Jayshree Ramkumar - A. K. Tyagi - Remedial and Analytical Separation Processes - (2025)

Remedial and Analytical
Separation Processes
This book describes a comprehensive, integrated view of separation science
backed by discussions about simple extraction and partition processes to give a
better understanding of advanced techniques like chromatography and membrane
separations. It paves the way for an understanding of the fundamental physical and
chemical phenomena involved in separations and a concise overview of transport
reactions. A chapter dedicated to phytoremediation gives an understanding of the
various processes involved in the bioremediation of environmental media.
FEATURES:
• Provides synchronous aspects of the separation process for remediation,
including phytoremediation and analysis using chromatography.
• Addresses basic separation techniques for water solutions.
• Discusses mechanistic views of various separation processes.
• Includes the mechanism of separation using membranes and sorbents.
• Helps the reader understand the connection between the different discrete
separation processes.
This book is aimed at senior undergraduate and graduate students in environmental

engineering and analytical chemistry.
Remedial and Analytical
Separation Processes
Jayshree Ramkumar and A.K. Tyagi

First edition published 2025
by CRC Press
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© 2025 Jayshree Ramkumar and A.K. Tyagi
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ISBN: 978-1-032-45885-4 (hbk)
ISBN: 978-1-032-58093-7 (pbk)
ISBN: 978-1-003-44251-6 (ebk)
DOI: 10.1201/9781003442516
Typeset in Times
by Apex CoVantage, LLC
Contents
Preface�� vii
About the authors�� ix
Chapter 1 Introduction to environment alteration and reshaping�� 1

1.1 What is environment?�� 1
1.2 Changing dynamics of environment�� 1
1.3 Water: the flow of life�� 2
1.4 Pollution: making environmental dustbins�� 5
1.5 Origins of water pollution�� 9
1.6 Scenario of water pollution: international and national�� 11
1.7 Effect of water pollution: human health and climate�� 11
1.8 Environmental sustainability: challenging but
not impossible�� 13
1.9 Conclusions�� 13
References�� 14
Chapter 2 Separation process: imperative to human life�� 19

2.1 Mixture and separation�� 19
2.2 Classification of separation techniques�� 20
References�� 25
Chapter 3 Membrane separation: primordial water treatment technique�� 26

3.1 What is a membrane?�� 26
3.2 Classification of membranes�� 27
3.2.1 Solid membranes�� 27
3.2.2 Liquid membranes�� 30
3.3 Mechanism of separation�� 35
3.3.1 Mechanism in solid membranes�� 35
3.3.2 Mechanism in liquid membranes�� 36
3.4 Applications�� 38
References�� 41
Chapter 4 Sorption: backbone of separation science�� 47

4.1 Introduction�� 47
4.2 Rudiments of sorption�� 47
v
vi Contents
4.3 Understanding sorption using models�� 49

4.3.1 Equilibrium models�� 50
4.3.2 Kinetic models�� 60
References�� 66
Chapter 5 Phytoremediation: an emerging green auxiliary technique�� 71

5.2 Types of phytoremediation�� 71
5.3 Steps involved in the process�� 76
5.4 Mechanisms�� 77
5.5 Nano-phytoremediation�� 79
5.6 Benefits and constraints of phytoremediation�� 80
References�� 82
Chapter 6 Chemical precipitation, coagulation, and flocculation: triad of

great versatility�� 87
6.2 Applications for the removal of metal ions and dyes�� 95
References�� 97
Chapter 7 Chromatographic techniques: workhorse of analytical

chemistry�� 101
7.1 What is analytical chemistry?�� 101
7.2 What is chromatography?�� 104
7.3 Classification of chromatography�� 105
7.4 Basic principles of liquid chromatography�� 109
7.5 Instrumentation of LC�� 116
7.5.1 Normal and reverse phase chromatography�� 117
7.5.2 Ion chromatography�� 120
7.6 Applications of chromatography�� 123
References�� 127
Chapter 8 Broad conclusions and future perspectives�� 131
Index�� 135
Preface
Human beings and the environment, being interconnected, tend to affect each other
in more than one way. Constant technological growth is bound to result in envi-
ronmental degradation. In order to remove these toxic species from environmen-
tal media like ground water and to achieve remediation, separation is essential.
Separation is a method by which a mixture or solution containing different compo-
nents is resolved into individual components, leading to the enrichment of a partic-
ular phase. Separation can be either analytical or preparative in nature and can be
carried out at a lab scale or an industrial level, respectively. In analytical methods,
separation is utilized to segregate the required component with a high degree of
purity to enable highly accurate and precise determination. The preparative separa-
tion aims at achieving a component with a high degree of purity for further applica-
tions. The latter can be understood to play a role in remedial applications.
In this book, an attempt is made to give a comprehensive and integrated view
of separation processes. The initial chapters are dedicated to discussions on the
use of these procedures for remediation purposes. Each chapter discusses the basic
concepts of the separation process, followed by their applications for the removal
of toxic species. The first chapter elaborates in general about environment and its
effect on mankind upon degradation. The second chapter gives an idea of the con-
cept of separation, starting with simple techniques which pave way for the compre-
hension of advanced techniques. The book is intended to provide an understanding
of the fundamental physical and chemical phenomena involved in membrane sep-
aration processes. A chapter dedicated to phytoremediation is aimed to provide an
understanding of this imminent technique found to be suitable for bioremediation.
However, since the technique is taking baby steps, not much work has been reported,
and no clear-cut strategy can be obtained. In addition to the different techniques
adopted for the removal of toxic species, the book also contains a chapter dedicated
to chromatography. This was found to fit within the scope of this book as this ana-
lytical methodology is based on separation. The book can be used to understand the
basics and also as a ready reference to carry out further research.
Due care has been taken to minimize errors, but some could have occurred due
to unintentional oversight. We shall be appreciative of the readers for bringing such
inadvertent mistakes to our notice. An attempt has been made to achieve a balance
in the contents to make it useful to a large spectrum of readers including students
and researchers.
vii
About the authors
Dr. Jayshree Ramkumar obtained her MSc (analytical
chemistry) in 1993 from Madras University, Chennai, and
joined Bhabha Atomic Research Centre (BARC) Training
School, Mumbai, in the same year. After completing a one-
year orientation course in nuclear science and technology, she
joined the Analytical Chemistry Division of BARC in 1994.
She is also an associate professor (Chemistry) at Homi Bhabha
National Institute (HBNI), Mumbai. She has been involved
in research in the areas of separation science and analytical
chemistry. Her PhD was on the studies using Nafion membranes and bulk liquid
membrane for achieving separation of various species like metal ions and organic
compounds. She was awarded MANA fellowship for carrying out postdoctoral
research at the National Institute for Materials Science (NIMS), Tsukuba, Japan. Her
work involved the synthesis of mesoporous materials for applications as sorbents for
the removal of toxic species. She has been collaborating with universities through
the BRNS and AERB projects as the principal collaborator. She is the reviewer of
many project proposals of different funding agencies for their suitability for funding.
She is a member of the Doctoral Committee of HBNI, editorial board of journals,
and serves as an external examiner for PhD students of different universities. She
has more than 75 publications, including papers in international journals and book
chapters, to her credit.
Dr. A.K. Tyagi joined Chemistry Division, BARC in 1986

through BARC Training School and received PhD degree in
1992. He did postdoctoral research at Max-Planck Institute,
Stuttgart, Germany (1995–96). He occupied various positions
at BARC such as Director, Chemistry Group, Director, Bio-
Science Group, Head, Chemistry Division, etc. He was a
Distinguished Scientist, Department of Atomic Energy (DAE).
Presently, he is Dean and Senior Professor, Homi Bhabha
National Institute (HBNI), Mumbai and Honorary Professor
at JNCASR, Bengaluru. His research interests are in the field of anomaterials,
functional materials, nuclear materials, metastable materials, and hybrid materials.
He has to credit his 47 PhD students and about 650 papers in journals. He has
been conferred with a number of awards such as DAE-Homi Bhabha Science and
Technology Award; DAE-SRC Outstanding Researcher Award; MRSI Medal;
MRSI-ICSC Materials Science Senior Award; MRSI-CNR Rao Prize in Advanced
Materials; MRSI Distinguished Materials Scientist of the year award; CRSI Bronze
Medal; CRSI-CNR Rao National Prize in Chemical Sciences; CRSI-Silver Medal;
RajibGoyal Prize in Chemical Sciences; Metallurgist of the Year award from
Ministry of Steel, GoI; National Prize in Solid State and Materials Chemistry from
JNCASR; ISCA Acharya PC Ray Memorial Award; NETZSCH – ITAS Award
ix
x About the authors
by Indian Thermal Analysis Society; DN Agarwal Memorial Award from Indian

Ceramics Society; Gold medal of Chirantan RasayanSanstha. He is Fellow of several
national and international science academies such as National Academy of Sciences,
India (FNASc); Indian Academy of Sciences (FASc); Indian National Academy of
Engineering (FNAE); Indian National Science Academy (FNA); Royal Society of
Chemistry (FRSC); and The World Academy of Sciences (FTWAS). Recently, he
was conferred with the restigious Vigyan Shri Award by Hon’ble President of India.
1 Introduction to
environment alteration
and reshaping
1.1 WHAT IS ENVIRONMENT?
Man and environment are connected to one another and cause changes in each other.
Environment gives life to mankind, but the changes caused by man lead to degrada-
tion of environment. The relationship between man and the environment has been
established in the early periods itself wherein humans lived in sync with the nature
and followed the laws of nature. The knowledge of environment through systematic
education can help work towards a sustainable future.
The term environment emanated from environia (French word), which means
“to surround”. Therefore, it is symptomatic of both abiotic (physical/non-living) and
biotic (living) surroundings within which humans live [1]. Thus, both environment
and humans are intertwined in a complex manner, and the environment controls
every aspect of life. It is very obvious that the interaction between humans and envi-
ronment is more prominent as compared to that of other species. Accordingly, envi-
ronment can be defined as the surrounding or conditions in which humans and other
living species are present and can refer to the elements of the physical and biological
world and the interactions between them. Consequently, environment can be con-
sidered as the conditions and interactions in toto at a given point of time and space.
As the environment consists of atmosphere, hydrosphere, lithosphere and biosphere
with the main components (soil, water and air), it is clear that there will be a direct
influence (natural, artificial, social, biological and psychological) on the lives of
human beings. Environment can be categorized into micro and macro environments
and also as non-biotic and biotic. Macro environment is the local surrounding of
an organism and involves physical and biotic conditions. The physical environment
includes abiotic factors like temperature, light, rain and soil, while biotic indicates all
living forms. Environment is productive (provides raw materials for various indus-
tries), aesthetic and provides an understanding of the value and importance of the
surroundings. Therefore, the need to preserve and reuse the resources becomes a
major facet of survival.
1.2 CHANGING DYNAMICS OF ENVIRONMENT

The incessant expansion of scientific know-how leads to immense apprehension on
the upshot of the milieu, thus necessitating the formulation of the modus operandi
of the removal of the different obnoxious waste generated during these processes.
Environment is all of those that are contiguous to a living organism. Due to the
DOI: 10.1201/9781003442516-1 1
2 Remedial and analytical separation processes
unremitting development, environment is never static and results in pollution due to

the introduction of unwanted species, normally referred to as either a contaminant
or a pollutant. But there is a subtle difference between the two terms. A contaminant
can be defined as a species which should not be present at a particular place. When
a contaminant is present at levels that cause damage to human life, it is defined as a
pollutant [2]. The unwanted species can be natural or man-made or can also be bio-
logical or chemical in nature [3]. Therefore, it can be easily understood that not every
contaminant is a pollutant, but every pollutant is definitely a contaminant [4]. The
famous quote of Paracelsus, the father of toxicology, sola dosisfacitvenenum is the
adage intended to indicate a basic principle of toxicology: “The dose makes the poi-
son” [5]. Thus, it is clear the concentration decides the toxicity of a substance. From
the famous quote of B. F. Skinner, “The environment will continue to deteriorate
until pollution practices are abandoned”, it is quite clear that the present practices of
mankind need to be altered to reduce the pollution in the environment.
1.3 WATER: THE FLOW OF LIFE

Water is one of the important components of the environment which is of great
importance to mankind. According to the famous quote of Vriddha Chanakya, water
is one of the gems of Mother Earth. Acharya Vagbhata also quoted that water is
the life of all living creatures on this earth, and the major portion of earth contains
water. It was understood everyone needs water irrespective of their health status [6].
Water, known as Ap in Sanskrit, is the fourth among the five elements of the uni-
verse (panchamahabhuta). The various forms of water like snowfall and dew have
also been mentioned. Since water is very important for the sustenance of life, even a
slightest deviation in its characteristics becomes quite a challenge for mankind [7].
The increasing stress on water environment leads to decreased availability of clean
water and also a greater damage to aquatic life. Preservation of our water environ-
ment must be integrated with development to make it sustainable. This therefore
needs the development of effective wastewater treatment protocols to be integrated
with policies for continuous development.
The total volume of water on earth is estimated at 1.386 billion km³ (333 million
cubic miles) and is present in various forms as shown schematically in Figure 1.1,
based on the literature reported [8]. Of the total amount of water, 97%is saline (salt
water) and only 3% is fresh water, and out of this, only 0.3% is present on the surface
and is accessible for use.
The water on the planet is in a state of continuous motion and is temporarily
stored as different water bodies or reservoirs (rivers, lakes, ponds and ice caps) on
the earth’s surface and as groundwater below the surface [9]. Residence time (time
of water present in these reservoirs) is not constant and is affected by various con-
ditions. This can be understood easily from the water cycle, also referred to as the
hydrological or hydrologic cycle [9]. Hydrological cycle denotes the sequential envi-
ronmental processes which lead to the continuous circulation of water on the earth’s
atmospheric system [9]. Water (in solid or liquid form) is converted to vapour, which
traverses substantial distance from its source prior to recondensation. Although the
total amount of water within the cycle remains essentially constant, its distribution
Introduction to environment alteration and reshaping 3
FIGURE 1.1 Schematic representation of the distribution of different types of water on earth
FIGURE 1.2 Schematic representation of the hydrological cycle
among the various processes changes continuously. Figure 1.2 gives a schematic rep-
resentation of the hydrological cycle. Generally, the starting point of the water cycle
is considered to be the starting point of the hydrological cycle (due to large quantities
of water). It is understood that the hydrological cycle is a complex process involving
different aspects which are linked to each other. It is now understood that the earth’s
freshwater supply is solely due to the hydrological cycle involving different stages,
namely, evaporation, condensation, runoff, streamflow, infiltration and transpiration
(evaporation from leaves). Water from the ocean evaporates, condenses into minute
particles suspended in the air, and finally precipitates on the earth’s surface due to
condensation of the vapour. The vapour condenses due to the movement of warm
air into a colder zone horizontally or vertically above the earth’s surface or due to
cooling when it moves across the mountains. A part of this vapour can directly form
ice and snow by the process of sublimation. Thus, the processes of condensation and
evaporation are together referred to as precipitation. The falling of rain on terrestrial
areas and capture by vegetation is known as interception, and the possibility of this
water being evaporated again is quite high (due to the exposure of a large area to
wind). The remaining amount which falls on the earth can either be trapped within
the soil surface (infiltration) or can flow as streams (surface runoff). Runoff is the
total of amount of water flowing as stream due to surface runoff and the amount of
water present as ground water. Infiltration is the percolation of water into the earth’s
crust by different modalities. The recharge of underground water occurs due to run-
off of water. The hydrological cycle may have a long cycle or many short cycles. In
the short cycles, water evaporates from the marine or freshwater system, condenses
immediately and precipitates in the same area, and this cycle can keep occurring.
In the long cycle, water evaporates from the oceans, forms clouds that move inland
and then precipitates. This water will return to the ocean. Thus, the precipitation can
occur quite close to or far away from the original source. It is estimated that the water
remains in the atmosphere for about 10 days. The hydrological cycle is essential to
maintain the balance in the ecosystem and provide fresh water. The sole source of
land water is atmospheric precipitation. It is estimated some of these flows into the
oceans while the majority is evaporated.
India has an area of 3, 287, 590 km2 with a 7, 500 -km-long coastline [10].
Throughout the country, there are huge variations in geographical features and cli-
mate. The river network is quite well spread across the entire country. The major
rivers of India are divided based on the ocean into which they flow [11]. The riv-
ers Brahmaputra, Yamuna, Ganga (with its main tributaries Ramganga, Gangan,
Kali or Sharda, Gomti, Yamuna, Chambal, Betwa, Ken, Tons, Ghaghara, Gandaki,
BurhiGandak, Koshi, Mahananda, Tamsa, Son, and Bagmati), Meghna, Mahanadi,
Godavari, Krishna (and its main tributaries) and Kaveri flow into the Bay of Bengal,
while the rivers Narmada, Tapi, Sindhu, Sabarmati, and Purna flow into the Arabian
Sea. The river basins are categorized based on the catchment area covered. There
are 13 major river basins with a catchment area of more than 20, 000 km2, contrib-
uting to 85% of the total surface flow [11]. The major river basins are Brahmaputra,
Ganga (including Yamuna sub-basin), Indus (including Satluj and Beas sub-basins),
Godavari, Krishna, Mahanadi, Narmada, Cauvery, Brahmini (including Baitarni
sub-basin), Tapi, Mahi, Pennar, and Sabarmati. There are 48 medium river basins
with a catchment area in the range of 2,000–20,000 km2, which contributes about
8% to the total surface flow. There are 52 minor river basins with a catchment area of
less than 2, 000 km2, contributing to about 9.6% of the total surface flow. There are
few desert rivers, which flow for some distance and are lost in deserts, while some
areas are completely arid (evaporation equals rainfall) with no surface flow. The
medium and minor river basins are mainly in the coastal areas. The rivers on the east
coast is about 100 km due to the large distance between the land and the sea. The
rivers in the west coast are much shorter as the width of the land between the sea and
mountains is about 10–40 km.
Despite nature’s bounty, water paucity results in deterioration of water quality in
aquatic resources and hence is an issue of national concern. The exponential increase
in population along with rapid technological development has affected both the quan-
tity and quality of water in India. The main aspect of urbanization is the skewed
distribution of more than 25% of the population within the metro cities alone. The
unregulated growth of urban areas has led to increased pollution, and the situation
warrants immediate redressal through radically improved water resource and water
quality management strategies. The availability of freshwater resources is declining
in India [12] as the requirements are increasing many folds.
1.4 POLLUTION: MAKING ENVIRONMENTAL DUSTBINS

The introduction of unwanted matter from various sources into large water bodies
leads to the degradation of the quality of water and, therefore, has a great impact
on life [13]. Jacques Cousteau, a French naval officer, scientist, and conservation-
ist, said: “We forget that the water cycle and the life cycle are one”. This is a very
true statement because water is the flow of life, and all life’s sustenance depends on
water quality. However, ongoing rapid industrial and commercial developments have
deteriorated water quality, so poor as can be understood from the quote of Jacques
Cousteau: “Water and air, the two essential fluids on which all life depends, have
become global garbage cans”. The contaminants found in groundwater can be phys-
ical, inorganic or organic chemicals, bacteriological and radioactive in nature. The
survival of mankind depends on the three basic natural resources water, air and soil.
The concept of pollution (cause and effects) has been discussed in 5,000-year-old
Indian classics like Sushruta Samhita and Charaka Samhita, wherein many methods
of purification have also been discussed [6, 14]. According to Susrutha (the Father of
Indian medicine), there are six types of pollution (dosha; sparsa, rupa, rasa, gandha,
virya, and vipaka) which have negative effects on man. It has observed that there is a
continuous increase in the demand for water due to the continuous increase in popula-
tion, urbanization and industrialization expansion combined with the increased need
for agricultural produce. The per capita availability of water (estimated by dividing
the annual average water availability by population) is also continuously decreasing.
Therefore, sustenance and management available water become a huge challenge.
Furthermore, statistics related to the adverse effects of consumption of contaminated
water is alarming, adding further complexity to the water stress. Although Asia has
36% of the available fresh water on the earth, the advantage is offset by its large
population (over 60% of the world population), leading to water scarcity. Australia
and the oceans have plenty of water followed by North, Central, and South Americas.
Africa is still in a better position than Asia [15]. It is projected that by the year 2050,
a huge percentage of people would be affected. The demand for water in India is pro-
jected to overtake the amount available. The main increase will be from the domes-
tic sector. The National Commission for Integrated Water Resources Development
(NCIWRD) has indicated that the water demand in the domestic and industrial sec-
tors would increase substantially. India is not a water deficit country, but neglect and
lack of monitoring have resulted in water stress. The concern regarding environ-
mental degradation at the global level was first emphasized at the UN Conference
in Stockholm in June 1972 [16]. Thereafter, topics like environment, sustainability
and water quality became the key aspects. Various studies suggested that not only
the need for water was more in urban areas than in rural areas, the quality of water
discharged in urban areas was also very poor.
Water quality is defined as a measure of the suitability of water for a particular
use based on select physical, chemical, and biological characteristics [17,18]. It is
also a measure of the conditions relative to the requirements [19,20]. Water can be
classified into different categories, namely, potable water, palatable water, contami-
nated (polluted) water, and infected water, based on its quality [21]. Potable water is
water which is safe to drink, pleasant to taste and usable for domestic purposes [21].
Palatable water is aesthetic but contains some contaminants at very low concentra-
tions such that they do not cause any adverse reactions to human life. Contaminated
water contains unwanted physical, chemical, biological, or radiological substances,
and it is unfit for drinking or domestic use, while polluted water causes adverse
health effects [22]. Infected water is polluted with pathogenic organisms. Physical,
chemical, and biological parameters are used to check and ensure the quality of
water [23,24].
(i) Physical parameters of water: The different physical parameters that are
generally checked are turbidity, temperature, colour, taste and odour, sus-
pended solids, and electrical conductivity.
Turbidity is the cloudiness of water [25] caused by suspended particles (clay, silt,
organic material, and plankton), making it unfit for consumption. It leads to increased
pretreatment cost [26], can hinder the disinfection process [27] (for removing toxic
microorganisms), can prove to be harmful to aquatic and human life and tends to
increase the concentrations of toxic heavy metal ions or organic compounds [28].
The presence of turbidity increases temperature and thus reduces dissolved oxygen
(DO). Turbidity is measured using nephelometric turbidimeter and is expressed in
units of NTU or TU (1 TU = 1 mg/L of silica in suspension) [25]. Turbidity of more
than 5 NTU is visible, and the value is greater than 100 NTU for muddy water [25].
Groundwater normally has very low turbidity because of the natural filtration that
occurs as water penetrates through soil [29].
Temperature affects the different characteristics of water, including oxygen con-
tent and metal ion biosorption [30,31]. Water at a temperature of 10–15°C is found to
be most palatable for many people [32]. An increase in the temperature of seas and
rivers will cause great harm to aquatic life.
Water colour can be caused by the decay of organic matter and the presence of
certain inorganic species. The presence of colour is not acceptable not only due to
aesthetic reasons but also because it can prove to be toxic to human health [33]. Water
colour is measured by comparing the water sample with standard odour solutions
or odoured glass disks [25]. One colour unit is equivalent to the colour produced by
a 1-mg/L solution of platinum [potassium chloroplatinate (K2PtCl6)] [25]. Colour
is graded on scale of 0 (clear) to 70 odour units. Pure water is colourless, which is

equivalent to 0 colour units [25].
Taste and odour of water can be altered due to the presence of organic materi-
als, inorganic compounds, or dissolved gasses which may be introduced from nat-
ural, domestic, or agricultural sources [34]. The numerical value of odour or taste
is determined quantitatively by diluting a known volume of a sample with a mea-
sured volume of distilled water (B) till the total volume is 200 mL [35]. Threshold
odour number (TON) and threshold taste number (TTN) are units of odour and taste,
respectively. These are whole numbers indicating how many dilutions it takes to
produce odour-free water.
When water is filtered, the suspended solids are retained on the filter, while dis-
solved solids tend to pass through the filter along with water [25]. When this sample
is evaporated, the dissolved solids are obtained as residue. The total concentration of
dissolved solids, referred to as total dissolved solids (TDS), is used to classify water.
The TDS values in fresh, brackish and saline waters are <1500 mg/L, 1500–5000
mg/L, and >5000 mg/L, respectively. The residue of TSS and TDS after heating to
dryness for a defined period of time and at a specific temperature are defined as fixed
solids. Volatile solids are solids lost on ignition (heating to 550°C) [25].
Electrical conductivity (EC) of water is a measure of the ability of water to con-
duct current [35] due to the presence of charged species and is expressed as milliSie-
mens per metre (mS/m). The values of conductivity for ultra-pure water, drinking
water and sea water are 5.5×10−6, 0.005 - 0.05, and 5 S/m, respectively. This value
can be correlated with the TDS value.
(ii) Chemical parameters of water quality
One of the important chemical parameters which decides the water quality is its
pH. Pure water is nearly neutral (pH ~7.0 at 25°C), while rainwater is slightly acidic
(pH ~5.6) due to the dissolution of carbon dioxide [36]. The pH value specified for
drinking water is 6.5 - 8.5 [36]. A very high pH value renders a bitter taste to water
and also makes the disinfection process ineffective. A high pH value makes water
corrosive and causes leaching out of different species. The changes in pH affect
the aquatic life (e.g. decreased hatching, and irritation and damage of membranes).
Similarly, alkalinity can also be used as a pollution indicator. The concentration
of certain inorganic ions can be used as a pollution indicator. Nitrogen in solution
can be present as organic nitrogen compound, ammonia, nitrite, and nitrate [25].
Hardness of water indicates the presence of high concentrations of minerals (bicar-
bonate and sulphate salts of calcium and magnesium), which can cause deposits on
the piping system. Temporary hardness is caused due to carbonates and bicarbon-
ates, while permanent hardness is due to the presence of sulphates and chlorides.
Temporary hardness unlike permanent hardness can be removed by boiling of water.
The unit of hardness is mg/L of CaCO3, and the values for soft, moderate, hard and
very hard water are <50, 50–150, 150–300, and >300 mg/L, respectively. A hardness
value of up to 500 mg/L is considered safe, and a value above this shows laxative
effects [37, 38].
DO is an important parameter indicating water quality [25]. Water with higher

DO is considered to be of very good quality. If the DO concentration decreases to
less than 4 mg/L, all fish will die, while a DO concentration less than 2 mg/L leads
to death of all organisms, and the water is called septic water. The ideal DO concen-
tration value is between 8 and 10 ppm, and the optimum value is 9 ppm. The DO
concentration is very sensitive to water temperature [35]. Cold water has more DO
than warm water (14.6 ppm at 0oC; 9.1 ppm at 20 C) as increased temperature leads
to denaturation of enzymes, thus leading to a decreased photosynthesis rate [39].
(iii) Biological parameters are the aquatic life in water which serves as an indi-
cator of water quality and can be estimated by calculating the species diversity index
(SDI) [40]. The multiplication rates of different species are different and also sen-
sitive to the external conditions. The quality of water and its level of pollution are
marked by various indicators, including pH, BOD, COD, and total coliform counts.
Biochemical oxygen demand (BOD) refers to the decrease in DO due to the activity
of bacteria and microorganisms [41] and can be used as a marker. Sewage water
will have high BOD values as it contains more organic matter. Food industry waste
water contains high organic loading compared to municipal waste water. Therefore,
BOD is used as a measure of the power of sewage (high BOD values indicate strong
sewage) [42]. It is known that microorganisms take 20 days to completely decom-
pose the organic matter in water [42]. The measure of oxygen required to completely
decompose organic matter in a specified volume of water is called the ultimate BOD
or BODL. Chemical oxygen demand (COD) is the total measurement of all chemi-
cals in water that can be oxidized, while BOD is the measure of food (organic car-
bon) that bacteria can oxidize. COD indicates the concentration of biodegradable and
non-biodegradable substances [41] and is used as a measure of organic pollutants in
water and is expressed in milligrams per litre (mg/L) or parts per million (ppm). It is
determined using a combination of strong oxidizing agents (potassium dichromate),
sulphuric acid and heat [25]. The most common application of COD is in quantifying
the amount of oxidizable pollutants found in water. The average values of COD and
BOD are in the ranges of 300–500 mg/L and 200–300 mg/L, respectively, while both
these values are in the range of 1,000 to >1,00,000 mg/L in food industry effluents
[42]. COD values are always higher than BOD values for the same sample [42]. BOD
measures the amount of oxygen required by aerobic organisms to decompose organic
matter, and COD measures the amount of oxygen required to decompose organic
and inorganic constituents present in waste water by chemical reaction. Hence, the
value of COD is greater than that of BOD. The ratio of BOD:COD is a good indica-
tor of pollution. It has been observed that the BOD value has a direct effect on the
value of DO in rivers and streams. The greater the BOD, the more rapidly oxygen
is depleted in the stream. This means less oxygen is available to higher forms of
aquatic life. Moderately polluted rivers may have a BOD value in the range of 2–8
mg/L. Rivers may be considered severely polluted when BOD values exceed 8 mg/L
[43]. Municipal sewage that is efficiently treated by a three-stage process would have
a BOD value of about 20 mg/L or less. The total coliform count gives a general
indication of the sanitary condition of a water supply [44]. A positive coliform test
means possible contamination and a risk of waterborne disease. A positive test for
total coliforms always requires more tests for faecal coliforms or E. coli. The EPA
maximum contaminant level (MCL) for coliform bacteria in drinking water is zero
(or no) total coliform per 100 ml of water.
When the parameters of water are altered due to various reasons, it is said to be
polluted and considered not potable. The water quality requirement for different uses of
water indicates the purity of water. It is crucial that drinking water should be very pure.
In order to set the standard of water quality, knowledge of its use becomes import-
ant. According to the Central Pollution Control Board (CPCB) of India, there are five
classes of water, as discussed below. Class A is drinking water source which can be
used without conventional treatment and with only disinfection. The pH of the water is
in the range of 6.5–8.5, with DO and BOD values of 6 and 2 mg/L, respectively. The
total coliform organism should be less than 50 MPN/100 mL. Class B water is used for
outdoor activities and should have pH in the range of 6.5–8.5. The DO is greater than 6
mg/L, while the BOD is around 2 mg/L and the total coliform organism is less than 50
MPN/100 mL. Class C water is a drinking water source pretreated with conventional
treatment followed by disinfection. The total coliform organisms should be less than
5,000 MPN/100 mL, and the pH is in the range of 6–9. The DO and BOD values should
be around 4 mg/L. Class D water is used for the propagation of wild life, fisheries, etc.,
and has pH in the range of 6.5–8.5 and DO of more than 4 mg/L with free ammonia of
up to a maximum of 1.2 mg/L. Class E water, with pH of 6–8.5, is used for irrigation,
industrial cooling, and controlled waste disposal. The last class is that below Class E,
wherein water does not meet any of the specifications. For easy understanding and
representation on maps, an universally accepted colour code is used. Blue water can
be directly used for drinking and industrial purposes. Green water depicts the water
present in soil and plants. White water refers to fast shallow stretches of water in a river.
White water is formed when the gradient of river being high causes turbulence making
the water appear white. Brown or grey water refers to various grades of waste water.
1.5 ORIGINS OF WATER POLLUTION

Water is essential for sustaining life, as the British poet W. H. Auden once noted,
“Thousands have lived without love, not one without water”. Nevertheless, it is not
treated with care. The dumping of waste water without any pretreatment into the
environment results in the pollution of all water bodies like rivers, lakes, and oceans.
Water pollution is the second most prevalent problem after air pollution. Water is
very vulnerable to pollution. Being referred to as “universal solvent”, water has the
ability to dissolve a large number of species of which many could make it toxic.
Water pollution can be categorized in different ways, namely, based on the type of
water polluted or the nature of the pollutant. In the first category, the different types
of water bodies can be understood. Groundwater is created when rain falls and seeps
into the earth, filling up the cracks, crevices, and porous structures, and is an import-
ant natural resource. Groundwater gets polluted with contaminants (pesticides, fer-
tilizers, and waste leachates). Surface water is the water present in oceans, lakes,
and rivers and comes from freshwater sources. The major pollutants are nitrates and
phosphates from fertilizers and agricultural runoffs. Municipal and industrial waste
discharges also result in the toxicity of water. Marine pollution is known to originate
from the land (coast or inland), and different chemicals and nutrients are carried
from farms and factories by streams and rivers into bays and estuaries and finally
into the sea. Marine debris (plastic) is blown by wind or washed via storms, drains,
and sewers. Oil spill is another contributing factor to the pollution of oceans. The
greatest source of pollution of fresh water is from agricultural run-offs. Sewage water
is also one of the major contributors to water pollution.
The different types of pollutants can be classified as biological (bacteria, viruses,
worms, and protozoa—added by excreta of animals), chemical (inorganic such as
phosphates, nitrates, fluorides, and chlorides, and organic such as phenols, plastics,
dyes, pesticides, and chloro compounds), heavy metal ions (cadmium, mercury, cop-
per, zinc, and their organometallic compounds), physical (waste heat from indus-
trial plants causing physical pollution involving changes in the physical properties
of water, e.g. turbidity and temperature). The different sources of pollutants are
domestic effluents, industrial effluents, surface runoffs, and waste heat. Domestic
effluents are those that are discharged into the common public sewerage system and
may contain excreta, food residue, detergents, and bacteria. The pollutants may be
present as suspended solids (sand, silt, and clay), colloidal particles (large-sized sus-
pended inorganic or organic compounds like faecal matter, bacteria, cloth, paper,
and fibres), or dissolved solids (nitrates, ammonia, phosphates, sodium, calcium,
toxic metallic ions, and organic compounds). Industrial effluents are discharges com-
ing from industries and contain inorganic pollutants (mercury, lead, copper, arse-
nic, cadmium, acids, alkalies, and bleaching liquors) and organic pollutants (phenol,
naphtha, proteins, cellulose fibres, aromatic compounds, putrescible organic matter)
and can be carcinogenic in nature. The main sources of mercury are combustion of
impure coal, thermal power plants, chloralkali industries producing caustic soda,
thermometers, blood pressure instruments, smelting of metallic ore, and paper and
paint industries, while lead comes from smelters, battery industry, chemical and pes-
ticide industries, automobile exhausts, etc. Cadmium is released from electroplat-
ing, pesticide, and phosphate industries. The surface runoff from the field introduces
pollutants like inorganic fertilizers, pesticides, insecticides, and manures, which are
non-degradable, into natural water bodies.
The different sources of water pollution can be categorized as point and non-point
sources [45], which are further classified into natural and anthropogenic sources.
Point source pollution is when pollutants (domestic/industrial waste waters) are
directly discharged into freshwater bodies from well-defined sources. The discharge
can be easily monitored and controlled. Non-point sources are spread over a large
area, leading to indirect introduction of pollutants (runoffs from agricultural farms,
construction sites, abandoned mines, and solid waste disposal sites) and making it
difficult to control. Natural source refers to the sudden increased concentration of
natural substances, e.g. siltation, which occurs due to haphazard deforestation (the
solid is loosened and displaced by flowing water). Anthropogenic sources are the
result of human activities from both increased population and technological growth
leading to increased domestic and industrial waste.
1.6 SCENARIO OF WATER POLLUTION:

INTERNATIONAL AND NATIONAL
The problem of water pollution is a global concern, with countries struggling to get
clean water and combat fatal waterborne diseases. It is also seen that individuals with
decreased immunity are more susceptible to fatality even with comparatively less
threatening waterborne diseases. The major water bodies present all over the world
[46–68] are affected in different ways, resulting in various hazardous effects on both
aquatic life and mankind. The presence of electroplating industries on riverbanks
results in high concentration levels of chromium, which can enter the food chain and
cause great damage. The discharge from sewage, laundry, agriculture, and municipal
activities can make the water alkaline and change the DO values.
1.7 EFFECT OF WATER POLLUTION: HUMAN

