Environmental Technology & Innovation: Parwathi Pillai, Swapnil Dharaskar, Sivakumar Pandian, Hitesh Panchal

Environmental Technology & Innovation 21 (2021) 101246
Contents lists available at ScienceDirect
Environmental Technology & Innovation

journal homepage: www.elsevier.com/locate/eti
Overview of fluoride removal from water using separation

techniques
∗
Parwathi Pillai a , Swapnil Dharaskar a , , Sivakumar Pandian b , Hitesh Panchal c
a
Nano-research Group, Department of Chemical Engineering, School of Technology Pandit Deendayal Petroleum
University, Raisan, Gandhinagar, 382007, India
b
School of Petroleum Technology, Pandit Deendayal Petroleum University, Gandhinagar 382007, India
c
Department of Mechanical Engineering, Government Engineering College, Patan, Gujarat, India
article info a b s t r a c t
Article history: Fluoride contamination due to natural and anthropogenic activities has become the
Received 12 June 2020 biggest threat to human health worldwide. Geological and anthropogenic factors are
Received in revised form 31 October 2020 responsible for contaminating groundwater with fluoride. Excess amounts of fluoride
Accepted 5 November 2020
in potable water may cause irreversible demineralization of bone and tooth tissues,
Available online 12 November 2020
a condition called fluorosis, and long-term damage to the brain, liver, thyroid, and
Keywords: kidney. For a long time there has been a need for fluoride removal from potable
Fluoride removal water to make it safe for human use. The present paper reviews the different methods
Methods used for defluoridation, for example, coagulation–precipitation, ion exchange, membrane
Review separation, and adsorption. Among the methods, membrane and ion exchange are not
regularly used in India due to their cost and high maintenance. On the other hand,
coagulation–precipitation and adsorption are mostly used in India. Nalgonda method is
used in developing nations like Kenya, Senegal, Tanzania, and India for fluoride removal.
Comparatively, adsorption is broadly used for defluoridation because of its low cost and
high efficiency in removal. This paper also discusses the merits and demerits of the
methods. It is evident from literature study that different methods show unique potential
for defluoridation. The most promising adsorbents tested so far from each category of
adsorbents are also highlighted. In any circumstance, there is an urgent requirement to
find the practical utility of such developed methods on a business scale and to initiate
a change in contamination control.
© 2020 Elsevier B.V. All rights reserved.
Contents
1. Introduction............................................................................................................................................................................................... 2
2. Methods for defluoridation of water ..................................................................................................................................................... 2
2.1. Coagulation–Precipitation and Nalgonda .................................................................................................................................. 3
2.2. Membrane process....................................................................................................................................................................... 4
2.2.1. Reverse osmosis (RO) and Nanofiltration (NF) ......................................................................................................... 4
2.2.2. Dialysis and electrodialysis ......................................................................................................................................... 5
2.3. Ion-exchange ................................................................................................................................................................................ 7
2.4. Adsorption .................................................................................................................................................................................... 7
2.4.1. Alumina and aluminum-based adsorbents ............................................................................................................... 8
2.4.2. Carbon based adsorbent .............................................................................................................................................. 9
∗ Corresponding author.
E-mail address: [email protected] (S. Dharaskar).
https://doi.org/10.1016/j.eti.2020.101246
2352-1864/© 2020 Elsevier B.V. All rights reserved.
P. Pillai, S. Dharaskar, S. Pandian et al. Environmental Technology & Innovation 21 (2021) 101246
2.4.3. Natural adsorbent......................................................................................................................................................... 9

2.4.4. Nanoparticles ................................................................................................................................................................ 14
2.4.5. Worldwide status of fluoride...................................................................................................................................... 14
3. Conclusion and future scope................................................................................................................................................................... 16
Declaration of competing interest.......................................................................................................................................................... 16
References ................................................................................................................................................................................................. 16
1. Introduction
Water is essential for living beings and animals. There is plenty of water on the earth’s surface; however, the chemical
composition of water is one of the important factors that makes the water unfit for consumption (Edmunds and Smedley,
2013). Freshwater comes from groundwater and surface water, where the groundwater accounts for only 0.6% of the
total water resources. Groundwater is polluted because of the intense activities of industrialization and urbanization
(Mohapatra et al., 2009). Groundwater is mainly used by people of rural and urban areas, mainly in India (Basu et al.,
2015). Physical and chemical qualities of water determine its potability. The quality of groundwater depends on the ions
of water, soil and water interaction, soil–gas interaction, contact of rocks with groundwater, and the residence time that
takes place within the aquifers (Selvakumar et al., 2017). There are many contaminations found in groundwater like
fluoride, arsenic, iron, lead, cadmium, etc. One of the most abundant ions present in groundwater worldwide posing
greater threats to health is fluoride. Fluoride contains ions that are unsafe thereby making the water importable. Due to
its electronegative properties, it reacts with all the elements present in the periodic table (Elhalil et al., 2016). It is not
found in elemental state because of its high reactivity. It is present either as organic or inorganic fluoride, having oxidation
number –1. Inorganic fluoride is more prevalent than organic fluoride in the environment (Zhang et al., 2017).
Fluoride can be beneficial to living entities if its concentration is <1.5 mg/L according to the reports by World Health
Organization (WHO), and the acceptable limit is 1.0 mg/L by Indian standards, and the limit according to the drinking
water specification of 1992 is 1.5 mg/L (Ahmad et al., 2018). The United States Environmental Policy and German Research
Council have classified fluoride as a priority pollutant (Goldar and Banerjee, 2004). It benefits the bones and prevents teeth
decay. However, if it exceeds the limit, it will create problems like brittleness of bones, tooth decay, cancer, etc. Koilraj
and Kannan (2013). Fluoride ions get attracted to calcium ions because of electronegative ion, causing problems in bones
and teeth as the teeth are composed of hydroxyapatite. Under normal conditions, the fluoride present in water ingests the
ions into the apatite crystal lattices of the calciferous tissue present in the enamel (Hillier et al., 2000). The presence of
fluoride in groundwater is attributed to the percolation of rocks and soil into the groundwater. The reaction between the
aquifers also plays a significant role in fluoride concentration. These also lead to the interpretation that longer residence
time of fluoride and aquifers increases fluoride concentration (Mohan et al., 2014). Besides natural sources, fluoride ions
are also present in the effluent from fertilizers, semiconductors, metal processing, and glass manufacturing industries. The
discharge from these industries causes an increase of fluoride in the surface water and groundwater (Kabay et al., 2008).
In tropical regions like Egypt, Pakistan, Malawi, Jordan, Ethiopia, South Africa, Mexico, Sri Lanka, India, etc. where water
consumption is more due to climatic conditions, their fluoride content is found to be in excess (Mohan et al., 2017). In
India, 200 million people living in 17 states, with 200 districts are affected by the complications caused due to excess
fluoride. Endemic fluorosis is a major problem in many parts of the world. The most affected states in India, where fluoride
is found in larger amounts, are Gujarat, Rajasthan, Orissa, West Bengal, Punjab, Maharashtra, etc. Edmunds and Smedley
(2013). Among these states, Rajasthan has the highest fluoride content because of the huge deposits of rocks, namely
mica, Fluorspar, and Fluorapatite (Yadav* and Khan, 2010). Fluoride concentration and its effects are given in Table 1.
There are various methods like Coagulation–precipitation, Membrane-based process, ion exchange, and adsorption to
remove fluoride (Ayoob et al., 2008). The greatest drawbacks of these techniques, apart from the adsorption used for
defluoridation, are the generation of a vast amount of sludge containing leachate and undesirable components, and its
high-cost membrane, and the stringent fouling process that make its removal from the membrane difficult (Eskandarpour
et al., 2008). Adsorption process is widely used because it is easy to use, disposes of less water, and is less costly (Dhillon
et al., 2017). This review, brings out an extensive study, on defluoridation methods which are reviewed in detail in
subsections.
2. Methods for defluoridation of water
Methods like coagulation–precipitation, ion exchange, membrane separation, and adsorption technique are available
for defluoridation. Though every method has its own drawbacks, it works well under ideal conditions for fluoride. The
methods, with their benefits and disadvantages, are explained briefly.
2
Table 1
Effects of fluoride concentration (Karunanithi et al., 2019).
Fluoride Concentration and effects
<0.5 Prevention of teeth cavities
0.5–1.5 Helps in bones and teeth development
1.5–4 Dental problems in children
>4 Dental and skelton fluorosis
>10 Cancer
Table 2
Advantages and disadvantages of the coagulation–precipitation and Nalgonda method.
Method Advantages Disadvantages
Coagulation and Precipitation • High efficiency • Expensive
(Dhillon et al., 2017) • Commercially available chemical • High aluminum residual,
• High disposal waste
• Presence of co-ions in water
Nalgonda technique • Regeneration not available • Pretreatment of water is needed if the total
(Ganvir and Das, 2011) • No need for caustic acids and alkaline solids exceed 1500 mg/L for desalination
• Easy to use • Hard water treatment is required if 200 mg/L to
• Can be used for larger community 600 mg/L is needed.
• Simple design • Large amounts of alumare used for fluoride
• No skilled workers needed treatment
• Efficient removal of fluoride from high concentration to • pH should be controlled
low concentration • High aluminum residuals
• No wastage of water and sludge formation
2.1. Coagulation–Precipitation and Nalgonda
Nalgonda technique, developed by NEERI, uses lime and alum for fluoride removal from water. Lime helps the fluoride
to precipitate at higher pH up to 11–12 to insoluble calcium (Neelo Razbe, 2013). After 8.0, fluoride removal increases
because alum treatment is carried out for defluoridation. The reaction occurs in two steps; in the first step, lime dosing
takes place because of precipitation while alum is added for coagulation. In the second reaction, alum comes in contact
with fluoride ion giving the best fluoride removal at 5.5–7.4 pH (Tikki, 2014). The reactions are as follows.
6Ca(OH)2 + 12H+ → 6Ca+ 18H2 O (1)

3+ 2+
Al2 (SO4 )3 · 18H2 O → 2Al + 3SO + 18H2 O (2)
2+ +
2Al + 6H2 O → 2Al(OH)3 + 6H (3)
F− + 2Al(OH)3 → Al − F complex + undefined product (4)
In the Nalgonda technique, alumina salts, along with the mixing of salt, lime, and bleaching, were used for precipitation,
after which flocculation, sedimentation, and filtration were carried out. Alumina salts were used to remove fluoride. The
dose of lime was 1/20th dose of alum, where the lime helped to make flocks that expanded in size and settled down
easily. Bleaching powder was included at a rate of 3 mg/L for the purpose of cleaning (Jinwal and Dixit, 2009). In a smaller
community, Nalgonda technique, used for defluoridation, gives water that can be utilized for household purposes. This
technique can produce 20 L of clean water per day. The remaining fluoride water concentration was around 1–1.5 mg/L
(Araga et al., 2019).
Recently, two models were developed by the Public Health Engineering Department (PHED), Rajasthan, in collaboration
with DST Rajasthan as studied by Chauhan et al. (2007). Here the size of the activated alumina was from 0.4–1.2 mm.
A defluoridation efficiency of 95% was retained with a 3–5 kg of activated alumina at a depth of defluoridation unit
from 5–13 cm. Gupta et al. have experimented the Nalgonda process using potash alum. This experiment was done in
Jharkhand with a 76.6% of removal efficiency. A kinetic study of the defluoridation of bentonites of different particle
sizes showed that as the particle size of bentonite increased, the fluoride removal capacity was reduced (Gupta et al.,
2014). Calcium containing ores was used for fluoride removal from wastewater with the help of coprecipitation method.
The removal efficiency was 96.20% for at a time of 30 min, and a dosage of calcite 2 g/L. Fluorite was added to
increase the sedimentation of the reactive precipitates (Wang et al., 2019). The advantages and disadvantages of the
coagulation–precipitation and the Nalgonda methods are given below in Table 2:
Pearceb et al. examined the coprecipitation method using bone char and hydroxyapatite with fluorapatite (soluble
fluoride salts). The result revealed that bone char was less effective than hydroxyapatite. The optimized time of 60 min
was considered best for fluoride removal (Pearceb, 1992). Nalgonda technique was used by Teshome et al. by adding
aluminum hydroxide (AO) and cow bone char in Ethiopia. The addition of AO and cow bone char removes fluoride at a
higher rate with lesser sludge generation. The initial concentration of fluoride was 9.3 mg/L which was then lowered to
3
Fig. 1. The layout of a smaller Nalgonda technique in Ethiopia (Yami et al., 2018).
2.5 mg/L. Nalgonda technique has been found to be not very effective because of anintrinsic issue. The drawback of the
pilot study was that alumina was leaching into the wastewater. Fig. 1 represents the Nalgonda technique layout for a
small community in Ethiopia. In this figure, the raw water goes to the reactor tank in which alum and lime are used for
defluoridation, and freshwater comes from the water point.
The water point area, is the place where people can collect water for drinking purpose (Yami et al., 2018). Dahi et al.
studied bone char mixed with sodium dihydrogen phosphate and calcium chloride in doses of 167 g/m3 and 333 g/m3 .
The experiment was carried out in Ngurdoto school, and it was also tested in villages using the contact precipitation
method. The price of fluoride (10 mg/L initial concentration)was estimated to be 0.22 US$/ m3 (Dahi, 1996). Liu and
Chang also performed coagulation and flocculation with polyaluminum chloride and polyacrylic acid using a little dose
of the adsorbent. Also, Aldaco et al. examined calcium fluoride in a fluidized bed to enhance the removal of fluoride from
granular calcite that was prepared from chemical precipitation. The fluoride conversion depended on the overdose of
calcium in a fluidized bed, which is illustrated in Fig. 2 (Aldaco et al., 2007).
2.2. Membrane process
Membrane separation process is used in many applications like wastewater treatment, desalination, fluoride removal.
In this process, the adsorbent is smaller in size and passes through a semi-permeable membrane. The materials used in
the semi-permeable membrane are ceramic, thin, mixed metal membranes, porous, and non-porous. This membrane does
not break or dissolve. The commonly used membranes for fluoride removal are reverse osmosis, Nanofiltration, dialysis,
and Electrodialysis.
2.2.1. Reverse osmosis (RO) and Nanofiltration (NF)

