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WATER RESOURCE PLANNING, DEVELOPMENT AND MANAGEMENT

DRINKING WATER

QUALITY CONTROL, DISTRIBUTION


SYSTEMS AND TREATMENT

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WATER RESOURCE PLANNING,
DEVELOPMENT AND MANAGEMENT

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WATER RESOURCE PLANNING, DEVELOPMENT AND MANAGEMENT

DRINKING WATER

QUALITY CONTROL, DISTRIBUTION


SYSTEMS AND TREATMENT

CÉCILE MARCIL
EDITOR
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Library of Congress Cataloging-in-Publication Data


Title: Drinking water : quality control, distribution systems and treatment. Description: New York : Nova Science Publishers, Inc., 2020. |
Series: Water resource planning, development and management | Includes bibliographical references and index. | Summary: "Drinking
Water: Quality Control, Distribution Systems and Treatment focuses on some of the technologies involved in water treatment processes,
such as adsorption, co-precipitation, flocculation, and coagulation. The authors emphasize the newest easy processes, inadequacies, and
prospects of drinking water treatment. In one study, a simple effective intervention for biochanin A in influent water using ZSM-5, a
nano-porous crystalline zeolite, is described. In closing, a Sphingomonas paucimobilis strain isolated from an Indian drinking water
system was evaluated for its ability to co-aggregate and form mixed biofilms with Salmonella typhimurium, Shigella flexneri, and
Escherichia coli O57:H7"-- Provided by publisher.
Identifiers: LCCN 2020022911 (print) | LCCN 2020022912 (ebook) | ISBN 9781536180701 (paperback) |
ISBN 9781536180718 (adobe pdf)
Subjects: LCSH: Water-supply engineering | Water--Distribution. | Water quality management. | Drinking water.
Classification: LCC TD345 .D75 2020 (print) | LCC TD345 (ebook) | DDC 628.1/62--dc23
LC record available at https://lccn.loc.gov/2020022911
LC ebook record available at https://lccn.loc.gov/2020022912

Published by Nova Science Publishers, Inc. † New York


CONTENTS

Preface vii
Chapter 1 New Generation Materials for the Adsorption of
Toxic Metal Ion from Drinking Water 1
Rekha Sharma, Sapna and Dinesh Kumar
Chapter 2 Water Treatment Methods for
Detoxification of Metal Ions:
State-of-the-Art, Future Scenario
and Challenges 37
Kritika S. Sharma, Rekha Sharma
and Dinesh Kumar
Chapter 3 A Rapid, Nanoporous Zeolite Based Approach
for Removal of Biochanin A in
Potable Water Destined for Distribution 63
Pawandeep Singh, Vivek Sharma
and Moushumi Ghosh
vi Contents

Chapter 4 The Role of Sphingomonas paucimobilis in


Intergeneric Co-Aggregation and Mixed Biofilm
Formation with Water Borne Pathogenic Bacteria
in the Distributed Drinking Water System:
Implications of Public Health Risk 83
Parul Gulati and Moushumi Ghosh
Index 109
PREFACE

Drinking Water: Quality Control, Distribution Systems and Treatment


focuses on some of the technologies involved in water treatment processes,
such as adsorption, co-precipitation, flocculation, and coagulation.
The authors emphasize the newest easy processes, inadequacies, and
prospects of drinking water treatment.
In one study, a simple effective intervention for biochanin A in influent
water using ZSM-5, a nano-porous crystalline zeolite, is described.
In closing, a Sphingomonas paucimobilis strain isolated from an Indian
drinking water system was evaluated for its ability to co-aggregate and form
mixed biofilms with Salmonella typhimurium, Shigella flexneri, and
Escherichia coli O57:H7. (Imprint: Nova)
Chapter 1 - Nowadays, heavy metal ion pollution in water has gained
considerable attention from many research groups across the world. These
are highly carcinogenic even at comparatively low concentrations because
of their tendency toward bioaccumulation and non-biodegradable nature.
Thus, water contamination has also increased public concern. Although,
various methods are being used to treat the water and waste water, which are
fast and cost-effective. In this continuation, effective water treatment
methods have been manufacturing; intense research has been carried out,
those having an insignificant effect on the environment and the minimum
use of chemicals at a lower cost. The three primary factors have been utilized
for the implementation and development of water treatment technologies,
viii Cécile Marcil

i.e., the proclamation of new water quality standards, cost efficiency, and
the discovery of new rarer contaminants. Previously, the only treatment
processes that have been virtually utilized in municipal water treatment are
granular media filtration, chlorination, and chemical clarification. Though,
in water treatment processes, a dramatic change has been seen in
consideration of alternative treatment technologies to the traditional
chlorination/filtration purification method from the past 20 years. This
chapter categorizes and focuses on some of these technologies such as
adsorption, co-precipitation, flocculation, and coagulation at substantial
scale water treatment. This chapter will focus on adsorption technologies to
treat water and wastewater.
Chapter 2 - Approximately two million people die annually because of
contaminated drinking water and unsafe sanitation practices. The generation
of heavy metal ions is one of the prominent causes of water pollution. Heavy
metals such as lead, mercury, chromium, and arsenic exist naturally, but
anthropogenic activities cause contamination in water. The World Health
Organization (WHO) reports that approximately 1 billion people across the
world don’t have an approach to clean drinking water. This count is
presumed to eventually increase with increasing population i.e., 7.7 billion
(2019) from 7.5 billion (2018), energy requirement and climate change.
There are many commercially available methods to detoxify water from
heavy metals, while they are liable to rejection because of: less efficient,
expensive, generate hazardous toxic waste and energy-consuming. This
chapter will explore some advanced treatment methods, which are in use like
metal-organic frameworks (MOFs), UV irradiation, etc. Some traditional
techniques are still in use like adsorption, reverse osmosis, electrodialysis
and so on. Although they serve the purpose, either cannot address these
problems quickly, economically, long-term stability or high performance
despite development on the technical side. The challenge is to provide
solutions which are a universal or single solution, inexpensive, has ease of
implementation, cent percent efficiency, and domestic use. The functional
integration of different technologies or treatments may solve the current
water hazards. Impending water shortage will lead to detoxifying the water,
which is now considered undrinkable. This chapter will emphasize the
Preface ix

newest easy process, inadequacy, hurdles, and prospects of drinking water


treatment.
Chapter 3 - The presence of Endocrine disrupting chemicals or EDCs in
water poses a serious threat to human health and several food production
systems. Apart from EDCs of synthetic origin, phytoestrogens which are
plant derived have received little attention in terms of affordable
interventions in potable water destined for distribution. This study reports a
simple effective intervention for Biochanin A in influent water using ZSM-
5, a Nano porous crystalline zeolite. The adsorbent ZSM-5 was prepared in
laboratory and characterized by x-ray diffraction (XRD), scanning electron
microscopy (SEM), transmission electron microscopy (TEM), Brunauer–
Emmett–Teller (BET) adsorption and Fourier transform infrared (FTIR)
spectroscopy. ZSM-5 was nonporous with a surface area of 653 m2 g-1. The
effect of different parameters such as contact time, adsorbent dose and initial
solute concentration for removal of Biochanin A by ZSM-5 was evaluated.
The equilibrium data for the adsorption of Biochanin A on ZSM-5 was tested
in Langmuir and Freundlich adsorption models. Results indicated that
Langmuir isotherm model fitted well to equilibrium data in contrast to
Freundlich isotherm model. Complete removal of Biochanin A using ZSM-
5 in water indicated the possibility of application in drinking water.
Chapter 4 - Sphingomonas a resident microorganism, is often
encountered in the drinking water systems (DWDS). Its capability of growth
over a range of temperatures, tolerance to chlorination and antimicrobial
resistance patterns have recently raised health concerns. Several
physiological aspects, for instance role of co-aggregation and biofilm
formation especially with water borne pathogens by Sphingomonas remains
largely unknown and deserve attention. In this study, a Sphingomonas
paucimobilis strain isolated from Indian drinking water system was
evaluated for its ability to co-aggregate and form mixed biofilms with
Salmonella typhimurium, Shigella flexneri, Escherichia coli O57:H7. Strong
co-aggregation of Sphingomonas with the waterborne pathogens
Escherichia coli O157:H7 ATCC 32150, Shigella flexneri 2a and
Salmonella typhimurium ATCC 25315 was observed by qualitative and
quantitative methods with individual pathogens as well with a cocktail of the
x Cécile Marcil

above three water borne pathogens. Highest aggregation index was observed
with Shigella flexneri 2a followed by Salmonella typhimurium and
Escherichia coli O157:H7. The aggregation with Escherichia coli O157:H7
could not be reversed by heat, protease and sugars (lactose and galactose).
The results of this study have a strong implication on risk of mixed biofilms
of these water borne pathogens in DWDS which may have re-grown or
introduced (either through leakage or faulty treatment processes) and
eventually develop into biofilms with preexisting Sphingomonas. An
effective, noninvasive treatment strategy preferably aimed in disrupting
signalling molecules of Sphingomonas may be of value, for assuring safety
of drinking water.
In: Drinking Water ISBN: 978-1-53618-070-1
Editor: Cécile Marcil © 2020 Nova Science Publishers, Inc.

Chapter 1

NEW GENERATION MATERIALS FOR THE


ADSORPTION OF TOXIC METAL ION
FROM DRINKING WATER

Rekha Sharma1, PhD, Sapna1


and Dinesh Kumar2,*, PhD
1
Department of Chemistry, Banasthali Vidyapith, Rajasthan, India
2
School of Chemical Sciences, Central University
of Gujarat, Gandhinagar, India

ABSTRACT
Nowadays, heavy metal ion pollution in water has gained considerable
attention from many research groups across the world. These are highly
carcinogenic even at comparatively low concentrations because of their
tendency toward bioaccumulation and non-biodegradable nature. Thus,
water contamination has also increased public concern. Although, various
methods are being used to treat the water and waste water, which are fast
and cost-effective. In this continuation, effective water treatment methods
have been manufacturing; intense research has been carried out, those
having an insignificant effect on the environment and the minimum use of

*
Corresponding Author’s E-mail: dinesh.kumar@cug.ac.in.
2 Rekha Sharma, Sapna and Dinesh Kumar

chemicals at a lower cost. The three primary factors have been utilized for
the implementation and development of water treatment technologies, i.e.,
the proclamation of new water quality standards, cost efficiency, and the
discovery of new rarer contaminants. Previously, the only treatment
processes that have been virtually utilized in municipal water treatment are
granular media filtration, chlorination, and chemical clarification. Though,
in water treatment processes, a dramatic change has been seen in
consideration of alternative treatment technologies to the traditional
chlorination/filtration purification method from the past 20 years. This
chapter categorizes and focuses on some of these technologies such as
adsorption, co-precipitation, flocculation, and coagulation at substantial
scale water treatment. This chapter will focus on adsorption technologies
to treat water and wastewater.

Keywords: water treatment, adsorption technologies, efficient,


contaminants

1. INTRODUCTION

For the survival of any life on earth, water is necessary to accomplish


daily life purposes. Unfortunately, quality of water systems are continuously
degrading because of population growth, industrial development, use of a
pesticide in agricultural fields, and domestic proposes [1−3]. In recent years,
water pollution has existed as a severe issue that disturbs the physiology of
all living creatures, fisheries, and many more commercial activities [4−6].
Widely, researchers, scientists, and supreme government bodies are taking
part in resolving this severe water pollution issue [7]. In last few decades
thousands of water contaminants found in water in the form of organic,
inorganic, and biological have caused lethal carcinogenic effects on the
living organism present in the aquatic medium and all over in the ecosystem
[8−10]. Many heavy metals are responsible for water pollution because of
their high carcinogenicity [11-13]. Since ancient times, arsenic considered
as the severe carcinogenic element. The total of 35 elements relates to the
environmental concern of toxicity. Out of these 23 metals categories into the
heavy metal series according to their specific gravity five times higher than
the water. For instance, As, Cd, Pb, Hg, showed 5.7, 8.65, 11.34, 13.54,
New Generation Materials for the Adsorption of Toxic Metal Ion … 3

comes into the hazardous top 20 elements list provided by the US Agency
Disease Registry (ATSDR) in cooperation with USEPA. The flourished
animal and plants present in the ecosystem is exposed with the heavy metals
which comes from various sources such as the industrial activity, coal power
plant, agricultural fields, coal and stone mining, acid mine, drainage, and
landfill leachates municipal wastewater treatment plants [14]. Different
arsenic species found in the water possesses the following toxicity order like
dimethyl arsenic acid (DMA) < monomethyl arsenic acid (MMA) < arsenate
< arsenite) [15, 16]. These heavy metals, when present in water beyond their
permissible limit, causes severe diseases such as vomiting, nausea, asthma,
and thyroid, gastrointestinal, and liver problems caused by cobalt [17−19].
Although zinc is the essential element which required for the nourishment
of the human body but causes poor growth and mental fever when exceeds
their permissible limit 3.0 mg L-1 which recommended by world health
organization (WHO) [20, 21]. Some other ions also show the toxic effect,
for instance, F-, NO3-, Cl-, SO42-, PO43-, etc. Excess intake of nitrate produces
the methemoglobinemia disease in children, also known as the blue babies’
disease [22]. Alternately, fluorosis occurred because of the higher
concentration of the fluoride. Besides these pollutants several other organic
pollutants, for example, plasticizers, biphenyls, pesticides, phenols, greases,
hydrocarbons, pharmaceuticals, fertilizers, oils, and detergents, etc.
originate from the different water resources. Several other harmful
pathogenic bacteria, fungi, microbes, viruses, amoebas, algae, planktons,
and bacteria also create water pollution and cause severe waterborne disease.
It has been estimated that the till 2020, the world population reach up to 7.9
billion may be world face the problem of water scarcity [23]. So, there is an
urgent requirement to develop an efficient strategy for the removal of
toxicants to supply safe drinking water to the world [24]. In previous
research, lots of methods and techniques were implied to resolve this major
issue which belongs to the ultra-filtration, filtration, flotation, adsorption,
crystallization, centrifugation, reverse osmosis, sedimentation and
precipitation, electrodialysis, distillation, ion-exchange, gravity separation,
and electrolysis, etc. Figure 1 shows various techniques for the purification
of water. This chapter will focus on new generation techniques, including
4 Rekha Sharma, Sapna and Dinesh Kumar

adsorption, co-precipitation, flocculation, and coagulation. Among all these,


adsorption-based methods are best and proper for wastewater treatment
because of their wide range availability because of smooth handling and
available in different forms. Researchers have used a variety of adsorbents
to absorb insoluble and soluble inorganic, biological, and organic pollutants.
With all these vital applications, this efficient method involves some
limitations, therefore not as much suitable for the commercial application.
Shortcomings like low adsorption ability, commercial-scale columns were
showed with many adsorbents.

2. REMEDIATION TECHNIQUES

2.1. Adsorption

Adsorption is the process through which toxicant as an adsorbate


adsorbed on the adsorbent surface. Adsorption is a surface-based
phenomenon which occurred because of physical forces. The pollutant also
adsorbed on the solid surface via weak chemical interaction like chemical
bonding responsible for adsorption [25]. It might depend on various factors
such as reaction temperature, pH, amount of adsorbent dose, contact time,
presence of the other pollutants, and the nature of the adsorbate and
adsorbent. After reaching a certain level in the adsorption process,
equilibrium achieved where the concentrations of adsorbed ion and water
become constant. It occurred the more adsorption when the concentration of
substance was according to their surface to the mass transfer process [26]. It
is a very eminent, efficient, and economically viable process to eliminate the
heavy metals from wastewater and exhibited the maximum adsorption. The
maximum adsorption occurs because of a specific area, which is a crucial
factor for the adsorption process, along with nanoparticles, showed a high
surface-to-volume ratio, which makes it perfect aspirants [27]. It has
considered that adsorbents mostly used to make the potable water are carbon
nanotube, graphene, polymers, metal oxide, and zeolite-based materials.
New Generation Materials for the Adsorption of Toxic Metal Ion … 5

Liu et al. reported a novel biomimetic SiO2@CS composite for the


exclusion of As5+ and Hg2+ showed an excellent adsorption capacity. Here,
SiO2 exhibits good mechanical strength and stable chemical properties,
which attributes the prohibition of the agglomeration of the adsorbent. The
amino and hydroxyl functional groups of chitosan played a key role in the
removal of heavy metal by supplying many active sites. The FESEM
technique determined a leaf-like morphology of SiO2@CS composite. It was
a notice that at even minute concentration of heavy metal showed the heavy
metal removal and found 204.1 and 198.6 mg g-1 regarding the Hg2+ and
As5+. This biomimetic composite attained up to 60% removal within a short
time interval of around 2 min. The minimum time period limit and excellent
adsorption capacity showed potential behavior. The good adsorption
properties show its potential for removing heavy metal ions [28].