HEALTH AND CLIMATE
Drinking water standards are the most important parameters when it comes to decid-
ing whether the water is safe or not. This is because the main objective is to select the
appropriate methodology to ensure complete removal of water pollutants. The pri-
mary aim of water treatment protocols is to produce biologically and chemically safe
water which is also aesthetically acceptable and also does not produce corrosion or
scaling problems. The standards set for drinking water are regulations set by various
regulatory bodies to control the level of contaminants in drinking water. Inorganic
substances at very low concentrations are in general important for sustenance of
human life, whereas at higher concentrations these tend to prove detrimental. For
each and every species, there are specific values given by different regulatory bod-
ies like WHO [69], EU [70], US [71], Canada [72], and BIS, India [73], to prevent
different adverse effects to mankind. Aluminium does not show any detrimental
effects, but the EU gives a value of 0.2 mg/L. Antimony in water leads to increase
in cholesterol, and the values given by different bodies is about 0.006 mg/L. Arsenic
being carcinogenic is specified at a value of 0.01 mg/L by various bodies. The pres-
ence of chromium causes allergic dermatitis, and the value is about 0.05 mg/L. Lead
is a toxic metal ion which leads to delay in the development of foetus and infants
and also kidney damage in adults. The limit in water has been specified by various
bodies to be about 0.01 mg/L. Mercury is another toxic heavy metal ion which leads
to severe kidney damage, and the limit given in water is about 0.001 mg/L. Fluoride
is one of the most abundant anions present in groundwater worldwide and creates a
major problem in safe drinking water supply [74]. It is always present as inorganic
or organic fluorides [75]. High fluoride concentrations can build up in groundwater
present in aquifers, while surface and shallow groundwater usually have low con-
centrations. The fluoride concentration is dependent on climatic condition [76, 77].
Excess fluoride in water causes bone diseases and mottled teeth, and values given as
specifications by different bodies range from 1 to 4 mg/L.
Dyes have been used extensively since ancient times. Dyes exist in nature, but
with time, researchers have gained expertise in synthesizing dyes [78]. According to
Witt theory [79], dyes have a chromophore group which imparts odour to the dye and
auxochromes that intensify the odour. The most important auxochromes are amine
( –NH), carboxyl ( –COOH), sulphonate ( –SO3 H), and hydroxyl (−OH). Depending
on the application method, most of the dyes can be classified into acid, basic, direct,
reactive, disperse, vat, mordant, and sulphur [80].
Textile industries devour huge amounts of water [81] and chemicals with miscel-
laneous chemical composition [82] and cause great environmental impact [83]. There
are very large numbers of dyes available, with over 10 5 tonne of dye-stuff produc-
tion annually. The main obstacle with dyes are that they are not easily degradable.
The Ecological and Toxicological Association of the Dyes and Organic Pigments
Manufacturers (ETAD, established in 1974) intends to minimize environmental
damage, protect users and consumers, and look into the concern regarding toxicity
of dyes. The highest rates of toxicity were found amongst basic and direct diazo dyes
[84]. Water-soluble reactive and acid dyes cause great damage [85] as removal is
difficult using conventional methods. Non-ionic dyes are disperse dyes which do not
ionize in solution and are carcinogenic in nature. The presence of fused ring struc-
tures reduces the degradation of anthraquinone dyes [86]. The resistance of these
dyes to degradation leads to their accumulation in the environment or partial degra-
dation, producing dangerous by-products. The xenobiotic nature of the dyes affects
the structure and functions of ecosystems. Continuous exposure to metal-complexed
dyes usually used in textile industries causes severe damage to aquatic biota and to
human health [87]. Textile dyes can cause dermatitis, disorders of the central nervous
system, or enzymatic deactivation [88]. Oral ingestion or inhalation leads to skin and
eye irritations, and textile industry workers were found to suffer from contact der-
matitis, allergic conjunctivitis, rhinitis, occupational asthma, and other allergic reac-
tions [88]. This is due to the formation of a conjugate between human serum albumin
and the reactive dye producing immunoglobulin E (IgE) antibodies, which combine
with histamine [89]. It is established that the dyes can cause mutation [89]. Azure B,
a widely used dye, is easily partitioned to the lipid membrane of the cells [90] and
tends to intercalate with the helical structure of the DNA [91] and duplex RNA [92].
This dye shows a great degree of cytotoxicity by acting as a reversible inhibitor of
an intracellular enzyme of the central nervous system, namely, monoamine oxidase
A (MAO-A) [93]. The enzyme inhibition tends to affect human behaviour and cel-
lular redox homeostasis [94, 95]. It is seen that Disperse Red 1 and Disperse Orange
1 dyes cause mutations due to the formation of DNA adducts and are carcinogenic
[96]. Sudan I dye (Solvent Yellow 14) is an azo-lipophilic compound used in differ-
ent industries and illegally in foods like paprika [97, 98]. As the dye is assimilated
into the body, enzymatic transformation into carcinogenic aromatic amines takes
place through the action of the intestinal flora [99]. Basic Red 9 dye (used in dif-
ferent industries like textile, leather, paper, and ink) is carcinogenic and toxic. It is
transformed under anaerobic conditions to carcinogenic aromatic amines, resulting
in allergic dermatitis, skin irritation, mutations, and cancer [100]. Crystal violet dye
(a cationic triphenylmethane group dye) has a very intense odour and causes mitotic
poisoning, chromosomal damage, and cancer [101].
The increase in population and constant development pollute the water bodies,
posing threats to humans and the aquatic ecosystem. The effect of water pollution on
climatic changes and the subsequent effect on the hydrological cycle are being studied
[102]. The two terms weather and climate are often used in lieu of one another,
but there is a difference between the two terms. Weather is defined as the current
atmospheric condition (temperature, rainfall, wind, or humidity) in a given place.
Climate is the average weather of a given place or a region. It can be understood as
the statistical information of weather variation of a place for a long period of 30 years
[103]. Climate variability refers to variations in the mean state and other climate sta-
tistics on all temporal and spatial scales beyond those of individual weather events.
Variability may result from natural internal processes or from anthropogenic pro-
cesses [104]. Various scientific communities like the National Aeronautics and Space
Administration (NASA), the National Oceanic and Atmospheric Administration
(NOAA), and the Environmental Protection Agency (EPA) of the United States have
studied this in detail. It is also reported that freshwater resources can be severely
affected as evident from the excerpt from the executive summary of a paper, which
states, “Observational records and climate projections provide abundant evidence
that freshwater resources are vulnerable and have the potential to be strongly
impacted by climate change, with wide-ranging consequences for human societies
and ecosystems” [105]. Thus, it is quite evident that the situation is indeed challeng-
ing as a vicious cycle is created between water pollution and climate change. This is
because a sequence of reciprocal cause and effect arises resulting in aggravation of
the situation, leading to inexorable deterioration of the situation due to the effect on
the water and hydrological cycles. Climate change can be tracked by various indica-
tors, which can be physical, ecological, or societal in nature. The indicators are the
values or trend of the values over a given area for a specified time period. The use of
indicators can help in understanding the impacts of climate change on the environ-
ment and mankind [106].
1.8 ENVIRONMENTAL SUSTAINABILITY:
CHALLENGING BUT NOT IMPOSSIBLE
Sustainable development implies the availability of good living conditions by pro-
viding solutions to various challenges without any threat to both humans and envi-
ronment. It involves the protection of resources from further damage by integrating
researchers and experts from various fields to understand the challenges and also
make correct policy decisions. Environmental sustainability is all encompassing as
it is both interdisciplinary and multidisciplinary in nature. Here it is appropriate to
quote Sidney Sheldon, who says, “Try to leave the Earth a better place than when you
arrived”. Therefore, wastewater treatment is a very effective mode of achieving such
sustained good living conditions. There are different methods available for water
treatment, but different parameters like ease of operation and cost-effectiveness
dominate the choice of treatment method.
1.9 CONCLUSIONS
From the earlier discussions, it is seen that in order to comprehend the effect of toxic
species on human health, different important aspects need to be integrated. The first
step involves the assessment of the nature and amount of toxic species present. This
is an important branch of science known as analytical chemistry. Experts in the

medical field are required to give an understanding of the hazardous effects of
the various species present in water bodies in order to place a maximum limit to
the concentration of these species. Therefore, an integrated approach is needed to
identify the problem and find ways to solve it. This form of integrative approach is
known as interdisciplinary approach. Interdisciplinary research (IDR) is a mode of
research by teams or individuals that integrates information, data, techniques, tools,
perspectives, concepts, and/or theories from two or more disciplines or bodies of
specialized knowledge to advance fundamental understanding or to solve problems
whose solutions are beyond the scope of a single discipline or field of research
practice.
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2 Imperative to human life
Separation process
2.1 MIXTURE AND SEPARATION

Matter is defined as anything that occupies space, has mass, and surrounds mankind.
Man has always been associated with material from ancient times. The civilization
periods have been named after the material used predominantly during that period
(e.g. Stone, Bronze, and Iron). Silicon Age is refers to the modern period of history
from the late 20th to the early 21st century. Matter can be classified into two broad
categories as pure and mixture. A pure substance has a constant composition and
property. It can be further divided into elements and compounds. Elements are sub-
stances which cannot be broken further into simpler substances, while compounds
constitute of more than one element and can be broken further. Mixture is composed
of two or more types of matter in varying amounts and can be separated using dif-
ferent techniques. The main difference between a mixture and a compound is that a
compound is formed by chemical combination of elements of a particular state, while
a mixture is usually a concoction of elements or even compounds of varying states of
matter in different amounts. A mixture can be homogeneous (same state of matter)
or heterogeneous (different states of matter). Mixtures form an essential part of man,
and the need to separate it becomes important. Therefore, humans have always been
associated with the process of separation for obtaining a pure material or removing
unwanted material. In our daily life, the most common practices like cleaning dirt
from one’s hand or clothes, filtering of tea dust prior to drinking, etc., are carried
out as part of the routine. Separation has always been part of human life as seen
from various ancient texts. In ancient India, separation for water treatment has been
mentioned in ancient texts. Sushruta demonstrated the use of nuts, gomedaka, lotus
bulbs, moss, pearls, thick cloth, etc., for the removal of impurities, including those
suspended in water (Sushruta, sutra 45.13) [1]. Some of the techniques that were
used for purification were separation processes involving the addition of sand, mud,
arjuna, musta, usira, nagakesara, kosataka, and amalaka, together with jetakaphala.
Different techniques like pindavasa [lump of earth (alum), well mixed with phana,
mustaka, ela, usira, and candana baked well in the fire of khadira and then dropped
in water], puspavasa (with flowers), and curnadhivasa (powders) were adopted. The
importance of water was also known to mankind and was always reminded to each
other and the next generations in their daily talks and stories. The famous proverb
in Tamil language of “Nīraiyumcīrāṭu”, which literally means “Rehabilitate water”,
shows the importance of separation for purification of water. An anthology of the
ancient Tamil period mentions the process of cleaning water using nuts (Kalitokai,
Neithar Kali by Poet Nallanthuvanar) [2]. Traditional practices of placing a mud pot
on sand and addition of herbs to water also indicate the use of separation processes in
daily life. African countries used drumstick for water purification [2].
DOI: 10.1201/9781003442516-2 19
Separation is defined as a method by which a mixture or solution containing dif-

ferent components is resolved into individual components [3]. Thus, separation leads
to enrichment of a particular phase with one of the components. It is seen that no
separation is nearly complete and may have to be repeated [3]. Separation can be
either analytical or preparative in nature and can be carried out at the lab scale or
industrial level, respectively. In the analytical method, separation is utilized to seg-
regate the required component with a high degree of purity to enable highly accurate
and precise determination. Preparative separation aims at achieving a component
with a high degree of purity for further applications.
Separation is a mass transfer process [4] which involves partitioning (distribution
of species between different phases) due to differences in properties, namely, chem-
ical (chemical affinity) and physical (size, shape, mass, and density) properties of
species. During separation, one of the two phases gets considerably enriched with
one component and the other phase with the second component of the starting mix-
ture. The respective distributed components can be recovered from the two phases
by using appropriate procedures. The different phase distributions lead to gas–gas,
gas–liquid, gas–solid, liquid–liquid, liquid–solid, and solid–solid separations with
large applications. Each of these phases leads to separation with different applica-
tions. These applications all contradict the old Latin axiom known to chemists from
ancient times: “Corpora non agunt nisi fluida (or liquida) seusoluta”, which simply
means “Compounds do not react unless fluid or if dissolved” [5]. However, it was
later thought that there could be some errors in the interpretation of the original text,
and it should possibly mean “it is chiefly the liquid substances which ‘react’” or “for
instance, liquids are the type of bodies most liable to mixing” [5]. It is quite under-
standable that solid-state chemists could not agree with the first version of Aristotle’s
statement. A large number of separation processes are available, and the appropriate
method should be chosen based on the application.
2.2 CLASSIFICATION OF SEPARATION TECHNIQUES

A large number of separation techniques are available. These techniques can be
grouped together under a specific classification to achieve a better understanding
and make a correct choice of the technique. There are many ways to classify the
techniques [6].
The first mode of classification is based on the nature of the mixture. In this
mode, the solute can be either a solid or a liquid dissolved in a solvent. These tech-
niques can be further divided into homogeneous and heterogeneous mixtures. If the
solid is completely dissolved in the solvent and only one phase is seen, then it is
known as a homogeneous mixture, e.g. saline solution. Such mixtures can be sep-
arated using evaporation. A heterogeneous solution of solid in liquid contains the
solid in a dispersed or colloidal form, e.g. muddy water. Sedimentation, filtration, and
centrifugation are some of the techniques which can be grouped into this category.
When the solute is in a liquid form and is completely miscible with the solvent, e.g.
alcohol–water homogeneous mixtures, the process of distillation is most appropriate.
However, if the liquid solute phase is not miscible with the matrix solvent, then it
forms heterogeneous liquid-in-liquid mixtures, e.g. oil in water mixture, which can
be separated using partition techniques.
Separation process 21
Separation techniques can also be classified based on the property of the solute
that is to be separated. The property used can be either physical or chemical in nature.
Some of the processes dependent on the physical property of the solute are crystalli-
zation, centrifugation, decantation, filtration, sieving, and magnetic separation.
Centrifugation is the modus operandi and is based on the use of centrifugal force
for the separation of particles from a solution based on physical properties (size,
shape, density, viscosity of the medium, and rotor speed), with the denser compo-
nents migrating away from the centre. The application of large effective gravitational
pull, as in a normal centrifuge, leads to faster and efficient separation of particles.
Crystallization (natural or artificial) involves nucleation (appearance of a crystalline
phase from either a super cooled liquid/supersaturated solvent) and crystal growth
(increase in particle size) and is used to separate mixtures of salts or even covalent
solids that have different solubilities in a solvent. It is a solid–liquid separation tech-
nique involving mass transfer from a liquid to a pure solid crystalline phase. It is used
for the purification of salt obtained from seawater. Size exclusion chromatography
(SEC) and gas chromatography (GC) are based on the physical properties of size
or physical sorption ability, respectively. SEC, also known as molecular sieve chro-
matography, leads to the separation of molecules in a solution based on their size or
molecular weight. It is usually applied to proteins and industrial polymers. Inverse
gas chromatography (IGC) is a physical characterization analytical technique used to
evaluate the surface and bulk properties of solids. In IGC, the roles of the stationary
(solid) and mobile (gas or vapour) phases are inverted from that of traditional analyt-
ical GC. Whereas in GC, a standard column is used to separate and analyse gases, in
IGC, a single gas or vapour (probe molecule) is injected into a column packed with
the solid sample under investigation, and the retention time of the probe gas mole-
cule is measured with traditional GC detectors (i.e. flame ionization detector or ther-
mal conductivity detector). Decantation is a separation process used for mixtures of
immiscible phases (two immiscible liquids or a solid suspension or settled in liquid),
where the less dense layer is just carefully poured off, leaving the other component
behind. This is not quite effective for separation of two immiscible liquids. Demister
is a device used to remove liquid droplets from a vapour stream by reducing the
residence time required to separate and is used for applications wherein high vapour
quality is crucial. Drying is a mass transfer process consisting of the removal of
water or another solvent by evaporation from a solid using a heat source and a means
to remove the vapour produced. Electrophoresis is the separation of charged spe-
cies under the influence of an applied electric field, based on preferential migration.
Gel electrophoresis is used to separate macromolecules (DNA, RNA, and proteins)
based on size and/or charge. Elutriation is a separation method (based on size, shape,
and density) for particles smaller than 1 μm using a stream of flowing gas or liquid
(in a direction usually opposite to the direction of sedimentation). Evaporation is a
type of vaporization on the surface of a liquid as it changes into the gas phase and
then reaches an equilibrium. Froth flotation is the process of gathering hydrophobic
materials from hydrophilic materials in and on the surface of a froth layer, leading to
selective separation. Fractional distillation is the separation of a mixture into its com-
ponents by heating to a temperature at which one or more fractions of the mixture will
vaporize and is distilled. Fractional freezing is the oft used method in process engi-
neering and chemistry for the separation of substances with different melting points
by partial melting of a solid. Magnetic separation is the process of separating com-

ponents of mixtures by using magnets to attract magnetic materials, thus separating
them from non-magnetic material. Porous neutral membranes used in processes like
ultrafiltration, microfiltration, and nanofiltration bring out separation based on size.
Recrystallization is a technique used to purify chemicals by dissolving a compound
in an appropriate solvent and remove either the desired compound or impurities from
the solution. Sedimentation is a process based on the motion of particles through
fluid before they settle against a barrier, leading to easy separation between solid and
solution phases. The motion of the suspended particles through the fluid can be an
effect of the forces (gravity, centrifugal acceleration, or electromagnetism) acting on
them. If the components have different specific weights, gravitational force becomes
important, and the process is known as gravity separation. Sieving is the separation
of particles based on the difference in sizes of the particles using sieves of different
sizes. The design of the industrial sieve is of primary importance. This separation
finds an important role in food industries wherein vibrating sieves are used to prevent
the contamination. Sublimation is an endothermic changeover of a substance from
the solid to gas state directly at temperatures and pressures below a substance’s triple
point, and its reverse is deposition or desublimation (a substance passes directly from
a gas to a solid phase). In recent times, the term sublimation is used to construe both
solid-to-gas and gas-to-solid transitions. It is to be understood that the change here
refers to a change in the physical state of the compound, and not a chemical change,
caused by the absorption of heat by molecules and conversion to the vapour phase.
Separation due to sublimation is possible because each compound has its own unique
sublimation temperature. Wind winnowing is a separation procedure used from time
immemorial for applications in agriculture. It involves the flinging of a mixture into
an air current so that heavier grains are retained while lighter impurities are wafted
away by the wind. The different methodologies adopt various parts like a winnowing
fan (a specially shaped basket shaken to raise the chaff) or use a tool (a winnowing
fork or a shovel) to facilitate separation. Zone melting (zone refining or floating-zone
process or travelling melting zone) is a group of similar methods used to decon-
taminate crystals by moving the impure melt containing impurities forward, leaving
behind the pure material.
All the above methods (based on differences in the physical properties of the sol-
ute) can be very selective and complete only if the differences in these properties are
very large. In order to make the separations more efficient and selective, differences
in the chemical properties of the solute have to be exploited. Some of the processes
are discussed. Ion exchange and chromatographic separations are mass transfer sorp-
tion processes involving selective transfer of sorbates from the fluid phase to the sur-
face of the insoluble, rigid solid phase. The differences in partition coefficients result
in differential retention on the stationary phase, and thus separation is achieved.
Chromatography can be preparative or analytical. Preparative chromatography sepa-
rates the components of a mixture which can be used in purified form for some other
applications. Analytical chromatography is carried out with smaller quantities and
can be used for the determination and identification of substances. High-performance
liquid chromatography (HPLC; formerly known as high-pressure liquid chromatog-
raphy) is a technique in analytical chemistry used to assess the nature and quantity of
components of a mixture due to their differences in the interaction with both the solid
and liquid phases. HPLC is different from traditional (low-pressure) liquid chroma-
tography in that the operational pressures are significantly higher in HPLC, while
ordinary liquid chromatography typically relies on the force of gravity to let the
mobile phase pass through the column. Thin layer chromatography (TLC) is a tech-
nique used to separate non-volatile mixtures on a sheet of glass, plastic, or alumin-
ium foil, coated with a thin layer of adsorbent material, usually silica gel, aluminium
oxide (alumina), or cellulose, known as the stationary phase. The stationary phase
with the sample is contacted with a solvent or solvent mixture (mobile phase), which
goes up due to capillary action and separation is achieved. It can be used to monitor
the progress of a reaction, identify compounds present in a given mixture, and deter-
mine the purity of a substance. Counter-current chromatography (CCC) is a form
of liquid–liquid chromatography that uses a liquid stationary phase which is held in
place by centrifugal force and used to separate, identify, and quantify the chemical
components of a mixture. The resulting dynamic mixing and settling action allows
the components to be separated by their respective solubility in the two phases. In
droplet counter-current chromatography (DCCC), the mobile phase passes through
the columns in the form of droplets. An excellent analytical method for the deter-
mination of coloured substances is paper chromatography. Two-dimensional paper
chromatography is very useful for separating complex mixtures of compounds with
comparable polarity, such as amino acids. The mobile phase (a mixture of non-polar
organic solvent) traverses up the stationary phase (polar water held inside the void
space of the cellulose network of the paper support) due to capillary action. This
technique contrasts with TLC as the stationary phase in TLC is a layer of sorbent
(usually silica gel or aluminium oxide). An excellent technique for the separation
of polar components and inorganic ions is ion chromatography (or ion-exchange
chromatography). This method is based on the affinity of these ions towards the ion
exchanger. There are two types of ion chromatography, namely, cation-exchange and
anion-exchange that are used for the separation of cations and anions, respectively.
When cations are separated, the stationary phase is negatively charged, while for
anions the stationary phase is positively charged. It is often used in water analy-
sis and quality control. Affinity chromatography, used extensively for biochemical
applications, works on the principle of a highly specific interaction (hydrogen bond-
ing, ionic interaction, disulphide bridges, and hydrophobic interaction) between an
antigen and an antibody. It is used for purifying biological molecules in a mixture
in a laboratory. Centrifugal partition chromatography is a special chromatographic
technique where both stationary and mobile phases are liquid, and the stationary
phase is immobilized by a strong centrifugal force. Centrifugal partition chroma-
tography consists of a series-connected network of extraction cells, which operate
as elemental extractors, and the efficiency is assured by the deluge. Sorption is the
adherence of atoms, ions, or molecules of a gas or liquid on to a surface, resulting in
a layer of the adsorbate on the surface of the adsorbent. This is in contrast to absorp-
tion, in which the absorbate permeates into the bulk of the absorbent. Nowadays both
these process are collectively known as sorption. Solid-phase extraction (SPE) is an
extractive technique used to concentrate and purify samples for analysis. The result
is that either the desired analytes of interest or undesired impurities in the sample
are retained on the stationary phase. A great number of materials can be used as
sorbents. Extraction is a separation process used for the separation of a substance
from a matrix and is usually carried out using equilibria involving a liquid–liquid or
a solid phase. The distribution of a solute between two phases is an equilibrium con-
dition described by partition theory. Liquid–liquid extraction (LLE), also known as
solvent extraction, separates compounds or metal complexes based on their relative
solubilities in two different immiscible liquids, usually polar (water) and non-polar
(organic solvent). There is a net transfer of one or more species generally from an
aqueous to an organic solution, and the solvent enriched in solute(s) is the extract,
while the feed solution depleted in solute(s) is known as a raffinate. LLE is a basic
laboratory separation technique. Supercritical fluid extraction (SFE) is the process of
separating one component (extractant) from another (the matrix) using supercritical
fluids as the extracting solvent. SFE can be used as a sample preparation step for ana-
lytical purposes, or on a larger scale to either strip unwanted material from a product
(e.g. decaffeination) or collect a desired product (e.g. essential oils). Carbon dioxide
(CO2 ) is the commonly employed supercritical fluid. Precipitation is the production
of a solid, known as precipitate, from a solution due to a reaction with the reagent
known as the precipitant. The precipitate-free liquid remaining above the solid is
called the “supernate” or “supernatant”. Precipitation occurs when the concentration
of a compound exceeds its solubility product; therefore, the kinetics of precipitation
is very high from a supersaturated solution.
Another mode of classification is that based on the mechanism followed. There
are three mechanisms, namely chemical equilibrium, kinetic, and mechanical, which
control the separation efficiency. The first is based on chemical equilibrium that is
achieved, and it depends on the different phases involved in separation. Distillation
is a process based on the equilibrium between the vapour and liquid phases, while
both sublimation and sorption involve solid and vapour phases. Sorption uses ion
exchange and charged membranes and sorbents, and sublimation is based on the
chemical equilibrium between a solid and a liquid, while LLE involves two immis-
cible liquid phases. The classification based on mechanical phase separation involves
procedures like precipitation, filtration, and extraction. It is seen that classification
based on kinetics would probably encompass all the processes. It is the difference in
the kinetics of a particular procedure which leads to separation irrespective of the
property of the solute, equilibrium, or mechanical phases involved. Ion exchange
membranes bring about selectivity due to their inherent property of permselectivity,
which refers to the difference in the permeability of ions of opposite charges, i.e. a
cation exchange membrane will not allow the transport of anions.
2.3 CONCLUSIONS
The separation process which can be used for treatment depends on various fac-
tors like wastewater characteristics [7]. The processes are associated with their own
merits and demerits assessed from various aspects like cost, feasibility, efficiency,
practicability, reliability, environmental impact, secondary waste generation, etc.
The development of cheaper, effective, and novel methods of decontamination is an
ongoing research. It is also difficult to define a universal method that could be used
for the removal of all pollutants from waste waters.
In the ensuing chapters, we will look into some of the commonly used techniques
for the removal of metal ions and cationic dyes from waste water. In these chapters,
the discussion will be focussed on the basic principles followed by some examples
of applications. The readers will surely appreciate the fact that since most of these
methods are continuously developing, a large number of systems are available in the
literature. Since it is not practically possible to cite all these works, some of these
studies have been given as representative examples.
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3 Primordial water
Membrane separation
treatment technique
3.1 WHAT IS A MEMBRANE?
The very first mention of membrane-based separation was in the mid-18th century. In
1748, Jean-Antoine Nollet, also known as Abbe Nollet, conducted an experiment. He
took a vial of alcohol (with air purged out), covered it securely with a pig’s bladder,
and then submerged it into a container of water. After 6 h, he noticed that a piece of
the pig’s bladder had bulged [1, 2]. However over years, membranes have become an
important aspect of separation used in different applications. Membrane separation
is a process in which different components in a mixture are separated using a mem-
brane [3]. Separation is achieved by the retention of unwanted species and allowing
permeation (transport) of species of interest. It is also possible to achieve separa-
tion at different permeation rates. Several factors are found to affect the separation
efficiency. The size, polarity, and ionic charge of the solute; physical and chemical
characteristics of the membrane; and external parameters like temperature and pH
of the solution are found to have a strong effect on permeation rates and selectivity.
According to the IUPAC nomenclature, a membrane is defined as a structure hav-
ing lateral dimensions much greater than its thickness, through which transfer may
occur under a variety of driving forces [4]. The barrier can result in the transfer of
various kinds of components in the liquid or vapour phase. Separation is achieved if
one component travels faster than the rest of them in the mixture. Separation using
membrane is schematically represented in Figure 3.1 [5].
A semipermeable (also known as partially or differentially permeable) membrane
is a barrier that will only allow some molecules to pass through (depending on the
attributes of the molecules such as size) while blocking the passage of other mole-
cules and acting as a filter. The passage of components occurs due to diffusion from
a region of high concentration (of a component) to a region of low concentration.
The membrane can be either natural (biological) or synthetic in nature. A biological
example of a semipermeable membrane is the kidney tissue, which allows only cer-
tain molecules to pass through while blocking others. Synthetic versions of a semiper-
meable membrane are polymers used for water filtration or desalination applications.
There are different types of permeable membranes. A permeable membrane allows
the passage of all materials through it, while an impermeable membrane does not
allow the passage of materials through it. A semipermeable membrane allows some
materials to pass through it based on size, while a selectively permeable membrane
allows only specific components to pass through. Generally, a semipermeable mem-
brane does not allow solutes to through pass through it, and only one type of solvent
26DOI: 10.1201/9781003442516-3
Membrane separation 27
FIGURE 3.1 Schematic representation of separation across a membrane
flows through it. It acts as an ideal partition between two osmotically active solu-
tions. A selectively permeable membrane allows selected solutes and solvents to pass
through it and acts as an imperfect partition. It permits the entry of both solvents and,
to a selected extent, solutes.
3.2 CLASSIFICATION OF MEMBRANES
Membranes can be either natural or synthetic in nature. However, in this chapter, the
discussion is restricted to synthetic membranes, which are used for the separation
of toxic species. Membranes are broadly classified into solid and liquid membranes
(LMs) [6].
3.2.1 Solid membranes
Synthetic solid membranes can be classified based on their nature into organic or
inorganic membranes [7]. The membrane material can be either natural or synthetic.
Synthetic membranes can be organic or inorganic in nature. Membrane structures
can be anisotropic or isotropic. Composites and membranes synthesized by the phase
separation method can give an anisotropic structure. Mesoporous, non-porous, and
electrically charged membranes have an isotropic structure.
Ceramic inorganic membranes (produced from inorganic oxides, glass, zeolites,
and carbide) are found to be possess excellent chemical and thermal stability. Organic
membranes are polymers (derived from the Greek words poly and mere, meaning
many and part, respectively) composed of many repeating units of an identical
structure. Polymers can be natural (protein, cellulose, and silk) or synthetic (poly-
styrene, polyethylene, and nylon). Ceramic membranes and polymeric membranes
have different properties. Ceramic membranes have uniform pores unlike polymeric
membranes, thus allowing the sieving mechanism to operate. Polymeric membranes
have a tendency to swell when in contact with aqueous solutions unlike ceramic
membranes. Ceramic membranes are chemically resistant and thermally stable com-
pared to polymeric membranes. However, the main disadvantages are that ceramic
membranes are more brittle and very expensive compared to polymeric membranes.
Synthetic membranes can be classified based on the charge associated with them into
neutral and electrically charged membranes. Neutral membranes do not have any
functional groups which can be used for the exchange of cations, and separation with
these neutral membranes is based on the sieving mechanism. Neutral membranes can
be classified based on their structure (morphology) into symmetric or asymmetric
membranes. Symmetric membranes (porous and non-porous) have thickness in the
range of 10–20 μm, while asymmetric membranes contain a very dense top layer
(0.1–0.5μm thick) supported by a porous sub-layer (50–150 μm thick). Symmetric
membranes can be porous or non-porous in nature. The non-porous membranes may
contain a very thin layer of a dense material and find great use for gas separations
and reverse osmosis (RO) applications. Dense membranes can be either amorphous
or heterogeneous in nature. Porous membranes are used in different membrane fil-
tration processes. The most commonly used theory for defining a porous membrane
assumes that the membrane structure consists of parallel, non-intersecting cylindri-
cal capillaries. However, actually, it may be a random network of different sizes
which are affected by synthetic conditions. The sizes of the pores give rise to vari-
ous membrane filtration processes, and the applications also vary. It is seen that the
membrane filtration processes are pressure driven in nature, and depending on the
nature of the membranes, the pressure applied will also vary. Microfiltration (MF)
membranes have pores that retain solutes of size ranging from 0.1 to 20mm and
operate at 20–100 kPa. The process is based on sieving mechanism and has replaced
the conventional sedimentation process. It is used for the retention of algae, animal-
cules, and bacteria. Ultrafiltration (UF) process uses 0.01-µm porous membranes and
operates at 100–1,000 kPa. The main mechanism is sieving, and it has replaced the
conventional centrifugation process. It is found to be suitable for the retention of sol-
utes of size 5–100 nm and can be used for the removal of small colloids and viruses.
Nanofiltration (NF) process using nanoporous membranes and an operating pressure
of 500–1,500 kPa is used to retain solutes of size in the range of 0.5–5nm and so
can retain dissolved oxygen matter (DOM) and divalent ions. The main operating
mechanism is that of dissolution and diffusion, and it has been found to replace the
conventional distillation and evaporation techniques in various applications. RO uses
non-porous membranes and retains solutes like monovalent ions in the size range
of 0.1–1 nm. The operating pressure is quite high, and the mechanism is based on
dissolution and diffusion. RO has been useful in replacing the conventional distilla-
tion and evaporation techniques. Synthetic ion-exchange membranes (with groups
similar to ion-exchange resins) are known as ionomers or polyelectrolytes depending
on the ionic content. Ionomers have an ionic content of about 10–15 mol.%, and this
is much higher in polyelectrolytes, making them water-soluble. The incompatibility
of ionic aggregates (multiplets) and non-ionic segments (clusters) results in micro-
phase separation in ionic polymers [8]. Ion pairs within multiplets induce temporary
ionic cross-links, while large clusters result in mechanical reinforcement. Thus, the
properties of these materials are very different from those of other polymers; thus,
applications are numerous and diversified, including permselective permeation of
ions and encapsulation. Perfluoro sulphonate ionomers (PFSIs) are copolymers of

tetrafluoroethylene and perfluorinated vinyl ether containing a terminal sulphonyl
fluoride (SO2 F) group. Walther Grot of DuPont de Nemours in the late 1960s devel-
oped a perfluoro sulphonate membrane, known as Nafion, with a polyfluoroethylene
backbone and regularly spaced perfluorvinyl ether pendant side chains terminated
by a sulphonate ionic group. Nafion membranes contain incompatible components:
the fluorocarbon phase and the ionic phase (containing ions and water molecules).
These are separated to the limit that the covalent bonds hold them together. There
are two kinds of arrangements visualized for Nafion structure, namely, the cluster-
network and the three-phase model. The cluster model proposes that the aqueous
ions are embedded in a continuous fluorocarbon phase, and the clusters thus formed
are interconnected by narrow channels (to determine the transport properties of ions
and water molecules). The water content of the membrane is of great importance for
its properties and is determined by the kind of polymers and counterions. According
to the three-phase model, there is an intermediate region which contains an ether side
chain, a fluorocarbon backbone, and also sulphonate groups and associated counte-
rions [8]. The equivalent weight (EW) of the ionomer is given by the relationship
EW = 100*m + 446, wherein m is the number of structural units. Therefore, for a
membrane of 1,100 EW, the side chains have 14 CF2 units. The designation “117”
refers to a film having 1,100 EW and a nominal thickness of 0.007 inch.
Solid membranes can also be classified based on the geometry of the membrane
used into tubular, hollow fibre, spiral wound, and flat sheet modules. Tubular mem-
branes are not self-supporting but are located within tubes. Tubular membranes have
a diameter of about 5–15 mm. Because of the size of the membrane surface, plugging
of tubular membranes is not likely to occur. A drawback of tubular membranes is
that the packing density is low. In the hollow fibre module, many of the fibres (each
in the tubular module) are placed in a large pipe in a compact module. Hollow fibre
membranes can be designed for dead-end circulation. The advantages of such mod-
ules are compact size, reduced cost, and high quality of water produced. In spiral
wound membrane, the membrane is cast as a film onto a flat sheet. Membranes are
sandwiched together with feed spacers (typical thickness 0.03 –0.1 inch) and a per-
meate carrier. They are sealed at each edge and wound up around a perforated tube.
The module has a diameter of 2.5–18 inch and a length of 30–60 inch. The hollow
fibre module with the lowest manufacturing cost and highest packing density is very
easily susceptible to fouling, and cleaning is very difficult [9] compared to other
configurations. This module is used for dialysis, reverse osmosis, and ultrafiltration
methods. The tubular wound module suited for RO and UF processes has the least
packing density and is also quite expensive. But it has very less tendency to be fouled
and can be easily cleaned.
Solid membranes have many advantages, which makes them very useful for a
variety of applications. The energy requirement of solid membrane separations is
low, making the design quite simple and very easy to operate. The process is made
very selective by using novel membranes, making it quite desirable. The availabil-
ity of a large number of organic polymers and inorganic materials makes it easy
to achieve selective separation with great ease. These membranes can be used to
remove trace-level components at low energy requirements. These processes are
environment-friendly due to the use of simple and non-toxic materials. Despite the
various advantages, solid membranes have some limitations. The separation can
never produce a completely pure product in a stream but can be only concentrated as a
retentate. The number of stages in membrane separation is usually one or at the max-
imum two, thus making it essential for the membrane to have high selectivity. The
membranes used may show chemical incompatibility with process solutions, leading
to dissolution, swelling, and weakening of the membrane structures. This reduces
the capacity and shortens the membrane lifetime. The temperature of an operation
cannot be very high as the membrane structure will be greatly affected. Scaling
up of the membrane process to accommodate very large stream sizes becomes dif-
ficult as there will be a substantial increase in the number of required membrane
modules. Another major associated problem is membrane fouling, which hampers
the permeation rate and affects the separation efficiency. In order to circumvent the
disadvantages of low permeation flux and decreased selectivity associated with solid
membranes, the use of liquid membranes is an attractive alternative.
3.2.2 Liquid membranes
Liquid membranes have several other names, such as liquid pertraction, carrier-
mediated extraction, facilitated transport, and two-stage extraction. The term liquid
membrane defies the conventional image of a membrane. However, the term liquid
pertraction [10] is useful to understand the process very clearly. It echoes a three-
phase system containing two homogeneous aqueous solutions, referred to as feed
(donor) and receiving (acceptor) solution, spatially separated by a third immiscible
liquid, denoted as the membrane phase (M). The favourable thermodynamics at the
feed–membrane interphase facilitates the extraction of solutes of interest into the
membrane phase through which it is transported to the membrane-receiving inter-
phase. Here it is stripped into the receiving phase using conditions different from
that of extraction. Hence, liquid pertraction can be visualized to be a combination
of solvent extraction and stripping processes in both time and space. This combina-
tion is advantageous over conventional extraction as it offers the maximum driving
force. Moreover, the extraction capability of organic media is not crucial, making it
possible to use inert and non-toxic organic liquids. In order to enhance extraction,
small amounts of carriers, which are organic complexing reagents, can be added to
the membrane liquid. The carrier forms a complex with the ions of interest, and the
metal complex is extracted into the organic phase. The use of carriers can improve
the selectivity of the membrane separation process. The chemical potential differ-
ence between the two aqueous solutions results in the transfer of mass, whereas the
extent of solute diffusion is controlled by concentration difference. Liquid membrane
can generally be classified as bulk liquid membrane (BLM), supported liquid mem-
brane (SLM), and emulsion liquid membrane (ELM) based on configurations and the
setup of feed (F), membrane (M), and receiving (R) phases [5,10, 11]. A schematic
representation of the three membrane setups is presented in Figure 3.2 [5,10, 11].
BLM involves a large volume of the membrane phase spatially separating the F
and R phases. In the SLM, the membrane phase is immobilized in the pores of a poly-
meric support, and this separates the two aqueous phases, namely, F and R. In the
ELM, small globules of the M phase containing droplets of the R phase are dispersed
FIGURE 3.2 Schematic representation of different liquid membranes (drawn based on

references in the literature [5,10, 11])
continuously in the F phase. The low solvent inventory of the SLM and the high flux
of the ELM make these techniques attractive, but poor membrane stability hampers
their extensive use. SLM is associated with the leaching out of the membrane layer,
out of the pores of the polymeric membrane, due to the wetting and osmotic pres-
sure across the membrane, while ELM is associated with the emulsion formulation
method. Progress in membrane contactors using liquid membranes with integrated
features of the SLM or ELM [hollow fibre SLM (HFSLM), pseudoemulsion-based
hollow-fibre strip dispersion, or hollow fibre renewal liquid membrane] has still
not been able to resolve the concern of membrane stability. However, BLM has no
such issues as the problems of membrane rupture or exhaustion of carriers do not
arise. The added advantages of BLM, such as its simplicity, cost-effectiveness, easy
manoeuvrability, constant interfacial area, and hydrodynamic conditions, make it an
excellent tool for the evaluation of carrier efficiency and reaction kinetics and mech-
anisms in the laboratory. BLM can be used in different setups based on the relative
density of the membrane liquid compared to water [11]. The schematic representation
of these configurations is shown in Figure 3.3.
The reduced solute flux (due to low interfacial area/volume) and slow kinetics
(due to longer transport path and higher membrane resistance) limit the industrial
applications of BLM. The different configurations of BLM affect the interfacial
area and transportation path, while membrane resistance is influenced by M-phase
viscosity, stirring speed, and operating temperature. Although BLM has superior
stability over SLM and ELM, BLM cannot be scaled up for industrial applications
due to its high membrane resistance resulting from the bulky membrane phase, thus
hampering solute transport and affecting BLM performance. Various factors like
M-phase viscosity, stirring speed, and operating temperature can have an effect on
membrane phase resistance. The membrane phase is made up of a carrier, diluent,
FIGURE 3.3 Schematic representation of different configurations of BLM
and modifier. Solvents like organophosphorus compounds, amines, oximes, quin-

