalities are also important in determining the
interactions among ligands. Increase in ligand density
results in narrower spacing among ligands and eases
more ligand-ligand interaction through hydrogen
bonds that may reduce active dentates for chelating
metal ion (Yang et al., 2004, Burmistrova et al., 2011,
Yamashita et al., 2003, Zhang et al., 2005).
 Wastewater Engineering: Advanced Wastewater Treatment Systems
Chapter 6: Wastewater Treatment by Membrane Techniques

Fig. 2: Effect of pH on copper removal %.

Figure 3 shows the equilibrium adsorption capacity,
qe of hydrogels increased from 0.0943 to 0.8397 mmol
g-1 as AA content incorporated in a hydrogel increased
from 0 mol% (PNIPAM monopolymer) to 30 mol%.
Nevertheless, as it was increased to 50 mol%, there is
a slight fall from 0.8397 to 0.7868 mmol g-1. This is
ascribed at too high AA content (50 mol% AA),
hydrogels has high tendency to agglomerate and
aggregate into colloids owing to excessive ligand-
ligand interaction. The active chelating sites and
surface area of hydrogel networks are greatly reduced.
This results in the lowering ratio of copper-binding
sites to total Cu2+ concentration (Yamashita et al.,
2003, Zhang et al., 2005).

Fig. 3: Effect of AA content in PNIPAM-co-AA on qe.

4.3. Effect of Temperature higher concentration gradient and osmotic pressure

Figure 4 compares the curves of qe versus initial Cu2+
concentrations (C0) at three different temperatures:
303, 313 and 323 K. It shows that at lower C0 ranging
from 20 to 50 mg L-1, temperature effect is apparently
significant on qe, where it decreases with increasing
temperature. This trend agrees with the postulates
proven by Morris et al. (1997) and Kagz et al. (2006)
that diffusional resistance is a problem for metal ions
adsorption as the reductions in both interior volume
and active chelating sites (ligands) at higher
temperature (Morris et al., 1997, Kagz et al., 2006,
Hou et al., 2008). However, as C0 rose from 60 to 80
mg L-1, the increase in qe is getting independent of
temperature effect. At higher concentration of Cu2+,
187
created by the copper ions is prevailing and
overcomes diffusional resistance within hydrogel
interior.
5. MEMBRANE FOULING BY
CONCENTRATION POLARIZATION (GEL
LAYER FORMATION)
Most of the PEUF systems are operated at constant
applied pressure typically in the range of 1 5 bar,
where the feed is circulated at a fixed pressure across
a membrane and the permeate is collected for
measurements over time. As steady pressure is
maintained throughout an operation, convective
transport of complex solutes by the bulk feed stream
 Chen et al.
Removal of Copper from Aqueous Solution by Using Thermo-responsive Polymer Hydrogel as Copper Chelator via
Polymer-enhanced Ultrafiltration (PEUF)
towards membrane could cause the accumulation of
retained solute particles at the active layer of
membrane. These retained solutes remain stagnant at
the membrane surface because their large size and
solute-membrane interactions prevent them from
diffusing back into the bulk stream (Porter, 1990,
Baker, 2012, Wang et al., 2011, Palencia et al., 2009,
Camarillo et al., 2010).
As the concentration of solutes deposited at
membrane surface (Cs) rises to the point of incipient
gel precipitation, the solute particles consolidate by
solute-solute interaction and form a gel layer which
acts as if a secondary membrane on the membrane
Fig. 4: Plot of qe of PNIPAM-co-AA as a function of C0 at different temperatures (303, 313 and 323 K).
Since the gel layer offers resistance to the
permeation of solvent through membrane, it leads to
decline in permeate flux. Hence, the formation of gel
layer is usually described in term of permeate flux
which is expressed mathematically as follows:
(1.7)
where is the solution dynamic viscosity (Pas);
P represents transmembrane pressure difference,
whereas Rm and Rc refer to hydraulic resistances of
membrane and gel layer, respectively (Porter, 1990,
Baker, 2012, Wang et al., 2011).
5.1. Effect of hydrogel (Chelator) Concentration
Figure 5(a) presents the permeate fluxes obtained for
different polymer PNIPAM-co-AA hydrogel
concentration, Ch. Increasing concentration of
hydrogel in the feed enhances the formation of gel
layer at membrane surface. As expected, the permeate
flux plunged sharply from 72.38 L m-2h-1 for the feed
with 0.01 g L-1 hydrogel to 11.75 L m-2h-1 in the
presence of 0.1 g L-1 hydrogel. Subsequently, the flux
188
surface. This gel layer of retained solutes creates a
fouling resistance (Rf) as secondary barrier to the
permeation of solvent flow through membrane. This
type of fouling phenomenon is known as
concentration polarization (CP). Concentration
polarization is the major fouling mechanism in nearly
all PEUF studies. It is reversible in nature when
solute-solute interaction is dominating in the process
as the gel layer can easily be scavenged by
backwashing or feed flow scouring, whereas it could
also become irreversible if solute-membrane
interaction is dominant instead (Wang et al., 2011,
Palencia et al., 2009).
decreases slowly from 11.75 to 6.90 L m-2h-1 as the
concentration increases from 0.1 to 0.7 g L-1. The
increase in hydrogel concentration provides more
available active site for chelating Cu2+ cations in the
feed. This factor in turn contributes to more copper-
hydrogel complexes formed and eases the formation
of gel layer at the membrane surface.
Figure 5(b) illustrates the percentage of copper
retained under different hydrogel concentrations. In
the absence of hydrogels, around 13.1% of Cu2+ was
retained by the functional groups at membrane active
layer. As hydrogel was added into the feed at
concentration of 0.1 g L-1, retention rises up to
81.45% and slightly increases again until 84% as
hydrogel concentration increased further to 0.7 g L-1.
Two phenomena responsible for the improved copper
rejection are: 1) gel layer formation due to CP driven
by the convective transport of hydrogels onto
membrane surface 2) The increase in hydrogel
concentration provides more ligands for chelating
Cu2+ (da Silva et al., 2007, Childress and Elimelech,
1996, Tokuyama et al., 2005, Wijmans et al., 1985).
 Wastewater Engineering: Advanced Wastewater Treatment Systems
Chapter 6: Wastewater Treatment by Membrane Techniques

(a) (b)

Fig. 5: Effect of P-30 hydrogel concentrations on: (a) permeate flux and (b) Cu 2+ rejection (50 ppm Cu2+ in feed; T = 303 K;
pH =5; transmembrane pressure, P = 1.5 bar).

The AFM images shown in Figure 6 illustrate the
effect of different hydrogel concentrations (0.01, 0.1,
0.5 and 0.7 g L-1) toward the membrane (cellulose
acetate) surface characteristic. At 0.01 g L-1, the
lowest density of hydrogels in its spherical structure
was found to be bound on the membrane surface with
a lot of unblocked membrane pores as shown in
Figure 6.0(a). These accounts for the highest permeate
flux (72.38 L m-2h-1) and the lowest Cu2+ rejection
(33.1 %). As hydrogel concentration increases, more
hydrogel particles are bound and consolidated at the
membrane surface as shown in Figure 6.0(b-d). At
higher concentration of 0.7 g L-1, hydrogels tend to
agglomerate into lumps by intense hydrophobic
interaction. However, these lumps did not improve
permeate flux at 50C owing to the fact that under
such high concentration, the feed is relatively more
viscous and hydrogels are more densely packed within
gel layer. As a result, the more rigid hydrophobic gel
layer hinders permeation of solvent.
6. CONCLUSION
PNIPAM-co-AA hydrogel is a potential chelating
agent for copper ion which present in abundance in
most of the industrial effluent. The chelating ability
of the hydrogel is very much depending on the
solution pH, ligand density as well as temperature due
to its thermoresponsive properties. At low copper
concentration, the adsorption process is highly
diffusional control therefore very sensitive to the
operating temperature. Lower temperature is more
favorable due to the swollen hydrogel that exerts less
diffusional resistance for copper to bind within the
interior marix. In a PEUF system, filtration at low
temperature (< 40 C) encountered low permeation
flux due to formation of gel layer of polymer
hydrogels at the membrane surface. However, high
copper rejection was achieved owing to the copper-
ligand complexation and gel layer provides hydraulic
resistance to the permeation of copper through
membrane. The same phenomenon was observed for
high polymer loading which shows that hydrogel
agglomeration at the surface greatly reduces the
membrane flux. Continuos effort to enhance both
copper removal as well as permeation flux is required.
ACKNOWLEDGEMENT
The authors wish to thank the financial support
granted by Ministry of Higher Education Malaysia
(MOHE) FRGS (203/PJKIMIA/6071252)

189
 Chen et al.
Removal of Copper from Aqueous Solution by Using Thermo-responsive Polymer Hydrogel as Copper Chelator via
Polymer-enhanced Ultrafiltration (PEUF)

(a) (b)

(c) (d)

Fig. 6: AFM images of membrane surface after PEUF processes for different hydrogel concentration: (a) 0.01 g L-1, (b) 0.1 g
L-1, (c) 0.5 g L-1 and (d) 0.7 g L-1.

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Wastewater Engineering: Advanced Wastewater Treatment Systems
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2014 IJSRPUB

Wastewater Engineering: Advanced Wastewater

Treatment Systems

Chapter 7: Wastewater Treatment by

Phytoremediation Technologies

193
Wastewater Engineering: Advanced Wastewater Treatment Systems
Available online at http://www.ijsrpub.com/books
2014 IJSRPUB

Wastewater Treatment by Phytoremediation Methods

Hossein Farraji

School of Civil Engineering, Engineering Campus, University Sains Malaysia, 14300 Nibong Tebal, Penang, Malaysia
Email: hosseinfarraji@gmail.com

Abstract. Nowadays many technologies are using for treatment of environmental pollutions and phytoremediation as a green
technology is going on to convert to one of the main ecofriendly technologies which scientist using in their researches. Aquatic
media as a fundamental and critical part of human environment have main role in water resources and food chain. In this
chapter we present different aspect and types of phytoremediation in aquatic media purification from metallic elements.

Keywords: Wastewater, Treatment, Phytoremediation

1. INTRODUCTION plants (Ndimele and Ndimele, 2013). Two approaches

The anthropogenic emissions of metallic elements
globally ends up to wastewater and industrialization
caused a lot of environmental problems .Heavy metals
spectacular Zn, Cu, Ni and Cr are most common
contain of industrial wastewater (Sun and Shi, 1998).
For example recently report from China indicate that
anthropogenic emissions of cadmium to atmosphere
from 1990 to 2010 increased from 474 to 2186 ton
(Shao et al., 2013). Most Cd is emitted to the
atmosphere at the first stage and then precipitate on to
water and soil (Yamagata, 1979). Meanwhile
vulnerability of ground water as drinking water
sources, is higher than surface water (Landmeyer,
2012). levels of arsenic in groundwater sources is
higher in comparing with surface-water sources
(Bissen and Frimmel, 2003). On the other hands,
concentrate ions and accumulation of some pollutants
same as 137Cs in aquatic media are higher than
sediment or soils (Ashraf et al., 2013), so it shows
critical statue of decontamination of wastewater (Shao
et al., 2013).
2. PYTOREMEDIATION
Phytoremediation is vast, emerging term which has
been used in recent decades for a group of green
ecofriendly technologies that fundamentally based on
plants (aquatic, semiaquatic and terrestrial) and
related associated enzymes, microorganism and water
consumption, uptake, remove, retain, transform,
degrade or immobilize contamination (organic and/or
inorganic) with different origin, from soil, sediment
and aquatic media or atmosphere (Mueller et al., 1999,
Pivetz, 2001, Ghosh and Singh, 2005; Vishnoi and
Srivastava, 2007; Mulbry et al., 2008; Ridzuan et al.
2010, Dhir 2013). To sum it up, phytoremediation in
aquatic media is directly up take and accumulation of
contaminant from water media and assimilation by
have been presented in literatures about
phytoremediation, natural or continuous
phytoremediation and chemically enhanced
phytoremediation (Lombi et al., 2001; Alkorta et al.,
2004).
2.1. Continuous or natural phytoremediation
This type of phytoremediation fundamentally based
on using natural hyperaccumulator plants with not
only exceptional metal accumulation in shoots but
also extraordinary tolerance to metal toxicity in root
around media (Assuno et al., 2003; Prasad, 2004).
2.2. Chemically enhanced phytoremediation
Natural phytoremediation have following drawbacks
(Hem, 1970; Prasad, 2004; Yoonet al., 2006):
(a) Low biomass and slow growth in
hyperaccumulator plants; (b) Low translocation of
metals in hyperaccumulator plants; (c) Insolubility or
immobility of metallic elements in media; (d) Low up
taking element by roots.
A chemical enhancement for phytoremediation
helps to overcome these limitations. Chelating ligands
like as ethylene diamine tetra-acetic acid (EDTA), 1,
3-propylene-diaminetetra-aceticacid (PTDA), nitrilo-
tri-acetic acid (NTA), diethyl triamine penta-acetic
acid (DTPA), etc. Which are microbial poorly
degradable and present in g/L concentration in
aquatic media (Knepper, 2003), reduce net shoot and
root biomass production (Rmkens et al., 2002).
Several aspect of phytoremediation improved and
established based on mechanism of decontamination,
kind of pollutions, affected factors and media of
remediation (Stout and Nsslein 2010; Dhir, 2013).
Table 1 is summarized typical kind of this green
technology and its process.

