ADSORPTION OF FLOURIDE USING

NANOPARTICLES OF ALUMINIUM OXIDE

BY

COKER HANNAH

FROM DEPARTMENT OF CHEMICAL ENGINEERING

LANDMARK UNIVERSITY, KWARA STATE

PRESENTED TO

THE SIWES SUPERVISORS, RESERVOIR AND PRODUCTION UNIT

FCT LOWER USUMA DAM WATER WORKS

USHAFA, BWARI, ABUJA.

OCTOBER, 2021
 TABLE OF CONTENTS
1.0 INTRODUCTION………………………………………………………………………………………………3-4
2.0 LITERATURE REVIEW……………………………………………………………………………………5-13
3.0 CONCLUSION AND RECOMMENDATION………………………………………………………..14
3.1 CONCLUSION……………………………………………………………………………………..14
3.2 RECOMMENDATION………………………………………………………………………….14
References……………………………………………………………………………………………….15

2
 CHAPTER ONE
1.0 INTRODUCTION

The quality of drinking water is very important for public

health and for better life. Optimum concentration of fluoride
(about 1 mg L−1) in drinking water is good for dental health
and for good bone development. Intake of excess fluoride
(beyond 1.5 mg L−1, WHO guideline) (WHO 2006) for long
periods can result in the incidence of fluorosis. Low
concentrations of fluoride in drinking water have been
considered beneficial to prevent dental carries. But
researchers are now debating on the health benefits of fluoride
even at low concentrations. It has long been known that
chronic intake of fluoride even though below 1 mg L−1 can lead
to severe dental and skeletal fluorosis. It not only affects teeth
and skeleton, but its accumulation over a long period can also
lead to loss of mobility, lowering of IQ of children, change in
the DNA structure and interference with liver and kidney
functioning (Chen et al. 2011; WHO 2008; Xiong et al. 2007).

High fluoride contents in the groundwater have been found in many

parts of the developing countries and fluorosis is endemic in around
25 countries of the world. The affected zones include arid parts of
northern China, India, Srilanka, African countries, Northern Mexico
and central Argentina. Out of 85 million tons of fluoride deposits on
the earth’s crust, 12 million are found in India (Teotia and Teotia,
1994). In India, about 62 million people in 17 states are affected with
dental, skeletal and or non-skeletal fluorosis (Susheela, 1999). Out of
6 lakh villages in India, atleast 50% have fluoride content in
groundwater with a concentration more than 1.0 ppm (Gupta, 1995).
Many rivers flowing through different states of India are reported to
have fluoride contents varying from 0.1 to 12.0 ppm (Bulusu et al.,
1979). Very low doses of fluoride (1.5 mg/l), can lead to dental
fluorosis or mottled enamel and excessively high concentration (>3.0
mg/l) of fluoride may cause skeletal fluorosis (Yadav and Khan,
2010). General clinical symptoms includes severe pain in the
backbone and joints, muscle weakness, increased density of bones,
arthritis, brittle bones, paralysis, cancer, infertility, brain damage,
3
thyroid disorder etc. 88 S. Bhattacharya During later stages,
calcification of the bones takes place, osteoporosis in long bones and
symptoms of osteosclerosis can be seen where the bones become
denser and develop abnormal crystalline structure. (Ibrahim et al.,
2011).

4
 CHAPTER TWO
2.0 LITERATURE REVIEW
2.2ADSORPTION
The use of solids for removing substances from either gaseous or liquid
solutions has been widely used since biblical times. This process, known
as adsorption, involves nothing more than the preferential partitioning of
substances from the gaseous or liquid phase onto the surface of a solid
substrate. From the early days of using bone char for decolorization of sugar
solutions and other foods, to the later implementation of activated carbon for
removing nerve gases from the battlefield, to today’s thousands of applications,
the adsorption phenomenon has become a useful tool for purification and
separation.

Adsorption phenomena are operative in most natural physical, biological, and

chemical systems, and adsorption operations employing solids such as
activated carbon and synthetic resins are used widely in industrial applications
and for purification of waters and wastewaters.

The process of adsorption involves separation of a substance from one phase

accompanied by its accumulation or concentration at the surface of another.
The adsorbing phase is the adsorbent, and the material concentrated or
adsorbed at the surface of that phase is the adsorbate. Adsorption is thus
different from absorption, a process in which material transferred from one
phase to another (e.g. liquid) interpenetrates the second phase to form a
“solution”. The term sorption is a general expression encompassing both
processes.

