Environmental Research

Removal of Fluoride from Drinking Water Using Different Adsorbents

--Manuscript Draft--

Manuscript Number:

Article Type: Research paper

Section/Category: Environmental Technology

Keywords: Water Treatment, Fluoride Removal , Adsorption, Ion Exchange, MOSR, Activated
Alumina (AA), Minitab

Corresponding Author: Hafiz Muhammad Rizwan, M.D.

University of Engineering and Technology
Lahore, Punjab PAKISTAN

First Author: Hafiz Muhammad Rizwan, MSc in Environmental Engineering

Order of Authors: Hafiz Muhammad Rizwan, MSc in Environmental Engineering

Dr. Umar Farooq, PhD

Abstract: Fluoride presence in drinking waters poses a hazard to the human health. Even though
an optimum concentration of fluoride in the range of 0.5 to 1.0 mg/L is acceptable for
dental health and better development of bones, the concentration beyond 1.5 mg/L if
consumed for longer time duration, imparts toxic impacts on the health. Excess fluoride
consumptions cause fluorosis, variation of structure of DNA, decrease in intelligence
quotient, interrupt kidney function and even death when consumed in range of 150 –
250 mg/L.  The Fluoride sources could be both, natural or anthropogenic. The natural
sources comprise the underground strata / rocks containing the Fluoride which leaches
out in case of contact with water for long periods. The contamination of Fluoride in
groundwater can also be attributed to occur from anthropogenic sources like use of
fertilizers, raw materials processing having phosphatic material, electroplating, ceramic
industries, and coal burning .
The removal of fluoride is necessary in drinking water owing to the associated risk and
lacking of information on fluorosis effective treatment and other relevant hazards to
health. Different technologies of de-fluoridation have been developed across the globe.
The present study aims on the use of two types of adsorbents for the removal of
fluoride namely, Moringa Oleifera Seeds Residue (MOSR) and Activated Alumina (AA).
Optimum values from Taguchi Design of Experiment for MOSR are; pH of 4, 120 min
contact time, 2 ppm initial concentration and 15g bio-sorbent dose. While the Optimum
values from Taguchi Design of Experiment for Activated Alumina (AA) are; pH of 4, 120
min contact time, 2 ppm initial concentration and 10g adsorbent dose. The Langmuir
isotherm was most suitable.  The Pseudo Second Order reaction determined the
adsorption kinetics of both the adsorbents.

Suggested Reviewers: Dr. Khurram Shehzad, Phd

Zhejiang University
Khurrams@zju.edu.cn

Dr. Asma Tufail shah

COMSATS Institute of Information Technology Department of Chemical Engineering
drasmashah@ciitlahore.edu.pk

Dr. Tayyab Ashfaq Butt

University of Hail
ta.butt@uoh.edu.sa

Dr. Shams Tabraiz

Canterbury Christ Church University
shamas.tabraiz@canterbury.ac.uk

Dr. Umar Farooq

University of Engineering and Technology
umarfarooq@uet.edu.pk

Dr. Ghulam Hussain

Powered by Editorial Manager® and ProduXion Manager® from Aries Systems Corporation
 University of Engineering and Technology
ghussain@uet.edu.pk

Powered by Editorial Manager® and ProduXion Manager® from Aries Systems Corporation
Cover Letter

Dear editor
Journal of Public Health.

Please find enclosed the manuscript entitled “REMOVAL OF FLUORIDE FROM DRINKING
WATER USING DIFFERENT ADSORBENTS”. We would like to submit it for publication as an
original research article.

This manuscript illustrates the removal of fluoride from drinking water by using two types of
adsorbents for the removal of fluoride namely, Moringa Oleifera Seeds Residue (MOSR) and
Activated Alumina (AA). Safe drinking water is the basic necessity to sustain human life. Fluoride
presence in drinking waters poses hazards to the human health. An optimum concentration of
fluoride in the range of 0.5 to 1.0 mg/L is acceptable for dental health and better development of
bones, however, the concentration beyond 1.5 mg/L if consumed for longer time durations, imparts
toxic impacts on the health. In order to remove fluoride, a low cost method is urgently needed.
The present study also focus on potential of Moringa Oleifera Seed Residue (MOSR) for Fluoride
removal from water. Additionally, its comparison with Activated Alumina has also not been done
in the past.

This manuscript has not been published and is not under consideration for publication elsewhere.
All co-authors have seen and agree with the contents of the manuscript and there is no conflict of
interest to disclose.

We look forward to hearing from you at your earliest convenience.