Figure 1. Various techniques to treat water. [Reproduced by permission of The Royal


Society of Chemistry@ https://pubs.rsc.org/en/content/articlelanding/
2012/ra/c2ra20340e#!divAbstract]
6 Rekha Sharma, Sapna and Dinesh Kumar

Yan et al. introduced the hollow gangue microspheres into the


geopolymer matrix using the geopolymeric approach to remove various
heavy metal ions like lead cadmium, copper, and zinc from aqueous
solution. It is a green and low-cost method using industrial solid waste
abbreviated as GM. The GM/KGP (Gangue microspheres into a geopolymer
matrix) adsorbent showed an amorphous structure and included different
functional groups like Si–O–Si, Si–O–Al, and–OH. The geopolymer matrix
comprises the hollow gangue microspheres consistently. They used the BET
surface area analyzer to determine the surface area, which was found up to
26.41 m2 g-1. The preferential adsorption order of heavy metal was lead >
copper > cadmium > zinc. The Langmuir isotherm model and the pseudo-
second-order kinetic model were best fitted for the adsorption and kinetic
data of the adsorption process, respectively. Adsorption of heavy metal over
the surface of the GM/KGP adsorbent was totally the endothermic process.
The adsorption process for the removal of metal ions is electrostatic
attractions, physical, ion-exchange, and chemical interactions. Authors
concluded that GM/KGP adsorbent is cost operative, safe, and active effort
to remove hazardous heavy metals from wastewater [29].
Wang et al. adsorbed heavy metal ions on incinerated sewage sludge
ash. The initial solution pH displayed an important part for the remediation
of heavy metal and higher adsorption found at pH six within the initial 15
min in the single and dual component systems of heavy metal. The presence
of other competing ions may diminish the rate of adsorption, which delays
the equilibrium state. The adsorption data were followed the Freundlich
isotherm explained the multilayer adsorption. Targeted heavy metal
followed the affinity order for adsorption as copper > cadmium > zinc and
showed the maximum adsorption capacity for copper, cadmium, and zinc
heavy metal ions as 0.13, 0.11 and 0.06 mmol g-1, respectively. They
considered the cation exchange mechanism to be the primary adsorption
mechanism. The adsorption process is mainly managed by ISSA
(Incinerated sewage sludge ash). Because of the practical solid-liquid
separation technique, additional studies must be attentive to the adsorption
performance of other metals ions [30].
New Generation Materials for the Adsorption of Toxic Metal Ion … 7

Chen et al. utilized the modified cellulose derivative by a different


functional group like a secondary amino group, amide, carboxyl, and
carbonyl sulfide to mitigate the removal of heavy cadmium metal. The
modified cellulose derivative was characterized by the XPS, FTIR, 13C
NMR, and XRD analytical tools. The changed form showed good adsorption
capacity was 401.1 mg g-1 than the bare cellulose exhibited greater affinity
with cadmium resulted from three times better performance than cellulose.
The adsorption experiment carried out spontaneous, well fitted with the
Freundlich model and followed the pseudo-second-order kinetics model
with high regression coefficient value R2 = 0.994, R2 > 0.997, respectively.
The DFT calculation characterized the affinity of functional groups with
Cd2+, and these groups showed synergistic interactions with the cellulose-
based adsorbent [31].
Wu et al. showed the adsorption of heavy metals includes copper,
cadmium, and lead by using magnetic polysaccharide gel beads made up of
a combination of the carboxymethyl chitosan, sodium alginate, with
magnetic graphene oxide. Various tools like SEM, FTIR, VSM, XRD, XPS,
and TGA were utilized to know the physicochemical properties of the
composite beads. Because of its magnetic behavior, it could easily separate
from wastewater and showed the 90% removal after the five-consecutive
adsorption-desorption cycle. To explain the adsorption process kinetics, the
obtained data were linearized, and according to a higher regression factor
value with a particular model order declared. Here the Langmuir isotherm
model and pseudo-second-order model best fitted for the adsorption and they
considered kinetics data as a chemical process. Based on FTIR and XRD
analysis assumed that they involved the chelation interaction among the
carboxyl groups, hydroxyl groups, and nitrogen groups with the lead ions. It
confirmed the magnetic polysaccharide beads had selectively worked for the
lead ion with maximum and minimum adsorption capacity 189.04 55.96,
and 86.28 mg g-1 for lead, copper, and cadmium, respectively. Good
regeneration ability and recyclability make it a right candidate for
wastewater treatment [32].
Jia et al. synthesized a magnetically separable iron silica core-shell
adsorbent where Fe3O4 act as core and SiO2 as shell further immobilized the
8 Rekha Sharma, Sapna and Dinesh Kumar

amine and anhydride including polyethyleneimine (PEI) and 1,4,5,8-


naphthalene tetracarboxylic-dianhydride (NTDA). After synthesis, SEM,
TEM, FTIR, XRD, VSM analyzed the adsorbent. SEM analysis attributes
the homogenous core-shell structure with three layers of 300 nm comprising
Fe3O4, nSiO2, PEI-NTDA layer was 200 nm, and 20 nm in diameter. During
the batch study, it favored the adsorption of lead simultaneously other heavy
metals such as nickel, cadmium, copper, and zinc present in the aqueous
solution. The largest adsorption was 285.3 mg g-1 at perfecting parameters
at an adsorbent dose 0.5 g L-1, pH 6.0, contact time 3 h, initial concentration
200 mg L-1. The Langmuir isotherm model and the pseudo-second-order
model were well fitted with the adsorption data. By applying the external
magnetic field, these nanoparticles easily recovered and used for the next six
cycles [33].
Arshad et al. prepared the graphene oxide incorporated
polyethyleneimine in the form of calcium bead showed removal towards the
lead, mercury, cadmium from wastewater. The Langmuir adsorption model
and the pseudo-second-order model were best fitted for the adsorption
process on functionalized-GOCA (Graphene oxide embedded calcium
alginate) beads. At room temperature, the adsorption capacity was
demonstrated up to 602, 374, 181 mg g-1 for lead, mercury, and cadmium,
respectively. They ascribe better adsorption capacity because of the
accessibility of active adsorption sites in varied functionalities as GO, and
polyamine exhibited complexation with alginates carboxylate groups. All
may synergistically reinforce the adsorption of metal ions. The preferential
order of removal of heavy metal by functionalized GOCA beads as follows
lead > mercury > cadmium. The five repetitive adsorption-desorption studies
displayed a similar trend after the studied of other ions showed the removal
efficiency of 75-80% for lead ions [34].
Xiao et al. employed magnetic Loofah sponges for the elimination of
chromium and copper ions from the polluted water. Here biochar obtained
from the Loofah sponges and pyrolyzed in a tube furnace in the N2
atmosphere further make accessible to support with chitosan. SEM
morphology depicts the smooth surface of the bare biochar, while CMLB
(chitosan combined with magnetic biochar) has a rough and mesopores
New Generation Materials for the Adsorption of Toxic Metal Ion … 9

network. The formation of a lined porous interconnection occurred because


of the breakdown of the lignocellulosic material because of temperature at
the time of heating in the furnace. Chitosan functionalized with different
weight ratios of biochar, which are assigned as 20-50 wt% composition.
During the adsorption experiment, 40 wt% changed biochar composition
achieved the best adsorption 30.14, 54.68 mg g-1 for chromium and copper.
FTIR, XPS, and XRD methods were used to understand the mechanism of
adsorption. Based on changing intensities and peak area after the
modification and the adsorption confirmed heavy metal ion removal.
Kinetics and isotherm studies showed that CMLB defined by pseudo-
second-order and the Freundlich models. They reduced the adsorption
capacity very less after the three-sorption experiment by CMLB were 23.34,
42.6 mg g-1 for chromium and copper, respectively. Alternatively, the XPS
analysis elucidated the primary adsorption mechanism of CMLB occurred.
The ion exchange and surface complexation, signifying that CMLB can be
a potential and environmental-friendly removal of heavy metal ions from the
wastewater [35].
Mnasri-Ghnimi showed the application of the mixed pillared and single
natural clay to remove inorganic pollutants in polluted water. Further, the
adsorption experiment was conducted by including various effective
parameters, such as initial ion concentration, amount of dose, the effect of
pH, temperature, and contact time. By comparing the pillared and natural
clay, pillared clay showed a higher affinity towards the heavy metal ion i.e.,
cadmium, cobalt, copper (M2+). Controlled pH attributes the adsorption of
cobalt, copper, at a particular pH. The pH ranges from 6.0 to 10.0 favored
the removal of cobalt and copper and 8.0 – 10.0 for cadmium. Alternatively,
with increasing initial concentration, the extent of adsorption of M2+
enhanced until the concentration of the M2+ increased in the solution.
Langmuir isotherm model and Second-order kinetics were associated with
the adsorption of heavy metal M2+, and the process seemed to endothermic
nature. Obtained coefficients well favored the adsorption process with M2+
ion interaction. Various characterization methods like BET, ZPC, CEC, and
FTIR were carried out to test the texture of adsorbent and draws the
experimentally changes occurred after adsorption. Desorption study also
10 Rekha Sharma, Sapna and Dinesh Kumar

performed to check reusability; it can also be regenerated. The application


of other isotherms such as Toth or Sips studied to find out the accuracy of
the adsorption process, and weight of adsorbent also tested in the presence
of the ions in the solution [36].
Wang et al. synthesized the 3D flower-like shape with sulfide functional
groups inserted LDH (Layered Double Hydroxide) ordered micro composite
sorbent to remove the lead, copper, zinc, cadmium, manganese selectively.
The affinity order of removal of divalent heavy metal was for removing
heavy metals, which displays an effective selective order toward various
divalent metal ions lead > copper > zinc > cadmium > manganese.
Particularly, lead and copper show high kd values as ~ 106, 105 mL g-1,
respectively. A systematic batch study was carried out to confirm the
selective removal of heavy metal, and they evaluated adsorption capacity
through the Langmuir isotherm. The Langmuir isotherm predicts the
monolayer adsorption in between the M2+ and NFL-S, while, kinetic study
shows the chemisorption was the rate-limiting step [37].
Dong et al. synthesized the hydrochar impregnated Ti3AlC2-derived
nanofibers by the carbonization of the biomass through the hydrothermal
process. To certify a manageable future, it becomes necessary to use rich
biomass to produce chemicals, transport fuels, and other raw materials.
Hydrochar is evolved as promising is candidates resulted by hydrothermal
carbonization of cellulose biomass, pinewood, sawdust in hot water at high
pressure. XRD, BET, SEM, TEM, and FTIR were used to characterize
formed hydrochar derived Ti3AlC2 adsorbent to investigate the crystal
structures, textural properties, morphologies, and surface nature. The
resulting product selectively targeted cadmium and copper [38].

2.1.1. Carbon-Based Nanoadsorbents


Nowadays, nanoadsorbents based on carbon has been extensively
utilized as a promising candidate for the removal of heavy metal ions from
wastewater and water. Recently, various carbon-based nanomaterials have
appeared as effective nanoadsorbents for wastewater treatment applications.
For example, activated carbon (AC) making up with graphene and carbon
nanotubes (CNTs) which is the utmost communal carbon-based practical
New Generation Materials for the Adsorption of Toxic Metal Ion … 11

adsorbent [39]. In the aqueous systems for the removal of inorganic and
organic pollutants, AC is documented as a common and effective adsorbent
because of a high surface reaction affinity, highly porous structure, and
higher surface area up to 3000 m2 g-1. In the last decade, researchers have
stalled the escalation of additional carbon adsorbents and have emphasized
the development of cheaper AC precursors, and it is coupled with other
adsorbents or chemical functionalization [40–45]. On the foundation of their
developed heavy metal elimination presentation, CNTs have a shorter intra-
particle diffusion distance and more available adsorption sites per unit mass
compared to AC [46]. To remove toxic heavy metals from water and
wastewater such as As3+, Cd2+, Cr3+, Co2+, Cu2+, Eu3+, Pb2+, Mn2+, Hg2+, Ni2+,
Sr2+, Th4+, U6+, V2+ and Zn2+ CNTs are accessible in the form of their
allotropes i.e., multi-walled (MWCNTs) and single-walled (SWCNTs)
carbon nanotubes. Various methods such as sorption, precipitation,
electrostatic attraction, and chemical interaction are ascribed to the
mechanisms to absorb heavy metal ions onto CNTs that are multifaceted.
Several factors handle the adsorption possessions of CNTs. Among these
issues, the significant morphological features are the role of discrete
adsorption sites and the fraction of unlocked and opened nanotubes [47].
The number of active sites in the capped CNTs is fewer than the opened
CNT bundles [48]. Interstitial channels, grooves, outer surfaces, and internal
sites are the four types of adsorption sites in CNTs. The purity of CNTs is
likewise a significant feature. Contaminants, for example, carbon-based
pollutants, soot, and catalyst particles may decrease the number of CNT
active adsorption sites by coating the surfaces of CNT bundles. Earlier
studies have shown that CNTs adapted thru oxygen display importantly
enhanced adsorption ability. During the oxidation or synthesis, a few oxygen
moieties, for instance, –COOH, –CO, and –OH might be accompanied with
the CNT surface through various plasma treatments, acids, and ozone. A
negative charge induces on the surface of CNTs by oxidation along with
advancing dispersibility in aqueous solution. Thus, the capacity of cation
exchange augmented [49]. As per, SWCNTs have enhanced adsorption
performance for Zn2+ and Ni2+ with functional acidic sites on negative zeta
potential and their surface. CNTs were changed using various metal oxide
12 Rekha Sharma, Sapna and Dinesh Kumar

materials, for example, aluminum oxide, [50, 51] manganese dioxide, [52]
and iron oxide [53], which resulted in favorable heavy metal ion removal.
The synergistic effect amongst metal oxides and CNTs is the key part of the
mechanisms for improved adsorption capacity. To absorb the toxic heavy
metals from water and wastewater streams, manufacturing novel adsorbents
[54, 55] such as graphene adsorbents incorporated with metal oxides have
been used as the newest affiliate of the allotropes of the carbon family. Smart
magnetic graphene was fruitfully synthesized by Gollavelli et al. thru
ferrocene precursors and graphene oxide (GO) using microwave irradiation
for the removal of heavy metals ions such as As5+, Pb2+, and Cr6+. The
adsorbent showed high established removal efficiency (99%) ppm level
down to the ppb level. For innocuous water intake in imminent regionalized
systems of water, the virtuous adsorption possessions, lucrative nature, and
effectual disinfection control accomplish it a potential adsorbent [56]. For
heavy metal adsorption, GO has also been extensively utilized in different
forms such as foam, aerogel, and powder. For the removal of Cu2+ ions, the
GO aerogel compared to AC (40 min) and oxidized CNT sheets (24 h) with
a 15 min adsorption rate to reach equilibrium. Various compounds, for
instance, poly(amidoamine), poly-3-aminopropyltriethoxysilane, chitosan,
polydopamine, ethylene diamine tetraacetic acid (EDTA), and cyclodextrin
have been used for effective surface functionalization of GO to reach further
heavy metal adsorption capacity. For heavy metal ion adsorption, EDTA
was displayed to advance the recital of GO through the formation of stable
metal ions chelates [57].

2.1.2. Zeolite Based Nanoadsorbents


In heavy metal ion remediation, zeolites and its associated crystalline
inorganic constituents play a key role in adsorption [58, 59]. Because of their
ion-exchange, unique catalytic, and adsorption properties, zeolites have
been extensively used in several industrial applications which are made of
crystal-like hydrated aluminosilicate materials having uniform pore size
[60]. Though owing to their pore sizes which deceits amongst 0.4-1 nm,
zeolite particle sizes usually range amongst 1-10 mm, and they are
considered as nanomaterials. Though, approximate outcomes with synthetic
New Generation Materials for the Adsorption of Toxic Metal Ion … 13

zeolites, for instance, zeolite X106 and zeolite 4A105 have also been chosen
as the natural zeolite clinoptilolite which has been frequently utilized for
heavy metal treatment. The removal of Cu2+, Cd2+, Pb2+, and Ni2+ ions has
been examined on natural zeolites by Sprynskyy et al. [61]. They determined
that the adsorption arises because of three discrete steps of fast adsorption
i.e., inversion stage, dispersion, and clinoptilolite microcrystal surface and
also has an ion-exchange nature. Furthermore, the ion-exchange adsorption
proves a major role in the removal of these metal ions. Because of the
competition of hydrogen ions, the adsorption process diminished sharply at
a lower pH. By associating the synthetic zeolites (NaPl) and the natural
zeolite clinoptilolite, removal competence on zeolite exchangers of the
heavy metal ions was examined [62, 63]. In comparison to natural zeolites,
synthetic zeolites have significantly enhanced exchange capacity. For the
remediation of Cr3+, Zn2+, Ni2+, Co2+, and Cu2+ ions, zeolite 4A have been
manufactured by Hui et al. These zeolites displayed an excellent adsorption
capacity and a good recital to re-mediate these above-mentioned heavy
metal ions. The hydration free energy, crystal structure of zeolite 4A, and
metal ions’ hydrated radii handle the difference in adsorption performance
[64]. For the fabrication of zeolites comparable to a needle-like
nanocrystalline shape, Luo et al. reported green and sustainable method
using metakaolin (MK) as a precursor clay mineral. Because of a specific
needle-like shape associated with raw MK with a layered structure, the
hydrothermally produced zeolite showed developed the specific surface area
and porosity. Therefore, the synthesized zeolites exhibited a 20-fold
augmentation associated with raw MK and remove the Pb2+ and Cu2+ metal
ions having a good adsorption capacity of 337.8 mg g-1 and 431.0 mg g-1,
respectively. The ion exchange reactions amongst heavy metal ions and the
sodium ion of zeolites are proved the adsorption mechanism of MK-based
zeolites [65].

2.1.3. Metal-Based Nanosorbents


For water and wastewater remediation, various nano metal oxides are
considered as low-cost and effective materials, for example, aluminum
oxides, magnesium oxides, titanium oxides [66], manganese oxides
14 Rekha Sharma, Sapna and Dinesh Kumar

comprising hydrous manganese oxide [67], ferric oxides counting hematite


(a-Fe2O3) and goethite (a-FeOOH) [68], magnetite (Fe3O4) [69], hydrous
ferric oxide, maghemite (g-Fe2O3) [70], zinc oxides [71], mixed-valence
manganese oxides [72], and cerium oxides [73]. Fundamentally, in the
aqueous condition, the communal adsorption mechanism depends on the
interaction amongst oxygen in the metal oxides and heavy metal ions [74].
Currently, because of their high reactivity with heavy metal ions, ease of
regeneration, desirable mechanical stability, and outstanding surface-to-
volume ratio, hierarchically structured metal oxides have attracted
significant attention of researchers [75, 76].
Arsenic has been removed from drinking water on granular ferric
hydroxide, which is the most extensively used metal-based materials that
previously been commercialized. Essentially, it comprises ferrihydrite
(Fe(OH)3) component embedded on akageneite (b-FeOOH) which utilized
in fixed bed absorbers showing high adsorption capacity. They show high
arsenic adsorption capacity having a specific area and porosity of granules
up to 330 m2 g-1 and 75% [77, 78]. Intended for the remediation of toxicants,
the several readily available and economically attractive low-cost bio
adsorbents have been composed of seafood waste, industrial by-products,
cellulose waste materials, food waste, and agricultural waste which shows
cost efficiency from moderate to in height competence [79-81].