194
 Faraji
Wastewater Treatment by Phytoremediation Methods
Table1: Phytoremediation process (Dhir, 2013)
2.3. Advantages of aquatic phytoremediation
These green technologies as an ecofriendly present
many advantages for decontamination of aquatic
polluted media comparing other treatment systems
(Ximnez-Embn et al., 2001; Bissen and Frimmel
2003; Ghosh and Singh, 2005; Kirkham, 2006; Verma
et al., 2007; Olgun and Snchez-Galvn, 2010;
Landmeyer, 2012; Wang and Calderon, 2012; Delmail
et al., 2013).
(a) Greatly cost effective; (b)
Environmentally Compatible, green aesthetically; (c)
Feasible globally technology (no need to high-tech
equipment or material); (d) Easy maintenance (supply
and energy) solar powered; (e) In situ and ex situ
operation available; (f) Inhibiting deployment of
contamination to atmosphere or soil by in situ
operation; (g) Suitable for shallow depth contaminated
water to hydrologic control of ground water; (h)
Periodic treatment against continued treatments; (i)
Different types of many contaminations can be treated
in one time; (j) Produce biomass for renewable energy
production; (k) Rapid mass propagation by tissue
culture available; (l) Almost treatable for all kind of
contaminations (organic, inorganic and radionuclides);
(m) Operable approximately in all media (aquatic,
sediment, soil and atmosphere); (n) Broad acceptable
pH (2-10) for treatment; (o) Chelating molecules
positively affected phytoremediation;
2.4. Disadvantages of aquatic phytoremediation
Same as each technology, phytoremediation suffer
from disadvantages which should considered through
applying (Mojiri et al. 2013; Assuno et al., 2003,
195
Alkorta et al., 2004; Ghosh and Singh, 2005; Shiyab
et al., 2009; Delmail et al., 2013, Kumar et al., 2013;
Nan et al., 2013).
(a) Harvested biomass contains hazardous
pollution; (b) Long time need for effective treatment;
(c) Deep polluted media are limited treating; (d)
Limited to climate growth condition (tropical,
subtropical and tempered zoon); (e) Restricted to low
concentration of polluted site; (f) Harvested biomass
managing required; (g) Limited hyperaccumulator
species introduced for aquatic media; (h) Leaves fall
may cause spread contaminant; (i) Most of
hyperaccumulator plants have limited roots and slow
growing; (j) Most of hyperaccumulator species up
take only limited elements; (k) Many of
hyperaccumulators propagation system is sexual; (l)
Recycling to soil and water by rain in volatilized
pollutions; (m) Possibility of entering contaminated
biomass to animal and human food chain
2.5. Phytovolatilization
This kind of phytoremediation involves the utilization
of plants to take up pollutions from contaminated
media, transforming them into volatile form and
finally transpiring them into the air.
phytovolatilization normally occurs in plants for up
taking water, organic and inorganic compounds so
some of contamination can pass through the plant
parts to the leaves and at low concentration ,volatilize
into the atmosphere (Mueller et al., 1999) In a
nutshell, the use of plant species for volatilize
contaminants from the leaves which can use for soil
and sediment pollutions (Mueller et al., 1999) air
contaminations (Burken and Schnoor, 1999) and water
 Wastewater Engineering: Advanced Wastewater Treatment Systems
Chapter 7: Wastewater Treatment by Phytoremediation Technologies
pollution (Baeder-Bederski-Anteda, 2003). The
phytovolatilization radionuclides such as Tritium(3H)
from soil (Dushenkov, 2003),significantly up taking
selenium compounds contain dimethyldiselenide and
dimethylselenide by Brassica species (Bauelos et al.,
2000) are some sample studies on phytovolatilization.
Disadvantages of mercury phytovolatilization is
recycling by rain and a residue back into the
ecosystem (Alkorta et al., 2004).
2.6. Phytodegradation
Phyodegradation or phytotransformation refers to two
kind of plant reactions it is independent on
rhizospheric microorganisms (Vishnoi and Srivastava,
2007) contain phytoreduction which is the reductive
transformation of oxidized organic compounds by
reducing plant enzymes and phytooxidation which is
the oxidative transformation reactions catalyzed by
plant oxidizing enzymes (Nzengung and Jeffers,
2001).Plant enzymes contain five various
nitroreductaces (Schnoor et al., 1995), dehalogenase
and oxygenase (Vishnoi and Srivastava, 2007)
degrade organic compounds. The main
phytodegradation process for organic contamination in
plants are, uptake, translocation and metabolism
(Dzantor et al., 2002).Taken up of most of Polycyclic
aromatic hydrocarbons (PAHs)is hard for plants and
less suitable for phytodegradation (Reichenauer and
Germida, 2008). Some of the main organic compound
that successfully degraded by plant species are
hexachloroethane (HCA),
dichlorodiphenyltrichloroethane (DDT) (Nzengung
and Jeffers, 2001) and carbon tetrachloride (Wang et
al., 2004). Inorganics compounds like as sulfur oxides
and atmospheric nitrogen oxides can be taken up by
plants for degradation. Genetically modified plant
species also had been used for phytodegradation (Doty
et al., 2000).
2.7. Rhizodegradation
Rhizodegradation is breakdown organic
compounds(fuels and solvents) to plants nutrients in
rhizospher trough microbial (fungi, yeast , bacteria
and other microorganisms )activity which is very
slower than phytodegradation process and also called
phytostimulation (Hutchinson et al., 2003; Ghosh and
Singh, 2005; Ridzuan et al., 2010).This technology
widely applied in treatment of soils so that in
Germany there are more than 100 years background
for rhizoremediation (Wand et al., 2002). Generally,
plant exudates same as carboxylic , amino acids and
carbohydrates are capable to stimulate entire
rhizosphere microbial action and enhance
rhizodegradation proceeding (Dzantor, 2007) Some of
196
plants which applied for Rhizodegradation are
Hibiscus cannabinus for used lubricating oil (Abioye
et al., 2012), Sorghum bicolor L. for crude oil (Banks
et al., 2003), Broadleaf plantain plant (Plantago
major L.) for Imidacloprid (insecticide) in water and
soil (Romeh, 2009), willow (Salix babylonica)used for
perchlorate in soil and water (Mwegoha et al.
2007).Some treatments used for enhancing
rhizodegradation like as supplying organic carbon
(Yifru and Nzengung, 2008),chicken manure
(Mwegoha et al., 2007) and organic waste treatment
(Dadrasnia and Agamuthu, 2013).
2.8. Phytomining
Phytomining or bio-ore is a green technology which
could generate revenue from saleable metallic
elements that accumulated in ash of plants biomass
(Ghosh and Singh, 2005). Mining of nickele has been
already a patented technology (Chaney et al., 1998).
Normally phytomining occurs in situ at the
contaminated mine lands or sub-economical ore
(Anderson et al., 1998). Phytoextraction or
bioextraction of metals for commercial gain contain
cropping, harvesting, drying and ashing are main
process of phytomining (Sheoran et al., 2009). Cattails
(Typha latifolia) used for absorbing boron (B) from
the effluent of biggest borax mine of the world and
250mgkg-1 boron absorbed in constructed wetland
system (Trker et al., 2013).
2.9. Phytostabilization
This technology applied for decreasing bioavailability
of contamination from environment and stabilizing of
pollutants occurs more than removing
them(commonly metallic elements) by plants
(hydraulic control) ? (Padmavathiamma and Li, 2007).
Enhancing appropriate soil modification by plants
,caused to decreasing bioavailability of metallic
elements on the other hands plant cover decreased
leaching and enhance environmental protection
(Houben et al., 2011).Plants can help to stabilize
pollutants with up taking in adsorption system or
accumulate them in root system (Vangronsveld et al.,
2009). Plant selection for phytostabilizing is a critical
issue and perennial species, well local
environmentally adapted ,high biomass production
and high resistance to pollution recommended (Pilon-
Smits, 2005). Since there is no natural
hyperaccumulator phytoremediator for mercury
controlling this toxic metallic element is critical so
Indian mustard (Brassica juncea L.) reported as a
suitable plant species for stabilization of mercury in
soil and wastewater (Shiyab, Chen et al. 2009).
Aquatic plant Hydrilla verticillata reported as
 Faraji
Wastewater Treatment by Phytoremediation Methods
potential species for phytostabilization of wastewater,
in this plant has high translocation factor (TF) and low
bio concentration factor (BCF) for toxic metals
(Pb,Cr) (Ahmad et al., 2011). Rapeseeds (Brassica
napus), sunflowers (Helianthus annuus), tomatoes
(Solanum lycopersicum) and soapworts (Saponaria
officinalis) reported as capable plants for
phytostabilization with less than one bioaccumulation
coefficients obtained in all of these plants (Sung et al.,
2011). Major metallic element removal in plant
species phragmites (Phragmites australis), Typha spp,
Juncus spp, Spartina spp and Scirpus spp from
different wastewater contaminated area are
phytoextraction and phytostabilization (Bhatia and
Goyal, 2013).
2.10. Phytofiltration
Phytofiltration or rhyzofiltration is a green technology
for removing contaminations by plants roots in aquatic
media like as ground water, most of wastewaters and
extracted ground water (Pivetz, 2001; Mukhopadhyay
and Maiti, 2010). Terrestrial, aquatic and wetland
plants are suitable material for phytofiltration and
constructed wetlands are the best method for
removing metallic elements from wastewater (Cheng
et al., 2002). Limnocharis flava (L.) reported as
suitable plant species for phytofiltration of low
concentration Cd contaminated water (Abhilash et al.
2009) Wolffia globosa is a suitable nominated for
arsenic metabolism studying via phytofiltration
(Zhang et al. 2009).For effective accumulation of
cadmium and hyperaccumulation of arsenic,
micranthemum umbrosum introduced as suitable
macrophyte (Islam et al., 2013). Indian mustard
(Brassica juncea (L.) Czern) could uptake 95%
mercury from contaminated water via phytofiltration
(Moreno et al., 2008). Aquatic plants, Pteris
creticacvMayii (Moonlight fern) and Pteris.vittata
(Chinese brake fern) as arsenic hyperaccumulator
plants, used via phytofiltration (Alkorta et al., 2004;
Tu et al. 2004; Baldwin and Butcher, 2007). The
mechanism of phytofiltration is similar to
phytoextraction containe 1) chemisorption 2)
complexation 3) ion exchange 4)micro precipitation
5)hydroxide condensation 6) surface adsorption
(Cheng et al., 2002; Gardea-Torresdey et al., 2004).
Plant specification in phytofiltration should be 1)
tolerance to high level of metallic elements 2) facile
handling 3) high root biomass or surface area 4)
reasonable maintenance cost 5) least secondary waste
requirement (Dushenkov, 2003).
197
2.11. Phycoremediation
Phycoremediation is using macro and micro algae for
bio transforming or removing pollutions from
wastewater furthermore CO2 as air pollution from
waste air (Mulbry et al., 2008; Rawat et al., 2011).
Algae is a suitable plant for decontamination of
metallic elements, xenobiotic, nutrients in various
wastewater and consume of carbon dioxide from
exhausts ( gu , 2003). Micro algae is a capable
plant for treatment of various type of wastewater such
as industrial wastewater ,domestic wastewater and
solid wastes both aerobically and anaerobically
(Safonova et al., 2004). For this technology ,oldest
scientific research carried out in half century ago
(Oswald and Gotaas, 1957). In a pilot study on
chrome sludge, phycoremediation with Desmococcus
olivaceus could effectively decrease nitrate,
phosphate, ammonia, TDS ,TSS and chrome
(Sivasubramanian et al., 2010). Fresh water blue green
algae used successfully for treatment of dairy manure
effluent(Mulbry et al., 2008). Sewage water treated by
different algae and Chlorella vulgaris could remove
almost all of contaminations and after treating process
it can be thrown in water bodies 1n 2013.
2.12. Phytoextraction
Phytoextraction /phytoaccumulation (Khan et al.,
2000) can be considered as suitable green technology
for removing metallic elements from aquatic media
(Wang et al., 2008). This kind of remediation used for
accumulation of Zinc by duckwood (Lemna gibba)
(Khellaf and Zerdaoui, 2009), Cadmium by water
spinach (Ipomea aquatic) (Wang et al., 2008),
Chromium with small pondweed (Potamogeton
pusillus) in presence of Cu2+ (Monferrn et al., 2012).
recently reported study carried out for accumulation of
Pb by Ceratophyllum demersum and Myriophyllum
spicatum and finally introduced as phytoremediator
and bioindicator of Pb. (El-Khatib et al., 2014) Water
hyacinth (Eichhornia Crassipes) used for removing
heavy metals from coastal water (Agunbiade et al.,
2009), Crude oil from artificial wastewater amended
by urea fertilizer (Ndimele and Ndimele 2013) and
palm oil mill effluent treatment (Christwardana and
Soetrisnanto, 2013). Furthermore, heavy metals from
industrial wastewater have been removed by vetiver
(Chrysopogan zizanioides) (Roongtanakiat, 2009).
3. HEAVY METAL
Generally speaking, heavy metals which nowadays
known as metallic elements (Mbengue et al., 2014),
confined as element with density higher than 4.5- 5
mg mL-1 /kg dm -3 (Sarkar, 2002)but the collective
 Wastewater Engineering: Advanced Wastewater Treatment Systems
Chapter 7: Wastewater Treatment by Phytoremediation Technologies

term includes arsenic(As), cadmium(Cd), lead(Pb),

Mercury (Hg), nickel(Ni), chromium (Cr), zinc (Zn),
copper (Cu), aluminum (Al), cesium (Cs), Ferrum
(Fe), manganese (Mn), molybdenum (Mo), radium
(Ra), uranium (U), strontium (Sr), platinum (Pt),
palladium (Pd), beryllium (Be) (McIntyre 2003)
Metallic elements are persistent and non-
biodegradable (Mahmood et al., 2010) .cooperation of
several disciplines engineering such as environmental,
civil, and chemical is fundamental requirement for
remediation of heavy metals (Bradl, 2005).
3.1. Metal removal rate
The rate of metallic elements removal from polluted
wetland depended on plant spices, climacteric
condition, statue of substrates, type of element
(Hg>Mn>Cd=Fe>Cr=Pb>Cu=Zn>Al>Ni>As), their
ionic forms (Marchand et al., 2010). Remediation
habit of plants species hyperaccumulator>
acuumulator> indicator> excluder (Figure 1) (Bradl,
2005).PH less than 5 is harmful for plants meanwhile
there is a report for a plant species (Lupinus) that can
growth in pH<2 and uptake 98% metallic elements
(Ximnez-Embn et al., 2001).Results of five aquatic
species indicated that all aluminum uptake increased
in low pH (Gallon et al., 2004).
3.2. Indexs of phytoremediation
There are some index that helps to calculate efficiency
of phytoremediation and assessment of plant ability in
up taking and translocation or mobilization (Kisku et
al., 2000) of metallic elements. these index use for
collecting hyperaccumulator plant species (McGrath
and Zhao, 2003).
3.2.1. Bioconcentration factor (BF)
The ratio of concentration of metallic elements in
plants tissue (roots, shoots) to that in contaminated
site (Tu et al., 2002),it also termed as bio
concentration factor (BCF) (Marchiol et al., 2004).
3.2.2. Enrichment Coefcient (EC)
It termed as degree of metallic elements accumulation
in plants (shoot, roots) to concentration of metallic
elements at contaminated site (Kisku et al., 2000). It
also termed as biological accumulation coefficient
(BAC).
3.2.3. Translocation (mobilization) factor (TF)
This factor calculated to determine the translocation of
metallic elements from the root of plant to shoot
(McGrath and Zhao, 2003).
where; TF in hyperaccumulator species is more than
one
3.2.4. Relative treatment efficiency index (RTEI)
Introduced by (Marchand et al., 2010)which is based
on comparing control treatment metal removal with
influent metal concentration and effluent treatment
metal removal ,meanwhile previous index are suitable
now (Kumar et al., 2013).