Sincerely yours,

Dr Muhammad Umar Farooq on behalf of the authors

Highlights

Removal of Fluoride from Drinking Water Using Different

Adsorbents
Manuscript File Click here to view linked References

Removal of Fluoride from Drinking Water using Different Adsorbents

Dr. Umar Farooq a Hafiz Muhammad Rizwan b
a
Institute of Environmental Engineering, University of Engineering & Technology, Lahore

ABSTRACT

Fluoride presence in drinking waters poses a hazard to the human health. Even though an
optimum concentration of fluoride in the range of 0.5 to 1.0 mg/L is acceptable for dental
health and better development of bones, the concentration beyond 1.5 mg/L if consumed
for longer time duration, imparts toxic impacts on the health. The excess fluoride
consumptions cause fluorosis, variation of structure of DNA, decrease in intelligence
quotient, interrupt kidney function and even death when consumed in range of 150 – 250
mg/L. The Fluoride sources could be both, natural or anthropogenic. The natural sources
comprise the underground strata / rocks containing the Fluoride which leaches out in case
of contact with water for long periods. The contamination of Fluoride in groundwater can
also be attributed to occur from anthropogenic sources like use of fertilizers, raw materials
processing having phosphatic material, electroplating, ceramic industries (use of clay), coal
burning and smelting operations (aluminum).
The removal of fluoride is necessary in drinking water owing to the associated risk and
lacking of information on fluorosis effective treatment and other relevant hazards to health.
Different technologies of de-fluoridation have been developed across the globe. The
present study aims on the use of two types of adsorbents for the removal of fluoride namely,
Moringa Oleifera Seeds Residue (MOSR) and Activated Alumina (AA).
For study of impacts of parameters namely adsorbent dose, pH, contact time and initial
concentration and to study different trends the contour plots were prepared in Minitab 19
and were observed in batch studies. Low pH corresponded to high removal efficiencies
while low initial concentration and higher doses with the different contact times resulted in
the higher removal of the fluoride.
Optimum values from Taguchi Design of Experiment for MOSR are; pH of 4, 120 min
contact time, 2 ppm initial concentration and 15g bio-sorbent dose. While the Optimum
values from Taguchi Design of Experiment for Activated Alumina (AA) are; pH of 4, 120
min contact time, 2 ppm initial concentration and 10g adsorbent dose.
Various isotherms namely Freundlich, Langmuir, Dubinin–Radushkevich (D–R), Flory
Huggins and Tempkin were studied for assessing the degree of Fluoride adsorption on the
designated adsorbents. It was revealed that the Langmuir isotherm was most suitable with
 better correlation coefficients as compared to the other isotherms for both the adsorbents.
The correlation factor of Langmuir isotherm was the highest (R2 = 0.997) which proves
adsorption is favorable. The Pseudo Second Order reaction determined the adsorption
kinetics of both the adsorbents. The cost of treatment through MOSR is PKR 30/ liter while
it is PKR 300/ liter in case of AA.

1 INTRODUCTION
Safe drinking water is the basic necessity to sustain human life. About 1.1 billion peoples
as per World Water Council, do not have the facility of safe drinking water and 2.6 billion
are lacking proper sanitation facilities. The water crisis could become the worst crisis of
humankind due to the increase in the population, changes in lifestyle, and increasing
agricultural and industrial needs. A major population in the developing countries like
Pakistan is also suffering from water-borne diseases due to absence of clean drinking water
and inadequate sanitation facilities.
Amongst all halogens, the fluoride is the most reactive and electronegative element. The
fluorine in elemental state cannot be found in nature due to its reactive nature. With an
oxidation state of -1, it always exists as organic fluoride compounds and inorganic
fluorides. In drinking water, it is present as F- ions and is a vital nutrient for humans as if
it is present in low quantity, it calcifies the bone formation and dental enamel, WHO
recommends a limit of 1.5 ppm for fluoride in drinking water. The major exposure sources
to fluoride include water, food and pesticides. The fluoride exposure can be from air and
certain consumer and pharmaceuticals products.
Groundwater is being utilized commonly for consumption across the globe. The
groundwater becomes unsuitable for different purposes when different ions are present in
low or high concentration with respect to standards and guidelines of respective ions. One
such ion is fluoride which imparts health issues to the population of about 25 nations across
the globe. The minimum required quantity of fluoride is 0.6 mg/l for human consumption
and it also support formation of stronger bones and teeth. Water with fluoride concentration
above 1.5 mg/l if consumed can result in chronic dental fluorosis wherein yellow to brown
color appear on teeth in addition to skeletal fluorosis that bends the bones and cause
weakness as a result of consuming water with higher fluoride concentrations.
Anthropogenic besides natural sources effect the concentration of fluoride in water. The
area geological conditions are one of the natural sources as various rocks contain fluoride-
based minerals like apatite, biotite, fluorite, and hornblende. The fluoride concentration in
 groundwater increases as a result of weathering of such rocks and percolation of rainwater
into the ground through such formations. Volcanic ash possesses high concentration of
fluoride that is easily dissolved in water and act as an other natural source. Fertilizers and
coal combustion comes under anthropogenic sources of fluoride. In irrigation lands.
fluoride combines with Phosphate fertilizers. In brick kilns and in various industries, coal
combustion is done which is another fluoride source.
In drinking water, maximum permissible limit of fluoride is 1.5 mg/ L by PEQs. Ingestion
of excess fluoride (up to 10 mg/ L), most occasionally in water, can cause fluorosis which
affects the teeth and bones. Medium concentrations result in dental effects, but long-term
ingestion of large amounts can lead to potentially severe skeletal problems. Water quality
analyses of 23 major cities of Pakistan revealed the presence of Fluoride (Kahlown, Tahir,
& Ashraf, 2003; TI, Tahir, & Rasheed, 2005).
There are many processes available such as electrodialysis, adsorption, coagulation/
precipitation, ion exchange, reverse osmosis, dialysis, ultra-filtration, nano-filtration, etc.
for the removal of fluoride from water (Maheshwari, 2006) but majority of these methods
are costlier. Therefore, there is emergent requirement for studying some cost effective
method.
This research aims to check the potential of Moringa Oleifera Seed Residue (MOSR) as
natural low-cost adsorbents and compare it with activated alumina as Chemical adsorbent.
These methods can be easily processed and used for Fluoride removal. By comparing
natural & chemical adsorbent, economical solution for de-fluoridation can be obtained.