2.2. Metal-Organic Frameworks

Metal-organic frameworks (MOFs)/porous coordination polymers


(PCPs) are rising as favorable aspirants in a massive amount of diverse
application and multifunctional materials in water remediation [82].
Because of self-assemblage by strong bonds amongst the organic linkers and
metal-containing species, the MOFs consist of organic linkers and metal
nodes. In the synthesis of MOFs, all the synthetic crystalline materials hold
ideal flexibility, a large area to mass ratios, and prominent porosity in
alteration of shape from the microporous to the mesoporous scale together
with their pore size [83–85]. Farha et al. reported a MOF in 2012 having a
New Generation Materials for the Adsorption of Toxic Metal Ion … 15

higher specific surface area reported so far of any porous material i.e., 14
600 m2 g-1 surface area which was the computer-simulated and actual surface
area of 7000 m2 g-1 [86, 87]. The performance of MOFs in the existence of
water can be accounted for as an adsorbent in an aqueous environment since
they might experience hydrolysis [88]. Compared to other covalent
materials, for example, zeolites and activated carbon, the MOFs are
additionally vulnerable to hydrolysis because of metal-ligand coordination
bonds. Though, a rising number of steady MOF structures have been
addressed in recent literature because of this reason [89–91]. MOFs are an
emerging class of adsorbents to undertake ecological contamination by
removing heavy metals from water and wastewater, and they can be
synthesized by simple and affordable techniques on a large scale supporting
their outstanding stability under harsh conditions [92]. Various heavy metals
such as Cd, Pb, As, Hg, and Cr are effectively removed from wastewater
using MOFs as an adsorbent [93]. The adsorption performance of MOFs on
heavy metal can be categorized into five main methods. These methods
comprise (i) the fictionalization of organic linkers and metal nodes to
improve selectivity and produce extra adsorption sites contrast to the pristine
MOFs (ii) to advantage as of their synergistic effects and properties, (iii)
increase their pore size by introducing defects in the structure, (iv) utilization
of large organic linkers to advance porosity and to produce additional
adsorption sites, and (v) hybridization of MOFs with other functional
materials, for instance, magnetic materials. A MOF/polymer composite,
which is water stable, has been synthesized by Sun et al. with biological and
environmentally friendly materials. This composite is identified as MIL-
100, as a polydopamine (PDA) and MOF instead a polymer phase composite
that comprises 1,3,5-benzenetricarboxylate (Fe-BTC). Fe-BTC/PDA
composites established 394 mg g-1 and 1634 mg g-1 of heavy metal
adsorption capacities for lead and mercury, respectively, which was found
to be 99.8% adsorption capacities of the composite. In addition, these novel
composites showed higher water stability, contrary to fouling, high
separation, and regenerable performance within short response time [94].
Depending on the composition, their pore size can range from 0.3 to10 nm,
which is a further significant characteristic of MOFs towards good
16 Rekha Sharma, Sapna and Dinesh Kumar

adsorption capacity. This formulates it promising to manufacture


nanofiltration membranes as separating agents based on MOFs [95, 96]. For
example, to produce NF hybrid membranes at a pressure of 7 bar with a flux
of 31 L m-2 h-1 and a Cu2+ rejection of 90%, a MOF/GO composite
functionalized with an amino group embellish with a PDA-coated substrate
surface was utilized [97]. The MOFs are a rising water treatment composite
material having wide-ranging applications due to high capacity, an
outstanding adsorption competence, and the possibility of alteration of their
pore size.
The removal of several key hazardous contaminants, mainly Cd2+ and
Pb2+ in different wastewater reported by Pournara et al. reported on MOF
[Ca(H4L)(DMA)2].2DMA (Ca-MOF) in which the MOFs was shown to be
an extremely competent and selective adsorbent. Similarly, an economic
column based on silica sand and Ca-MOF was set up efficient to remove a
moderately huge amount of replicated wastewater having a co-existing ions
series in higher concentrations and traces of Pb2+ (100 ppb). The concluding
consequence selected that water remediation may be a practical application
of Ca-MOF. The pair distribution function (PDF) data can determine the
construction of M2+. The authors have synthesized an easy and ready-to-use
electrochemical sensor to removal toxicants aggravated by the outstanding
adsorption belongings of Ca-MOF based on changed graphite paste with Ca-
MOF. The anodic stripping voltammetry (ASV) was utilized to detect Cd2+,
Zn2+, Pb2+, and Cu2+ by this sensor and it showed low detection limits up to
0.64–1 to 4 mg L–1. In fact, the MOF was found to have a dual nature proper
for electrochemical determination together with adsorption of heavy metal
ions for the first time reported till date. Therefore, to synthesize a series of
composite materials, an opportunity is opened that would be utilized in
ecological monitoring and remediation [98].
Lv et al. described a simple one-step approach for the development of
cost-effective and a scalable fluorescence sensor known as MIL-101-NH2.
The outcome confirmed that the detection of Cu2+, Pb2+, and Fe3+ having the
detection limit of 0.0016, 0.0052, and 0.0018 mM, respectively was
occurred on fluorescent MIL-101-NH2. Prominently, showing this easy
manufacturing procedure of luminescent MOFs was of extensive utilities to
New Generation Materials for the Adsorption of Toxic Metal Ion … 17

manufacturing other four MOFs functionalized by the similar alteration


process displayed suitable fluorescence possessions. To gain immense
fluorescence emission, this technique merely required to embellish amino
groups with an organic linker in which no other fluorescein was
indispensable. In addition, the as-synthesized MIL-101-NH2 showed soaked
adsorption capacities of Pb2+, Cu2+, and Fe3+ carried out up to 0.9, 1.1, and
3.5 mM/g and had immense adsorption aptitude for these metal ions.
Similarly, in water and wastewater, the adsorption of heavy metals on the
other four amino-functionalized MOFs displayed virtuous adsorption
capacity. In the removal and detection of Cu2+, Pb2+, and Fe3+ via MIL-101-
NH2 the investigation of FTIR and XPS studies recommended that the
chelation amongst metal ions and amine groups showed a vigorous part. In
conclusion, in the concurrent removal and detection of heavy metal ions, the
suggested process had remarkable potential for applied requests [99].
Zhang et al. reported the removal and detection of Pb2+ from an aqueous
solution. The ligands have N, in the structure of a water-stable metal-organic
framework (CAU-7-TATB) which offers binding sites for metal ions. For
the removal of Pb2+ metal ions, CAU-7-TATB displays fast adsorption
kinetics and high adsorption capacity. Noticeably, the potentially applicable
CAU-7-TATB remnants in height preceding adsorption towards Pb2+ in the
occurrence of interfering ions like Mn2+, Mg2+, Ca2+, Ni2+, Cr3+, Co2+, and
Zn2+ which does not interfere in removing Pb2+ from industrial water. In
brief, the elimination of Pb2+ ions, the synthesized CAU-7-TATB was
proved as an innovative adsorbent. The effect of various parameters, such as
the interfering ions, adsorption kinetics, effect of pH, and adsorption
isotherms, were thoroughly considered on the adsorption capacity. In
conclusion, to absorb Pb2+ ions effectively, the N in triazine was found to be
accountable. This study offers an alternate path of fabricating potentially
viable prolonged MOFs adsorbents having nitrogen atoms in their ligands
towards metal ions [100].
Guo et al. reported BUC-17 ultrafine powder, which was synthesized by
the introduction of absolute ethanol and showed ultra-high adsorption
capacity toward Cr6+ up to 121 mg g-1. It showed much more adsorption
capacity toward Cr6+ ions. The adsorption process was found to be
18 Rekha Sharma, Sapna and Dinesh Kumar

endothermic, spontaneous, and randomness increases by the demonstration


of equilibrium and kinetic data. The accessible overall data showed that both
ion-exchange and electrostatic interactions give Cr6+ adsorption onto BUC-
17. pH and co-existing anions showed significant characters divulged from
the experimental data. To eliminate anionic heavy metals from wastewater,
it was predictable to utilize BUC-17 as an effective adsorbent [101].
For the removal of Nd ions in aqueous systems, Najafi et al. reported the
solvothermal pathway for the fabrication of hydro stable mixed-lanthanide
MOF included with BTC as the ligand and La3+ and Ce3+ as metal ions. To
study the possessions of Ce0.8La0.2BTC (DMF), many experimental tests and
analyzing approaches have been employed. The fruitful development of
lanthanide BTC-MOF was proved using FTIR spectroscopy. The crystalline
and microporous structure of MM-MOF showed the XRD and SEM
characterization. The specific BET surface area of the synthesized adsorbent
was 627 m2 g-1. The largest adsorption capacity was found to be 142.8 mg g-
1
which has been calculated using Langmuir isotherm which proves the
operative cooperation of two lanthanides in the MOF structure and increase
of the nonlinear possessions of MOF to absorb Nd3+ ions. They assessed
various optimizing parameters, such as initial metal ion concentration,
contact time, co-existing ions, temperature, and pH for the adsorption
process. The electrostatic interaction amongst a carboxyl group of MOFs
and Nd3+ ions shows the adsorption process and is found to be a promising
candidate as an adsorbent. The kinetic data and equilibrium data were best
fitted to the pseudo-second-order model and the Temkin isotherm model.
They found the adsorption process of Nd3+ ions to be spontaneous and
endothermic [102].
Mahmoodi et al. reported magnetic eggshell membrane (Fe3O4@ESM),
which was considered as a MOF support bed and produced by a low-
temperature co-precipitation method. To synthesize the water-based ZIF-
67@Fe3O4@ESM composite by ultrasound-assisted method, zeolitic
imidazolate framework-67 (ZIF-67) crystals having large porous volume
and high surface area up to 1403.7 m2 g-1 subclass of MOFs were
successfully stabilized and grown on the surface of the Fe3O4@ESM.
Various characterization techniques such as FTIR, EDS-Mapping, XRD,
New Generation Materials for the Adsorption of Toxic Metal Ion … 19

BET, VSM, and SEM were utilized to analyze the synthesized samples. For
the removal of Cu2+ and BR18 dye from wastewater, the ZIF-
67@Fe3O4@ESM composite showed better performance and faster
adsorption rate due to the high-surface-area contrast to other equipped
adsorbents. The adsorption data were best fitted to the Langmuir isotherm
model. The synthesized adsorbent showed the maximum adsorption
capacity for BR18 and Cu2+ was found to be 250.81 and 344.82 mg g-1,
respectively. The pseudo-second-order model was best fitted for kinetic
studies [103].

2.3. Electrocoagulation

The grouping of flotation, electrochemistry, and coagulation is known


as electrocoagulation (EC), which is an alternative emergent technique
toward heavy metal removal. In the EC technique, the succeeding
development of bigger particles and accumulation of particles achieved
through the advantage of flocculation/coagulation in which the system is
destabilized by the neutralization of the repulsive forces amongst particles
which results in the separation of toxicants. In EC there is no need to add
external chemical coagulants because through applying electric current over
the electrodes for the electrolytic oxidation of a sacrificial anode electrode
the metal coagulants and polyelectrolytes or salts are produced in situ [104,
105]. There is a need to add up to three chemicals and pH change in some
chemical coagulation procedures for reaching the greatest recitals, which
brands chemical coagulation as a labor-intensive and expensive technique
[106]. Characteristically, because of their low price, non-toxicity, high
valence, and availability, EC electrodes are made of iron and aluminum
metals [107, 108].
Though Gilhotra et al. reported that the EC procedure was utilized to
remove arsenic successfully by utilizing stainless steel electrodes [109]. The
aluminum electrodes were used in EC to remove zinc reported by Chen et
al. The outcomes proved that the disturbance in the speed of coagulant
formation and manufacture of Al3+ ions by alteration in current density the
20 Rekha Sharma, Sapna and Dinesh Kumar

EC energy consumption and removal efficiency of zinc was affected. They


performed the adsorption experiment with a wide-ranging initial zinc
concentration of 50-2000 ppm in the EC technique. From the results, they
concluded that after given some pre-treatments, the utilization of EC as a
final treatment step is more favorable, which achieve advanced removal
efficiencies at subordinate concentrations. In the EC technique, at the
cathode, the electrochemical reactions occur through reduction of Zn2+
besides the precipitation by aluminum hydroxide, which similarly shows a
vital role [110].
Doggaz et al. reported a similar EC process for the operative separation
of iron from wastewater [111]. In continuation of the environmental research
to treat wastewater making up the concentration of inorganic salts and
toxicants, Xua et al. reported Fe0-electrocoagulation (Fe0-EC) for the
removal of Cd2+ from wastewater thru examination of the effect of SO42− and
Cl−. This study shows that the Fe0-electrocoagulation (Fe0-EC) were
explored through assessing the alteration of Fe mineral. It was concluded
from the experimental results that the property of Fe minerals handles the
removal of Cd2+ from wastewater. From the results of co-ion studies on the
adsorption efficiency, it was concluded that the attendance of SO42−
exhibited the greatest adsorption for Cd2+ than the chloride green rust (GRCl)
because of the generation of sulfate green rust (GRSO4) which was found in
the mixture SO42− and Cl− solutions. This adsorption occurs because Fe2+–
Fe3+ GRs (layered double hydroxides, LDHs) displayed a weaker affinity for
monovalent Cl− than divalent SO42−. The negatively charged Fe flocs were
generated in wastewater because of a high concentration of inorganic anions.
Augmented the concentration of Cl− improved the ratio of Fe3+/Fe2+ in Fe
flocs and endorsed the oxidation of Fe2+ to Fe3+ by chlorine-containing
oxidants and subordinately owing to the increase of pH the Fe mineral
magnetite (Fe3O4) was formed. So, by the process of adsorption i.e., co-
precipitation and coagulation, the removal of Cd2+ ions increased in the
presence of GRSO4 intermediate and then through using oxygen from the
air, the produced GRSO4 was progressively altered into lepidocrocite (γ–
FeOOH). Various parameters were optimized to check the adsorption
efficiency, for example, initial Cd2+ concentration (C°), current density (j),
New Generation Materials for the Adsorption of Toxic Metal Ion … 21

regulating the ratio of SO42− and Cl− (RC:S), temperature (T°), and initial pH
(pHi). Under the best parameters, the synthesized Fe°-EC showed the
removal efficiency of 99.5% for Cd2+ ions and the equilibrium was reached
in 10 min at temperature 40°C and pH 7–9 [112].
In the EC technique, an electrocoagulation reactor comprising triple
aluminum tubes reported by Al Jaberi et al. for the removal of lead and it
was built concentric, putting cathode electrode in between the tubes of the
anode electrode. Various optimizing parameters are checked on the
adsorption process i.e., initial lead concentration (10-300) ppm, electric
current (0.2 - 2.6) Amps, the mixing speed of the neutral solution (150 rpm)
and the electrolysis time (2-30) min. In this work, the lead ions are removed
on the electrocoagulation reactor, which is an autocatalytic reactor and
improved the kinetics of the adsorption process [113].
Xu et al. reported that in iron–electrocoagulation processes, the redox
conditions governed the formation of functional products, which is an
extraordinary parameter. They studied the removal of cadmium from
wastewater on a newly synthesized rotating disc electrocoagulation system
(RDEC) supported through sodium sulfite. The redox atmosphere is altered
and regulated with sodium sulfite and rotate speed, respectively. First,
various optimizing parameters such as current density (j), initial Cd2+
concentration (C0), electrode distance (d), rotate speed (n), initial pH (pHi),
and Na2SO3 dosage (CS) in RDEC (Rotating disc electrocoagulation system)
process are assessed by an iron disc as sacrificial electrodes. Outcomes show
that electrode distance and rotate speed display a reverse, while effect
current density, Na2SO3 dosage, and initial pH have a positive effect on Cd2+
removal. The upsurge removal efficiency of Cd2+ may be ascribed to the
formation of Fe2+ – Fe3+ layered double hydroxides (LDHs) at high Na2SO3
dosage or low rotate speed. Thus, it was concluded that owing to oxygen-
free solution environment, and it is found to be a vital intermediate for the
removal of cadmium. In conclusion, to investigate the interactional
influences, Response Surface Methodology (RSM) is performed amongst
Na2SO3 dosage, rotate speed, and current density, and the experiment based
on a single factor experimental result. The actual energy consumption (EEC)
22 Rekha Sharma, Sapna and Dinesh Kumar

was found to be 2.98 kWh m-3, and removal efficiency was 98.11% for Cd2+
ions at the optimum operating conditions [114].

CONCLUSION

A critical examination of adsorbents, Carbon nanotubes,


electrochemical methods, electrocoagulation in this chapter demonstrates
the all the mentioned innovative method have been utilized for the mitigation
of heavy metal, inorganic, anions, organic and biological pathogens.
Synthesized adsorbents have the tendency to remove the toxic ions even at
the minimum concentration at different variable factors like pH,
temperature, adsorbent dose, etc. A lesser amount of adsorbent dose
consumption makes the adsorbents economically viable. Additionally, is has
been noticed the short time interval required by some composites like
biomimetic SiO2@CS composite around 2 min. The higher adsorption up to
602 mg g-1 for mercury ions was reported by graphene oxide embedded
calcium alginate. All diagnosed tremendous properties related to higher
adsorption capacity, required low concentration, amount of dose,
appropriate pH, fast removal during batch experiment contributed the goal
of new generation methods at the pilot, and industrial-scale columns. Most
early studies and current work have a dazzling future of new generation
methods in wastewater treatment. This chapter will give an insight to the
readers to put better effort to materialize economically, and workable water
treatment technology to solve the globally biggest issue.

ACKNOWLEDGMENTS

The authors gratefully acknowledge the support from the Ministry of


Human Resource Development Department of Higher Education,
Government of India under the scheme of Establishment of Centre of
Excellence for Training and Research in Frontier Areas of Science and
Technology (FAST), for providing the financial support to perform this
New Generation Materials for the Adsorption of Toxic Metal Ion … 23

study vide letter No, F. No. 5–5/201 4–TS.Vll. Dinesh Kumar is also
thankful DST, New Delhi for financial support to this work (sanctioned vide
project Sanction Order F. No. DST/TM/WTI/WIC/2K17/124(C).

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BIOGRAPHICAL SKETCHES

Rekha Sharma

Affiliation: Banasthali Vidyapith


Education: MSc, PhD
Research and Professional Experience: 4.5 years
Professional Appointments: Assistant Professor in Banasthali Vidyapith
Publications from the Last 3 Years: 4 research papers and 6 book chapters.

Sapna

Affiliation: Banasthali Vidyapith


Education: MSc, PhD
36 Rekha Sharma, Sapna and Dinesh Kumar

Research and Professional Experience: 4 years


Professional Appointments: Research Scholar
Publications from the Last 3 Years: 1 research papers and 6 book chapters.

Dinesh Kumar

Affiliation: Central University of Gujarat, Gandhinagar


Education: MSc, PhD
Research and Professional Experience: 17 years
Professional Appointments: Associate Professor
Publications from the Last 3 Years: 25
In: Drinking Water ISBN: 978-1-53618-070-1
Editor: Cécile Marcil © 2020 Nova Science Publishers, Inc.

Chapter 2

WATER TREATMENT METHODS FOR


DETOXIFICATION OF METAL IONS:
STATE-OF-THE-ART, FUTURE SCENARIO
AND CHALLENGES

Kritika S. Sharma1, Rekha Sharma2, PhD


and Dinesh Kumar1,, PhD
1
School of Chemical Sciences, Central University of Gujarat,
Gandhinagar, India
2
Department of Chemistry, Banasthali Vidyapith, Rajasthan, India

ABSTRACT
Approximately two million people die annually because of
contaminated drinking water and unsafe sanitation practices. The
generation of heavy metal ions is one of the prominent causes of water
pollution. Heavy metals such as lead, mercury, chromium, and arsenic exist
naturally, but anthropogenic activities cause contamination in water. The
World Health Organization (WHO) reports that approximately 1 billion
people across the world don’t have an approach to clean drinking water.
This count is presumed to eventually increase with increasing population


Corresponding Author’s E-mail: dsbchoudhary2002@gmail.com.
38 Kritika S. Sharma, Rekha Sharma and Dinesh Kumar

i.e., 7.7 billion (2019) from 7.5 billion (2018), energy requirement and
climate change. There are many commercially available methods to
detoxify water from heavy metals, while they are liable to rejection because
of: less efficient, expensive, generate hazardous toxic waste and energy-
consuming. This chapter will explore some advanced treatment methods,
which are in use like metal-organic frameworks (MOFs), UV irradiation,
etc. Some traditional techniques are still in use like adsorption, reverse
osmosis, electrodialysis and so on. Although they serve the purpose, either
cannot address these problems quickly, economically, long-term stability
or high performance despite development on the technical side. The
challenge is to provide solutions which are a universal or single solution,
inexpensive, has ease of implementation, cent percent efficiency, and
domestic use. The functional integration of different technologies or
treatments may solve the current water hazards. Impending water shortage
will lead to detoxifying the water, which is now considered undrinkable.
This chapter will emphasize the newest easy process, inadequacy, hurdles,
and prospects of drinking water treatment.