Fig. 1: Relative uptake and biological accumulation potential in plant species (Bradl, 2005)

198
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Wastewater Treatment by Phytoremediation Methods
4. HYPERACCUMULATORH
Hyperaccumulator used as first time in 1948 by Italian
scientist (Fingerman and Nagabhushanam, 2005). The
plant spices which accumulate heavy metals more
than 1% dry weight, named hyperaccumulator
(Zavoda et al., 2001). Most common aquatic
hyperaccumulators are Spirodelta polyrhiza,
Eichhornia crassipes and Elodeu nuttali (Dhir et al.,
2009), meanwhile Marchand reported there is no
aquatic hyperaccumulator plant species(Marchand et
al., 2010). Tow pictures of native natural terrestrial
hyperaccumulator plants(Figure 2 and Figure 3)
collected in China and Malaysia(Xue et al. 2004; van
der Ent et al., 2013) .Effective phytoremediation
highly correlated to suitable plant selection
(Manousaki, Kadukova et al., 2008).High biomass
,deep and/or wide roots, easy harvesting easily
provide renewable energy and resistance to high
concentration of pollutant are common characters of
phytoremediators (Ghosh and Singh, 2005).
Collecting plants from high polluted area is scientist
preferred method for finding metallic elements
hyperaccumulators (Gleba et al., 1999).Through the
all plant species only 400 species (Brooks, 1998) or
500 species (Ma et al., 2001)reported as
hyperaccumulators. Heavy metals hyperaccumulators
belong to approximately 500 tax of angiosperm (less
than 0.2%) (Krmer, 2010). Recently study in China
introduced three aquatic hyperaccumulator species
for heavy metals Najas marina for arsenic (As) and
cadmium (Cd), Vallisneria natans for lead (Pb) and
Ceratophyllum demersum for cobalt (Co), chromium
(Cr) and ferrum (Fe) plant species selection for this
study carried out from native nominated plants from
Fig. 2: Nickel hyperaccumulator ultramafic area
Malaysia and the Philippine (van der Ent et al., 2013)
199
studying site (Xing et al., 2013).Some of recently
carried out studies are listed in Table 2, and a number
of old researches added because of their importance.
5. FUTURE STUDIES
Micro propagation is the best way for mass production
of some aquatic machrophyte, since produce a lot of
unique genetically plants in short time for analytical
data collection (Kan et al. 1990),which may use for
phytoremediation of contamination particular metallic
elements, first report in this area reported by (Delmail
et al., 2013), There is no reports on natural Mercury
phytoremediator plants(Shiyab et al., 2009)and high
toxicity of this element for human (Harris et al.
2003)presents a critical circumstance for introducing
suitable candidate for phytoremediation of Mercury.
A genetically studying is trying to make Hg
hyperaccumulator by the Meagher laboratory
(Fingerman and Nagabhushanam, 2005).Nowadays
researches on different concentration of heavy metals
in sediments, soil and water, in unique case study also
(Falinski et al. 2014), introducing suitable spectacular
plant species for water, soil and sediment
phytoremediation(Nan, et al., 2013) and using
different enhancers like as microbial and Zeolite in
phytoremediation process(Karimzadeh et al., 2012) is
leading researches toward using constructed wetland
(CW) as a complete ecological system for treating
wastewater spectacular for continues
phytoremediation in practical treatment for example
removing metals from road runoff (Borne et al.
2014),electric industry wastewater (Yang et al., 2013)
fresh oilfield produced water (Alley et al., 2013).
Fig. 3: Phytolacca acinosa Roxb.
Growing at Xiangtan manganese tailing ,China (Xue
et al., 2004)
 Wastewater Engineering: Advanced Wastewater Treatment Systems
Chapter 7: Wastewater Treatment by Phytoremediation Technologies

Table 2: Summary of recent studies on aquatic hyperaccumulation

Plant species Metallic Results Media Reference
elements
Salvinia Minima(fern) Pb2+ Phytochelatins cope with Artificially polluted (Snchez-Galvn et al.,
pb2+ as one of mechanism water 2008)
Chara Australis (algae) Cd Chara is not a Sediment (Clabeaux et al., 2011)
hyperaccumulator
Talinum Triangular Cu, Pb, Ni, Stem cuttings are new Cu Hydroponic system (Rajkumar et al., 2009)
Cd hyperaccumulator
Cyperus rotundus L. Heavy New Sn Soil and water media. (Ashraf et al., 2011)
metals Hyperaccumulator
Pteris vittata L. As In pH:5.21 fern is hydroponic (Tu et al., 2004)
hyperaccumilator experiment
Nasturtium officials As These are not Sediment soil (Falinski et al., 2014)
diplazium Esculentum Hyperaccumulator water
Eichhornia crassipes Heavy Pb,Zn,Cr,Cu and Ni Artificially polluted (Mahmood et al., 2010)
(Ash) metals Hyperaccumulator water
pistia stratiotens Cd Cd hyperaccumulator surface waters (Das et al., 2013)
Lemna minor Hg Phytoremediator Natural lake water (Isaksson et al., 2007)
Ceratophyllum demersum Pb, Cr 2 Effective Artificially (Abdallah, 2012)
Lemna gibba phytoremediators contaminated water
Eleacharis acicularis Heavy Pb hyperaccumulators abandoned mining and (Ha et al., 2009)
metals sediment
Salvinia minima (fern) Pb2+ Accumulation of Pb artificially (Estrella-Gmez et al., 2012)
increased Glutathiane contaminated
synthase water
Echonrnnia crassipes Fe, Mn, Suitable electric industries (Sahu et al., 2007)
Spirodela polyrhiza Cu, Cd, Bioindicators or waste water
Pb, Cr bioaccumulator
Eichhornia crassipes Fe,Zn,Cu, 3 Suitable artificially (Mishra and Tripathi, 2008)
Spirodela polyrrhiza Cr,Cd phytoremediators contaminated
pistia stratiotens water
Myriophyllum Cd,Cu Hyperaccumulator aquatic media (Delmail et al., 2013)
aterniflorum
1-Najas marina Heavy 1-As and Cd 24 eutrophic lakes (Xing et al., 2013)
2-Ceratophyllum metals hyperaccumulator
demersum 2- Co,Cr and Fe
3-Vallisneria natanas hyperaccumulator
3-Pb hyperaccumulator
Alternantbera philoxeroids heavy Zn and Cd local river (Nan et al., 2013)
metals hyperaccumulator
Myriophyllum vercillatum Pb,Cu,Cd May be hyperaccumulator hydroponic system (Ucer et al., 2013)
and Zn for Pb2+
Pistia stratiotes L. heavy Cr,Cu,Fe,Mn,Ni,Pb, and Surface water (Pant and Singh, 2013)
metals Zn hyperaccumulator
Eichhorna crassipes Cd,Ni The roots are effective in Artificially (Elfeky et al., 2013)
absorbing most of Cd and contaminated water
Ni
Potamogeton natans Cu,Zn,Pb These plants are the most Storm water (Fritioff and Greger, 2003)
Alismaplantago aquatica efficient plant for up taking
Filipendula ulmaria heavy metals
137
Catharanthus roseus Cs Ideal hyperaccumulator Artificially (Eapen et al., 2009)
90
Sr For radionuclides contaminated water
Chrysopagann zizanioides Mn, Harvested plant safely can Industrial wastewater (Roongtanakiat, 2009)
Fe,Cu,Zn, use for compost or
Pb handicrafts
Leersiahexandra Cr Hyperaccumulator electroplating factory (Zhang et al., 2007)
wastewater
Callitriche cophocarpa Cr Suitable bioaccumulator Artificially (Augustynowicz et al., 2013)
contaminated water
Eichhorna crassipes Zn,Cu,Pb, Three native aquatic plants Sediment and water (Kumar et al., 2008)
Ipomea aquatic Ni, Co,Cd are suitable species for Gujarat wetland
Typha angustata phytoremediation
Lemna minor Pb Suitable phytoremediator Artificially (Bianconi et al., 2013)
in low concentration contaminated water

200
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Wastewater Treatment by Phytoremediation Methods
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Treatment Systems

Chapter 8: Landfill Leachate Treatment Techniques

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Wastewater Engineering: Advanced Wastewater Treatment Systems
Available online at http://www.ijsrpub.com/books
2014 IJSRPUB

Municipal Landfill Leachate Treatment Techniques: An Overview

Shuokr Qarani Aziz1, 2, *, Hamidi Abdul Aziz2, Mohammed J.K. Bashir3, Amin Mojiri2
1
Department of Civil Engineering, College of Engineering, University of SalahaddinErbil, Iraq
2
School of Civil Engineering, Engineering Campus, Universiti Sains Malaysia, 14300 Nibong Tebal, Penang, Malaysia
3
Faculty of Eng. and Green Tech. (FEGT), Universiti Tunku Abdul Rahman, 31900 Kampar, Perak, Malaysia
*Corresponding Author, shoker71@eng-usalah.org, shoker71@yahoo.com, H/P: 00964 750 462 5426

Abstract. Production of raw leachate from landfills regards as shortcoming for the sanitary landfills. Unprocessed landfill
leachate requires treatment prior disposal to the natural environment. In this work, leachate channeling, biological, and
physical-chemical treatment processes for treatment of formed landfill leachate were presented in details. Definite treatment
processes were resulted in high removal of pollutants such as ammonia (NH3-N), chemical oxygen demand (COD),
biochemical oxygen demand (BOD5), phenols, color etc. Practically, age of produced leachate have influence on the treatment
systems. Efficient treatment methods were explained for fresh, medium, and stabilized landfill leachates.

Keywords: Landfill, leachate, treatment, municipal solid waste, pollutants, removal efficiency

1. INTRODUCTION adsorbent, reverse osmosis, coagulationflocculation,

Sanitary landfill is the most common municipal solid
waste (MSW) disposal method due to such advantages
as simple disposal procedure, low cost, and landscape-
restoring effect on holes from mineral workings.
However, the production of highly contaminated
landfill leachate is a chief weakness of this system
(Aziz et al., 2010). The generation of highly
contaminated leachate that can seep into the ground
and contaminate the ground water, surface water, and
soil is principally a main negative aspect associated to
municipal sanitary landfill disposal method (Bashir et
al., 2012. Additionally, leachate is liquid contain large
amounts of organic compounds measured as chemical
oxygen demand (COD), biochemical oxygen demand
(BOD5), ammoniacal nitrogen (NH3-N), halogenated
hydrocarbons suspended solid, significant
concentration of heavy metals, and inorganic salts
(Aziz, 2013; Bashir et al., 2012; Aziz et al., 2010;
Uygur and Kargi, 2004).
If not treated and disposed safely, landfill leachate
could be a major source of water contamination
because it could percolate through soil and subsoil,
causing high pollution to receiving waters. Thus, the
treatment of hazardous leachate constituents before
discharge has been made a legal requirement to
prevent pollution of water resources and to avoid both
acute and chronic toxicities (Aziz et al., 2011).
To reduce the negative impacts of discharged
leachate on the environment, several techniques of
water and wastewater treatment have been used,
including aerobic and anaerobic biological treatment,
chemical and electrochemical oxidation processes,
chemical precipitation, adsorption using various
membrane processes, and ion exchange (Aziz et al.
2013; Bashir et al., 2012; Aziz et al., 2011; Abbas et
al 2009; Renou et al., 2008).
The current work was aimed to present appropriate
landfill leachate treatment techniques for unprocessed
landfill leachates. Giving detailed information on
leachate channeling, biological, and physical-chemical
treatment processes for raw leachates was another
goal for the present study. Furthermore, suggestion of
efficient treatment methods for different sorts of
produced landfill leachates from various sanitary
landfills was illustrated as well.
2. LANDFILL LEACHATE
2.1 Types of leachate based on landfill design
According to Yamamoto, (2002) and Matsufuji et al.
(1993), in an anaerobic landfill, solid wastes are
dumped in an excavated area of a plane field, which is
filled with water in an anaerobic condition. Typically,
anaerobic sanitary landfills are recognized by its
sandwich-shaped cover. On the other hand, semi-
aerobic landfills have a leachate collection duct. The
opening of the duct is surrounded by air, and the duct
is covered with small crushed stones. Moisture
content in solid waste is small, and oxygen is supplied
to the solid waste from the leachate collection duct.
The schematic diagram of anaerobic and semi-aerobic
(Fukuoka method) landfills is demonstrated in Figure
1 (JICA, 2005). Characteristics of fresh landfill
leachates at semi-aerobic and anaerobic landfills are
given in Table 1.