Physical adsorption is caused mainly by van der Waals forces and electrostatic
forces between adsorbate molecules and the atoms which compose the
adsorbent surface. Thus adsorbents are characterized first by surface
properties such as surface area and polarity.

A large specific surface area is preferable for providing large adsorption

capacity, but the creation of a large internal surface area in a limited volume
inevitably gives rise to large numbers of small sized pores between adsorption
surfaces. The size of the micropores determines the accessibility of adsorbate
molecules to the internal adsorption surface, so the pore size distribution of
micropores is another important property for characterizing adsorptivity of
adsorbents. Especially materials such as zeolite and carbon molecular sieves
can be specifically engineered with precise pore size distributions and hence
tuned for a particular separation.

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Figure.1 Adsorption—a simple technique for effective fluoride removal

2.2 FLUORIDE

Fluoride is the element that is naturally found in minerals, rock sediments,

and geological deposits, it is named as “double-edged sword” due to the
inadequacy of this element in the human body causes dental caries,
whereas if intake is more than it leads to dental, skeletal and soft tissue
fluorosis. According to the latest research, about 25 countries around the

6
globe shows that fluorosis is endemic. In 1993 UNICEF identified 15 states
in India as endemic for fluorosis.

Fluorosis is not curable. The only way to prevent fluorosis is supplying the
drinking water with optimum content of fluoride. The permissible limit for
the concentration of fluoride in drinking water as per Indian standards (IS
10500) is 1 – 1.5 mg/L. This standard limit for fluoride revokes us to
develop more different methods that are efficient and make the water
consumable. 
At present, the methods for removing the fluoride from water are of 3
different categories they are adsorption, membrane-based methods, and
precipitation depending on the removal process of fluoride. The
membrane-based and chemical methods for defluorination are
uneconomical and have problems such as huge disposal of sludge and
therefore they are not recommended. Adsorption is globally accepted as a
suitable technique for defluorination due to its availability of the raw
materials (absorbents) for processing and simplicity in nature. Many
studies have done around the world with different materials such as
aluminium hydroxide, clay-based composites, activated alumina, etc.
However, use of these materials is not so successful for the removal of
fluoride due to low efficiency and high cost. Therefore, it is of paramount
importance to identify and study the materials with high removal
efficiency.
Surface area is a key factor that influences the adsorption to a larger
extent higher the surface area of adsorbent, higher will be its adsorbing
capacity. This makes nano absorbents best for water treatment. Nanoscale
materials due to their smaller size (<100 nm) can provide a larger surface
area required for efficient adsorption. These nano materials when used in
water treatment are highly efficient but these may not be economical in
large scale operation and the removal of nanomaterials from water is
difficult.

Fluoride Effects International Permissible Limit

Concentration (mg Standards (mg L−1)

7
 L−1) Organization

<0.5 Prevention of teeth World Health 0.6–1.5

cavities Organization
(WHO)

0.5–1.5 Helps in bones and Bureau of Indian 0.6–1.5

teeth development Standards (BIS)

1.5–4 Dental problems in US Public Health 0.8

children Standards

>4 Dental and skeleton Indian Council of 1.0

fluorosis Medical Research
(ICMR)

>10 Crippling skeletal Directive 98/83/EC 1.5

fluorosis, possibly
cancer

Table 1. Fluoride health effect associated with concentration levels and

permissible limits of fluoride in drinking water according to the International
Standards organization.

2.3 FLUORIDE REMOVAL TECHNOLOGIES:

NANOMATERIAL APPLICATION

Fluoride poisoning can be prevented or minimized by using

alternative water sources (surface water, rainwater, and low-fluoride
groundwater), by improving the nutritional status of populations at
risk and by removing excessive fluoride from drinking water.
Defluoridation of groundwater is one of the feasible options to
overcome the problem of excessive fluoride in drinking water. The
methods developed for this purpose are divided as follows depending
upon the mode of action.