Keywords: detoxification, heavy metals, metal-organic frameworks,


ubiquitous solution

1. INTRODUCTION

Water covers 70% of the Earth, out of which only approximately 2.5%
is freshwater. But, 2.1% out of 2.5% freshwater is unreachable by the
human, as it is trapped in: glaciers, atmosphere and in massive depth of earth
surface [1]. Thus, only 0.4% of fresh drinkable water is available for 7.7
billion people (2019) [1]. Figure 1 illustrates the distribution of water on
Earth. Thus, because of increasing population and water pollution, there is
an alarming situation in the drinking water crisis across the world. There are
many sources of water pollution. Out of all the sources, contamination of
drinking water with metal ions is severe global distress. Metals like lead,
mercury, arsenic, chromium and so on occur in nature, but man-made
industrial activities such as mining and printing cause metal ion
contamination in water [2]. The notable characteristics of these metal ions
are bioaccumulation propensity, non-biodegradability because of these, they
are highly toxic even at a less concentration [3]. These pollutants have
Water Treatment Methods for Detoxification of Metal Ions 39

various adverse health effects in humans, ranging from losing listening and
vision power to fatal diseases such as kidney impairment and cancer [4].
Because of the consumption of contaminated water and unsound sanitation
practice, around two million people die per year. Thus, metal ions in water
are dangerous for mankind and require treatment [5].
This chapter will explore conventional and advanced treatment methods.
The limitations of conventional decontamination methods are lengthy or
expensive or possess operative hurdles or all [6, 7, 8]. Thus, there is an
urgent need to find new alternatives to traditional or conventional methods
used to treat water. Water crises will lead to the treatment and utilization of
water sources, which are now observed as hazardous if consumed by humans
[8]. Implementing nanotechnology has a broad scope in water treatment
technologies, as much research studies have shown favorable results.
Nanotechnology is considered as a costly method. However, the
nanotechnology-based techniques were not only inexpensive but also highly
efficient than traditional treatment methods was found in a study [9].
Nanotechnology-based treatment methods may be immensely vital in severe
water treatment solutions for a new and a trace amount of pollutants [9]. The
challenge is to find a single solution to all water pollutants with high
efficiency and cost-effectiveness. The combination of various treatment
methods may be a unique solution. However, much research on this idea is
still not performed.
The idea of developing a universal or single solution which is cost-
effective, has ease of implementation, 100% efficiency, and can be used
domestically paves the way for more research on alternatives that can be
used in future. Thus if these aspects achieved in the future, they will further
provide a wide spectrum of implementation of next generation water
treatment methods on large scale. This chapter will deliberate on the State-
of-the-Art, challenges, and future scenario for detoxification of metal ions
in an aqueous environment.
Figure 1. Distribution of water on Earth.
Water Treatment Methods for Detoxification of Metal Ions 41

2. STATE-OF-THE-ART OF WATER TREATMENT METHODS

Herein, the most modern treatment methods for water treatment will be
discussed. Water treatment comprises multi-step processes, as shown in
Figure 2. Industrial and municipal water treatments consist of primary,
secondary, and tertiary processes to get safe water. The primary treatment
process is another or introductory process applied before any treatment
method applied to the purification of water. It comprises many methods such
as sedimentation, centrifugation and so on, out of which microfiltration and
chemical precipitation are used.
For detoxification of metal ions from water; the secondary process is
generally applied for organic contaminant removal and is not discussed here
as per the interest of the topic. Tertiary processes are more refined methods
used at an end or final stage to get safe water. Out of several tertiary
processes used electrochemical precipitation, adsorption, membrane-based
technologies are used for detoxification of metal ions from water. Primary,
secondary, and tertiary processes comprise several methods; however, here,
we will only discuss methods for detoxification of metal ions in water as per
the interest of the topic.

Figure 2. Multi-step water treatment process.


42 Kritika S. Sharma, Rekha Sharma and Dinesh Kumar

2.1. Primary Process

2.1.1. Microfiltration
Microfiltration, with large pore size 100-1000 nm, is a membrane
filtration technology, which is based on the polymer or ceramic membrane.
It removes and filters some heavy metal ions, bacteria, microorganisms
bigger than micro-pollutants and viruses, total dissolved solids (TDS), and
algae [10], however, the efficiency of metal ions removal is not high. Thus,
after this primary treatment process, this water can be further treated in
tertiary purification processes such as ion-exchange and adsorption and so
on for more efficient detoxification of metal ions from water [11].

2.1.2. Chemical Precipitation


In this treatment, pH alteration of heavy metal ions and treatment
methods with chemical reagents such as sulfides, hydroxides, etc. leads to
an insoluble particle generation. These insoluble particles are separated via
sedimentation. Chemical precipitation is being used on a large scale in the
industrial treatment process for heavy metal ion removal. This process is
comparatively simple and is a cost-efficient and smooth operation
characteristic, which makes it helpful over other techniques [12]. However,
it has a big disadvantage of a compulsory requirement of post-treatment as
heavy metal ion amount does not reach the safe discharge range. Other
disadvantages are secondary contamination, massive sludge production, and
thus, the sludge discard process becomes mandatory [11].

2.2. Tertiary Process

2.2.1. Electrochemical Precipitation


Formation of a thin layer of metal ions can get the elemental state of
metal on a surface of the cathode using electrochemical methods [13]. This
process is eco-friendly, simple, and requires relatively lesser labor and
energy requirements. This process can also remove chemical oxygen
Water Treatment Methods for Detoxification of Metal Ions 43

demand from polluted water. But, the effectivity of heavy metal ions
removal is relatively less than tertiary treatment processes.

2.2.2. Adsorption
In the adsorption process, a substance (adsorbate) adheres to the
adsorbent surface because of the mass transfer process [14]. Similarly, this
concept is used in the water treatment process. The contaminants are
removed by stimulating adsorption on the adsorbent [15]. This treatment
process is popular, efficient, and cost-effective for heavy metal ion removal
[26]. It has several advantages, such as effective removal, the chance of
adsorbent regeneration and tunable: operation and design. Nanoparticles
(NPs) have a large surface-to-volume ratio, thus making them favorable for
adsorption because it is a surface-based phenomenon [17]. Carbon, zeolite,
and metal-based nanoadsorbents are different classes of adsorbent mostly
used. Other than these adsorbents, bioadsorbents are a new emerging class
of adsorbents with potential use.

2.2.2.1. Carbon-Based Nanoadsorbents


For heavy metal ion treatment, carbon-based nanoadsorbents is being
massively used. Nowadays most commercially used carbon-based adsorbent
is activated carbon (AC) [14]. Activated carbon has many advantages of
higher: surface area, porous structure, surface reaction affinity. Thus it is
effective and used for inorganic and organic contaminant removal from
water [18, 19]. Other emerging nanoadsorbents like graphene, carbon
nanotubes (CNTs) have also shown effectiveness in water treatment. Carbon
nanotubes show relatively more removal of heavy metal than AC. Thus,
researchers have shifted from AC to CNTs in the last decennary [20, 21].
Carbon nanotubes are further characterized into two major allotropes: single
and multi-walled carbon nanotubes. These two allotropes show efficiency in
removing heavy metal ions such as cadmium, cobalt, chromium, copper,
mercury, lead, europium, manganese, nickel, thorium, and arsenic. The
mechanism of heavy metal adsorption on CNTs is complicated and is
assigned to the chemical interaction, electrostatic attraction, and sorption
precipitation [21].
44 Kritika S. Sharma, Rekha Sharma and Dinesh Kumar

2.2.2.2. Metal-Based Nanoadsorbents


Efficient and cost-effective heavy metal ion removal is shown by nano
metal oxides of iron, magnesium, cerium, and zinc, etc. The heavy metal ion
removal mechanism is attributed to the oxygen present in the metal oxides-
heavy metal ions complex formation in a water sample [22, 23]. Nowadays,
the metal oxide has attracted much attention because of its favorable
characteristics such as higher surface/ volume ratio, mechanical sturdiness,
and easy regeneration. These characteristics lead to higher reactivity with
heavy metal ions [24, 25]. For removal of arsenic from water samples, the
most extensively used metal-based material is granular ferric hydroxide.

2.2.2.3. Zeolite Based Nanoadsorbents


The crystalline hydrated aluminosilicate materials with uniform-sized
pores are called zeolites. Zeolite based nanoadsorbents have been used for
heavy metal ion treatment [26-28]. Characteristics such as ion-exchange,
adsorption, and catalysis make zeolite-based nanoadsorbents favorable for
industrial use [29]. They are classified as nanomaterials because of their 0.4-
1 nm pore size. However, their particle size lies in a range of 1-10 mm [14].
The most widely used natural zeolite is Clinoptilolite. Synthetic zeolite
X106 and zeolite 4A105 are also reported. Sprynskyy et al. used natural
zeolites to remove multi-metal ions such as cadmium, lead, copper, and
nickel [26] simultaneously. The sorption occurred over three different steps
of fast adsorption on the external surface of clinoptilolite microcrystal by the
ion-exchange mechanism. They concluded that the sorption happened via
reversal step and scattering. Further authors observed that ion-exchange
adsorption is dependent on pH significantly. The detrimental effect on
adsorption was observed at a lower pH, and it may be due to H+ ions
competition [26]. Zeolite exchangers were examined by comparison of the
natural zeolite Clinoptilolite and the synthetic zeolites NaPl to effectively
remove metal ions [30, 31]. Synthetic or changed zeolites showed
significantly upgraded exchange capacity than the natural zeolites.

2.2.2.4. Bioadsorbents
Bioadsorbtion technique is used for the binding of a metal ion with itself
to separate metal ion pollutants from water. This method is even more
Water Treatment Methods for Detoxification of Metal Ions 45

efficient at less metal ion concentration, like ion-exchange methods [22].


Several adsorbents have also been derived from a waste of seafood,
agriculture, cellulose, etc. These adsorbents are eco-friendly, inexpensive
and thus are seen as potential alternatives to treat heavy metal ions [32, 33].

2.2.3. Membrane-Based Technologies


Water treatment membrane-based technologies have further subdivided
into different classes: reverse osmosis ultrafiltration, nanofiltration,
electrodialysis, and nanohybrid membranes.

2.2.3.1. Reverse Osmosis


It is the most widely used desalination technique across the globe. Thus,
it is also known as reverse seawater osmosis (SWRO). It is most useful for
the removal of several ions except As(III) from water. It is being used in
paper industries, dairy, pulp, food, and power plants, and so forth. A
semipermeable membrane is used for the separation of ions by RO from
water by exerting hydrostatic pressure in opposition to osmotic pressure. The
osmotic pressure settles the threshold of hydrostatic pressure. The water-
loving characteristics of RO membranes augment the transport of water [34].
However, the significant disadvantages of RO are losses of treated water,
more energy requirements, and expensive. Also, RO requires post-treatment
and readjustment because of a non-selective way to remove ions.

2.2.3.2. Ultrafiltration
Ultrafiltration (UF) has a membrane pore size that lies in a range of 10-
100 nm. It is used widely for the removal of bacteria, natural organic
colloids, viruses, and color pigments [35]. It has a favorable characteristic
of less energy requirement than reverse osmosis (RO). However, its
membrane pore size is greater than hydrated metal ions. Thus, these metal
ions easily go across UF membranes. This leads to unsatisfactory metal ion
rejection. To deal with this undesirable result, the surfactants are exteriorly
added to water, which leads to the generation of micellar-enhanced
ultrafiltration (MEUF). This improves the heavy metal ion rejection to
≥99% [36].
46 Kritika S. Sharma, Rekha Sharma and Dinesh Kumar

2.2.3.3. Nanofiltration
Nanofiltration (NF) membranes are used to treat contaminants <10 nm.
It is used on a large scale for heavy metal ion removal and water softening.
The mechanism for separation is attributed to both theories: steric, Donnan
exclusion [37]. The membranes compromise negatively charged or neutral
surfaces. However, the theory of Donnan exclusion showed that a positively
charged surface possesses greater flux and cation rejection, such as heavy
metal ions. Thus, the interest of researchers has now shifted to the
formulation of positively charged surface membranes for more efficient
treatment of heavy metal ions [38].

2.2.3.4. Electrodialysis
Electrodialysis (ED) is a membrane technique that electricity drives by
electricity. This process can be advanced by integrating with other processes
[39]. It is massively used in industries because of its characteristics of
substantial water recovery and minimal chemical use [40]. The ion-
exchange membranes (IEMs) are a core of ED systems. Both types of ion
exchange membranes comprise secure ionic groups on their support. The
current research has been emphasized to engineer a variety of new IEMs
with reduced electrical resistance, upgraded penetrability, and better
selectivity for particular ions. Integrating these characteristics of ED with
higher thermal, mechanical, and chemical stabilities leads to lower costs.

2.2.3.5. Nanohybrid Membranes


These are advanced membranes produced by integrating inorganic
particles and polymeric membrane raw material to enhance the polymer
component characteristics [41]. Scientist further subdivides this membrane
into two classes: mixed matrix membranes (MMMs) and nanocomposite
membranes (NCMs) [42]. Porous inorganic molecular sieves like zeolites
and carbon-based molecular sieves [43-45] are used to fabricate MMMs, to
get a superior separation performance [29, 46]. The incorporation changes
the membrane surface characteristics. The molecular sieves are used for
selective and preferential pathways for the H20 molecules inside the
polymeric matrices. It enhances water penetrability and the rejection of ions
[42].
Water Treatment Methods for Detoxification of Metal Ions 47

The NCMs is formed using nanoparticles such as Ag2O [47] within the
thin layer of the polymer to advance the membranes’ water-loving
(hydrophilicity) and antibacterial and photocatalytic characteristics [11, 48].

3. NEW GENERATION TECHNIQUES

3.1. Metal-Organic Framework/Polydopamine Composite

To treat water samples from the real world, an inexpensive, water-stable


FeBTC/PDA (metal-organic framework/polymer composite) that shows fast
removal of heavy metals like mercury and lead ions has been developed.
Chemical treatment of FeBTC (BTC = 1,3,5-benzenetricaboxylate) with
dopamine (DA), which undergoes a spontaneous polymerization to
polydopamine (PDA) within its pores via the ferric ion open metal sites. The
PDA, attached on the MOF interior surface, achieves better porosity, leads
in a composite that binds up to 1634 mg, 394 mg of mercury, lead ions per
gram composite, respectively. This MOF polymer-composite also produced
safe drinking water within seconds, by removal of >99.8% of these ions from
a 1 ppm sample. Also, composite characteristics are well kept in real water
samples of the river and spiked seawater with a minimal quantity of lead.
Thus, extraordinary selectivity is shown by this composite. Selectivity was
also constant in the presence of interferential ions like sodium ions, humic
acid in high concentrations [6].
MOF-polymer composite, FeBTC/PDA showed excellent selectivity
and extraction rate for a massive amount of lead and mercury. Also, this
composite by advancing the reduction of tiny quantities of lead ions can
make seawater drinkable in 1 minute. These noticeable characteristics are
obtained by adding porosity externally to a nonporous polymer-MOF
template. The advantage of a nanoporous window of the template is that it
prevents draining of hydrophilic polymer into the water, thus promoting
consistent performance, simple separation, and cycling. This nanoporous
window also prevents the damage of the composite by preventing the
organic interferents dispersal in a composite. This FeBTC/PDA composite
48 Kritika S. Sharma, Rekha Sharma and Dinesh Kumar

showed more performance, inexpensive separation, simple tunability,


renewability, and extended stability. Thus, potential results are shown by
this composite, and it may be used in domestic and water technologies in a
water shortage situation. The wise selection of MOF-polymer units may lead
to selective removal of a broad range of trace pollutants in water and air.
Further study and tuning of the characteristics of the FeBTC/PDA composite
will pave the way for its various unexplored applications [6].

3.2. Cathodic Hydrogen Peroxide Generation and UV Photolysis

Adsorption on oxides of iron for removing trace toxic elements is an


economical and potent technique. However, a generation of iron precipitates
is restricted in natural water resources at a comparatively low concentration
of iron. This is because of the existence of metal-complexing ligands linked
with natural organic matter (NOM). Thus, this situation arises the need to
add iron, and this makes the procedure complex as it leads to more quantities
of solids to be discarded. Although usually generation of an iron precipitate
is blocked because of the existence of metal complexing ligand linked with
NOM. A device composed of a cathodic cell generated H2O2 by UV
illumination to reduce NOM colloid stability and metal-complexing ability
in groundwater was developed. UV illumination changed NOM and
converted approximately six μm of iron oxides into precipitated form. This
led to the removal of 0.5-1 μm of copper, lead, and arsenic by adsorption on
iron oxides. After treatment, consistent changes in NOM with the loss of
iron-complexing carboxylate ligands were observed [8].

3.3. Photocatalytic Converter

Porphyrin (PP) dye-sensitized nanohybrids or nanomaterials possess a


new absorption band that corresponds to the solar irradiance spectrum. This
property makes the nanohybrid favorable for photocatalysis use. Here we
have infused protoporphyrin IX with copper(II) ions and sensitized porous
Water Treatment Methods for Detoxification of Metal Ions 49

TiO2 microspheres (approximately 1.5 mm in diameter) to generate a


functional nanohybrid for application in visible light photocatalysis. In
water, Cr6+ is carcinogenic, thus a dangerous heavy metal pollutant.
However, Cr3+ is not a toxic and vital nutrient for life forms. In the water on
UV light illumination, nanohybrid reduces Cr6+ to Cr3+. The favorable
impact of the Cu ion infusion into the sensitizing PP dye is noticeable from
the effectiveness in the photocatalytic reduction in the presence of water
dissolved metal ions (Cr3+ and Fe3+) is demonstrated. During photocatalytic
reduction, nanohybrid with the absence of Cu(II) experience other metal ion
intrusion [49].
(Cu)PP–TiO2 nanohybrids demonstrates effective recyclability,
increased photostability, and photocatalytic activity than PP–TiO2. Also,
PP–TiO2 demonstrates a notable decrease in photocatalytic activity because
of the existence of Cr3+ and Fe3+ in potable water. However, negligible
decrease in photocatalytic activity is shown by (Cu)PP–TiO2. Further, in this
study, a model for the real world or practical use was developed. In this
context, the (Cu)PP–TiO2 nanohybrid fabricated on a stainless-steel mesh
shows effective Cr6+ reduction. The (Cu) PP–TiO2 photocatalyst acts as a
detoxifying agent to reduce Cr6+ to Cr3+. The stainless-steel mesh serves as
a filter to eliminate dispersed matter, such as an insoluble photo-reduced
product. Thus, there is a two-fold cleaning action by the model developed.
Thus, to tackle chromium pollutants in water, this unique prototype or model
may serve as a potential device in future [49].

3.4. Graphene-Based Microbots

A graphene oxide microbots (GOx-microbots) for treatment of lead


(heavy metal) through an adsorption process was developed. These
microbots are self-propelling, and it seizes, transplants remove and
recuperates for recycling. These microbots comprise many layers of
platinum, graphene oxide and nickel, and each layer provides divergent
functions, as shown in Figure 3. Motile GOx-microbots is tenfold effective
than non-motile microbots. GOx-microbots cleanse water by a decreasing
50 Kritika S. Sharma, Rekha Sharma and Dinesh Kumar

level of lead from 1000 to 50 ppb in 1 hour. The microbots can be recycled
and used again after the chemical removal of Pb from the microbots surface.

Figure 3. Diagrammatic representation of GOx-microbots.

Microbots can be removed and recovered quickly by magnets. In a


microfluidic system under the magnetic influence, the microbots removal
and recovery was proved.
The GOx-microbots may be used as an advanced device for the
eradication of Pb because of its effective eradication and probability of Pb
recovery and reusability. Thus, more functions such as sensing, drug
delivery, and so forth of graphene-based nanomaterials can be explored in
future research [5].

4. FUTURE OUTLOOK

In 21st centenary with the increase in population and water pollution and
climate variation, there is an urgent need for new water treatment methods
for secure drinking water. To supply safe drinking water in sufficient volume
by improvement in terms of cost-efficiency and sturdy materials is the
requirement of water industries. With an increment in water demand, more
Water Treatment Methods for Detoxification of Metal Ions 51

firm health guidelines and emerging pollutants, the traditional methods show
inefficiency for supplying secure water. There is a need for inexpensive and
sturdy treatment methods that can not only provide safe drinking water. In
future modifications of nanotechnology treatment methods to conventional
methods will pave the way for advancement in drinking water treatment
processes. Nanotechnology water treatment methods have advantages such
as inexpensive, non-dependency on colossal infrastructure and fulfill several
functions. Also, the NPs can be used for catalysis, adsorption for oxidative
degradation, and removal of virulent pollutants from water. The vast
potential to remove organic contaminants is shown by the integration of
membrane technology with NPs. To remove metallic contaminants such as
Cd, Cu, As, Zn, Hg, and Cr from water, several minerals, agriculture waste,
and clay have been used continuously for a long time.
Today, nanostructured materials and nanoparticles are considered a
significant substitution for traditional adsorbent materials. There is a need
for further research in inherent characteristics, mechanisms, and
commercialization of nanotechnology-based and other alternative water
treatment methods [50]. Nanotechnology is seen as a new opportunity to be
explored by researchers. However, much knowledge of this field is still
unrevealed because of its originality. Thus, in future nanotechnology
treatment methods will be implemented on a massive scale because of its
advantages over conventional or traditional water treatment methods. Metal
nanoparticles (MNPs) are thus appropriate for the expulsion of many heavy
metals such as arsenic. Less toxicity and elevated efficiency for the removal
of heavy metal from potable or drinking water is shown by MNPs.
Disinfection via MNPs is less expensive, handy than alternative disinfection
treatments. Thus, MNP applications in water treatment have a full scope
[51].