olines, and crown ethers are used in low levels (< 10%) as carriers, while dilu-
ents constitute more than 85% of volume of the membrane phase, and solvents like
alkanes, cycloalkanes, chlorinated alkanes, acyclic and cyclic ketones, alcohols, and
aromatic compounds can be used. Sometimes solvents like alcohols, organophos-
phorus compounds, etc., are used in low concentrations (< 5% / vol ) as modifiers
[12]. The carrier binds with the ion of interest and transports it from the feed to the
receiving phase, while the diluent alters the metal ion hydration by increasing hydro-
phobicity and synergistically enhances the carrier activity. A modifier is normally
used in cases where the problem of third-phase formation is severe. Volatile solvents
are not preferred due to the instability of the liquid membrane and their quicker
evaporation alongside environmental pollution. Low viscous, non-volatile solvents
are ideal for LM applications. All these solvents have different viscosities attribut-
able to the divergences in the intermolecular forces and shapes, which contribute to
different extents of molecular resistance of the BLM. The viscosities are measured
using water as a reference. It is seen that non-polar solvents are less viscous than
polar solvents; the lowest and highest values of viscosity are 1.30 and 21.22 MPa*s
for cyclohexane and di-2-ethylhexyl phosphoric acid, respectively, at room tempera-
ture [13]. Amongst the non-polar solvents, the least and most viscous solvents are
hexane and kerosene with viscosity values of 0.30 and 1.64 MPa*s, respectively, at
room temperature. Amongst polar solvents, the least and most viscous solvents are
cyclohexanone and di-2-ethylhexyl phosphoric acid with values of 2.02 and 21.22
MPa*s, respectively, at room temperature [13]. The low viscosity of the non-polar
solvents is attributed to the zero or quite small dipole moment values, resulting in
a weak bond formation (van der Waals) between solvent molecules, which allows
the molecules to easily slide over each other. The increased molecular size leads
to increased van der Waals forces, thus making long-chain non-polar solvents (e.g.
dodecane and kerosene) viscous. The low viscosity of water despite its high polar-
ity and the presence of strong hydrogen bonds is due to its small molecular size.
Therefore, the correct choice of membrane solvent helps in reducing the membrane
resistance, leading to an increased transport rate with a high diffusion coefficient.
Evaluation of the effect of a solvent on transport flux showed a substantial increase
in flux values when the diluent was changed from viscous carbon tetrachloride to the
less viscous chloroform or dichloromethane. This shows that a reduction in viscos-

ity could increase the flux values [13]. The viscous resistance can be overcome by
continuous stirring of the membrane phase as it reduces the viscous resistance and
improves the hydrodynamics. Thus, the solute is transported at a faster rate due to
convection as a result of stirring than by molecular diffusion in the unstirred state.
The stirring exerts fluid forces on the solutes, which are physically moved from one
spot to another by the random motion of small masses of fluid. The greater stirring
speed results in higher fluid velocity, leading to enhanced solute transport. However,
the increase in stirring speed does not increase the flux values as substantially as
observed in the case of viscosity changes. There are reports on the distortion of feed/
membrane and membrane/receiving interphases and also mixing of the two aqueous
phases. The increase in operating temperature can also reduce viscous resistance
in the membrane phase due to the decrease in cohesive forces between molecules,
leading to an increase in kinetic energy of solvent molecules [13]. This reduces
the fluid shear stress, and the solvent molecules become less viscous, leading to a
substantial increase in the flux values. The effect of the increase in temperature on
flux is more than that of stirring but still less than the effect of membrane solvent
viscosity. The activation energy calculated indicated a diffusion-controlled, and not
a chemical-controlled, reaction. The efficiency of a solvent is characterized by its
distribution coefficient. Distribution coefficient is defined as the ratio of the amount
of target solute present in the organic phase and the aqueous phase after equilibrium
is reached [13]. A very high distribution coefficient indicates excellent extraction
and vice versa. A strong extractant will not release the solute easily at the strip–
membrane interphase. Therefore, thorough investigation is necessary to identify a
suitable solvent–carrier combination that would give the best possible separation for
a target solute. In this transport mechanism, the transported substance dissolves in
the organic membrane phase and diffuses to the receiving phase due to the concen-
tration gradient between these two phases. The selectivity of separation and/or the
pertraction capacity can be increased if the permeant undergoes a chemical reaction
in the stripping phase. The separation effectiveness is significantly improved if the
component to be removed is transformed almost quantitatively into an impermeable
form in the receiving phase. In this way, the concentration gradient can be main-
tained across the membrane, hence facilitating solute enrichment. Also, selectivity
can be further enhanced by proper choice of the reaction window in the stripping
solution so that only the compounds of interest are ionized and trapped.
Although BLM can remove metal ions effectively, it cannot be scaled up due to the
toxicity and non-biodegradability of the solvents used. To reduce the toxicity, ionic
liquids or vegetable oils are used to formulate the membrane phase [14]. Although
the removal efficiency is quite comparable to that of the petroleum-based solvents
already in use, the high viscosity hampers the kinetics. Ionic liquids are more advan-
tageous than vegetable oils as their molecular structure can be easily modified, thus
making it possible to tune their viscosity. However, their high cost, compared to that
of vegetable oils, and probable toxic effects pose some reservation on its application
on a large scale. To overcome all these disadvantages, new designs of BLM with fea-
tures of spiral wound SLM and HFSLM and ELM are examined. The driving forces
for improving the fluxes such as the electrical potential difference applied across a
BLM, by transporting metal ions between the phases and reducing solvent viscosity,
make it possible to use safe but viscous solvents like oils for the membrane phase.
SLM is a non-dispersive-type LM, formed by the immobilization of a thin layer
of an organic liquid phase (with dissolved reagents) onto a suitable inert microporous
hydrophobic polymer support which does not play an active role in separation [15].
Based on the size, shape, surface area, and applications, an SLM can be further clas-
sified as flat sheet, hollow fibre, and spiral wound SLM. Flat sheet SLM (FSSLM) is
the simplest form, uses a sheet to incorporate the solvent, and can be placed between
two half compartments containing the feed and receiving solutions which are under
continuous stirring. HFSLM consists of a hollow fibre module made of a single
non-porous material. Inside this, many thin fibres are packed in rows through which
the feed solution passes and the receiving phase outside. The solid support in SLM
must be hydrophobic in nature to be able to retain the organic solvent in the mem-
brane pores by capillary action and should have excellent thermal chemical stability.
Polymers such as polytetrafluoroethene (PTFE), polypropylene, and polysulphones
are generally used for this purpose. The extractant used for SLM is an organic sol-
vent, which has specificity for components and can cause extraction by complex
formation, ion pair formation, or solvation. The extractants used for extraction by
complex formation may be chelating, such as LIX 84-I, LIX 64N, LIX 62N, and
LIX 860, or acidic, such as D2EHPA, PC88A, and Cyanex-272 (phosphoric acid
derivatives). Extraction by ion pair formation is common for amine-based extract-
ants, which extract acid and then by anion exchange reaction extract metal ions, e.g.
Alamine 336, Aliquat 336, and Alamine 304. Solvating extractants are weakly basic
in nature, and thus, they extract either neutral metal complexes or acids by forming
a solvate. A very good example is crown ethers, which are cyclic polyethers, but as
they are costly, they are rarely used. The other extractants that are commonly used
are tri-n-octylphosphine oxide (TOPO), TBP, and MIBK. The diluents are gener-
ally used for the preparation of various concentrations of organic extractants, and
they should have dielectric constant, low viscosity, should be cheap, etc. Diluents
like xylene, toluene, hexane, and cyclohexane are generally used. The different steps
involved are diffusion of metal ions from the bulk of the feed phase to the inner sur-
face of the membrane, proton diffusion from the inner surface to the bulk of the feed
phase, metal complex formation, and its diffusion from the inner to the outer surface
of the membrane, wherein when in contact with the receiving phase, metal ions are
stripped out while protons combine with the carrier and regenerate it, which diffuses
back into the inner surface of the membrane. The stripped metal ion diffuses to the
bulk of the receiving phase [15].
ELM was invented in 1968 and consists of an emulsion (a mixture of two or
more immiscible liquids) of the organic membrane and aqueous receiving phases
[16]. This is then dispersed into the continuous aqueous feed phase. The mass
transfer of the solutes towards the internal receiving phase occurs, and it is simpler
than in the conventional process, energy efficient, and compact in size. ELMs are
powerful and have a large number of applications. The main limitation of ELMs
is the stability of the emulsion. ELMs have many advantages like high efficiency,
large interfacial area, continuous simple operation, and simultaneous extraction
and stripping.
3.3 MECHANISM OF SEPARATION
Separation through membranes can proceed via either chemical or physical pro-
cesses. Separations that are based on chemical processes involve chemical interac-
tions between the solute of interest and the membrane components. This is quite
common in separations using ion exchange solid membranes or liquid membranes
and biological membranes. Since the latter is out of scope of the present discus-
sion, our focus will remain on liquid membranes and solid membranes. Separation
with membranes can be either equilibrium or non-equilibrium processes, which are
further controlled or not controlled by pressure [17]. Separations based on liquid
membranes and pressure-driven membrane distillation are equilibrium processes,
whereas pressure-driven membrane filtration and non-pressure-driven electrodialy-
sis are examples of non-equilibrium processes. A schematic representation of these
processes is presented in Figure 3.4.
3.3.1 Mechanism in solid membranes

Separation processes can be driven by pressure (MF, UF, NF, and RO), diffu-
sion (dialysis), vacuum (membrane distillation), and electrical gradient (electro-
dialysis). Separation in membranes can be achieved by sieving (based on sizes
of solute and membrane pores) or diffusion through membrane [18]. Two basic
models can be used to understand the mass transfer through membranes, namely,
the solution-diffusion model and the hydrodynamic model. In actual studies, it
is possible that both of these mechanisms can operate. According to the solu-
tion-diffusion model, the transport of solutes from the feed to the receiving phase
occurs only by diffusion across the membrane phase. It is also assumed that the
two phases are in equilibrium with the adjacent membrane phase. This principle is
more important for dense membranes without natural pores. During the filtration
FIGURE 3.4 Schematic representation of membrane-based separation

process, a boundary layer forms on the membrane. This concentration gradient

is created by molecules which cannot pass through the membrane. The effect is
referred to as concentration polarization and, occurring during the filtration, leads
to a reduced transmembrane flow (flux). Concentration polarization is, in principle,
reversible by cleaning the membrane, which results in the initial flux being almost
totally restored. Using a tangential flow to the membrane (cross-flow filtration)
can also minimize concentration polarization. According to the hydrodynamic
model, transport through pores, in the simplest case, is through convection. This
requires the size of the pores to be smaller than the diameter of the two separate
components. Membranes which function according to this principle are mainly
used in microfiltration and UF. They are used to separate macromolecules from
solutions and colloids from a dispersion, or remove bacteria. During this process,
the retained particles or molecules form a pulpy mass (filter cake) on the mem-
brane, and this blockage of the membrane hampers the filtration. This blockage
can be reduced by the use of the cross-flow method (cross-flow filtration). Here,
the liquid to be filtered flows along the front of the membrane and is separated
by the pressure difference between the front and back of the membrane into the
retentate (the flowing concentrate) on the front and the permeate (filtrate) on the
back. The tangential flow on the front creates a shear stress that cracks the filter
cake and reduces fouling. In electrically charged membranes, permselectivity is
the main property that governs separation. The term permselectivity refers to the
selective permeability of solutes of oppositely charged ions. A polymeric matrix
with covalently bound ionizable groups swells with water when immersed. The
charges are dissociated, and the counter ions can be easily exchanged with ions
of interest. Thus, permeation can occur through the membranes. The flux can be
affected by different conditions [19]. Figure 3.5 gives a general idea of separations
using neutral and cation exchange membranes.
3.3.2 Mechanism in liquid membranes

The transport of solutes through liquid membranes is classified based on the role
of the membrane phase. The membrane may be a simple solvent for the solute or for
the carrier, which will complex with metal ions of interest [20]. The membrane liquid
solubilizes the permeate from the feed and behaves like a solvent. The removal of the
permeate from the feed is dependent on the solubility of the permeate in the mem-
brane liquid. The transport is governed by the concentration gradient and occurs till
the concentrations in both the feed and receiving phases are equal. This is known as a
simple transfer process. However, if the receiving phase contains a reagent that com-
bines with the solute of interest, then there is a continuous transport against the con-
centration gradient, and this is known as “uphill transport”. The presence of a carrier
in the membrane liquid results in the formation of a metal–carrier complex, which is
then transported through the membrane phase. This is known as carrier-facilitated
transport. When a permeate is transported using a carrier and, during its transport, if
an equivalent amount of another species is co-transported from the receiving to the
feed phase, the process is known as carrier-facilitated coupled transfer.
The metal ion transport can be represented by two different models. The most
recurrently used model [21] deals with concentration diffusion layers. In this, the
FIGURE 3.5 Schematic representation of separation using a solid membrane based on (a)
sieving mechanism and (b) cation exchange
aqueous–organic interphase is treated as a platform for the processes of complexation

and decomplexation to occur. The transport can be divided into various steps. The
solute traverses the diffusion boundary layer (DBL) from the bulk of the feed to the
membrane surface with a linear concentration gradient. The metal–carrier complex-
ation at the feed/membrane interphase is faster than the diffusion of ions. The complex
formed disperses through the organic layer by convection due to continuous stirring
and reaches the membrane/receiving interphase, where the complex breaks and the
metal ion again has to traverse through the DBL with a linear concentration change.
The transport of solutes occurs along with the simultaneous co-transfer of different
ions of the same charge from the receiving to the feed phase. The second approach
that is less accepted is the “Big Carrousel” mechanism [22], wherein the carrier moves
slightly out from the organic membrane in the aqueous reaction layer and then transfers
from one aqueous phase to another through the membrane before finally moving back.
3.4 APPLICATIONS
Solid membranes are used in various processes such as reverse osmosis, microfil-
tration, and UF, wherein separation is based on membrane pore size, or in processes
such as electrodialysis and fuel cells, where electrically charged membranes are
used. Membrane filtration process is dependent on the size of the pores and solute to
be separated. Adsorptive membranes operate on the basis of electrical double layer
theory [23]. The separation efficiency of UF membranes obtained in its pristine form
[24] can be enhanced using polymers [25, 26], micelles [27, 28], or powder [29, 30]
as an alternative membrane technology to obtain safe drinking water. The enhanced
technologies tend to reduce the formation of toxic species and also reduce leakage.
Adsorptive membranes prove to be a benign alternative and reduce the risk of leak-
age and production of toxic species. This process is known as “membrane adsorp-
tive filtration” [31] (or adsorptive membrane filtration [32]) and offers advantages of
high removal efficiency with a high permeability flux and low operating pressure.
The technique allows easy regeneration and is compact [33]. Adsorptive membranes
or membrane sorbents [34, 35] tend to behave as affinity membranes [36], which
tend to bind to metal ions by chelation [37, 38] or ion exchange [39]. To enhance
selectivity, ion-imprinted membranes (with a specific ion template) [40] or mixed
matrix membranes (MMMs; contain polymer or inorganic fillers or grains in the
membrane matrix) [41, 42] are used. These membranes contain pores in addition to
the functional groups [43, 44] and can be used for membrane filtration processes.
Generally, polymeric filtration membranes show low affinity towards metal ions, and
they need to be modified. Polyvinylidene difluoride (PVDF) membranes incorpo-
rated with amine-functionalized MCM-41 could be used for the removal of Cu(II)
at near-neutral pH [45]. Novel polyethersulphone (PES)/hydrous manganese dioxide
(HMO) UF MMMs were found to be useful for the removal of Pb(II) [46]. There are
large numbers of studies reported on the use of similar modified membranes for the
removal of metal ions [47–88]. It is seen that different materials like g-PAAm(poly-
acrylamide); iminodiacetate; hyper-branched poly(amido amine) 8-hydroxyquino-
line; peracetic acid (PAA); polybenzimidazole; modified proclavaminic acid (PCV);
and oxides of Al, Ti, Fe, etc., could be used as sorbents into membranes made of
polyethylene (PE), PTFE, cellulose acetate (CA), PVDF, etc. It is seen that in most of
the studies, the separation could be achieved under mild pH conditions, and elution
of the separated ions was also achieved using dilute acids or complexing agents.
The membranes can be classified as mixed matrix adsorptive membranes, pore-filled
adsorptive membranes, and surface adsorptive membranes.
Ion exchange membranes are most commonly used for the treatment of brackish
water. Membrane electrofiltration is the amalgamation of membrane and filtration
technologies. The problem of membrane fouling is a challenge in this process [89].
The removal of heavy metal ions is an important application of electrodialysis [90–
92]. The transport property of the membrane and the effect of various conditions
were analysed on the removal of metal ions such as Cu and Zn [93–116].
Nafion ionomer membrane is an excellent ionomer with a large number of appli-
cations, e.g. as an electrochemical separator and catalysts. Extensive studies have
been carried out on the structural elucidation of the membrane and the transport
properties in line with its industrial applications. Nonetheless, it has not been used to
a great extent for the separation of toxic cationic species. The selective permeation
of Cu 2+° and UO2 2+o in the presence of common cations through a Nafion membrane
[117] was studied in detail using appropriate masking agents [117]. It was found that
the masking agents could result in either a positive or negative effect on selectivity.
Permeation of some nitrogen heterocyclic bases could be achieved using metal ion-
loaded Nafion membranes, and it was observed that the presence of certain ions
showed an enhancement of permeation flux [118]. The studies showed the effect of
metal ions and also the structure of solutes on the permeation rate. The separation
of some binary mixtures under favourable conditions was achieved. Permselectivity of
Nafion membranes could be altered by structural modification, and permeation of
common anions could be achieved [119]. The nature of modification and the size
of anions were found to have a strong influence on permeation rates. Ion exchange
studies of alkali and transition metal ions were carried out using Nafion [117] mem-
branes in the protonic form [120, 121]. It was observed that the water sorption iso-
therms obtained were quite different. The results showed an alteration of the physical
structure of the exchangers upon long-storage or ageing. It was also observed that the
amount of water sorbed was low and the counterions were less hydrated, resulting
in high discrepancy in the ion exchange behaviour. Pretreatment of Nafion [117]
membranes resulted in the modification of the membrane structure and arrangement
of ionogenic groups. Thus, the state of water present in the membrane was quite dif-
ferent, and it altered the ion exchange property of the membrane. It can be concluded
that the ageing of ion exchangers results in the loss of their elasticity and showed poor
water uptake. To get a better understanding, the values of swelling pressure and free
energy of swelling were calculated. It was observed that the presence of transition
metal ions in Nafion resulted in a higher value of free energy of swelling compared
to the protonated form. This could be correlated to increased hydration of metal ion-
incorporated membranes. The uptake of metal ions was subjected to modelling using
different isotherm models, and it was established that the process was chemisorp-
tion. The role of pretreatment was also found to be predominant. The permeation of
transition metal ions (Cu 2+ , Co 2+ , Ni 2+ , Zn 2+ ) through H+ and alkali metal ion forms
of Nafion membrane was carried out. It was observed that the diffusion coefficient
values (D) were directly proportional to the individual ion exchange selectivity val-
ues (K). Thus, it could be established that the initial stage of permeation is governed
by the ion exchange process. The uptake of transition metal ions (Cu 2+ , Co 2+ ) by
Nafion membrane was carried out in the presence of different complexing organic
reagents or ligands. This was carried out to understand how uptake can be affected
in a sample mixture. The studies were also carried out using differently pretreated
Nafion membranes. It was observed that the strength and the charge of the metal–
ligand complexes had an effect on the uptake capacity [122]. In order to get an insight
of the uptake and permeation process, the studies were carried out using two cationic
dyes [123]. In this study, the Nafion membrane was pretreated in two different ways
prior to its use. Different characterization techniques were used to understand the
changes. The presence of water clusters could be identified by spectrophotometric
and thermal measurements, and the changes in the water cluster upon pretreatment
were also established. It was also possible to clearly see the differences in the inter-
actions of the two dyes with the membranes. Image analysis of the dye-loaded mem-
branes could clearly depict the structural changes due to pretreatment. Permeation
studies established the dependence of permeability and diffusion coefficients on the
nature of the dye and the pretreatment protocols adopted [123].
Membrane pertraction methods can have applications at the lab scale and at the
industrial level. BLMs can be used in the laboratory to test the carrier activity of
various compounds (well-known gravimetric reagents or novel complexing agents).
The reports in the literature indicate that a massive amount of studies have been car-
ried out using BLMs for the transport of metals, ions, organic dyes, etc. Therefore, it
is pragmatic to restrict the discussion to few examples to give an overall idea to the
readers. The use of 8-hydroxyquinoline (oxine) as a carrier has demonstrated the pos-
sibility of achieving selective metal ion transport using a well-known non-selective
gravimetric reagent as the carrier [124,125]. The main approach is to modify the
solution conditions. The use of amino acids or other reagents results in enhanced
metal ion transport due to synergistic effects. BLM studies using newly synthesized
phenoxy ethers demonstrated a high degree of selectivity [126]. The mechanism
of transport was carrier-facilitated coupled transport, wherein protons migrated in
the direction opposite to the alkali metal ions. The transport of radionuclides like
uranium using BLMs could be achieved using carriers like potassium ion selective
crown ethers [127] and calixarenes [128]. When crown ether was used as a car-
rier, the uranyl ion was converted to its anionic uranyl thiocyanate complex using
potassium thiocyanate (KSCN) at a pH of 1 and thus transported along with the
potassium ions. Masking agents could be used to remove interferences from dif-
ferent metal ions. The main limitation was the transport was achieved only in the
presence of KSCN at a pH of 1. It was observed that the limitations of low pH and
interferences could be eradicated using uranyl ion-selective calixarenes as carriers.
The studies showed that in the presence of TOPO as synergistic reagent, more than
95% transport could be achieved, and this was applied to actual seawater samples
[128]. The transport of uranium using a mixture of thenoyltrifluoroacetone (HTTA)
and d icyclohexyl-18C6 as carriers was nearly complete without any interferences
from most of the ions except Th(IV) and Cu2+. The use of masking agents further
enhanced the selectivity of separation [129].
SLMs have received considerable interest due to their ease of operation, high
selectivity, and low operating cost [130]. They have been used extensively for the
separation and pre-concentration of metal ions [131–160]. It has been observed that
different solvents like kerosene, toluene, xylene, and dodecane can be used as sol-
vents like chloroform. Several research studies are being carried out at the laboratory
and pilot plant levels for the use of ELMs for the removal of metal ions [161,162].
Membrane processes can be used for the removal of dyes [163,164]. The selective
removal of malachite green dye from waste water using SLMs has been reported
[165]. The separation of reactive dyes, namely, Gold Yellow (GYHE-R) and Reactive
Green HE4BD (RGHE-4BD), has been achieved using Aliquot-336 carrier [166].
The extraction of Congo red (CR), an anionic disazo direct dye, from aqueous solu-
tions by using ELMs has been carried out [167]. Salicylic acid in benzene has been
used for the removal of methylene blue dye from textile waste water [168], while
di-(2-ethyl hexyl) phosphoric acid (D2EHPA) as carrier could be used for the trans-
port of methyl violet and rhodamine B [169]. The anionic dye Cibacron Red FN-R
was separated using a BLM using tetrabutylammonium bromide (TBAB) carrier dis-
solved in methylene chloride solvent [170].
3.5 CONCLUSIONS
Membrane processes are non-destructive methods. Membrane filtration methods
have matured to a great extent, with a wide range of membranes available for appli-
cations. This technique is simple, rapid, and efficient even at high concentrations.
The quality of effluent treated is quite high. The main disadvantages are the low
throughput with a limited flow rate and is not suited for low concentration levels.
Membrane selection is based on the application, making this process more cumber-
some. In addition to this, the high installation and maintenance costs coupled with
high energy requirements make this process quite unwieldly. Solid membranes are
also prone to fouling, leading to deterioration of membrane efficiency.
To overcome these difficulties and to have an effective separation method, espe-
cially for low concentration levels, sorption seems to be quite an attractive method.
This method is discussed in the next chapter.
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4 Backbone of separation
Sorption
science
4.1 INTRODUCTION
Sorption is part of our daily life in many ways. Some of the simple happenings denote
the sorption process. Every time we buy a new item, there is always a small silica gel
packet kept in the cardboard box. This is to remove the moisture away from the item
by the sorption of water vapour on the exterior of silica gel particles. Pandemic and
surgical situations necessitate the use of masks, which act as a filter. Another daily
application of sorption is in the process of water purification by using alum or water
softening using ion exchangers. The removal of colour and impurities from water
also occurs through sorption, wherein impurities are deposited on the surface of a
solid. A very common example is the removal of spilt ink using cotton.
There is always an ongoing research on the development of new separation techniques

which are more efficient and also cost-effective. Sorption is one such technique which
is simple and also cost-effective. It is a kinetically driven process based on the differ-
ences in chemical properties of solutes. Sorption has been known for ages when differ-
ent materials were used for the treatment of polluted water. Finely divided and porous
materials were well-known since ancient times, and adsorption was quite prevalent
in old times as can be seen from the book Glauberusconcentratus; oder, Kern der.
Glauberschen, written by the famous alchemist Johann Rudolf Glauber (1604–1670)
[1]. In the book, it is mentioned that the best precipitation is performed using special
sand, the origin of which I don’t like to reveal. It is able to remove all salt, slime, stench
and pollution from water and liquid matter. It removes the innate redness of red wine,
beer etc., etc. in few hours so that all becomes clear and bright like spring-water, so that
all can be drunk well and that red wine becomes white wine. Sea water becomes sweet
if it runs through sand and leaves behind all its salt. When this happens naturally, why
not by arts? But the actual scientific approach was in the 1900s when isotherms were
measured by J.M. van Bemmelen [1].
4.2 RUDIMENTS OF SORPTION
Sorption can be defined as a phenomenon of fixation or capture of a gas or vapour
(sorbate) by a substance in the condensed state (solid or liquid) called sorbent [2]. The
general definition pertains to gas sorption. Sorption phenomena involve both ther-
mophysical and thermochemical aspects [3]. Sorption is a universal name encom-
passing both absorption and adsorption processes [4]. Absorption is the process in
which a liquid or a gas enters into the bulk of a solid (absorbent) [4], while adsorption
refers to the binding of a gas or liquid on a solid surface. Adsorption can be physical
DOI: 10.1201/9781003442516-4 47
(physisorption) and/or chemical (chemisorption) in nature [5]. Physisorption occurs

via weak van der Waals forces of attraction and so is reversible as no new compound
is formed. Chemisorption involves the formation of strong chemical bonds between
the sorbate and sorbent, leading to the formation of new complexes/compounds, mak-
ing this process irreversible. Generally in chemisorption, new ion pairs are formed
which can be broken to retrieve the sorbent in its original form. This requires change
of solution conditions, thus making this process not really reversible. The enthalpy
values for physisorption lies in the range of 20–40 kJ/mol, while for chemisorp-
tion it is in the range of 40–400 kJ/mol (equivalent to chemical bond formation).
Physisorption is favoured at low temperatures, while higher temperatures could suit
chemisorption. The process of chemisorption is monolayer, while physisorption is
multilayer in nature. Sorption is now used for the removal of species known as sor-
bate from aqueous solutions using solids known as sorbents. Thus, sorption can be
understood as a process (physical/chemical) by which one substance is attached to
another in one of the three ways, namely, absorption (assimilation of a substance
present in one state into another substance of a different state, e.g. liquids sorbed by
solid, and gases sorbed by liquids); adsorption (physical adherence or bonding of ions
and molecules onto the surface of another phase (e.g. reagents adsorbed to the sur-
face of a solid catalyst); and ion exchange (exchange of ions between two electrolytes
or between an electrolyte solution and a solid phase). Thus, sorption can be defined
as a phenomenon of fixation or capture of a sorbate (gas or ions) by a substance called
sorbent (solid or liquid). The reverse of sorption is desorption. Sorption is carried out
in batch mode, and the schematic representation is given in Figure 4.1. The method
involves the equilibration of a fixed volume of solution with a weighed amount of
sorbent for a known period. The solution contains a known concentration of solute
and is maintained at a particular pH. Once the time of equilibration is over, the two
phases (solid/liquid) are separated (by centrifugation/filtration), and the amount of
sorbate left behind in the solution is analysed using different techniques (Figure 4.1).
Various experimental conditions (pH, time, sorbent amount, solute concentration,
and temperature) are optimized to attain maximum sorption.
The amount of sorbate taken up by the sorbent is denoted as qe, which is expressed
as mg/g of sorbent. It is calculated using the difference in concentrations per unit
volume (mg/L) before (Co) and after equilibration (Ci) per unit mass of sorbent using
Eq. 1. The removal efficiency expressed in terms of % can be calculated using Eq. 2:
(C0 − Ct ) * V
qe = (4.1)
M
(C0 − Ct )*100
Removal Efficiency = (4.2)
C0
Recyclability of sorbents is an important aspect; therefore, desorption studies

have to be carried out in conditions opposite to that of sorption; that is, if sorption
occurs at slightly acidic or near-neutral conditions, then desorption will occur in
highly acidic conditions. Desorption ratio (%) can be calculated as the ratio of the
solute concentration sorbed to desorbed.
Sorption 49
FIGURE 4.1 Schematic representation of sorption in batch mode
4.3 UNDERSTANDING SORPTION USING MODELS

When there is a contact between the sorbate and sorbent for a sufficient time period,
an equilibrium is attained. The understanding of sorption equilibria is very important
as it can give crucial information regarding the interactions of the different species
with solid [6]. Sorption isotherms are curves obtained using mathematical expres-
sions describing the equilibrium of sorbate distribution between two heterogeneous
phases of solid and liquid at a constant temperature. It is used to calculate the max-
imum sorption capacity [amount of solute sorbed per unit mass of sorbent (mg/g)]
and can give an idea of sorbent efficiency. However in general, it is seen that the
efficiency is greatly affected by the nature of the sorbate, sorbent, pH, ionic strength,
etc. [7–10]. Usually, it is quite easy to use linear regression analysis [11] to find the
best suitable models as it computes the sorbate distribution and authenticates the
postulations of the particular model. The inherent bias created by assuming a linear
relation leads to erroneous results. The use of non-linear isotherm modelling is now
gaining popularity to reduce the errors to a great extent. The adsorption isotherm
of gas which was used traditionally is the plot of the amount adsorbed nads versus
the relative pressure (P/P0 ). It is reported that these isotherms could be categorized
based on their shape [8, 12–16]. The independent domain theory [12] states that the
relative vapour pressure should be larger during pore filling as compared to that of
vacant pores to result in hysteresis. The different types of isotherms are as follows:
(i) type I isotherm (convex upwards) is characterized by a horizontal plateau for high
values of gas pressure and can be described by Langmuir equation, e.g. sorption of
water vapour on zeolite or hydrogen on charcoal; (ii) type II isotherm (sigmoid curve)
describes the monolayer adsorption on mesoporous materials at low pressure and
multilayer sorption at high pressure near saturation with no hysteresis but a single
inflection point (usually observed in microporous, non-porous, or disperse solids

with >50 nm pore diameter). The adsorption of nitrogen on silica gel or a catalyst is
an example of type II isotherm. (iii) Type III isotherm is a hyperbolic curve which
concaves upwards. This arises when the interactions between two adsorbate mol-
ecules are more stronger than the adsorbate–adsorbent interactions. Adsorption of
water on hydrophobic zeolites and activated carbon, bromine, and iodine on silica
gel, and carbon tetrachloride adsorption on mesoporous gel follow type III isotherm.
(iv) Type IV isotherms with two inflexion points describe the adsorption behaviour of
mesoporous materials with pore condensation behaviour. This isotherm is obtained
during the adsorption of benzene on iron oxide and on silica gel. (v) Type V isotherm
with one inflexion point indicates the presence of mesopores formed due to pore con-
densation. The adsorption of water on activated carbon fibre follows this isotherm.
(vi) Type VI isotherms with several inflexion points and steps indicate the formation
of layers at low temperatures. Adsorption of noble gases on the surfaces of planar
graphite, adsorption of butanol on aluminium silicate, and adsorption of CH4 on
MgO follow this type of isotherm.
A large number of isotherm models have been formulated to understand the iso-
therms, taking into account that the sorption is an equilibrium process (rates of sorp-
tion and desorption are equal) and also its thermodynamics. The conventional linear
least-squares method is ideal for the determination of the most appropriate model and
involves the goodness fit of a particular model with its regression correlation coeffi-
cient value close to 1 [17]. However, it is now seen that several restrictions related to
the linearized isotherm expressions can result in a bias in the data [18, 19] as can be
seen from the error analysis [20–22]. The performance of a sorbent can be estimated
by the fitting of experimental data to different equilibrium and kinetic models. This
helps in understanding the sorption mechanism and comparing the performance of
different sorbents to help in the effective design of sorption procedures. It is essential
to select the exact isotherm and calculate the parameters of this model to understand
the behaviour of both the sorbate and sorbent and also the outcome of the overall
process. The experimentally obtained data are subjected to different models to get an
idea of the equilibrium and kinetic aspects of the sorption.
4.3.1 Equilibrium models

A large number of equilibrium models are available. It is seen that each of them have
varying numbers of parameters. One-parameter model (Henry), two-parameter mod-
els (Langmuir, Freundlich, Dubinin–Radushkevich, Temkin, Hill–Deboer, Fowler–
Guggenheim, Flory–Huggins, Halsey, Harkins–Jura, Jovanovic, Elovich, and Kiselev),
three-parameter models (Hill, Redlich–Peterson, Sips, Langmuir–Freundlich,
Fritz–Schlunder-III, Radke–Prausnitz-I, Radke–Prausnitz-II, Radke–Prausnitz-III,
Toth, Khan, Koble–Corrigan, Jossens, Jovanovic–Freundlich, Brouers–Sotolongo,
Vieth–Sladek, Unilan, Holl‒Krich, and Langmuir‒Jovanovic), four-parameter mod-
els (Fritz–Schlunder-IV, Baudu Weber‒van Vliet, and Marczewski‒Jaroniec), and
five-parameter model (Fritz–Schlunder-V) can be used to analyse the experimental
equilibrium sorption data. The meaningfulness of these models with respect to the
sorption experimental data to envisage sorption is achieved using software to esti-
mate not only the model parameters but also the values of the non-linear regression
Sorption 51
coefficient ( R 2 ), sum of squares due to error (SSE), and root mean squared error
(RMSE). In the following section, the different models discussed are classified based
on the number of parameters involved [23, 24].
1. One-parameter model: Henry’s one-parameter isotherm model is the sim-

plest relation between the amount of sorbate (substance sorbed on to the
sorbent) and its partial pressure (for gas sorption) and is applied to low gas
concentrations (sorbed molecules are far from their nearest neighbours).
The equilibrium sorbate concentrations on the sorbent and in gas can be
related by a simple equation (Eq. 3), where qe (mg/g) and Ce (mg/g) are
concentrations on the sorbent and solution, respectively, at equilibrium, the
amount of the sorbate at equilibrium, and kHE is Henry’s sorption constant.
The linear isotherm can be used to describe the initial part of many practi-
cal isotherms. It is valid for low surface coverages, and the sorption energy
is independent of the coverage (due to the absence of inhomogeneities on the
sorbent surface):
qe = K HE Ce , (4.3)
2. Two-parameter models: In this section, the discussion is with respect to

twelve models.
(i) Langmuir isotherm model: Langmuir model presupposes that the
sorbent surface is homogeneous (all sites have equal sorptive energy),
sorption is localized (atoms/molecules are sorbed at definite localized
sites), and each site can accommodate only one molecule/atom and
sorption on one site does not affect sorption on the adjacent site (lead-
ing to monolayer coverage of the sorbent sites). Langmuir proposi-
tioned that the rate at which the sorbate molecules strike a sorbent
surface is proportional to the product of the concentration of the sorb-
ate and the fraction of the sorbent surface remaining uncovered by the
sorbate. This model suggests that the rates of sorption and desorption
are nearly equal at equilibrium and are proportional to the fractions
of sorbent sites that are unoccupied and occupied, respectively, and
are represented by Eq. 4 [wherein b is the Langmuir constant related
to sorption capacity (mg/g), which correlates with the variation of the
suitable area and porosity of the sorbent]. The capacity values com-
puted using this model is useful for comparing the efficiency of vari-
ous sorbents. The dimensionless constant, Langmuir separation factor
RL (Eq. 5), is used to predict whether the sorption is unfavourable
( RL >1), linear ( RL >1), favourable (0–1), or irreversible ( RL = 0).
Ce 1 C
= o + eo (4.4)
qe Q *b Q
1
RL = (4.5)
1 + Ce * b
(ii) Freundlich isotherm model: The Freundlich model gives an idea of

heterogeneity of sorbent surface and is given by Eq. 6, wherein aF
is Freundlich sorption capacity (L mg/g) and nF is sorption intensity.
The value of 1/n F is in the range 0–1 for favourable sorption, with the
value close to zero indicates more heterogeneous nature of sorption
sites.
1
lnqe = lnK F + lnCe (4.6)
n
(iii) Dubinin–Radushkevich (D-R) isotherm model: This empirical model,

applied originally for vapour sorption onto microporous solids,
assumes a multilayer sorption involving van Der Waals forces leading
to a pore-filling mechanism. It is used to estimate the porosity and free
energy of sorption. This isotherm is applicable for intermediary values
of sorbate concentrations and can be used to differentiate between phy-
sisorption and chemisorption processes based on the energy calculated
(E < 8 ( kJ/mol) for physisorption; E = 8 – 16 ( kJ/mol) for chemisorp-
tion). D-R isotherm is dependent on the temperature of sorption. The
model is represented by Eq. 7, wherein the degree of heterogeneity
(0 < < 1) and the Polanyi potential ε given by RT/ln (1+1/Ce )
can be calculated. The apparent or free mean energy (kJ mol) of the
sorption/sorbate molecule Es for sorption from infinity in the solution
to the solid surface can be computed by Eq. 8.
2
lnqe = − + lnQ (4.7)
1
Es = (4.8)
2 ×b
(iv) Temkin isotherm model: This model was originally used for gas sorp-
tion in an intermediate concentration range and gives an idea of the
effect of sorbate–sorbate interactions on the overall sorption process.
According to this model, the heat of sorption decreases linearly with
the increase in coverage, and sorption is characterized by the uniform
distribution of binding energies. The model is represented in Eq. 9,
wherein RT/bT correlates the heat of sorption, while the equilibrium
binding constant AT (L/mg) represents the maximum binding energy.
(
qe = RT
b )*lnA + ( RT b )*lnC e (4.9)
(v) Hill–Deboer isotherm model: This model explains the mobile sorption
and lateral interactions between sorbed molecules and is given in Eq.
10. K1 (L/mg) and K2 (kJ/mol) are Hill–Deboer and energetic con-
stants, respectively. The positive value of K2 indicates the attraction
between sorbed species, while the negative value indicates repulsion
Sorption 53
and a zero value of K2 indicates no interaction between sorbed mole-

cules, and it reduces to the Volmer equation.
Ce (1 − q ) q Kq
ln − = −lnK1 − 2 (4.10)
q 1− q RT
(vi) Fowler–Guggenheim isotherm model: This model gives information

on the lateral interaction of sorbed molecules. It indicates that the heat
of sorption varies in a linear relationship with loading. The expres-
sion for the model is given in Eq. 11. The positive and negative val-
ues of W are indicative of the interaction and repulsion, respectively,
between the sorbed molecules. When there is no interaction, the value
becomes zero, and the model is reduced to the Langmuir model. This
model also relates the interaction between the sorbed molecules and
the heat of sorption. The attraction between sorbed molecules leads to
an increase in the heat of sorption, while repulsion decreases the heat
of adsorption.
Ce (1 − q ) q 2W * q
ln − = −lnK FC + (4.11)
q 1− q RT
(vii) Flory–Huggins isotherm model: This model, given in Eq. 12, is useful
in estimating the degree of surface coverage. This model also helps
in understanding whether the sorption process is spontaneous. In Eq.
12, θ is the degree of surface coverage (1Ce/Co), KFH is the Flory–
Huggins model constant, and n is the number of adsorbate occupying
a given site. The free energy of the sorption is calculated using K FH .
q
log = −lnK FH + nlog (1 − q ) (4.12)
Ce
(viii) Halsey isotherm model: This model gives an idea of multilayer sorp-
tion in a space quite far away from the sorbent surface. The fitting of
the experimental data to this equation proves the heterogeneous distri-
bution of active sites and also multilayer sorption. The mathematical
expression of this model is given in Eq. 13:
lnqe = l * lnK − l * lnCe (4.13)

n n
(ix) Harkins–Jura isotherm model: This model explains the multilayer

sorption on the surface of sorbents with heterogeneous pore distribu-
tion, and the mathematical expression is given in Eq. 14. The plot of
1/qe2 vs log Ce can give the values of the constants A and B.
1
qe2 A A ( )
= B − 1 * logCe (4.14)
(x) Jovanovic isotherm model: This model is similar to that of the