2.3.1 Based on precipitation–coagulation (Nalgonda technique)

Precipitation processes involve the addition of chemicals and

formation of fluoride precipitates. Among these, one of the effective
methods are precipitations with calcium and aluminium salts.
Precipitation chemicals must be added daily in batches and

8
precipitation techniques produce a certain amount of sludge every
day. Lime and alum are the most commonly used coagulants (John,
1996; Parker and Fong, 1975). Nalgonda Technique is an
economical and simple method for fluoride removal which involves
addition of aluminium salts, lime and bleaching powder followed by
rapid mixing, flocculation, sedimentation, filtration and disinfection
(Nawalakhe et al., 1975). Aluminium salt is only responsible for
removal of fluoride from water. Lime facilitates the formation of
dense floc for rapid settling. However, the process removes only a
smaller portion of fluoride (18–33%) in the form of precipitates and
converts a greater portion of ionic fluoride (67–82%) into soluble
aluminium fluoride complex ion, which is a neurotoxin. Hence
adoption of Nalgonda technique for defluoridation of water is not
desirable. The residual aluminium in excess of 0.2 mg.L-1 in treated
water can cause pathophysiological, neurobehavioral, structural and
biochemical changes (Nayak, 2002). The maintenance cost of the
plant is very high, and the process is not automatic and large space is
required for the drying of sludge (Meenakshi and Maheshwari,
2006).

2.3.2 Based on electrochemical method

A technology of defluoridation through electrochemical route has

been developed. The process utilizes 0.3 to 0.6 kw.h-1 of electricity
per 1000 L of water containing 5- 10 mg.L-1 of fluoride. The anode is
continuously consumed and needs to be replenished. The process
generates sludge at the rate of 80 – 100 g per 1000 L (on dry basis).
However, high cost of electricity in third world countries like India
makes the use of this method unsuitable (Feng et al., 2003).

2.3.3 Based on Ion exchange mechanism

Strong Base Exchange resins remove fluorides either on hydroxyl

cycle or chloride cycle along with anions (Runaska et al., 1951).
Some inorganic ion exchangers, eg. Complex metal chloride silicates,
formed from barium or ferric chloride with silicic acid, also
exchanged fluoride for chloride. Polystyrene anion exchange resins
and strongly basic quaternary ammonium type resins are known to
remove fluorides from water along with other anions. Cation
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exchange resins impregnable with alum solution have been found to
act as defluoridating agents. “Avaram bark” based cation exchange
resin works effectively in removing fluoride from water (Meenakshi
and Maheshwari, 2006).

2.3.4 Based on adsorption process

Many researchers are being focused on adsorption technology since

last two decades for contaminated ground and surface water
treatment. Adsorption appears to be an effective method for fluoride
removal because it is eco-friendly, simple and cost effective option
for the common people using groundwater as a main source.
Activated alumina, activated carbon, activated alumina coated silica
gel, calcite, activated saw dust, activated coconut shell carbon and
activated fly ash, groundnut shell, coffee husk, rice husk, magnesia,
serpentine, tricalcium phosphate, bone charcoal, activated soil
sorbent, carbion, defluoron-1, defluoron-2, etc. are different kinds of
adsorbents reported in the previous research works (Min et al., 1999;
Wang and Reardon, 2001; Nava et al., 2003). Several bone
formulations, synthetic tricalcium phosphate and ydroxyl apatite etc.
were investigated for their fluoride removal efficiency. Biosorption is
an emerging technique for water treatment utilizing abundantly
available biomaterials. Various biosorbents have been developed for
fluoride removal. Chitin and chitosan are attractive adsorbents
because of their unique properties like biodegradability,
biocompatibility and low cost, in addition to their particular physical
and mechanical properties, resulting from the presence of chemical
reactive groups (hydroxyl, acetamido or amino functions) in polymer
chains (Yao et al., 2009).

Sujana et al. (2013) synthesized new biopolymer beads, composite of

hydrous ferric oxide (HFO) and alginate, characterized and
examined it, with aim of fluoride removal from water. The authors
concluded that Ph had significant effect on fluoride adsorption
efficiency of the beads. The biomass of the natural plant Tinospora
cordifolia demonstrated a good capacity of fluoride biosorption,
highlig+hting its potential for the drinking water treatment process
(Pandey et al., 2012). Fungal biosorbent prepared from Fusarium
moniliforme for removal of fluoride was investigated by Merugu et al.
(2012). A new type of adsorbent was prepared from orange waste by
a simple method of saponification reaction with lime water and used
for the removal of some metal ions and, after that, for fluoride
removal from water (Paudyal et al., 2012). Gopal et al. (2004) and
Yadav et al. (2013) studied the removal of fluoride from water using
10
sawdust, groundnut husk and sand. The obtained results indicate that
these chemically treated natural adsorbents can remove fluoride
effectively. Conducting the experiments on water defluoridation with
bauxite, Sajidu et al. (2008) reported that up to 93.8% fluoride was
removed from fluoride solution with initial concentration of 8 mg/L
when adsorbent dose of 2.5 g/200 Ml were used. Sivasankar et al.
(2010) showed the defluoridation capacities of activated tamarind
fruit shell (ATFS) and MnO2 coated tamarind fruit shell (MTFS).
Alagumuthu and Rajan (2010) studied zirconium-impregnated
cashew nut shell carbon (ZICNSC) to assess its capacity for the
adsorption of fluoride from aqueous solutions. The method is simple
and has shown great potential for the removal of fluoride ions.