5. CHALLENGES

In this chapter, we have discussed current widely used water treatment


methods for metal ion treatment in water. Several aspects of treatment
52 Kritika S. Sharma, Rekha Sharma and Dinesh Kumar

methods such as efficiency implementation, advantages, disadvanatges, etc.


are discussed.
A single treatment method that can perform treatment of all current
pollutants is still not found because of the limitations or disadvantages of
each method, as shown in Table 1. This gap can be used as a stepping stone
for future research. A solution for this idea of single or ubiquitous treatment
may combine the developed methods which may challenge in terms of
commercialization feasibility. Also, it is also noticeable that not even a
single treatment technique with cent percent efficiency under real world
samples is yet to be developed.
Improvement on the technical side is very rapid. However, improvement
in aspects of cost-effectiveness, efficiency, and commercialization
feasibility is at a much lower rate than technical development or
improvement. The causes for such a difference in the rate of development of
these aspects are also various and divergent [11].

Table 1. Widely used treatment methods and their


limitations/disadvantages

Treatment methods Limitations/disadvantages


Microfiltration Large pore size, less efficiency in the removal of metal ions,
requires further treatment.
Chemical Precipitation secondary contamination, massive sludge production, and thus,
the sludge discard process becomes mandatory, less efficiency in
removal of metal ions, requires further treatment.
Electrochemical Precipitation less efficiency in removal of metal ions
Adsorption and Ion Exchange Efficiency limit is thermodynamically forbidden by the
equilibrium nature of the process between bound and unbound
ions on a physical adsorption/exchange surface. In ion exchange:
the nominal 100% efficiency is impeded by defects present on
real membranes, which lead to a small, yet not negligible leakage
and highly ion-specific [52].
Reverse osmosis significant losses of treated water, more energy requirements,
expensive, requires post-treatment and readjustment because of a
non-selective way to remove ions.
Ultrafiltration membrane pore size is greater than hydrated metal ions. Thus,
these metal ions easily go across UF membranes. This leads to
unsatisfactory metal ion rejection.
Electrodialysis Electricity driven process
Water Treatment Methods for Detoxification of Metal Ions 53

Although Nanotechnology-based technique is seen as potential


alternatives to conventional methods used for treatment of water. The
challenge is to thoroughly study its environment toxicity and effects on
human health. In fact, gold standards for assessing the toxicity of
nanomaterials are still relatively scarce at present times. Hence,
comprehensive evaluation of the potential toxicity of nanomaterials is an
urgent need to enable and secure the full use of nanomaterials in real water
treatment applications [53, 54].
Well developed and widely used techniques like RO, electrodialysis and
nanofilteration have major challenges such as high capital and operating
costs [55]. And solution for these challenges should be found out for more
efficient treatment methods that can be used in future.
However, in spite of the above attempts to discuss the different methods
used for treatment, it is important to notice that water treatment is a
extremely important and complicated problem. The treatment process is
complicated and challenging due to the use of different highly specific
treatment processes with different water pollutants. Thus, hierarchy
arrangement of different process is not fair, as all the process remains highly
specific to the different varieties of pollutants, and no single treatment
process provide a ubiquitous or universal solution to all current
contaminants in water.

ACKNOWLEDGMENTS

Dinesh Kumar and Kritika S. Sharma are thankful DST, New Delhi for
financial support to this work (sanctioned vide project Sanction Order F. No.
DST/TM/WTI/WIC/2K17/124(C).

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60 Kritika S. Sharma, Rekha Sharma and Dinesh Kumar

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BIOGRAPHICAL SKETCHES

Kritika S. Sharma

Affiliation: Central University of Gujarat, Gandhinagar 382030


Education: MSc
Research and Professional Experience: 01 years
Professional Appointments: Research Scholar
Publications from the Last 3 Years: 5 book chapters

Rekha Sharma

Affiliation: Banasthali Vidyapith


Education: MSc, PhD
Research and Professional Experience: 4.5 years
Professional Appointments: Assistant Professor in Banasthali Vidyapith
Publications from the Last 3 Years: 4 research papers and 6 book chapters.
Water Treatment Methods for Detoxification of Metal Ions 61

Dinesh Kumar

Affiliation: Central University of Gujarat, Gandhinagar 382030


Education: MSc, PhD
Research and Professional Experience: 17 years
Professional Appointments: Associate Professor
Publications from the Last 3 Years: 25
In: Drinking Water ISBN: 978-1-53618-070-1
Editor: Cécile Marcil © 2020 Nova Science Publishers, Inc.

Chapter 3

A RAPID, NANOPOROUS ZEOLITE BASED


APPROACH FOR REMOVAL OF
BIOCHANIN A IN POTABLE WATER
DESTINED FOR DISTRIBUTION

Pawandeep Singh1, Vivek Sharma2


and Moushumi Ghosh1,*
1
Department of Biotechnology,
Thapar Institute of Engineering and Technology, Patiala, India
2
School of Life and Basic Science, Jaipur National University, Jaipur

ABSTRACT
The presence of Endocrine disrupting chemicals or EDCs in water
poses a serious threat to human health and several food production systems.
Apart from EDCs of synthetic origin, phytoestrogens which are plant
derived have received little attention in terms of affordable interventions
in potable water destined for distribution. This study reports a simple
effective intervention for Biochanin A in influent water using ZSM-5, a
Nano porous crystalline zeolite. The adsorbent ZSM-5 was prepared in
laboratory and characterized by x-ray diffraction (XRD), scanning electron
microscopy (SEM), transmission electron microscopy (TEM), Brunauer–

*
Corresponding Author’s E-mail: mghosh@thapar.edu.
64 Pawandeep Singh, Vivek Sharma and Moushumi Ghosh

Emmett–Teller (BET) adsorption and Fourier transform infrared (FTIR)


spectroscopy. ZSM-5 was nonporous with a surface area of 653 m2 g-1.
The effect of different parameters such as contact time, adsorbent dose and
initial solute concentration for removal of Biochanin A by ZSM-5 was
evaluated. The equilibrium data for the adsorption of Biochanin A on
ZSM-5 was tested in Langmuir and Freundlich adsorption models. Results
indicated that Langmuir isotherm model fitted well to equilibrium data in
contrast to Freundlich isotherm model. Complete removal of Biochanin A
using ZSM-5 in water indicated the possibility of application in drinking
water.

Keywords: phytoestrogens, ZSM-5, removal, drinking water, safety,


Biochanin A

1. INTRODUCTION

The application of appropriate methods for the development,


management and use of water resources contributes to availability and safety
of water (WHO1989) for sustainable food production (Jime´nez 2005).
Intensive agricultural practices and waste disposal systems release a number
of contaminants into surface water. Therefore, the quality of influent water
prior to conventional treatment for consumption varies in terms of
constituents many of which escape usual treatment processes. A number of
studies in the past decade have addressed the issue of human exposure and
risk of phytoestrogens through water. Regulatory norms for these, however,
exist in few countries (e.g., Japan). Besides, the effect of sub lethal
consequences for androgenic, estrogenic and anti-androgenic contaminants
of these compounds has largely been ignored.
Phytoestrogens are naturally occurring plant compounds that are
structurally or functionally similar to mammalian estrogens and their active
metabolites. Among them lignans, isoflavones, flavonoids and coumestains
form a major class (Wang et al., 2002, Patisaul & Jeffron. 2010, Knight &
Eden. 1996). Many isoflavones have the ability to inhibit cell proliferation
and growth. Moreover it is found that phytoestrogens interfere with
organizational role of estrogens in developing brain and reproductive system
A Rapid, Nanoporous Zeolite Based Approach for Removal … 65

(Crain et al. 2008). Manipulation in estrogen level during critical


development phases such as gestation and early infancy leads to adverse
health outcomes including malformations in the ovary, uterus, mammary
gland and prostate, early puberty, reduced fertility, disrupted brain
organization, and reproductive tract cancers (Gorski 1963, Lindzey &
Korac1997). Presence of phytoestrogens in lakes and other water bodies
have a significant effect of skewed sex ratio in fishes resulting gross decline
in productivity. To date several reports have clearly indicated the potential
loss of fish productivity upon exposure to phytoestrogens and synthetic
endocrine disruptors. It is imperative that apart from other features the
presence of phytoestrogens in water used for drinking purposes should be
minimal to ensure safety. The occurrence of phytoesterogens in surface
water varies widely depending upon their sources. Few strategies however
exist or have been advocated for this purpose. Zeolite, a microporous,
crystalline solid has a well defined structure of which framework is
composed of silicon, Aluminum and oxygen (Ohlin et. al., 2013, Tavolaro
& Drioli 1999). Presence of uniform micropores render zeolites unique and
responsible of characteristics separating molecules based on their sizes,
shape and polarity (Davis M. 2002). Nanocrystalline zeolites have emerged
as promising adsorbent materials as they have higher surface areas and
reduced diffusion path lengths relative to conventional micrometer-sized
zeolites (Song et al. 2004, Lindmark & Hedlund. 2010) and have been used
safely for water purification.
The application of zeolites especially nanocrystalline zeolites may prove
to be useful in rapid removal of phytoestrogens in water destined for
distribution. The economy and simplicity for such adsorptive removal using
nanozeolites can help enable practicability of this approach to regulate
phytoestrogen contents in potable water. The purpose of this study was
therefore development and applicability of nanocrystalline zeolites with an
aim of removing the phytoesterogen, Biochnain A from potable water. The
main parameters considered were contact time, adsorbent dose and initial
adsorbate concentration. The data was fitted in various adsorption models to
elucidate the adsorption mechanism and a final validation for determining
real time removal was attempted. We envisaged that a simple affordable
66 Pawandeep Singh, Vivek Sharma and Moushumi Ghosh

process may help assure safety of influent water through removal of


phytoestrogens effectively, thereby assuring safety to consumers.

2. METHODS

2.1. Synthesis of Zeolite (ZSM) and Its Characterization

The synthesis of nanoporous zeolite ZSM-5 was carried out by the


method proposed by Darzi et al. (2013). Tetraethylorthosilicate and
Aluminum Isopropoxide were used as a silica and aluminum sources and
TPAOH (Tetrapropylammonium hydroxide) was used as structure directing
agent (SDA) respectively. In the synthesis reaction, add 0.24 g of aluminum
isopropoxide in 17.7 mL solution of TPAOH (1 M) with stirring, followed
by successive addition of NaOH (0.0071 g) and double distilled water (22.8
mL). In the above mixture, add 15.87 mL of Tetraethylorthosilicate (TEOS)
and stirred at ambient temperature (ca. 25°C) for 24 h. Thereafter, the
synthesized gel was stirred under reflux at 100°C for 48 h. The crystals so
obtained were centrifuged, washed several times with distilled water and
dried at 90°C overnight. The synthesized nano porous zeolite was calcinated
in an electrical furnace at 550°C for 5 h to remove of organic template.
Crystal size and crystalline phase purity (Gursesa et al. 2006) of the
synthesized sample was determined by X-ray powder diffractometer
(XPERT-PRO). The XRD pattern for ZSM-5 was recorded by X-ray
diffractometer (Xpert Pro MPD, DY3190) at 35.4 kV and 28 mA. The
scanning range of 2h was set between 2° and 60° with a scan rate of 0.05
degree/second. Energy Dispersive X ray spectroscopy (EDX) were recorded
on INCAx- act (Oxford instruments) and employed to study the elemental
composition of nano crystals. Fourier transform infrared spectroscopy was
recorded at room temperature using FT-IR spectrometer (Aligent resolution
Pro, Cary 660). Scanning electron microscope (JEOL JSM-6100) was
employed to study the size and morphology of obtained nano porous crystals
(Harlick & Tezel. 2003); the specific surface area of ZSM-5 was determined
by Nitrogen adsorption-desorption isotherm (BET-Brunauer-Emmett-
A Rapid, Nanoporous Zeolite Based Approach for Removal … 67

Teller) analysis (Kaur, 2015). Analysis of Biochanin A following adsorption


studies was performed by UV-VIS spectrophotometer (Shimadzu UV-
1800).

2.2. Coating of ZSM-5 on PVDF Membrane

ZSM-5 corresponding to concentrations ranging from 0.01 - 0.6 g/L


were weighed and added in 5 mM phosphate buffer having pH 7.4. This
suspension was ultrasonicated for 30 min. PVDF (Polyvinylidene fluoride)
filter was then placed in filter assembly connected with vacuum
pump(Millipore, model no X15522050) and suspension was passed through
the filter assembly for three times. The coated filter membranes were placed
in an oven preset at 80ºC for 1.5 hours.

2.3. Adsorption Studies

Adsorption studies were carried out using zeolite coated membrane


filter. Different concentrations of Biochanin A (20, 40, 60, 80, 100 µg/L)
and ZSM-5 (0.01, 0.05, 0.1, 0.2, 0.4, 0.6 g/L) was used for adsorption
studies. The standard solution of Biochanin A was passed through zeolite
coated membrane filter and at different time intervals residual concentration
of Biochanin A was determined with a 1.0 cm light path quartz cells using
UV-VIS spectrophotometer at a maximum wavelength of 258 nm. All
experiments were performed in duplicates, and only the mean values are
reported. The maximum deviation observed was less than 5%. The removal
efficiency of BiochaninA was calculated according to the following
equation:

%R = C0-CF × 100 (1)


C0
68 Pawandeep Singh, Vivek Sharma and Moushumi Ghosh

Where C0 and CF (micrograms per liter) are the initial and final concentration
of element, respectively. The adsorption capacity qe after equilibrium
(micrograms per gram) was calculated by the following mass balance
relationship:

qe = (C0-Ce) × V (2)
W

Where, Co and Ce (micrograms per liter) are the initial and equilibrium
liquid–solid phase concentrations of element, respectively, V is the volume
of the solution (milliliters) and W is the mass of adsorbate (grams). The
sorption data for optimized contact time and Biochanin A concentration was
fitted to isotherm equation using MATLAB (Foo & Hameed. 2010). The
goodness of fit was determined based on coefficient of determination (R2)
and rigorous error functions (Ho. 2004).

Figure 1. XRD pattern of nanoporous ZSM-5.


A Rapid, Nanoporous Zeolite Based Approach for Removal … 69

3. RESULTS AND DISCUSSION

3.1. Characterization of ZSM-5 and Membrane Coated ZSM-5

The XRD pattern of powdered ZSM -5 is depicted in Figure 1. The peaks


observed at 20 = 7.9°, 8.9°, 23.2°, 24.5° indicates the purity of ZSM-5
nanoporous zeolite obtained in comparison to references obtained from the
literature (Darji et al. 2013). Field Emission Scanning Electron Microscope
(FE-SEM) images of ZSM-5 nanoporous zeolite (Figure 2) indicated the
formation of spherical nano sized particles of average diameter of less than
100 nm. Figure 3 depicts the FT-IR spectra of synthesized ZSM-5. The
formation of SiO4 tetrahedron units were confirmed from the bands located
at 790, 1080-1200 cm-1 characteristic of SiO4 (Darji et al. 2013). The external
asymmetric stretching vibration near 1,219 cm-1 may be attributed to the
presence of structures containing four chains of four-member rings of zeolite
structure. The band near 833 cm-1 is assigned to the symmetric stretching of
external linkages and the one near 542 cm-1 is attributed to a structure-
sensitive vibration caused by the double four-member rings of the external
linkages (Li & Armor. 2012).

Figure 2. Fe-SEM images of nanoporous ZSM-5.


70 Pawandeep Singh, Vivek Sharma and Moushumi Ghosh

Figure 3. FTIR spectra of nanoporous ZSM-5.

Energy-dispersive X-ray spectroscopy (EDX) technique provides useful


information about the presence of elements and their composition in the
synthesized zeolites. The EDX spectrum of ZSM-5 nanoporous zeolite is
illustrated in Figure 4. The elemental distribution comprises maximal
proportions of oxygen; aluminum and silicon are in the synthesized ZSM-5
(Table 1), the silicon rich nature, it is evident from the above data that silicon
contributes 45.03% by weight. Moreover aluminum and oxygen are also
present in ZSM-5 in line with those reported by Darzi et al. (2013). The
Scanning Electron Micrographs (Figure 5) depicts formation of few zeolite
layers over the surface of surface of membrane and a homogenous
distribution of ZSM-5 layers on membrane surface. The N2
adsorption/desorption isotherms at 77 K and pore sizes distribution of ZSM-
5 (results not shown) indicated characteristics of nano porous material. The
specific surface area was found to be 653m2 g-1. A high surface area has
been suggested to be an important parameter for effective adsorption.

Table 1. Elemental composition of synthesized ZSM-5

Elements Weight percentage Atomic percentage


Oxygen 53.79 67.29
Aluminium 1.00 0.74
Silicon 45.03 31.97
Total 100.00 100.00
A Rapid, Nanoporous Zeolite Based Approach for Removal … 71

Figure 4. EDX spectra of nanoporous ZSM-5.

Figure 5. Scanning Electron Microscope (SEM) images of uncoated membrane (a) and
ZSM-5 coated membrane.

3.2. Adsorption Studies

3.2.1. Effect of Initial Concentration and Time on Biochanin A


Removal
Effect of initial concentrations on Biochanin A removal by ZSM-5
coated filter membrane was studied using different concentration ranging
from 20µg/L to 100µg/L and adsorbent dose 0.6 g/L.
The removal of different concentration of Biochanin A increased with
time and attained maximum value at about 20 min, thereafter the values
72 Pawandeep Singh, Vivek Sharma and Moushumi Ghosh

remained constant (Figure 6). At lower initial concentration of 20µg/L


almost 50% removal was observed in first 5 min in contrast to 40% removal
at the concentration of 100 µg/L. Thus, Biochanin A removal was dependent
on contact time and its initial concentrations. Table 4 depicts the adsorption
kinetics of Biochanin A; during the early stages of adsorption, the rapid
removal of Biochanin A was observed which, in turn, attains constant value
for longer contact time with negligible effect on the rate of adsorption of
Biochanin A (Zhang & Wang. 2015). Hence, the equilibrium time of 20mins
was used for Biochanin A removal on ZSM-5 coated membrane. Iryani et
al. (2017) reported a similar observation during adsorption of Congo Red
dye using ZSM-5. An increase in adsorption rate was observed during the
first stage which slows down with the approach of equilibrium stage
Equilibrium sorption time depends upon several parameters include
agitation rate in liquid phase, physical properties of the adsorbent such as
surface charge density, porosity and surface area, amount of adsorbent,
properties of the adsorbate to be removed, initial concentration of adsorbate
and the presence of other molecules that may compete with the adsorbate
molecule of interest for the active sites (Say et al. 2003). The mechanism of
solute transfer to the solid includes diffusion through the fluid film around
the adsorbent particle and diffusion through the pores to the internal
adsorption sites. In the initial stages of Biochanin A adsorption, the
concentration gradient between the film and the available pore sites is large,
resulting in faster rate of adsorption. However, in later stages of Biochanin
A removal, rate of adsorption decreases due to slow pore diffusion of solute
in the bulk of adsorbent. At low concentration, the ratio of available surface
to the initial Biochanin A concentration is larger, so the removal observed is
greater in comparison to higher concentrations, where the available surface
area to initial Biochanin A ratio is low; this explains the reason for lower
Biochanin A removal.
Few studies have carried out adsorptive removal of Biochanin A and
Table 3 summarizes the maximum efficiency of adsorbents reported. In
comparison to activated carbon which shows good removal efficiencies,
ZSM-5 does not require prior activation and therefore can be a better option.
A Rapid, Nanoporous Zeolite Based Approach for Removal … 73

Figure 6. Effect of contact time and initial Biochanin A concentration on adsorption by


ZSM-5 coated membrane filters.