Langmuir model with respect to monolayer localized sorption, but
there is also a possible interaction or contact between the sorbed and
desorbed molecules. The mathematical expression is given in Eq.
15. At high concentrations of the sorbate, it becomes the Langmuir
isotherm.
lnqe = lnqmax − K f Ce (4.15)
(xi) Elovich isotherm model: The model assumes multilayer adsorption

and is used for describing chemisorption on highly heterogeneous
sorbents. The Elovich isotherm model is given in Eq. 16, wherein
qm is the Elovich adsorption capacity and K e is the Elovich constant
obtained from the plots of ln (qe /Ce ) vs qe.
qe q
ln = ln ( Ke * qm ) − e (4.16)
Ce qm
(xii) Kiselev isotherm model: This model explains the localized sorbate
monolayer formation on sorbents. This model is applicable when sur-
face coverage is larger than 0.68 . The Kiselev adsorption isotherm
model is given in Eq. 17, wherein K1 and Kn are the Kiselev equilib-
rium constant and complex (between adsorbate molecules) formation
constant, respectively.
1 K
= 1 + K1 K n (4.17)
Ce (1 − q ) q
3. Three-parameter models: The models containing three parameters to explain

the mechanism of adsorption are discussed using sixteen models, viz.,
Hill, Redlich–Peterson, Sips, Langmuir–Freundlich, Fritz– Schlunder-III,
Radke–Prausnitz, Toth, Khan, Koble–Corrigan, Jossens, Jovanovic–
Freundlich, Brouers–Sotolongo, Vieth–Sladek, Unilan, Holl–Krich, and
Langmuir–Jovanovic.
(i) Hill isotherm model: The model is developed to illustrate the sorp-
tion on homogeneous substrates. This model assumes that the sorbed
molecule on one site would influence the sorption on other sites
of the sorbent via a cooperative mechanism. The model is given in
Eq. 18. The values of nH give an idea of the nature of cooperation;
values are greater, equal to, or less than 1 for positive cooperation,
non-cooperation, and negative cooperation, respectively, in binding.
qmax CeqnH
qeq = nH
(4.18)
K H +Ceq
Sorption 55
(ii) Redlich–Peterson (R-P) isotherm model: The R-P isotherm model has
characteristics of both Langmuir and Freundlich isotherms. Therefore,
the mechanism is an amalgamation of both and is not ideally mon-
olayer sorption. The R-P isotherm model is given in Eq. 19. This
model is applicable over a wide concentration range and applicable to
both homogeneous and heterogeneous systems. At high liquid-phase
concentrations of the sorbate, this model reduces to Freundlich model
and towards Henrys law at low concentration. The value of the expo-
nent is in the range of 0–1; at 1, the model approaches the Langmuir
model, while at 0, it approaches the Freundlich model.
ARP Ceq
qeq = (4.19)
1+BRP Ceqb
(iii) Sips isotherm model: This model deals with the localized sorption of
the sorbate without any interactions with the sorbent. This model is
a combination of Langmuir and Freundlich models and is used for
heterogeneous adsorption systems. At low sorbate concentrations, the
model changes to the Freundlich model, and at high concentrations,
it predicts a monolayer sorption that is characteristic of the Langmuir
model. Sips adsorption isotherm model is given in Eq. 20.
qm K s Ceqs
qeq = (4.20)
1+K s Ceqs
(iv) Langmuir–Freundlich isotherm model: This model describes the

sorption in heterogeneous surfaces. At low sorbate concentration, the
model approaches the Freundlich model, while at high concentrations,
it approaches the Langmuir isotherm model. The model is represented
in Eq. 21, wherein mLF is the heterogeneous parameter with a value
between 0 and 1. The decrease in surface heterogeneity results in an
increase in mLF , and when it equals 1, it becomes the Langmuir model.
qmax ( K LF Ceq )
mLF
qeq = (4.21)
1+ ( K LF Ceq )
mLF
(v) Fritz–Schlunder-III isotherm model: This three-parameter isotherm

model is developed to fit over an extensive range of experimental
results. The sorption is expressed in Eq. 22, wherein the values of
mFS3 of 1 or 0 leads to the change of the Fritz‒Schlunder-III model to
Langmuir and Freundlich models, respectively.
qmax K FS3Ceq
qeq = (4.22)
1+q max CeqmFS3
(vi) Radke–Prausnitz isotherm model: This is a preferred model for low

sorbate concentration and is applicable over a wide concentration
range. At low sorbate concentration, the model reduces to the linear
Henry law, and at higher sorbate concentration, it tends to become
the Freundlich model. When the value of the Radke–Prausnitz expo-
nent (mRaP3) is zero, this model becomes the Langmuir model. The
mathematical expressions of the model are given in Eqs. 23–25. If the
values of both mRaP1 and mRaP2 are 1, the Radke–Prausnitz-I, II mod-
els reduce to the Langmuir model. At low concentrations, the mod-
els become the Henry model, but for high sorbate concentration, the
Radke–Prausnitz-I and II models become the Freundlich model. The
Radke–prausnitz-III equation reduces to Henry and Langmuir models
when the values of mRaP3 are 1 and 0, respectively.
qmax K RaP1Ceq
Model 1 qeq = mRaP1
(4.23)
1+K RP1Ceq
qmax K RaP2Ceq
Model 2 qeq = (4.24)
1+K RP2Ceq mRaP2
qmax K RaP3CeqmRaP3
Model 3 qeq = (4.25)
1+K RP3Ceq mRaP3-1
(vii) Toth isotherm model: This model is developed to describe the hetero-
geneous sorption systems at both low and high sorbate concentrations.
This model can be considered as a modified form of the Langmuir
model, with an aim to reduce the error between experimental and com-
puted data and is given in Eq. 26; at n = 1, this equation becomes the
Langmuir isotherm equation, indicating that the process approaches a
homogeneous surface, and values deviating from 1 indicates a hetero-
geneous surface. Thus, the parameter n is an attribute of heterogeneity
of sorption and is suited for modelling multilayer and heterogeneous
sorption.
qmax Ceq
qeq = 1
(4.26)
1 nr
mr
+Ceq
KT
(viii) Khan isotherm model: This model is developed for the sorption of
bi-adsorbates, and it reaches Freundlich and Langmuir isotherms at
the two concentration levels. The mathematical expression is given in
Eq. 27; at aK = 1, the model approaches the Langmuir isotherm, and
at higher concentration values, it becomes the Freundlich isotherm
model.
Sorption 57
qm bK Ceq
qeq = (4.27)
(1+b K Ceq )
aK
(ix) Koble–Corrigan isotherm model: This model incorporates both

Langmuir and Freundlich isotherms and is similar to the Sips isotherm
model. This is expressed as given in Eq. 28. This model reduces to
the Freundlich model at high sorbate concentrations and is valid for
n ≥ 1 and becomes incapable of defining the experimental data despite
high concentration at 1 ≤ n.
AKCCeqmKC
qeq = (4.28)
1+BKCCeq mKC
(x) Jossens isotherm model: The model is based on the energy distribu-
tion of sorbate–sorbent interactions at sorption sites. The assumption
made in this model is that the sorbent has a heterogeneous surface
with respect to the sorbate interactions. At low concentrations, this
model is reduced to Henryʼs law. The mathematical expression is
given in Eq. 29, wherein J is Henryʼs constant at low capacities, bJ the
Jossens isotherm constant characteristic of the sorbent, irrespective of
temperature.
K J Ceq
qeq = bJ
(4.29)
1+JCeq
(xi) Jovanovic–Freundlich isotherm model: This model is developed to

describe single-component sorption equilibrium on heterogeneous
surfaces. The main assumption is that the rate of decrease in the frac-
tion of the sorbent surface unoccupied by the sorbate molecules is
proportional to a certain power of the partial pressure of the sorbate.
For homogenous sorbent surface, this model reduces to Jovanovic. At
low and high pressures, the model becomes Freundlich and Langmuir,
respectively. Similar to the Jovanovic model, this model also takes
into account the contact between sorbed and desorbed molecules. The
mathematical expression is given in Eq. 30.
(
- K JF Ceq nJF )
q eq = q max 1-e (4.30)
(xii) Brouers–Sotolongo isotherm model: This isotherm is in the form of

a deformed exponential function for sorption onto a heterogeneous
surface, and it appears to be the extension of the Langmuir isotherm
to irregular sorbent surfaces. The main assumption is that the surface
consists of clusters of active sites of equal energies. The mathematical
expression of this model is given in Eq. 31. The exponential term is

related to the sorption energy distribution and gives the value energy
of heterogeneity at a particular temperature.
(-K HSCeqnHS )
qeq =q 1-e (4.31)
max
(xiii) Vieth–Sladek isotherm model: This model integrates two discrete seg-
ments for the calculation of diffusion rates in sorbents. The first one
is defined by a linear section (Henryʼs law), and the second one is
a non-linear section (Langmuir isotherm). The linear section corre-
lates to the physisorption of gas molecules onto amorphous sorbent
surfaces, while the non-linear section explains the adherence of gas
molecules on the porous sorbent sites. The mathematical expression is
given by Eq. 32.
qmax bVSCeq
qeq =K VSCeq + (4.32)
1+bVSCeq
(xiv) Unilan isotherm model: This model is applicable for Langmuir iso-
therm and uniform energy distribution. This equation becomes
Henryʼs law at very low sorbate concentration and is applied to gas
sorption on a heterogeneous sorbent surface. This model is given in
Eq. 33. The value of the model exponent $U is a measure of hetero-
geneity; the higher the value, the more the heterogeneity. If $U = 0,
the isotherm model becomes the classical Langmuir model as energy
distribution is zero.
qmax 1+K U Ceq eb U

qeq = Ln (4.33)
2bU 1+K U Ceq e- b U
(xv) Holl–Krich isotherm model: This model is a modified version of

Langmuir isotherm, and at low concentrations, it becomes Freundlich
isotherm. The capacity saturates more slowly as compared to Langmuir
isotherm at high concentrations. The expression is given in Eq. 34:
qmax K HK CeqnHK
qeq = (4.34)
1+K HK CeqnHK
(xvi) Langmuir–Jovanovic isotherm model: This pragmatic model is an

amalgamation of Langmuir and Jovanovic isotherms and is given by
Eq. 35.
nLJ
K LJ Ceq
qmax Ceq 1-e
qeq = (4.35)
1+Ceq
Sorption 59
4. Four-parameter models:
(i) Fritz–Schlunder-IV isotherm model: This is a four-parameter model
with collective facets of Langmuir–Freundlich isotherms and is given
by Eq. 36. This isotherm is valid when the values of αFS5 and βFS5 are
≤ 1. At high sorbate concentrations, the Fritz–Schlunder-IV isotherm
becomes Freundlich equation, and when αFS5 and βFS5 are = 1, this
equation reduces to a Langmuir isotherm. At high sorbate concentra-
tions, this isotherm becomes a Freundlich isotherm.
AFS5CeqFS5
qeq = (4.36)
1+BFS5CeqFS5
(ii) Baudu isotherm model: This has been developed mainly due to the
discrepancy in the calculation of Langmuir constant and coefficient
for a wide range of concentrations. It can be considered to be the
altered form of the Langmuir isotherm and is given in Eq. 37. This
model is only applicable in the range of (1+x+y)<1 and (1+x)<1. For
lower surface coverage, the Baudu model reduces to the Freundlich
equation and is given in Eq. 38.
(1+x+y )
qmaxbo Ceq
qeq = ( 1+x )
(4.37)
1+b o Ceq
( 1+x+y )
qmo boCeq
qeq = (4.38)
1+b o
(iii) Weber–van Vliet isotherm model: This model is another four-parameter

model and is given in Eq. 39. The isotherm parameters P1, P2, P3, and
P4 can be defined by multiple non-linear curve fitting techniques using
minimization of sum of square of residual.
(P qP3 +P4)
Ceq =P1qeq2 eq (4.39)
(iv) Marczewski–Jaroniec isotherm model: This model resembles the

Langmuir model and was developed on the belief that localized sorp-
tion showed Langmuir coverage and there is a distribution of sorption
energies. The model is given in Eq. 40, wherein KMJ and nMJ describe
the spreading of distribution in the path of higher and lesser sorption
energies, respectively. When nMJ = KMJ, the isotherm reduces to the
Langmuir–Freundlich model, and when both are equal to 1, it reduces
to the Langmuir isotherm.
( K MJ Ceq )nMJ
qeq =q max (4.40)
1+( K MJ Ceq )nMJ
5. Five-parameter models: The high parameter model will provide very lucid
information on sorption mechanism under equilibrium conditions. The
Fritz–Schlunder-V isotherm model is developed with the aim of replicat-
ing the variations precisely over a wide concentration range. The isotherm
model is given in Eq. 41.
qmax K1FS5CeqFS5
qeq = (4.41)
1+K 2FS5CeqFS5
There are many models to which the experimentally obtained sorption data
can be fitted to. However, it is the curve with the best fit that predicts the
optimum model. The next important aspect is that the parameters obtained
from the model should be realistic.
4.3.2 Kinetic models
Sorption kinetics portrays the progression of the sorption process with time, till its
equilibrium is reached. This presents information regarding the probable sorption
mechanism. There are two kinetic models, namely “pseudo-first-order” and “pseu-
do-second-order” rate expressions, and two sorption mechanism models, namely,
Webber–Morris intraparticle and Boyd’s film diffusion models.
(i) Pseudo-first-order kinetic model: Lagergren or pseudo-first-order

equation is the earliest equation describing the sorption rate and is
given in Eq. 42, wherein qt and qe are the amounts of sorbate sorbed
at time t and at equilibrium, respectively, and kads is the rate constant
or time-scaling parameter. The straight line plot of log (qe – qt) vs t is
used for the calculation of Kads and qe from the slope and intercept,
respectively. Accurate determination of qe is a difficult task because, in
many sorbate–sorbent interactions, chemisorption becomes very slow
after the initial fast response, and it is difficult to ascertain whether
equilibrium can be reached. It is usually observed that sorption pro-
cesses normally follow the Lagergren or pseudo-first-order model only
for the initial 20–30 minutes of interaction. The value of kads decides
how fast the equilibrium can be reached in the system. The experimen-
tal studies show that the value of kads can be either dependent on the
initial concentration of the sorbate or independent of the experimental
conditions.
kads × t
log(qe − qt ) = log qe − (4.42)
2.303
(ii) Pseudo-second-order kinetic model: This deals with the situation
when the rate of direct sorption/desorption process (considered as a
chemical reaction) controls the overall sorption kinetics. The model
developed by Ho and McKay is expressed in Eq. 43, wherein k2ads (rate
Sorption 61
constant) and qe (amount sorbed at equilibrium) can be easily com-

puted from the linear plot of t/qt vs t. It is understood that the value of
k2ads has a strong dependence on the applied operating conditions, such
as the initial solute concentration, pH of the solution, and temperature.
t 1 t
= 2
+ (4.43)
qt k2 ads × qe qe
(iii) Webber–Morris intraparticle diffusion model: The intraparticle diffu-

sion process rivets around ion migration into the internal surface of the
sorbent due to the presence of pores. The boundary layer diffusion and
the surface sorption rates (characteristic of sorbents) affect intraparti-
cle diffusion. The model is articulated by the mathematical expression
given in Eq. 44. In this equation, kd is the intraparticle diffusion rate, and
I (mg/g) is a constant indicating the size of the boundary layer, which
are the slope and intercept, respectively, of the linear plot of qt vs t1/2.
qt = kd t 0.5 + I (4.44)
(iv) Boyd diffusion model: This model is used to ascertain if sorption pro-
gresses via film diffusion or intraparticle diffusion mechanism. The
mathematical expression of Boyd’s equation is given in Eq. 45, in which
F = qt/qe, where qt and qe are the amounts of metal ion sorbed on the
surface (μg/g) at time t and at equilibrium, respectively. The value of
B was used to calculate the effective diffusion coefficients Di (cm2/s)
using Eq. 46, wherein r is the radius of the sorbent. The linearity of the
Bt vs. t plot provides useful information to distinguish between the film
and intraparticle diffusion. A straight line passing through the origin is
indicative of intraparticle diffusion-controlled sorption.
B * t = −ln (1 − F ) − 0.4977 (4.45)

2
p
B = Di * (4.46)
r
4.4 APPLICATIONS
Sorption is proving to be a lucrative protocol for the eradication of toxic species.
The main aspect of using any sorbent is that it itself should not impart any further
aberration to the ground water system. Thus, it becomes important that the sorbent
material be of great stability.
The use of charcoal was first reported for the elimination of taste and odour from
contaminated water [25, 26]. Activated carbon can be prepared from a variety of
materials (bones, coconut coir, human hair, paper, tree bark, sunflower seeds, corn
cobs, tea leaves, coffee beans, fish, municipal waste, etc), and the functional groups
present are governed by the nature of the precursor and activation method [27–31].
The activation process creates reproducible porous structures with mesopores,
micropores, and ultra-micropores having a large surface area. Activated carbon is a
very effective sorbent due to its high surface area, but it is expensive and is also not
suited for hydrophilic species. Furthermore, the regeneration is even more costly, and
loss of sorbent is encountered. Therefore, various other materials have been evalu-
ated for their potential use as sorbents for remediation. Ion exchange resins appear
to be attractive due to their selectivity and ease of regeneration but find limited use
in water remediation applications due to their high cost and change in structure due
to pH. As it is understood that sorption is primarily a surface phenomenon, surface
area is expected to play a role. Hence, it is of great interest to examine the sorption
efficiency of particles with reduced size. Nanoparticles (NPs; size 11–100 nm) make
up a new realm of matter wherein physical and chemical properties are drastically
different and sensitive to size changes, leading to a wide range of applications [32].
Residual surface hydroxides can also add to the rich surface chemistry of metal
oxides, including sorption characteristics [33]. The use of nanomaterials for reme-
diation of waste water is gaining a lot of attention [34, 35]. In order to enhance the
uptake capacity and obtain selective sorption performance, modification of sorbents
is an attractive option. This can be carried out by either surface functionalization
using specific ligands or impregnation of the ligands within the sorbent material.
There are large numbers of studies on the use of different materials for remediation
of various kinds of pollutants. As expected, the work reported in the literature in the
field of sorption is immeasurable, and it is not possible to include all work in the pres-
ent chapter. Therefore, some specific examples relating to certain types of sorbents
or based on some common pollutants have been given to provide an understanding
of the application of the sorption process.
Transition metal nanooxides such as ferrites, mixed ferrites, and manganese
oxide were found to take up lead ions without any surface modification. It has been
observed that the nature of the metal oxide played a key role in the characteristics
of the nanoparticles and subsequently on the sorption process [36]. Nanocrystalline
manganese oxide with a small particle size and high surface was found to sorb various
metal ions at different pH values with different kinetics [37]. Zinc oxide, a multifunc-
tional nanomaterial, was used for sorption of different species. The use of zinc oxide
as sorbent is also quite interesting. The charge on its surface relied on the synthesis
protocol [38–40]. It was seen that pyrolysis and gel combustion methods imparted
a positive surface charge, while the co-precipitation method made the surface nega-
tive. It is more interesting to note that the ZnO NPs obtained by the three syntheses
protocols had identical structures. Thus, the zinc oxide applications vary according
to the surface charge, and ZnO NPs (obtained from pyrolysis and gel combustion)
were found to be excellent sorbents for anionic chromate species. The mechanism
of sorption proposed was a combination of electrostatic interaction, pore filling, and
complex formation. Negatively charged ZnO NPs (obtained from the co-precipitation
method) showed predilection to Cu (II) ions. In order to introduce selectivity in the
sorption ability of ZnO NPs with respect to lead and mercury, surface modification
or functionalization by the introduction of appropriate ligand during synthesis was
applied [41]. X-ray diffraction (XRD) shows that ligand introduction does not alter
the structure or average size of ZNO NPs, but crystallinity was affected.
Sorption 63
Fluoride is considered to be one of the most common pollutants, and WHO has
specified a limit of 1.5 mg/L in drinking water. Iron-based composites with polypyr-
role (PPy)/FE3O4 showed excellent fluoride sorption efficiency [42, 43]. Amorphous
FE/Al mixed hydroxides with a high surface area showed that fluoride formed new
complexes on the sorbent surface [44, 45]. The sorption was adversely affected by
phosphate, sulphate, and arsenate [45]. The granulated mixture of Fe/Al–Ce nano-sor-
bent sprayed onto glass beads as column materials for fluidized bed was used for
fluoride removal [46]. The complex formation with Fe(III)-modified natural stilbite
zeolite was liable for fluoride removal [47]. Calcium-based sorbents showed that the
mechanism of removal was a combination of both surface sorption and precipitation,
and the sorption was affected by surface area [48–53]. Al–Ce hybrid sorbents pre-
pared by co-precipitation were found to contain nanoparticle aggregates amidst an
amorphous structure as revealed by SEM and XRD studies and were found to have an
uptake capacity of 27.5 mg/g for fluoride. Magnesium-based sorbents were found to
show excellent sorption efficiency for the removal of fluoride from aqueous solutions
[54–57]. Nanocrystalline magnesia–alumina mixed oxide synthesized by the com-
bustion method could remove fluoride at a near-neutral pH (~6) within 1 hour [58].
Carbon-based composites [59–62] obtained from biomaterials like Murrayakoeingii
(curry leaf seeds) [63] were found to have excellent sorption capacity of fluoride.
Carbon-based materials have excellent defluoridation capacity due to their proper-
ties, but the need to make them more cost-effective and environmental friendly is a
challenge to and interest of many researchers [64]. Non-conventional sorbents based
on cement [65–67] prove useful for the removal of fluoride. The use of hydroxyap-
atite and its modified forms as sorbents for water defluoridation has been reported
[68]. Nanocomposites like cellulose/hydroxyapatite [69] and aluminium-modified
hydroxyapatite (Al-HAP) [70] show excellent fluoride removal capacity. Zirconium-
based sorbents are very attractive due to their high efficiency [71–76]. Activated
alumina (AA) without and with modification have been found to show excellent
deflouridation property [77–82]. Unmodified alumina can be used only for pH below
6 due to its leaching. Therefore, modification can reduce the leaching and show appli-
cation in a wider range of pH. Lanthanum(III) and ytterbium(III) impregnated on
alumina have shown very promising results for defluoridation of water. Chromium is
another pollutant which is of great concern. However, in case of chromium, toxicity
depends on the specific form of chromium. Trivalent chromium, or chromium(III),
is an essential micronutrient, whereas hexavalent chromium, or chromium(VI), is
unequivocally toxic, leading to haemolysis and, ultimately, kidney and liver failure.
The maximum allowable concentration of Cr(VI) according to WHO is 0.05 mg/L
in drinking water. Commercially available activated carbons (bare or modified) have
been used for the sorption of chromium [83–87]. It is seen that sorption results in
the reduction of the hexavalent form to the trivalent form. The sorption capacity of
the oxidized carbon was greater than that of the original carbon due to increased
surface charge of the ionized oxygen atoms (resulting in an increase in the electro-
static attraction between the carbon surface and metal cations). Low-cost sorbents
such as coir pith [88], sawdust [89, 90], straw [91], and leaf mould [92] have been
used for chromium removal from water. Carboxylic, phenolic, and protonated amide
groups help in the removal of hexavalent chromium; therefore, pretreatment with
these groups resulted in a positive effect. The nature of shells of different nuts like
coconut (CS), almond (AS), ground nut (GS), and walnut (WS) was found to affect
sorption, with walnut being most efficient and coconut being the least. Although
the mechanism is chemisorption, it is not clear as to the nature of the species being
sorbed (anionic chromate or cationic Cr(III) formed by reduction) [92, 93]. Arsenic
like chromium is a pernicious species whose toxicity is dependent on its valency. The
period of exposure leads to various health issues from vomiting, abdominal pain, to
more dangerous problems of skin darkening and cancer. According to WHO, the
recommended level in water is less than 50 µg/L. Thus the removal of arsenic from
water media becomes very crucial. Activated carbons have been extensively used for
arsenic sorption [94] from aqueous solutions. It is seen that modification of activated
carbon showed a marked enhancement of sorption efficiency [95, 96]. Agricultural
waste [97] or its biochar material [98], bone char [99], and red mud [100, 101] have
been used for arsenic sorption. Radionuclides are a very important class of metal ions
which need to be removed from water bodies. Borosilicate glasses are extensively
used in the immobilization of radioactive waste by the process of vitrification [102].
Thus, it was of interest to explore the room temperature and sorption capacity of these
materials. Boroaluminosilicate glass could be used for the selective uptake of tho-
rium from a mixture containing uranium [103]. The pH of the solution and composi-
tion of the glass have a profound consequence on selectivity. The use of glass as room
temperature sorbents for transition metal ions has been studied [104]. It was seen
that glasses in general can behave as ion exchangers due to their structural features,
and to enhance selectivity and sorption kinetics, modification proved to be effectual.
The use of tri-n-octylphosphine oxide (TOPO) and 8-hydroxyquinoline (oxine) was
found to enhance the selectivity and kinetics of the removal of uranyl ions from its
mixture [105]. The success of utilization of ligand-incorporated glass sorbents paved
the way for the work on the use of AmberLite XAD 4 beads infused with n-benzo-
yl-n-phenylhydroxylamine (n-BPHA) for the selective and highly efficient removal of
Th(IV) from its mixture [106]. The modified sorbent was characterized to confirm
the presence of n-BPHA within the macroreticular resin structure. The uptake was
nearly complete and highly selective in the pH range of 3–7.5, and selective capac-
ity was calculated to be 500 mg/g. Polyaniline (PANI) synthesized by the chemical
oxidation of aniline was studied for the uptake of uranyl ions [107]. This system
was applied for the preconcentration of uranyl ions from seawater. Highly crystal-
line monoclinic antimony phosphate synthesized as both particles (size ~ 14 nm) and
nanoribbons (length 500–700 nm with particles of size 1–5 nm) was found to show
increased sorption efficiency for uranyl ions as compared to other metal ions [108].
Nanocrystalline manganese oxide (prepared by the hydrolysis of KMnO4) with size
of 8 nm and surface area of 145 m2/g was found to show high uptake efficiency for
most of the metal ions. However, it was observed that equilibration pH and time were
parameters which could be used to achieve separation [109]. Functionalization of
multi-walled carbon nanotubes (MWCNTs) in different ways was found to enhance
the removal of Th 4+ ions in aqueous solution [110]. The pH of a solution and nature
of functionalization had a strong effect on the sorption efficiency.
Dyes are another class of contaminants that have attracted many researchers.
Untreated wood and coal were found to be good sorbents for different dyes [111–113].
Peat, a natural sorbent, has been proven to be useful for the removal of dyes [114,
Sorption 65
115]. Chitin and chitosan can be used as flakes, gels, beads, or fibres for the success-
ful removal of dyes [116]. It is reported that a gamut of clay materials (bentonite,
common clay, sepiolite, fire clay, fuller’s earth, and kaolin) [117, 118] and industrial
waste or by products [119, 120] can be used as sorbents for dyes. The mechanism
of removal was attributed to the electrostatic attraction between the negative clay
surface and dye cations. Boroaluminosilicate and barium borosilicate glasses have
also been used for the removal of dyes like rhodamine 6G (R6G) and methylene blue
(MB) [121, 122]. It has been observed that upon sorption of dyes, the glass matrix
is not affected and the dye characteristics are also not altered. The glass structure
contains a random arrangement of Si-O groups and thus the Si-O group is known as
network former. Network modifiers tend to change the arrangement in various ways.
Hence the glass composition can have different ratios of both the network former and
modifier groups. In barium borosilicate glass, the oxides of alkali and alkaline metal
ions are the modifiers while silica is the network former. Thus for the same ratio of
network:modifier, it was seen that addition of barium oxide as compared to sodium
oxide as modifier enhanced the dye uptake efficiency. This is attributed to the vari-
ation in the structural aspects between the two glasses, which have been compared
using NMR studies. Novel nano-sorbents with exotic structures have been found to
have excellent capacity for dyes with very fast kinetics. MnWO 4 o and MnMoO 4 o
nanoparticles synthesized using a sonochemical technique had a high surface area
and could remove cationic dyes within a very short time period [123]. It was also seen
that MnWO 4 could sorb Cu (II) ions. The thermal regeneration allowed the reuse of
these novel nanomaterials for ten consecutive cycles. It was seen that the sonochem-
ically synthesized barium molybdate (BaMoO 4 ) nanoparticles demonstrated excel-
lent sorption efficiency with respect to dyes [124]. The excellent property of BaWO4
[125] as a sorbent was discovered serendipitously when the photocatalytic property
of this material was evaluated. It was observed that the sorption of dyes was very
fast and nearly complete. The tungstate and molybdate nanoparticles of Sr and Y
synthesized by the sonochemical method could be used for the removal of cationic
dyes and metal ions (non-radioactive and radioactive) [126]. SrWO 4 could selectively
remove rhodamine dye from its mixture containing MB. It has been observed that
the sorption efficiency correlated well with the surface charge and crystal structure.
A composite is made up of two or more materials that can be engineered or are
naturally occurring. The two components have significantly different physical or
chemical properties, but a composite has a combination of these properties. A simple
system of iron oxide–silica composites shows that both the individual components
have excellent applications. The two components have opposite surface charges,
and therefore, the study of the sorption efficiency of the nanocomposite could prove
useful to understand the sorption mechanism of metal ions and cationic dyes. Iron
oxide–silica nanocomposites showed the uptake of toxic species like inorganic metal
ions ( UO2 , Zn , Cu , Ni , Co ) and cationic dyes (MB and R6G) from aqueous
2+ 2+ 2+ 2+ 2+
streams at room temperature [127]. The modelling of sorption data was carried out
to understand the sorption mechanism and understand the selectivity amongst the
species. The surface modification of the sorbent enhanced its selectivity with respect
to uranyl ion sorption. When the composites consist of natural products, they are
termed as green composites [128], which can be defined as “materials composed
wholly or in part of constituents which come ultimately from renewable sources”.

Green composites combine plant fibres with natural resins to create natural com-
posite materials. Biodegradable polymers, which are the second component used
for the production of green composites, can be classified into natural and synthetic
biopolymers. Natural biopolymers can be further classified into two, namely, those
obtained from the extraction of biomass and the others that are produced by organ-
isms. Biopolymers obtained from extraction procedures are polysaccharides (like
thermoplastic starch, chitin and chitosan, cellulose, and lignocellulose), polypeptides
(like collagen, gelatin, corn, wheat, soy protein, caesin, and whey protein), and lipids
(usually cross-linked). Biopolymers obtained from microorganisms are further clas-
sified based on the route of production, namely, microbial (polyhydroxy alkanoate,
polyhydroxy butyrate, and polyhydroxybutyrate-hydroxyvalerate) and bacterial, and
polyesters obtained from microorganisms (polylactic acid and polyglycolic acid).
Synthetic biopolymers can be further classified into aliphatic polyesters and poly-
vinyl-based esters. The cell structures of natural fibres are relatively complicated,
and they are a composite of rigid cellulose microfibrils implanted in a soft lignin and
hemicellulose matrix.
4.5 CONCLUSIONS
Sorption is a non-destructive process which is technologically simple (simple equip-
ment) and adaptable to modifications. A wide range of materials can be used as
sorbents for different types of pollutants. It is highly effective with very fast kinetics
and produces a high quality of treated effluent. In order to make this process greener,
the process of uptake by growing plants is being explored as an alternative green
technique. This process is known as phytoremediation, which is discussed in the
next chapter.
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5 An emerging green
Phytoremediation
auxiliary technique
5.1 INTRODUCTION
Bioremediation is an important process for the removal of pollutants using living
or dead organisms [1]. When living organisms utilize pollutants as their source
of food, they break them in situ or ex situ into carbon dioxide and water at opti-
mal temperature. The process is slow, but being a natural process, it is benign, less
labour-intensive, and cost-effective. Some of the bioremediation methods are bio-
augmentation, rhizofiltration, biostimulation, phytoremediation, mycoremediation,
composting, etc. In this chapter, the focus will be on phytoremediation of pollutants.
Phytoremediation is a subset of bioremediation wherein living plants and vegetation
are used to destroy toxic pollutants present in environmental media (surface water,
ground water, waste water, sediments, soils, and/or external atmosphere). The word
“phytoremediation” is derived from the Greek word “phyton”, meaning “plant”, and
the Latin word “remedium”, which means “to remedy/restore”. Phytoremediation can
be considered as an in situ method of bioremediation possessing the intrinsic bene-
fits of bioremediation [2]. The removal of toxic species from ground water and soil
by plants can occur through different mechanisms. The interface of plants with the
environmental medium and microorganisms present plays a very crucial role. The
competence of the process is largely dependent on the nature of the contaminant,
plant species, and medium.
5.2 TYPES OF PHYTOREMEDIATION
The classification of the different phytoremediation strategies is based upon the char-
acteristics of contaminants and plants. Figure 5.1 shows the schematic representation
of the different processes (drawn based on Ref. 3).
(i) Phytostimulation (biodegradation of enhanced rhizosphere or rhizosphere

degradation or “rhizo degradation”) is a process in which the microbial
activity of soil (surrounding the roots of a plant) is enhanced to degrade
contaminants by organisms of the roots by aerobic conversions (through
oxygenate rhizosphere) and also increase the bioavailability of organic car-
bon. The distribution of nutrients is heterogeneous, thus leading to varying
spread of microbes. This microbial degradation in the rhizosphere of media
such as soil sediment and sludge is stimulated by plants like grass, alfalfa,
Cassia, and Typha for the degradation of organic compounds like herbi-
cides, phenols, and chlorinated solvents.
DOI: 10.1201/9781003442516-5 71
FIGURE 5.1 Schematic representation of different phytoremediation processes
(ii) Phytoextraction is the uptake (phytoabsorption), accumulation (phyto-

accumulation), and concentration of pollutants by the roots of plants and
amassing into their aerial parts (shoots/leaves). Such plants are known as
hyperaccumulator plants (Pteris vittata, Elsholtzia splendens, Thlaspi-
caerulescens, and Alyssum bertolonii), and they can concentrate specific
pollutants to as high as 1% dry weight depending on the nature of the pollut-
ant. The specific species can then be retrieved from these parts of the plants.
This is also known as phytoaccumulation and involves the sorption of toxic
metals by plant roots followed by translocation of sorbed metals to shoots
and deposition at the vacuole, cell wall, cell membrane, and other metabol-
ically inactive parts in plant tissues. Hyperaccumulator plants accumulate
Phytoremediation 73
a higher concentration of toxic metals in their root and shoot tissues by

the formation of a metal–phytochelatin complex (M-PC) or metal–ligand
complex formation inside plant cells, which are translocated to the plants’
vacuole in which the ions are amassed. The removal efficiency of a plant is
controlled by the plant biomass, and so the plant should grow fast to be suit-
able for the process. This involves the extraction of metal ions like Co, Cu,
Ni, Pb, Zn, Hg, Mo, Ag, Cd, Sr, Cs, and U from soil sediments and sludge
within the shoots of plants like sunflower and Brassica.
(iii) Phytodegradation (phytotransformation) is the enzyme-catalysed [laccases
(for anilines), dehalogenases (for chlorinated solvents and pesticides), and
nitroreductases (for nitro-aromatic compounds)] breakdown of organic con-
taminant in tissues of plants (Myriophyllum spicatum, Canna, and Populus).
The changes caused results in degradation, inactivation, or immobilization
(phytostabilization), or conversion to a non-toxic form. Thus, the plant can
lead to metabolism and subsequent destruction of toxic species within plant
tissues. This is more appropriate for organic pollutants. It is to be understood
that the nature of the plants plays a critical function directly or indirectly in
this process. The direct process involves the absorption of pollutants by the
plants and break down into non-toxic compounds inside the plant tissue.
However, if the pollutants are degraded within the soil and the plants tend
to absorb the benign by-products, the process is known as rhizodegradation,
and the plants have an indirect role in the process.
(iv) Phytostabilization (phytoimmobilization) is the process by which toxic spe-
cies are immobilized within the rhizosphere or roots of plants. The mech-
anism involves the formation of chelates by the chelating agents present
within certain plants like Alyssum, Haumaniastrum, Eragrostis, Gladiolus,
and Ascolepis. Thus, chelation tends to immobilize metal pollutants into
the rhizosphere or roots. The fibrous roots of phreatophytic trees could be
used for controlling water flow and soil erosion in addition to the uptake of
heavy metal ions (Cu, Pb, Zn, Cu, As, U, Se). Rhizostabilization involves
the fixing of metal ions (As, Cd, Cu, Cr, Pb, Zn) within the soil sediment by
complexation using the roots of plants like sunflower and Chenopodium.
(v) Phytovolatilization is the ability of certain plants to convert some of the
absorbed metals/metalloids (Hg, Se, As, and elements IIB, VA, and VIA of
the periodic table) by the roots into a benign form and then release it into
the atmosphere. The contaminants are translocated to the leaves and are
volatilized through plant stomata (with sites for gaseous exchange for plant
transpiration). This involves many sequential stages. The main requirement
of this technique is that volatile products should be less toxic than heavy
metal ions. The process of volatilization can be direct or be influenced by the
interactions between the root and the soil. The discharge can occur through
hydrophobic barriers like cuts, epidermis, suberin, and other dermal layers.
At times, there is an upward movement, and release occurs during transpi-
ration. This process is used to remove chlorinated solvents, Hg, Se, and As
from the soil sediment using plants like Populus and Scirpus.
(vi) Rhizofiltration (phytofiltration) is the process through which plants