208
 Aziz et al.
Municipal Landfill Leachate Treatment Techniques: An Overview
Fig.1: Schematic diagram of anaerobic and semi-aerobic landfill
2.2 Significance of leachate problem
Tatsi et al. (2003) and Renou et al. (2008) reported
that landfill leachate can be characterized by two main
factors: quantity (volumetric flow rate) and quality
(chemical composition). El-Fadel et al. (2002)
indicated that the quantity of leachate generation is
affected by landfill moisture distribution influencers
namely refuse age, pretreatment, permeability,
compaction, particle size and density and direct
landfill moisture contributors like rainfall, snowmelt,
groundwater intrusion, initial moisture and leachate
recirculation. Seriously, leachate production is rapid
in tropical countries such as Malaysia since the
rainfall normally exceeds the quantity that can be
evaporated during the rainy season (Lema et al.,
1988).
Usually, leachate contains a complex variety of
substances and organic compounds such as humic
substances, fatty acids, heavy metals and many other
hazardous chemicals. Regardless of the concentration
changes and show a discrepancy based on a complex
set of interconnected factors, the complexity of the
landfill leachate can be categorized on the basis of
four major groups of pollutants i.e. dissolved organic
substances, inorganic macro-components, heavy
metals and xenobiotic organic compounds
(Widziewicz et al., 2012; Schrab et al., 1993).
Bashir et al (2010; 2012) and Aziz et al. (2011)
reported that the common features of raw leachate
generated from Malaysian landfill sites are its high
strength of recalcitrant compounds (as reflected by its
chemical oxygen demand (COD) value) and high
concentrations of ammonia nitrogen (NH3-N).
Ammonia resulting from the decomposition process of
organic nitrogen, has been recognized not only as a
major long-term noxious waste, but also as the
209
primary cause of acute toxicity (Ernst et al., 1994;
Baun et al., 1999). Bashir et al. (2010) stated that the
existence of high amount of NH3N in leachate over a
long period of time is one of the most important
problems routinely faced by landfill operators. This
high quantity of unprocessed NH3N leads to the
depletion of dissolved oxygen which is also
recognized as eutrophication. Because NH3-N is stable
under anaerobic situations, it typically accumulates in
the leachate (Ernst et al., 1994). With a concentration
of higher than 100 mg/L, untreated NH3-N is highly
toxic to aquatic organisms (Widziewicz et al., 2012;
Burton and Watson-Craik, 1998; Silva et al., 2004;
Bagchi, 1994). Unless appropriately treated, leachate
that seeps from a landfill can get into and contaminate
the underlying groundwater.
In line with the abovementioned, if the leachate
escapes to the water bodies, it is very complicated and
costly to have it controlled and cleaned up,
consequently posing potentially serious hazards to
living organisms, as well as public health in the long
term. In most cases, it is very hard to restore the
contaminated water bodies to its original state.
Recently, the hazard of groundwater pollution due to
leachate seepage has turn out to be a main
environmental concern worldwide. Therefore, an
adequate engineering plan and design of a municipal
landfill can avoid or reduce the seepage of leachate
from reaching the water bodies.
Typically, the concentration of leachate parameters
changes with the age of the leachate. The phases of
leachate are transition (0 -5 years), acid-formation (5 -
10 years), methane fermentation (15 - 20 years), and
final maturation (greater than 20 years). The age of
the landfill is one of the most important factors that
affect leachate characteristics (Kostova, 2006; Aziz,
2013) The levels of some leachate characteristics such
 Wastewater Engineering: Advanced Wastewater Treatment Systems
Chapter 8: Landfill Leachate Treatment Techniques

as biochemical oxygen demand (BOD5), COD, total
organic carbon (TOC), NH3-N, nitrite ( NO2-N) and
total dissolved salts (TDS) in different phases are
presented in Table 1.
According to the literature, as a landfill becomes
older, the biological decomposition of the deposited
wastes shifts from a relatively shorter initial period to
a longer decomposition period, which has two distinct
sub-phases: acidic and methanogenic. Leachates from
these distinct stages contain different constituents;
therefore, young leachates tend to be acidic due to the
presence of volatile fatty acids.

Fig. 2: Diagram of landfill leachate treatment techniques, based on Abbas et al. (2009); Renou et al. (2008)

3. RESULTS AND DISCUSSIONS potentially hazardous constituents of leachate prior to

If raw leachate is disposed without treatment, it could
become a major source of water pollution because it
can percolate through soils and sub-soils, causing high
contamination of the receiving water. The treatment of
discharge is a legal requirement to avoid
contamination of water resources to prevent both
acute and chronic toxicity (Ziyang et al., 2009; Oman
and Junestedt, 2008; Sanphoti et al. 2006; ARRPET,
2004).

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 Aziz et al.
Municipal Landfill Leachate Treatment Techniques: An Overview
To reduce the negative impact of discharged
leachate on environment, several techniques of water
and wastewater treatment have been used. The
technologies which were developed for the treatment
of landfill leachate could be classified as physical,
chemical, and biological (Abbast et al., 2009; Renou
et al., 2008). Normally, the techniques are applied as
an integrated system because it is not easy to achieve
the satisfying treatment efficiency by using only one
technology. Traditional treatment techniques
generally demand multistage process treatment. To set
up acceptable treatment process for removal of
contaminates from leachates, various physicochemical
and biological techniques and/or their different
combinations could be applied.
The implementation of the most suitable technique
for the treatment of leachate is directly governed by
the characteristics of the leachate. An overview of
leachate treatment methods is shown in Figure 2,
(Abbas et al., 2009; Renou et al., 2008)
Comparison of the above techniques for different
landfill ages with changeable success is illustrated in
Table 2. In addition, the most important advantages
and disadvantages of the different leachate treatment
methods are reviewed in the following sections. In
general, biological treatment processes are effective
for young or freshly (<5 years) produced leachate, but
are ineffective for leachate from older landfills (>10
years old). In contrast, physicalchemical methods
which are not favoured for young leachate treatment
are advised for older leachate treatment (Ghafari et al.,
2009).
3.1. Leachate Channeling
3.1.1. Combined treatment with domestic sewage
General means of landfill leachate disposal is piping
into the sewerage system for discharge into the sea or,
if possible, for combined treatment with domestic
sewage at traditional wastewater treatment plant. It
was favoured for its low operating costs and simple
maintenance (Ahn et al., 2002). This alternative has
been increasingly inquired due to the presence of
organic inhibitory compounds in leachate with low
BOD5/COD and heavy metals that might decrease
treatment efficiency and increase concentrations in the
211
effluent (Cecen and Aktas, 2004). A disagreement to
this treatment option is that phosphorus (brought by
sewage) and nitrogen (brought by leachate) are not
required to be added to the treatment scheme (Abbas
et al., 2009).
Cecen and Aktas (2001) investigated the combined
biological treatability of domestic wastewater and
landfill leachate in both continuous flow and semi-
continuously fed batch activated sludges, with
recycling mechanism. In addition, the researchers
added powdered activated carbon (PAC) in order to
examine the improvement in nitrification process and
organic carbon removal. The obtained results showed
that in both types of operations, NH3-N and COD
removal efficiencies decreased with an increase in the
leachate to total wastewater ratio. When the leachate
ratio increased, the positive effects of PAC on the
removal of COD and nitrification process became
more obvious.
3.1.2. Recycling
A common system used in many landfills consists of
recycling landfill leachate back through the tip
because it was one of the cheapest alternatives (Lema
et al., 1988). Bae et al. (1998) explained that the
leachate recirculation increased the moisture content
in a controlled reactor method and offered the
distribution of enzymes and nutrients between
solids/liquids and methanogens. Chugh et al., (1998)
stated that lowering COD and methane production
was observed to be important as the recycled leachate
quantity was 30% of the initial waste bed quantity.
The recirculation of leachate not only improves the
leachate characteristics, but also shortens the required
time for stabilization of leachate from several decades
to 2-3 years (Reinhart and Al-Yousisfi, 1996). High
recirculation rates of leachate could negatively
influence anaerobic degradation of solid wastes.
Recirculation of leachate could cause the inhibition of
methanogenesis as it may lead to high concentrations
of organic acids, pH less than 5, which are toxic for
the methanogens. In addition, if the amount of
recycled leachate is very high, problems such as
saturation, acidic conditions, and ponding may happen
(Abbas et al., 2009).
 Wastewater Engineering: Advanced Wastewater Treatment Systems
Chapter 8: Landfill Leachate Treatment Techniques

Table 1: Characteristics of raw leachate at semi-aerobic and anaerobic landfills (Aziz et al., 2010)
Semi- aerobic Pulau Burung site Kulim site Standard B
No. Parameter Unaerated Intermittently aerated Anaerobic
Discharge limit b
Range Averagea Range Averagea Range Averagea
1 Phenols (mg/L) 0.35-2.07 1.2 2.85-10.5 6.7 1-5.25 2.6
2 Total nitrogen (mg/L N-TN) 200-700 483 700-1800 1200 100-600 300
3 Ammonia-N (mg/L NH3-N) 360-730 542 1145-2150 1568 130-1039 538
-
4 Nitrate-N (mg/L NO3 -N) 900-3200 2200 2900-7900 5233 400-2600 1283
5 Nitrite-N (mg/L NO2--N) 44-270 91 20-120 49 30-60 52
6 Total phosphorus (mg/L PO43--TNT) 10-43.0 21 10.0-25 17 8.0-40 19
7 Ortho-Phosphorus (mg/L PO43- mv ) 84-274 141 94-210 159 57-197 94
8 BOD5 (mg/L) 67-93 83 146-336 243 135-476 326 50
9 COD (mg/L) 600-1300 935 1680-4020 2345 630-2860 1892 100
10 BOD5/COD 0.051-0.12 0.096 0.036-0.186 0.124 0.088-0.35 0.205 0.5
11 pH 8.05-8.35 8.20 8.14-8.37 8.28 6.93-8.26 7.76 5.5-9
12 Electrical conductivity (ms/cm) 10.14-13.630 12.17 21.500-22.500 22.10 5.250-13.92 8.55
13 Turbidity (FAU) 600-3404 1546 149-211 180 490-4500 1936
14 Color (Pt Co) 1944-4050 3334 2310-4390 3347 1950-7475 4041
15 Total solids (mg/L) 5138-7404 6271 8860-11084 9925 4520-10568 6336
16 Suspended solids (mg/L) 906-2220 1437 374-1372 837 232-1374 707 100

17 Total iron (mg/L Fe) 2-29.5 7.9 0.9-8.8 3.4 0.6-11.4 5.3 5
18 Zinc (mg/L Zn) 0-3 0.6 0.01-2 0.5 0-1 0.2 1
19 Total coliform <50 (0.77-0.85)x104 0.81x104

20 E-Coli 0.00 (0.18-0.22)x104 0.20x104

a
Average value of six samples
b
Standard B of the Environmental Quality (Sewage and Industrial Effluents) Regulations 1979, under the Environmental Quality Act of Malaysia, 1974 (MDC, 1997).

212
 Aziz et al.
Municipal Landfill Leachate Treatment Techniques: An Overview

Table 2: Effectiveness of leachate treatment techniques versus leachate age (Abbas et al., 2009)
No. Type of treatment Leacgate age (year)

Young (<5) Medium (5-10) Old (>10)