Table 2. Isotherm parameters of Langmuir and Freundlich isotherm


models for Biochanin A adsorption onto ZSM-5 coated membrane

Name Equation Constant R-square


Langmuir qe = QmKaCe/1 + KaCe Qm = 95.38 0.9931
Ka = 0.09073
Freundlich qe = KfCe1/n Kf = 0.06317 0.7841
N = 0.02275

Table 3. Comparison of maximum adsorptive capacities of Biochanin


A (qe) of various reported adsorbates

Qe (mg/g) reported for Adsorbate Reference


Biochanin A adsorption
6.54 Granular Activated Kaur, K (2015) Adsorptive Removal
carbon and regeneration study of Biochanin A.
MSc thesis, ThaparUniversity, Patiala,
INDIA
0.04 Biopolymer from starch Sehgal, S (2013) Surface Assimilation
degrading bacterial of phytoesterogens by microbial
isolate from the polymers. MSc thesis, Thapar
environment University, Patiala, INDIA
2.20 Na A zeolite Goyal et al. (2015)
5.80 ZSM-5 nanozeolite Current study
74 Pawandeep Singh, Vivek Sharma and Moushumi Ghosh

3.2.2. Effect of Adsorbent Dose, Initial Concentration, pH and


Temperature on Biochanin A Removal
The influence of adsorbent amount varying from 0.01- 0.6 g/L onto the
Biochanin A adsorption at different initial concentration (20µg/L to
100µg/L) is depicted in Figure 7. As observed from the figure, the Biochanin
A removal at lower initial concentration reaches almost 70% as dose
increased from 0.01 to 0.6 g/L. With increase in initial concentrations from
20µg/L to 100µg/L the removal percentage decreases from 70 to 50%. This
decrease in Biochanin A removal can be explained by the fact that adsorbent
molecules i.e., ZSM 5 posess a limited number of active sites, which is
saturated above a certain concentration (Sharoff & Vaidya. 2011). Increase
of the initial Biochanin A concentration results in a decrease in the initial
rate of external diffusion and increase in the intra particle diffusion. The
increase in Biochanin A removal with the adsorbent dose can be attributed
to increased surface area and the sorption sites. A pH of 6 was found to be
most favorable for maximal adsorption since higher concentrations resulted
in insignificant adsorption. This can be explained by considering that an
increase in pH over 6, leads to higher pHPZC(point of zero charge) on the
adsorbent i.e., net negative charge; since Biochanin A has the same charge,
adsorption is not favored. A temperature of 25°C was noted for maximal
adsorption of Biochanin A. Increasing temperature decreased the adsorptive
capacity. The adsorption spectra characterized by pi-pi *transition exhibits
a red shift and a total adsorption intensity with decreasing temperature when
hydrogen bonds are formed between solute and solvent molecules (Mitsuo,
1960) and explains the observations. These results were similar to those
reported by Aziz et. al., (2017) where ZSM -5 was effectively used to adsorb
VOCs.

3.2.3. Adsorption Isotherms


Different adsorption mechanisms and interactions between adsorbent
and adsorbate molecules are described using adsorption isotherm (Gupta &
Kundu, 2006). The authors reported that the distribution of adsorbed
molecules between solid and liquid phase occurred when the adsorption
process reaches equilibrium state. Equilibrium studies are useful to obtain
A Rapid, Nanoporous Zeolite Based Approach for Removal … 75

the adsorption capacity of ZSM-5 for Biochanin A removal. The equilibrium


data for the adsorption of Biochanin A using ZSM-5 fit into various isotherm
models which results in a suitable model that describes the interaction
between adsorbent and adsorbate molecules and adsorption mechanism. In
the present study, two equilibrium models were analyzed to investigate the
most appropriate adsorption isotherm for Biochanin A removal using
ZSM-5.

Langmuir Isotherm
The Langmuir equation is based on the assumption that maximum
adsorption corresponds to a saturated monolayer of solute on specific
homogenous sites of the adsorbent surface containing a finite number of
identical sites. The energy of the adsorption is constant, and there is no
transmigration of the adsorbate in the plane of the surface (Dada et. al.,
2012). The non-linear equation of Langmuir isotherm model can be
expressed in the following non-linear form:

qe= QmKaCe/1 + KaCe (3)

Figure 7. Effect of initial Biochanin A concentration and adsorbent dose on Biochanin


A removal percentage.
76 Pawandeep Singh, Vivek Sharma and Moushumi Ghosh

Where qe = amount of Biochanin A adsorbed per gram of adsorbent at


equilibrium, Qm = maximum monolayer coverage capacity (µg/g), Ka =
Langmuir isotherm constant, Ce = equilibrium concentration of adsorbate
(µg/L).
The results obtained from Langmuir isotherm are shown in Table 2. The
high value of correlation coefficient i.e., R2 = 0.9931 indicate the best fitted
model for this equilibrium data. This high value indicates a good agreement
between isotherm parameters and experimental values confirms the
monolayer adsorption of Biochanin A onto ZSM-5 surface shows the
homogenous nature of ZSM-5 coated membrane i.e., each molecule of ZSM-
5 has equal adsorption activation energy. The essential characteristics of
Langmuir isotherm and adsorption favorability can be expressed in terms of
dimensionless constant called the separation factor or equilibrium parameter
(RL), which is defined by the following equation (Kadirvelu et al. 2001):

RL = 1/1 + KaCo (4)

Where Ka is the Langmuir constant and Co is the initial concentration of


Biochanin A with different concentration as mentioned from (20–100 µg/L).
The value of RL is found in the range of (0.099 – 0.355) i.e., (0 < RL < 1)
which confirms the favorable adsorption process for Biochanin A removal
using ZSM 5 coated membrane under conditions used in this study.

Freundlich Isotherm
This isotherm is commonly used to describe the non-ideal and reversible
adsorption which is not restricted to the formation of monolayer. The
empirical model is applied for multilayer adsorption, with non-uniform
distribution of adsorption heat and affinities over heterogeneous surface
(Foo & Hameed, 2010). The non linear equation proposed by Freundlich is
as follows:

qe = KfCe1/n (5)
A Rapid, Nanoporous Zeolite Based Approach for Removal … 77

Figure 8. Langmuir and Freundlich isotherm models fitted in experimental


adsorption data.

Where Kf = Freundlich isotherm constant (µg/g), 1/n = adsorption intensity,


Ce = equilibrium concentration of adsorbate (µg/L), qe = amount of
Biochanin A absorbed per gram of adsorbent at equilibrium. The constant
“n” gives an indication of how favorable the adsorption processes are. The
slope 1/n is a measure of adsorption intensity or surface heterogeneity that
represents the deviation from linearity of adsorption as follows: if the value
of 1/n = 1, the adsorption is linear, 1/n < 1, the adsorption process is
chemical, if 1/n > 1, the adsorption is a favorable physical process and
adsorption is cooperative (Crini et al. 2007).
The results obtained from Freundlich isotherm are shown in Figure 8.
The correlation coefficient, R2 = 0.7841, for Freundlich model shows that
experimental data does not fit in this isotherm in comparison to Langmuir
adsorption model. In real time surface water, significant (removal of
Biochanin A was observed with 0.6g/L of ZSM-5 (Table 5). These results
indicated that apart from effectively removing Biochanin A, interfering
substances had possibly little effect on the process itself and therefore can
be applied practically. The adsorption kinetics studied by evaluating the
pseudo first-order and second-order adsorption rate models indicated that
the pseudo second order model could describe the process better (results not
78 Pawandeep Singh, Vivek Sharma and Moushumi Ghosh

shown). The adsorptive process was also endothermic. Similar results have
been indicated by Goyal et al., (2016). Overall, the ZSM-5 synthesized in
the present study could remove Biochanin A effectively from water destined
for supply. We are currently evaluating the possibility of Vitellogenin as a
biomarker for evaluating EDC levels especially in surface water at various
locations, to study phytoestrogen impacted water. This should afford a
possibility of application of ZSM-5 and subsequent monitoring to ensure
safety of water as an additional treatment in influent water mandated for
public distribution.

Table 4. Effect of contact time on removal of Biochanin A by ZSM-5

Time (minutes) Biochanin A removal (%)


0 0
5 50%
10 55%
15 58%
20 60%
25 63
30 66%
40 68%
50 69.5%
60 70%
70 75.2%

Table 5. Removal of Biochanin A from randomly sampled influent


water (6 domestic water treatment locations) with ZSM-5 coated
membrane. ZSM-5 was used at a dosage of 0.6g/L. ND = below
detection threshold. Figures in parenthesis indicate mean + S.D (n = 3)

Concentration of Biochanin A (µg/mL) in six Residual concentration of Biochanin A


randomly smpled water samples. (µg/mL) after ZSM-5 filtration
30 1.3 ± 0.02
12 ND
20 1.2 ± 0.04
6 ND
19 ND
22 ND
A Rapid, Nanoporous Zeolite Based Approach for Removal … 79

CONCLUSION

Overall, in this study Biochanin A, a prevalent phytoestrogen in influent


water mandated for treatment and distribution could be effectively removed
using nanoporous zeolite ZSM-5 synthesized in this study. Levels of
phytoestrogens are usually not analyzed in either influent water or finished
water. In view of the large variability of surface water especially in India,
the phytoestrogen contamination of influent water from various sources
(occurring from agricultural operations, wood processing industries, soya
industries and others) assumes relevance. The removal of Biochanin A was
a function of on the quantity of adsorbent, time and initial concentration of
adsorbate. The removal of Biochanin A increased with time and maximum
value of 70% at about 20 min at ambient temperature. Furthermore, almost
70% removal of Biochanin A occurred at lower initial concentration (20
µg/L) as the dose increased from 0.01 to 0.6 g/L. The equilibrium adsorption
data were tested using Langmuir and Freundlich Isotherm model and data
fitted well in Langmuir isotherm model which indicates the monolayer
adsorption of Biochanin A onto ZSM-5 coated filter membrane. Given the
actual concentration of Biochanin A as observed from analysis of surface
water samples (Table 3), a near complete removal can be expected (within
the MOE or Margin for exposure set forth for endocrine disruptors in
drinking water, USEPA) prior to supply . Therefore safety of influent water
following treatment resulting from potential estrogenic activities of
Biochanin A is evident. In addition, the applicability of this method for water
reuse especially for aquaculture and other purposes should also be possible.

ACKNOWLEDGMENTS

The authors wish to acknowledge CSIR, Govt of India, for funding a


part of this work.
80 Pawandeep Singh, Vivek Sharma and Moushumi Ghosh

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In: Drinking Water ISBN: 978-1-53618-070-1
Editor: Cécile Marcil © 2020 Nova Science Publishers, Inc.

Chapter 4

THE ROLE OF SPHINGOMONAS


PAUCIMOBILIS IN INTERGENERIC
CO-AGGREGATION AND MIXED BIOFILM
FORMATION WITH WATER BORNE
PATHOGENIC BACTERIA IN THE
DISTRIBUTED DRINKING WATER SYSTEM:
IMPLICATIONS OF PUBLIC HEALTH RISK

Parul Gulati and Moushumi Ghosh*


Department of Biotechnology,
Thapar Institute of Engineering and Technology, Patiala, India

ABSTRACT
Sphingomonas a resident microorganism, is often encountered in the
drinking water systems (DWDS). Its capability of growth over a range of
temperatures, tolerance to chlorination and antimicrobial resistance
patterns have recently raised health concerns. Several physiological
aspects, for instance role of co-aggregation and biofilm formation

*
Corresponding Author’s E-mail: mghosh@thapar.edu.
84 Parul Gulati and Moushumi Ghosh

especially with water borne pathogens by Sphingomonas remains largely


unknown and deserve attention. In this study, a Sphingomonas
paucimobilis strain isolated from Indian drinking water system was
evaluated for its ability to co-aggregate and form mixed biofilms with
Salmonella typhimurium, Shigella flexneri, Escherichia coli O57:H7.
Strong co-aggregation of Sphingomonas with the waterborne pathogens
Escherichia coli O157:H7 ATCC 32150, Shigella flexneri 2a and
Salmonella typhimurium ATCC 25315 was observed by qualitative and
quantitative methods with individual pathogens as well with a cocktail of
the above three water borne pathogens. Highest aggregation index was
observed with Shigella flexneri 2a followed by Salmonella typhimurium
and Escherichia coli O157:H7. The aggregation with Escherichia coli
O157:H7 could not be reversed by heat, protease and sugars (lactose and
galactose). The results of this study have a strong implication on risk of
mixed biofilms of these water borne pathogens in DWDS which may have
re-grown or introduced (either through leakage or faulty treatment
processes) and eventually develop into biofilms with pre existing
Sphingomonas. An effective, non invasive treatment strategy preferably
aimed in disrupting signalling molecules of Sphingomonas may be of
value, for assuring safety of drinking water.

Keywords: co-aggregation, adhesin, biofilms, sphingomonas, protease

INTRODUCTION

The microbial ecology of water distribution systems has been an area of


continued research, driven by the necessity to design innovative and
effective control strategies for ensuring safe and high-quality drinking water.
Existing results of microbial ecology of drinking water distribution systems
indicate that pathogen resistance is greatly affected by the biodiversity of
community and interspecies relationships. Biofilms have assumed
considerable significance in this regard and biofilm formation and adhesion
of bacteria on different surfaces and the EPS production by biofilm forming
microbes have been well studied in general (Flemming et al., 2007; Furuhata
et al., 2008; Simoes et al., 2007a; Skillman et al., 1998; Tsuneda et al., 2003).
Sphingomonas has been a recent focus for study on account of its ubiquitous
presence in water, persistence under low nutrient conditions and potentially
pathogenic features highlighting the concern in the presence of these
The Role of Sphingomonas paucimobilis in Intergeneric … 85

bacteria in drinking water distribution system. The biological safety issues


which are caused by Sphingomonas in the distribution systems stem from
their persistence and ability to secrete exopolysaccharides as major
components of biofilm (Johnsen et al., 2000). Bereschenko et al. (2010)
demonstrated that Sphingomonads were responsible for initial biofilm
formation. Aggregation has been established as one of the essential steps
towards biofilm formation and it depends on a range of interactions such as
synergistic, antagonistic, mutualistic, competitive, and commensalism
interactions (Simoes et al., 2007b). Bacterial co-aggregation is essential for
the development of multispecies biofilm communities’ i.e., the adherence of
different bacterial species to each other. Furthermore, co-aggregation is a
significant phenomenon that facilitates interaction among different bacterial
species in the biofilm (Foster et al., 2004; Rickard et al., 2003a). The
interactions may occur between protein adhesins and polysaccharide
receptors (Kline et al. 2009; Kolenbrander et al., 2006) or between
proteinaceous adhesin-receptors (Daep et al., 2008). Therefore co-
aggregation of Sphingomonas with waterborne pathogens may assume
significance in view of development of multispecies biofilms of potential
concern. Few studies, however have systematically analyzed aggregation,
co-aggregation and biofilm formation by Sphingomonas sp. isolated from
drinking water (Buswell et al., 1997; Simoes et al., 2007a,b; Simoes et al.,
2008; Yu et al., 2010) In an earlier study, we isolated a Sphingomonas sp.
from public drinking water system and characterized its biofilm formation
(Gulati and Ghosh, 2017); simulation studies indicated that this strain was
able to form biofilms on various plumbing materials used in drinking water
systems. The objective of the present study was to further characterize the
aggregation and co-aggregation behavior with water borne pathogens of this
Sphingomonas strain. We envisaged that investigations of these interactions
will help shed light on the role of Sphingomonas in formation of mixed
species biofilms and enable designing of effective treatment strategies for
safe drinking water.
86 Parul Gulati and Moushumi Ghosh

MATERIAL AND METHODS

Bacterial Strains and Culture Conditions

Drinking water samples were collected from twenty different municipal


sites and one hundred and forty isolates were screened by growing on
Sphingomonas- specific growth medium (Yim et al., 2010) at 30ºC and 120
rpm for 24 hours. One isolate with demonstrable biofilm forming ability was
selected for further studies. 16S sequence of the isolate was submitted in
genbank database as Sphingomonas paucimobilis strain MG6. The standard
strain of Sphingomonas terrae MTCC 7766 was used in parallel for the sake
of comparison. The following water borne pathogens were used in
coaggregation studies: Escherichia coli O157:H7 ATCC 32150, Shigella
flexneri 2a and Salmonella typhimurium ATCC 25315. Prior to experiments,
cultures were revived, grown on BHI agar thrice, individual colonies were
inoculated in BHI (Brain Heart Infusion Broth, Himedia, India) broth and
processed as described above.

Mixed Biofilm Profile by S. Paucimobilis MG6

The mixed biofilm of S. paucimobilis MG6 and S. terrae 7766 with


water borne pathogens was formed by Crystal violet assay with
modifications of Merritt et al. (2005). Standardized suspension of mid-log
phase bacterial cultures were dispensed in each well of the polystyrene plates
and incubated at 30°C. The unbound cells were removed by inverting the
micro titer plate and vigorous tapping followed by rinsing the wells with
phosphate buffer (pH 7.2). The adherent cells were stained with 200µl of 1%
(w/v) crystal violet solution for 5 minutes. The wells were washed with
deionized water extensively and the plates were allowed to dry. Following
washing, 200µl of 30% (v/v) acetic acid was added to each well for 15
minutes; 100µl aliquots were then transferred to fresh micro titer plate and
the absorbance measured at 585 nm. The variation from control S.
paucimobilis MG6 was further confirmed by SEM.
The Role of Sphingomonas paucimobilis in Intergeneric … 87

Aggregation Assay

Both S. terrae MTCC 7766 and S. paucimobilis MG6 were further


explored for their aggregation property. Fifty ml of the strains were
harvested in their growth phases at 7000 *g for 5 minutes at 4ºC. After
washing it twice in Phosphate Buffered Saline (PBS), the cells were
resuspended in PBS and OD600 was adjusted to 1.0. The adjusted stock was
used for aggregation analysis.

Visual Aggregation Assay

The degree of auto- and co-aggregation was determined qualitatively by


the scoring method of Cisar et al. (1979). To determine auto aggregation,
both the strains were transferred to different test tubes, while in the case of
co-aggregation, the cultures were mixed in pairs with each of the three
pathogen, i.e., Escherichia coli O157:H7 ATCC 32150, Salmonella
typhimurium ATCC 25315 and Shigella flexneri 2a. The pure and mixed
cultures in pairs were vortexed for 30 sec and incubated at room temperature
for 72 hours. The scoring range used is as follows: 0 represents no
aggregation and turbid suspension; 1 represents small uniform aggregates in
a turbid suspension; 2- easily visible aggregates in a turbid suspension; 3 -
clearly visible aggregates which settles leaving a clear supernatant; 4 - large
flocs of aggregates that settle instantaneously (Cisar et al. 1979; Simoes et
al. 2008).