(Fontinalis antipyretica, Helianthus annuus, Phragmites australis, Brassica
juncea, and several species of Callitriche, Salix, Lemna, and Populus) con-
centrate, sorb, and/or precipitate pollutants through the plant root system.
The contaminants remain sorbed in the roots, which are specifically grown
to a large size prior to their contact with contaminated water. Once the roots
are saturated, the plants are harvested and disposed of safely. This process
can be used to remove ions like Cd, Cu, Ni, Zn, and Cr from water bodies
using roots of plants like Lemna.
Of all the techniques, phytoextraction and phytostabilization are most useful

[4]. Plants used for phytoextraction should be easy to farm, grow rapidly, and result
in high biomass for the process to be economical. In addition to this, the plants
should have a copious root system to absorb the metal ions and excellent tolerance
to high metal concentrations [5]. Phytoextraction is effective only if the accumulated
contaminant is subsequently removed through harvesting before leaf fall or death,
warranting that contaminants do not diffuse back to the soil [6]. The processing of
biomass to obtain metals is known as phytomining [2]. Alternatively, the biomass can
be incinerated. The commercial value recovery of precious metals (Ni, Zn, Cu, and
Co) and energy production by incineration [7] are factors that favour the phytoreme-
diation process. These processes need great care to avoid further contamination or
pollution.
The efficiency of the different processes depends on the optimization of the two
key parameters, namely, the ability to hyperaccumulate metals and the yield of bio-
mass. The affixing of organic or inorganic reagents to contaminated soil improves
extraction by the alteration of metal speciation and reduction of heavy metal solubility
and bioavailability by changing the pH value and redox status of the soil [8–12]. The
increase in organic matter content and essential nutrients in soil leads to enhanced
performance of the plant. The mechanism involves the assistance of microorgan-
isms in the rhizosphere (bacteria and mycorrhiza) for phytostabilization, resulting in
improved metal immobilization due to sorption on cell walls which contain chelators
[13, 14]. Cell walls also behave as a filtration barrier to the translocation of metal
ions from roots to shoots [15]. The different parameters that affect the extraction
efficiency are plant type, heavy metal bioavailability, soil, and rhizosphere proper-
ties. Appropriate selection of the plant species is vital for effective phytoextraction
[16, 17]. Therefore, two different strategies are adopted for the selection of the plant,
which involves the use of hyperaccumulator plants (which can accumulate heavy
metals in above-ground parts to a greater extent) or plants with high above-ground
biomass production (even with lower metal-accumulating capacities) [18, 19]. Plants
which accumulate high concentrations of heavy metals in their aerial parts without
showing any phytotoxicity symptoms are known as hyperaccumulators [20, 21]. It
has been observed that hyperaccumulators are found to accumulate nearly 100-fold
greater concentration levels as compared to normal plants under the same conditions
[20]. Thus, for a plant to be defined as a hyperaccumulator, the ratio of concentrations
of heavy metals in the shoot with respect to that in soil and the root is greater than 1.
This indicates effective uptake from soil and transport through the plant, respectively
Phytoremediation 75
[22, 23]. Moreover, the concentration levels of metal ions in the shoot should be of
greater than a specified value (10 mg/kg for Hg; 100 mg/kg for Cd and selenium
(Se); 10, 000 mg/kg for Co , Cu , Cr, Ni, and Pb ; and 10, 000 mg/kg for Zn and Mn)
[24]. Thus, choosing the right hyperaccumulator is critical for the successful phytore-
mediation of heavy metals. More than 450 plant species (Brassicaceae, Fabaceae,
Euphorbiaceae, Asteraceae, Lamiaceae, and Scrophulariaceae families) [19, 25] have
been recognized as hyperaccumulators [26]. It is reported that some species can even
accumulate more than two elements, e.g. Sedum alfredii can hyperaccumulate Zn,
Pb, and Cd [28-30]. It is important to ensure that edible plants are not used for phy-
toextraction to avoid introduction of heavy metals into the food chain. The use of
plant growth-promoting rhizobacteria (PGPR) has gained popularity due to the fact
that PGPR promotes plant growth, protects plants from pathogens, and enhances
the metal tolerance and uptake property [14, 30, 31]. Arbuscular mycorrhizal fungi
(AMF) is an important microbe used to assist phytoremediation by increasing the
surface area of roots (network formation) [32] and also the production of phytohor-
mones [33].
Bioconcentration factor (or biological absorption coefficient) and transloca-
tion factor are the two parameters which indicate phytoextraction efficiency.
Bioconcentration factor (BCF = Cplant / Csoil ) is the ratio of the total concentration
of an element in the harvested plant tissue (Cplant ) to its concentration in the soil in
which the plant was growing (Csoil ) [34, 35]. Translocation factor (TF = Cplant / Croot )
is the ratio of the total concentration of elements in the aerial parts of the plant (Cshoot)
to the concentration in the root (Croot ) [36]. The commercial efficiency of phytoex-
traction is estimated as the amount of metal ions removed per hectare in a year. This
is the mathematical product of rate of metal accumulation [metal (g)/plant tissue
(kg)] and biomass yield [plant tissue (kg)/hectare/year]. This value should be at least
1 kg/ha/year for it to be commercially viable, but even then, phytoremediation may
occur in 15–20 years. Hence, it is not practical to wait for an unrealistic time period,
and fast growing crops are used instead [37].
There are other phytoremediation strategies which are combinations or variations
of the above mechanisms. These are discussed as follows:
(i) Hydraulic barriers: Deep-rooted large trees like Populus sp. consume large
quantities of groundwater during transpiration. The contaminants present
in the water are metabolized by plant enzymes and vaporized together with
water or simply sequestered within the plant tissues [38].
(ii) Vegetation covers: Grasses and trees on landfills or tailing behave as a vege-
tation cover, minimizing rain water infiltration and averting the dispersal of
pollutants. Soil aeration is increased, resulting in biodegradation, evapora-
tion, and transpiration. The complexity of this technique is that tailings are
not suited for root development [39].
(iii) Constructed wetlands consist of organic soils, microorganisms, algae, and
vascular aquatic plants in areas where the water level is at/near the surface.
However, the technique is mainly used in the treatment of domestic water,
agricultural water, industrial waste water, and acid mine drainages due to
its advantages like high removal efficiency, low assembly rate, effortless
manoeuvre, and maintenance [40].
(iv) Phytodesalination is a technique using halophytes to remove excess salts
(from saline soils), and this is similar to phytoextraction [41].
5.3 STEPS INVOLVED IN THE PROCESS

The general process of phytoremediation consists of various steps which are usually
followed in a linear manner. The first step is plant selection and positioning. Since
the process of phytoremediation is time consuming, it is very essential to make the
correct decision on the type and quantity of the plants required. The nature of the soil
usually determines the type of plant that is appropriate. However, extensive studies
are needed on the effects of toxins on the plants. Usually plants which yield large
amounts of biomass (more than 3 tonnes/acre) are chosen. Plants known as “hyperac-
cumulators” are very much needed for circumventing inorganic pollutants, as these
plants will take up very high levels of these pollutants as compared to the soil itself.
Deep-rooted trees like poplar, cottonwood, and willow are normally planted in rows,
perpendicular to the flowing groundwater, to remove pollutants. The next step is irri-
gation and soil amendment. This is important because, more than often, solids need
be altered and irrigated to ensure plant viability. At times, flooding of soil is carried
out to enhance pollutant dissolution. Removal of pollutants can be accompanied with
the depletion of nutrients from the soil. Therefore, soil pH is affected and the use
of chelating agents can retain the metal ions in the solution, thereby enhancing the
chances of phytoextraction. Monitoring is the next step, which has to be carried out
on a regular schedule. The effectiveness of the process is measured from the change
in the contaminant concentration over a time period. If the process is too time-con-
suming, an alternate protocol involving either using a different plant species or soil
amendments can be carried out. Harvesting is an essential step which involves the
removal of plants including the roots (containing contaminants). Therefore, a simple
and efficient disposal protocol is needed. One of the most attractive procedure is the
process of incineration, which results in the oxidation or vaporization of contami-
nants. There are instances when the biomass with the contaminant can be used as
such. This is usually seen in the case of Se, which is now recognized as an essential
trace element for ruminants. It is required in cattle for normal growth and fertility and
for helping prevent other health disorders such as mastitis and calf scours. Therefore,
the biomass with Se can be sold to livestock farmers as bioenhanced and reduce the
cost of purchasing Se salts to be added to normal livestock feed [42]. Similarly, ash
from the nickel-accumulator Alyssum murale can be economically processed into ore
if the content is above 20% by weight [42]. It is usually seen that inorganic pollut-
ants are mostly retained in the roots followed by the leaves and stems, with the least
retention in the fruits. However, for nightshade plants like cucumbers and tomatoes,
it has been observed that the concentration is much higher in their leaves and stems
than in the roots.
Phytomining is the process of recovery of extracted heavy metals from biomass
[43]. The plant biomass with the accumulated metals is then burnt in oxygen to obtain
energy, and the remaining ash, known as bio-ore, is treated for recovery of the heavy
Phytoremediation 77
metal. Thus, phytomining offers a dual advantage of production of energy and recov-
ery of precious metals from biowaste. Studies have showed that the energy obtained
is quite comparable to that from other sources and also leads to reduction of air pol-
lution to a great extent. It has also been observed that processing of bio-ores results
in low SO X emissions into the atmosphere due to the low sulphur content, making
phytomining an environmentally benign and cost-effective process. But the main
controlling factor that makes this process commercially viable is its phytoextraction
efficiency and the market for the recovered heavy metal ions. Phytomining is being
carried out commercially for nickel, and the method has been found to be more
attractive than conventional extraction methods.
Another aspect of removal of heavy metals is the role of plant phytochelatins
(PCs) and metallothioneins (MTs) in phytoextraction [44]. These are loaded with
cysteine sulphadryls which bind and sequester heavy metal ions in very stable com-
plexes. PCs are small glutathione-derived enzymatically synthesized peptides, which
bind metals and are a principal part of the metal detoxification system in plants.
5.4 MECHANISMS
The removal of metal ions by phytoextraction from environmental media like water
is dependent on factors like pH, interfering ions, biomass, organic matter, and exu-
dates. Although heavy metal ions degrade soil and water resources, posing serious
threats to human life, it is often seen that plants can grow in contaminated soil and
water bodies without any undesirable consequences. Some plants eliminate the met-
als due to decreased uptake, while some plants show tolerance to high concentration
levels due to complexation [45, 46]. Heavy metal tolerance is the ability of plants to
survive in soil which is toxic to other plants [47]. When a particular metal is accumu-
lated by the roots, it may be taken to root tissues (phytoimmobilization) or may be
translocated to the aerial shoot parts of the plant through xylem vessels by symplastic
and/or apoplastic pathway and accumulated in vacuoles (cellular organelles with low
metabolic activity) [48]. This is done to avoid the interference of detrimental metals
with important cellular metabolic processes. In order for a plant to be useful for phy-
toremediation, it needs to have high tolerance of trace metals as accumulation within
plant tissues occurs. This characteristic of a plant is dependent on active metal ion
transport into the vacuoles, cell wall metal binding, and complex formation (with
proteins and peptides).
The corporeal task of ion channels was known for a very long time. The mem-
branes of nerve and muscle cells show variations in electrical membrane potential
depending on the surrounding milieu [49]. It was later discovered that the currents
for Na+ and K+ are independent of each other. This could be attributed to the fact
that the membranes contain separate and specific ion channels for Na+ and K+ con-
duction. These ion channels were made of specific transmembrane proteins [50–
54]. Ion channels do not require an energy source to function, and ions flow only
if there is imbalance inside and outside of a cell. Thus, electrochemical gradient
(combination of electrical transmembrane potential and ion concentration gradient
across a membrane) leads to the passage of ions through an ion channel [51]. The
work on ion channels was so important that the Nobel Prize in Chemistry 2003
was awarded “for discoveries concerning channels in cell membranes” jointly with
one half to Peter Agre “for the discovery of water channels” and with one half to
Roderick MacKinnon “for structural and mechanistic studies of ion channels”. There
are four indistinguishable symmetrically arranged subunits, two outer (M1) and two
inner (M2) transmembrane α-helices [53], that surround the ion conduction pore.
The channel has regions of different diameters. The tapered region contains the K+-
specific protein, resulting in the functioning of a potassium-selective filter. The struc-
ture contains five oxygen atoms (of the carbonyl group) per subunit in the direction
of the ion conduction pathway, and K+ ion is located at the centre of a caged structure
with 8 oxygen atoms. Potassium ion conduction occurs when there is a complexation
or an alteration of membrane potential. The process of alternate conduction/non-con-
duction, known as gating, occurs due to conformational changes in protein leading
to the occlusion or abetment of the ionic conduction pathway [54]. When the ionic
channel is closed, the pore is obstructed at the intracellular gate by a bundle of inner
transmembrane helices (M2). The ion channel measures 12 Å in the centre and tapers
down to a narrow region with a diameter of 3.5 Å, wherein the inner helix bundle
(M2) comes together at an angle tilted away from the pore axis [55]. The intracel-
lular gate of the channel is located right below the cavity. At this point, the electro-
static repulsion between any two K+ ions in adjacent sites is very large (40 kcal/mol),
indicating the non-occupancy of the neighbouring sites due to unfavourable energy
conditions. The conductance is very high (allowing more than 1,000 ions to pass per
millisecond) [56]. Therefore, it is clear that pore diameter, solvation, and binding
play a major role in selective transport. The literature reveals that KcsA shows two
different pore conformations, enhancing potassium ion conduction [57].
Phytoremediation is a summation of chronological processes like metal fixing,
uptake by roots, transport from the roots to shoots, incorporation of metal ions into
the xylem, cellular compartmentalization, and sequestration [58]. In general, heavy
metal ions are present as insoluble precipitates in soil, making it arduous for the
plants to extract the ions. Therefore, root exudates are released by the plants to alter
the pH conditions of the rhizosphere, facilitating the uptake of metal ions by the
roots [59] by apoplastic (passive diffusion) and symplastic (active transport against
electrochemical potential gradients and concentration across the plasma membrane)
pathways [60]. The heavy metal ions form complexes with various chelating agents
after entering into the root cells [17] or are sequestered inside the vacuoles, enter
into the xylem, and are subsequently translocated to the shoots [48] and leaves [61]
by specialized transporters [62, 63]. The members of the ZIP gene family present in
the roots of Thlaspicaerulescens and Arabidopsis halleri prove to be excellent metal
transporters (e.g. cadmium, iron, manganese, and zinc) [64]. Other proteins like
HMA3, a vacuolar P1B-ATPase, are excellent bioaccumulators (tend to sorb/accu-
mulate heavy metal ions, which might perhaps be functional for their development)
of heavy metal ions [65–68], with an extremely long-distance root-to-shoot translo-
cation of Zn and Cd [68]. The metal transporters involved in the regulation of metal
homeostasis lead to the translocation of metals like Zn and Ni towards the internal
partition [69]. It is reported that MTP1, an antiporter located on the vacuoles and
plasma membrane, can lead to the bioaccumulation of zinc [70] and also of nickel
in the vacuoles [71]. Natural resistance-associated macrophage proteins (NRAMPs)
Phytoremediation 79
transport heavy metal ions including copper and cobalt [71]. Apart from these metal
transporter proteins, complexing agents like citrate and histidine can result in the
chelation of metal ions like iron and nickel [72, 73]. The main requirement of phy-
toremediation is that detoxification has to be carried out. This is done using two
different strategies, namely, avoidance and tolerance [74]. Avoidance is the capability
of plants to demonstrate diminished uptake of heavy metal ions and additionally
curb their transport within the plants [59]. This is achieved due to reduced uptake by
roots and metal ion precipitation by complexation with chelators [59], thus restrain-
ing toxicity at the extracellular level. A similar barrier reduces the transport from the
root to the shoot system of plants, thus preventing the aerial parts from these heavy
metal ions [74]. The incorporation of metal ions within plant cell walls is also an
avoidance mechanism [75]. Cell wall pectin contains carboxylic acid groups which
can form complexes and also behave as ion exchangers [76–79]. The chelation can be
caused by the presence of different organic ligands in various parts of plants [80–83].
The metal chelates are transported from the cytosol and stored into inactive spaces
like vacuoles [84–86], thus decreasing their toxic effects. However, if the amount of
metal ions in the plants is of higher concentration levels and cannot be mitigated by
the above methods, there is an enhanced production of enzymatic and non-enzymatic
antioxidants [87–89]. This has been found to be an excellent alternative mitigation
process adopted by many plants.
5.5 NANO-PHYTOREMEDIATION
This technique is a combination of nanotechnology and phytoremediation. Due to
the large surface area and small size, nanomaterials can be utilized to enhance phy-
toremediation efficiency. The large surface area contributes to increased surface
activity, while the small particle size makes it easy to access contaminated sites
[90]. The efficiency of this process is affected by the properties of contaminants,
plants, and nanomaterials as well as the environmental conditions. The characteris-
tics of the contaminants that play a major role are molecular weight, type of bonds,
mobility, flexibility, toxicity, hydrophobic and hydrophilic interactions, and reactiv-
ity. Properties of a plant such as its type, degree of branching, nature of the root
system, tolerance capacity and accumulation ability, fast growth, and high biomass
are crucial for the right choice of phytoremediation plants. The structure, size, shape,
composition, concentration, and surface properties of nanomaterials play a crucial
role in the selection of an appropriate nanomaterial. Apart from these, environmen-
tal conditions such as temperature, pressure, pH, and humidity and also the nature
of minerals and microorganisms present around the plant have a definite impact on
phytoremediation efficiency. The interactions between plants and nanoparticles are
affected by the size and penetration ability of the nanomaterials [91]. Once the nano-
materials enter the plant roots, there are two modes of transport within the plant
tissues, namely, apoplastic transport (occurs outside the plasma membrane, xylem
vessels) [92] and symplastic transport (movement of water between the cytoplasm and
sieve plates) [93]. The different applications have been discussed in the Applications
section of the chapter. The application of nanomaterials to the soil for the remedia-
tion process is site-specific and is carried out using methods such as injection under
pressure, recirculation, pressure pulse technology, and hydraulics. Some of the chal-
lenges of nano-phytoremediation need to be overcome and are as follows: (i) this is a
new field, hence studies are few; (ii) more realistic studies need to be performed; (iii)
long-term studies are essential to assess the impact of nanomaterials on soil charac-
teristics and their toxicity; and (iv) studies focussing on ways to avoid the aggregation
of nanomaterials and (v) on understanding the effect of meteorological conditions
need to be conducted.
5.6 BENEFITS AND CONSTRAINTS OF PHYTOREMEDIATION

Like any process, phytoremediation has both advantages and disadvantages [94]. The
low cost of the process is overshadowed by the long time period of study. Moreover,
the nature and concentration of pollutants, the correct choice of plants, and the possi-
ble side effects have to be considered in detail prior to opting for this technique. The
process of phytoremediation has several advantages. The process is in situ and pas-
sive in nature and is low cost as it uses solar energy. This has a reduced impact on the
environment. The presence of plants leads to the reduction of dispersion of contam-
inants by wind and also by surface runoff and leaching. Harvesting is a well-estab-
lished technique for the extraction of accumulated metals, and this technique is quite
viable. Despite several advantages, phytoremediation is still in the infancy stage, and
not much information is available regarding the remediation properties of different
plants. The process is limited to surface and shallow soils and is very slow. The metal
ions taken up can prove to be toxic to the food chain if animals eat plants with large
quantities of heavy metal ions. The process is not adapted to climatic and environ-
mental conditions. The compounds from plants may percolate into groundwater, and
this becomes difficult to handle if the nature of degraded products is hazardous.
5.7 APPLICATIONS
A number of plants have been used for their applications in the field of phytoremedi-
ation [95–105]. Despite the availability of many plants as hyperaccumulators, their
short life, poor biomass yield, and slow growth rate prove to be a hindrance to the
process. So the possible use of plants that produce high biomass but are normally not
known to be hyperaccumulators could be evaluated for their phytoextraction effi-
ciency. In such instances, it has been observed that although these plants assimilate
lower levels of heavy metals in their above-ground tissues, the high biomass produc-
tion can circumvent this limitation and enhance the overall absorption compared to
hyperaccumulators [106–108]. Thus, crops like Helianthus annuus, Cannabis sativa,
Nicotiana tabacum, and Zea mays, which produce high biomass, have been useful
for the removal of heavy metal ions [109–111]. Due to several hindering factors,
large-scale applications of hyperaccumulators are limited [112]. The limitation can
be overcome using protocols such as plant hybridization or genetic engineering to
generate transgenic plants [89, 113]. Chemical mutagen [ethyl methane sulphonate
(EMS)]-treated sunflowers produced giant mutant sunflowers with very high phyto-
extraction efficiency [114]. Genetic engineering also shows potential for improving
phytoextraction efficiency. The genetic modification is carried out by the transfer
Phytoremediation 81
and insertion of a gene from a foreign source (plant, bacteria, or animals) into the
target plant. This process is more advantageous as it allows the modification of plants
with required traits within a shorter time period [115]. The selection of genes for
genetic engineering is very crucial to achieve the desired results. It has also been
observed that heavy metals produce ROS, leading to oxidative stress. Therefore, it is
important to enhance antioxidant activity to improve tolerance to metal ions [116].
Genetic engineering involved gene introduction, which could facilitate the processes
of uptake, translocation, and sequestration [117–119]. Despite its advantages, genetic
engineering has some limitations. Since heavy metal accumulation is a complex pro-
cess, manipulation of multiple genes is essential, and this is laborious and time-con-
suming. At times, the modified plant may also prove to be toxic in nature. Thus, the
use of microorganisms to stimulate root proliferation and to subsequently lead to
improved plant growth with increased heavy metal tolerance is gaining popularity
[120]. Plant growth-promoting rhizobacteria (PGPR) produce various compounds
and follow different paths to enhance growth [14, 33, 121, 122]. The use of nano-phy-
toremediation for the removal of heavy metal ions is an attractive technique [123].
Nano-zero-valent iron (NZVI) is used extensively as an effective sorbent, reductant,
and catalyst for many heavy metal ions [124–130]. The use of waste water (industrial,
municipal, and household liquid waste) for irrigation and decontamination has also
been evaluated [131].
It is of great interest to explore the plausibility of phytoremediation for treating
dye-contaminated water bodies. As the study is in the initial stages, it is not very
clear about the mechanism involved. The use of phytoremediation for dye removal is
a research in a new dimension due to the structural complexity and chemical char-
acteristics of the dyes. It is further to be understood that the presence of the dyes not
only affects the aesthetic value of water but also alters certain parameters, which
could hamper the phytoremediation process. The studies have been carried out using
different types of weeds, ferns, grasses, or agricultural wastes. Phragmites australis
could be used for the removal of textile dyes like acid orange 7 [132], while Lemna
minor L. was found to be efficient for many dyes [133, 134]. Different mechanisms
of treatment of waste water using plants like degradation, accumulation, dissipa-
tion, and immobilization are reported. The tolerance of Lemna minor plants and its
stress response were evaluated using two triphenylmethane dyes (crystal violet and
malachite green) [135]. It was seen that both phytoextraction and phytodegradation
processes played a major role in the treatment of the dye-contaminated water stream.
The biodegradation of brilliant green dye using callus cultures of Tecoma stans var.
angustata plants [136] showed that the dye was completely degraded to minor non-
toxic metabolites via complete degradation of the aromatic rings and by cleavage of
functional groups. The removal of methylene blue (MB) and methyl orange (MO)
has been achieved using the roots of water hyacinth Eichhornia crassipes [137]. The
decolourization of malachite green could be achieved using Blumeamalcolmii due
to the involvement of laccase, veratryl alcohol oxidase, and dichlorophenol indophe-
nol reductase enzymes [138]. It is also seen that the presence of plant microbiome,
plant-associated microorganisms (fungi/bacteria), enhances the decolourization pro-
cess due to their ability to transform organic and inorganic compounds. It has been
observed that Medicago sativa L. and Sesbania cannabina Pers. plants could be
used in conjunction with Gracilibacillus sp. GTY (a salt-tolerant bacteria) to easily

degrade acid red B or acid scarlet GR dyes [139]. Nano-phytoremediation has been
used for the removal of dyes. However, this area of research deals with the use of
nanomaterials synthesized using plant extracts.
5.8 CONCLUSIONS
The uptake of toxic species by plants is known as phytoremediation. This technology
is gaining importance due to its unique advantages. However, since the technique is
still in baby steps, not much work has been reported. Therefore, no clearcut strategy
can be obtained. However, this provides a large scope for future work in this expand-
ing field. It has been observed that basic chemical processes such as precipitation
occur during the phytoremediation process. Thus, it can be understood that precipi-
tation forms the basis for the separation of metal ions. In the next chapter, the uses of
processes such as precipitation and flocculation with respect to metal ion separation
are discussed.
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6 Chemical precipitation,
coagulation, and
flocculation
Triad of great versatility
6.1 INTRODUCTION
In meteorology, the term precipitation refers to water that falls back on the earth’s
surface due to condensation. But in science it is the formation of particles or pow-
ders from solutions under different conditions. This phenomenon is not new to man.
Some such problems encountered in daily life due to precipitation are clogging of
water pipes at home [1] or even the formation of kidney stones [2]. Thus, suspended
colloidal particles are bound to be more dangerous to human health [3,4]. However,
this concept can be used for the removal of toxic species from solution.
Chemical precipitation is a separation technique based on the solubility of the
components present in a mixture. According to the IUPAC, solubility can be defined
as the analytical composition of a saturated solution expressed as the proportion of
a designated solute in a designated solvent [5]. The solubility of a solute lies in the
range of being insoluble (poorly soluble like silver chloride in water) to infinitely
soluble without limit (miscible like ethanol in water) [6]. Solubility can be expressed
in any one of the units such as molarity, molality, mole fraction, mole ratio, or mass
(solute) per volume (solvent). According to US Pharmacopeia [7], the unit of sol-
ubility is defined as the mass parts of a solvent needed for dissolution of 1 mass
part of a solute. The threshold limit of insolubility depends on the application of
precipitation reaction [8] as solubility depends on various factors like ionic strength
and pH of a solution and the reaction temperature. Therefore, solubility is defined as
the maximum amount of a substance that dissolves in a given amount of solvent at a
specified temperature. Hence, the fine-tuning of experimental conditions to render a
solute insoluble is known as precipitation, and the insoluble solid formed is known
as precipitate. The precipitate primarily exists as a well-dispersed suspension, which
finally agglomerates and can be removed by sedimentation, centrifugation, or filtra-
tion. Different parameters like pH and temperature have a strong effect on precipita-
tion. Chemical precipitation is the process by which a substance soluble in a solution
can be converted into an insoluble form (precipitate) from a supersaturated solution.
The clear solution present along with the precipitate is referred to as a supernatant or
supernate. A supersaturated solution contains a particular species in concentrations
greater than its solubility limit. Precipitation is a complex phenomenon resulting
from the formation of conditions of supersaturation [9]. Three steps are involved
in the process: nucleation (germination), crystal growth, and flocculation [10].
DOI: 10.1201/9781003442516-6 87
FIGURE 6.1 Schematic representation of separation of metal ions by precipitation
Nucleation is the stage at which the first germ appears due to condensation. The germ
then aggregates until supersaturation of the solution occurs, and the solid is finally
formed. Metal ions in the solution are precipitated as oxides, hydroxides, sulphides,
carbonates, phosphates, etc. The precipitate is separated from the supernatant solu-
tion using methods like filtration, centrifugation, etc. Figure 6.1 presents a schematic
representation of the precipitation of successive groups of metal ions with nearly
similar chemical properties. The separation involves the chronological precipitation
of the filtrate obtained in the previous step. In the first step, the aqueous solution
containing a mixture of ions is treated with hydrochloric acid. The ions that form
insoluble chloride salts are precipitated, while others are present in the filtrate. The
filtrate is subsequently treated to obtain sequential separation using an appropriate
precipitating agent. It is known that most of the metal chlorides are water-soluble,
and the only ions that form precipitates are Ag+ , Pb 2+ , and Hg 2 2+, which could be
removed by chloride precipitation. The use of sulphide reagent results in the pre-
cipitation of metal sulphides of As3+ , Bi3+ , Cd 2 + , Cu 2 + , Hg 2 + , Sb3+ , and Sn 2+, and
hence their separation in the second stage. The addition of sodium hydroxide results
in the hydroxo precipitation of Al3+ and Cr 3+, while the addition of alkaline sulphide
precipitates most of the transition metal ions such as CO2+, Fe2+, Mn2+, Ni2+, and Zn2+.
The addition of carbonate or phosphate promotes the precipitation of alkaline earth
metal ions such as Ca 2+ , Mg 2+ , Sr 2+ , and Ba 2+. The filtrate obtained finally contains
the alkali metal ions (Li+ , Na + , K + , Rb+ , and Cs+ ) and ammonium (NH 4 + ). Thus,
precipitation is useful for the simple qualitative separation prior to analysis.
Chemical precipitation by hydroxide addition is a popular protocol due to its sim-
plicity, its low cost, and ease of controlling of experimental conditions. In the pH
range of 8–11, the solubility of various metal hydroxides are minimum and so they
Chemical precipitation, coagulation, and flocculation 89
can be removed easily. Lime is the most preferred choice of base [11]. There are differ-
ent classes of reagents known as true metal precipitants, and the most common metal
precipitant is dithiocarbamate (DTC; as sodium dimethyl or diethyldithiocarbamate,
DDTC), which forms stoichiometric compounds which are formed as co-precipitates
with hydroxides [12]. However, care should be taken to avoid large concentrations of
DTC due to its degeneration into sulphates and nitrates, which can change the water
quality. To avoid possible contamination, non-sulphur-containing precipitants like
clay-based products, aluminium, and cationic polymers impregnated with iron and
polymerized aluminium derivatives are gaining popularity. Clay-based products are
basically coagulants that are generally used to treat organic pollutants.
Coagulation and flocculation are processes that have been used from ancient
times to treat dirty water [13, 14]. These two processes can be utilized for the sepa-
ration of finely dispersed colloidal particles having different characteristics such as
charge, size, shape, and density. For obtaining stable dispersion, aggregation should
be minimum. But upon the addition of a coagulant or flocculant, the particles aggre-
gate due to destabilization of colloids. The mostly used reagents are alum, ferric
sulphate, ferric chloride, etc. Coagulation by charge neutralization is accomplished
either by reducing the zeta potential of colloids or by flooding the medium with an
excess of oppositely charged ions [15]. Agglomeration is a sum of sequential steps of
coagulation, flocculation, and sedimentation. It is very essential that each step must
be completed for the successive stages to be completed and successful. Coagulation
by charge neutralization results in the formation of microflocs, which upon gentle
mixing become larger in size and are known as pinflocs. The continued increase of
the floc size results in the formation of macroflocs that settle down and are separated
as sedimentation. As the size of the floc increases, the mixing velocity and energy
are decreased to prevent the tearing of the floc. The coagulant is chosen based on the
nature of the chemical species to be removed. Inorganic coagulants such as alumin-
ium and iron salts are used to neutralize suspended particles. Inorganic hydroxides
are formed as small polymers, which enhance the microfloc formation. Inorganic
coagulants are very economical and can remove microorganisms. The addition of
coagulants results in a change in the pH of water. Long-chained polymer coagulants
work over a wide pH range compared to inorganic coagulants. This is because a very
small amount of polymer is used, and the water parameters are not affected. The
suspended solid in fluid media is a heterogeneous hydrodynamic system that can
be controlled by gravity, centrifugal force, buoyancy, pressure, and electric current.
Sedimentation is controlled by gravity, while centrifugal force operates in a centrif-
ugation system. When the particle is suspended in solution, the fluid (liquid) flows
over the particle and a resistance is created. To reduce this, the flow of fluid is made
uniform and smooth by using energy. Thus, the resistance developed and the energy
required are dependent on the geometry of the solid particle. When flow velocity
is low, laminar flow conditions prevail, leading to the formation of a well-defined
layer around the particle to get a uniform flow. Increase in the fluid velocity makes
the flow turbulent, and the boundary reduces. Thus by using various mathematical
expressions, the settling velocities can be calculated. The resistance of surround-
ing water will also increase as the particle descends and finally becomes equal to
accelerating forces. From this point, the particle starts falling down with a constant
maximum velocity, known as terminal velocity. Sedimentation is the removal of sus-

pended particles due to gravitational settling, and the clear liquid is decanted. The
most common coagulants are the inorganic salts of Al and Fe. Both of them form
insoluble gelatinous hydroxides that can be used to remove suspended particles. The
following equations show the various chemical reactions that occur upon the addition
of salts. It has been found that aluminium salt is suited for a pH range of 5–8, while
iron salts work better in higher pHs of 8–10.
Al 2 (SO 4 )3 + 3Ca (HCO3 )2 2 Al (OH)3 + 3CaSO 4 + 6CO2