RO is a process that involves anion removal by applying pressure to feed water, which passes through a semi-permeable
membrane. It works on high pressure with dissolved solids at the rejection side. This experiment was carried out in
North Gujarat at a cottage industry selling 10 L of packed water at an estimated price of Rs 1500 per day (Indu, 2002).
It produced pure water, and after regeneration, a rejection of 98% fluoride ions at the end of a set of experiments was
observed. The membrane area was 10 m2 and the cost reduction was £3000/d as investigated by Ndiaye et al. (2005).
Nanofiltration selectivity is advantageous when compared to reverse osmosis according to experimental and theoretical
research. This brings out a clear picture of solute retention that helps in production and optimization of the targeted
membrane. Steric and charge effects are related to solute retention, and fluoride ion is a very small ion having a high
charge density compared to chloride and nitrate in desalination and defluoridation water. Lhassani et al. carried out
selective demineralization of fluoride contaminated water taken from the brackish water pilot plant as shown in Fig. 3.
The results concluded that small size ions are better at low pressure and easier to retain where chemical selectivity occurs
at Nanofiltration (Lhassani et al., 2001). Drioloi et al. made a comparative study on the usage of Nanofiltration membranes
for desalination. Multiple membranes and pretreatments were used for desalination, where the salt concentration was 45
g/L at 25 ◦ C (Drioli et al., 1999).
Tahaikt et al. studied fluoride removal from groundwater using a Nanofiltration pilot plant with two modules. The
authors also carried out a study using two spiral membranes. Parameters like fluoride concentration, volume reduction,
4
Fig. 2. The Fluidized bed reactor of CaF2 (Aldaco et al., 2007).
and pressure were also tested (Tahaikt et al., 2007). Furthermore, Tahaikt et al. used commercial modules of Nanofiltration
in the pilot scale wherein they tested with different parameters like time, pressure, and fluoride content. The experiment
was run in batches and with different types of configuration like simple pass, double pass, and with one type of membrane.
The behavior of the membrane was also tested (Tahaikt et al., 2008). Diawara et al. performed LPRO (Low-pressure reverse
osmosis) for fluoride removal from brackish water with 97 to 98% rejection in a village in Senegal. Fluoride retention in
NF with 63.3% and 71% were recovered in Senegal (Diawara et al., 2011). The study was conducted in Moradgaon village
of Chandrapur district using Polyamide spiral wound RO membrane. The fluoride removal efficiency was 95 to 98%, and
different contaminants undervarious operating conditions of RO were also studied by Gedam et al. (2012).
Schoeman studied defluoridation in RO having a fluoride concentrations of 10–17 mg/L and low pressure using AA.
They also studied with high pressure and concentrations of 4, 8, and 20 mg/L (Schoeman, 2010). Briano et al. investigated
the Guarani Aquifer system for potable water with 100% rejection, total dissolved solids (TDS) of 97%, and sulfate ions
of 94% of RO from southern Brazil. The 93% recovery rate was obtained by blending groundwater with permeate. The
operating condition of 2 MPa and 1.61 m/s was considered as the best removal from desalination water using RO (Brião
et al., 2014). Pontie et al. used NF90 for brackish water in South Morocco (Lhassani et al., 2001). Bejaoui et al. used
NF and RO to decrease fluoride ions and total salinity in metal packing. The fluoride retention was higher than 90% in
both the membranes from model water and metal packing industrial effluent. Spiegler–Kedem was able to determine
the reflection coefficient in membrane and solute permeability ions. The advantages and disadvantages of RO and NF are
shown in Table 3.
2.2.2. Dialysis and electrodialysis

Dialysis differentiates the solutes by transporting through the membrane; furthermore, RO and NF are needed to hold
the solutes. Here, the membrane pores are not in excess when compared to NF, and Donnan dialysis, and electric effect are
the driving forces of the solute. Donnan dialysis is also known as diffusion dialysis, which is similar to the ion exchange
membrane (Dhillon et al., 2016). The difference between these processes is that the ion exchange, which is the driving
force, is an electric current, while the dialysis driving force is the chemical potential. In Donnan dialysis, the difference in
concentration is the only driving force in the feed solution. The negative ion with the anion exchange membrane utilizes
a second alkaline stream. The concentration difference in hydroxide ion between the two solutions dissolves in the feed
solution (Tripathy et al., 2006). Thus, it creates electrical field, leading to the extraction of negative ion in the feed solution.
Hichour et al. conducted Donnan dialysis in a counter-current system using an anion exchange membrane. This process
involves sodium chloride, where the feed concentration is 0.01 M of NaF along with other salts. The experiment was
performed for high fluoride content present in Africa groundwater >30 mg/L, and the author successfully brought down
the fluoride concentration below 1.5 mg/L (Hichour et al., 2000). The hybrid method for adsorption uses aluminum
oxide and zirconium oxide to treat water having 4 mg/L fluoride concentration due to phosphate mining in Morocco
which brings down the concentration to permissible limit with the help of Donnan dialysis with ACS anion exchanger
5
Fig. 3. Nanofiltration of Pilot plant (Lhassani et al., 2001).
Table 3
Advantages and disadvantages of RO and NF methods.
Method Advantages Disadvantages
RO (Gordon et al., • The membrane can be recovered quickly. • Expensive technique
2008) • It can remove more than 90% fluoride from water • Require valuable minerals for demineralization after
• It also gives a pathway to remove other dissolved solids. treatment.
• It has a wide pH range • Water gets treated in saline solution, and salts are an
• Chemical process is not used, and it makes use of less issue.
manpower • Water is an acidic medium, and pH increases.
• Allows treatment and purification of water.
• Guarantee water quality
NF (Zhang et al., •High productivity • Highly expensive

2016) •No chemicals • The problem of fouling, scaling, and membrane
•Ions interference is not observed degradation
•A barrier for suspended solids, inorganic toxic, organic • Removal of ions which helps in the ordinary development
micropollutants
using aluminum and zirconium as suggested by Garmes et al. (2002). Boubakri et al. used a full factorial design with
Donnan dialysis for defluoridation of dilute solutions. The removal efficiency increased with an increase in temperature
and agitation speed, while the flow of the feed did not change much. The figure shows the experiment carried out in a
laboratory cell, consisting of two compartments. Two peristaltic pumps transported fluoride from the feed compartment
(F) to the receiver compartment. The receiver and feed tanks were fitted with 250 mL Erlenmeyer flask. The experiments
were carried out in a batch stirred cell where the compartments consisted of 0.1 M NaHCO3 as shown in Fig. 4 (Boubakri
et al., 2013).
Electrodialysis is an exchange of ions using electric current. The only difference is that it uses current pressure
in RO to separate the ions from water. Rural people are not able to use this process because it requires electricity,
which is not available, in many rural areas of Asian countries. Adhikary et al. studied defluoridation of brackish water
having a concentration of 10 mg/L and TDS of 5000 mg/L. After conducting the experiments at energy <1 kWh/Kg,
the fluoride concentration was brought down to 15 mg/L and TDS to 600 (Adhikary et al., 1989). Amor et al. studied
electrodialysis process in water having 3000 TDS and 3 mg/L of fluoride concentration (Amor et al., 1998). Annouar et al.
used chitosan adsorbent for defluoridation of synthetic water and groundwater from Youssoufla city with the help of CMX-
ACS membrane and brought down the concentration to the acceptable limit through electrodialysis process (Annouar et al.,
2004). Sahil et al. studied Electrodialysis using chitosan by comparing two methods and treated the water of Morocco city,
having 3000 mg/L of TDS and fluoride concentration of 3 mg/L (Sahli et al., 2007). Lahnid et al. used the industrial and
economic data for fluoride removal by Electrodialysis (Lahnid et al., 2008). Kabay et al. studied fluoride removal using
parameters and ionic species, affecting the electrodialysis process (Kabay et al., 2008). Zeni et al. studied the effect of
Electrodialys is on artesian wells for fluoride reduction (Zeni et al., 2005). The advantages of ED is its inexpensive process,
seasonal operation, lesser use of chemical, higher water recovery while the disadvantages of ED are separation of ionic
components; potential formation; higher power consumption for pumping; the need for concentrate treatment (Amof
et al., 2001).
6
Fig. 4. Donnan dialysis laboratory cell (Boubakri et al., 2013).
2.3. Ion-exchange
The ion exchange is a process in which water flows through a bed of ions exchange for the removal of undesirable
ions. The reaction is as follows:
Matrix − NR3 + Cl− + F− → Matrix − NR3 + F− + Cl−
Here the fluoride ions have replaced the chloride ions from resin. The process continues till all the resins are empty.
The resins are back washed with dissolved sodium chloride salts after which the chloride ions replace the fluoride ion.
When this happens, the process starts once again (Ojekunle et al., 2016). Electronegativity is the driving force for the
chloride ion to replace fluoride. Alizarin et al. used lanthanum for anion exchange and modified the anion exchange
for fluoride removal (Alizarin and Blue, 1987). Chikuma and Nishimura conducted the fluoride removal on an aqueous
solution with Amberlite IRA -400. The chloride ion was replaced by fluoride ion (Chikuma and Nishimura, 1990). Castel
experimented with fluoride removal in two ways in the ion-exchange cycle (Castel et al., 2000). Ho et al. studied the use
of titanium iron oxyhydroxide in the ion-exchange process. Silica and zirconium were doped on iron oxyhydroxide which
is a mesaporous material. The result showed that the process was costly, and also membrane fouling occurred during the
experiments (Ho et al., 2004). Chubar et al. carried out ion exchange process on different anions like bromide, chloride,
fluoride, and bromate as novel solutions taking into consideration the two-fold hydrous oxide (Fe2 O3 .Al2 O3 .x H2 O) (Chubar
et al., 2005). Menakshi et al. studied FR 10 (IND) and Ceralite IRA 400 (CER) for fluoride removal using Chelating resin.
The authors also studied the various parameters used with the selective adsorbent (Meenakshi and Viswanathan, 2007).
Sundaram et al. performed an organic–inorganic type of ion exchangers for defluoridation. The ion exchanger
polyacrylamide was altered with Ce(SO4 )2 •4H2 O, Al(NO3 )3 •9H2 O, and ZrOCl2 •8H2 O. Moreover, it was used for actual
water to lower the level of fluoride concentration from 1.96 mg/L to the acceptable level using 0.25 g of exchangers for
50 ml of samples for 30 min. The mechanism is illustrated in Fig. 5 (Sairam Sundaram and Meenakshi, 2009). Aluminum
doped with Duolite C-467 resin was used for fluoride removal from water. The obtained pH proved to be a good result
for fluoride removal by Ku et al. (2011). Singh et al. studied leachates with ion exchange to remove fluoride. Removal of
arsenic and phosphate can also be used by this method. Freundlich and the second-order were the best for this process
(Singh et al., 1999). The advantages of ion exchange are high productivity, retains water and disadvantages of ion exchange
are high cost of the technique, lower pH and the need for a high chloride concentration, the problem of regeneration,
longer reaction time (Rao, 2003).
2.4. Adsorption
Adsorption is a surface phenomenon where the interaction between the ions gets adsorbed on the surface. This process
can occur in two interfaces, i.e., between any two phases like liquid–liquid, gas–solid or liquid–solid. Van der Waals force
occurs in adsorption, i.e., physical adsorption or physisorption. The adsorption process occurs in three steps (1) diffusion of
the adsorbent occurs by external mass transfer phenomenon, (2) Adsorption of fluoride ion on the surface of the adsorbent
and (3) intraparticle diffusion (Fan et al., 2003). The mechanism, adsorption capacity, adsorption isotherms, and the results
of defluoridation with various adsorbents are reviewed below. For a detailed methodology and conditions, the full article
cited in the reference list can be referred to. The advantages of adsorption are low cost, less maintenance, simple to use,
high removal efficiency and disadvantages are higher Ph substitute; the occurrence of higher TDS at the column study
(Islam and Patel, 2007).
7
Fig. 5. Mechanism of fluoride removal by hybrid ion exchange (Sairam Sundaram and Meenakshi, 2009).
2.4.1. Alumina and aluminum-based adsorbents

Alumina has been used by many researchers and it is considered as the most effective adsorbent for fluoride removal
from water. Alumina is used as an activated alumina (AA) to increase the affinity and efficiency and is prepared by either
slow or rapid pyrolysis of gibbsite or materials containing gibbsite, i.e., flash calcination. The adsorption capacity of AA
depends on the pH and the crystalline formation of the adsorbent (Mohapatra et al., 2009). Goswami et al. used acidic
alumina for defluoridation which resulted in maximum fluoride removal at pH 4.4. The adsorption capacity was found to
be 8.4 mg/g and was followed by pseudo-second-order kinetics. AA is improved by scientists either chemically or thermally
to increase the adsorption efficiency (Goswami and Purkait, 2012). Tripathy et al. prepared alum impregnated with AA
and found it to be more competent for fluoride removal from water. The surface area of AA was increased from 113 m2 /g
to 176 m2 /g when impregnated with alum. The removal efficiency was 99% when the pH was 6.5 pH, the adsorbent dose
8 g/L, contact time 3 h, and the initial fluoride concentration was 20 mg/L in 50 mL of water. At higher pH, the adsorption
capacity decreases. Energy dispersion analysis of X-rays shows that fluoride removal occurs due to surface precipitation,
and not by adsorption (Tripathy et al., 2006).
Maliyekkal et al. synthesized magnesium oxide coated alumina (MOCA). The fluoride adsorption rate was higher than
activated alumina at pH 4–7. The fluoride adsorption capacity for MOCA and AA was found to be 2.85 and 1.08 mg/g,
respectively. MOCA follows Langmuir isotherm and second-order kinetics. For the regeneration of MOCA, 2.5% NaOH
eluent was used (Maliyekkal et al., 2006). The redox process was used for the preparation of hydrous manganese oxide
coated alumina (HMOCA). The Langmuir adsorption was the best fit and the adsorption capacity obtained was 7.09 mg/g.
The optimized pH was in the range of 4–6 (Teng et al., 2009). Manganese dioxide coated activated alumina (MCAA)
for fluoride removal was investigated by Tripathy and Raichuret. al. The adsorbent was able to reduce fluoride from
10 mg/L to 0.2 mg/L. The MCAA adsorbent follows Langmuir isotherm and second-order kinetics. Dubinin Raduskevich
isotherm, second-order kinetics and EDAX analysis confirm that the adsorbent has physical adsorption and intraparticle
diffusion (Tripathy and Raichur, 2008). Karthikeyan et al. investigated the defluoridation of AA with regeneration using
HCL, NaOH, and H2 SO4 . Activated and ordinary quick lime was studied for defluoridation of synthetic water. The result
obtained was 80.6% of fluoride removal at optimized parameters for an initial fluoride concentration of 50 mg/L. Langmuir
isotherm was the best fit for fluoride removal with 16.67 mg/g of adsorption capacity (Srimurali and Karthikeyan, 2008).
Jain and Jayaram examined hydroxide impregnated limestone (A1LS) for fluoride removal from real water. Due to the
dissolution of the alumina in the acidic medium, the pH of the alumina decreased to 2. The maximum adsorption capacities
of the limestone and AlLS adsorbents were found to be 43.10 mg/g and 84.03 mg/g, respectively (Jain and Jayaram, 2009).
Cheng et al. used lanthanum modified AA (La-AA) by mixing 2 g of adsorbent with 40 mL of lanthanum nitrate
solution which was kept aside for 2 days. The result showed that La-AA was superior to AA and followed Langmuir
and pseudo second-order isotherm (Cheng and Zheng, 2014). Rafique et al. prepared immobilized AA modified with alum
using sol–gel method (MIAA). The fluoride adsorption rate of AA was 1.35 times higher than the normal immobilized AA.
The optimized results of the factors were 10 g/L of adsorbent dose, 1 h of contact time, 150 rpm of stirring rate, and
12 mg/L of initial fluoride concentration. The adsorption was confirmed by Langmuir and Freundlich isotherms. MIAA
was regenerated by thermal and chemical processes (Rafique et al., 2015). Tomar et al. synthesized the new adsorbent
Hydroxyapatite modified activated alumina (HMAA) by dispersing nanoparticles of hydroxyapatite within AA granules.
For fluoride removal HMAA was five times more efficient than AA with 14.4 mg/g adsorption capacity at pH 8. HMAA was
regenerated using a solution containing innocuous chemicals (Tomar et al., 2015). Maliyekkal et al. prepared magnesia
8
amended AA (MAAA) for fluoride removal. >95% removal efficiency was achieved at 10 mg/L within 3 h of contact time
at pH 7. The BET surface area was found to be 193.5 m2 /g of MAAA. The adsorption data well fitted with the pseudo
second order capacity. In coexisting ions, higher concentration of bicarbonate and sulfate reduced the adsorption capacity
(Maliyekkal et al., 2008). Jagtap et al. developed chitosan based mesoporous alumina (MA450) and found that the highest
adsorption capacity was 8.26 mg/g for 5 mg/L concentration of fluoride. The pseudo second order and Langmuir were
fitted for adsorption data (Jagtap et al., 2009). More alumina adsorbents are shown in Table 4.
2.4.2. Carbon based adsorbent