Spectrophotometric Assay

In order to quantitatively determine aggregation, test cultures in


triplicates were prepared as described above for auto- and co-aggregation
and incubated at room temperature. One hundred microlitre of the aqueous
phase was transferred to microtitre plate and absorbance was recorded at 0,
88 Parul Gulati and Moushumi Ghosh

2, 4, 24, 48 and 72 hours. Percentage of aggregation was measured using the


following formula:

Percentage of Aggregation = [(A600 initial - A600 after incubation)/


A600 initial] *100

Aggregation Studies by Fluorescence Microscopy

Cell aggregates were fixed in 10 ml of a 1% paraformaldehyde solution


in 1X PBS for 2 hours at room temperature. The aggregates were mounted
on a sterile glass slide and allowed to dry. Stained the slides with DAPI
(4’,6’-Diamidino-2-phenylindole) and observed under epifluorescence
microscope (Zeiss Axio Scope A1 Microscope, USA).

Coaggregation Reversal: Effect of Heat, Protease and Sugars

To study the effect of heat treatment on the aggregation ability of


Sphingomonas and the waterborne pathogens, both treated and untreated
auto- and co-aggregating bacterial pairs were used for visual and
spectrophotometric analysis. The bacterial cultures were incubated at 85ºC
for 30 minutes for describing co-aggregation reversal by heat treatment
(Kolenbrander et al., 1985). The method described by Rickard et al. (2003b)
and Simoes et al. (2008) was used to understand the protease sensitivity of
the aggregation. The protease type XVI from Streptomyces griseus
(Himedia, India) was added at the final concentration of 2mg ml-1 and
incubated at 30°C for 2 hours. After incubation, cells were harvested,
washed twice and O.D. was adjusted to 1.0 at 600 nm. The untreated and
treated strains were mixed in equal ratios. The experiment was carried out
in triplicates (Ramalinganam et al. 2013). To study the effect of sugars on
aggregation, filter-sterilized solutions of lactose and galactose were added
to coaggregating partners to final concentrations of 50 mM to study the
The Role of Sphingomonas paucimobilis in Intergeneric … 89

effect of sugars. Mixtures were vortexed and tested for coaggregation using
the method of Rickard et al. (2003a).

RESULTS

Mixed Biofilm Profile by Sphingomonas

The sequence of the isolate has been deposited in GenBank database


(Accession No KX594380). Both biomass quantity and microbial activity
are the parameters mostly used to estimate the amount of biofilm (Characklis
et al., 1990). The Crystal violet assay has been described as a rapid method
for calculating cell biomass; maximum biofilm production occurred between
24 to 48 hours as the cells are in the late stationary phase before senescence
phase starts. Cells in the stationary phase start synthesizing the EPS which
facilitates the attachment of cells to the surface (Dunne 2002). Mixed
biofilms (S. paucimobilis MG6/S. terrae 7766 + E. coli, S. flexneri 2a and
S. typhimurium) exhibited variation than that observed in the controls and
reached maturation with 65-70 hours by the kinetics (Figure 1). Scanning
electron microscopy (SEM) was used to visualize the cell-surface of biofilm
forming Sphingomonas with adhered pathogens on PVC coupons. Tight
adherence of the biofilm cells with PVC was observed for S. paucimobilis
with the cells being enmeshed in exopolysaccharides (Figure 2). Though S.
terrae produced less exopolysaccharides, adherence was observed on PVC.
The results suggested stable attachment of pathogen-S. paucimobilis bifilm
on PVC matrix.

Visual Aggregation Assay

Based on the scoring method, results of auto- and co-aggregation were


analyzed. No aggregation of pure cultures as well as combinations after zero
hour of incubation was observed. Hence the cultures were further incubated
at room temperature. Aggregation was visible as turbid suspension after 24
90 Parul Gulati and Moushumi Ghosh

hours and clear supernatant with clear aggregates after 72 hours (Figure 3).
Based on the visual observation, scores were provided following the scoring
range used in literature (Cisar et al., 1979; Simoes et al., 2008).

Spectrophotometric Analysis

The incubation time is an important requisite for determining the


aggregation index of auto-aggregating bacteria as well as co-aggregating
bacterial pairs as reported by Saravan et al. (2014). Therefore the
aggregation index was determined for all the cases at 0, 2, 4, 24, 48 and 72
hours. Aggregation indices of S. terrae MTCC 7766 and S. paucimobilis
MG6 were calculated to be 74.5% and 82.75% respectively after 72 hours
of incubation (Figure 4). Aggregation index of Sphingomonas with Shigella
flexneri 2a was found to be approx. 84.8% -highest when compared to other
pathogens.

1.5 1.5
CONTROL CONTROL
MIXED MIXED
O.D. (585 nm)

O.D. (585 nm)

1.0 1.0

0.5 0.5

0.0 0.0
0 20 40 60 80 0 20 40 60 80
Time (in hours) Time (in hours)

(a) (b)

Figure 1. Kinetics of mixed biofilm formation of (a) S. paucimobilis MG6 (b) S. terrae
7766 with water borne pathogens (E. coli, S. flexneri 2a and S. typhimurium).
The Role of Sphingomonas paucimobilis in Intergeneric … 91

A A+C+D+E B B+C+D+E
Figure 2. Scanning electron Micrographs of mixed biofilms of (a) S. paucimobilis MG6 (b) S. terrae 7766,
Figure
where,2.A=Sphingomonas
Scanning electronisolate;
Micrographs of mixed biofilms
B=Sphingomonas of (a) 7766;
terrae MTCC S. paucimobilis
C= Salmonella typhimurium ATCC
MG6 (b) S. terrae 7766, where, A=Sphingomonas isolate; B=Sphingomonas terraebiofilms were developed
25315; D= Escherichia coli O157:H7 ATCC 32150; E= Shigella flexneri 2a. Mixed
MTCC
on PVC7766; C= Salmonella typhimurium ATCC 25315; D= Escherichia coli
coupons.
O157:H7 ATCC 32150; E= Shigella flexneri 2a. Mixed biofilms were developed on
PVC coupons.

(a) 0 hours (a) 72 hours

(b) 0 hours (b) 72 hours

Figure 3. Visual aggregation assay of (a) Sphingomonas paucimobilis strain MG6 (b)
Sphingomonas terrae MTCC 7766.
Percentage of Aggregation 100 100 100 100 100

Percentage of Aggregation

Percentage of Aggregation

Percentage of Aggregation

Percentage of Aggregation
80 80 80 80 80

60 60 60 60 60

40 40 40 40 40

20 20 20 20 20

0 0 0 0 0
2

4
24

48

72

24

48

72

24

48

72

24

48

72
Time (hours) Time (hours) Time (hours) Time (hours) Time (hours)

A A+D A+C A+E A+C+D+E


(a)
80 100 100 100 100
Percentage of Aggregation

Percentage of Aggregation

Percentage of Aggregation

Percentage of Aggregation
Percentage of Aggregation
80 80 80 80
60

60 60 60 60
40
40 40 40 40
20
20 20 20 20

0 0 0 0 0
24

48

72

24

48

72

24

48

72

24

48

72
2

4
24

48

72
2

4
Time (hours) Time (hours) Time (hours) Time (hours) Time (hours)

B B+D B+C B+E B+C+D+E


(b)

Figure 4. Aggregation Index at different interval of time (a) Sphingomonas paucimobilis MG6 and its various combinatons
(b) Sphingomonas terrae MTCC 7766 and its combinations; where, A = Sphingomonas paucimobilis MG6; B = Sphingomonas terrae
MTCC 7766;C = Salmonella typhimurium ATCC 25315; D = Escherichia coli O157:H7 ATCC 32150; E = Shigella flexneri 2a.
The Role of Sphingomonas Paucimobilis in Intergeneric … 93

Visualization of Aggregates by DAPI

Direct staining by DAPI (4’,6-diamidino-2-phenylindole) is a method of


choice, the DAPI molecules bind to DNA and fluoresce intensely. The
enhancement in aggregation ability of S. paucimobilis MG6 in the presence
of three pathogens could be clearly depicted by DAPI staining. Furthermore,
a cocktail of all three pathogens used to co-aggregate with Sphingomonas
indicated a similar result. In fact the aggregating pairs showed a higher level
of interactions as compared to the visual aggregation test for these strains
when observed by microscopy (Figure 5 and 6).

Nature of Interactions between Bacterial Strains

The heat treated and untreated pure cultures did not aggregate either
after zero hour of incubation or following 2 hours of incubation. Co-
aggregation between different combinations was significantly affected (p <
0.05) upon heat treatment with the exception of E.coli O157:H7, since
aggregation index remained at 80% in both treated and untreated samples
(Figure 7). Several E. coli O157:H7 surface proteins are thought to be
important for adhesion and/or biofilm formation, therefore it is possible that
the treatment processes failed to exert a substantial effect on binding. Co-
aggregation reversal by Lactose and galactose was not observed, suggesting
possibilities with other sugars.
The inhibition of aggregation of Sphingomonas with its aggregating
partners might be due to surface protein like attachment (Figure 8s).
Sphingomonas with its aggregating partner, E.coli O157:H7 showed no
decrease in aggregation index. Treatment with sugars-lactose and galactose
failed to revert co-aggregation (Figure 9 & 10)–. The differential behavior
observed may be attributed to the enzyme type and concentration (Goldhar,
1995) important for affecting lectins during the treatment process, in
addition to the nutritive media which modulates lectin production (Gilboa-
Garber, 1988; Goldhar, 1995). However, further possibility of co-
aggregation reversal need also be examined with other sugars.
94 Parul Gulati and Moushumi Ghosh

A A+D A+C

A+E A+C+D+E

Figure 5. Photomicrograph of DAPI stained cells of auto- and co aggregating S.


paucimobilis MG6 and its various combinations with pathogens.

B B+D B+C

B+E B+C+D+E

Figure 6. Photomicrograph of DAPI stained cells of auto- and co aggregating


Sphingomonas terrae MTCC 7766 and its various combinations.
A A+D A+C A+E A+C+D+E

(a)

B B+C B+D B+E B+C+D+E


(b)

Figure 7. Aggregation Index observed at different time intervals after heat treatment (a) S. paucimobilis MG6 and various combinations
(b) Sphingomonas terrae MTCC 7766 and various combinations.
A A+D A+E A+C A+C+D+E

(a)

B B+D B+E B+C B+C+D+E


(b)
Figure 8. Aggregation Index observed at different time intervals after protease treatment (a) S. paucimobilis MG6 and its various combinations (b) S.
Figure 8. Aggregation
terrae Index observed
7766 and its various at different time intervals after protease treatment (a) S. paucimobilis MG6 and its various
combinations
combinations (b) S. terrae 7766 and its various combinations.
80 80 80
Percentage of Aggregation

Percentage of Aggregation
Percentage of Aggregation
80 80

Percentage of Aggregation

Percentage of Aggregation
60 60 60
60 60

40 40 40
40 40

20 20 20
20 20

0 0 0
0 0
2 4 24 48 72 2 4 24 48 72 2 4 24 48 72 2 4 24 48 72 2 4 24 48 72
Time (in hours) Time (in hours) Time (in hours)
Time (in hours) Time (in hours)

A A+D A+C A+E A+C+D+E

(a)

Percentage of Aggregation
80 80
Percentage of Aggregation

Percentage of Aggregation
Percentage of Aggregation

80 80

Percentage of Aggregation
80

60 60 60 60 60

40 40 40 40 40

20 20 20 20 20

0 0 0 0 0
24

48

72
2

24

48

72
2

24

48

72
2

4
24

48

72

24

48

72
2

4
Time (in hours) Time (in hours) Time (in hours) Time (in hours) Time (in hours)

B B+D B+C B+E B+C+D+E

(b)

Figure 9. Aggregation Index observed at different time intervals after treatment with lactose (a) Sphingomonas paucimobilis MG6 and
various combinations (b) Sphingomonas terrae MTCC 7766 and various combinations.
80

Percentage of Aggregation
100 80

Percentage of Aggregation
100

Percentage of Aggregation
80

Percentage of Aggregation
Percentage of Aggregation

80 60 80
60 60
60 60
40 40 40
40 40

20 20 20
20 20

0
0 0 0
2 4 24 48 72
0
2 4 24 48 72 2 4 24 48 72 2 4 24 48 72
Time (in hours)
Time (in hours)
2 4 24 48 72
Time (in hours) Time (in hours)
Time (in hours)
A A+D A+C A+E A+C+D+E

(a)
80

Percentage of Aggregation
80 80
Percentage of Aggregation

Percentage of Aggregation
80
Percentage of Aggregation

Percentage of Aggregation
80

60 60 60 60
60

40 40 40 40
40

20 20 20 20
20

0 0 0
0 0
24

48

72
2

4
2

24

48

72
24

48

72

24

48

72

24

48

72
Time (in hours) Time (in hours) Time (in hours)
Time (in hours) Time (in hours)
B B+D B+E B+C+D+E
B+C

(b)

Figure 10. Aggregation Index observed at different time intervals after galactose treatment (a) Sphingomonas paucimobilis MG6and
various combinations (b) Sphingomonas terrae MTCC 7766 and various combinations.
The Role of Sphingomonas Paucimobilis in Intergeneric … 99

DISCUSSION

Previous studies have demonstrated that pathogens can be incorporated


into heterotrophilic drinking water biofilms enhancing their persistence
(Gião et al., 2008, 2009). It has also been suggested that for multi-species
biofilms, it is very difficult to determine the positive or negative impact of
different sessile microorganisms on pathogens, particularly the associations
that occur within biofilms. Bacterial cells can interact within their own type
or with other bacterial cells and facilitate the formation of biofilm.
Aggregation has been well described for dental plaque isolates in complex
media and aquatic species in potable water (Buswell et al., 1997;
Kolenbrander and London, 1993; Rickard et al., 2003a). Cell to cell
communication is requisite for initial colonization and therefore, biofilm
formation. Both, autoaggregation and co-aggregation are significant in the
process of communication. Autoaggregation in the biofilm boosts the
adherence of genetically identical strains; these interactions are enhanced by
increased hydrophobicity (Basson et al., 2008). Whereas, in co-aggregation
genetically different bacteria adhere to each other via specific molecules
(Rickard et al., 2003b). In the present study, we isolated and identified the
Sphingomonas strain from municipal sites. This strain was chlorine resistant
and could form biofilm in several plumbing materials commonly used in
water distribution pipelines (unpublished observations). Detection of
Shigella, Salmonella and E.coli O157:H7 from water samples of the
Sphingomonas isolate prompted further exploration of the physiology of
interactions of this isolate with water borne pathogenic bacteria. The
aggregation, co-aggregation and biofilm formation by both the
Sphingomonas sp. were evaluated. To the best of our knowledge,
coaggregation of Sphingomonas with E.coli O157:H7, Shigella and
Salmonella have not been reported. Our preliminary studies with the
Sphingomonas have demonstrated the capability of this strain to produce
EPS in line with earlier observations (Ashtaputre and Shah, 1995) and it also
determines the immediate conditions of the life of biofilm cell (Flemming et
al., 2007) by providing a variable gel matrix.
100 Parul Gulati and Moushumi Ghosh

Spectrophotometric analysis of aggregates indicated that with the


increase in incubation time, percentage of aggregation increased. Also, co-
aggregation of Sphingomonas with different pathogens was higher as
compared to autoaggregation of Sphingomonas. It was observed that co-
aggregation by bacteria promotes biofilm development by facilitating the
attachment to the partner species, indicating the possibility of Sphingomonas
to form biofilms with Shigella flexneri (Min and Rickard, 2009). This
observation may be explained by the fact that aggregation depend on
morphological features of bacteria such as size and density (Cisar et al.,
1979) and require adequate incubation time prior to visualization. The
results indicated both S. terrae and S. paucimobilis MG6 as floc formers. It
was reported that visual aggregation testing is not an authentic method of
measuring interactions between aggregating pairs (Buswell et al., 1997).
Therefore, use of microscopic methods to investigate the potential
aggregation between co-aggregating partners becomes inevitable beyond the
screening test of the visual aggregation. DAPI staining was further used to
investigate the role played by this bacterium in the co-aggregate formation.
Autoaggregation has been proposed to be an important mechanism
whereby a bacterial strain within a biofilm expressed polymers to enhance
the integration of genetically identical strains. Autoaggregating strains of
freshwater bacteria were found to be numerically dominant in freshwater
biofilm communities; moreover, autoaggregation together with co-
aggregation has been shown to enhance the development of freshwater
biofilms (Rickard et al., 2003a). Therefore, it was important to further
investigate the co-aggregative abilities of Sphingomonas with waterborne
pathogens.
Previous studies reported that the formation of co-aggregates by bacteria
is the result of specific lectin-carbohydrate interactions between aggregating
partners (Cisar et al., 1979; Simoes et al., 2008). Protein molecules present
on cell surface of one partner behaves like adhesin and the saccharide
molecule present on other one behave like receptor (Rickard et al., 2000;
Rickard et al., 2003a). The sensitivity of adhesin molecules to heat and
protease has been suggested as evidence for presence of lectin-carbohydrate
The Role of Sphingomonas Paucimobilis in Intergeneric … 101

interactions occurring between aquatic bacteria as well as pathogens


(Rickard et al., 2000; Rickard et al., 2003a).
Co-aggregation by Sphingomonas natatoria have been shown to be
important in promoting dual species biofims (Rickard et al., 2000) and the
importance of surface proteins in mediating co-aggregation and biofilm
development has been emphasized. The results of our study suggest the
ability of Sphingomonas terrae and Sphingomonas paucimobilis MG6 to
show aggregation and co-aggregate three water borne pathogens (albeit with
variation) and role of surface proteins/lectins in according the interactions;
both strains could form biofilms. The ability to co-aggregate supposedly
confers protection of the Sphingomonas cells from directed shear forces and
enables them to proceed to a multigeneric biofilm. Overall our results imply
that mixed biofilms involving either or more of the pathogens with
Sphingomonas could be of public health concern in drinking water
distribution system and more effective treatment systems need to be
developed in light of these observations.

CONCLUSION

The present study demonstrated that Sphingomonas terrae MTCC 7766


and Sphingomonas paucimobilis MG6 isolated from Indian drinking water
distribution system possessed abilities to form biofilm, aggregation. Co-
aggregation was observed with the water borne pathogens: Shigella flelneri,
Salmonella typhimurium and E.Coli O157:H7; coaggregation reversal
studies involving heat, protease treatment and sugars (lactose and galactose)
indicated possibility of surface proteins or lectin to be in mediating the
interaction; however conclusive evidence of interaction in case of E.coli
O157:H7 could not be obtained. The results of this study provide valuable
insights in the physiological behavior of Sphingononas specifically towards
waterborne pathogens which could be important when designing
interventions for water safety.
102 Parul Gulati and Moushumi Ghosh

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BIOGRAPHICAL SKETCH

Moushumi Ghosh

Affiliation: Professor & Head, Department of Biotechnology, Thapar


Institute of Engineering & Technology (TIET), Patiala, India

Education: MSc (Biochemistry), PhD (Biotechnology), Banaras Hindu


University, Varanasi, INDIA

Research and Professional Experience: Over 16 years of research


expertise in fundamental and translational aspects of microbial biopolymers
106 Parul Gulati and Moushumi Ghosh

and biofilms. Led, as principal investigator more than 10 research projects


funded by national agencies (DST, WTI, UGC, CSIR) supervised 5 doctoral
students and over 48 masters and M. Tech students. Developed novel
microarray based detection methods for water borne bacterial and protozoan
pathogens in collaboration with Heriot Watt University and University of
Edinburgh, UK as bilateral INDO UKIERI project. Scientific contributions
have been documented as policy and science based advocacy for sustainable
water resources, in over 145 articles published in peer reviewed international
journals, conferences, monographs, press and public media.