Al 2 (SO 4 )3 + 3Na 2 (CO3 ) + 3 H 2O 2 Al (OH)3 + 3Na 2 SO 4 + 3CO2
Al 2 (SO 4 )3 + 6 NaOH 2 Al (OH)3 + 3Na 2 SO 4
Different species can behave as coagulants, but each of them has its own mer-
its and demerits [16]. Aluminium sulphate [alum: Al 2 (SO 4 )3 ×18H 2 O ] is the com-
monly used coagulant as it produces less sludge, is effective in mild pH conditions
(6.5 − 7.5), and is very easy to handle. But the main disadvantages are its applica-
bility in a limited pH range and solubility in alkaline conditions. Sodium aluminate
(Na 2 Al2 O 4 ) is very effective in hard waters and can be used in very small amounts.
The main limitations are its cost and ineffectiveness in soft water. Polyaluminium
chloride [PAC; Al13(OH)20(SO)4Cl15] results in a more denser floc compared to alum,
and this settles faster. Despite these advantages, there are not much reports on the
use of PAC. Ferric sulphate [Fe2(SO4)3] is effective in both mildly acidic (pH 4–6)
and mildly alkaline conditions (8.8 − 9.2), but the water becomes alkaline due to
solubilization. Ferric chloride (FeCl3 .6H 2 O) is effective for a wide pH range of 4–11,
but dissolution hampers its use. Similarly, ferrous sulphate (FeSO 4 .7H 2 O) is not
quite sensitive to pH change, but its solubility leads to a change in pH of the water.
Lime (Ca (OH)2 ) is very commonly used because it is effective and does not have
solubilization issues, but it produces large amounts of sludge. Inorganic coagulants
with many advantages are still less attractive as sludge production is high, and the
sludge does not dry up rapidly. Therefore, pre-polymerized aluminium solutions
(with variable degrees of polymerization) like PAC, polyaluminium sulphates (PAS),
or polyaluminium chloro-sulphates (PACS) are used. The PAC have found appli-
cations due to their inherent advantages of being applicable over a wide pH range,
being resistant to temperature and colloidal concentrations, and requirement of low
coagulant dosage. These polymeric structures are produced from soluble anionic alu-
minium hydroxo complexes [Al(OH)4−], formed due to hydrolysis at pH > 3. These
polymerized coagulants are not as efficient as organic polyelectrolytes [16], whose
higher molecular weight (MW) leads to better flocculation. However, their very high
molecular weight might lead to viscous solution, and appropriate dilution is required
[17]. The two important characteristics of polymers, namely, high charge density (for
efficient charge neutralization) and low molecular weight (for easy diffusion around
particles), make polymers suited as coagulants or flocculants [18, 19]. Organic poly-
mers can be classified into low, medium, and high when their molecular weights are
less than 105, 105–106, and greater than 106, respectively. The initial mixing is very
essential for complete dispersion of the polymer. Flocculation is the second stage,
which commences once coagulation is nearly complete. Sometimes bridging of two

turbid particles to different chains of the polymer also occurs. For aggregation to
occur, the mixing energy should be sufficient to ensure particle collision but not very
high, resulting in the collapse of aggregates. Inorganic or organic flocculant aids
are used to overcome the issues of aggregate disintegration. Polymerized silica is
generally used to improve flocculation via composite polymerization (introduction of
polymerized silica in the pre-polymerized metal solution) or copolymerization (intro-
ducing polymerized silica in the metal solution) [20]. The increasing concentration of
monosilicic acid to levels greater than the solubility limit results in the precipitation
of the polymer. It is seen that different silica species can form depending on various
experimental parameters such as temperature, silica concentration, pH, other ions,
and time of ageing [21]. The most important parameter that affects silica polymeriza-
tion is the pH value as hydroxyl ions probably catalyse the reaction. However beyond
pH of 9, the polymerization decreases, and with ageing, gel formation is observed
[22]. The gel formation can be circumvented by amending the pH. Polyaluminium
silicate chloride is superior to conventional or simple pre-polymerized coagulants
[23]. Acrylamide-based polymers and copolymers like hydrolysed polyacrylamides
(anionic, molecular weight: 104–107 g/mol) and polydiallyldimethyl ammonium
chloride (poly-DADMAC; cationic, molecular weight: 104–107 g/mol) are useful.
In general, organic polymers prove to be more useful as flocculant aids rather than
as primary coagulants. Natural polymers (biopolymers) like pre-gelatinized starch
derivatives, amine-treated cationic starches, guar gums, tannins, chitosan, and algi-
nates behave as flocculants (bioflocculants) [25, 26].
It is seen that co-precipitation with inorganic precipitants is carried out along
with colloidal precipitates (sulphides and hydroxides) having a large surface area
[27]. Thus, co-precipitation has been studied with hydroxides of iron(III) and man-
ganese(IV) to a greater extent and with that of Al, Be, La , and Zr to a lesser extent.
Co-precipitation is used to separate and concentrate trace elements from very dilute
solutions, such as natural water. Since the solubilities of metal hydroxides or sulphi-
des are mainly governed by the pH value of the solution, it is known that many of
the metal ions can be co-precipitated with iron hydroxide in the pH range of 9–10.
However, different parameters like pH, quantity of precipitant, coexisting salts,
precipitate ageing time, etc., have a profound effect on the yield. Co-precipitation
can occur due to different mechanisms like an ion exchange reaction (between
the hydrogen on the hydrated oxide surface and trace metal ions in the solution
(nSH + Mm+ knSnM (m − n) + +nH + ), sorption of metal ions and then
hydroxide ions onto the surface of the metal oxide, or sorption of the hydroxo metal
complex onto the surface. Dithiocarbamate (DTC) is very commonly used to achieve
separation between heavy metal ions by precipitation. Clay-based products are pri-
marily used as coagulant aids due to the excellent swelling ability of the material and
the ease of functionalization.
Coagulation is carried out in a conventional clarification system [28], which con-
tains a large tank with separate chambers for mixing and settling. The periods for
coagulation (retention), flocculation, and settling are in the range of 3–5 minutes,
15–30 minutes, and 4–6 hours, respectively [29]. The first two steps are very cru-
cial to achieve excellent clarification. Hence, the initial mixing is quite turbulent,
ensuring complete contact between the coagulant and suspended particles. The
flocculated particles settle down at the bottom, while clean water passes out to the
circumferences onto clean weir. The accumulated sludge is scraped off. This hori-
zontal basin clarifier can produce high-quality effluent in an upflow clarifier (when
the water flow is in the upward direction). Air flotation systems can remove solids,
oil, grease, and fibrous materials. Air flotation is the production of microscopic air
bubbles, which enhance the natural tendency of some materials to float by recycling
back a small part of the clarified flow. Dissolved air flotation (DAF) unit is a water
treatment process that clarifies waste waters by the removal of suspended matter
by dissolving air in the water or waste water under pressure. The pressurized air
released at atmospheric pressure in a flotation tank basin forms tiny bubbles. These
bubbles adhere to suspended matter, making it float on the surface, which is removed
by skimming [30, 31]. In flotation, it is not essential to obtain a large quantity of
heavy flocs to achieve efficient removal of solids. Therefore, it becomes easy to use
DAF as both flocculation time and reagent dosages are low. The forces applied to
sludge by bubble agglomerates enhance the efficiency of chemical use and reduce the
volume of residuals to be treated.
Filtration is a separation process wherein suspension is passed through a porous
membrane or medium [32]. The medium retains the solid particles on its surface or
within its pores. The solid is known as filter, while filtrate is the fluid passing through
the membrane. A filter is characterized by four features, namely, porosity, permea-
bility, tortuosity, and connectivity. Porosity is the fraction of the medium with voids.
The pores can be ordered or random. Conductivity is dependent on the porous struc-
ture. There are two modes of the passing of liquid through the filter: (i) gravity filter
(liquid flows through the filter under the gravity) and (ii) vacuum filter (gravity is not
sufficient to induce flow, and a vacuum is applied on the discharge side). Filtration
along with clarification can remove suspended particles. The interaction between the
particles and the filter medium determines the filtration mechanism. In practice, cake
filtration is quite common. Cake formation refers to the deposition of a thin layer of
residual particles on the surface of the filter medium [33]. The edifice of the cake
formed (determined by cake porosity, mean particle size, size distribution, and par-
ticle-specific surface area and sphericity) and its resistance to liquid flow depend on
the properties of suspension and filtration experimental conditions (coagulation rate,
applied pressure, and temperature). The resistance to liquid flows leads to reduced fil-
tration efficiency and increased operation time. In general, most of the cakes formed
are compressible, and the rate of compressibility is inversely proportional to particle
size. The presence of differently sized particles affects the cake structure from the
time of formation until the end. This is because small particles may be transported
from the top surface of the cake to near the filter or sometimes within the pores of
the filter, resulting in pore clogging, and exhibit of an increased resistance to the
flow. Dewatering is the process of washing the filter cake to effect clean separation
of the solid and mother liquor [34]. In this, a clean fluid is passed through the cake
to recover the residual liquids in the pores. However, this causes the structure of the
cake to disintegrate. There are different types of setup of filtration medium. The
assembly of plates and frames is the most common arrangement. In this setup, there
is an opening at one corner for the introduction of feed slurry, and the hollow centre
has an auxiliary channel. As the feed flows into the setup, the formation of cake in
the hollow centre commences. The filtrate streams all the way through the medium
onto the grooves present on the filter plate and finally through an outlet channel in
each configuration. This continues until the flow of the filtrate decreases below a
practical level (or pressure builds up too much). Upon termination of filtration, the
wash liquid is passed in the same mode to wash the cake. However, for better perfor-
mance, special wash plates arranged within the configuration are used. The setup is
such that every other plate is a wash plate. During washing, the outlets of wash plates
are closed, and the washed liquid is sent through a special inlet channel. The cake
is removed manually once the entire process is over. An alternate but familiar setup
is the one which uses a recessed-plate press, in which the cake gets collected within
the recesses in the plates and no frames are used. The feed is sent in at the centre
and removed from the corners of the configuration. The substitution of the slurry by
the wash liquid is the protocol adopted to wash the cake. The vertical plate filter is
a simple but widely used design, which is compact, economical, and workable, and
thus finds extensive use in the industry. The design needs labour and is costly due
to replacement of the filter cloth. The filters are classified based on the method of
capture, i.e. exclusion at the filter surface (straining and deposition) within the media
(in-depth filtration). Strainer is a simple thin physical barrier (metal/plastic) used at
the inlet of the water treatment process to preclude large contaminants (leaves, fish,
and coarse detritus) with an interspacing of 1–10 cm. Microstrainers with lower inter-
spacing are used to remove fine silt and algae. Metallic microstrainers can be used
as a perforated sheet or woven wire. However, a plastic one is in the form of a woven
or fused grid. The straining medium for wastewater treatment consists of a bundle of
twisted fibres. A filter used normally for point-of-use treatment is disposed of after
use. Cartridge filter consists of a disposable cartridge, which contains a porous and
non-compressible material wound on a cylindrical support. It finds utility in small-
scale applications like domestic point-of-use water treatment. In-depth granular
media filtration with filters containing sand or crushed anthracite is used in munic-
ipal water treatment. Slow-sand filtration and rapid gravity or pressure filtration are
two modes of operation using granular media filters. Pre-coat filtration uses a thin
inert medium coated with loose fibres or powders [35]. Slow-sand filters reduce the
filtration rate to avoid the capture of contaminants deep within the bed. It involves
straining and capture within top 20 cm of the sand. The accumulated fragments,
known as schmutzdecke [36], contribute to biological treatment of water. However,
it is essential that the water entering the filters must not contain any disinfectant that
might interrupt the biological activity of schmutzdecke. It is also essential to remove
the floc particles formed to reduce the build-up of resistance to the flow. Rapid grav-
ity and pressure filters are used under gravity (rapid gravity filtration) or in pressure
(pressure filtration)-driven processes [37]. The basic mechanisms of particle removal
are fundamentally the same in both gravity and pressure modes and differ only in the
flow. Different granular media filters with unique applications have their own merits
and demerits. Membrane filters using cloth or fabric in ancient times and synthetic
membranes in modern times have become very popular.
Electrocoagulation is the means of using electric current to subvert colloidal
particles in waste water [38] by simultaneous oxidation and reduction processes.
Universally, the anodes are fabricated from iron. It has been observed that many
hydrolysed species are formed depending on the metal ion concentration and pH of
the solution.
2+
Anodic Reaction : Fe s Fe aq + 2e−
Cathodic Reaction : 2 H 2O + 2e− H 2(gas) + 2OH−
2+
Overall Reaction : Fe s + 2 H 2O Fe aq + H 2(gas) + 2OH−aq
Electroflotation (EF) is a process wherein bubbles of hydrogen and oxygen are

produced by electrolysis at the cathode and anode, respectively. These bubbles then
collide with the suspended particles in the waste water and make them float. The
water treatment is achieved by skimming floating particles containing the suspended
solid.
Crystallization is a separation process based on the limited solubility of a com-
pound in a solvent at a certain temperature, pressure, etc. [39]. The change in con-
ditions leading to decreased solubility leads to the formation of a crystalline solid.
Crystallization has been used for ages for the production of salt, but the mechanisms
of nucleation and crystallization of complex solutes are still intangible and also there
is a lack of proper facility for carrying out the same. However, the increased require-
ment for excellent product quality deems crystallization as an attractive technique.
The theoretical background of crystallization being a process of formation of crys-
talline solids with highly regular internal structures (crystal lattice) from liquid, gas,
or amorphous solids is well known. The formation of such a highly ordered structure
excludes impurities from the lattice, leading to high purity. The important develop-
ment during crystallization is lucid from the rates of nucleation B (#/m3s) and growth
G (m/s). The nucleation rate B is the number of new crystals formed per unit time
and volume of suspension, while the rate of growth G is the rate at which the size
of the crystals increases. Supersaturation influences the rate of the two reactions.
Once crystal formation has commenced, secondary nucleation occurs at lower levels
of supersaturation and is dependent on the stirring rate. Stable nuclei are formed
only if the increase in interfacial energy (from solid–liquid interface formation) is
counterbalanced by the energy decrease due to the release during the formation of a
thermodynamically stable solid. The unpredictable nature of nucleation, coalesced
with its effect on the crystal size distribution, makes the process uncontrolled, and
this limitation is overcome by seeded crystallization (addition of small, previously
produced crystals) for industrial applications. In cooling crystallization, the decrease
in temperature can lead to supersaturation, and cooling has a great effect on the end
product. When the solution and surroundings have a huge temperature difference,
the cooling rate will be high, with a very sharp change in the initial stages which
becomes least at the end of crystallization. Thus, the seed crystals cannot grow fast
enough to consume the supersaturation, resulting in products with a wide distribution
of crystal sizes. If the cooling is carried out in a linear manner, the initial supersat-
uration is reduced, and this can result in nucleation. Hence, it is of immense impor-
tance to maintain the conditions of supersaturation [10, 40, 41].
6.2 APPLICATIONS FOR THE REMOVAL

OF METAL IONS AND DYES
The efficiency chemical precipitation depends on different experimental factors such
as pH, precipitate, mixing time and speed, sludge volume, and complexing agents.
The complete removal of Cr from tannery effluents using alkaline precipitation is
difficult due to the presence of organic ligands in waste solutions. The use of hydrox-
ides of calcium [Ca(OH)2] and sodium (NaOH), and calcium magnesium carbonate
[CaMg(CO3)2] is found to be useful for the removal of chromium from tannery waste
water [42, 43]. It has been observed that more than 99% of Cr could be removed
with minimum sludge production upon using a combination of NaOH and Ca(OH)2
[44]. Another study reported that MgO is a better precipitating agent than NaOH
or Ca(OH)2 at pH 9.8–10.3 [45], but a combination of MgO and Ca (OH) 2 is very
effective [46]. Heavy metal precipitation by hydrolysis is found to be quite effective
using common precipitants [47]. The formation of bridged compounds was attributed
to improved efficiency of a mixture of CaO and MgO compared to NaOH [48, 49].
Under acidic conditions, secondary precipitates contributing to sludge formation are
formed upon the use of calcium hydroxide precipitants. The formation of secondary
waste makes it necessary to develop a method to dispose the waste, thereby mak-
ing the whole process economically unfavourable. In sulphide precipitation [50–52],
neutralization of acidic effluents is essential to avoid the generation of toxic H 2 S gas
[50]. Metal sulphides have lower solubility than hydroxides, resulting in complete
precipitation, and show improved stability over a wide pH range. Sulphide precip-
itation has more advantages compared to hydroxides due to lower residual metal
concentration, less interference from chelating agents (present in waste water), bet-
ter selectivity, and faster reaction rate. Moreover, sulphide sludges dry better and
can be treated to recover metal ions. However, the main disadvantages are the high
cost of the reaction and the possible formation of toxic H 2 S gas (acidic conditions
or when the molar concentrations of sulphide ions are in excess of metal ions). The
metal ions can be precipitated as metal carbonates using reagents like Na 2 CO3 and
CaCO3 [53]. The majority of carbonates have a greater solubility than metal hydrox-
ides. Separation of metal ions as their phosphates [54, 55] has also been reported
but not used extensively. The majority of phosphates have a lower solubility than
metal hydroxides. Various other precipitants have also been synthesized and used for
separation. The most commonly used reagent is DTC [56, 57]. Precipitants can be
classified as macromolecular trapping agents and small molecular precipitants [58].
Xanthate, polymerized ethylene dichloride–ammonia dithiocarbamates, or polyd-
ialkyl amine dithiocarbamates are macromolecular trapping agents, while DDTC
and dimethyldithiocarbamate (DMTC) are small molecular precipitants [59, 60].
Reagents like 2,4,6-trimercapto-1,3,5-triazine (TMT) trisodium salt nonahydrate
and Thio-Red (potassium/sodium thiocarbonate, STC) are found to be useful for the
precipitation of different toxic species [61]. Co-ordination polymerization precipi-
tation involves the use of a co-ordinating ligand to form the precipitate [62]. Novel
ligands based on pyridine thiol have been found to be suited for the removal of toxic
species [63]. Fenton reaction is usually used to improve the removal efficiency of
chemical precipitation methods [64–68]. The removal of dyes is carried out using
precipitation. Alkaline white mud (AWM) is found to be useful for the removal of
acid blue 80 [69]. It has been found that precipitation is the prominent mechanism
for the removal of high concentrations of dye. The use of chlorides of divalent mag-
nesium and manganese has been reported for the removal of synthetic textile waste
waters containing the azo-dye pigment Levafix Brilliant Blue EBRA [70]. It has been
observed that chloride of manganese was more superior to that of magnesium as a
coagulant. The coagulation occurs due to the formation of hydroxide species. It was
established that brucite[Mg(OH)2] particles were formed when applying (MgCl2 ),
whereas a mixture of feitknechite (b − MnOOH) and hausmannite (Mn 3 O 4 ) is
obtained when using MnCl2 . The azo-dye pigment sorbs onto the surface of precip-
itating phases, and charge neutralization occurs leading to the formation of aggre-
gates. Leaching solutions of white mud could remove different dyes like acid orange
II, reactive light yellow K-6G, reactive bright red K-2BP, and direct yellow R within
90 seconds [71]. Water quality was maintained by using precipitation. Separation of
different metal ions with precipitation has been reported [72–75]. Table 6.1 presents
a list of the radionuclides separated using different reagents. Separation is achieved
by altering the acidity or alkalinity of a solution.
Coagulation and flocculation find applications in the treatment of dye-loaded
waste water. Calcium carbonate and hydroxide green synthesized from gastropod
shells and in situ hybridization of dyes (methylene blue and Congo red) have been
impregnated into the growing calcium salt derivatives [76]. It has been observed that
precipitation of methylene blue was about 80%, while that of Congo red was 98%.
The process was independent of pH, initial dye concentration, presence of anions, and
ionic strength. The presence of anions increased the quantity of sludge produced. To
TABLE 6.1
List of precipitants for radionuclide separation
Precipitants Trace Elements
Hydroxide Al Cr(III), Mo, W, Ce, Eu, La, Lu, Nd, Sm, Tb, Th, Tm, Yb, Th, U
Be As, P
Bi(III) + In(III) Co, Cu, Fe, Mg, Ni
Fe(III) Cd, Co, Eu, Mo, Cr(III), (VI), As, Ge, P, Sb, Se, Te, W, Cu, Mn,
Ni, Pb, Zn, V, Ag, Ce, Cr, Cs, Er, Gd, La, Mn, Rb, Sr, Yb, Zn
Ga(III) Al, As, Cd, Co, Cr, Cu, Fe, La, Mn, Ni, Pb, Ti, Zn
Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb
La(III) As, Bi, Sb, Se, Te
Co, Fe, Mn, Ni, Zn
Mn(IV) Mo Ga, As, Se
Sulphides Pb(II) Cu
Cd(II) Co, Cr, Cu, Mn, Zn
Sulphate Na Cr(III)/Cr(VI)
Fluoride Ca(II) U, Th
overcome this, emulsion splitting electrolysis (similar to electroflotation) in combi-

nation with classical liquid–liquid separation operation is reported [77]. The removal
of cibacron red FN-R using an inorganic–organic composite polymer through a floc-
culation system was found to be dependent on polymer dosage, solution pH, dye
concentration, agitation speed, time, and nature of coagulants [78]. The use of ferric
chloride as coagulants for the removal of disperse red dye [79–81] was found to be
more efficient than the use of aluminium sulphate, with an efficiency of greater than
90%. The presence of high salt content decreased the efficiency. Natural occurring
biodegradable coagulants like chitosan, surjana seed powder, and maize seed powder
were found to be very effective [82]. Bittern, a by-product of solar salt production,
contains high concentrations of magnesium ions, enabling its use as coagulants in
the removal of indigo blue dye [83]. Acid cyanine 5R and direct violet N dyes were
removed by flocculation using epichlorohydrin–dimethylamine [84].
6.3 CONCLUSIONS
Chemical precipitation is used for the uptake of pollutants and separation of the
products formed. This process is quite simple, efficient, and also cost effective. It
can be applied to very high concentration levels of toxic species, but it is not highly
selective. However, this process also has some disadvantages. The first disadvantage
is the large quantity of chemicals consumed in the process. It is not useful for low
concentration levels of toxic species. It is also not suitable if the metal ions are not
free in the solution. This process leads to sludge formation, which needs extra effi-
ciency to be handled and disposed. The additional steps make the cost higher.
Coagulation and flocculation are processes used for the removal of pollutants.
This combination process is simple and cost-effective. A wide range of chemicals
can be used as coagulants, and the sludge formed can be easily removed from the
water body. This process can be used to reduce the chemical and biochemical oxygen
demands and also the bacterial activity in water. However, this process also has cer-
tain limitations. It needs large amounts of chemicals, and the effluent parameters can
be altered. There is an increase in the sludge volume, which needs to be managed and
treated, resulting in an increase in the cost of the process. It is not suited for many
species, especially arsenic.
Flotation or froth flotation is an integrated physicochemical separation process.
Different types of collectors (ionic and non-ionic) are used for the efficient removal
of small particles which would normally not settle down quite fast. It is used for
the primary clarification method and is found to be selective. However, the process
requires very high initial capital cost and also has high energy requirements. The
maintenance and operation costs are also significant, and the choice of chemicals is
critical to obtain proper forth characteristics, and the process is sensitive to pH.
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7 Chromatographic
techniques
Workhorse of analytical
chemistry
7.1 WHAT IS ANALYTICAL CHEMISTRY?
Analytical chemistry is too broad and too active a discipline to be defined completely.
It is often described as the area of chemistry used to characterize matter by answer-
ing the two fundamental questions of what is there (qualitative) and how much is
there (quantitative). Thus, if we need to know if a particular species is present in a
sample, then it is known as qualitative analysis, and if we want to know how much of
the species is present in a sample, then it is known as quantitative analysis. In daily
routine, both qualitative and quantitative measurements are carried out. Analytical
chemistry can be understood to be the process of improving established methods to
counter new challenges that arise due to the nature of samples [1]. An exceptional
feature of analytical chemistry is the advance of new analytical methods/techniques
to address scientific questions. This field can be defined as “the science of inventing
and applying the concepts, principles, and . . . strategies for measuring the charac-
teristics of chemical systems” [2]. If these new analytical methods are adopted by
other scientists, they may serve as enabling technologies that can advance the work
of an entire field. Charles N. Reilley said: “Analytical chemistry is what analytical
chemists do”. Izaak Maurits Kolthoff (1894–1993) is widely regarded as the father of
modern analytical chemistry. His research transformed the ways by which scientists
separate, identify, and quantify chemical substances and built the field upon solid
theoretical principles and experimental techniques. Kolthoff had commented during
an interview at Beckman Center (15 March 1984):
In 1912 I went to a book sale and bought ten books for fifty cents. One of the books was
by Ostwald The Scientific Foundations of Analytical Chemistry. Ostwald wrote at the
beginning of that book that analytical chemists are the maidservants of other chemists.
This made quite an impression on me, because I didn’t want to be a maidservant.
This comment is sent as recorded on tape held by The Chemical Heritage Foundation,
Philadelphia, and the quotation was provided by W. H. Brock.
Analytical chemistry is carried by obtaining answers for the basic questions of
what, where, how much, and what form about a material sample. Analyte is the con-
stituent of interest, while matrix is the constituent except for the analyte in a sample.
The discipline has expanded beyond the bounds of just chemistry, and many have
DOI: 10.1201/9781003442516-7 101

advocated using the name analytical science to describe the field. Analytical chem-
ists use the analytical approach for problem solving. An analytical approach involves
the following steps: (i) identifying and defining of the problem, (ii) designing or
planning the experimental procedure, (iii) carrying out experiments and collecting
relevant data, (iv) analysing the data, and finally (v) providing a solution to the prob-
lem. In the planning stage, the most important step is the selection of the appropriate
method. Upon selection of the method, sampling is done to obtain samples for fur-
ther analysis. The samples obtained are prepared and pretreated prior to analysis, and
the appropriate parameters need to be measured. The Valid Analytical Measurement
(VAM) programme was set up in 1988 by the Department of Trade and Industry
(DTI) to improve the quality of analytical measurements. This was replaced by the
National Measurement System (NMS). According to this system [3], measurements
should be made for a requirement using tested methods and calibrated instruments
by a qualified and competent analyst. It is necessary that the measurements need to
be checked with those in other laboratories using the same well-defined procedures.
It is also necessary to carry out continuous assessment of the laboratory [3]. The
validation should check the recovery and also the values obtained with an alternate
protocol. It also involves replicate analyses and tests on blanks and the use of cer-
tified materials. Proficiency testing schemes between laboratories are also crucial.
Method validation is crucial to establish reference methods. This is carried out using
relevant performance indicators such as selectivity, specificity, accuracy, precision,
linearity, range, limit of detection (LOD), limit of quantification (LOQ), ruggedness,
and robustness.
(i) Specificity and selectivity are performance characteristics of analytical

methods frequently used in analytical literature [4]. Specificity is the ability
to assess the exact components in a mixture and gives a measure of the
degree of interference by other substances in a sample on the analysis of
a particular analyte. However, it does not require the identification of all
components in the sample. According to the official guideline to be applied
for method validation ICH Q2(R1), specificity is defined as the “ability to
assess unequivocally the analyte in the presence of components which may
be expected to be present”. Specificity refers to the degree of interference
by other substances also present in the sample while analysing the analyte.
For analytical methods, specificity defines the identity of an analyte among
a mixture of similar components in a sample, where the identity of the
components is not important. The second approach known as matrix inter-
ference studies is applied to evaluate if the matrix may have an influence
on the results. Quality control (QC) laboratory methods for identification
tests, impurity tests, and assays rely upon specificity. According to IUPAC,
“Specificity is the ultimate of Selectivity” [5, 6]. Selectivity is the ability to
differentiate the components in a mixture and is defined as “The analytical
method should be able to differentiate the analyte(s) of interest and IS [IS =
internal standard] from endogenous components in the matrix or other com-
ponents in the sample”. Specificity indicates that the method can respond
to only one analyte. In the context of analytical chemistry, selectivity is
preferred as per IUPAC recommendations.
Chromatographic techniques 103
(ii) Types of errors: The main aim of carrying out an analysis is to have a correct
measurement. However, what does this mean? It is important to realize that
the meaning of the term correct is valid only if the analyst is aware of the
true value. Nevertheless, in practice, this is not the case, and a measurement
will always be associated with an uncertainty with respect to this value that
is an inherent error. In order to achieve the correct value, the analysis is car-
ried out in replicate. Error is the difference between the true and experimen-
tally obtained values. However, if the true value is known, then analysis is
not required. The main aim of an analyst is to minimize and quantify errors.
There are three categories of errors, namely, gross error (human error), sys-
tematic error (bias), and random error. Gross error includes human errors
while performing measurement and recording data. This can be spotted from
values that are very different from the set of values. Data points that statisti-
cally fall outside the range of a data set are called outliers. Gross errors can
be reduced by (i) careful recording of data and subsequent calculation and
(ii) increasing the number of analysts. A systematic error can be described as
a measurement that is always too high or always too low, and the magnitude
of the deviation from the “true” value is constant. A systematic error is often
difficult to identify. These errors can be divided into subgroups, namely,
environmental errors, observational errors, and instrumental errors. Envi-
ronmental errors arise in the measurement due to the effect of the external
conditions (temperature, pressure, humidity, and external magnetic field).
Observational errors are the errors due to an individual’s bias or careless-
ness, or lack of proper setting of the apparatus. Measurement errors include
wrong readings due to parallax errors. Instrumental errors arise due to faulty
construction and calibration of the measuring instruments. Such errors arise
due to the hysteresis of the equipment or due to friction. Zero error (positive
or negative) is a very common type of error (especially in devices such as
Vernier calipers and screw gauge). Sometimes the readings of the scale are
erased off, resulting in errors. Instrumental errors can be due to an inherent
constraint of devices, misuse of apparatus, and effect of loading. Instru-
mental systematic errors can result from drift noise, external interference,
or improper calibration of the instrument. These errors can be identified by
analysing signals of standards on a regular basis; e.g. baseline drift is a com-
mon problem in atomic absorption spectroscopy (AAS) analysis, and so it
is a common practice to analyse a blank and a known standard after every 5
or 10 samples. Chemical systematic errors can occur in the wrong standards
used for calibration or from the reagents used in various steps (e.g. yield
in derivatization prior to the analysis of the derivative, or loss in extraction
prior to analysis). Random errors are those errors that occur irregularly due
to arbitrary and unpredictable variations in experimental conditions (e.g.
unpredictable fluctuations in temperature, voltage supply, etc.). An absolute
error is calculated by the difference between the measured value of a quan-
tity and its actual value, while a relative error is the ratio of absolute errors
to the measured value.
(iii) Precision and accuracy of a method are two important parameters. Precision
of a method is the degree of agreement among individual test results when
the procedure is applied repeatedly to multiple samples. Precision is related

to reproducibility and repeatability. This can be measured by analysing a
series of samples from multiple samplings of a homogeneous lot. Accuracy
is the degree of closeness of measurements of a quantity to that quantity’s
true value.
(iv) Statistical tools: These are used to understand the analytical data. The field
of statistics, where the interpretation of measurements plays a central role,
prefers to use the terms bias and variability instead of accuracy and pre-
cision: bias is the amount of inaccuracy, and variability is the amount of
imprecision. For the measured values, two criteria are used to compare these
results, namely, the average value or mean (technically known as a measure
of location) and the degree of spread (or dispersion). The average value or
mean is computed by the ratio of sum of all the values to the number of
measurements. Spread or dispersion is the difference between the highest
and lowest values. A more useful measure that utilizes all the values is stan-
dard deviation (SD) (s ), which is defined as the measure of the dispersion
of data from its mean. It measures the absolute variability of a distribu-
tion. The higher the dispersion or variability of data, the larger the standard
deviation and the larger the magnitude of the deviation of value from the
mean, and vice versa. It is important to observe that the SD value can never
be negative. There are two types of SDs, namely, population SD and sam-
ple SD. The sample mean is the average value for a finite set of replicate
measurements on a sample. It provides an estimate of the population mean
for the sample using a specific measurement method. Mean is obtained by
dividing the sum of all the data points by the number of data points and is
calculated by the formula of ( ×i) /n. SD is the most basic statistic related
to uncertainty. Suppose a chemist analysed one solution n times to estimate
the concentration of a given substance. SD represents the variability in the
data set of n results and is calculated by SD = [ ( x − xavg ) / (n −1)]0.5 . In
2
statistics, SD (s ) is a measure of the amount of variation or dispersion of

a set of values. A low SD indicates that the values tend to be close to the
mean (also called the expected value) of the set, while a high SD indicates
that the values are spread out over a wider range. The square of SD (s ) is
a very important statistical quantity known as variance. Precision is calcu-
lated as relative SD (% RSD), using the relation %RSD = (SD*100) / 100.
Thus in chromatography, all the considerations of analytical chemistry are
also applicable.
7.2 WHAT IS CHROMATOGRAPHY?
The historical perspective of modern chromatography is as early as the late 19th and
early 20th centuries [7]. It originated from the works of David T. Day, a distinguished
American geologist, and Mikhail Tswett, a Russian botanist. Day developed proce-
dures for crude petroleum fractionation using Fuller’s earth [8], while Tswett used a
chalk-filled column packed for separation of pigments of leaves [9]. Tswett was the
one to interpret the process and termed it as chromatography (meaning “to write with
odours” – literally translated from its Greek roots chroma and graphein), and so he
is known as the father of chromatography. The revolution of chromatography was
in the 1940s due to the development of column partition chromatography by A.J.P.
Martin and R.L.M. Synge [10], for which they were awarded the Nobel Prize in
1952. In partition chromatography, the distribution of the solute occurs between two
liquid phases, of which one of them is within a solid support. Thus, techniques such
as paper and thin layer chromatography were developed in the early 1940s [11–14].
The 1950s was dominated by the development of ion exchange chromatography in
the early years [15], while in the later part of the decade, the concept of gel filtration
chromatography was introduced, paving the way for the development of gel perme-
ation chromatography (GPC) in early 1960s [16]. The use of ion exchangers became
quite common in the 1930s [17, 18], but their application for chromatographic deter-
mination of organic compounds was reported in 1958 [19]. This system was a pre-
cursor of high-pressure liquid chromatography (HPLC) that incorporated automatic
pumping, efficient ion-exchange chromatography (IEC) columns, and continuous
odour detection. Prior to the development of the first HPLC systems, gas chromatog-
raphy (GC) gave an idea of the possible applications and ease of automation and sen-
sitivity of HPLC. The early 1960s saw the automation of liquid chromatography (LC)
and GPC [20–22]. The use of smaller particles in well-packed beds could increase
both separation speed and efficiency, but high pressure is needed to pump the mobile
phase through the column. Later, HPLC was developed [23], and by 1970, HPLC was
marketed by Waters Associates and Du Pont. Horváth, Huber, and Kirkland can be
considered the “fathers” of HPLC [24].
Chromatography refers to the separation techniques based on the partitioning or
distribution of a sample (solute) between a moving or mobile phase (MP) and a fixed
or stationary phase (SP) [25–27]. The process can be considered to be a combination
of a series of equilibrations between the MP and SP. This phenomena can be mathe-
matically expressed by the partition (K) or distribution (D) coefficient (ratio of con-
centrations of solute in SP to MP). Separation arises due to the differential affinity of
the solute for the two phases. Therefore, if it has affinity for the MP, then it will move
rapidly through the column and be detected earlier than the one that shows more
affinity for the SP. Chromatography is based on a physical equilibrium that results
when a solute is transferred between the MP and SP. By definition, chromatography
is a separation technique in which a sample is equilibrated between a MP and a SP.
The two phases are chosen such that the degree of distribution of various components
of the sample between two phases is variable. Normally, the SP is a solid or liquid
entrapped in a solid, while the MP can be a liquid, gas, or supercritical fluid.
7.3 CLASSIFICATION OF CHROMATOGRAPHY
The chromatography technique is classified into different categories depending on
the technique involved or physicochemical principles involved.
The first type of classification is based on the combination of different parame-
ters, namely, solute–SP interactions, chromatographic bed shape, physical state of
the MP, and molecular characteristics. Therefore, the techniques can be classified
into column chromatography, paper chromatography, thin-layer chromatography

(TLC), gas chromatography (GC), HPLC, IEC, gel filtration chromatography, and
supercritical fluid chromatography (SFC). On the basis of solute interactions with
the SP, the techniques can be classified into adsorption, partition, ion exchange,
molecular exclusion, and affinity chromatography. Partition chromatography utilizes
a mobile liquid or gaseous phase entrapped within a solid support, while the mobile
liquid sorbed on the surface of the SP acts as the SP. In IEC, a stationary solid
phase covalently attaches anions or cations onto it. Thus, solute ions of the opposite
charge in the mobile liquid phase are attracted to the resin by electrostatic forces.
The difference in the extent of interaction leads to the separation of inorganic ions.
In molecular exclusion chromatography, the liquid or gaseous phase passes through
a porous gel that separates the molecules according to its size. Affinity chroma-
tography utilizes the specific interaction between one kind of solute molecule and
a second molecule that is immobilized on a SP. Thus, the above techniques can be
classified based on the bed shape, namely, planar and column chromatography. In
planar chromatography, the SP is supported on a flat plate or in the pores of a paper.
The MP moves through the SP by capillary action or under the influence of gravity.
Paper chromatography and TLC techniques are planar in configuration. Paper chro-
matography, introduced in 1944, has a liquid SP and MP (partition chromatography).
Paper serves as a support for the liquid SP, and the sample solution is applied as a
spot or streak one half inch or more from the edge of a filter paper strip. The paper
with the dried spot is dangled in a closed container with the MP. The solvent, while
moving up the paper length, will take different components to different distances
through capillary action. The SP in this chromatography is the water within the pores
of the paper, making it a partition chromatography. 2D technique is used for complex
mixtures. In this, the sample spot is first developed in one direction using one solvent
and then dried. After this, the paper is turned to right angles and developed using
the second solvent of different polarity. Paper chromatography can be made more
selective by using ion exchange groups incorporated within the cellulose structure.
Paper chromatography and TLC are used to characterize the components based on
the relative mobility values, which depend on the quality of the SP and its thickness,
humidity, temperature, etc. TLC was first described in 1938 and became popular as it
replaced paper chromatography due to its speed, sensitivity, and reproducibility. The
resolution in TLC is higher than that of paper chromatography due to the presence
of smaller and regular particles in the plate compared to paper fibres. TLC has many
advantages such as high sample throughput, low cost, minimum sample preparation,
and retrieval of plates and finds applications in various fields. The most commonly
used sorbents are silica gel, alumina, diatomaceous earth, and cellulose. The sepa-
ration using silica gel, aluminium oxide, and magnesium silicate as sorbent is based
on adsorption, while that with cellulose is a partition mechanism. Small and uniform
particles of silica with polar or non-polar groups are used in high-performance thin-
layer chromatography (HPTLC). Sorption TLC involves the activation of sorbents
by drying at a specified temperature for a specified time. The initial protocol of
TLC matches with that of paper chromatography. Once the zones are separated, the
detection is carried out using an appropriate technique (either in situ or by scrapping
of a band from the plate, eluting the component, and determining) like derivatization
(char using sulphuric acid or produce a coloured complex using iodine), fluores-
cence, autoradiography, biological assay (measurement inhibition of cholinesterase
activity by organophosphate pesticides), etc. Different factors such as nature of the
compounds, type of SP, solvent strength (the higher the strength, the greater the R f
value), type of developing chamber, vapour phase conditions, and development mode
affect separations. The other classification of chromatography based on the column
bed is column chromatography. In this, the SP is held in a narrow tube and the MP
passes through the column, taking along with it the more soluble solute faster than
the more firmly held solute. Column liquid chromatography, or known popularly
as column chromatography, is a very well used separation technique involving the
differential migration of solutes within a closed tube containing a packed SP. The
liquid MP passes through a SP (solid or liquid impregnated into an inert solid) at low
pressure conditions or under gravity. The most common technique for wet packing
of a column involves the pouring of sorbent slurry into the column and draining of
excess solvent once the sorbent is uniformly packed into the column. The packing
may require repeated pouring of slurry and draining of excess solvent. The sample
dissolved in a minimum volume of the MP is poured at the top of the column, while
the eluent is passed at a constant rate using a peristaltic pump. The MP composition
can be kept constant throughout the process (isocractic) or varying (gradient). The
eluate coming from the column passes to a detector, wherein the individual compo-
nents are analysed.
Based on the physical state of the MP, the column chromatographic techniques
can be classified into LC, GC, and SFC techniques. In gas–liquid chromatography,
the SP is a non-volatile liquid coated onto a porous support or the walls of a capillary
tube, while the MP is an inert carrier gas (helium). Separation occurs due to differ-
ences in vapour pressure, and the solute with higher vapour pressures pass through
the column faster. GC can be either partition or sorption based on the column mate-
rial used. In HPLC (or more commonly LC), separation occurs due to adsorption on
a column through which the MP is passed through under pressure. The column mate-
rial can lead to separation by different mechanisms such as partition, ion exchange,
or molecular permeation. IEC is a liquid–solid chromatography used to analyse ions
as the SP is functionalized appropriately. In gel filtration chromatography, the SP
is a gel, and separation is achieved using a HPLC instrument by the sieving mech-
anism. SFC uses carbon dioxide supercritical fluid at conditions above the critical
pressure ( Pc ) and critical temperature (Tc ). Carbon dioxide is not suited for polar and
high-molecular-weight compounds, and therefore, small amounts of a polar solvent
(methanol) is added. This results in enhanced solute solubility and leads to better
peak shapes and efficient separation. There are other supercritical fluids like nitrous
oxide, trifluoromethane, sulphur hexafluoride, pentane, and ammonia which find
applications in food industries. SFC has properties transitional to both LC and GC
but with unique features of fast analysis, better resolution, and high selectivity range
by varying the pressure, temperature, MP composition, SP, etc. SFC can also be used
for the analysis of non-volatile, thermally labile compounds (unlike GC). SFC can
be performed using either packed columns (with small size, porous, high surface
area, hydrated silica particles like in HPLC) or capillaries (coated with polysiloxane
film whose polarity is varied using different functional groups). The instrument of
packed-column SFC is similar to that of HPLC, but a back pressure regulator is used
to control the outlet pressure of the system. The separations can be carried out in an
enclosed bed (column) or in an open bed (thin-layer plate coated with an appropriate
SP). Liquid–solid adsorption chromatography uses a column (packed with an adsor-
bent like alumina or silica gel), and the sample is eluted with a suitable solvent by
gravity flow through the column. In column separations, MP flow is achieved by a
pressure drop along the column, while in open-bed chromatography the flow is due
to capillary wetting. In open-bed chromatography, the SP is open and no column is
used. This is known as planar chromatography.
The second classification is based on the retention mode on the SP. The retention
of the solutes on the SP can be through any of the following mechanisms, namely,
sorption, exclusion, or ion exchange. Sorption is a general term used for both adsorp-
tion and partition of the solutes onto the SP. Chromatographic separation can be
based on only adsorption or partition, leading to adsorption or partition chromatog-
raphy. Exclusion refers to the separation technique based on sample size. This is the
sieving mechanism that operates in gel permeation chromatography or size-exclusion
chromatography. Ion exchange refers to the exchange of ions in a solution with those
on the SP. Generally, the solutes are inorganic cations or anions. But organic ionic
species can also be separated.
Chromatographic techniques can be classified based on the mode of sample intro-
duction into the column as frontal chromatography, displacement chromatography,
and elution chromatography. In frontal chromatography, the sample is introduced
into the bed continuously, and it behaves like a MP. The sample components are
selectively separated as fronts rather than as bands, with the least retained compo-
nent emerging out of the column. Therefore, complete recovery of the pure sample
is difficult. In displacement chromatography, the MP is much more strongly retained
by the SP compared to the sample, leading to dislodgment of the sample by the MP.
The main advantage of this technique is that greater loads of sample can be applied
and can be useful for preparative- or production-scale samples. However, the main
hitch is to find the correct displacing reagent. This is useful in the bioseparation of
proteins. Elution chromatography involves the separation of components into bands
due to the migration of sample components at a pace slower than the MP at pre-
set experimental conditions. This is exploited solely for analytical determinations.
Elution separations can be non-linear or linear (as determined by the peak under the
conditions of separations). Non-linear elution is usually observed when high sam-
ple concentrations are used (preparative separations), and so Gaussian bands are not
obtained with tailing or leading of peaks. Since distribution constant K depends on
the sample size, it becomes difficult to identify compounds based on their migra-
tion rates. Therefore, most of the separations (analytical/preparative) are carried out
under linear isotherm conditions, wherein the distribution constant K is independent
of the sample concentration.
LC is a column separation method used for separating and analysing compounds
based on differences in their interaction with a SP. The interactions can be adsorption,
partition, ion exchange, molecular exclusion, or affinity. There are many different
ways to use LC for separation purpose, and the choice depends on the physicochem-
ical characteristics of the molecule of interest. The solid phases are highly porous,
chemically inert supports functionalized with various chemical groups that control
the interactions with the molecules to be separated. The different commonly used
modes of separation are based on specific binding interactions (affinity chromatog-
raphy), charge (IEC), size (size exclusion chromatography/gel filtration chromatog-
raphy), and hydrophobic surface area (normal/reverse phase chromatography; NPC/
RPC). In this chapter, further discussion will be restricted to the chromatographic
techniques normally employed for the determination of inorganic ions. The most
commonly used technique is the ion chromatography, while reverse-phase HPLC
also finds applications in these analyses.
7.4 BASIC PRINCIPLES OF LIQUID CHROMATOGRAPHY