Carbon-based adsorbents were studied widely for fluoride adsorption because carbon has a higher active surface
area and higher affinity towards F− ions (Mohapatra et al., 2009). Karthikeyan et al. prepared graphite as an adsorbent
for defluoridation of aqueous ions. The maximum fluoride was achieved at a lower pH and a higher temperature. The
adsorption data were fitted on Langmuir and Freundlich isotherm and followed first-order kinetics. The thermodynamic
data follows endothermic process (Karthikeyan and Elango, 2008). Joshi et al. used zirconyl impregnated activated carbon
from seed stone. The fluoride removal was achieved at 3–4 pH at 3 h. The Langmuir isotherm model was the best fit (Joshi
et al., 2013a). Said and Machunda developed fluoride removal using coconut shell. The batch experiment was studied to
evaluate the factors affecting the adsorbent. The maximum adsorption capacity was achieved at 58.4% and in an acidic
medium at pH 2. Langmuir and Freundlich isotherms were a good fit for the adsorption capacity on coconut shell activated
carbon (Said and Machunda, 2014). Gupta et al. synthesized carbon slurry for defluoridation. The adsorbent was prepared
from oil-based generator in fertilizer industry. The maximum adsorption capacity of 4.861 mg/g was observed at 15 mg/L
at an initial fluoride concentration of 1 g/L. Langmuir and second-order kinetics were fitted with the experimental data.
Desorption from fluoride loaded carbon slurry was conducted under alkaline conditions (Gupta et al., 2007).
SaiSathish et al. studied zirconium ion impregnated coconut fiber (ZICFC) for defluoridation. The surface area was
163.2 m2 /g which was calculated from BET. ZICFC adsorb 93% of fluoride at 4 pH and 6 h of agitation time. The
adsorption data were fitted on Langmuir isotherm of ZICFC because of Chemisorption and physisorption with intraparticle
diffusion (Sathish et al., 2008). Poudyal and Babel did the experiment on granular activated carbon (GAC) and domestic
sewage for defluoridation. The fluoride removal efficiency was achieved at 88% and 78%, respectively. Freundlich isotherm
was better than Langmuir isotherm. Vences-Alvarez et al. performed granular activated carbon through the impregnation
of lanthanum oxyhydroxide (GAC-La). The adsorption capacity of GAC was 5 times higher than that of unmodified GAC.
The reason behind the higher adsorption of GAC was the higher number of -OH active sites on the adsorbent. The
highest adsorption capacity achieved was 9.98 mg/g, and the best fit was Langmuir isotherm (Vences-Alvarez et al., 2015).
Different carbon based adsorbent are shown in Table 5.
2.4.3. Natural adsorbent

Many researchers have tried natural adsorbents like soil, chitosan, leaves, the bark of trees, zeolite, etc. as they are
cheaper to manufacture. Natural soil is considered to be a very efficient adsorbent because of its higher surface area and
in-built chemical and mechanical properties. Properties like molecular sieve structure, different surfaces, and structural
factors also make it more effective to be an adsorbent (Vinati et al., 2015). Peter examined soil rich in bauxite and in
kaolinite. The result showed that soil rich in bauxite has adequate adsorption capacity than non-activated soil because of
which it has higher removal efficiency (Kalista, 2009). Gogoi and Baruah et al. used acid-activated kaolinite clay that has
more potential than raw kaolinite. The kalinite was activated with concentrated Sulfuric acid (Gogoi and Baruah, 2008).
Sarkar et al. reported that the laterite soil has 78.2% removal efficiency with 10 mg/dm of fluoride. Thermodynamic study
found that the process is exothermic and spontaneous (Sarkar et al., 2006a). Ngulube has found silica-rich reddish black
Mukondeni clay soil with optimized factors of 25 ◦ C, pH 2, 1.5 g of dosage, 9 mg/L fluoride concentration, and time 1 h has
been reported to have an adsorption capacity of 58.65 kJ/mol as given by the Arrhenius equation. Thermodynamic study
shows that the process is due to chemisorptions. Radha et al. studied fluoride removal using tea waste and drumstick.
Neutral pH is shown to have good removal efficiency. For a dosage of 400 mg/L and a contact time of 150 min, the
adsorption capacity of tea and drumstick was found to be 212 mg/L, and 600 mg/L. Between the two adsorbents, tea has
shown the highest efficiency because of its smaller size (Radha and T, 2019).
Ramesh et al. examined for batch and continuous process. The contact time was 105 min, and the dosage 70 mg/L.
Column study was also performed by fluctuating the bed height and contact time (Ramesh et al., 2012). The study was also
carried out with various types of bio adsorbents like banana peel powder, passion fruit seed powder, and its peel powder
by Saranya et al. The best removal efficiency was achieved by banana peel powder. The author concluded that adsorption
increases with an increase in the dosage of the adsorbent (Saranya and Anu, 2016). Aleena et al. researched fluoride
removal using tulsi leaves and Moringaoleifera seed powder. The author concluded that as the adsorbent increases, the
removal also increases. The experiment was conducted on a dose between −.1 mg/L and 0.5 mg/L in synthetic water. The
removal efficiency of 0.5 mg/L of tulsi and moringaOlefera was 23% and 40% (Haneef and Kurup, 2016). Sutapa Chakrabarty
et al. carried out defluoridation using neem stem. The removal efficiency of neem stem was 94% from aqueous solution
with a concentration of 10 mg/L. The author found out that pH plays an important role in the adsorption of fluoride on
neem stem (Chakrabarty and Sarma, 2012). Various natural adsorbents are shown in Table 6.
9
P. Pillai, S. Dharaskar, S. Pandian et al.
Table 4
Various alumina adsorbent for fluoride removal using adsorption.
Sr Adsorbent pH Adsorption Concentration Contact Dose Temp. Isotherm Kinetic Regeneration Removal Ref.
no capacity time study efficiency
1 AA 4.4 8.4 mg/g 15 mg/L 90 min 4.5 g/L 25 ◦ C L PSO 85% 94% Goswami and Purkait
(2012)
◦
2 MCA 7 0.16 mg/g 10 mg/L 3 h 8 g/L 25 C L SO – 98% Tripathy and Raichur
(2008)
3 LAA 4–8 6.7 mg/g 10 mg/L 2 h 2 g/L – L PSO – – Cheng et al. (2014)
◦
4 MAA 7 0.76 mg/g 12 mg/L 1 h 10 g/L 20 C L & F – 85% 95% Rafique et al. (2015)
5 HAA 8 14.4 mg/g 9 mg/L 8 h 7 g/L – L & F – – – Tomar et al. (2015)
◦
6 MAAA 7 10.12 mg/g 10 mg/L 3 h 4 g/L 30 C Slips PSO 90% 95% Maliyekkal et al. (2008)
10
◦
7 CMA 3–9 8.26 mg/g 5 mg/L 24 h 4 g/L 30 C L PSO – 78% Jagtap et al. (2011)
◦
8 COMA 6.8 137 mg/g 10 mg/L 8 h 3 g/L 30 C L PSO – 90% Dayananda et al. (2014)
◦
9 GMN 6.3–7.3 5.6 mg/g 5 mg/L 140 min 0.5 g/L 35 C L PSO – 85% Nazari and Halladj
(2014)
◦
10 LAA 7.6–8.6 16.9 mg/g 10 mg/L – 1 g/L 25 C L – 98% 77.2% Shi et al. (2013)
◦
11 CCA 4.9 7.22 mg/g 10 mg/L 24 h 0.4 g/L 30 C L PSO 97% 98% Bansiwal et al. (2010)
◦
12 CAM 3–11 4.37 mg/g 8.9 mg/L 24 h 3 g/L 25 C L PSO 84% 85% Sakhare et al. (2012)

◦
13 AAB 7.4–8.2 17 mg/g 1–100 mg/L 5 h 2 g/L 22 C L PSO – 99.9% Basu et al. (2013)
AA = Acidic alumina; MCA = Magnesium dioxide coated alumina; LAA = Lanthanum impregnated activated alumina; MAA = Modified immobilized activated alumina; HAA = Hydroxyapatite modified
activated alumina; MAAA = Magnesia amended activated alumina; CMA = Chitosan based mesoporous alumina 450; COMA = Calcium oxide loaded mesoporous alumina; GMN = Gaama alumina with
magnesium oxide nanocrystals;; LAA = Lanthanum impregnated activated alumina; CCA = Copper oxide coated alumina; CAM = calcium aluminate material; AAB = alumina impregnated calcium
alginate beads; PFA = Pseudo first order; PSO = Pseudo second order; IPD = Intraparticle diffusion; FO — First order; SO = second order; L — Langmuir; F — Freundlich; RP — redlichpeterson.
Table 5
Various carbon adsorbent for fluoride removal using adsorption.
◦
1 ZLAC 3 3.25 mg/g 10 mg/L 2.5 h 2 g/L 25 C L – – – Joshi et al. (2013a)
◦
2 WCS – 4.86 mg/g 15 mg/L – 1 g/L 25 C L SO 92% – Gupta et al. (2007)
◦
3 ZIMCF 4 1.95 mg/g 20 mg/L 6 h 20 g/L 25 C L PSO 100% 93% Sathish et al. (2008)
◦
4 LOAC 7 9.98 mg/g 20 mg/L – 0.1 g/L 25 C L PSO 87% 92% Vences-Alvarez et al.
(2015)
◦
5 NC 4 5.9 mg/g 5 mg/L 1 h 3 g/L 24 C L – – 82% Regassa et al. (2016)
◦
6 PAC 2 8.36 mg/g 5 mg/L 1 h 3 g/L 24 C L – – 86% Regassa et al. (2016)
◦
7 CAC 2 11.35 mg/g 5 mg/L 1.5 h 3 g/L 24 C L – – 90% Regassa et al. (2016)
◦
8 KRC 2 23.3 mg/g 20 mg/L 3 h 1.5 g/L 25 C L& F PSO – 100% Daifullah et al. (2007)
◦
9 ACBG 5–5.5 4.720 mg/g 3 mg/L 105 min 12.5 g/L 25 C L&RP – 67.4% 83.77% Alagumuthu et al. (2010)
◦
10 ZCSC 4 0.99 mg/g 10 mg/L 6 h 1 g/L 25 C L PSO 100% 91% Sathish et al. (2008)
◦
11 ZOA 7 7.40 mg/g 40 mg/L – – 25 C L& F – – 94% Velazquez-Jimenez et al.
(2014)
12 IGC 4 2.16 mg/g 10 mg/L 48 h 20 g/L 30 ◦ C L& F PSO – 94% Chen et al. (2011b)
11
13 ZGSC 3 2.32 mg/g 3 mg/L 3 h 2 g/L 25 ◦ C F PSO – 94% Rajan and Alagumuthu
(2013)
14 ZWSC 3 6.38 mg/g 3 mg/L 3 h 15 g/L 25 ◦ C F PSO 96.2% 94% Joshi et al. (2013b)
15 ZCSC 7.6 1.83 mg/g 3 mg/L 3 h 0.015 25 ◦ C L PSO 96.2% 80.33% Alagumuthu and Rajan
g/L (2010)
◦
16 CWC 7.53 15 mg/g 2 mg/L 40 min 2 g/L 25 C F PSO 100% 99% Rajkumar et al. (2015)
◦
17 MSW 4 18.95 mg/g – 20 min 2 g/L 30 C L PSO – 97.2% Dutta et al. (2012)