1 Combined treatment with Good Fair poor

domestic sewage
2 Recycling Good Fair poor

3 Aerobic processes Good Fair poor

4 Anaerobic processes Good Fair poor

5 Coagulation/flocculation Poor Fair Fair

6 Chemical precipitation Poor Fair Poor

7 Adsorption Poor Fair Good

8 Oxidation Poor Fair Fair

9 Stripping Poor Fair Fair

10 Ion exchange Good Good Good

11 Microfiltration Poor - -

12 Ultrafiltration Poor - -

13 Nanofiltration Good Good Good

14 Reverse osmosis Good Good Good

3.2. Biological treatment The main fraction of mature or biologically treated

The biological purification processes have been well
recognized and effectively employed for the treatment
of domestic wastewater. Biological treatments are
categorized as aerobic or anaerobic depending on
whether or not the biological processing medium
needs oxygen (O2) supply. In aerobic treatment,
organic contaminants are mostly transformed into
carbon dioxide (CO2) and sludge by using the
atmospheric O2 transferred to the wastewater. While,
in anaerobic processing, organic matter is converted
into biogas, a mixture mainly comprising of CO2 and
CH4, and biological sludge (Lema et al., 1988).
Because of its simplicity, reliability, and high-cost
effectiveness, biological purification (suspended or
attached growth) is mainly employed to treat landfill
leachate containing extreme concentrations of BOD5
(Renou et al., 2008). Biological techniques have been
recognized to be very effective for young leachate
treatment since the BOD5/COD ratio is high (> 0.5).
However, the biodegradability ratio commonly
decreases as the landfill ages, due to the presence of
pollutants that decrease biomass activity and/or are
refractory to biological processes (Lema et al., 1988).
213
leachate is large unmanageable organic compounds
that are not easily removed through biological
treatment. Thus, to meet the allowable standards for
direct discharge of leachate into the environment, a
development of integrated treatment methods is
required, i.e. a combination of biological, physical,
and chemical, and other process steps (Tauchert et al.,
2006).
3.2.1 Aerobic treatment
Destruction of biodegradable organic matter occurs
via aeration in aerobic process. Aerobic biological
methods consist of suspended-growth and attached-
growth biomass processes. The former method has
been extensively applied for treatment of municipal
landfill leachate and wastewater (Abbas et al., 2009;
Renou et al., 2008).
i) Suspended-growth biomass process
Aerated lagoons
Aerated lagoons have commonly been viewed as a
successful and economical technique for the removal
 Wastewater Engineering: Advanced Wastewater Treatment Systems
Chapter 8: Landfill Leachate Treatment Techniques
of pathogens, organic and inorganic matters. Low
operation and maintenance costs have made them an
accepted option for wastewater treatment, particularly
in developing countries. Further, it requires a little
professional skill to operate the system (Maynard et
al., 1999). Maehlum (1995) studied biological
treatment of leachate using anaerobicaerobic lagoons
and constructed wetlands and more than 70% of
nitrogen, phosphorus and ferrous removals were
obtained for diluted landfill leachate. Generally,
treatment of landfill leachate in lagoons and wetlands
need 10 to 20 days retention time (Robinson et al,
1992, Maehlum, 1995). In spite of its lower costs, this
process might not be entirely satisfactory treatment
option for leachate treatment (Zaloum and Abbott,
1997). Finally, large area requirements, aerosol and
formation are other shortcomings of this method
(Robinson et al, 1992, Maehlum, 1995).
Activated sludge process
Activated sludge process could be defined as a
suspended growth process that utilizes aerobic
microorganisms to biodegrade organic matters in
wastewater or leachate. Activated sludge technology
has been extensively used for the treatment of
wastewater and leachate. However this process has a
good ability in the removal of nutrients but it has
some weaknesses such as: 1) Excess sludge
production, 2) Sludge settleability (i.e. high SVI
values), 3) High energy requirements, 4) The need for
longer contact times, and 5) Microbial inhibition due
to high ammonium-nitrogen (NH4-N) strength
(Loukidou and Zouboulis, 2001; Lin et al., 2000;
Lema et al., 1988).
Hoilijoki et al. (2000) added plastic carrier
material to activated sludge process and examined
nitrification of anaerobically pre-treated landfill
leachate in a lab-scale at different temperatures (5-
10C). They stated that the concentration of effluent
parameters (COD, BOD5, and NH3-N) for aerobic
post-treatment were 150-500 mg/L, < 7 mg/L , and <
133 mg/L, respectively. PAC supplemented to
activated sludge processes improved nitrification
efficiency in biological treatment of landfill leachate.
Aghamohammadi (2006) studied treatment of
semi-aerobic landfill leachate from PBLS by using
PAC augmented activated sludge process. The author
reported that the leachate characteristic had great
affect on the removal of organic matter using
activated sludge treatment. Removal efficiencies of
colour, COD, and NH3-N during the treatment of
landfill leachate for leachate from PBLS were 21%,
29%, and 60%, respectively.
214
SBR (Sequencing batch reactor)
SBR process varies from activated-sludge
techniques, because SBR merges all treatment units
and processes into a single basin; whereas traditional
systems rely on various tanks. Typical SBR is divided
into five time periods: fill, react, settle, draw, and idle.
SBR is used for the treatment of wastewater and
landfill leachates (Mahvi 2008; Al-Rekabi et al.,
2007). Due to low BOD5/COD ratio, high
concentration of COD, NH3-N, heavy metals, and
other compounds in landfill leachate, the capability of
SBR in leachate treatment is relatively weaker than
for municipal and industrial wastes (Uygur and Kargi,
2004). In literature, SBR was used for the treatment of
leachate with low BOD5/COD ratio of 0.09 to 0.37
(Guo et al., 2010; Spagni et al., 2008; Klimiuk and
Kulikowska, 2006).
SBR augmented powdered activated carbon (PAC-
SBR) showed higher removal efficiencies of NH3-N,
COD, colour, and TDS when compared with normal
SBR. Furthermore, PAC-SBR improved sludge
volume index (SVI) (Aziz et al. 2011; 2013)
ii) Attached-growth biomass systems
A number of attached-growth biomass processes by
using biofilm have been recently developed to
overcome the problems of activated sludge,
specifically sludge bulking (Dollerer and Wilderer,
1996). These methods offer the advantage of not
suffering from loss of active biomass. In addition,
nitrification is less affected by low temperature than in
suspended-growth methods, and by inhibition due to
high nitrogen content.
Moving-bed biofilm reactor (MBBR)
MBBR technique is based on the use of suspended
porous polymeric carriers, kept in continuous
movement in the aeration basin; whereas the active
biomass grows like a biofilm on their surfaces. The
main advantages of this process compared to normal
suspended growth methods seems to be:1) Higher
biomass concentrations, 2) Lower sensitivity to toxic
compounds, 3) Lower sludge-settling periods, and 4)
Both organic and high NH3-N removals in a single
process. Based on literature, this system could remove
60-81% of COD and 85-90% of NH3-N from landfill
leachate (Loukidou and Zouboulis, 2001; Horan et al.,
1997). Welander et al. (1998) reported that MBBR
resulted in about 90% and 20% removal of nitrogen
and COD while no inhibition of nitrification was
encountered during the treatment of high strength
ammonia leachate. Further, using adsorbent (i.e.
granular activated carbon) offers a suitable surface to
adsorb organic substance and enhanced
biodegradation. Thus, a steady-state equilibrium is
 Aziz et al.
Municipal Landfill Leachate Treatment Techniques: An Overview
recognized between adsorption and biodegradation
(Horan et al., 1997).
Trickling filters
Trickling filters have been tested for lowering the
biological nitrogen from landfill leachate. Because of
low-cost filter media, biofilters remain an attractive
and interesting alternative for nitrification process
(Jokela et al., 2002). In literature, biological nitrogen
removal from municipal landfill leachate was
examined by Jokela et al. (2002) and nitrification of
leachate over 90% was achieved by using biofilters.
They concluded that nitrification in a low-cost
biofilter followed by denitrification in a landfill body
appeared to be applicable for the removal of nitrogen
in landfill leachate in colder climates (Jokela et al.,
2002). Maximum NH3-N removal of 75 % was
obtained by Martienssen and Schops (1997).
3.2.2. Anaerobic treatment
Anaerobic digestion is the oldest system used for
treatment of wastewater. It is suitable for the
treatment of high strength organic pollutants, such as
young leachate. Opposite to aerobic processes,
anaerobic digestion method saves energy and
produces very few solids; but it suffers from low
reaction rates. Further, the produced CH4 could be
used for warming the digester that generally works at
35C (Renou et al., 2008; Sung et al., 1997).
Anaerobic digestion comprises suspended-growth
digester (anaerobic SBR and up-flow anaerobic sludge
blanket reactor, UASBR) and attached-growth
biomass system (anaerobic filter, hybrid filter, and
fluidized bed filter).
i) Suspended-growth digester
Bull et al. (1983) and Sung et al. (1997) studied the
performances of conventional anaerobic suspended
growth digester. The researchers reported that the
typical values for COD removal in anaerobic lab-scale
basin at 35C and ambient temperature were 80-90%
and nearly 55%, respectively.
Anaerobic SBR
Anaerobic SBR is a type of suspended-growth
digester. Some studies have shown good
performances of anaerobic SBRs. These technologies
are able to obtain solid capture and organic lowering
in one reactor (Timur and Ozturk, 1999). Uygar and
Kargi (2004) used lab-scale SBR for the reduction of
nutrient from pre-treated leachate. The researchers
reported that, at the end of cycle time of 21 h,
sequential anaerobic/aerobic operations offered
removal efficiencies of 62% for COD, 31% for NH3-
215
N, and 19 % for PO43--P. Kettunen and Rintala (1995)
explained that COD removal in the anaerobic stage
was 35%; whereas removal efficiencies of COD and
BOD5 in the combined process were up to 75% and
99%, respectively.
Timur and Ozturk (1999) examined anaerobic
treatability of municipal landfill leachate by using lab-
scale anaerobic SBR at 35oC. Based on the obtained
results, about 83% of COD removed during the
treatment was converted to methane. In addition, the
average biomass yield was 0.12 g volatile suspended
solids per gram of COD removed.
Upflow-anaerobic sludge blanket reactor (UASBR)
UASBR technique is a modern anaerobic treatment
process that can have high treatment efficiency and a
short HRT (Lin et al., 2000). In addition, Garcia et al.
(1996) reported that UASBR exhibited higher
performances compared to other types of anaerobic
reactors, when they submitted to high volumetric
organic loading rates.
A pilot-scale UASBR at low temperature was used
for the treatment of municipal landfill leachate.
Removal efficiencies of COD and BOD5 at organic
loading rate of 2-4 kg/m3/d of COD were 65-75 % and
up to 95 %, respectively (Kettunen and Rintala, 1995).
At organic loading rates between 6 and 19.7 g/L/d of
COD, Kennedy and Lentz (2000) obtained COD
removal efficiency of 92%. Generally, for anaerobic
treatment with UASBRs, the process temperatures are
reported to be between 2035 C. (Akkaya et al.,
2010). However, several studies were conducted at
temperatures between 11 to 23C (Kettunen and
Rintala, 1995; Garcia et al., 1996). Sensitivity to toxic
substances is the main disadvantages of UASBRs
(Sung et al., 1997).
ii) Attached-growth biomass systems
Anaerobic filter
Anaerobic filter method is a high rate system that
collects the advantages of other anaerobic methods
and decreases the shortcomings. The filtration process
may be down-flow or up-flow. Packed filter media
provides the mechanism for separating the solids and
the gas that are produced within the digestion process.
In an up-flow anaerobic filtration process, biomass is
retained as biofilms on the supporting material, such
as plastic rings (Nedwell and Reynolds, 1996). At
loading rates of 1.26-1.45 kg/m3/d of COD and for
different ages of landfill leachate, anaerobic filter
removed 90% of COD. Further, anaerobic filter
resulted in total biogas production ranged between
400 to 500 Lgas/kg COD destroyed and methane
content of 75% and 85% (Henry et al., 1987).
 Wastewater Engineering: Advanced Wastewater Treatment Systems
Chapter 8: Landfill Leachate Treatment Techniques
Hybrid filter
Hybrid bed filter consists of an up-flow sludge
blanket at the bed and an anaerobic filter on the top.
This technique acts as a gas-solid separator and
improves solids retention without causing
channelling or short-circuiting. A hybrid bed filter
(consisted of anaerobic filter and up-flow anaerobic
sludge blanket reactor) with a filter volume of 2.75 L
and HRT of 2.4 d at temperature of 35 oC resulted in
removal of about 37.5 to 76 % COD from landfill
leachate (Timur and Ozturk, 1997). Nedwell and
Reynolds(1996) showed steady state COD removal
efficiencies of 81-97% under methanogenic digestion
was based on organic loading rate; and effective
treatment occurred up to a volumetric COD loading
rate of 3.75 kg COD/m3d1. One disadvantage of
hybrid bed filter, as well as anaerobic filter, is the
additional cost of the supporting media.
Fluidized bed filter
Imai et al. (1993) applied microorganism-attached
activated carbon fluidized bed technique for the
treatment of real landfill leachate containing
refractory organics and a high concentration of NH4-
N. They reported that the microorganism-attached
activated carbon fluidized bed method removed about
60% and 70% of refractory organics and nitrogen,
respectively. A number of researches on carbon-
assisted fluidized beds have been conducted (Gulsen
and Turan, 2004; Suidan et al., 1993). Suidan et al.
(1993) stated that about 82% of COD was removed
from leachate via fluidized bed reactor at temperature
of 35 oC and volume of 7.9 L.
3.3. Physical/chemical treatment
Physico-chemical processes are used along with the
biological processes generally to enhance treatment
efficiency or to enhance biodegradability when the
biological oxidation method is disadvantaged by the
occurrence of bio-refractory materials. A number of
physical/chemical treatment techniques which
includes coagulation/flocculation, flotation, chemical
precipitation, adsorption, ammonium stripping,
chemical oxidation, ion exchange, electrochemical
oxidation, and membrane filtration are used for
removing non-biodegradable (humic and fulvic acid)
and/or unwanted compounds (such as heavy metals)
from the landfill leachate (Abbas et al., 2009; Renou
et al., 2008; Zouboulis et al., 2004)
3.3.1. Coagulation/flocculation
Coagulationflocculation technique is considered as a
simple physicalchemical process in landfill leachate
treatment (Aziz et al. 2009; Ghafari et al., 2009). It is
216
an effective pretreatment process if used prior to
reverse osmosis or biological treatment or as a last
polishing treatment so as to remove or decrease non-
biodegradable organic matter in landfill leachate
(Amokrane et al., 1997). Due to its limited efficiency
for the removal of organic matter, it is not suitable for
a full treatment of landfill leachate. Duan and Gregory
(2003) reported that the removal mechanism of the
coagulation process mainly consists of charge
neutralization of negatively charged impurities by
cationic hydrolysis products followed by integration
of colloids in an amorphous hydroxide precipitate
during flocculation process.
In literature, aluminum sulfate, ferrous sulfate,
ferric chlorosulfate, and ferric chloride were generally
used as coagulants (Zouboulis et al., 2004; Amokrane
et al. 1997). Dialynas et al. (2008) investigated that
ferric chloride is more effective than alum in
eliminating organic constituent of landfill leachate,
particularly at pH values more than 9. It was sued to
the fact that ferric chloride enlarges floc size and
reduces settling time more than alum.
Ghafari et al. (2009) explained that by using alum
as coagulant, the optimum removal efficiencies of
COD, colour, turbidity, and suspended solids from
stabilized leachae were 62.8 %, 86.4%, 88.4%, and
90.1 %, respectively. Aziz et al. (2007) used
aluminum (III) sulphate (alum), ferric (III) chloride,
ferrous (III) sulphate and ferric (III) sulphate as
coagulants. The obtained results showed that ferric
chloride was better than the other coagulants with a
colour removal of 94 %.
However, coagulation/flocculation process have a
number of shortcomings, such as inefficiency in NH3-