2.3.5 Use of nanostructured materials

Nanomaterials are fast emerging as potent candidates for water

treatment in place of conventional technologies because of their low
cost and high efficiency. This would be beneficial for developing
nations like India and Bangladesh. Nanoparticles can be used as
potent sorbents as separation media, as catalysts for photochemical
destruction of contaminants; nano-size zerovalent iron used for the
removal of metals and organic compounds from water and
nanofiltration membranes (Savage and Diallo, 2005).

Adsorption of fluoride on to solid adsorbent usually occurs through

three phases (Mohapatra et al., 2009; Fan et al., 2003):

1. Diffusion or transport of fluoride ions to the external surface of

the adsorbent from bulk solution across the boundary layer
surrounding the adsorbent particle, called external mass transfer;

2. Adsorption of fluoride ions on to particle surfaces;

3. The adsorbed fluoride ions probably exchange with the structural

elements inside adsorbent particles depending on the chemistry of
solids, or the adsorbed fluoride ions are transferred to the internal
surfaces for porous materials (intra particle diffusion).

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 Figure 2. Commonly applied techniques for fluoride removal from drinking water

2.4 CARBON-BASED ADSORBENTS

Carbon-based materials have been proved to be very beneficial in the
potabilization of water since they demonstrate outstanding adsorption
characteristics. Research findings have shown that activated carbon, graphene
oxide, and carbon nanotube have plentiful surface functional groups and
substantial specific surface areas. The aim of this section is to summarize and
assess carbon-based materials for de-fluoridation of water on the basis of their
effectiveness, cost-effectiveness, and readiness for application.

2.4.1. Activated Carbon

AC is a common adsorptive material, used for removing pollutants from water
sources due to its enhanced porosity, significant surface area, and also its
adaptable surface chemistry. Modified activated carbon materials with the
oxides and hydroxides of metals have been used to expand its available surface
area [48] and to strengthen its interactions with fluoride.

2.4.2. Graphene Oxide

Recently, GO has been widely effectively applied in water treatment. However,
pure GO materials show inadequate adsorption ability. Besides, they are very
slight and stable in water, making them very challenging to recover after

12
adsorption. One efficient way to overcome this challenge is to amend its
surface. Considerable research studies in this direction have been dedicated to
changing the local reactivity via doping or grafting elements such as Al, Mn, Fe,
Mg, Au, Ti, B, and Si among others.

13
 CHAPTER THREE
3.O CONCLUSION AND RECOMMENDATION
3.1 CONCLUSION
Various types of recent and novel fluoride removal techniques involving
nanotechnology are summarized in this review. Water fluoridation was
initiated by few countries in order to prevent dental fluorosis caused by tooth
decay. Ultimately, it ends with the abundance of fluoride in drinking water
which develops health hazards to the community. Hence, researchers
recommended that fluoride in drinking water is not safe. Consequently,
defluoridation has been tested using various types of adsorbents.

3.2 RECOMMENDATION
1. The development of cost-effective, locally available, and environmentally
benign adsorbents for fluoride removal from contaminated water sources is
absolutely required in LUD.
2. Treating the water with an adsorbent like aluminium hydroxide solution is
required in LUD.

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2. https://www.hindawi.com/
3. https://www.ewra.net/
4. https://link.springer.com/
5. https://www.skyfilabs.com/
6. Barghouthi, Z.; Amereih, S. Spectrophotometric Determination of Fluoride in
Groundwater Using Resorcin Blue Complexes. Am. J. Anal. Chem. 2012, 3, 651–655.
[CrossRef]
7. Chavali, R.; Gunda, N.S.K.; Naicker, S.; Mitra, S.K. Rapid detection of fluoride in potable
water using a novel fluorogenic compound 7-O-tert-butyldiphenylsilyl-4-
methylcoumarin. Anal. Chem. Res. 2015, 6, 26–31. [CrossRef]
8. WHO, World Health Organization Guidelines for Drinking-Water Quality, First Addendum
to Third Edition, World Health Organization: Geneva, Switzerland; 2006.

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