◦
18 ABS 6 2.4 mg/g 8 mg/L 1 h 2 g/L 30 C L&RP PSO 8% 52% Singh et al. (2017)
◦
19 ACRP 7 1.65 mg/g 5 mg/L 1 h 4 g/L 30 C L PFO – 88% Ravulapalli and
Ravindhranath (2017)
20 ABC 6 1.15 mg/g 2.5 mg/L 1 h 4 g/L 28 ◦ C F PSO – 57.6% Yadav et al. (2013)
ZLAC — Zirconyl impregnated lapsi seed stone activated carbon; WCS — waste carbon slurry; ZIMCF — zirconium ion-impregnated coconut fiber carbon; LOAC — lanthanum oxyhydroxide-impregnated
granulated activated carbon; NC — Natural coal; PAC — Physically activated coal; CAC — chemically activated coal; KRC — KMnO4 modified activated carbon derived from steam pyrolysis of rice straw;
ACBG- Activated carbon from Bermuda grass; ZCSC — Zirconium-impregnated coconut shell carbon; ZOA — zirconium-impregnated activated carbon mixed with oxalic acid; IGC — iron-impregnated
granular ceramics; ZGSC — zirconium-impregnated groundnut shell carbon; ZWSC — zirconium-impregnated walnut shell carbon; ZCSC — Zirconium impregnated cashew nut shell carbon; CWC — Cow
dung carbon @500 ◦ C; MSW — microwave assisted activated carbon derived from Acacia auriculiformis scrap wood; ABS — Activated carbon prepared from bael shell; ACRP — Activated carbon derived
from bark of Ficusracemosa plant; ABC — Activated bagasse carbon; PFA — Pseudo first order; PSO — Pseudo second order; IPD — Intraparticle diffusion; FO — First order; SO — second order; L —
Langmuir; F — Freundlich; RP — redlichpeterson.
Table 6
Various natural adsorbents for fluoride removal using adsorption.
1 LS 6.8 0.8461 mg/g 20 mg/L – 1 g/L 303 K L PFO 80.4% 80.4% Sarkar et al. (2006b)
2 MC 2 1.836 mg/g 3 mg/L 50 min 70 g/L 298 K L IPD – 97% Karthikeyan and Elango
(2008)
3 CMH 6 18.409 mg/g 5 mg/L 30 min 1.25 g/L – F PSO – 96.5% Dang-I Apea et al. (2015)
4 MBC 3–10 2.26 mg/g 5 mg/L 12 h 3 g/L 25 ◦ C L PFO 97% 95.47% Thakre et al. (2010)
5 ABC 2–12 5.7 mg/g 60 mg/L 30 min 10 g/L 26 ◦ C L& F PSO – 99.97% Vhahangwele et al. (2014)
6 FBC 2–10 2.91 mg/g 10 mg/L 30 min 20 g/L 26 ◦ C L – – 100% Gitari et al. (2020)
7 CIC 3–10 2.34 mg/g 50 mg/L 1.5 h 10 g/L – L, F & D-R PSO 84.3% 90% S and PC (2016)
8 CAMZ 4–8 8.03 mg/g 10 mg/L 6 h 1.5 g/L 25 ◦ C F PSO 90% 96% Waghmare et al. (2015)
9 ZMZ 7 28.57 mg/g 40 mg/L 1 h 10 g/L Room F PSO – 97.63% Zhou et al. (2018)
10 GCB 2 0.426 mg/g 5 mg/L 176 h 10 g/L 20 ◦ C L PSO – 94.1% Salifu et al. (2016)
11 CA 4–11 2.16 mg/g 10 mg/L 48 h 20 g/L 30 ◦ C L& F PSO – 94.4% Chen et al. (2010)
12 KM 5–7 3.06 mg/g 10 mg/L 2 h 20 g/L 30 ◦ C F PSO 85% 90% Chen et al. (2011a)
13 P 4.9 2.2 mg/g 10 mg/L 2 h 4 g/L 24 ◦ C L PSO – 85% Goswami and Purkait
(2011)
14 SAMC 4 1.324 mg/g 6 mg/L 30 min 3 g/L – L – – 88% Ramdani et al. (2010)
15 CM – 16.1 mg/g 75 mg/L 50 h – 20 ◦ C L& F FO 61% 97.3% Guo and Reardon (2012)
12
16 AL 5 39.10 mg/g 10 mg/L 24 h 0.5 g/L 305 K L & F SCM 96% 96% Maiti et al. (2011)
17 B 5.36 36.26 mg/g 49.06 mg/L 2 h 1.5 g/L 31.96 ◦ C L PSO – 90.83% Mourabet et al. (2017)
18 P 7 0.31 mg/g 7 mg/L 3 h 20 g/L 25 ◦ C F PSO – 85.75% Malakootian et al. (2011)
19 HMP 6 11.765 mg/g 10 mg/L 210 min 6 g/L 293–333 F PSO 98% 70.8% Sepehr et al. (2013)
K
20 ATDE 3.4 51.1 mg/g 400 mg/L 10 min 500 g/L 298 K L – – 92% Wambu et al. (2011)
21 MCMDE 6.52 12.633 mg/g 40 mg/L 1 h 6 g/L 24 ◦ C L PSO 60.8% 97.1% Gitari et al. (2020)

22 RB 5.5 0.275 mg/g 6.17 mg/L 90 min 120 g/L 283–308 – FO – 96.1% Kayira et al. (2014)
K
23 LIB 8.5 18.18 mg/g 20 mg/L 120 min 2 g/L 25 ◦ C L PSO 95% 99% Vivek Vardhan and
Srimurali (2016)
24 IO 6 1.72 mg/g 14.22 mg/L 2 h 5 g/L 22 ◦ C F PFO – 89% Kebede et al. (2016)
25 SM 3.4 12.4 mg/g 200 mg/L 20 min 500 g/L 293 K L – – 100% Wambu et al. (2013)
26 M 6 0.263 mg/g 4 mg/L 3 h 8 g/L 25 ◦ C F NL 93% 65% Tor (2006)
27 CS 3 93.45 mg/g – 24 h – – L – – 85% Hamdi and Srasra (2009)
28 V 4 2.36 mg/g 4 mg/L 70 min 2 g/L 25 ◦ C F PSO – 51% Ologundudu et al. (2016)
29 B 4 33.6 mg/g 8 mg/L 2 h 125 g/L – L PFO – 93.8% Sajidu et al. (2008)
30 GDH 6.72 17.34 mg/g 100 mg/L 12 h 5 g/L 35 ◦ C F SO – 96.6% Liang et al. (2011)
31 CBB – 3.15 mg/g 10 mg/L 3 h 8 g/L 27 ◦ C F PSO – 60.27% Gourouza et al. (2014)
32 AMH 5 32.57 mg/g 10 mg/L – 0.5 g/L 25 ◦ C L PSO – 75% Nie et al. (2012)
33 SB 5.4 4.12 mg/g 4 mg/L 1 h 1 g/L 30 ◦ C RP PSO 3%–4% 45% Singh et al. (2016)
(continued on next page)
Table 6 (continued).
34 MPP 7 1.35 mg/g 5 mg/L 30 min 10 g/L 30 ◦ C F PSO – 82.5% Shubha et al. (2014)
35 MGS 6 15.6 mg/g 100 mg/L 6 h 80 g/L 25 ◦ C L& F PSO – 85% Sánchez-sánchez et al.
(2013)
36 RL 7.93 15.8 mg/g 3 mg/L – 8 g/L – L PSO – 95% Msagati et al. (2014)
37 PPC 2 33.34 mg/g 2–10 mg/L 5 h 15 g/L 28 ◦ C F PSO – 97% Angelina Thanga Ajisha
and Rajagopal (2015)
38 TPP 7 25 mg/g 5 mg/L 2 h 140 g/L – L& F PSO – 70% Kant Pandey et al. (2012)
◦
39 AJR 6 1.03 mg/g 0.52 mmol/L 4 h 1 g/L 30 C L PSO – 80% Paudyal et al. (2011)
◦
40 PLP 7 2.24 mg/g 20 mg/L 45 min 10 g/L 29 C F PSO – 85.7% Dwivedi et al. (2014)
41 LCS 7 94.34 mg/g 20 mg/L 4 h 0.4 g/L – L – – 90% Yu et al. (2015)
◦
42 SLP 7.5 1.28 mg/g 5 mg/L 25 min 60 g/L 30 C F – – 98.6%
◦
43 PC 7 0.81 mg/g 3 mg/L 40 min 3 g/L 25 C L FO 91 81.6% Emmanuel et al. (2015)
◦
44 CES 7 2.3 mg/g 20 mg/L – 8 g/L 30 C L – – 84% Hernández-Montoya et al.
(2012)
45 ASC 2 1.27 mg/g 2 mg/L 3 h 5 g/L 30 ◦ C L& F PSO – 94% Chakrabarty and Sarma
(2012)
13
◦
46 AEG 2–10 7 mg/g 5 mg/L 210 min 1.5 g/L 30 C L IDP – 85% Manna et al. (2015)
◦
47 BB 8 1.12 mg/g 5 mg/L 8 h 5 g/L 30 C L PSO – 77.04% Bhagyashree et al. (2002)
◦
48 CGC 7 1.68 mg/g 2–10 mg/L 75 min 0.75 g/L 25 C F – – 78.1% Kanaujia et al. (2015)
◦
49 BP 6 1.340 mg/g 20 mg/L 1 h 14 g/L 30 C L PSO – 94.34% Abas et al. (2013)
◦
50 PA 7 1.65 mg/g 8 mg/L 5 min 48 g/L 25 C F PSO&IDP – 97% Dobaradaran et al. (2016)
◦
51 SR 6 1.73 mg/g 2.5 mg/L 1 h 4 g/L 28 C F PSO – 56.4% Yadav et al. (2013)
◦

52 WSR 6 1.93 mg/g 2.5 mg/L 1 h 4 g/L 28 C F PSO – 49.8% Yadav et al. (2013)
LS = Laterite soil; MC = Montmorillonite clay; CMH = Clay mixed hydroxyapatite; MBC = Magnesium incorporated bentonite clay; ABC = Al3+ modified bentonite clay; FBC = Fe3+ modified bentonite
clay; CIC = Chitosan iron complex; CAMZ = Calcium aluminum modified zeolite; ZMZ = Zirconium modified zeolite; GCB = Granular aluminum coated bauxite; CA = Ceramic adsorbent; KM =
Kanuma mud; P = Pyrophyllite;; SAMC = Sodium activated Algerian non calcium montmorillonite clay; CM = Calcinedmeixnerite; AL = Acid treated raw laterite; B = Brushite; P = Pumice; HMP =
Hydrogen peroxide modified pumice; ATDE = Acid treated diatomaceous earth; MCMDE = Mg/Ce/Mn oxide-modified diatomaceous earth; RB = Raw bauxite; LIB = Lanthanum-impregnated bauxite;
IO = Iron ore; SM = Siliceous mineral; M = Montmorillonite; CS = Clay soil; V = Vermiculite; B = Bauxite; GDH = Glass derived hydroxyapatite; CBB = Charred beef shoulder blade bones; AMH =
Aluminum modified hydroxyapatite; SB = Sugarcane bagasse; MPP = Mosambi peel powder; MGS = Mechanically modified guava seed; RL = Restructured lignite; PPC = pyrolyzedDelonixregia pod
carbon; TPP = Tinosporacordifolia plant powder; AJR = Al3+ loaded saponified orange juice residue; PLP = Peepal leaf powder; LCS = Lanthanum modified carbon from sargassum; SLP = Sal leaf
powder; PC = pithacelobiumdulce carbon; CESCarbons obtained from pecan nut shell modified with calcium solution from egg shell; ASC = Activated neem stem charcoal; AEG = Alkali stem treated
elephant grass; BB = Bark of babool; CGC = carbonized Punicagranatum carbon; BP = Banana peel; PA = Padinasanctaecrucis algae; SR = Sawdust raw; WSR = Wheat straw raw; PFA = Pseudo
first order; PSO = Pseudo second order; IPD = Intraparticle diffusion; FO — First order; SO = second order; L = Langmuir; F = Freundlich; RP = redlich Peterson; D-R = Dubininradushkevich,; NL =
nonlinear; SCM = Shrinking core method.
Fig. 6. Mechanism of fluoride removal using ZIF-8 (Pillai et al., 2019a).
2.4.4. Nanoparticles
Nanotechnology has become an important field of research. Nanotechnology includes the synthesis and characteriza-
tion of nano-sized particles (1–100 nm) and is used in many applications. Currently, Nanoparticles (NPs) are being mostly
used for purifying contaminated water. Patel et al. prepared CaO NPs through sol–gel method. The highest adsorption
capacity of CaO was 92% at 30 min, 0.6 g/L adsorbent dose, and 100 mg/L of initial fluoride concentration. The best
data fit were the Freundlich isotherm model and pseudo-first-order kinetic equation. The reaction was endothermic and
spontaneous, which was predicted by thermodynamic parameters. The mechanism of CaO NPs and fluoride ions was
because of the ion exchange uptake (Patel et al., 2009). Devi. et al. synthesized nano-sized magnesium oxide for fluoride
removal and achieved 90% removal efficiency with 0.6 g/L adsorbent dose. The adsorption of fluoride was influenced by
the presence of OH− ions. The presence of other ions and pH variation were negligible. Freundlich model was a better fit
than the Langmuir isotherm for the equilibrium data. The regeneration study shows that 1 M HCL was the best eluent
for defluoridation having 95% desorption capacity with 2 M of NaOH and 25% regeneration of the adsorbent (Devi et al.,
2014).
Kumar et al. prepared nano alumina in batch experiment. Different parameters like pH, temperature, contact time,
initial fluoride concentration, and co-existing ions were used. Characterization like SEM, XRD, EDX, and FTIR was done
on the nano alumina. The result showed that 14 mg/g of fluoride was removed at 25 ◦ C and pH 6.15. Langmuir isotherm
was the best fit and delivered pseudo-second order. Coexisting ions like phosphate, sulfate, and carbonate were found
to be influenced by nano-alumina (Kumar et al., 2011). Raul et al. synthesized iron oxyhydroxide NPs for defluoridation.
The highest adsorption capacity was found to be 16.70 mg/L. The best fit was Freundlich isotherm. The adsorption of
the NPs was reduced in the hydroxide ions and no change was observed in the other co-anions ions. The mechanism
shows that ion exchange and physical adsorption take place between the adsorbent and the adsorbate. Regeneration
shows 76% using 0.2 M and 0.5 M NaOH as an eluent (Raul et al., 2012). P Pillai et al. studied ZIF-8 (Zeolite imidazole
framework) because of its hexagonal structure, which increases fluoride adsorption. The outcome of the fluoride removal
comes at 92% with pH 8. The mechanism is shown in Fig. 6 (Pillai et al., 2019a). P Pillai performed an experiment on iron
oxyhydroxide coated with rice husk, having high active sites. Defluoridation efficiency was 92%, with 26 mg/g adsorption
capacity. Pseudo-second-order and kinetic studies were followed (Pillai et al., 2019b).
Calcium and zirconium modified with activated alumina were examined for fluoride removal. The optimized pH was
achieved at 6 and an adsorbent dose 6 g/L (Kumari et al., 2020). Prabhu et al. prepared the Nanosized by hydroxyapatite
(GOs-nHAp) using situ coprecipitation fabrication method. The highest monolayer adsorption capacity was calculated to be
44.068 mg/g. Freundlich isotherm fitted well with the isotherm data. The kinetics were defined well by pseudo-second-
order rate law. Thermodynamic parameters revealed that the physical force of attraction and the spontaneous nature
were the main causes of fluoride adsorption (Prabhu et al., 2016). Chinnakoti et al. studied developed nanosized gamma-
alumina using a surfactant-assisted combination method. The 96% removal efficiency was achieved within 1 h using 1 g/L
dosage at pH 4. The data follows Langmuir isotherm and pseudo-second-order kinetics. The fluoride adsorption was due
to physical adsorption and intraparticle diffusion. Regeneration was studied using 0.1M of NaOH (Chinnakoti et al., 2017).
Carbon nanotubes are used in recent years, and their controlled pore size distribution, large active sites, smaller size, and
hollow and layered structure have been a great help. These allotropes of carbon are formed in a cylindrical shape, and
they are rolled up in a tube-like structure (Tiraferri et al., 2011). Balarak et al. synthesized single-walled carbon nanotubes
for defluoridation. The adsorption capacity was 50–150 mg/g, and the removal efficiency of fluoride was 87%–100%. The
adsorption process was endothermic and spontaneous. The highest adsorption capacity of 4.42 mg/g was achieved for
zirconium/multi-walled carbon nanotubes by Ramamurthy et al. (2011). Some of the adsorbents are shown in Table 7.
2.4.5. Worldwide status of fluoride