N removal, low removal efficiency of high strength
landfill leachate, an increase on the concentration of
iron or aluminum could also be noticed in the liquid
phase, and production of huge volume of sludge
(Duan and Gregory, 2003; Tatsi et al., 2003; Silva et
al., 2004; Amokrane et al., 1997).
Al-Hamadani et al. (2011) studied the feasibility of
using psyllium husk as coagulant and coagulant aid
(with poly-aluminum chloride and aluminum sulfate)
for the treatment of semi-aerobic landfill leachate
from PBLS. When psyllium husk was used as primary
coagulant, the removal efficiencies for COD, colour
and suspended solids were 55 %, 80% and 95%,
respectively; whereas the removal efficiencies of
COD, colour, and suspended solids for psyllium husk
as coagulant aid with poly-aluminum chloride were
64, 90 and 96%, respectively. The researchers
reported that psyllium husk was more effective as
coagulant aid with poly-aluminum chloride in the
removal of COD, colour and suspended solids, as
compared to aluminum sulfate.
 Aziz et al.
Municipal Landfill Leachate Treatment Techniques: An Overview
3.3.2. Flotation
Dissolved air flotation could be defined as
disconnection of suspended solids from liquids by
carrying the particles to the surface of the liquid (Al-
Shamrani et al., 2002). For many years, flotation
technique has been widely used and focused on the
reduction of ions, colloids, microorganisms,
macromolecules, and fibers (Zouboulis et al., 2003).
This technique was used extensively for the treatment
of oily wastewater.
Zouboulis et al. (2003) examined the use of
flotation in column, as a post-treatment step for the
removal of residual humic acids (non-biodegradable
compounds) from simulated landfill leachates. Under
optimum operational conditions, the researchers
obtained about 60% humic acids removal.
Lately, using dissolved air flotation process for the
treatment of landfill leachate in the presence and
absence of coagulation process was studied by Adlan
et al. (2011) and Palaniandy et al. (2010). Based on
the obtained results by Palaniandy et al. (2010), the
removal efficiencies of colour, COD, and turbidity
from leachate using dissolved air flotation process
(without coagulation process) were 36%, 33%, and
32%, respectively; whereas the removal efficiencies
with the coagulation process were 70%, 79%, and
42%, respectively.
3.3.3. Chemical precipitation
Chemical precipitation method has been extensively
employed as leachate pre-treatment because of its
simplicity, capability, and low-cost equipment used.
This method is efficient in removing NH3-N, non-
biodegradable compounds, and heavy metals from
landfill leachate (Akkaya et al., 2010; Zhang et al.,
2009; Calli et al., 2005; Ozturk et al., 2003).
Li et al. (1999) stated that the performance of a
conventional activated sludge technique could be
significantly affected by the high concentration of
NH4+-N. Struvite (magnesium ammonium phosphate
hexahydrate, MgNH4PO4.6H2O) precipitation was
firstly distinguished as a phenomenon to be controlled
because it could cause problems throughout the
operation of wastewater treatment and other processes
where high concentrations of ammonium, magnesium,
and phosphate are present.
Ozturk et al. (2003) used Struvite as precipitant for
the removal of NH3-N from anaerobically pre-treated
leachate. The removal efficiency of NH3-N and COD
were 90% and 50%, respectively. It is confirmed that
the ammonium concentration in leachate could be
considerably reduced by struvite precipitation.
However, this process requires relatively expensive
chemicals (Kochany and Lipczynska-Kochany, 2009).
217
3.3.4. Adsorption
Adsorption technique is recognized as the efficient
and promising elementary approach in wastewater
treatment processes (Foo and Hameed, 2009). It is
used as a stage of integrated chemical-physical-
biological method for leachate treatment, or
simultaneously with a biological process. The most
commonly used adsorbent is granular activated carbon
or PAC (Abbas et al., 2009).
PAC as adsorbent improved performance of SBR
process. Results revealed that the PAC-SBR offered
better removal efficiencies of pollutants and improved
sludge characteristics (Aziz et al. 2011; 2013)
3.3.5. Ammonium stripping
Because of its high removal efficiency, the
ammonium stripping treatment method is the most
widely used for the removal of NH3-N from landfill
leachate. High concentrations of NH4-N are
commonly found in landfill leachates, which lead to
increasing wastewater toxicity. This method usually
changes dissolved NH3-N and dissolved CH4 in
leachate to gases. High pH values must be provided in
this method so as the column works efficiently (Hao
et al., 2010; Ozturk et al., 2003; Marttinen et al.,
2002).
Sincero and Sincero (2003) explained that
stripping was completed via introducing wastewater at
the upper part of the stripping column and permitting
it to flow the air down in the column. Marttinen et al.
(2002) reported that this method at operation
condition of pH value equal to 11, temperature of
20C, and retention time of 24 h resulted in NH3-N
removal of 89%. In a research conducted by Silva et
al. (2004), the researchers obtained NH3-N removal
efficiency of 99.5%. Calli et al. (2005) explained that
the removal efficiencies of NH3-N and COD for initial
concentration of 3260 mg/L were 94 % and <15%,
respectively.
Comparing with other treatment techniques such as
reverse osmosis and nanofiltration ammonium
stripping discovered to be more economical in terms
of operational costs. Regardless of its advantages, the
main disadvantages of this technique are: 1) The
release of NH3-N gas to the atmosphere, 2) The
scaling of CaCO3 when lime is used for pH adjustment
in the stripping tower, and 3) Adjustment of effluent
pH value prior discharge (Li et al., 1999).
3.3.6. Chemical oxidation
Oxidation and reduction process are based on transfer
of electrons. In this process, one compound gives
electrons whereas the other receives electrons. When
 Wastewater Engineering: Advanced Wastewater Treatment Systems
Chapter 8: Landfill Leachate Treatment Techniques
biological treatments are inefficient, this method is
used to achieve desired objectives. Chemical
oxidation process is required for the treatment of
wastewater containing non-biodegradable and/or toxic
pollutants. So, this method is an efficient technique
for the treatment of low BOD5/COD (i.e. stabilized)
landfill leachates (Derco et al., 2010; Mohajeri et al.,
2010; Rivas et al., 2003; Droste, 1997; Marco et al.,
1997).
Amokrane et al. (1997) used oxidants, such as
chlorine, potassium permanganate, ozone, and
calcium hydrochloride, for landfill leachate treatment
and found COD removal of 2050%. Researchers
reported that the efficiency of COD reduction for
mature and biologically pretreated landfill leachates
were 60 to 75 %, respectively by using Fenton reagent
(Lopez et al., 2004; Kang and Hwang, 2000).
Fenton oxidation was used by Mohajeri et al.
(2010) for the removal of colour and COD from Pulau
Burung stabilized landfill leachate whereby colour
and COD removal were 78% and 58%, respectively
(Mohajeri et al., 2010). Additionally, Gotvajn et al.
(2009) mentioned that the removal efficiency of NH3-
N by using Fenton oxidation was 40%.
According to Lopez et al. (2004), Fenton process
seemed to be the best compromise because it is
technically simple. In spite of simplicity of Fenton
process, it requires low pH and a modification of this
parameter is necessary. Further, high demand of
electrical energy and high oxidant doses are other
disadvantages of this method that makes the process
expensive (Bashir, 2011).
3.3.7. Ion exchange
Ion exchange process could be defined as reversible
interchange of ions among the liquid and solid phases
where no significant change in the structure of the
solid is observed. This treatment process is capable of
efficiently removing the traces of metal impurities to
meet the increasingly strict discharge standards in
developed countries. However, the application of ion
exchange is not generally used for the treatment of
landfill leachate, but it received great attention in
Germany for the removal of non-biodegradable
compounds that contained humic substances (Fettig,
1999).
Researchers explained that ion exchange resins are
generally and capably used for the removal of organic
compounds and ions from water and wastewater and
as a polishing step in landfill leachate treatment. Prior
to ion exchange process, leachate should initially be
subjected to biological treatment (Bashir et al., 2010;
Kurniawan et al., 2006). All soluble metallic elements
(anionic or cationic) could be efficiently removed or
reduced by using ion exchange technique. The resin is
218
prepared of synthetic organic polymers or natural
zeolite. Ions such as H+, OH-, Na+, and Cl- are joined
to the resin by weak electrostatic forces. These ions
are exchanged with ions in the contaminated product
that have more similarity for the resin. Resins could
be prepared to pick particular ions. The application of
ion exchange is economically limited due to high
operational cost. Another limitation is the requirement
of suitable pre-treatment system such as the removal
of suspended solids from landfill leachate. However,
ion exchange process is proper for heavy metal
removal from leachate (Kurniawan et al., 2006).
3.3.8. Electrochemical oxidation
Recently, electrochemical oxidation process has
received important consideration for wastewater
treatment because of its efficient and simple
operation. This treatment process has the ability to
destroy refractory pollutants. In this process,
refractory pollutants could be destroyed by direct
anodic oxidation, electro-chemically, or by indirect
oxidation (Atmaca, 2009; Deng and Englehrdt, 2007,
Chiang et al., 1995). Several types of electrodes have
been examined for electrochemical treatment such as
Ti, TiO2, PbO2/Ti, SnO2/Ti, Fe, aluminum, iron, and
graphite (Atmaca, 2009; Irdemez et al., 2006; Shen et
al., 2006; Chiang et al., 1995).
Atmaca (2009) used cast iron plates for both
anodes and cathodes with surface area of 22.6 cm2. At
operational conditions of 20 min treatment duration,
constant DC current of 3A, H2O2 concentration of
2000 mg/L, and at initial pH 3, removal efficiencies of
colour and COD were 90% and 72 %, respectively.
Electrochemical oxidation process was used for the
treatment of Pulau Burung semi-aerobic landfill
leachate, Malaysia. Sodium sulphate Na2SO4 (as
electrolyte) and carbon electrodes were used in the
treatment process. At optimum operational conditions
(1414 mg/L influent COD, 79.8 m A/cm2 current
density and 4 h reaction time), the removal
efficiencies of BOD5, COD, and colour were 69.8 %,
67.6 %, and 83.7 %, respectively. Further, graphite
carbon electrode showed better performance in the
removal of BOD5, COD and colour (Bashir, 2007).
The disadvantages of this method are: 1) It is more
expensive than other treatment processes because of
high energy consumption, 2) It is less widely used for
the treatment of stabilized leachate, 3) High current
density could increase corrosion rate of electrodes,
and 4) It is inefficient for the removal of inorganic
substances and NH3-N.
 Aziz et al.
Municipal Landfill Leachate Treatment Techniques: An Overview
3.3.9. Membrane filtration
A membrane could be defined as a material that
creates a thin barrier capable of selectively resisting
the move of different constituents of a fluid and
therefore affecting separation of the constituents
(Visvanathan et al., 2000). Usually, a thin layer of
material with a high surface porosity and a narrow
domain of pore size affect the physical structure of the
membrane. Different membrane filtration techniques:
microfiltration, ultrafiltration, nanofiltration, and
reverse osmosis are used in landfill leachate treatment.
i) Microfiltration
Microfiltration with pore sizes of 0.05 to 10 microns
is employed to capture microbial cells, small particles,
and large colloidal. According to landfill leachate
treatment, this method is not suitable to be used alone.
It is recommended to be used as pretreatment process
with other membrane processes (i.e. ultrafiltration,
nanofiltration or reverse osmosis) or in combination
with chemical treatment processes so as to remove
suspended matters and colloids. Piatkiewicz et al.
(2001) used this method as pre-filtration stage and
obtained COD removal of 25% to 35 %.
ii) Ultrafiltration
Ultrafiltration is a selective process utilizing pressures
up to 10 bar. This technique is efficient to remove
suspended matters either by direct filtration or with
biological treatment to replace sedimentation unit. It is
strongly dependant on the kind of material
constituting the membrane. Syzdek and Ahlert (1984)
proposed that this process might prove to be useful as
a pre-treatment method for reverse osmosis. It could
be employed to eliminate the larger molecular weight
components of leachate that tend to foul reverse
osmosis membranes (Bohdziewicz et al., 2001;
Rautenbach et al., 1996). COD removal of 50% was
obtained by using ultrafiltration alone (Bohdziewicz et
al., 2001)
Lastly, Tabet et al. (2002) reported that
ultrafiltration membranes have been successfully
employed in full scale membrane bioreactor plants by
combination of bioreactors and membrane technology.
High levels for landfill leachate treatment have been
obtained by using this method.
iii) Nanofiltration
Because of its unique properties between
ultrafiltration and reverse osmosis membranes,
nanofiltration has discovered a place in the
elimination of refractory organic compounds and
219
heavy metals from landfill leachate (Ozturk et al.,
2003). Removals of COD and NH3-N from landfill
leachate by using this process were 60 % to 70 % and
50 %, respectively (Trebouet et al., 2001; Linde and
Jonsson, 1995). In another research conducted by
Trebouet et al. (2001), nanofiltration was employed in
combination with physical processes which offered
acceptable COD removal (70% to 80 %) from landfill
leachate. Based on the results achieved by Linde and
Jonsson (1995), removal efficiencies of sulphate salts,
chloride, and other (Pb2+, Zn2+, and Cd2+) from landfill
leachate were 88-96%, 12-47 %, and > 88 %,
respectively.
On the other hand, successful use of membrane
technique needs effective control of membrane
fouling. An extensive spectrum of components could
contribute to membrane fouling in leachate
nanofiltration which includes inorganic substances,
dissolved organic, suspended particles, and colloidals
(Trebouet et al., 2001).
iv) Reverse osmosis
Membrane techniques, specifically reverse osmosis, is
a relatively new method that seems to be a more
efficient alternative than traditional methods for
mature landfill leachate treatment. This method
involves separating two solutions with various
concentrations by using a semi-permeable membrane
(Kurniawan et al., 2006; Ahn et al., 2002; Chianese et
al., 1999).
Ahn et al. (2002) stated that a landfill leachate
treatment plant in Korea was retrofitted to improve
treatment efficiency by employing integrated
membrane technique that was composed of membrane
bioreactor and reverse osmosis method. The removal
efficiencies of COD and NH3-N from young landfill
leachate were 96 % and 97 %, respectively. Other
researchers stated that the removal of COD and NH3-
N from landfill leachate was 98% (Linde et al., 1995).
Although, reverse osmosis technique was reported
as the most efficient in the removal of COD among
various physical-chemical technologies assessed
(Peters 1998), some disadvantages have been noticed
for membrane techniques. They include membrane
clogging which reduces the overall process
performance by lowering the reject concentration
while the cleaning of such membranes also reduces
their lifetime. Additionally, the production of large
quantitities of residuals which are generally useless
and required to be discharged or need further
treatment (Li et al., 2009; Wiszniowski et al., 2006).
 Wastewater Engineering: Advanced Wastewater Treatment Systems
Chapter 8: Landfill Leachate Treatment Techniques
4. CONCLUSIONS
Design of landfill, age of landfill leachate, climate etc.
have great effect on leachate treatment. In this work,
detailed review on various treatment techniques were
explained. Results revealed that combined treatment
with domestic sewage, recycling, and biological
systems are efficient for processing young landfill
leachate. Commonly, physical-chemical treatment
methods are competent for treating medium and
old/stabilized leachates. Further, augmenting physical
and chemical methods or biological and physical-
chemical processes enhanced treatment of stabilized
leachate.
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Wastewater Engineering: Advanced Wastewater Treatment Systems
Available online at http://www.ijsrpub.com/books
2014 IJSRPUB