The basic principle is based on the movement of analytes through the column which
is governed by their partition coefficients between the two phases [28]. The concen-
trations involved in chromatographic analysis are quite low, and the problems of
saturation leading to column overloading and subsequent problems of loss of column
efficiency and poor resolution do not arise [29]. The process of chromatography pro-
duces peaks of analyte components due to separation into discrete bands. However,
optimization of a successful separation requires that researchers are aware of the
various aspects of chromatography apart from its instrumentation. The chromato-
gram is a plot of detector response produced due to the entry of the analyte into the
detector, as a function of elution time. The peaks may be symmetrical or asymmetri-
cal in nature based on the entire separation process. When the volume of the eluent is
considered instead of the time of elution, it is possible to obtain void volume, which
is defined as the time taken by one volume of the MP [30]. If the solute is partitioned
between the two phases, then the volume of the eluent that passes through the col-
umn before the solute elutes out is known as retention volume VT , and it is the sum
of the void volume (Vm) and the volume fraction due to the partitioning between
the two phases (Vm*Kx). The time taken for the solute to reach out of the column is
known as the retention time. It is quite understandable that different components will
have different retention time values due to their differences in partitioning efficiency
between the two phases. The volume of the MP required to elute a component from
the SP and out of a chromatography column is called the retention volume (VR ), and
the time associated is t R [31]. The free space between the SP particles packed in the
column is known as void volume V0 . All molecules spend the same total amount of
time in the MP, and this time is called the column dead time or holdup time, t0 . This
time is measured by injecting a completely unretained compound and measuring
the time required for the peak (measured at peak height) to reach the detector. The
retention time, t , is the time from when the sample is introduced into the column to
when the detector senses the maximum of the retained peak. This value is greater
than the column holdup time by the amount of time that the compound has spent in
the SP and is called the adjusted retention time (tRʹ). If the analytes do not partition
between the two phases, then the retention time will be the same and is denoted
as t M . The adjusted retention time tRʹ is the time for which the analyte is retained
on the SP, and it is given by tRʹ = tR – tM. The retention factor or the capacity factor
( k ) explains the migration rate of an analyte in a given column. It is represented as
k = t R − t M /t M = t R /t M . The retention factor has no units, and ideally it should be

between 1 and 10. If the value is less than 1, it indicates very fast elution, thus mak-
ing it difficult to achieve precise determination; a value greater than 10 is indicative
of very slow separation. The separation of two molecules (A and B) on a column is
expressed by the selectivity factor α, which is given as the ratio of capacity factors
of the two solutes.
The peak broadening that occurs quite commonly is a general term used to
describe the overall dispersion or widening of a sample peak as it passes through a
separation system. It occurs as a result of several factors such as diffusion processes
and solute distribution between phases. The width of the peak is quite important to
understand various concepts of chromatography. Resolution (RS) may be expressed
by Eq. 7.1, wherein t = difference between retention times of the two solutes with
peak widths at baseline of w1 and w2, respectively [32–36]. Resolution is greatly
affected by column efficiency, selectivity, and capacity and can be mathematically
expressed by Eq. 7.2, wherein the first, second, and third terms denote the column
efficiency, selectivity, and capacity, respectively. In case of poor resolution, the col-
umn efficiency should be the first parameter that has to be evaluated. Separation on
an efficient column results in narrow and less spread peaks in the chromatogram.
2 t
Rs = (7.1)
(w2 + w1 )
N a −1 k
Rs = * * (7.2)
4 a k +1
When the partition coefficient (K) of a solute [K = (solute concentration in SP)/

(solute concentration in MP)] is the same for all solute concentrations, the elution will
ideally follow a symmetrical Gaussian peak. If the elution does not follow this trend,
the chromatographic peak will be asymmetric in shape. The Gaussian nature of the
chromatographic peak is understood using the Plate theory. The separation factor,
a, is a measure of the resolution between two peaks and is the ratio of the adjusted
retention time values of the two solutes. It is dependent on various factors such as
temperature, SP, and MP.
Column efficiency can be explained by two approaches, namely, plate theory pro-
posed by Martin and Synge in 1941, and rate theory, proposed by van Deemter in
1956 [37,38]. Both rate theory and plate theory are important in chromatographic
analysis [39,40]. The major difference between the two theories is that rate theory
describes the efficiency of separation by comparing the rates of analytes eluted
through the column, whereas plate theory describes the process by the determination
of the number of hypothetical plates (where distribution between two phases occur)
in the column.
According to the plate theory, a chromatographic column of length L is viewed to
be made up of a number (N) of series of narrow, discrete sections called theoretical
plates of height equivalent H, which can be expressed by Eq. 7.3. The schematic
representation of the plate theory is given in Figure 7.1. The figure shows that at each
FIGURE 7.1 Schematic representation of plate theory of chromatography
plate, there is an equilibrium. In this, the analyte is distributed between the MP and
SP. The movement of the analyte and MP is seen as a series of transfers from one
theoretical plate to another. The correlation between the height equivalent of a the-
oretical plate to the column length (L) and number of plates (N) is given by Eq. 7.3:
L
HETP = (7.3)
N
Thus, it can be easily understood that column efficiency is higher if there are more
numbers of theoretical plates due to the increased number of equilibrations. Also, the
higher number of theoretical plates suggests that the height equivalent of a theoreti-
cal plate, i.e. height of each plate H, is smaller. Thus, smaller heights promote better
equilibration between the SP and MP. Thus, columns with low plate numbers are less
efficient than columns with higher plate counts. The peak parameters can be used
for the calculation of N (number of theoretical plates). For a simple Gaussian peak,
N can be related to the retention time, as given in Eq. 7.3a, wherein tR is the retention
time and s is the SD. The different methods like the USP method and the half-peak-
height method are used for the calculation of N using the peak features. Both the
methods first involve the determination of peak width, which is the distance between
points where lines tangent to the peak’s left and right inflection points intersect the
baseline. The calculations can be carried out assuming the chromatographic peak to
be a Gaussian distribution (normal distribution), as shown in Figure 7.2 (a). The peak
has a height of H and width of w, and the width at half peak height (H0.5) is w0.5. The
SD of the peak is given by σ.
2
tR
N= (7.3a)
s
H is given in terms of SD and also variance in Eqs. 7.3b and 7.3c, respectively.
2
L
N= (7.3b)
s
2 2
s s
H = L* = (7.3c)
L L
Since variances (s 2 ) are additive in nature, it can be safely understood that the
total plate height observed for a system ( H tot ) is a sum of variances of plate height for
each individual process, leading to an increase in peak band-broadening.
The US Pharmacopeia method of calculation of N involves the use of a simple
relation given in Eq. 7.3d, wherein tR is the retention time and w is the peak width
[30,31]. This calculation results in small N values when peaks overlap or there is dis-
tortion in peak shape or the peak has multiple inflection points. The second method is
the half-peak-height method, which involves the use of width at half the peak height
(w1/2). This is the most extensively used method and is also used by the German
Pharmacopeia (DAB), British Pharmacopoeia (BP), and European Pharmacopoeia
(EP). This involves the calculation of N by Eq. 7.3e.
2
tR
N = 16 * (7.3d)
w
2
tR
N = 5.5 * (7.3e)
w1
2
Symmetry factor (S, also called “tailing factor”) is a coefficient that shows the
degree of peak symmetry. It is represented in Eq. 7.3f, wherein w0.05 is the width at
the height of 1 / 20 th peak height. The value of f can be calculated from the peak
shown in Figure 7.4B. The values of S indicates the nature of the peak; S > 1, = 1,
and <1 refer to the tailing peak, peak with Gaussian distribution (symmetry), and
leading peak, respectively.
w0.05
S= (7.3f)
f
The peak broadening due to the contribution from the solute movement through
the chromatography column can be explained by rate theory. This is represented
schematically in Figure 7.2.
The first factor is eddy diffusion, which occurs as the analyte molecules adopt
different routes of travel across the column. These routes have different widths and
lengths across the column. If the column is packed with very large and inhomoge-
neous particles, then eddy diffusion becomes a major factor responsible for peak
broadening. In a packed column, the particle size is directly related to the height of
the plate, as given by Eq. 7.4, wherein d p is the diameter of a particle. Therefore,
increased particle size leads to an increase in eddy diffusion, and so in open tubular
columns, eddy diffusion is not a major concern. In LC, eddy diffusion is responsible
for a major part of the peak or band broadening in the column. Since eddy diffusion
is a combination of diffusion and convection, the term eddy dispersion might be
FIGURE 7.2 Schematic representation of rate theory of chromatography
more appropriate. The contributions to eddy dispersion arises from internal diame-
ter, length, and packing efficiency of the column and also the size and homogeneity
of particles.
H = Ce * d p (7.4)
The second factor that contributes to peak broadening is longitudinal diffusion.

This is due to the fact that diffusion occurs across a concentration gradient from the
concentrated region in the centre to a dilute one at boundary. The contribution of
longitudinal band broadening is proportional to the diffusion constant. Since the dif-
fusion in gases is about 104 times higher than that in liquids, longitudinal broadening
is more prominent in GC than in HPLC. At high velocity of the MP, the analyte does
not get sufficient time to be retained onto the column, and so the effect of longitudi-
nal diffusion is reduced.
The third factor that contributes to peak broadening is the resistance to mass trans-
fer. For every equilibrium between the two phases, the time involved tends to vary if
the solute prefers one particular phase, leading to peak broadening. Therefore, this
broadening is due to the analyte diffusion and convection between the two phases.
The resistance to mass transfer is inversely relational to the diffusion constants in
either phase. In the MP, there is an additional link to eddy diffusion. Thus, the total
contribution to the plate height can be described by band broadening taking place
in the MP, stagnant MP [41], and SP. Different mathematical equations are given to
understand the relationship in the different phases.
(i) Resistance to mass transfer in the MP, or MP mass transfer is a process of

peak broadening caused by the presence of different flow profiles within
channels or between particles of the support in the column.
(ii) Resistance to mass transfer in the stagnant MP: This is common in a packed
column where MP can be stagnant within the pores of SP and solutes dif-
fuse into and out of it. This is a major source of band dispersion [32], which
is affected by particle shape and size distribution and by the hydrodynamics
of the stagnant boundary layer and packing density, which presents diffu-
sional mass transfer resistance [36]. This affects the value of H as shown
below.
cm * dc2 * u
(a) In an open tubular column, H = .
Dm
cm * dc2 * u c * d2 * u
(b) In a packed column, H = , where H = m c .
Dm Dm
(c) Resistance to mass transfer in the SP: It takes the solute molecules some
time to reach the SP, to enter it, to remain there for a duration that is gov-
erned by statistics, and to leave the SP and enter the MP again.
1 + 6 k + 11k 2
Cm =
96 * (1 + k )2
The van Deemter equation combines the different contributions in a simplified
equation, wherein A is eddy diffusion, B is the longitudinal diffusion in the MP, and
C is the resistance to mass transfer in the SP (in GC) or in both the phases (LC).
B
H = A+ +C *u
u
The contribution of a stagnant MP is valid only with large particles and is, there-
fore, usually neglected in the van Deemter equation for high-performance systems.
The contribution of resistance to mass transfer in the MP can be neglected in GC,
but not in HPLC.
The assumptions made in the classical derivation of the van Deemter height
equivalent to a theoretical plate (HETP) equation show a mathematical expression
between the Gaussian distribution curves of the solute concentrations in the eluent
provided by the plate theory [37–40] and by the rate theory applied to a continuous
column. In the rate theory, the axial dispersion coefficient DL (m2/s) is applicable only
to the MP of volume fraction FI as there is no axial dispersion in the SP of volume
fraction (1−FI). The linearly flowing liquid phase moves the solute between itself and
the SP. According to plate theory, it is assumed that the volume of eluent required
to elute an analyte through one plate is lower than the elution volume (volume of
the eluent that elutes from the column before a particular analyte comes out with
the eluent). Similarly, rate theory considers the elution distance of an analyte to be
greater than the sum of the distance in the mixing stage and the height of transfer.
Another assumption is the effect of injection volume on the peak features, and this is
applicable to GC. The fundamental assumptions of the van Deemter HETP equation
were formulated in 1956. But it is seen that there are serious errors in the interpreta-
tions using the original equation. In this work, it was seen that there was an excellent
fit of the equation for small molecules, but there are instances as to why this model
becomes inadequate. Longitudinal diffusion takes place not only in the interparticle
MP but also in the pores (within/surface). The overall eddy dispersion term is due
not only to constant flow-controlled eddies but also to asymptotic transchannel and
short-range interchannel eddy dispersion. The mass transfer resistance in the MP
cannot be represented by a linear liquid driving force model as this approach leads to
a retention-dependent HETP term. The mass transfer resistance in the SP cannot be
accurately represented by a simplified version of diffusion across a spherical particle
[41]. The accurate and correct expression was derived earlier.
Therefore, in a nutshell, it will prove to be useful to understand the differences
between the two theories. Rate theory is a concept in chemistry that describes the
process of peak dispersion, and it provides an equation to calculate the variance per
unit length of the column. This theory is very useful in column chromatography. It
describes the features of chromatographic separation by comparing the rate of the
analyte that elutes through the column. So it provides a more realistic description of
the processes that work inside the column. Plate theory is a concept that describes
separation in the form of theoretical plates, which is the site where the equilibrations
between the SP and MP occur. Thus, it provides a hypothetical description of the
processes that work inside a column.
From the Van Deemter plot, the flow rate corresponding to minimum plate height
and subsequently maximum column efficiency can be obtained. Values higher than
this will lead to peak broadening. The temperature of separation will affect the lon-
gitudinal diffusion and the mass transfer, and an increase in temperature enhances
the rate of movement of the solute between the two phases, resulting in faster elution
and narrow peaks on the chromatogram.
Column selectivity also affects the resolution in addition to efficiency. Column
selectivity is defined by the relative separation α between the two peaks and is rep-
resented mathematically as below, wherein tR1, tR2, and to are the retention times of
solutes l, 2, and retained components, respectively, and K1 and K2 are the distribution
coefficients of solutes l and 2, respectively. For a good resolution, selectivity is more
important than efficiency as resolution is directly related to selectivity but is qua-
dratically related to efficiency; thus, a fourfold increase in N is needed to double RS.
t R 2 − t0 K
a= = 2 (7.4)
t R1 − t 0 K1
Band broadening can occur in the injector, connecting tubings (the parabolic flow
profile caused by friction at the walls), inside the detector, and sometimes due to slow
electronics in the detector or the data system.
Column capacity or retention factor k′ is the time a solute spends in/on the SP rela-
tive to the MP. The low values of k′ signify less retention, and components get eluted
close to the solvent front, leading to poor separations, and this problem normally
arises due to overuse/misuse of the column (loss of functional groups). The higher
values of k′ result in improved separation but can result in broad peaks and longer
analysis time. For a good separation of practical importance, the k′ values should be
within the range of 1–15.
Quantitation is the final step in chromatography once well-resolved peaks are
obtained. The peaks are identified by comparing VR / t R (or preferably the adjusted
retention times) to that of standards separated under identical conditions. But there
is always a danger of different compounds having identical retention times, and thus,
this is countered by using different techniques like spiking of samples with known
compounds and comparing the chromatograms of original and spiked samples to
confirm the peak identity. In order to calculate the concentration of the solute using
peak area or peak height, the quantification can be carried out using either external
standard or internal standard methods. In the external standard method, a series of
standards of known analyte concentration is analysed. The peak height or area is
plotted as a function of analyte concentration, giving a curve known as calibration
curve. The sample is then analysed under identical condition, and using its peak
height or area, the concentration can be computed from the calibration curve. In
this technique, irreproducible injections can cause errors in analysis. Therefore,
automatic injectors and sampling valves can be used instead of manual injection
to reduce these errors. If there are no suitable external standards available, then at
times, the detector response factors may be used to allow calibration with one com-
pound. Here, the ratio of concentrations of the unknown to known is equated to the
response of the two, thus allowing easy calculation of the unknown concentration. In
the internal standard method, an internal standard (compounds with sufficient simi-
larity to the target analytes but not present in the sample) is added to the sample prior
to analysis. Internal standard compounds must also be readily separated from any of
the compounds in the sample. It is better to add internal standard compounds at the
beginning itself, thus making the procedure quite easy to follow. The concentration
of the internal standard should be in the same range as that of the sample. The area
of the internal standard is used to normalize the areas of all other sample peaks, thus
eliminating the effect of differences in injection volumes or dilutions.
7.5 INSTRUMENTATION OF LC
The basic components of a LC system are schematically represented in Figure 7.3.
The process involves sample injection into a column packed with a SP, wherein the
individual sample components traverse through the column by a liquid (MP). The
components of the sample are separated from one another on the column due to
chemical and/or physical interactions between solute components and the SP. The
separated components are collected at the column exit and identified using a detector.
High-performance columns filled with packing materials of very small particle
size (diameter: 3–10 microns) are used, making it essential to force the eluent using
a high-pressure pump (unlike in conventional column chromatography where gravity
plays a major role). The pump can be single-piston or dual-piston, which ensures a
pulse-free flow of the eluent (using pulse dampeners with a single-piston pump and
electronic circuitry with a dual-piston pump). The sample is injected into the system
at atmospheric pressure via a three-way valve (volume of 10 µL–100 µL), of which
two ports are connected to the sample. The valve is then switched to inject mode to
FIGURE 7.3 Schematic representation of instrumentation of LC (drawn with reference to

https://commons.wikimedia.org/wiki/File:HPLC_apparatus.svg)
allow the sample to mix with the MP. After switching the injection valve, the sample
is transported to the separator by the MP. The column is very important, and the
choice of a suitable SP and the use of appropriate experimental conditions become
very critical in deciding the quality of analysis. HPLC can be divided most com-
monly into RPC, NPC, and ion chromatography. The method of selection is based on
the nature of the solutes to be separated.
7.5.1 Normal and reverse phase chromatography

NPC was invented first, and hence it is termed normal. In this, a highly polar material
(silica) is used as the SP, while non-polar solvents are used as the MP [42]. Alumina
is favoured for the separation of unsaturated bonds. Moderately polar-bonded
phases (egcyanopropyl- (CH 2 ) 3−CN , diol−(CH 2 ) 3−O−CH 2−CHOH−CH 2−OH ,
aminopropyl−(CH 2 ) 3−NH 2 ), chemically bonded on a silica gel support can also
be used in the NPC mode. This technique was earlier known as adsorption or
liquid–solid chromatography as the retention on inorganic sorbents is due to interac-
tions of the polar surface groups with the analytes. MP is a mixture of two or more
organic solvents of different polarities. The polarity of SPs in NPC is stronger in
comparison to that of the MP. Sample retention increases on more polar SPs and in
less polar MPs. The strength of interactions with analytes increases in the order of
cyanopropyl<diol<aminopropyl<< silica ≈ alumina SPs. The silanol groups in silica
gel strongly attract basic analytes, while the presence of aminopropyl groups on sil-
ica makes it useful for the separation of acidic solutes (alcohols, esters, ethers, and
ketones). Monolayer sorption is the main mechanism of retention of solutes on the
SP by displacing the solvent molecules already sorbed onto the surface. This is gov-
erned by the sorption efficiency and also the solvent strength of the MP. In addition to
this, liquid–liquid partition may also occur. It is essential to use dehydrated solvents
to achieve excellent separations in NPC. The elution times in NPC is the least for
alkanes and the highest for carboxylic acids (alkanes < alkenes < aromatic hydrocar-
bons ≈ chloroalkanes< sulphides < ethers < ketones ≈ aldehydes ≈ esters < alcohols
< amides << phenols, amines, and carboxylic acids). The retention also decreases as
the size of the alkyl group in the solute increases. NPC has several practical advan-
tages like its applicability for the separation of positional isomers (due to different
shapes such as rigid planar, rod-like, or flexible chain structure) and reduced pressure
drop across columns which are quite stable and do not deteriorate. It is quite easy to
understand that NPC is not suited for the separation of ionic and polar compounds.
Very hydrophilic or ionic compounds are usually too strongly retained on polar sor-
bents with very less or no solubility in the organic MPs commonly used in NPC.
The chromatography that uses conditions in reverse to normal chromatography is
known as reverse phase liquid chromatography (RPLC) [43]. RPLC uses a column
containing highly non-polar modified silica produced by its reaction with a halo-
gen-substituted organosilane. Thus, the modified silica may contain two, eight, or
eighteen carbons, bonded at their ends through Si-O- Si groups to the surface of the
support. Usually, octa C8 (8-carbon chain) and octadecyl C18 (18-carbon chain) are
used. C8 column is less hydrophobic and less dense compared to the C18 column,
leading to decreased retention times and reduced separation in C8 compared to the
C18 column. Since the columns are highly non-polar in nature, the solutes (usually
organic molecules) are retained due to dispersion within the medium.
Solvent delivery system is used for pumping solvents. The solvent is filtered to
remove suspended particles to avoid damage to pumps and column plugging. The
filtered solvent is then degassed by purging with helium to remove dissolved air to
avoid disruption of detector signal. Vacuum filtration helps achieve both the pretreat-
ments simultaneously. A HPLC pump should deliver a constant, pulse-free flow, and
a reciprocating dual-piston pump is commonly used. Each piston moves in a small
chamber with a very low volume of eluent, which is continuously passed through by
check valves. When one piston slows, another one filled with MP pushes the MP,
leading to pulse-free flow. Before shutting down the instrument, it is crucial to rinse
the pump to remove salts, which will cause abrasion of pump components. Narrow-
bore stainless steel tubing connectors are used as increased diameter or length of a
tubing will affect the separation efficiency. Solvent gradient systems used for a mix-
ture of solvent composition at low pressure. A six-port injector is used for high-pres-
sure systems. These systems are equipped with a fixed volume loop of tubing that
serves as the sample loop that is loaded with a standard blunt-tipped syringe. Sample
loop sizes range from 1 to 100 µL for the analytical or preparatory scale. The advan-
tage of an automatic sampler is that numerous samples can be automatically analysed
by a computer-controlled system. An in-line filter is present immediately after the
injection valve to remove any remaining particles in the MP to prevent clogging of
the guard or analytical column. Guard columns are miniature versions of the analyti-
cal (separation) column containing the same material as SP. Guard columns typically
cost one-fourth or less of the cost of an analytical column. The analytical column
on which solutes are separated is very important and are available in different sizes,
namely, preparatory column (20 – 50 mm in diameter X 50 – 250 mm in length),
analytical column (4.5 mm in diameter X 12 – 25 mm in length), narrow-bore ana-
lytical columns (1 – 2 mm in diameter X 10 cm in length), capillary columns for MS
detectors (from 0.075 to 0.1 mm in diameter). Larger columns require more volume
of the MP to push the analytes through the system.
The choice of eluent is dependent on the nature of sample and the column to be
used. In RPC, polar eluents like water and low-chain alcohols are used. The most
polar solutes come out first from the column as they are least retained. Polarity index
P’ gives the strength of polarity of the MP. A higher value of P’ indicates a more
polar eluent. Generally, in separation, a mixture of solvents is used. The polarity
index of the mixture M (PM) containing solvents A and B can be calculated using
individual polarity indices (PA and PB, respectively) and their respective volume frac-
tions (VA and VB, respectively).
PM = PA * VA + PB * VB (7.4)
The effect of eluent polarity on the capacity factor k’ of a solute is expressed math-
ematically by Eq. 7.5, wherein P1 and P2 are the polarity indices of two eluent mix-
tures. The eluent must be able to keep the sample components in solution. Viscosity
of an eluent is also important because a less viscous solvent can be passed at a high
flow rate without increasing the pressure to a great extent.
k2 ( P2 − P1 )
= 10 2
(7.5)
k1
In RPC, the separation is carried out with a MP, e.g. a mixture of water and polar
organic solvent like acetonitrile or methanol. This typically ensures the proper inter-
action of analytes with the non-polar, hydrophobic particle surface. A C18-bonded
silica (ODS) is the most popular type of reversed-phase HPLC packing. The more
polar analytes elute first, leaving the less polar analytes to be retained longer on the
column.
The detection system is a very important part of instrumentation. In HPLC, a
refractive index detector is considered to be a universal detector. But this detector
needs excellent thermostat conditions and should be less selective and not suited
for gradient elution. Ultraviolet absorption detectors are quite extensively used in
the wavelength region of 210–900 nm. Below 210 nm, this is not suitable as most
of the solvents would absorb in this spectral region. The sensitivity of the detector
is found to be excellent. Fixed-wavelength detectors, PMT and photo diode array
(PDA), are different types of detectors that can be used. A fixed-wavelength detec-
tor is not versatile as only compounds absorbing in that particular wavelength can
be analysed. However, variable wavelength detectors with a continuum source are
much more versatile. These detectors have a monochromator to select the desired
wavelength. Detectors like PDA can rapidly scan over a range of wavelengths and
so give both qualitative and quantitative information. In this detector, the diodes are
arranged such that each diode intercepts different bands of wavelength. The flow
detectors are designed in Z-shape to have a large path length within a small vol-
ume. Fluorescence detectors are quite sensitive but are limited to fluorescent com-
pounds. Non-fluorescent compounds may be derivatized by adding a post-column
reagent or may be determined by monitoring the reduction of the fluorescence of the
eluent. This is known as “vacancy chromatography”. Fluorescence detectors use a

high intensity energy line (mercury lamp) or continuous source (deuterium or xenon
arc) sources. A monochromator is used to select the wavelength for excitation and
for emission, and a photomultiplier is used to amplify the weak emission signals.
Fluorescence detectors are very sensitive but require very stringent conditions. The
dissolved gases in solvents lead to quenching of signals, so degassing of solvents is
important. Mass spectrometer is a very useful detector, but its interfacing with a
HPLC system is difficult. Care should be taken that the solvent does not reach the
vacuum system. Hence, the instrumentation is quite complex.
7.5.2 Ion chromatography
Ion chromatography is used for the separation of ionic species by using an ion
exchanger resin as SP. The principles of ion exchange govern the separation [39].
Modern ion chromatography separations can follow any of the basic mechanisms
of ion exchange, ion exclusion, and ion pair formation. IEC (commonly high-perfor-
mance ion chromatography) is based on an ion-exchange process occurring between
the MP and ion-exchange groups bonded to the support material (SP) (generally
a polymer containing sulphonate or quaternary ammonium groups). Ion-exclusion
chromatography (high-performance ion chromatography exclusion, HPICE) is
steered by exclusion (Donnan and steric) and sorption using a sulphonated polysty-
rene/divinylbenzene-based cation ion exchanger as the SP. Ion-exclusion chromatog-
raphy is useful for the separation of weak inorganic and organic acids (amino acids,
aldehydes, and alcohols) from completely dissociated acids that are unretained and
eluted without resolution along with void volume. Ion-pair chromatography (mobile
phase ion chromatography, MPIC) uses neutral porous divinylbenzene resin or chem-
ically bonded silica (octyl/octadecyl) of low polarity and high specific surface area
as SPs. The selectivity is determined solely by the MP, which contains an ion-pair
reagent which will react with the components of the sample to a different extent. It is
suited for the separation of transition metal ion complexes.
Ion exchange is the process wherein ions in the liquid phase (electrolyte solu-
tion) stoichiometrically exchange with the labile ions of the insoluble solid phase (ion
exchanger) containing fixed ionic sites. Cation exchange resins have fixed anionic
sites and labile cations, while anionic exchange resins have fixed cationic sites
and labile anions [44]. Amphoteric ion exchangers can exchange both cations and
anions. It is very common that the labile cation in a cationic exchanger is a proton
that is released in stoichiometric amounts when a cation in solution, say Na+, gets
exchanged. Similarly, anionic exchangers have the labile OH anion, which can be
released into a solution by different anions like chloride, iodide, etc. Ion exchangers
possess a fixed surplus positive or negative charge (depending on the nature of resin
AER/CER). This is charge neutralized by ions of opposite charge, known as counte-
rions. The counterions move within the matrix and can be replaced by ions of same
charge present in the solution. This is thought of as a sponge with the ions floating
in pores [39]. When put in an ionic solution, the ions move in and out of the sponge
in a stoichiometric ratio until equilibrium is reached. This simple model helps in
understanding the electrostatic interactions but not the selectivity. Ion exchange is
a stoichiometric reaction between the labile ions on the resin and similarly charged
ions in the solution. Ion exchange resins classified as cation and anion exchange resins
can be further classified as strong and weak resins depending the functional groups
on the resin (the fixed ion). Apart from being classified into cationic and anionic, ion
exchangers can be further classified into strong and weak. Resins having SO3H and
COOH functional groups are classified as strong and weak cation exchange resins,
respectively. The pH of operation for a strong resin is in the range of 0–14, while for
a weak resin, the optimum pH is 7–14. The regenerant used for a cationic exchanger
is acid. In case of an anionic exchanger resin, the presence of a tetrammonium group
makes it a strong anion exchanger, which is useful in the high alkaline pH range of
10–14. The presence of a polyamine group makes the resin weak, and this resin can
be used in the pH range of 1–7. Anionic exchanger resins are regenerated using a
base.
Capacity is the parameter used to characterize the ion exchangers and is inde-
pendent of experimental conditions. It is defined as the number of ionogenic groups
present per specified amount of ion exchanger with units of meq/g of dry resin (H+
and Cl− for CER and AER, respectively). For a resin-packed column bed, technical
volume capacity is expressed as eq/L. Apparent or effective capacity is the experi-
mentally determined capacity that is dependent on experimental condition (pH and
solution concentration) and is lower than maximum capacity. The selectivity coeffi-
cient, K, gives an idea of selectivity between ions and is dependent on various factors
of the ions such as valency (higher valent ions preferred: tetra > tri > di > mono),
ionic radius (the higher the radius, the less the hydration and higher the uptake),
polarizability (the higher the polarizability, the better uptake), and complexing abil-
ity (the lower the tendency to form complexes, the higher the uptake).
SPs in ion chromatography contain organic polymers with good chemical sta-
bility. Different types of materials such as polymer-based, latex-agglomerated, and
silica-based anion exchangers are used as SP. Styrene/divinylbenzene copolymers
are favoured due to their stability in the pH range of 0–14. Latex-agglomerated anion
exchangers are a special type of pellicular anion exchangers consisting of fully ami-
nated porous polymer beads of high capacity, called latex particles (diameter 0.1 µm)
agglomerated to the surface-sulfonated polystyrene/divinylbenzene substrate (with
particle diameters 5–25 µm). The SP consists of three chemically distinct regions,
namely, an inert and mechanically stable substrate, a thin coating of sulphonic acid
groups over the substrate, and an outer layer of latex beads containing the anion
exchange groups. Although the latex polymer has a very high exchange capacity
(due to its complete amination), the small size decreases the ion exchange efficiency.
The surface sulphonation thwarts the diffusion within the SP. These anion exchang-
ers have better mechanical and chemical stability, faster ion exchange process, and
better separation efficiency compared to silica-based anion exchangers and directly
aminated resins. The high chromatographic efficiency of the separator column is
attributed to the reduced swelling and shrinking of the small-sized latex beads owing
to surface functionalization. Silica-based anion exchangers, contrary to organic
polymers, have the advantages of higher chromatographic efficiency and greater
mechanical stability even at elevated temperatures as there are no issues associated
with the shrinking or swelling of particles with change in experimental conditions.
However, they have a restriction of use in a narrow pH range of 2–7. Macrocyclic