Fluoride has caused problems in many countries because of the excessive F -ions present in drinking water. The status
shows more than 35 countries having higher fluoride content in water. Countries like India, China, Ethiopia, Kenya,
14
Table 7
Various adsorbents for fluoride removal using adsorption.
1 ABE 3.5 7.752 5–45 mg/dm3 30 min 0.375 g – F IPD 96% Mahramanlioglu et al.
(2002)
2 AS 6 5.394 20 mg/L 240 min 4 g/L 305 K L – – 82% Sujana et al. (1998)
3 AA 5–6 0.86 mmol/g 20 mg dm−3− 16–24 h – 30 ◦ C L & F SO – – Ku and Chiou (2002)
4 AACS 7 1450 mg/kg 2.5–14 mg/L – 200 g – L & F FO 94% 96% Ghorai and Pant (2005)
5 MGA 5–6 12.57 mg/g 50 ppm 1 h – 20 ◦ C L – – – Pietrelli (2005)
6 AAA 6.5 40.68 mg/g 1–35 mg/L 3 h 8 g/L Room temp B – 98% 99% Tripathy et al. (2006)
7 MCA 7 2.851 mg/g 2.5–30 mg/L 3 h 5 g/L 30 ◦ C L SO 94.6% 91% Maliyekkal et al. (2006)
8 HCA 5.2 7.09 mg/g 10–70 mg/L 4 h – 25 ◦ C L PSO 85% 95% Teng et al. (2009)
9 CAA 5.5 101.01 mg/g 1–1000 mg/L 48 h – 25 ◦ C F & L PSO & – – Camacho et al. (2010)
and 10.18 IPD
mg/g
10 H 4–16 3.12 mg/g 20 mg/L 1.5 h 0.28 g/L 20–40 ◦ C L & F PSO – 86.34% Mourabet et al. (2017)
11 QL 12.71 16.67 mg/g 50 mg/L 75 min 5 g/L 25 ◦ C L FO 6% 80.6% Islam and Patel (2007)
12 RC 5.5 40 mg/g 10 mg/L 40 min 0.9 g 298 K L PSO – 98% Nehra et al. (2019)
13 LA 6 26.45 mg/g 10 mg/L 12 h 2 g/L – S Elovich 70.07% 86.66% He et al. (2019)
15
kinetic
14 Fe/Al/Ti 5 – 10 ppm 300 min 0.2 g/100 mL 30 ◦ C L PSO – – Mukherjee et al. (2019)
15 IRH 4 26 mg/g 10 mg/L 60 min 0.8 g/L 30 ◦ C L PSO 74% 92% Pillai et al. (2019b)
16 Y-Zr-Al 7 31.0 mg/g 50 mg/L – 1 g/L 298 K L PSO 50% 98.47% Jiang et al. (2019)
17 Mg-Mn-Zr 10 26.27 mg/g 10 mg/L 3 h 1 g/L 303 K L PSO – 96% Mullick and Neogi
(2019)
18 CCN 2 0.36 mg/g 4.4 mg/L 3 h 10 g/L 323 K L PSO – 71.14% Araga et al. (2019)