Wastewater Engineering: Advanced Wastewater

Treatment Systems

Chapter 9: Application of Optimization in Treatment

225
Wastewater Engineering: Advanced Wastewater Treatment Systems
Available online at http://www.ijsrpub.com/books
2014 IJSRPUB

Application of Optimization in Wastewater Treatment

Yee Ling Lim, Yeek Chia Ho, Abbas F. M. Alkarkhi*

School of Industrial Technology, Universiti Sains Malaysia, 11800 Penang, Malaysia

*Corresponding Author: abbas@usm.my

Abstract. Design and analysis of experiments (DOE) helps researchers achieves the research objective with less effort, cost
and time. In wastewater treatment process, DOE is used to study the effect of input variables such as flow rate/speed,
temperature, chemical dosing and retention time on the output and then optimize the process by finding the best operating
conditions for the input variables that meet the objective for the output variables and summarize the results in terms of model
to describe the behavior of the process. First-order and second-order models are usually used to describe the behavior of most
cases.

Keywords: Optimization, Wastewater Treatment,

1. INTRODUCTION Experimental design is frequently used in industry

Design and analysis of experiments (DOE) have been
widely used in planning, analyzing and running
experiments in different areas of research, such as
wastewater treatment, food analysis, material
production and medication intake helping the
researchers to achieve the research objective with less
effort, cost and time. The application of DOE in
wastewater industries has increased since the
application of experimental design and analysis of
experiments enables us to collect data effectively and
reduce the error by excluding non-significant factor/s
in the experiment and effectively improves the results
to the target range. Three basic principles should be
considered in using experimental design, namely,
replication, randomization and blocking. Replication
allows experimenter to get an estimation of
experimental error and to increase the precision.
Randomization is the allocation of the experimental
materials and the order that the individual runs or
trials of experiment are to be carried out in random
manner. Furthermore, randomization eliminates bias
and to make sure independence among the
observations. Blocking technique is used to enhance
the accuracy by reducing or eliminates variability that
may affect the response (output) such as the difference
in skills of two or more operators and weather
conditions (rainy, cloudy, sunny) (Montgomery, 2012).
Researchers should provide clear objective of the
project before using experimental design, for instance
number of input variables and levels of each variable
(the region of each selected variable). As an example,
an outcome of an experiment includes the
identification of which factors contribute to overall
wastewater treatment process, for instance the factors
involved may include chemical dosing and total
retention time, while their levels may be 100g/L or
500g/L of chemical dosing and 3 days or 7 days for
the total retention time.
226
to optimize different experiments in order to find the
best operating conditions that produce desirable
product. Moreover, the application of DOE enables a
wastewater treatment system to optimize the
effectiveness of the process in removing the impurities,
particularly to fulfill the government regulation on the
effluent water. Optimization enables processes to
achieve highest possible removal rate within the given
range of factors at the lowest cost possible. For
instance, in a conventional treatment plant, the input
factors are flow rate/speed, temperature, chemical
dosing and retention time and the response (output) is
often more than one responses such as biochemical
oxygen demand (BOD), chemical oxygen demand
(COD), pH, concentration of cadmium, concentration
of lead and others. Thus, it is not quite possible to run
and plan a proper design for the experiment for good
yield without finding the best operating conditions
which results in highest removal.
2. APPLICATION OF DOE IN WASTEWATER
RESEARCH
The applications of design and analysis of
experiments in wastewater researches can be listed
down as follows:
(a) Production of adsorbent for wastewater, factors
involved may include heating temperature, heating
time and chemical composition while the response
may include removal of heavy metal, color removal or
even COD removal.
(b) For the cultivation of bacteria for the usage in
treatment plant on the other hand may include dosage
of carbon supply, shaking speed and incubation
temperature while the response is the growth of
bacteria.
(c) Conventional batch study involves parameters
of shaking speed, temperature, chemical dosage and
pH while the response will be the removal of the
target compound.
 Lim et al.
Application of Optimization in Wastewater Treatment

(d) Study of flocculating activity involving
different physico-chemical parameters such as pH,
concentration of polymer, and mixing speed.
3. FACTORIAL DESIGN
Factorial designs are designs consist of several factors
(input variables) that influence one or more responses.
The advantage of factorial designs is to study the
effect of several factors and the interaction between
different factors simultaneously whilst the
disadvantage appears when the number of factors
included in the study increases which result in
increasing of the number of experiments. General
factorial design studies experiments with more than
one factor; each has at least two levels while special
cases of factorial designs are two-level factorial
design 2k and three-level factorial design 3k.
3.1. Two-level Factorial Design
Two-level factorial design with k factors (2k) is more
commonly used for screening purposes in order to
identify insignificant factors and to prepare for
optimization step (Ryan, 2007). Researchers usually
collect experimental data by running only a fraction of
the factorial design which is known as fractional
factorial design (Srinivasan and Viraraghavan, 2010).
The two levels are represented by (-1) to indicate that
the factor is at low level and (+1) to represents the
high level. Two-level factorial design is used to fit
first-order polynomial model.
The levels of each factor in the actual form are
known as natural variable. The levels can be
converted into -1 and 1 by using Eq. 1, this formula is
called coded form. The relationship between the
natural variable i and the coded variables X i is
given in Eq.1.
i ( High level Low level) / 2
xi (1)
( High level Low level) / 2
The benefit of using fractional factorial design is to
reduce the number of runs (experiments) as long as
the purpose of the experiment is to choose influential
factors, for instance, assume that 5 factors involved in
a process (25), the total number of runs is 32
experimental runs for each replicate to cover all
possible combinations whilst fraction factorial design
of 2k-1 (half factorial design) will use only 16 runs
which means less effort, time and cost to identify the
influential factors.
Example 3.1
Suppose a 25-1 two-level fractional factorial designs
with 16 runs were used to study the effects of
concentration of phenolic compounds, adsorbent
dosage, contact time, temperature and shaking speed
on phenolic compound removal (y) in wastewater.
The levels of each factor in coded and actual forms
are given in Table 1. The data for this experiment in
actual levels are given in Table 2.

Table 1: The factors and levels used for screening experiment

Factor Symbol Levels

Actual Coded
Concentration of phenolic compound (mg/L) x1 20 40 -1 1
Adsorbent dosage (g/100ml) x2 0.10 0.30 -1 1
Contact time (hours) x3 120 300 -1 1
o
Temperature ( C) x4 50 80 -1 1

Shaking speed (rpm) x5 300 400 -1 1

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 Wastewater Engineering: Advanced Wastewater Treatment Systems
Chapter 9: Application of Optimization in Treatment

Table 2: The results of two-level fractional factorial design

Concentration of Adsorbent Contact % Removal by
Shaking speed
phenolic compound dosage time Temperature (oC) phenolic
(rpm)
(mg/L) (g/100ml) (hours) compounds
20 0.1 2 50 400 30.29
40 0.1 2 50 300 8.16
20 0.3 2 50 300 67.70
40 0.3 2 50 400 46.36
20 0.1 5 50 300 35.04
40 0.1 5 50 400 10.16
20 0.3 5 50 400 66.45
40 0.3 5 50 300 52.08
20 0.1 2 80 300 29.69
40 0.1 2 80 400 11.11
20 0.3 2 80 400 58.52
40 0.3 2 80 300 30.06
20 0.1 5 80 400 33.40
40 0.1 5 80 300 7.17
20 0.3 5 80 300 57.82
40 0.3 5 80 400 39.83

This experiment represents one-half fractional
factorial design with 16-runs, since the number of runs
is 16 which is not enough to provide degrees of
freedom to the error term in the analysis of variance
(ANOVA). Thus, in order to analyze this experiment
we will use normal probability plot or half normal
probability plot. Minitab statistical software (version
16) was used to analyze the data obtained from this
experiment. The analysis in the form of normal
probability plot is shown in Fig. 1. It can be seen that
shaking speed and contact time did not exhibit a
significant effect on the percentage removal of
phenolic compound. Only three factors showed
significant effect, namely concentration of phenolic
compound, adsorbent dosage and temperature.

Fig. 1: Normal probability plot of effects

An ANOVA table can be built after excluding non- adsorbent dosage and temperature as a 23 design with
significant terms and analyze the result with only two replicates. Table 3 shows the results of ANOVA
three factors, concentration of phenolic compounds, for phenolic compound removal.
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 Lim et al.
Application of Optimization in Wastewater Treatment
Table 3: ANOVA table for phenolic compound removal
Source of variation DF Sum of square
Main effects 3 6065.58
2-Way interaction 3 131.83
3-Way interaction 1 10.47
Residual error 8 93.04
Pure error 8 93.04
Total 15 6300.92
It can be seen that three-factor interaction and two-
factor interaction were insignificant whilst the main
effect for selected factors was significant. Two-factor
interaction will be included in the model since this
interaction is significant at p<0.07.
y 36.49 10.87 x1 15.86x 2 - 3.04x 4 0.60x1 x 2 0.53x1 x 4
- 2.76x 2 x 4 0.81x1 x 2 x 4
3.2. 3k Factorial Design
Three-level factorial design (3k) is a special case of
factorial design where all factors included in the study
have three levels. This design is used for fitting
second-order polynomial model to the experimental
runs. The levels in 3k design are denoted as low,
intermediate and high with the assumption of 0 for
low, 1 for intermediate and 2 for high, given that k
represents the number of factors included in the study.
If the factors are quantitative, we may denote the low,
intermediate and high level as 1, 0 and +1 respectively
to facilitate the calculation.
4. RESPONSE SURFACE METHODOLOGY
(RSM)
Response Surface Methodology is very well known by
RSM which consists mathematical and statistical
techniques that are useful for modeling and analysis of
problems in which the objective is to optimize the
response or responses by finding the best operating
conditions of the input variables (independent
variables) that influence the response
(Prakobvaitayakit and Nimmannit, 2003; Montgomery,
2012).
The objective of RSM is to guide the researcher to
find the levels of independent variables that optimize
the response which means maximize, minimize or
keep in a range. RSM is widely used in water and
wastewater treatment to evaluate the effect of several
independent variables and their interactions such as
speed, flow rate and chemical dosage on a response or
responses such as COD, BOD, colour, turbidity etc.
Special designs are used to carry out experiment in
229
Mean sum of square F-value P-value
2021.86 173.85 0.000
43.94 3.78 0.059
10.47 0.90 0.371
11.63
11.63
The results are summarized in a regression model
to describe the behavior of the process. Regression
model for this experiment in coded units is given in
Eq. 2.
(2)
RSM. These designs are capable to fit second-order
and second-order models for instance central
composite design (CCD) with Box-Behnken design
(BBD) and three-level factorial design.
4.1. Steps in RSM
The main purpose of using RSM is to optimize a
process. This purpose can be achieved by using the
following steps:
(1) Choosing the right design that serves your
objective. All information regarding the experiment
should be available to help in choosing the design by
involving all people who work in the project.
(2) Run the experiment and analyze the data
obtained then summarize the data in a model form
usually first-order or second-order model.
(3) Validate the model obtained by checking its
precision in predicting the response and whether this
model can be used for finding the optimum conditions.
(Montgomery, 2012)
To optimize the response, it is necessary to
approximate the functional relationship between the
independent variables and the response surface. For
example, suppose an engineer would like to know the
best condition for the highest removal (yield, y) of
heavy metal from its wastewater, given the
independent influencing factors are temperature (x1)
and heavy metal concentration (x2) in wastewater.
The yield for this process can be represented by the
following function:
Removal of heavy metal = f(temperature, heavy
metal concentration)
 Wastewater Engineering: Advanced Wastewater Treatment Systems
Chapter 9: Application of Optimization in Treatment
5. OPTIMIZATION
Optimization is a procedure to select the best target
output from a process. This selection is made from a
series of experiments testing from a range of values
and the combination of each all factors. Optimization
may be a maximizing, minimizing and to keep the
target within range depending on the objective.
5.1. Concept of optimization
Concept of optimization is to select a combination of
the levels of factors which will result in a product with
desirable properties. This means solving problems
involving the optimization of several responses
(output), which depends upon a number of factors or
sets of parameters (input). Each desirable output
requires a special setting of input factors. For instance,
in an experimental study to maximize dye adsorption
capacity of an adsorbent made from coconut husk, the
two responses involved are decoloration and COD
removal of the dye wastewater. It can be achieved by
having higher temperature and retention time and at
the same time, reducing the rotation speed and
concentration of dye. In this optimization process, an
attempt was made to fulfill the requirement of the
wastewater treatment plant discharge (maximize the
dye adsorption capacity to reduce the discharge of dye
concentration in wastewater) while at the same time
reduces the material used (chemical dosage), obtain an
energy saving condition and reduces the duration of
the runs and most importantly to save cost. . selected target value. Assume that L, U and T
5.2. Desirability approach for Multiple Response
As we have mentioned before, optimization of a
process begins with selecting a proper design which
0 if y L
[ y L ]m if L y T
T L
D( y )
[ U y ]n if T y U
T U
0 if y U
Whereas, for a process response that requires a maximum yield, then the desirability function would be;
0 if y L
yL m
D ( y ) [ ] if L y T
T L
1 if y T
230
suit the process and then build a response surface
model for the response/s. The process of choosing a
set of operating conditions that is able to meet the
properties of each response is a challenge task;
however, it is possible in most cases to optimize all
responses by finding a combination of the levels of
input variables that meet the criteria of each response.
In such case, desirability approach is employed to
optimize the multiple responses process. This method
enables the process to obtain the most desirable
response/s by finding the suitable sets of operating
conditions, which means finding the most suitable
combination of the input variable (parameters). Given
that the process has a number of factors, all of these
selected factors must be in the desirable range.
A desirability function D(y) derives from the
process responses range from 0 to 1 and d(y) = 0
means the solution cannot be obtained and the
properties for one or more responses should be
changed while d(y) = 1 means the solution is possible
and is located in the desire region (Derringer and
Suich, 1980). This equation was modified by
Harrington, 1965 (Harrington, 1965). Desirability
function of each factor can be written in the form of
geometric mean as given in (3).
D = [(d1 y1) (d2 y2) (d3 y3) (dk yk)]1/k (3)
with k representing the number of responses.
Upon the need of the output, the response of the
yield, y can be either maximize, minimize or at a
represent the lower, upper and target value,
respectively, for the desired response y. Desirability
function for optimizing a process to the target yield is
given in (4).
(4)
(5)
 Lim et al.
Application of Optimization in Wastewater Treatment