Professional Appointments:

 July, 2019,Coordinator, TIET/TAU CoE for Food Security, Thapar


Institute of Engineering & Technology, Patiala
 February 2017 –present; Head, Department of Biotechnology,
Thapar Institute of Engineering & Technology, Patiala
 July 2015 –till date: Professor, Department of Biotechnology
 June 2010 – July 2015: Associate Professor, Dept of
Biotechnology, Thapar University, Patiala
 June 2006 – June 2010: Assistant professor, Department of
Biotechnology & Environmental Sciences, Thapar University,
Patiala
 Jan 2002 – June 2006: Lecturer, Dept of Biotechnology & Env
sciences, Thapar University, Patiala
 Jan 2001 – December 2002: Postdoctoral Scientist,
 GSF Research Centre for Environment and Health, Munich,
Germany

Honors:

 Science and Technology Award for Research Excellence, EET CRS


2017; 11th June Bangalore.
 Advisor, Scientific Committee of American Academy of Sciences,
Environmental Technology
The Role of Sphingomonas Paucimobilis in Intergeneric … 107

 Overseas travel grant for scientific exchange, Department of Science


& Technology, Govt of India (2016)
 UKIERI, Department of Science & Technology, Govt of India
(2014)
 Noel Derr Gold medal: Sugar Technologist Association of India
(2003)
 Junior and Senior Research fellowship: Ministry of Food and Civil
supplies, Govt of India (1996-1999)
 GATE, Ministry of Human Resource Development, Govt of India
(1996)
 Performance Excellence Award, TU (2006 -2015)
 Nominated Member, lifetime: Biotech Research Society of India,
 Association of Microbiologists of India (AMI),
 European Federation of Biosciences (FEBS),
 Organization of Women in Science, (OWSD), Trieste, Italy.

Publications from the Last 3 Years:

Ghosh, M. (201). Lychee Juice and Pulp Extracts as Potential Components


for Production of Extracellular Phosphate-Binding Biopolymer from
Acinetobacter haemolyticus. In Lychee Disease Management, (pp. 181-
190). Springer Nature, Singapore.
Ghosh, M. (2017). Microbial biopolymers as innovative, exploitable ‘green
tools’ for sustainable treatment of water. Asia Pacific Technology
Monitor, 34(3), 45-51.
Gulati, P. & Ghosh, M. (2017). Biofilm forming ability of Sphingomonas
paucimobilisSphingomonas paucimobilis isolated from community
drinking water systems on plumbing materials used in water
distribution. Journal of Water & Health., 15 (6), 942-946.
Gulati, P., Singh, P., Chatterjee, A. K. & Ghosh, M. (2016). Monitoring of
biofilm ageing in a Sphingomonas sp. strain from public drinking water
sites through changes in capacitance. Environmental Technology, 30, 1-
8
108 Parul Gulati and Moushumi Ghosh

Jain, S. & Ghosh, M. (2019). Effective removal of Bisphenol A from plastic


waste leachates by microbial polymer impregnated with activated
carbon International Journal of Environmental Science & Technology.
DOI: 10.1007/s13762-019-02452-x.
Kaur, T. & Ghosh, M. (2017). Characterization and toxicity of a phosphate-
binding exobiopolymer produced by Acinetobacter haemolyticus
MG606. Journal of Water & Health, 15, 103-111
Khaira, G. K. & Ghosh, M. (2016). Surface Engineered Green Polymers for
Enhanced Water Decontamination. Environmental Science &
Technology, 1, 143-153.
Sharma, V., Kaur, T., Bridle, H. & Ghosh, M. (2017). Antimicrobial efficacy
and safety of mucoadhesive exopolymer produced by Acinetobacter
haemolyticus. International Journal of Biological Macromolecules, 94,
187-193.
INDEX

A B

activated carbon, 10, 15, 27, 43, 72, 108 bacteria, 3, 42, 45, 84, 90, 99, 100, 102,
activation energy, 76 103, 104, 105
active site, 5, 11, 72, 74 bacterial cells, 99
adhesin, 84, 85, 100 bacterial strains, 104
adhesion, 84, 93, 102, 105 bacterium, 100, 104, 105
adsorption, iv, v, vii, viii, ix, 1, 2, 3, 4, 5, 6, bioaccumulation, vii, 1, 38
7, 8, 9, 10, 11, 12, 14, 15, 16, 17, 18, 19, biochanin A, iv, v, vii, ix, 63, 64, 67, 68, 71,
20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 72, 73, 74, 75, 76, 77, 78, 79
31, 32, 38, 41, 42, 43, 44, 48, 49, 51, 52, biodegradability, 38
54, 56, 57, 64, 65, 66, 67, 68, 70, 71, 72, biodiversity, 84
73, 74, 75, 76, 77, 79, 80, 81, 82 biofilms, iv, vii, ix, 84, 89, 91, 99, 100, 101,
adsorption isotherms, 17 102, 103, 104, 105, 106
adsorption technologies, viii, 2 biological samples, 28
aggregation, ix, 83, 84, 85, 87, 88, 89, 90, biomass, 10, 89
91, 93, 99, 100, 101, 102, 104 biopolymers, 105, 107
agriculture, 45, 51 Bisphenol A, 108
aluminum oxide, 12, 13 by-products, 14, 56
aqueous solutions, 24, 25, 26, 30, 80
arsenic, viii, 2, 14, 19, 24, 31, 34, 37, 38,
C
43, 44, 48, 51, 81
atmosphere, 8, 21, 38
cadmium, 6, 7, 8, 9, 10, 21, 26, 27, 28, 35,
attachment, 89, 93, 100
43, 44, 81
110 Index

calcium, 8, 22, 24
D
carbon, 4, 10, 27, 28, 43, 46, 73
carbon nanotubes, 10, 27, 28, 43
decontamination, 39
carcinogenic, vii, 1, 2, 49
desorption, 7, 8, 66, 70
carcinogenicity, 2
detection, 16, 17, 24, 33, 78, 106
cellulose, 7, 10, 14, 26, 45
detoxification, v, 23, 37, 38, 39, 41, 42, 54
cerium, 14, 30, 44
developing brain, 64
challenges, 34, 39, 53
diffusion, 11, 65, 72, 74
charge density, 72
diseases, 3, 39, 103
chemical, viii, 2, 4, 5, 6, 7, 11, 19, 26, 35,
disinfection, 12, 28, 51
41, 42, 43, 46, 50, 77
dispersion, 13, 32
chemical functionalization, 11
distribution, ix, 16, 38, 63, 65, 70, 74, 76,
chemical interaction, 4, 6, 11, 43
78, 79, 84, 99, 101, 103, 105, 107
chemical properties, 5
distribution function, 16
chemisorption, 10
drinking water, iv, v, vi, vii, viii, ix, 1, 3, 14,
chitosan, 5, 7, 8, 12, 25, 26
23, 25, 28, 37, 38, 47, 50, 51, 54, 64, 79,
chlorination, viii, ix, 2, 83
83, 84, 86, 99, 101, 103, 104, 105, 107
chromium, viii, 8, 37, 38, 43, 49
co-aggregation, vi, ix, 83, 84, 85, 87, 88, 89,
93, 99, 100, 101 E
communities, 85, 100, 104
community, 84, 102, 103, 107 ecosystem, 2, 32
composites, 15, 22, 28, 31 efficient, viii, 2, 3, 4, 16, 25, 26, 28, 29, 30,
composition, 9, 15, 66, 70, 105 31, 33, 38, 39, 42, 43, 44, 45, 46, 53
compounds, 12, 64, 80 electric current, 19, 21
contact time, ix, 4, 8, 9, 18, 64, 65, 68, 72, electrical resistance, 46
73, 78 electrochemistry, 19
contaminants, viii, 2, 11, 16, 43, 46, 51, 53, electrodes, 19, 21, 34
64 electrodialysis, viii, 3, 38, 45, 46, 52, 53, 58
contaminated water, 39 electrolysis, 3, 21
contamination, vii, viii, 1, 15, 25, 37, 38, 42, electron, 66, 89, 91
52, 79 electron microscopy, 89
copper, 6, 7, 8, 9, 10, 30, 43, 44, 48 electroplating, 29, 57
correlation coefficient, 76, 77 endocrine, 65, 79, 80
cost, vii, 1, 6, 13, 14, 16, 25, 31, 39, 42, 43, endothermic, 6, 9, 18, 78
44, 50, 52 energy, viii, 20, 21, 38, 42, 45, 52, 59, 75
crystal structure, 10, 13 energy consumption, 20, 21
crystalline, vii, ix, 12, 14, 18, 44, 63, 65, 66, environment, vii, 1, 15, 21, 23, 39, 53, 73,
81 104
crystallization, 3 environmental management, 25, 27, 29, 34,
crystals, 18, 66 35
culture, 103, 104
Index 111

equilibrium, ix, 4, 6, 12, 18, 21, 52, 64, 68, human exposure, 64
72, 74, 76, 77, 79, 80, 81 human health, ix, 53, 63
equilibrium sorption, 80 hybridization, 15, 103
estrogen, 65, 80, 81 hydrogen, 13, 74
evidence, 100, 101, 105 hydrogen bonds, 74
exopolysaccharides, 85, 89, 105 hydrophilicity, 47
hydrophobicity, 99, 102
hydrothermal process, 10
F
hydroxide, 14, 20, 26, 31, 44, 66
fabrication, 13, 18
family physician, 25 I
filters, 31, 42, 73
filtration, viii, 2, 3, 42, 78 incubation time, 90, 100
financial, 22, 53 industries, 45, 46, 50, 79
financial support, 22, 53 infrared spectroscopy, 66
flocculation, vii, viii, 2, 4, 19 integration, viii, 38, 51, 100
food, ix, 14, 25, 45, 63, 64 intervention, vii, ix, 63
food production, ix, 63, 64 ion-exchange, 3, 6, 12, 18, 42, 44, 45, 46
formation, ix, 9, 12, 19, 21, 29, 44, 69, 70, ions, 3, 6, 7, 8, 10, 11, 13, 14, 16, 17, 18,
76, 83, 84, 90, 93, 99, 100, 102, 104 19, 20, 21, 22, 28, 33, 38, 41, 42, 43, 44,
free energy, 13 45, 46, 47, 48, 52, 81
freshwater, 38, 100, 104 IR spectra, 69
FTIR, ix, 7, 8, 9, 10, 17, 18, 64, 70, 81 iron, 7, 12, 19, 20, 21, 28, 34, 44, 48, 81
FTIR spectroscopy, 18

K
G
kidney, 39
groundwater, 48 kinetic model, 6
growth, ix, 3, 64, 83, 86, 87, 104, 105 kinetic studies, 19
kinetics, 7, 9, 17, 21, 27, 34, 72, 77, 80, 89

H
L
hazardous materials, 28, 30, 31
health, ix, 3, 24, 39, 51, 65, 83, 103 lactose, x, 84, 88, 93, 97, 101
health effects, 39 landfill leachates, 3
heavy metals, viii, 2, 4, 6, 7, 8, 10, 11, 15, layered double hydroxides, 20, 21
17, 18, 25, 26, 27, 28, 29, 30, 31, 32, 38, ligand, 15, 18, 48
47, 51, 55, 57, 58 light, 49, 67, 85, 101
human, ix, 3, 38, 53, 63, 64, 102 liquid phase, 72, 74
human body, 3
112 Index

non-biodegradable, vii, 1
M
nucleic acid, 103
nutrient, 49, 84
magnetic composites, 28
magnetic materials, 15
manganese, 10, 12, 13, 25, 30, 31, 43 O
manufacturing, vii, 1, 12, 16
materials, 4, 12, 13, 14, 16, 24, 27, 29, 30, optimization, 34, 35, 81
31, 32, 33, 44, 50, 51, 65, 85, 99, 103, organic matter, 48
105, 107 osmotic pressure, 45
matrix, 6, 23, 29, 46, 99, 103 oxidation, 11, 19, 20, 25
media, viii, 2, 33, 34, 93, 99, 106 oxide nanoparticles, 30
membranes, 16, 23, 29, 31, 33, 45, 46, 47, oxygen, 11, 14, 20, 21, 42, 44, 65, 70
52, 54, 67, 102
mercury, viii, 8, 15, 22, 24, 28, 37, 38, 43,
P
47, 81
metal ion, vii, viii, 1, 5, 6, 8, 9, 10, 12, 14, pathogens, ix, 22, 84, 85, 86, 88, 89, 90, 93,
16, 17, 18, 24, 25, 26, 27, 28, 29, 31, 32,
94, 99, 100, 101, 106
33, 37, 38, 39, 41, 42, 43, 44, 45, 46, 49, pH, 4, 6, 8, 9, 13, 17, 18, 19, 20, 21, 22, 42,
51, 52
44, 67, 74, 86
metal oxides, 12, 13, 30, 44 phosphate, 34, 67, 86, 108
metal-organic frameworks, viii, 14, 31, 32,
physical properties, 72
38 physico-chemical parameters, 103
metals, viii, 2, 6, 12, 15, 19, 27, 30, 37
physicochemical properties, 7
methemoglobinemia, 3 physiology, 2, 80, 99
methodology, 35
phytoestrogens, ix, 63, 64, 65, 79, 81, 82
methylene blue, 80 pollutants, 3, 4, 9, 11, 29, 38, 39, 42, 44, 48,
microorganism, ix, 83
49, 51, 52, 53
microorganisms, 42, 99 pollution, vii, viii, 1, 2, 23, 24, 27, 37, 38,
microscope, 66, 88
50
microscopy, 93 polymer, 15, 23, 42, 46, 47, 108
microspheres, 6, 49
polymeric materials, 23
molecules, x, 46, 65, 72, 74, 84, 93, 99, 100 polymeric matrices, 46
monolayer, 10, 75, 76, 79
polymerization, 47
morphology, 5, 8, 30, 66 polymers, 4, 14, 26, 73, 100
municipal solid waste, 23
polysaccharide, 7, 26, 85
population, viii, 2, 37, 38, 50
N porosity, 13, 14, 47, 72
porous materials, 80
nanomaterials, 10, 12, 44, 48, 50, 53 precipitation, vii, viii, 2, 3, 11, 18, 20, 31,
nanoparticles, 4, 8, 24, 25, 26, 30, 47, 51 41, 42, 43
nanostructured materials, 51 preparation, iv, 27, 104
Index 113

protease, x, 84, 88, 96, 100, 101 sorption, 9, 11, 25, 30, 33, 43, 44, 68, 72,
purification, viii, 2, 3, 41, 42 74, 81
purity, 11, 66, 69 species, 3, 14, 85, 99, 100, 101, 103, 104,
105
specific surface, 13, 15, 66, 70
R
spectroscopy, ix, 64, 66, 70
sphingomonas, iv, vi, vii, ix, 83, 84, 86, 88,
reaction temperature, 4
89, 90, 91, 92, 93, 94, 95, 97, 98, 99,
reactions, 13, 20, 102
100, 101, 102, 103, 104, 105, 107
receptor, 81, 100, 102
stability, viii, 14, 15, 26, 32, 38, 48
recovery, 24, 25, 30, 46, 50
structure, 6, 8, 11, 13, 15, 17, 18, 43, 65, 66,
regeneration, 7, 14, 43, 44, 73
69
regression analysis, 81
superparamagnetic, 30
rejection, viii, 16, 38, 45, 46, 52
surface area, ix, 6, 11, 15, 18, 32, 43, 64, 65,
remediation, 6, 12, 13, 14, 16, 23, 30, 32
70, 72, 74
removal, v, ix, 3, 5, 6, 7, 8, 9, 10, 13, 16, 17,
surface modification, 30
18, 19, 20, 21, 22, 24, 25, 26, 27, 28, 29,
surface reaction, 11, 43
30, 31, 32, 33, 34, 35, 41, 42, 43, 44, 45,
synthesis, 8, 11, 14, 26, 28, 29, 30, 33, 34,
46, 47, 48, 50, 51, 52, 54, 55, 56, 57, 58,
66
63, 64, 65, 67, 71, 72, 73, 74, 75, 76, 77,
78, 79, 80, 108
requirement, viii, 3, 38, 42, 45, 50 T
requirements, 42, 45, 52
researchers, 2, 11, 14, 43, 46, 51 techniques, viii, 3, 5, 15, 18, 38, 39, 42, 53
resistance, ix, 83, 84, 105 technologies, vii, viii, 2, 25, 32, 38, 39, 41,
reverse osmosis, viii, 3, 25, 38, 45, 102 45, 48
room temperature, 8, 66, 87, 88, 89 temperature, 9, 18, 21, 22, 66, 74, 79
toxic effect, 3
toxic waste, viii, 38
S
toxicity, 2, 19, 25, 51, 53, 108
transmission electron microscopy, ix, 63
safety, x, 34, 64, 65, 66, 78, 79, 84, 85, 101,
treatment, vii, viii, x, 1, 2, 3, 7, 10, 13, 16,
108
20, 22, 25, 27, 34, 38, 39, 41, 42, 43, 44,
scanning electron microscopy, ix, 63
45, 46, 47, 48, 49, 50, 51, 52, 53, 58, 64,
science, 23, 26, 29, 31, 33, 53, 106
78, 79, 84, 85, 88, 93, 95, 96, 97, 98,
sedimentation, 3, 41, 42
101, 107
selectivity, 15, 46, 47
treatment methods, vii, viii, 1, 38, 39, 41,
sewage sludge, 6, 26
42, 50, 51, 52, 53
shortage, viii, 38, 48
solid phase, 28, 68
solution, viii, 6, 8, 9, 11, 17, 21, 26, 27, 28, U
38, 39, 52, 53, 66, 67, 68, 80, 86, 88
ubiquitous solution, 38
114 Index

uniform, 12, 44, 65, 76, 87 water purification, 28, 65


UV irradiation, viii, 38 water quality, viii, 2
UV light, 49 water quality standards, viii, 2
water resources, 3, 48, 64, 106
water treatment, iv, v, vii, ix, 1, 2, 16, 22,
W
27, 34, 37, 38, 39, 41, 43, 45, 50, 51, 53,
55, 58, 59, 78
waste, vii, 1, 14, 24, 25, 27, 29, 45, 51, 57,
64, 108
waste disposal, 64 Z
wastewater, viii, 2, 3, 4, 6, 7, 8, 9, 10, 13,
15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 27, zeolite, iv, v, vii, ix, 4, 12, 29, 43, 44, 56,
28, 29, 30, 31, 33, 34, 35, 54 57, 58, 59, 63, 65, 66, 67, 69, 70, 73, 79,
water, vii, viii, ix, 1, 2, 4, 5, 8, 9, 10, 13, 14, 80, 81, 82
16, 17, 18, 22, 24, 25, 28, 30, 31, 32, 33, zinc, 3, 6, 8, 10, 14, 19, 24, 27, 44
34, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, zinc oxide, 14
47, 48, 49, 50, 51, 52, 53, 58, 63, 64, 65, ZSM-5, iv, vii, ix, 63, 64, 66, 67, 68, 69, 70,
66, 77, 78, 79, 84, 86, 90, 99, 101, 102, 71, 72, 73, 75, 76, 77, 78, 79, 80, 81, 82
103, 105, 106, 107

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