19 RCP 5 55 mg/g 10 mg/L 65 min 1.1 g/L 30 ◦ C Temkin PSO 58% 94% Pillai et al. (2020a)
20 SRH 8 12 mg/g 10 mg/L 60 min 4 g 30 ◦ C L PSO 57% 72% Pillai et al. (2020b)
21 Zr-Mg-Al 7 84.24 mg/g 10 mg/L 24 h 0.5 g/L 298 K L PSO 70% – Gao et al. (2020)
22 IOIL 8 67.9 mg/g 10 mg/L 30 min 0.06 g/L 30 ◦ C L PSO 85% 96% Pillai et al. (2020c)
23 Mg/Ce/Mn- 6.52 12.63 mg/g 40 mg/L 60 min 6 g/L 297 K L PSO – 97.1% Gitari et al. (2020)
DE
ABE = Acid Treated spent bleaching earth; AS = Alum sludge; AA = Activated alumina; AACS = Activated alumina (Grade OA-25) Column study; MGA = Metallurgical grade alumina; AAA = Alum
impregnated activated alumina; MCA = Magnesium oxide coated alumina; HCA = Hydrous magnesium oxide coated alumina; CAA = Calcium oxide modified activated alumina and manganese oxide
modified activated alumina;; H = Hydroxyapatite; CAB — Ce-Zr oxide nanospheres encapsulating calcium alginate bead; NCA = natural crystalline apatite; MH = magnesium incorporated hydroxyapatite;
CH — Ca-deficient hydroxyapatite; H = hydroxyapatite; QL = Quick lime; RC = Rod shaped Ca-Zn @Chitin composite; LA = La and Ce modified alumina; Fe/Al/Ti–Fe/Al/Ti; IRH Iron oxyhydroxide with
rice husk; Y-Zr-Al–Y-Zr-Al; Mg-Mn-Zr–Mg-Mn-Zr; CCN = Coconut shell derived carbon/carbon nanotubes; RCP — Rice husk derived silica nano doped calcium peroxide; SRH = Silica nano modified
from rice husk; Zr-Mg-Al- 3D flower like hierarchical zinc magnesium–aluminum; IOIL = Iron oxide modified with ionic liquid; Mg/Ce/Mn-DE- Mg/Ce/Mn = modified diatomaceous earth; PFA =
Pseudo first order; PSO = Pseudo second order; IPD = Intraparticle diffusion; FO = First order; SO = second order; L = Langmuir; F = Freundlich; RP =redlich Peterson; D-R = Dubininradushkevich;
NL = nonlinear; SCM = Shrinking core method; B = Bradley; T = Toth; T = Temkin; QSO — Quasi-2nd order, S = Sips isotherm.
Fig. 7. World map showing fluoride affected countries (Yadav et al., 2018).
Pakistan, Iran, Germany, Sri Lanka, Tanzania, Nigeria, and South Africa have reported excess fluoride, as shown in Fig. 7.
The problems in developing countries to carry out defluoridation are the expensive technology, adsorbent costly and
insufficient. These problems need to be overcome in countries suffering from excess fluoride content. There should be
inspections and issues of fluoride and fluorosis in developing countries.
3. Conclusion and future scope
The review has attempted to cover the methods used for fluoride removal from water. Defluoridation methods have
been categorized into two types, namely membrane and adsorption techniques. Reverse osmosis, Electrodialysis, ion
exchange have been discussed under membrane techniques. Several methods of defluoridation techniques are used
for fluoride removal, though not all the methods are suitable under all circumstances, and hence, proper validation
is required to adopt suitable methods. A technique like adsorption is very commonly used for fluoride removal due
to its less cost and easy implementation in rural areas. However, adsorbent characteristics, like selectivity, physical
and chemical stability, and regeneration, play an important role in adsorption. Future research ought to focus on the
improvement of methods that can be used regularly and that are cost-effective and feasible. In the developing world,
people always are in contact with the immediate environment, and they prefer to use drinking water directly from the
source or tap. Such household filter systems are not effective due to this reason. Most of the techniques do not have social
acceptance and the implementation fails. Very limited studies have been carried out on bioremediation of fluoride. It may
be important to focus on the bioremediation potential for defluoridation. Although defluoridation research has made
significant advancement, no sustainable solution to this crisis exists. Hence, still there is need for the best technology for
defluoridation of drinking water.
Declaration of competing interest
The authors declare that they have no known competing financial interests or personal relationships that could have
appeared to influence the work reported in this paper.
References
Abas, S.N.A., Ismail, M.H.S., Kamal, M.L., Izhar, S., 2013. Adsorption process of heavy metals by low-cost adsorbent: A review. World Appl. Sci. J. 28,
1518–1530. http://dx.doi.org/10.5829/idosi.wasj.2013.28.11.1874.
Adhikary, S.K., Tipnis, U.K., Harkare, W.P., Govindan, K.P., 1989. Defluoridation During Desalination of Brackish Water By Electrodialysis *, Vol. 71.
pp. 301–312.
Ahmad, Z.U., Lian, Q., Zappi, M.E., Buchireddy, P.R., Gang, D.D., 2018. Adsorptive removal of resorcinol on a novel ordered mesoporous carbon (OMC)
employing COK-19 silica scaffold: Kinetics and equilibrium study. J. Environ. Sci. 1–11. http://dx.doi.org/10.1016/j.jes.2018.04.014.
Alagumuthu, G., Rajan, M., 2010. Equilibrium and kinetics of adsorption of fluoride onto zirconium impregnated cashew nut shell carbon. Chem. Eng.
J. 158, 451–457. http://dx.doi.org/10.1016/j.cej.2010.01.017.
Alagumuthu, G., Veeraputhiran, V., Venkataraman, R., 2010. Adsorption Isotherms on Fluoride removal: Batch Techniques. Arch. Appl. Sci. Res. 2,
170–185.
16
Aldaco, R., Garea, A., Irabien, A., 2007. Modeling of particle growth: Application to water treatment in a fluidized bed reactor. 134, 66–71.
http://dx.doi.org/10.1016/j.cej.2007.03.068.
Alizarin, F., Blue, F., 1987. Separation and Determination of Fluoride Exchange Resin Loaded with Alizarin Ion by Using Ion Fluorine Blue A new
functional resin for the selective collection of fluoride ion was prepared from anion- exchange resin and lanthanum complex of Alizarin Fluor.
35, 3734–3739.
Amof, Z., Barioub, B., Mameri, N., Taky, M., Nicolasb, S., Elmidaoui, A., 2001. Fluoride removal Corn brackish water by electrodialysis. 133, 215–223.
Amor, Z., Malki, S., Taky, M., Bariou, B., Mameri, N., Elmidaoui, A., 1998. Optimization of fluoride removal from brackish water by electrodialysis.
120, 263–271.
Angelina Thanga Ajisha, M., Rajagopal, K., 2015. Fluoride removal study using pyrolyzed Delonix regia pod, an unconventional adsorbent. Int. J.
Environ. Sci. Technol. 12, 223–236. http://dx.doi.org/10.1007/s13762-013-0485-8.
Annouar, S., Mountadap, M., Soufiane, A., Elmidaoui, A., Sahli, M.A.M., 2004. Defluoridation of underground water by adsorption on the chitosan and
by electrodialysis. 165, 9164.
Araga, R., Kali, S., Sharma, C.S., 2019. Coconut-Shell-derived Carbon/Carbon nanotube composite for fluoride adsorption from aqueous Solution. Clean
- Soil Air Water 47, 1–9. http://dx.doi.org/10.1002/clen.201800286.
Ayoob, S., Gupta, A.K., Bhat, V.T., 2008. A conceptual overview on sustainable technologies for the defluoridation of drinking water. Crit. Rev. Environ.
Sci. Technol. http://dx.doi.org/10.1080/10643380701413310.
Bansiwal, A., Pillewan, P., Biniwale, R.B., Rayalu, S.S., 2010. Copper oxide incorporated mesoporous alumina for defluoridation of drinking water.
Microporous Mesoporous Mater. 129, 54–61. http://dx.doi.org/10.1016/j.micromeso.2009.08.032.
Basu, M., Hoshino, S., Hashimoto, S., 2015. Many issues, limited responses: Coping with water insecurity in rural India. Water Resour. Rural Dev. 5,
47–63. http://dx.doi.org/10.1016/j.wrr.2015.07.001.
Basu, H., Singhal, R.K., Pimple, M.V., Reddy, A.V.R., 2013. Synthesis and characterization of alumina impregnated alginate beads for fluoride removal
from potable water. Water. Air. Soil Pollut. 224, http://dx.doi.org/10.1007/s11270-013-1572-7.
Bhagyashree, M., Mamilwar, A.G., Bhole, A.M.S., 2002. Removal of fluoride from ground water by using Adsorbent. Int. J. Eng. Res. Appl. 2, 334–338.
Boubakri, A., Helali, N., Tlili, M., Amor, M., Ben, 2013. Fluoride removal from diluted solutions by Donnan dialysis using full factorial design. 30, 1–6.
http://dx.doi.org/10.1007/s11814-013-0263-9.
Brião, V.B., Magoga, J., Hemkemeier, M., Brião, E.B., Girardelli, L., Sbeghen, L., Paula, D., Favaretto, C., 2014. Reverse osmosis for desalination of water
from the Guarani Aquifer System to produce drinking water in southern Brazil. DES 344, 402–411. http://dx.doi.org/10.1016/j.desal.2014.04.008.
Camacho, L.M., Torres, A., Saha, D., Deng, S., 2010. Adsorption equilibrium and kinetics of fluoride on sol–gel-derived activated alumina adsorbents.
J. Colloid Interface Sci. 349, 307–313. http://dx.doi.org/10.1016/j.jcis.2010.05.066.
Castel, C., Schweizer, M., Simonnot, M.O., Sardin, M., 2000. Selective removal of fluoride ions by a two-way ion-exchange cyclic process. Chem. Eng.
Sci. 55, 3341–3352. http://dx.doi.org/10.1016/S0009-2509(00)00009-9.
Chakrabarty, S., Sarma, H.P., 2012. Defluoridation of contaminated drinking water using neem charcoal adsorbent: Kinetics and equilibrium studies.
Int. J. ChemTech. Res. 4, 511–516.
Chauhan, V.S., Dwivedi, P.K., Iyengar, L., 2007. Investigations on activated alumina based domestic defluoridation units. 139, 103–107. http:
//dx.doi.org/10.1016/j.jhazmat.2006.06.014.
Chen, N., Zhang, Z., Feng, C., Li, M., Chen, R., Sugiura, N., 2011a. Investigations on the batch and fixed-bed column performance of fluoride adsorption
by Kanuma mud. Desalination 268, 76–82. http://dx.doi.org/10.1016/j.desal.2010.09.053.
Chen, N., Zhang, Z., Feng, C., Li, M., Zhu, D., Chen, R., Sugiura, N., 2010. An excellent fluoride sorption behavior of ceramic adsorbent. J. Hazard. Mater.
183, 460–465. http://dx.doi.org/10.1016/j.jhazmat.2010.07.046.
Chen, N., Zhang, Z., Feng, C., Li, M., Zhu, D., Sugiura, N., 2011b. Studies on fluoride adsorption of iron-impregnated granular ceramics from aqueous
solution. Mater. Chem. Phys. 125, 293–298. http://dx.doi.org/10.1016/j.matchemphys.2010.09.037.
Cheng, J., Meng, X., Jing, C., Hao, J., 2014. La3+-modified activated alumina for fluoride removal from water. J. Hazard. Mater. 278, 343–349.
http://dx.doi.org/10.1016/j.jhazmat.2014.06.008.
Cheng, G., Zheng, S.Y., 2014. Construction of a high-performance magnetic enzyme nanosystem for rapid tryptic digestion. Sci. Rep. 4, http:
//dx.doi.org/10.1038/srep06947.
Chikuma, M., Nishimura, M., 1990. Selective sorption of fluoride ions by anion-exchange resin modified with alizarin fluorine blue-praseodymium(III)
complex. React. Polym. 13, 131–138. http://dx.doi.org/10.1016/0923-1137(90)90047-8.
Chinnakoti, P., Chunduri, A.L.A., Vankayala, R.K., Patnaik, S., Kamisetti, V., 2017. Enhanced fluoride adsorption by nano crystalline γ -alumina: adsorption
kinetics, isotherm modeling and thermodynamic studies. Appl. Water Sci. 7, 2413–2423. http://dx.doi.org/10.1007/s13201-016-0437-9.
Chubar, N.I., Samanidou, V.F., Kouts, V.S., Gallios, G.G., Kanibolotsky, V.A., Strelko, V.V., Zhuravlev, I.Z., 2005. Adsorption of fluoride, chloride, bromide,
and bromate ions on a novel ion exchanger. J. Colloid Interface Sci. 291, 67–74. http://dx.doi.org/10.1016/j.jcis.2005.04.086.
Dahi, E., 1996. Contact precipitation for defluoridation of water.
Daifullah, A.A.M., Yakout, S.M., Elreefy, S.A., 2007. Adsorption of fluoride in aqueous solutions using KMnO4-modified activated carbon derived from
steam pyrolysis of rice straw. J. Hazard. Mater. 147, 633–643. http://dx.doi.org/10.1016/j.jhazmat.2007.01.062.
Dang-I Apea, A.Y., Boansi, O., Pedevoah, M.-M., 2015. Reduction of fluorine in Water using clay mixed with hydroxyapatite. Int. J. Appl. Sci. Technol.
5, 45–55.
Dayananda, D., Sarva, V.R., Prasad, S.V., Arunachalam, J., Ghosh, N.N., 2014. Preparation of CaO loaded mesoporous Al2O3: Efficient adsorbent for
fluoride removal from water. Chem. Eng. J. 248, 430–439. http://dx.doi.org/10.1016/j.cej.2014.03.064.
Devi, R.R., Umlong, I.M., Raul, P.K., Das, B., Banerjee, S., Singh, L., 2014. Defluoridation of water using nano-magnesium oxide. J. Exp. Nanosci. 9,
512–524. http://dx.doi.org/10.1080/17458080.2012.675522.
Dhillon, A., Kumar Sharma, T., Soni, S.K., Kumar, D., 2016. Fluoride adsorption on a cubical ceria nanoadsorbent: Function of surface properties. RSC
Adv. 6, 89198–89209. http://dx.doi.org/10.1039/c6ra16962g.
Dhillon, A., Prasad, S., Kumar, D., 2017. Recent advances and spectroscopic perspectives in fluoride removal. Appl. Spectrosc. Rev. 52, 175–230.
http://dx.doi.org/10.1080/05704928.2016.1213737.
Diawara, C.K., Diop, S.N., Diallo, M.A., Farcy, M., Deratani, A., Corporation, P., Germain, S., 2011. Performance of Nanofiltration ( NF ) and Low
Pressure Reverse Osmosis ( LPRO ) Membranes in the Removal of Fluorine and Salinity from Brackish Drinking Water 2011. pp. 912–917.
http://dx.doi.org/10.4236/jwarp.2011.312101.
Dobaradaran, S., Ali Zazuli, M., Keshtkar, M., Noshadi, S., Khorsand, M., Faraji Ghasemi, F., Noroozi Karbasdehi, V., Amiri, L., Soleimani, F., 2016.
Biosorption of fluoride from aqueous phase onto Padina sanctae crucis algae: evaluation of biosorption kinetics and isotherms. Desalination
Water Treat. 57, 28405–28416. http://dx.doi.org/10.1080/19443994.2016.1182081.
Drioli, E., Laganh, F., Crlscuoh, A., Barbieri, G., 1999. Integrated membrane operations in desalination processes. 122, 141–145.
Dutta, M., Ray, T., Basu, J.K., 2012. Batch adsorption of fluoride ions onto microwave assisted activated carbon derived from acacia auriculiformis
scrap wood. Arch. Appl. Sci. Res. 4, 536–550.
Dwivedi, S., Mondal, P., Balomajumder, C., 2014. Bioadsorption of Fluoride by Ficusreligiosa ( Peepal Leaf Powder ): Optimization of process Parameters
and Equilibrium study. Res. J. Chem. Sci. 4, 52–60.
17
Edmunds, W.M., Smedley, P.L., 2013. Fluoride in natural waters. Essent. Med. Geol. Revis. Ed. 31, 1–336. http://dx.doi.org/10.1007/978-94-007-4375-
5_13.
Elhalil, A., Qourzal, S., Mahjoubi, F.Z., Elmoubarki, R., Farnane, M., Tounsadi, H., Sadiq, M., Abdennouri, M., Barka, N., 2016. Defluoridation of
groundwater by calcined Mg/Al layered double hydroxide. Emerg. Contam. 2, 42–48. http://dx.doi.org/10.1016/j.emcon.2016.03.002.
Emmanuel, K.A., Veerabhadrarao, A., Nagalakshmi, T.V., Gurupratap Reddy, M., Diwakar, P.P., Sureshbabu, C., 2015. Factors influencing the removal
of fluoride from aqueous solution by Pithacelobium dulce Carbon. Der Pharm. Chem. 7, 225–236.
Eskandarpour, A., Onyango, M.S., Ochieng, A., Asai, S., 2008. Removal of fluoride ions from aqueous solution at low pH using schwertmannite. J.
Hazard. Mater. 152, 571–579. http://dx.doi.org/10.1016/j.jhazmat.2007.07.020.
Fan, X., Parker, D.J., Smith, M.D., 2003. Adsorption kinetics of fluoride on low cost materials. Water Res. 37, 4929–4937. http://dx.doi.org/10.1016/j.
watres.2003.08.014.
Ganvir, V., Das, K., 2011. Removal of fluoride from drinking water using aluminum hydroxide coated rice husk ash. J. Hazard. Mater. 185, 1287–1294.
Gao, M., Wang, W., Yang, H., Ye, B.C., 2020. Efficient removal of fluoride from aqueous solutions using 3D flower-like hierarchical
zinc-magnesium-aluminum ternary oxide microspheres. Chem. Eng. J. 380, 122459. http://dx.doi.org/10.1016/j.cej.2019.122459.
Garmes, H., Persinb, F., Sandeauxb, J., Pourcellyb, G., Mountadar, M., 2002. Defluoridation of groundwater by a hybrid process combining adsorption
and Donnan dialysis. 145, 287–291.