Lastly, for a process response that requires a minimum yield, then the desirability function would be:

1 if y T

y U n
D ( y ) [ ] if T y U (6)
T U

0 if y U

with notation m and n vital in determining the k

relationship of the target value and yield, respectively.
If m=n=1, then the desirability function is linear
towards the target value. However, if m<1 and n<1,
the function would be convex and if m>1 and n>1,
the function would be concave.
6. DESIGNS USED FOR OPTIMIZATION
Selecting a suitable experimental design will greatly
help in describing the real behaviour of the process
over the region of interest. Some important properties
should be provided by the design such as rotatability
which means the predicted response is a function of
distance and not a function of direction and uniform
precision. As the location of optimum solution is
unknown before running the experiment, rotatability
provides equal precision of estimation in all directions.
Designs that have these properties are CCD and BBD
while three-level factorial design is not rotatable.
CCD and BBD design required a small number of
runs to fit a response surface model to the data
compared with full factorial designs such as three-
level factorial design and higher order. The model
obtained will be either first-order or second-order
polynomial model that fits the data. The model should
be checked for normality assumption, and model
adequacy.
6.1. Model
The most commonly response surface models used to
fit the data are first-order and second-order
polynomial models.
6.1.1. First order model
In most experimental condition, the relationship
between the response or the yield and independent
factors are unknown. In order to obtain a suitable
approximation for the relationship, a linear function or
lower order polynomial is engaged. This function is
known as a first-order model. The first order model
with k variables is given in (7).
y = o + ixi (7)
i=1
where, 0 , and i are regression coefficients, and
xi are the coded variables.
Two-level factorial (2k) is usually used since the
number of runs is smaller than other designs and
allows the assessment of linear effects of the factors
and interactions.
6.2.2. Second order model
Second-order model is used if there is a curvature in
the first order model which means that the first-order
model is insufficient, then a higher degree of
polynomial should be used to describe the real
relationship between the response and selected
independent variables. A second-order model is given
in (8).
k k
y 0 i xi ii xi2 ij xi x j (8)
i 1 i 1 i j
where, 0 , i , ii , and ij are regression
coefficients, and xi are the coded variables
(Montgomery, 2012).
It is important for the second-order model to
provide good prediction throughout the region of
interest. Hence, Box and Hunter (1957) suggested that
a second-order response surface design should be
rotatable. BBD and CCD are the most commonly used
designs to fit second-order model while three-level
factorial design is less use compared to other designs.
There is other second-order designs, which are not
frequently used, for instance, Hoke designs, Box
Draper saturated designs, uniform shell and hybrid
designs (Khuri and Mukhopadhyay, 2010).
6.2.2.1. Central Composite Design
CCD is a very efficient design for fitting a second-
order model. CCD is a rotatable design that provides
equal precision for fitted response at points (factor
level combinations) that are at equal distances from
the center of the factor space. CCD usually has axial

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 Wastewater Engineering: Advanced Wastewater Treatment Systems
Chapter 9: Application of Optimization in Treatment

or star points () outside the cube. The value of
depends on the number of variables in the design.
Furthermore, the choice of in the CCD is usually
based on the region of interest. CCD consists of three
components (i) a complete 2k factorial design with nF
runs, (ii) 2k axial runs and (iii) n0 center runs
(Montgomery, 2012). Therefore, the total number of
runs is equal to 2k +2k+n0. The response surface plots
can be employed to study the surfaces and locate the
optimum. An example for CCD with two factors in
coded form is given below:

x1 x2
-1 -1
1 -1 Factorial
-1 1 Points
1 1
-1.41421 0
1.41421 0 Axial
0 -1.41421 Points
0 1.41421
0 0
0 0
0 0 Centre
Points
0 0
0 0

It can be seen that there are three parts of CCD, (i)
factorial points nF = 4, (ii) axial (star) points = 4 and
(iii) four or five runs at the centre. In case of axial
point equals to 1 the CCD is called face centred
design (FCCD) (Montgomery, 2012).
Example 6.1
Suppose a chemist would like to extract vegetable
oil by using supercritical CO2 from a sample prepared
without giving any pretreatment. Three factors are
thought to be influential factors, namely, pressure,
temperature and time. The levels of each factor in
actual and coded forms are given in Table 4. FCCD
was used to carry out the experiment. The data are
given in Table 5.

Table 4: Experimental conditions in actual and coded form

Factor Symbol Levels

Actual Coded
Pressure (MPa) x1 27.58 48.26 -1 1
Temperature (C) x2 40 80 -1 1
Time (min) x3 45 70 -1 1

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 Lim et al.
Application of Optimization in Wastewater Treatment

Table 5: Face centred composite design in natural variables

Pressure (MPa) Temperature (C) Time Percent yield
(min) (%)
27.58 80 45 42.5
48.26 80 45 35.0
27.58 40 70 27.1
48.26 40 70 66.7
27.58 80 70 59.5
48.26 80 70 50.1
27.58 60 57.5 38.2
48.26 60 57.5 75.9
37.92 40 57.5 44.3
37.92 80 57.5 68.9
37.92 60 45 46.8
37.92 60 70 74.4
27.58 40 45 65.4
48.26 40 45 67.6
37.92 60 57.5 67.1
37.92 60 57.5 66.9
37.92 60 57.5 68.3
37.92 60 57.5 68.7
37.92 60 57.5 68.3

19 runs were required to cover all possible obtained from this experiment. The results of
combination of factor levels. Design Expert statistical ANOVA are given in Table 6.
software (version 6) was used to analyze the data

Table 6: ANOVA table for vegetable oil extraction

Mean
Source of variation Sum of squares Degree of Freedom sum square F-value P-value
Model 3911.79 9 434.64 13.25 <0.0003
Pressure 892.95 1 892.95 27.22 <0.0006
Temperature 50.90 1 50.90 1.55 <0.2444
Time 1200.73 1 1200.73 36.60 <0.0002
PressurePressure 663.93 1 663.93 20.24 <0.0015
TemperatureTemperature 296.65 1 296.65 9.04 <0.0148
TimeTime 10.30 1 10.30 0.31 <0.5888

PressureTemperature 13.42 1 13.42 0.41 <0.5383

PressureTime 785.76 1 785.76 23.95 <0.0009
TemperatureTime 119.00 1 119.00 3.63 <0.0892
Residual 119.00 1 32.80
Total 4207.03 18

The results of the ANOVA for vegetable oil
extraction showed that the main effects of pressure
and time of extraction are statistically significant.
Furthermore, the quadratic contribution for pressure
and temperature over the main effect was significant,
whilst time did not show a significant effect. In
addition, the interaction between pressure and time
was significant at P < 0.10.
A model that best describes the yield result was
built in order to optimize the process by finding the
optimal settings of pressure, temperature, and time so
as to maximize the yield for each response. A second-
order model for the yield of oil extracted from the
sample in terms of coded variables was obtained as
given in Eq. 9. Three-dimensional response surface
plot is given in Fig. 6 to illustrate the maximum yield.

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 Wastewater Engineering: Advanced Wastewater Treatment Systems
Chapter 9: Application of Optimization in Treatment

Yield 65.83 9.45x1 2.26x2 10.96x3 15.59x12 10.42x22 1.94x32

(9)
1.30x1 x2 9.91x1 x3 3.86x2 x3

Fig. 2: Three-dimensional response surface diagram of percent yield as a function of pressure and temperature

It was found that the maximum yield in percent
can be achieved at 41.68 MPa, 74.54C and at
duration of 62.16 min may achieved 70.07% yield.
6.2.2.2. Box behnken design
The BBD is one of the most efficient designs used to
fit a second order model. It is a three-level design
based upon the combination of two-level factorial
designs and incomplete block designs. BBD is
rotatable or nearly rotatable and spherical design
(contains no embedded factorial or fractional factorial
design), in which the treatment combinations are at
the midpoints of the edges of the process space and at
the center. The advantage of the BBD is that it does
not contain combinations for which all factors are
simultaneously at their highest or lowest levels. Hence,
these designs are useful in avoiding experiments
performed under extreme conditions, in which
unsatisfactory results are often obtained. Furthermore,
BBD does not have axial points. Thus, all design
points fall within the safe operating zone. These
designs also ensure that all factors are never set at
their high levels, simultaneously (Ragonese, Macka et
al., 2002; Govender, 2005; Ferreira, 2007).
BBD is popular to be employed in industrial
research due to its economical design and requires
only three levels for each factor (-1, 0, 1). Typically,
BBD has the number of design arrangements of k is 3,
4, 5, 6, 7, 9, 10, 11, 12, and 16 factors (Khuri and
Mukhopadhyay, 2010).
An example for BBD with three factors will
consist of 3 sets of 22 factorial points, and 3 center
points or intermediate points. The total number of runs
is 15 as given below:

x1 x2 x3
-1 -1 0
1 -1 0
-1 1 0
1 1 0
-1 0 -1 Factorial
Points
1 0 -1
-1 0 1
1 0 1
0 -1 -1

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 Lim et al.
Application of Optimization in Wastewater Treatment

0 1 -1
0 -1 1
0 1 1
0 0 0
0 0 0 Center Point/
Intermediate
0 0 0

Example 6.2 reduction as response. The experimental ranges for all

A biopolymer clarifies turbid water added during independent variables were based on the preliminary
coagulation-flocculation process. The performance of trials as depicted in Table 7.
clarifying water is examined by using the turbidity

Table 7: Experimental range for turbid water treatment

Factor Symbol Levels

Actual Coded
pH x1 3 9 -1 1

Cation concentration (mM) x2 0.1 1.0 -1 1

Biopolymer dosage (mg/L) x3 10 50 -1 1

Seventeen runs were required to cover all possible carried out randomly to minimize the effect of
combination of factor levels. The experiments were unexpected variability in the observed responses. The
designed and analyzed using the Design Expert experiment runs are given in Table 8. The results of
statistical software (version 6). The experiment was the analysis are summarized in Table 9.

Table 8: Box-Behnken design in natural variables

pH Cation concentration Biopolymer dosage Turbidity reduction
(mM) (mg/L) (%)
3 0.10 30 55.5
9 0.10 30 91.1
3 1.00 30 99.7
9 1.00 30 98.8
3 0.55 10 97.0
9 0.55 10 98.4
3 0.55 50 68.7
9 0.55 50 99.7
6 0.10 10 99.0
6 1.00 10 99.8
6 0.10 50 76.2
6 1.00 50 99.7
6 0.55 30 99.6
6 0.55 30 99.7
6 0.55 30 99.0
6 0.55 30 99.3
6 0.55 30 99.4

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 Wastewater Engineering: Advanced Wastewater Treatment Systems
Chapter 9: Application of Optimization in Treatment

Table 9: The result of analysis of variance (ANOVA) for turbidity reduction

Degree Mean
Sum of of sum
Source of variation squares Freedom square F-value P-value
Model 2685.11 9 298.35 21.25 <0.0003
pH 562.80 1 562.80 40.08 <0.0004
Cation concentration 725.81 1 725.81 51.69 <0.0002
Biopolymer dosage 311.25 1 311.25 22.17 <0.0022
pH pH 264.44 1 264.44 18.83 <0.0034
Cation concentration Cation
concentration 113.85 1 113.85 8.11 <0.0248
Biopolymer dosage
Biopolymer dosage 1.16 1 1.16 0.083 <0.7821
pH Cation concentration 333.06 1 333.06 23.72 <0.0018
pH Biopolymer dosage 219.04 1 219.04 15.60 <0.0055
Cation concentration
Biopolymer dosage 128.82 1 128.82 9.18 <0.0191
Residual 98.28 7
Total 2783.39 16

As can be seen, the analysis of variance revealed cation concentration, pH and cation concentration,
that a second-order model adequately fitted the cation concentration and biopolymer dosage was
experimental data. As shown in Table 6.6, the linear significant at P<0.10. A second-order models that
effects of pH, cation concentration and biopolymer describe the behavior of turbidity reduction are built
dosage were significant. The contribution of quadratic in order to optimize the process by finding the best
effect over the linear effect for pH and cation settings of pH, cation concentration and biopolymer
concentration was significant, whilst the quadratic dosage that maximize turbidity reduction. The second-
contribution of biopolymer dosage was insignificant. order model for turbidity reduction in terms of coded
On the other hand, the interaction between pH and variable are given in Eq. 10,
Turbidity reduction 99.40 8.39x1 9.53x 2 - 6.24x3 - 7.93x12 - 5.20x 22
(10)
0.52x32 - 9.13x1 x 2 7.40x1 x3 5.68x 2 x3
Lastly, to better present the optimization setting, 3 to have a clear picture on the maximum turbidity
three dimensional response surface plot is given in Fig. reduction.

Fig. 3: Three-dimensional response surface for turbidity reduction as a function of pH and concentration of cation

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