SPs with electrically neutral macrocyclic compounds (crown ethers, cryptands, and
calixarenes) can be used for separating anions (they form complexes with metal ions
selectively, and anions will be part of the complex). The metal ion of the MP forms
a complex with the macrocyclic compound, leading to a positive surface which can
separate anions in the sample.
MPs generally are organic solvent buffers that have several specifications with
respect to MP pH, buffer capacity, elution strength, complexing ability, counterion
quality and concentration, and compatibility with the detection method. For the
determination of anions and cations, multi-protic weak acids and bases, respectively,
are added to the MP. The increase in pH of the MP increases its interaction with the
SP, leading to displacement of ions from the SP. The pH maintained by the buffer
should be as close as possible to that of the samples. Moreover, very high buffer con-
centrations can affect the retention of the ions on the SP and sometimes the complex-
ing ability of the MP in the case of cation separation. The nature of the eluent used in
anion chromatography is mainly dependent on the detection mode.
Chemical suppression is an important aspect of ion chromatography. Previous
advances in suppressor functionality have focused on continuity, capacity, and high
sensitivity, thus negating the need for chemical reagents for suppression. However,
the use of a suppressor has become an imperative element in the anion analysis using
conductivity detection. The suppressor is placed between the column and the detec-
tor to reduce the eluent background conductivity and also to enhance the conductiv-
ity of analyte ions. A high-capacity cation exchange membrane or resin in the acid
form is used as a suppressor, which will remove the metal ions from both the eluent
and the sample solution. This will not only reduce the background conductivity of
the eluent but also enhance the signal of the analyte. The suppressor module consists
of three cartridges filled with cation exchanger material, which will be sequentially
placed prior to the analysis. The first cartridge is used for suppression, and at the
same time, the second one is regenerated (with dilute sulphuric acid) and the third
cartridge is rinsed with the eluate or water. Prior to each analysis, a freshly regen-
erated and rinsed cartridge is made available by rotation to 120°. Some instruments
also have an electrolytically regenerated suppressor, which has features similar to
that of a chemically regenerated suppressor. The only difference is that suppression is
carried out by protons generated by water electrolysis. The use of hyphenated detec-
tion increases the back pressure placed on the suppressor, and the efficiency of newly
developed packed columns also depends a great deal on the suppressor’s efficiency.
Thus, next-generation suppressors must have lower peak dispersion properties to
support these columns. Previous generation electrolytic suppressors are very good
at maintaining their regenerated form electrolytically, but if the suppressor loses its
regenerated form (e.g. due to operation without current during installation), the per-
formance suffers, and chemical regeneration is needed before again proceeding with
electrolytic regeneration. Thus, future generation suppressors should be more current
efficient and have sufficient static capacity to recover from this condition without the
need for chemical regeneration. This is known as electrolytically regenerated sup-
pressor, which has very high back pressure tolerance and is used in Reagent-Free™
Ion Chromatography (RFIC™) systems.
Detectors that are normally used ion chromatography, conductivity detectors, and
UV-visible spectrophotometry are very commonly used. Fluorescence-based and
electrochemical detectors are used for specific analysis. The other detection modes
that can be combined with IC are atom absorption (AAS), inductively coupled plasma
atomic emission spectrometer (ICP), and mass spectrometry (MS).
7.6 APPLICATIONS OF CHROMATOGRAPHY
Chromatography is considered as an omnipresent technique due to its versatility,
simplicity, well-developed properties. The applications of chromatography are vast
and often interdisciplinary. However, there is ongoing research on its applications
in the analysis of various water bodies such as waste water and seawater. The great
potential of chromatography in the analysis of water samples is due to the high-speed
separations which are very simple. LC holds a special place in order to circumvent
the limitations associated with other techniques (time-consuming, difficult to auto-
mate, low sensitivity, and poor selectivity due to spectral and chemical interferences).
Ion chromatography is the most oft-used technique for the determination of ionic
solutes. Ion chromatography was developed by Small et al. for the determination of
alkali, alkaline earth, and ammonia cations using surface-sulphonated styrene–divi-
nylbenzene copolymer resin.
The development of latex-coated DionexIonPac CS3 columns made it possible for
the determination of ammonium ions [45] and different cations [46]. Analytical
columns packed with iminodiacetic acid (IDA)-derivatized silica were used to sepa-
rate alkali metal ions and ammonium ions in combination with non-suppressed
conductivity detection [47]. The simultaneous separation of alkali and transition
metals under isocratic conditions was achieved with an eluent comprising
10 mmol/l 18-crown-6 , 1.5 mmol/l dipicolinic acid , and 1.9 mmol/l nitric acid . The
chromatographic system enabled the quantitation of alkali metal ions with detection
limits in the low parts per billion range and excellent linearity. Ion chromatography
has been successfully used for the simultaneous determination of cations and anions.
The simultaneous determination of cations and anions in one sample injection has
been shown to depend on eluent selection [48]. Ion chromatography has scored over
atomic spectrometric techniques due to its relatively low cost, ease of automation,
online capability, and relatively wide dynamic range. Lanthanides have been deter-
mined by either cation or anion exchange chromatography using spectrometric detec-
tors. Low- and high-molecular-weight amines were determined by either cation
exchange or ion-pair chromatography, using conductivity detector in the suppressed
or non-suppressed mode. The International Standard Organization (ISO) published
Method 14911 for the simultaneous determination of dissolved alkali and alkaline
earth cations, ammonia, and manganese in water and waste water is based on sup-
pressed ion chromatography. Chromatography has become a well-established method
for regulatory purposes as adopted by ISO, US EPA, and the American Society for
Testing and Materials (ASTM) for environmental samples. ISO 14911 (1998) is a
method for water quality monitoring involving the determination of
Li+ , Na + , NH 4 + , K + , Mn 2+ , Ca 2+ , Mg 2+ , Sr 2+, and Ba 2+ in drinking water, waste
water, and groundwater. ISO 10304-3 (1997) involves the determination of dissolved
anions like chromate, iodide, sulphite, thiocyanate, and thiosulphate by in waste

water. ISO 16749 (2005) is the IC method for the determination of hexavalent chro-
mium in airborne particulate matter using spectrophotometric determination using
diphenylcarbazide. US EPA Method 200.10 (1997) is used for trace element determi-
nation in marine water, brines, seawater, and estuarial waters for the determination of
Cd 2+ , Co 2+ , Cu 2+ , Pb 2+ , Ni 2+ , VO2+ , VO2 2+ , UO2 2+ by online chelation pre-concentra-
tion and inductively coupled plasma mass spectrometry detection. US EPA Method
200.13 (1997) gives the protocol for the determination of trace elements
Cd 2+ , Co 2+ , Cu 2+ , Pb 2+ , Ni 2+ in marine water, brines, seawater, and estuarial water by
offline chelation pre-concentration with graphite furnace atomic absorption detec-
tion. US EPA Method 218.6 (1994) gives the standardized method for the determina-
tion of dissolved hexavalent chromium in drinking water, groundwater, and industrial
effluent waste waters by ion chromatography. Different ASTM methods using ion
chromatography have been developed. D5257 - 93 Standard Test Method is used for
the determination of dissolved hexavalent chromium in drinking water, groundwater,
and waste waters. D6504-00 standard practice is used for online determination of
total conductivity of cations like Li+ , Na + , NH 4 + , K + , Mg 2+, and Ca 2+ in high purity
water. D6832-02 Standard Test Method is used for the determination of hexavalent
chromium in workplace air by ion chromatography coupled with spectrophotometric
measurement using 1,5-Diphenylcarbazide as the chromophore. D6919-03 Standard
Test Method is utilized for the determination of alkali and alkaline earth cations
and ammonium (Li+ , Na + , NH 4 + , K + , Mg 2+ , Ca 2+ ) in reagents, surface water,
groundwater, and waste waters by ion chromatography. D6994-04 Standard Test
3-
Method is used for the determination of metal cyanide complexes (Fe (CN)6 ,
4- 4- 4- 4- 5-
Fe(CN)6 , Co(CN)6 , Cu(CN)6 , Ni(CN)6 , Ag(CN)6 ) in waste water, surface
water, groundwater, and drinking waters using anion exchange chromatography cou-
pled with UV detection. UOP 959-98 is a method for the determination of ammo-
nium ions in drinking and waste waters using ion chromatography. WK653 is the
method for the determination of dissolved alkali, alkaline earth cations, and ammo-
nium in reagents, surface water, groundwater, and waste waters by ion chromatogra-
phy. Dionex published methods for determination in various types of samples. AN4
is the method for the analysis of engine coolants, while AN25 is used for the determi-
nation of inorganic ions and organic acids in non-alcoholic carbonated beverages.
AN69 and AN72 are the established protocols for Al in complex matrices and the
determination of trace metals (Cd 2+ , Co 2+ , Cu 2+ , Fe 2+ , Fe 3+ , Pb 2+ , Ni 2+ , Mn + , Zn 2+ ,
VO2+ , VO2 2+ ) in water-miscible organic solvents (water, alcohols, and acetonitrile)
by ion chromatography/inductively coupled argon plasma spectroscopy (IC/ICAP),
respectively. AN73 is the method for the determination of trace transition metals
(Cd 2+ , Co2+ , Cu2+ , Pb2+ , Ni2+ , Mn+ , Zn 2+ , Al3+ ) in reagent-grade acids, bases, and
their salts with IC/ICAP. AN77 gives the protocol for the determination of transition
metals using chelation ion chromatography after the elimination of interferences of
iron and aluminium. AN79 gives the protocol for the estimation of U and Th in com-
plex matrix water samples, while AN80 is the method for the determination of dis-
solved hexavalent chromium in drinking water, groundwater, and industrial waste
waters. Trace-level determination of cations in power plant samples and concentrated
acids is given by protocols AN86 and AN94, respectively. The determination of

alkali, alkaline earth, and ammonium ions in pharmaceuticals is given by AN106.
AN108 is the protocol for the determination of transition metals in serum and whole
blood by IC. The determination of Ca and Mg in brines is described in protocol
AN120. The determination of transition metal ions in ppt levels in high purity water
is given by AN131. Trace-level lithium determination in industrial process waters is
illustrated in AU137. AN141 gives the details of the estimation of inorganic cations
and ammonium in river, lake, ground, and sea waters using the IonPac CS16 column.
AN144 is the methodology for the determination of hexavalent chromium in drinking
water, while AN152 gives the details for the determination of Na (ppt) in the pres-
ence of high concentrations of ethanolamine in power plant waters. A reagent-free
method is reported (AN 155) for the determination of cations and amines in hydrogen
peroxide. AN158 is the method for the determination of trace sodium and transition
metals in power industry waste and reagent waters. TN24 and TN26 give methods
for the determination of Cr (Cr 3+ , CrO 4 2− ) by IC in wastewater and solid
waste extracts. TN27 is the protocol for the determination of lanthanides
(La 3+ , Nd3+ , Pr 3+ , Ce3+ , Gd3+ , Tb3+ , Dy3+ , Tm3+ , Yb3+ ) in digested rock samples by
chelation ion chromatography. The most common application of ion chromatography
is in the determination of alkali, alkaline earth metals, and ammonia. With the publi-
cation of ISO14911 Method, there was a surge in the utility of ion chromatography
for cation analysis. All these methods used a wide range of separation columns, both
commercially available (DionexIonPac CS12 and DionexIonPac CS12) and laborato-
ry-made (IDA-bonded silica column). The eluents were also varied to a great range
including EDTA, sulphosalicylic acid, and sulphuric acid, to name a few.
Determination and, more specifically, the speciation studies of heavy, transition, and
rare earth metal ions have become crucial due to the absence of simple and sensitive
spectrometric methods. Therefore, hyphenated techniques based on chromatographic
separation (IC) combined with highly selective and accurate detection modes
(ICP-MS and ICP-AES) have gained more popularity [49, 50]. But the high cost is
the main hurdle in the extensive use of hyphenated techniques. The determination of
heavy metal ions requires complexation prior to separation in order to reduce hydro-
lysis of these metal ions and also to induce selectivity. The main care that needs to be
taken is that the complexes do not precipitate within the column. Different ligands
like oxalic acid, tartaric acid, citric acid, pyridine-2,6-dicarboxylicacid (PDCA),
α-hydroxyisobutyric acid (HIBA), ethylenediaminetetraacetic acid (EDTA), etc., are
used. Ion chromatography of metal–EDTA complexes can be carried out using
anion-exchange columns enabling the separation of anions and cations
(Fe2+ , Pb2+ , Cu2+ , Zn 2+ , Ni2+ , Co2+ , Cd 2+ , Fe3+ ) as anionic complexes in the same run
[46–48]. It has also been observed that the interferences may be overcome by using
chemically bonded phases [49, 50]. Different approaches including hyphenated tech-
niques [51–54] have been used for the separation of metal ions. A large number of
methods have been reported wherein different combinations of SP, eluents, and
detectors have been used for the analyses of transition metal ions in a variety of sam-
ples [55–80]. The analysis of natural waters by ion chromatography alone covered
about 99.96% of total cation and anion composition, and an excellent correspondence
of the anion–cation balance was achieved. The use of various columns like AG4A,
AS4A 1, AG5, AS5 1, AG12, CS12 1, Dionex, and IonPac in conjunction with elu-
ents like sodium carbonate, bicarbonate, benzoate, citrate, methanesulphonic acid,
oxalic acid, etc., have been utilized for analytical purposes using conductivity and
spectrophotometric detectors.
In any method or instrumental development, the classical editorial of Herbert
Laitinen on “The Seven Ages of an Analytical Method” [81], developed in analogy
to Shakespeare’s Seven stages of Man, should be kept in mind. According to this, the
first stage is the initiation or conception phase [81], and the work carried out by H.
Small was indeed the first stage in ion chromatography. When the work was awarded
the Pittsburgh Applied Analytical Chemistry Award, the direction for the second
stage was laid out to carry out a large number of experiments in different laborato-
ries. The results were presented in the conference on Ion Chromatographic Analysis
of Environmental Pollutants in 1978 [82]. This conference was dedicated “To the
individual who does the best (s)he can with what (s)he’s got” – best indicates the state
of the field at this period [82]. The third stage is instrumentation development. In this
stage, the method is brought into the hands of a non-specialist, and Model 10 Ion
Chromatograph was demonstrated in the 1975 American Chemical Society (ACS)
meeting in Chicago, IL, for which Dionex Corporation and Dow were awarded the
1977 Vaaler Award and 1977 IR100 Award [82]. The fourth stage involves detailed
studies and improved instrumentation and ion chromatography matured as an analyt-
ical technique and various changes in both instrumentation and development of meth-
ods for specific samples were carried out [83]. It was in this stage that ASTM method
for anions in water was first approved in 1984. IN 1898, an organization known as
American Society for Testing and Materials (ASTM) was founded to improve prod-
uct quality and personnel safety. ASTM test procedures are developed by experts
for every industry. Thus the development of ASTM methods for anions was a mark
of authentication of ion chromatographic analysis. Different ASTM methods were
developed for determination of anions in water by suppressed ion chromatography
(ASTM D 4327); for chloride, nitrate, and sulphate in atmospheric wet deposition
by chemically suppressed ion chromatography (ASTM D 5085); and for dissolved
hexavalent chromium in water by ion chromatography (ASTM D 5257). The deter-
mination of dissolved alkali, alkaline earth, and ammonium cations in drinking,
ground, and municipal water samples has been reported (ASTM D 6919-032).
In the fifth and sixth stages, the applications become extensive into a wide range of
fields with suitable modifications to the procedures. The seventh stage is the period of
senescence when there are competing techniques that try to overshadow this method.
Ion chromatography has undergone a tremendous development and offers an enor-
mous range of possibilities for the selection of SPs and MPs, fabrication of novel
separation modes, and hyphenation with different detection techniques. Ion chroma-
tography can be carried out in 2D-IC and hyphenation techniques like ion chroma-
tography-mass spectrometry (IC-MS) and in capillary mode resulting in capillary
ion chromatography (CIC). High temperature IC is the new development based on
the fact that at temperatures above 140°C, the dielectric constant of water is similar
to that of hydrophobic organic solvents, and also the viscosity of a MP is decreased
leading to reduced back pressure of the column. This leads to improvement of mass
transfer within the column, enabling rapid separations with no peak tailings for com-
plex separations. For anion exchange separations, the effect of temperature on selec-
tivity can be quite complex coupled with the possible degradation of the column
materials at above 60°C. Conversely, temperature offers significant opportunities for
cationic separations as these columns are stable. Ion chromatography has been used
for the analysis of nuclear materials. A recent review discussing the methodologies
developed for the characterization of nuclear materials and related trace impurities
using ion chromatography has been reported [84]. The studies used for monitoring
of fuels, coolants, and control rods of a nuclear reactor have been discussed. Due to
scientific and technical progression, modern instrumentation with elegant instrumen-
tation, and efficient columns, IC finds extensive applications in various fields.
7.7 CONCLUSIONS
LC appears to be a versatile analytical technique. It separates the species present in a
solution based on their affinities for the two phases. Ion chromatography is used for
the separation of ions based on their affinities for an ion exchanger (SP). It has been
observed that many detectors like AAS, multiple collector ICP-MS, thermal ioniza-
tion mass spectrometry (TIMS), electrical conductivity, and UV detectors are used.
IEC is a popular purification method of proteins, peptides, nucleic acids, and other
charged biomolecules, preferred for its high resolving power, high protein binding
capacity, versatility with different types of ion exchangers, versatility with compo-
sition of buffers and pH, straightforward separation principle (primarily accord-
ing to differences in charges), and ease of performance. IEC is a technique often
used in protein purification, water analysis, and quality control, and it can be used
for large proteins, small nucleotides, and amino acids. The principle of IEC is that
charged molecules bind electrostatically to oppositely charged groups that have been
bound covalently on the matrix. Wastewater samples can also be analysed using the
ion chromatography as it has many advantages like good accuracy and precision,
high selectivity, high speed, and separation efficiency. It is also used to develop the
method, and the consumables are not expensive. But there is always a scope to impro-
vise and develop new methods to improve the analysis parameters.
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8 Broad conclusions and
future perspectives
Analytical chemistry is known to be the basis of all studies. In this field, separation
and sensing are two most important aspects. Separation science plays a crucial role
in our daily life. It not only helps us in carrying out our daily activities but also helps
in maintaining the quality of our life. The incessant growth of industries has made it
crucial for the development of separation processes, not only for purification but also
for monitoring of various important species. The role of separation also becomes
very important in the overgrowing need for remediation of environmental media. It
is very true that the field of separation science is ever growing due to the new chal-
lenges that arise and also to fill in the gaps of the present challenges. Thus, the field
of separation science could be used to achieve improved living for mankind and also
have efficient production, thus reducing costs.
The need for providing sustainable good quality water makes it necessary to adopt
remedial techniques and also have a set of standards not only for the specifications
of potable water but also for the reusability of water. For the past many years, reuse
of water has become an important requirement, and therefore, separate guidelines
are needed. EPA has developed the 2012 Guidelines for Water Reuse to incorpo-
rate this information through a Cooperative Research and Development Agreement
(CRADA) with CDM Smith and an interagency agreement with US Agency for
International Development (USAID). This shows the ever-growing research on the
advances in methodologies adopted for water reuse. With the presence of excellent
methodologies, it is possible to treat waste water and produce water deemed fit for
use. Thus, an integrated approach of water management is adopted, wherein non-con-
ventional water sources are also considered and the findings of various regulatory
bodies [National Research Council’s (NRC) Water Science and Technology Board
report, Water Reuse: Potential for Expanding the Nation’s Water Supply Through
Reuse of Municipal Waste water (NRC, 2012)] are integrated. Similarly, WHO has
also updated its guidelines. The guidelines can prove beneficial to those involved in
various aspects of water management, reclamation, or reuse. In such a study of inter-
disciplinary nature, the knowledge of various technical terms becomes very crucial.
De facto reuse is when the reuse is being practised but not officially recognized.
Direct potable reuse (DPR) is the introduction of remediated water into drinking
water treatment plants. Indirect potable reuse (IPR) refers to the augmentation of a
drinking water source (surface or groundwater) with reclaimed water followed by
an environmental buffer that precedes drinking water treatment. Non-potable reuse
refers to all other applications except that used for potable reuse (drinking purposes).
There are different types of applications of reuse of reclaimed water. In the urban
applications, the use of reclaimed water for non-potable applications in municipal
settings is known as unrestricted or restricted depending upon whether public access,
DOI: 10.1201/9781003442516-8 131

respectively. Public access can be controlled or restricted by physical or institutional

barriers (fencing or advisory signage). The water can be used for agricultural reuse
for irrigation of food crops and also other types of crops. The main motivation for
reuse is to augment the water resources to cope up with the ever-increasing demands
for water. The various benefits of reuse of water involve improved agriculture pro-
duce, decreased energy consumption of treatment processes, reduced nutrient loads,
etc. The main focus of all this integration is to address water supply scarcity, efficient
resource use, and environmental and public health protection. However, the key to
all these developments is sustainability. As per the Brundtland Commission report,
“Sustainable development is development that meets the needs of the present without
compromising the ability of future generations to meet their own needs”(WCED,
1987). Therefore, sustainable water management involves management of the present
resources to have no strain on future generations. It is now well understood by envi-
ronmentalists that both water and energy being interconnected make it essential to
consider each other. Therefore, the practice of water reuse can not only offset water
demands but also provide additional water for energy production. EPA has developed
principles for an energy–water future which emphasize on the use of waste water or
reusable water as a resource (EPA, 2012). Since water reuse is a great opportunity,
EPA has developed a handbook entitled Leveraging the Water–Energy Connection –
An Integrated Resource Management Handbook for Community Planners and
Decision-Makers, as a manual to be followed. The manual will address water conser-
vation and efficiency; alternative water sources, building codes for improved water
and energy use efficiency; and renewable energy sources from/for both water and
wastewater systems. In India, it is only in recent times that water and wastewater
sectors, especially wastewater reuse, have started attracting the attention of many.
However, many challenges like poor infrastructure and low social acceptance need
to be overcome to make the concept of water reuse a reality. The Central Public
Health & Environmental Engineering Organisation (CPHEEO) estimates indicate
that about 70 – 80% of total water supplied for domestic use gets generated as waste
water. As per CPCB estimates, the total wastewater generation from class I cities
(498) and class II (410) towns in the country is around 35, 558 and 2, 696 MLD,
respectively, while the installed sewage treatment capacity is 11, 553 and 233 MLD,
respectively, thereby leading to a gap of 26, 468 MLD in sewage treatment capacity.
It is known that states like Maharashtra, Uttar Pradesh, West Bengal, and Gujarat and
Delhi contribute to the major share (63%) of waste water (CPCB, 2007a), and reports
have shown that the industrial water use productivity of India is lowest. It is projected
that water scarcity would increase tremendously by 2050, and there would be a con-
current depletion of freshwater resources and also increased wastewater generation.
Thus, treated waste water can be used for irrigation of crops, maintaining parks
and golf courses, etc. Research on efficient, cost-effective, and sustainable treatment
protocols needs to be encouraged, and also the concept of phytoremediation should
be more seriously adopted. It is also important to have in-depth knowledge of indig-
enous or traditional methods, and the methods should be easily available for further
research.
It is to be understood that wastewater reuse has still not gained lot of attention due
to the associated problems and challenges. The great challenge is the development
Broad conclusions and future perspectives 133
of economically viable and easy-to-use techniques without causing huge changes

in the environmental system. The use of constructed wetlands as a means of phy-
toremediation is catching up due to inherent advantages like energy efficiency, ease
of operation, no secondary waste, and no need of highly qualified technical staff
to carry out the treatment. Thus, it is seen that wastewater treatment can not only
provide a healthy environment but can also increase the scope for reuse to overcome
water scarcity issues.
Water resource management is a complex process that not only looks for treatment
of waste water but also plays a major role in its sustenance. It is indeed a challenge due
to the increase in the demands and also the deterioration of water quality. So there are
different types of approaches involved. Unidisciplinarity is when a researcher is from
a single discipline who tends to work alone or collaboratively to address a common
question, problem, topic, or theme. Multidisciplinarity involves the focus of different
disciplines on a particular problem, resulting in an array of information, knowledge,
and methods, but disciplines remain separate. The existing structure of knowledge
is not questioned. Interdisciplinarity leads to the integration of information, data,
methods, tools, concepts, and/or theories from two or more disciplines focused on a
complex question or problem. The key defining concept of interdisciplinarity is inte-
gration of diverse inputs. The team would draw on multiple, integrated data sources
generated through the lens of interdisciplinary theory and use of interdisciplinary
methods. Transdisciplinarity leads to the transcending of disciplinary approaches
using more comprehensive frameworks, including synthetic paradigms. The con-
struct goes beyond interdisciplinary combinations of existing approaches and fosters
new worldviews or domains. Thus, water management requires extensive know-how
of hydrological aspects and conservation and treatment procedures, and should most
importantly be able to implement and integrate strategies to make it a community
and then a global effort. Researchers have suggested an interdisciplinary approach
to addressing challenges to water-related issues. Since the issues are complex, an
interdisciplinary approach was often needed to effectively confront these challenges.
Interdisciplinary research involves researchers with very different backgrounds to
understand and communicate with each other. But such collaborations may lead to
the need to cross one’s own field of expertise, which proves to be a stumbling block
in the success of such collaborations. The apprehensions and challenges can be easily
understood from the words of Hannes Alfven, “Scientists tend to resist interdisci-
plinary inquiries into their own territory. In many instances, such parochialism is
founded on the fear that intrusion from other disciplines would compete unfairly for
limited financial resources and thus diminish their own opportunity for research”.
But in the long run, this will be useful as pointed out by Robert J. Shiller, who said
“In the longer run and for wide-reaching issues, more creative solutions tend to come
from imaginative interdisciplinary collaboration”.
When it comes to water, a very famous quote by Poet Samuel Taylor Coleridge
(1772–1834) in The Rime of the Ancient Mariner (1798) goes: “Water, water, every-
where, And all the boards did shrink; Water, water, everywhere, Nor any drop to
drink”. It can be understood that despite having the resources, you cannot benefit
from it. In the case of water systems, this is directly related and conveys the fact that
the level of pollution has made it difficult to use the resources, and in common usage,
the above line is usually misquoted as “Water, water everywhere, but not a drop to
drink”. In this era, this is an intimidating reservation that scientists and technologists
and various other experts are trying to address. This intensive collaboration aims not
only to remove the toxic species from water bodies but also to reduce the discharge
of these effluents. As there are a large number of techniques that are developed and
still developing, it is only indicating how important the issues of water pollution and
subsequent remediation are.
In the end, it is only justifiable to quote Juan Evo Morales Ayma, a Bolivian poli-
tician, who said “Sooner or later, we will have to recognise that the Earth has rights,
too, to live without pollution. What mankind must know is that human beings can-
not live without Mother Earth, but the planet can live without humans”. Therefore,
the combined efforts of all the people is the only key to it, as Margaret Mead, an
American cultural anthropologist, pointed out: “Never doubt that a small group of
thoughtful, committed citizens can change the world; indeed, it’s the only thing that
ever has”.
Index
Note: Page numbers in italics indicate a figure on the corresponding page.
absolute errors 103 liquid (HPLC) 22 – 23, 109, 119;

absorption 23, 47 – 48 high-performance thin-layer
accuracy 103 – 104 (HPTLC) 106; high-pressure liquid
activated carbons 64 (HPLC) 105, 107; instrumentation
adsorption 47 – 48 of liquid chromatography 116 – 123;
Agre, Peter 78 ion-exchange (IEC) 105, 127; liquid
air flotation 92 chromatography 109 – 116; normal
alkaline white mud (AWM) 96 phase (NPC) 117 – 120; paper 106;
American Society for Testing and Materials partition 105; preparative 22; reverse
(ASTM) 126 phase (RPC) 117 – 120; reverse phase
analytical chemistry 101 – 104, 131 liquid (RPLC) 118 – 119; size exclusion
analytical chromatography 22 (SEC) 21; supercritical fluid (SFC)
atomic absorption spectroscopy (AAS) 103 106 – 108; thin-layer (TLC) 23, 106
chromium 63 – 64
Basic Red 9 dye 12 climate 12 – 13
Baudu isotherm model 59 climate change 13
bias 49 – 50, 103 – 104 co-precipitation 91
Big Carrousel mechanism 37 coagulation 89, 91 – 92, 95 – 97
biochemical oxygen demand (BOD) 8, 97 coliform 9 – 10
bioconcentration factor 75 column efficiency 110 – 111
biopolymers 66, 91 column liquid chromatography 107
bioremediation 71; see also phytoremediation column selectivity 115
blue water 9 composites 65 – 66
borosilicate glasses 64 compounds 19
Boyd diffusion model 61 conductivity 7
Brouers–Sotolongo isotherm model 57 – 58 constructed wetlands 75 – 76
contaminants 2, 64, 71, 74 – 76; see also dyes;
cadmium 10; see also heavy metals heavy metals
cake formation 92 – 93 counter-current chromatography (CCC) 23
calcium 63, 95 – 96 Cousteau, Jacques 5
capillary ion chromatography (CIC) 126 crystallization 21, 94
carbon dioxide (CO2) 7, 24, 107
cation exchange 37, 120 Day, David T. 104
centrifugal partition chromatography 23 desorption ratio 48
centrifugation 20, 21 dewatering 92
charcoal 61 – 62 diffusion boundary layer (DBL) 37
chemical oxygen demand (COD) 8 direct potable reuse (DPR) 131
chemical precipitation 87 – 94; applications of Disperse Orange 1 dye 12
95 – 97; metals and 88; precipitants for Disperse Red 1 dye 12, 97
radionuclide separation 96 dissolved air flotation (DAF) 92
chemical suppression 122 dissolved oxygen matter (DOM) 28
chemisorption 48 distillation 24
chromatography 22 – 23, 104 – 105, 110; affinity dithiocarbamate (DTC) 89, 91
23; analytical chemistry and DO 7 – 8
101 – 104; applications of 123 – 127; domestic effluents 10
chromatography and 104 – 105; drinking water 11
classification of 105 – 109; gas droplet counter-current chromatography
(GC) 21, 105 – 107; gel permeation (DCCC) 23
(GPC) 105; high-performance drying 21
135
136 Index
Dubinin–Radushkevich (D-R) isotherm model 52 interdisciplinarity 133

dyes 11 – 12, 40 – 41, 64; phytoremediation and interdisciplinary research (IDR) 14
81; removal by chemical precipitation internal standards 116
95 – 97; see also textiles inverse gas chromatography (IGC) 21
ion channels 77 – 78
electrocoagulation 93 – 94 ion chromatography 23, 120 – 123
electroflotation (EF) 94 ion exchange 120
Elovich isotherm model 54 isotherms 49 – 50
elution chromatography 108
elutriation 21 Jossens isotherm model 57
environment alteration 1 – 2 Jovanovic isotherm model 54
environmental sustainability 13 Jovanovic–Freundlich isotherm model 57
equivalent weight (EW) 29
errors 103, 116 Khan isotherm model 56 – 57
evaporation 20, 21 Kiselev isotherm model 54
extraction 23 – 24 Koble–Corrigan isotherm model 57
ferric chloride 90 Laitinen, Herbert 126

ferric sulphate 90 Langmuir isotherm model 51
filtration 20, 92 Langmuir–Freundlich isotherm model 55
flat sheet SLM (FSSLM) 34 Langmuir–Jovanovic isotherm model 58
flocculation 89, 95 – 97 lime 89
Flory–Huggins isotherm model 53 liquid chromatography (LC) 105, 107, 108 – 116;
flotation 97 instrumentation of 116 – 123, 117
fluoride 63 liquid petraction 30
Fowler–Guggenheim isotherm model 53 liquid-liquid extraction (LLE) 24
fractional distillazation 21
fractional freezing 21 MacKinnon, Roderick 78
Freundlich isotherm model 52 macro environment 1
Fritz–Schlunder-III isotherm model 55 magnesium 63
Fritz–Schlunder-IV isotherm model 59 magnetic separation 22
Fritz–Schlunder-V isotherm model 60 Marczewski–Jaroniec isotherm model 59
froth flotation 21 marine pollution 10
mass transfer 20, 22
genetic engineering 80 – 81 mass transfer resistance 113 – 115
green water 9 matter 19
gross errors 103 membrane phase (M) 30
Grot, Walther 29 membranes: bulk liquid (BLM) 30 – 33, 32, 40;
ground water 9 – 10 ceramic 27; emulsion liquid (ELM)
guard columns 118 30 – 31, 33 – 35, 40; hollow fibre 29;
ion exchange 38; liquid membranes
Halsey isotherm model 53 30 – 34, 31; microfiltration (MF) 28;
Harkins–Jura isotherm model 53 mixed matrix (MMMs) 38; neutral
heavy metals 11, 77, 81 28; permeable 26 – 27; semipermeable
Henry’s one-parameter isotherm model 51 26 – 27; solid 27 – 30, 37, 41; supported
Hill isotherm model 54 liquid (SLM) 30 – 31, 33 – 34, 40;
Hill–Deboer isotherm model 52 – 53 symmetric 28; synthetic 28;
Holl–Krich isotherm model 58 tubular 29
hollow fibre SLM (HFSLM) 31 membranes and membrane separation 26 – 27,
hydraulic barriers 75 35; applications of 341; classification
hydrological cycle 2 – 4, 3 of membranes 27; liquid membranes
hyperaccumulators 76 30 – 34; mechanisms of separation
35 – 37; solid membranes 27 – 30
indirect potable reuse (IPR) 131 metal sulphides 95
industrial effluents 10 metals 39; precipitation and 88, 88; removal by
infected water 6 chemical precipitation 95 – 97
Index 137
micelles 38 precipitation see chemical precipitation

micro environment 1 precision 103 – 104
microstrainers 93 pseudo-first-order kinetic model 60
mixture: separation and 19 – 20; vs compounds 19 pseudo-second-order kinetic model 60 – 61
mobile phase (MP) 105, 107, 116, 121 – 122 purification 19
modifiers 32
multi-walled carbon nanotubes (MWCNTs) 64 Radke–Prausnitz isotherm model 56
multidisciplinarity 133 rate theory 112 – 113, 113, 115
municipal sewage 8 Redlich–Peterson (R-P) isotherm model 55
removal efficiency 48
Nafion 29, 38 – 39 reverse osmosis (RO) 28
nano-phytoremediation 79 – 80 rhizofiltration 74
nano-zero-valent iron (NZVI) 81
nanofiltration (NF) 28 sedimentation 20, 22, 90
nanoparticles 62 separation techniques 20 – 25
National Measurement System (NMS) 102 sieving 22, 37
natural resistance-associated macrophage proteins Silicon Age 19
(NRAMPs) 78 – 79 Sips isotherm model 55
nitrogen 7 Skinner, B. F. 2
Nollet, Jean-Antoine 26 sodium aluminate 90
non-point source pollution 10 solid-phase extraction (SPE) 23
nucleation 88 solubility 87
sorption 24, 47 – 48, 49; applications of 61 – 66;
odour 7 five-parameter models 60 – 61;
four-parameter models 59; models
peak broadening 110, 112 – 113 of 49 – 51; one-parameter models
perfluoro sulphonate ionomers (PFSIs) 29 51; three-parameter models 54 – 58;
pH 7 two-parameter models 51 – 54
photo diode array (PDA) 119 specificity 102
physisorption 48 spread 104
phytodegradation 73 standard deviation (SD) 104
phytodesalination 76 stationary phase (SP) 105, 107, 116, 121 – 122
phytoextraction 72 – 73 statistical tools 104
phytomining 76 – 77 sublimation 22
phytoremediation 66, 72; applications of supercritical fluid extraction (SFE) 24
80 – 82; mechanisms 77 – 79; supersaturation 94
nano-phytoremediation 79 – 80; process surface runoffs 10
of 76 – 77; types of 71 – 76 surface water 9 – 10
phytostabilization 73 symmetry factor 112
phytostimulation 71 systematic errors 103
phytovolatilization 73
plants see phytoremediation tailing factor see symmetry factor
plate theory 110, 110 – 111, 115 taste 7
point source pollution 10 Temkin isotherm model 52
pollution and pollutants 2; see also dyes temperature 6
pollution and pollutants 5 – 9; see also textiles 12; see also dyes
contaminants; heavy metals thenoyltrifluoroacetone (HTTA) 40
polyaluminium chloride 90 thermal ionization mass spectrometry (TIMS) 127
polyaluminium chloro-sulphates (PACS) 90 threshold odour number (TON) 7
polymerized silica 91 threshold taste number (TTN) 7
polymers and polymeric membranes 27 – 28 Toth isotherm model 56
polytetrafluoroethene (PTFE) 34 toxins and toxicity 2, 13 – 14
polyvinylidene difluoride (PVDF) 38 transition metal nanooxides 62
porosity 92 translocation factor 75
potable water 6, 131 – 132 Tswett, Mikhail 104 – 105
potassium thiocyanate (KSCN) 40 turbidity 6
138 Index
ultrafiltration (UF) 28 water hardness 7

Unilan isotherm model 58 water pollution 9 – 13
uphill transport 36 water quality 6 – 7
urbanization 5 water resource management 133
water stress 6
Valid Analytical Measurement (VAM) 102 weather 13
van Deemter equation 114 – 115 Webber–Morris intraparticle diffusion model
vapour 4 60, 61
vegetation covers 75 Weber–van Vliet isotherm model 59
Vieth–Sladek isotherm model 58
X-ray diffraction (XRD) 62
waste heat 10
wastewater treatment 13 zinc oxide 62
water colour 6 zone melting 22

Jayshree Ramkumar - A. K. Tyagi - Remedial and Analytical Separation Processes - (2025)

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Remedial and Analytical

This book is aimed at senior undergraduate and graduate students in environmental

Jayshree Ramkumar and A.K. Tyagi

Chapter 1 Introduction to environment alteration and reshaping�������������������������� 1

Chapter 2 Separation process: imperative to human life������������������������������������ 19

Chapter 3 Membrane separation: primordial water treatment technique������������ 26

Chapter 4 Sorption: backbone of separation science������������������������������������������ 47

4.3 Understanding sorption using models������������������������������������� 49

Chapter 5 Phytoremediation: an emerging green auxiliary technique���������������� 71

Chapter 6 Chemical precipitation, coagulation, and flocculation: triad of

Chapter 7 Chromatographic techniques: workhorse of analytical

Chapter 8 Broad conclusions and future perspectives�������������������������������������� 131

Dr. A.K. Tyagi joined Chemistry Division, BARC in 1986

by Indian Thermal Analysis Society; DN Agarwal Memorial Award from Indian

1.2 CHANGING DYNAMICS OF ENVIRONMENT

unremitting development, environment is never static and results in pollution due to

1.3 WATER: THE FLOW OF LIFE

FIGURE 1.2 Schematic representation of the hydrological cycle

1.4 POLLUTION: MAKING ENVIRONMENTAL DUSTBINS

is graded on scale of 0 (clear) to 70 odour units. Pure water is colourless, which is

(ii) Chemical parameters of water quality

DO is an important parameter indicating water quality [25]. Water with higher

1.5 ORIGINS OF WATER POLLUTION

1.6 SCENARIO OF WATER POLLUTION:

1.7 EFFECT OF WATER POLLUTION: HUMAN

is an important branch of science known as analytical chemistry. Experts in the

2.1 MIXTURE AND SEPARATION

Separation is defined as a method by which a mixture or solution containing dif-

2.2 CLASSIFICATION OF SEPARATION TECHNIQUES

by partial melting of a solid. Magnetic separation is the process of separating com-

FIGURE 3.1 Schematic representation of separation across a membrane

ions and encapsulation. Perfluoro sulphonate ionomers (PFSIs) are copolymers of

FIGURE 3.2 Schematic representation of different liquid membranes (drawn based on

FIGURE 3.3 Schematic representation of different configurations of BLM

and modifier. Solvents like organophosphorus compounds, amines, oximes, quin-

less viscous chloroform or dichloromethane. This shows that a reduction in viscos-

3.3.1 Mechanism in solid membranes

FIGURE 3.4 Schematic representation of membrane-based separation

process, a boundary layer forms on the membrane. This concentration gradient

3.3.2 Mechanism in liquid membranes

aqueous–organic interphase is treated as a platform for the processes of complexation

8. Jayshree Ramkumar, Nafion Perfluorosulphonate Membrane: Unique Properties and

36. E. Klein, J. Membr. Sci. 179 (2000) 1–27.

There is always an ongoing research on the development of new separation techniques

(physisorption) and/or chemical (chemisorption) in nature [5]. Physisorption occurs

Recyclability of sorbents is an important aspect; therefore, desorption studies

FIGURE 4.1 Schematic representation of sorption in batch mode

4.3 UNDERSTANDING SORPTION USING MODELS

inflection point (usually observed in microporous, non-porous, or disperse solids

4.3.1 Equilibrium models

1. One-parameter model: Henry’s one-parameter isotherm model is the sim-

2. Two-parameter models: In this section, the discussion is with respect to

(ii) Freundlich isotherm model: The Freundlich model gives an idea of

(iii) Dubinin–Radushkevich (D-R) isotherm model: This empirical model,

and a zero value of K2 indicates no interaction between sorbed mole-

(vi) Fowler–Guggenheim isotherm model: This model gives information

lnqe = l * lnK − l * lnCe (4.13)

(ix) Harkins–Jura isotherm model: This model explains the multilayer

(x) Jovanovic isotherm model: This model is similar to that of the

Chapter 1 Introduction to environment alteration and reshaping�� 1

Chapter 2 Separation process: imperative to human life�� 19

Chapter 3 Membrane separation: primordial water treatment technique�� 26

Chapter 4 Sorption: backbone of separation science�� 47

4.3 Understanding sorption using models�� 49

Chapter 5 Phytoremediation: an emerging green auxiliary technique�� 71

Chapter 8 Broad conclusions and future perspectives�� 131

1.2 CHANGING DYNAMICS OF ENVIRONMENT

1.3 WATER: THE FLOW OF LIFE

1.4 POLLUTION: MAKING ENVIRONMENTAL DUSTBINS

1.5 ORIGINS OF WATER POLLUTION

1.6 SCENARIO OF WATER POLLUTION:

1.7 EFFECT OF WATER POLLUTION: HUMAN

2.1 MIXTURE AND SEPARATION

2.2 CLASSIFICATION OF SEPARATION TECHNIQUES

3.3.1 Mechanism in solid membranes

3.3.2 Mechanism in liquid membranes

4.3 UNDERSTANDING SORPTION USING MODELS

4.3.1 Equilibrium models

5.3 STEPS INVOLVED IN THE PROCESS

5.6 BENEFITS AND CONSTRAINTS OF PHYTOREMEDIATION

6.2 APPLICATIONS FOR THE REMOVAL

DOI: 10.1201/9781003442516-7 101

7.4 BASIC PRINCIPLES OF LIQUID CHROMATOGRAPHY

7.5.1 Normal and reverse phase chromatography

DOI: 10.1201/9781003442516-8 131