Gedam, V.V., Patil, J.L., Kagne, S., Sirsam, R.S., Labhasetwar, P., 2012. Performance evaluation of polyamide Reverse Osmosis membrane for removal
of contaminants in ground water collected from chandrapur performance evaluation of polyamide reverse Osmosis Membrane for removal of
contaminants in ground water collected from chan. http://dx.doi.org/10.4172/2155-9589.1000117.
Ghorai, S., Pant, K.K., 2005. Equilibrium, kinetics and breakthrough studies for adsorption of fluoride on activated alumina. Sep. Purif. Technol. 42,
265–271. http://dx.doi.org/10.1016/j.seppur.2004.09.001.
Gitari, W.M., Izuagie, A.A., Gumbo, J.R., 2020. Synthesis, characterization and batch assessment of groundwater fluoride removal capacity of trimetal
Mg/Ce/Mn oxide-modified diatomaceous earth. Arab. J. Chem. 13, 1–16. http://dx.doi.org/10.1016/j.arabjc.2017.01.002.
Gogoi, P.K., Baruah, R., 2008. Fluoride removal from water by adsorption on acid activated kaolinite clay. Indian J. Chem. Technol. 15, 500–503.
Goldar, B., Banerjee, N., 2004. Impact of informal regulation of pollution on water quality in rivers in India. J. Environ. Manag. 73, 117–130.
http://dx.doi.org/10.1016/j.jenvman.2004.06.008.
Gordon, B., Callan, P., Vickers, C., 2008. WHO guidelines for drinking-water quality. WHO Chron. 38, 564. http://dx.doi.org/10.1016/S1462-0758(00)
00006-6.
Goswami, A., Purkait, M.K., 2011. Kinetic and equilibrium study for the fluoride adsorption using pyrophyllite. Sep. Sci. Technol. 46, 1797–1807.
http://dx.doi.org/10.1080/01496395.2011.572327.
Goswami, A., Purkait, M.K., 2012. The defluoridation of water by acidic alumina. Chem. Eng. Res. Des. 90, 2316–2324. http://dx.doi.org/10.1016/j.
cherd.2012.05.002.
Gourouza, M., Natatou, I., Boos, A., 2014. Elimination of fluoride ions from an aqueous solution with charred beef shoulder blade bones. J. Mater.
Environ. Sci. 5, 416–425.
Guo, Q., Reardon, E.J., 2012. Fluoride removal from water by meixnerite and its calcination product. Appl. Clay Sci. 56, 7–15. http://dx.doi.org/10.
1016/j.clay.2011.11.013.
Gupta, V.K., Ali, I., Saini, V.K., 2007. Defluoridation of wastewaters using waste carbon slurry. Water Res. 41, 3307–3316. http://dx.doi.org/10.1016/j.
watres.2007.04.029.
Gupta, A., Amitabh, V., Kumari, B., Mishra, B., 2014. Defluoridation capability of Jharkhand raw Bentonite without transferring Neurotoxin Aluminium
by Potash Alum of Nalgonda Technique. 7, pp. 1–10.
Hamdi, N., Srasra, E., 2009. Retention of fluoride from industrial acidic wastewater and NaF solution by three tunisian clayey soils. Fluoride 42,
39–45.
Haneef, A.R., Kurup, N., 2016. Comparative study of Fluoride removal from water by using Muringa oleifera and Thulsi (Ocimum Sanctum). Int. J.
Sci. Eng. Res. 7, 222–225.
He, Y., Zhang, L., An, X., Wan, G., Zhu, W., Luo, Y., 2019. Enhanced fluoride removal from water by rare earth (La and Ce) modified alumina: Adsorption
isotherms, kinetics, thermodynamics and mechanism. Sci. Total Environ. 688, 184–198. http://dx.doi.org/10.1016/j.scitotenv.2019.06.175.
Hernández-Montoya, V., Ramírez-Montoya, L.A., Bonilla-Petriciolet, A., Montes-Morán, M.A., 2012. Optimizing the removal of fluoride from water
using new carbons obtained by modification of nut shell with a calcium solution from egg shell. Biochem. Eng. J. 62, 1–7. http://dx.doi.org/10.
1016/j.bej.2011.12.011.
Hichour, M., Sandeaux, J., Gavach, C., 2000. Fluoride removal from waters by Donnan dialysis. 18, 1–11.
Hillier, S., Cooper, C., Kellingray, S., Russell, G., Hughes, H., Coggon, D., 2000. Fluoride in drinking water and risk of hip fracture in the UK: A
case-control study. Lancet 355, 265–269. http://dx.doi.org/10.1016/S0140-6736(99)07161-5.
Ho, L.N., Ishihara, T., Ueshima, S., Nishiguchi, H., Takita, Y., 2004. Removal of fluoride from water through ion exchange by mesoporous Ti oxohydroxide.
Indu, R., 2002. Fluoride-free drinking water supply North Gujarat the rise of Reverse Osmosis plants as A cottage industry an exploratory study. pp.
1–49.
Islam, M., Patel, R.K., 2007. Evaluation of removal efficiency of fluoride from aqueous solution using quick lime. J. Hazard. Mater. 143, 303–310.
Jagtap, S., Thakre, D., Wanjari, S., Kamble, S., Labhsetwar, N., Rayalu, S., 2009. New modified chitosan-based adsorbent for defluoridation of water. J.
Colloid Interface Sci. 332, 280–290. http://dx.doi.org/10.1016/j.jcis.2008.11.080.
Jagtap, S., Yenkie, M.K.N., Labhsetwar, N., Rayalu, S., 2011. Defluoridation of drinking water using chitosan based mesoporous alumina. Microporous
Mesoporous Mater. 142, 454–463. http://dx.doi.org/10.1016/j.micromeso.2010.12.028.
Jain, S., Jayaram, R.V., 2009. Removal of fluoride from contaminated drinking water using unmodified and aluminium hydroxide impregnated blue
lime stone waste. Sep. Sci. Technol. 44, 1436–1451. http://dx.doi.org/10.1080/01496390902766074.
Jiang, H., Li, X., Tian, L., Wang, T., Wang, Q., Niu, P., Chen, P., Luo, X., 2019. Defluoridation investigation of Yttrium by laminated Y-Zr-Al tri-metal
nanocomposite and analysis of the fluoride sorption mechanism. Sci. Total Environ. 648, 1342–1353. http://dx.doi.org/10.1016/j.scitotenv.2018.
08.258.
Jinwal, A., Dixit, S., 2009. An assessment of fluoride concentrations in different districts of madhya pradesh. India. Int. J. Chem. Sci. 7, 147–154.
Joshi, S., Adhikari, M., Pradhananga, R.R., 2013a. Adsorption of fluoride Ion onto Zirconyl-Impregnated activated carbon prepared from Lapsi seed
stone. J. Nepal Chem. Soc. 30, 13–23. http://dx.doi.org/10.3126/jncs.v30i0.9330.
Joshi, S., Adhikari, M., Pradhananga, R.R., 2013b. Adsorption of fluoride Ion onto Zirconyl-impregnated activated Carbon prepared from Lapsi Seed
Stone. J. Nepal Chem. Soc. 30, 13–23. http://dx.doi.org/10.3126/jncs.v30i0.9330.
Kabay, N., Arar, Ö., Samatya, S., Yüksel, Ü., Yüksel, M., 2008. Separation of fluoride from aqueous solution by electrodialysis: Effect of process
parameters and other ionic species. J. Hazard. Mater. 153, 107–113. http://dx.doi.org/10.1016/j.jhazmat.2007.08.024.
Kalista, P.H., 2009. Defluoridation of high fluoride waters from Natural Water sources by using soils rich in Bauxite and Kaolinite. J. Eng. Appl. Sci..
18
Kanaujia, S., Singh, B., Singh, S.K., 2015. Removal of fluoride from groundwater by carbonised <i&gt Punica granatum </i> Carbon (‘‘CPGC’’)
Bio-Adsorbent. J. Geosci. Environ. Prot. 03, 1–9. http://dx.doi.org/10.4236/gep.2015.34001.
Kant Pandey, P., Pandey, M., Sharma, R., 2012. Defluoridation of Water by a Biomass: <i&gt Tinospora cordifolia </i>. J. Environ. Prot. (Irvine,.
Calif.) 03, 610–616. http://dx.doi.org/10.4236/jep.2012.37074.
Karthikeyan, M., Elango, K.P., 2008. Removal of fluoride from aqueous solution using graphite: A kinetic and thermodynamic study. Indian J. Chem.
Technol. 15, 525–532.
Karunanithi, M., Agarwal, R., Qanungo, K., 2019. A review of fluoride removal from groundwater. Period. Polytech. Chem. Eng. 63, 425–437.
http://dx.doi.org/10.3311/PPch.12076.
Kayira, C., Sajidu, S., Masamba, W., Mwatseteza, J., 2014. Defluoridation of groundwater using raw bauxite: Kinetics and thermodynamics. Clean -
Soil Air Water 42, 546–551. http://dx.doi.org/10.1002/clen.201200488.
Kebede, B., Beyene, A., Fufa, F., Megersa, M., Behm, M., 2016. Experimental evaluation of sorptive removal of fluoride from drinking water using iron
ore. Appl. Water Sci. 6, 57–65. http://dx.doi.org/10.1007/s13201-014-0210-x.
Koilraj, P., Kannan, S., 2013. Aqueous fluoride removal using ZnCr layered double hydroxides and their polymeric composites: Batch and column
studies. Chem. Eng. J. 234, 406–415. http://dx.doi.org/10.1016/j.cej.2013.08.101.
Ku, Y., Chiou, H.M., 2002. The adsorption of fluoride ion from aqueous solution by activated alumina. Water Air Soil Pollut. 133, 349–361.
http://dx.doi.org/10.1023/A:1012929900113.
Ku, Y., Chiou, H.M., Chen, H.W., 2011. Removal of fluoride from aqueous solution by aluminum-loaded duolite C-467 resin. J. Chin. Inst. Eng. Trans.
Chin. Inst. Eng. A 34, 801–807. http://dx.doi.org/10.1080/02533839.2011.591551.
Kumar, V., Talreja, N., Deva, D., Sankararamakrishnan, N., Sharma, A., Verma, N., 2011. Development of bi-metal doped micro- and nano multi-
functional polymeric adsorbents for the removal of fluoride and arsenic(V) from wastewater. Desalination 282, 27–38. http://dx.doi.org/10.1016/
j.desal.2011.05.013.
Kumari, U., Siddiqi, H., Bal, M., Meikap, B.C., 2020. Calcium and zirconium modified acid activated alumina for adsorptive removal of fluoride:
Performance evaluation , kinetics , isotherm , characterization and industrial wastewater treatment. Adv. Powder Technol. http://dx.doi.org/10.
1016/j.apt.2020.02.035.
Lahnid, S., Tahaikt, M., Elaroui, K., Idrissi, I., Hafsi, M., Laaziz, I., Amor, Z., Tiyal, F., Elmidaoui, A., 2008. Economic evaluation of fluoride removal by
electrodialysis. Desalination 230, 213–219. http://dx.doi.org/10.1016/j.desal.2007.11.027.
Lhassani, A., Rumeau, M., Benjelloun, D., Pontie, M., 2001. Selective demineralization of water by nanofiltration application to the defluorination of
brackish water. 35, 3260–3264.
Liang, W., Zhan, L., Piao, L., Rssel, C., 2011. Fluoride removal performance of glass derived hydroxyapatite. Mater. Res. Bull. 46, 205–209. http:
//dx.doi.org/10.1016/j.materresbull.2010.11.015.
Mahramanlioglu, M., Kizilcikli, I., Bicer, I.O., 2002. Adsorption of fluoride from aqueous solution by acid treated spent bleaching earth. J. Fluor. Chem.
115, 41–47. http://dx.doi.org/10.1016/S0022-1139(02)00003-9.
Maiti, A., Basu, J.K., De, S., 2011. Chemical treated laterite as promising fluoride adsorbent for aqueous system and kinetic modeling. Desalination
265, 28–36. http://dx.doi.org/10.1016/j.desal.2010.07.026.
Malakootian, M., Moosazadeh, M., Yousefi, N., Fatehizadeh, a., 2011. Fluoride removal from aqueous solution by pumice: case study on Kuhbonan
water. Afr. J. Environ. Sci. Technol. 5, 299–306. http://dx.doi.org/10.5897/AJEST10.308.
Maliyekkal, S.M., Sharma, A.K., Philip, L., 2006. Manganese-oxide-coated alumina: A promising sorbent for defluoridation of water. Water Res. 40,
3497–3506. http://dx.doi.org/10.1016/j.watres.2006.08.007.
Maliyekkal, S.M., Shukla, S., Philip, L., Nambi, I.M., 2008. Enhanced fluoride removal from drinking water by magnesia-amended activated alumina
granules. Chem. Eng. J. 140, 183–192. http://dx.doi.org/10.1016/j.cej.2007.09.049.
Manna, S., Roy, D., Saha, P., Adhikari, B., 2015. Defluoridation of aqueous solution using alkali-steam treated water hyacinth and elephant grass. J.
Taiwan Inst. Chem. Eng. 50, 215–222. http://dx.doi.org/10.1016/j.jtice.2014.12.003.
Meenakshi, S., Viswanathan, N., 2007. Identification of selective ion-exchange resin for fluoride sorption. J. Colloid Interface Sci. 308, 438–450.
http://dx.doi.org/10.1016/j.jcis.2006.12.032.
Mohan, D., Kumar, S., Srivastava, A., 2014. Fluoride removal from ground water using magnetic and nonmagnetic corn stover biochars. Ecol. Eng. 73,
798–808. http://dx.doi.org/10.1016/j.ecoleng.2014.08.017.
Mohan, S., Singh, D.K., Kumar, V., Hasan, S.H., 2017. Effective removal of Fluoride ions by rGO/ZrO2nanocomposite from aqueous solution: Fixed bed
column adsorption modelling and its adsorption mechanism. J. Fluor. Chem. http://dx.doi.org/10.1016/j.jfluchem.2016.12.014, Elsevier B.V.
Mohapatra, M., Anand, S., Mishra, B.K., Giles, D.E., Singh, P., 2009. Review of fluoride removal from drinking water. J. Environ. Manag. 91, 67–77.
http://dx.doi.org/10.1016/j.jenvman.2009.08.015.
Mourabet, M., El Rhilassi, A., El Boujaady, H., Bennani-Ziatni, M., Taitai, A., 2017. Use of response surface methodology for optimization of fluoride
adsorption in an aqueous solution by Brushite. Arab. J. Chem. 10, S3292–S3302. http://dx.doi.org/10.1016/j.arabjc.2013.12.028.
Msagati, T.A.M., Mamba, B.B., Sivasankar, V., Omine, K., 2014. Surface restructuring of lignite by bio-char of cuminum cyminum - Exploring the
prospects in defluoridation followed by fuel applications. Appl. Surf. Sci. 301, 235–243. http://dx.doi.org/10.1016/j.apsusc.2014.02.052.
Mukherjee, A., Adak, M.K., Upadhyay, S., Khatun, J., Dhak, P., Khawas, S., Ghorai, U.K., Dhak, D., 2019. Efficient fluoride removal and Dye Degradation
of contaminated water using Fe/Al/Ti Oxide nanocomposite. ACS Omega 4, 9686–9696. http://dx.doi.org/10.1021/acsomega.9b00252.
Mullick, A., Neogi, S., 2019. Ultrasound assisted synthesis of Mg-Mn-Zr impregnated activated carbon for effective fluoride adsorption from water.
Ultrason. Sonochem. 50, 126–137. http://dx.doi.org/10.1016/j.ultsonch.2018.09.010.
Nazari, M., Halladj, R., 2014. Adsorptive removal of fluoride ions from aqueous solution by using sonochemically synthesized nanomagnesia/alumina
adsorbents: An experimental and modeling study. J. Taiwan Inst. Chem. Eng. 45, 2518–2525. http://dx.doi.org/10.1016/j.jtice.2014.05.020.
Ndiaye, P.I., Moulln, P., Dominguez, L., Millet, J.C., 2005. Removal of fluoride from electronic industrial effluent by RO membrane separation. 173,
25–32. http://dx.doi.org/10.1016/j.desal.2004.07.042.
Neelo Razbe, N.R., 2013. Various options for removal of fluoride from Drinking Water. IOSR J. Appl. Phys. 3, 40–47. http://dx.doi.org/10.9790/4861-
0324047.
Nehra, S., Raghav, S., Kumar, D., 2019. Rod–shaped Ca–Zn@Chitin composite for fluoride removal studies by adsorption and statistical experiments.
Environ. Nanotechnol. Monit. Manage. 12, http://dx.doi.org/10.1016/j.enmm.2019.100264.
Nie, Y., Hu, C., Kong, C., 2012. Enhanced fluoride adsorption using Al (III) modified calcium hydroxyapatite. J. Hazard. Mater. 233–234, 194–199.
Ojekunle, O.Z., Ojekunle, O.V., Adeyemi, A.A., Taiwo, A.G., Sangowusi, O.R., Taiwo, A.M., Adekitan, A.A., 2016. Evaluation of surface water quality indices
and ecological risk assessment for heavy metals in scrap yard neighbourhood. Springerplus 5, http://dx.doi.org/10.1186/s40064-016-2158-9.
Ologundudu, T.O., Odiyo, J.O., Ekosse, G.I.E., 2016. Fluoride sorption efficiency of vermiculite functionalised with cationic surfactant: Isotherm and
kinetics. Appl. Sci. 6, 1–15. http://dx.doi.org/10.3390/app6100277.
Patel, G., Pal, U., Menon, S., 2009. Removal of fluoride from aqueous solution by CaO nanoparticles. Sep. Sci. Technol. 44, 2806–2826. http:
//dx.doi.org/10.1080/01496390903014425.
19
Paudyal, H., Pangeni, B., Inoue, K., Kawakita, H., Ohto, K., Harada, H., Alam, S., 2011. Adsorptive removal of fluoride from aqueous solution using
orange waste loaded with multi-valent metal ions. J. Hazard. Mater. 192, 676–682. http://dx.doi.org/10.1016/j.jhazmat.2011.05.070.
Pearceb, E.I.F., 1992. Partial defluoridation of drinking water using fluorapatite precipitation. pp. 22–28.
Pietrelli, L., 2005. Fluoride wastewater treatment by adsorption onto metallurgical grade alumina. Ann. Chim. 95, 303–312. http://dx.doi.org/10.1002/
adic.200590035.
Pillai, P., Dharaskar, S., Pandian, S., 2020a. Environmental Technology & Innovation Rice husk derived silica nano doped on calcium peroxide
for fluoride: Performance , characterization , kinetic , isotherm , and groundwater treatment. Environ. Technol. Innov. 19, 100901. http:
//dx.doi.org/10.1016/j.eti.2020.100901.
Pillai, P., Dharaskar, S., Sasikumar, S., Khalid, M., 2019a. Zeolitic imidazolate framework - 8 nanoparticle: a promising adsorbent for effective fluoride
removal from aqueous solution. Appl. Water Sci. 1–12. http://dx.doi.org/10.1007/s13201-019-1030-9.
Pillai, P., Dharaskar, S., Shah, M., Sultania, R., 2020b. Determination of fluoride removal using silica nano adsorbent modified by rice husk from water.
Groundw. Sustain. Dev. 11, 100423. http://dx.doi.org/10.1016/j.gsd.2020.100423.
Pillai, P., Dharaskar, S., Sinha, M.K., Sillanpää, M., Khalid, M., 2020c. Iron oxide nanoparticles modified with ionic liquid as an efficient adsorbent for
fluoride removal from groundwater. Environ. Technol. Innov. 19, 100842. http://dx.doi.org/10.1016/j.eti.2020.100842.
Pillai, P., Lakhtaria, Y., Dharaskar, S., Khalid, M., 2019b. Synthesis, characterization, and application of iron oxyhydroxide coated with rice husk for
fluoride removal from aqueous media. Environ. Sci. Pollut. Res. http://dx.doi.org/10.1007/s11356-019-05948-8.
Prabhu, S.M., Elanchezhiyan, S.S., Lee, G., Khan, A., Meenakshi, S., 2016. Assembly of nano-sized hydroxyapatite onto graphene oxide sheets via in-situ
fabrication method and its prospective application for defluoridation studies. Chem. Eng. J. 300, 334–342. http://dx.doi.org/10.1016/j.cej.2016.04.
111.
Radha, N., T, B.P., 2019. A Review on the Removal of Fluoride U Sing Inexpensive Adsorbents, Vol. 8. pp. 303–309.
Rafique, T., Chadhar, K.M., Usmani, T.H., Memon, S.Q., Shirin, K., Kamaluddin, S., Soomro, F., 2015. Adsorption behavior of fluoride ion on trimetal-oxide
adsorbent. Desalination Water Treat. 56, 1669–1680. http://dx.doi.org/10.1080/19443994.2014.963160.
Rajan, M., Alagumuthu, G., 2013. Study of fluoride affinity by zirconium impregnated walnut shell carbon in aqueous phase: Kinetic and isotherm
evaluation. J. Chem. 2013. http://dx.doi.org/10.1155/2013/235048.
Rajkumar, S., Murugesh, S., Sivasankar, V., Darchen, A., Msagati, T.A.M., Chaabane, T., 2015. Low-cost fluoride adsorbents prepared from a renewable
biowaste: Syntheses, characterization and modeling studies. Arab. J. Chem. http://dx.doi.org/10.1016/j.arabjc.2015.06.028.
Ramamurthy, S.S., Chen, Y., Kalyan, M.K., Rao, G.N., Chelli, J., Mitra, S., 2011. Carbon nanotube-zirconium dioxide hybrid for defluoridation of water.
J. Nanosci. Nanotechnol. 11, 3552–3559. http://dx.doi.org/10.1166/jnn.2011.3806.
Ramdani, A., Taleb, S., Benghalem, A., Ghaffour, N., 2010. Removal of excess fluoride ions from saharan brackish water by adsorption on natural
materials. Desalination 250, 408–413. http://dx.doi.org/10.1016/j.desal.2009.09.066.
Ramesh, S.T., Gandhimathi, R., Nidheesh, P.V., Taywade, M., 2012. Batch and column operations for the removal of Fluoride from aqueous solution
using Bottom Ash. Environ. Res. Eng. Manage. 60, http://dx.doi.org/10.5755/j01.erem.60.2.1396.
Rao, N., 2003. Fluoride and environment - a review. In: Proc. Third Int. Conf. Environ. Heal. pp. 386–399.
Raul, P.K., Devi, R.R., Umlong, I.M., Banerjee, S., Singh, L., Purkait, M., 2012. Removal of Fluoride from water using Iron Oxide-Hydroxide nanoparticles.
J. Nanosci. Nanotechnol. 12, 3922–3930. http://dx.doi.org/10.1166/jnn.2012.5870.
Ravulapalli, S., Ravindhranath, K., 2017. Defluoridation studies using active carbon derived from the barks of Ficus racemosa plant. J. Fluor. Chem.
193, 58–66. http://dx.doi.org/10.1016/j.jfluchem.2016.11.013.
Regassa, M., Melak, F., Birke, W., Alemayehu, E., 2016. Defluoridation of Water using Natural and Activated Coal. Iarjset 3, 1–7. http://dx.doi.org/10.
17148/iarjset.2016.3101.
S, P., PC, M., 2016. Removal of fluoride from Aqueous solution using Chitosan-Iron complex. J. Anal. Bioanal. Tech. 7, http://dx.doi.org/10.4172/2155-
9872.1000326.
Sahli, M.A.M., Annouar, S., Tahaikt, M., Mountadar, M., Soufiane, A., 2007. Fluoride removal for underground brackish water by adsorption on the
natural chitosan and by electrodialysis. 212, 37–45. http://dx.doi.org/10.1016/j.desal.2006.09.018.
Said, M., Machunda, R.L., 2014. Defluoridation of water supplies using Coconut Shells activated Carbon: Batch studies. Int. J. Sci. Res. 3, 2327–2331.
Sairam Sundaram, C., Meenakshi, S., 2009. Fluoride sorption using organic–inorganic hybrid type ion exchangers. J. Colloid Interface Sci. 333, 58–62.
http://dx.doi.org/10.1016/j.jcis.2009.01.022.
Sajidu, S.M.I., Masamba, W.R.L., Thole, B., Mwatseteza, J.F., 2008. Groundwater fluoride levels in villages of southern malawi and removal studies
using bauxite. Int. J. Phys. Sci. 3, 1–11.
Sakhare, N., Lunge, S., Rayalu, S., Bakardjiva, S., Subrt, J., Devotta, S., Labhsetwar, N., 2012. Defluoridation of water using calcium aluminate material.
Chem. Eng. J. 203, 406–414. http://dx.doi.org/10.1016/j.cej.2012.07.065.
Salifu, A., Petrusevski, B., Mwampashi, E.S., Pazi, I.A., Ghebremichael, K., Buamah, R., Aubry, C., Amy, G.L., Kenedy, M.D., 2016. Defluoridation of
groundwater using aluminum-coated bauxite: Optimization of synthesis process conditions and equilibrium study. J. Environ. Manage. 181,
108–117. http://dx.doi.org/10.1016/j.jenvman.2016.06.011.
Sánchez-sánchez, H.A., Cortés-martínez, R., Alfaro-cuevas, R., 2013. Fluoride removal from Aqueous solutions by mechanically modified Guava Seeds.
Int. J. Sci. Basic Appl. Res. 11, 159–172.
Saranya, S.R., Anu, N., 2016. Comparative Study of Fluoride Removal from Synthetic Wastewater by using Bio-adsorbents. 7, 300–303.
Sarkar, M., Banerjee, A., Pramanick, P.P., 2006a. Kinetics and mechanism of fluoride removal using latrite. Ind. Eng. Chem. Res. 45, 5920–5927.
http://dx.doi.org/10.1021/ie060016j.
Sarkar, M., Banerjee, A., Pramanick, P.P., Sarkar, A.R., 2006b. Use of laterite for the removal of fluoride from contaminated drinking water. J. Colloid
Interface Sci. 302, 432–441. http://dx.doi.org/10.1016/j.jcis.2006.07.001.
Sathish, R.S., Sairam, S., Raja, V.G., Rao, G.N., Janardhana, C., 2008. Defluoridation of water using zirconium impregnated coconut fiber carbon. Sep.
Sci. Technol. 43, 3676–3694. http://dx.doi.org/10.1080/01496390802222541.
Schoeman, J.J., 2010. Water defluoridation, water denitrification and Water Desalination in Rural Areas in South Africa. pp. 244–247.
Selvakumar, S., Ramkumar, K., Chandrasekar, N., Magesh, N.S., Kaliraj, S., 2017. Groundwater quality and its suitability for drinking and irrigational
use in the Southern Tiruchirappalli district, Tamil Nadu, India. Appl. Water Sci. 7, 411–420. http://dx.doi.org/10.1007/s13201-014-0256-9.
Sepehr, M.N., Sivasankar, V., Zarrabi, M., Senthil Kumar, M., 2013. Surface modification of pumice enhancing its fluoride adsorption capacity: An
insight into kinetic and thermodynamic studies. Chem. Eng. J. 228, 192–204. http://dx.doi.org/10.1016/j.cej.2013.04.089.
Shi, Q., Huang, Y., Jing, C., 2013. Synthesis, characterization and application of lanthanum-impregnated activated alumina for F removal. J. Mater.
Chem. A 1, 12797–12803. http://dx.doi.org/10.1039/c3ta12548c.
Shubha, D., Prasenjit, M., Chandrajit, B., 2014. Removal of Fluoride using Citrus limetta in batch Reactor: Kinetics and Equilibrium studies. Res. J.
Chem. Sci. 4, 50–58.
Singh, G., Kumar, B., Sen, P.K., Majumdar, J., 1999. Removal of Fluoride from spent Pot Liner Leachate using Ion Exchange. Water Environ. Res. 71,
36–42. http://dx.doi.org/10.2175/106143099x121571.
Singh, K., Lataye, D.H., Wasewar, K.L., 2016. Removal of fluoride from aqueous solution by using low-cost sugarcane bagasse: Kinetic study and
equilibrium isotherm analyses. J. Hazard. Toxic Radioact. Waste 20, 1–13. http://dx.doi.org/10.1061/(ASCE)HZ.2153-5515.0000309.
20
Singh, K., Lataye, D.H., Wasewar, K.L., 2017. Removal of fluoride from aqueous solution by using bael (Aegle marmelos) shell activated carbon: Kinetic,
equilibrium and thermodynamic study. J. Fluor. Chem. 194, 23–32. http://dx.doi.org/10.1016/j.jfluchem.2016.12.009.
Srimurali, M., Karthikeyan, J., 2008. Activated Alumina: Defluoridation of water and Household application – a study. Water Technol. 1–13.
Sujana, M.G., Thakur, R.S., Rao, S.B., 1998. Removal of fluoride from aqueous solution by using alum sludge. J. Colloid Interface Sci. 206, 94–101.
http://dx.doi.org/10.1006/jcis.1998.5611.
Tahaikt, M., El Habbani, R., Ait Haddou, A., Achary, I., Amor, Z., Taky, M., Alami, A., Boughriba, A., Hafsi, M., Elmidaoui, A., 2007. Fluoride removal
from groundwater by nanofiltration. Desalination 212, 46–53. http://dx.doi.org/10.1016/j.desal.2006.10.003.
Tahaikt, M., Haddou, A.A., Habbani, R., El Amor, Z., Elhannouni, F., Taky, M., 2008. Comparison of the performances of three commercial membranes
in fluoride removal by nanofiltration. Contin. Oper. 225, 209–219. http://dx.doi.org/10.1016/j.desal.2007.07.007.
Teng, S.X., Wang, S.G., Gong, W.X., Liu, X.W., Gao, B.Y., 2009. Removal of fluoride by hydrous manganese oxide-coated alumina: Performance and
mechanism. J. Hazard. Mater. 168, 1004–1011. http://dx.doi.org/10.1016/j.jhazmat.2009.02.133.
Thakre, D., Rayalu, S., Kawade, R., Meshram, S., Subrt, J., Labhsetwar, N., 2010. Magnesium incorporated bentonite clay for defluoridation of drinking
water. J. Hazard. Mater. 180, 122–130. http://dx.doi.org/10.1016/j.jhazmat.2010.04.001.
Tikki, M.A., 2014. Fluoride removal from water – a review. Int. J. Sci. Eng. Res. 5, 515–519.
Tiraferri, A., Vecitis, C.D., Elimelech, M., 2011. Covalent binding of single-walled carbon nanotubes to polyamide membranes for antimicrobial surface
properties. ACS Appl. Mater. Interfaces 3, 2869–2877. http://dx.doi.org/10.1021/am200536p.
Tomar, G., Thareja, A., Sarkar, S., 2015. Enhanced fluoride removal by hydroxyapatite-modified activated alumina. Int. J. Environ. Sci. Technol. 12,
2809–2818. http://dx.doi.org/10.1007/s13762-014-0653-5.
Tor, A., 2006. Removal of fluoride from an aqueous solution by using montmorillonite. Desalination 201, 267–276. http://dx.doi.org/10.1016/j.desal.
2006.06.003.
Tripathy, S.S., Bersillon, J.L., Gopal, K., 2006. Removal of fluoride from drinking water by adsorption onto alum-impregnated activated alumina. Sep.
Purif. Technol. 50, 310–317. http://dx.doi.org/10.1016/j.seppur.2005.11.036.
Tripathy, S.S., Raichur, A.M., 2008. Abatement of fluoride from water using manganese dioxide-coated activated alumina. J. Hazard. Mater. 153,
1043–1051. http://dx.doi.org/10.1016/j.jhazmat.2007.09.100.
Velazquez-Jimenez, L.H., Hurt, R.H., Matos, J., Rangel-Mendez, J.R., 2014. Zirconium-carbon hybrid sorbent for removal of fluoride from water: Oxalic
acid mediated Zr(IV) assembly and adsorption mechanism. Environ. Sci. Technol. 48, 1166–1174. http://dx.doi.org/10.1021/es403929b.
Vences-Alvarez, E., Velazquez-Jimenez, L.H., Chazaro-Ruiz, L.F., Diaz-Flores, P.E., Rangel-Mendez, J.R., 2015. Fluoride removal in water by a hybrid
adsorbent lanthanum-carbon. J. Colloid Interface Sci. 455, 194–202. http://dx.doi.org/10.1016/j.jcis.2015.05.048.
Vhahangwele, M., Mugera, G.W., Tholiso, N., 2014. Defluoridation of drinking water using Al3+-modified bentonite clay: optimization of fluoride
adsorption conditions. Toxicol. Environ. Chem. 96, 1294–1309. http://dx.doi.org/10.1080/02772248.2014.977289.
Vinati, A., Mahanty, B., Behera, S.K., 2015. Clay and clay minerals for fluoride removal from water: A state-of-the-art review. Appl. Clay Sci. 114,
340–348. http://dx.doi.org/10.1016/j.clay.2015.06.013.
Vivek Vardhan, C.M., Srimurali, M., 2016. Removal of fluoride from water using a novel sorbent lanthanum-impregnated bauxite. Springerplus 5,
http://dx.doi.org/10.1186/s40064-016-3112-6.
Waghmare, S., Lataye, D.H., Arfin, T., Rayalu, S., 2015. Defluoridation by Nano-Materials , Building Materials and Other Miscellaneous Materials: A
Systematic Review. pp. 11998–12010. http://dx.doi.org/10.15680/IJIRSET.2015.0412046.
Wambu, E.W., Onindo, C.O., Ambusso, W.J., Muthakia, G.K., 2011. Fluoride adsorption onto Acid-treated Diatomaceous mineral from Kenya. Mater.
Sci. Appl. 02, 1654–1660. http://dx.doi.org/10.4236/msa.2011.211220.
Wambu, E.W., Onindo, C.O., Ambusso, W., Muthakia, G.K., 2013. Removal of fluoride from aqueous solutions by adsorption using a siliceous mineral
of a kenyan origin. Clean - Soil Air Water 41, 340–348. http://dx.doi.org/10.1002/clen.201100171.
Wang, L., Zhang, Y., Sun, N., Sun, W., Hu, Y., Tang, H., 2019. Precipitation methods using calcium-containing ores for Fluoride Removal in wastewater.
pp. 30–33. http://dx.doi.org/10.3390/min9090511.
Yadav, A.K., Abbassi, R., Gupta, A., Dadashzadeh, M., 2013. Removal of fluoride from aqueous solution and groundwater by wheat straw, Sawdust
and activated bagasse carbon of sugarcane. Ecol. Eng. 52, 211–218. http://dx.doi.org/10.1016/j.ecoleng.2012.12.069.
Yadav, K.K., Gupta, N., Kumar, V., Khan, S.A., Kumar, A., 2018. A review of emerging adsorbents and current demand for defluoridation of water:
Bright future in water sustainability. Environ. Int. 111, 80–108. http://dx.doi.org/10.1016/j.envint.2017.11.014.
Yadav*, Ashok Kumar, Khan, Parveen, 2010. Fluoride and flurosis status in groundwater of Todaraisingh Area of district Tonk (Rajasthan, India): A
case study. Chem. Environ. Pharm. Res. 1, 6–11.
Yami, T.L., Chamberlain, J.F., Zewge, F., Sabatini, D.A., 2018. Performance enhancement of Nalgonda technique and pilot testing electrolytic
defluoridation system for removing fluoride from drinking water in East Africa. http://dx.doi.org/10.5897/AJEST2018.2545.
Yu, Y., Wang, C., Guo, X., Paul Chen, J., 2015. Modification of carbon derived from Sargassum sp. by lanthanum for enhanced adsorption of fluoride.
Zeni, M., Riveros, R., Melo, K., Primieri, R., Lorenzini, S., 2005. Study on fluoride reduction in artesian well - Water from electrodialysis process.
Desalination 185, 241–244. http://dx.doi.org/10.1016/j.desal.2005.03.080.
Zhang, C., Li, Y., Jiang, Y., Wang, T.-J., 2017. Size-dependent fluoride removal performance of a magnetic fe3 O4 @Fe–Ti adsorbent and its defluoridation
in a fluidized bed. Ind. Eng. Chem. Res. 56, 2425–2432. http://dx.doi.org/10.1021/acs.iecr.6b03856.
Zhang, Y., Wu, B., Xu, H., Liu, H., Wang, M., He, Y., Pan, B., 2016. Nanomaterials-enabled water and wastewater treatment. NanoImpact 3–4, 22–39.
http://dx.doi.org/10.1016/j.impact.2016.09.004.
Zhou, J., Zhu, W., Yu, J., Zhang, H., Zhang, Y., Lin, X., Luo, X., 2018. Highly selective and efficient removal of fluoride from ground water by layered
Al-Zr-La Tri-metal hydroxide. Appl. Surf. Sci. 435, 920–927. http://dx.doi.org/10.1016/j.apsusc.2017.11.108.
21

Environmental Technology & Innovation: Parwathi Pillai, Swapnil Dharaskar, Sivakumar Pandian, Hitesh Panchal

Uploaded by

Copyright:

Available Formats

Environmental Technology & Innovation: Parwathi Pillai, Swapnil Dharaskar, Sivakumar Pandian, Hitesh Panchal

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Environmental Technology & Innovation: Parwathi Pillai, Swapnil Dharaskar, Sivakumar Pandian, Hitesh Panchal

Uploaded by

Copyright:

Available Formats

Environmental Technology & Innovation 21 (2021) 101246

Contents lists available at ScienceDirect