2 MATERIALS AND METHODS

2.1 Materials

For the experimental purposes, the following two adsorbents were used:
i) Activated Alumina (Chemical Adsorbent); and
ii) Moringa Oleifera Seeds Residues (MOSR, Bio-adsorbent).
Fluoride standard solution (Hach) was obtained from the market for the preparation of
working solutions of Fluoride having different concentrations.

2.2 Methods

Methodology adopted for is described in step wise details in following discussion.

 Preparation of Adsorbents

Activated Alumina as obtained from the market was used directly as adsorbent. Different
doses of activated alumina i.e. 20, 30, 40 and 50 mg were used in study.
Moringa Oleifera was obtained locally from markets. The seed’s residues of Moringa were
separated which were was oven dried for 2 days in hot air oven. The dried MOSR was
grinded using grinder into fine powder and then sieved using 250 µm sieves. Different
doses of MOSR i.e. 2.0, 0, 6.0 and 8.0 g were used in study.
Preparation of Fluoride Solution

Fluoride standard solution of 1000 ppm was obtained from the market for the preparation
of working solutions of Fluoride having 1, 2, 3 and 4 ppm concentrations.
Preparation of Calibration Curve for Fluoride

The calibration curve between log of Fluoride Ion Concentration (mg/L) on abscissa and
electrode potential (millivolts) on ordinate was prepared for Fluoride Ion Selective
Electrode. The fluoride ion concentration was prepared from standard stock solution in the
range of of 1, 2, 3, 4 and 5 mg/l. The logarithm of concentrations was taken and plotted on
x-axis. The electrode potential against each concentration was measured using ISE and
plotted against respective concentration of Fluoride on y-axis. A linear curve was obtained
from plotting the results on a graph paper. The equation of curve was obtained and used
further for determination of fluoride concentration against millivolts measured using ISE.
Design of Experiments (DOE)

The Design of Experiments (DOE) was performed using MINITAB tool. The sets of
experiments with different combinations for the initial concentration of Fluoride,
Absorbent Dose, Contact Time and pH were obtained from DOE.
The experiments were performed on the combinations obtained from DOE to evaluate the
removal efficiency of Fluoride.
pH Adjustment

In order to obtain the solutions having different pH, H2SO4 was used to lower the pH to
desired range while NaOH was used to raise the pH of sample.
Experimental Equipment and Procedure

Batch studies were carried out to find out various optimized parameters. For batch studies,
refer Table 1.
 Table 1 Equipment Used

Classification Item
pH meter (Method: EPA-9040-B)
Ion Selective Electrode (ISE) for Fluoride with
Analytical
temperature probe
Jar Test Apparatus
Filtering Apparatus
Non-Analytical Oven
Grinder

The adsorbent was removed through filtration with filter paper after each experiment. To
analyses the filtrate for Fluoride Ion Selective Electrode (ISE) was used. The Fluoride ion
uptake percentage was calculated as difference of concentration at initial and final after the
batch study by using the equation 1.
C0 − Ce
𝑅𝑒𝑚𝑜𝑣𝑎𝑙𝐸𝑓𝑓𝑒𝑐𝑖𝑒𝑛𝑐𝑦 (%) = 𝑥 100 ……… (1)
C0

Where

C0 =Concentration (Initial), mg/L

Ce =Concentration (Final) of Fluoride ion (mg/L)

Design of Experiments using Minitab

Since the project involves handling of intense numerical data of research and statistics-
based calculations, therefore, Minitab 19 was used for the statistical analysis of the data.
The experiments were design in Minitab 19 using Taguchi approach. The set of
experiments derived from the software were later performed in the lab. Sixteen (16) sets of
experiments were derived varying different parameter under the study including pH,
Contact Time, Initial Concentration and Dose. Table 2 & Table 3 presents the experiments
designed of Moringa Oleifera Seed Residue (MOSR)& Activated Alumina respectively by
using Minitab 19.
Table 2 Experiments Designed of MOSR on Minitab 19

Experiments pH Contact Time Initial Conc. Dose

1 4 15 2 5
2 4 30 4 10
3 4 60 6 15
4 4 120 8 20
5 6 15 4 15
 Experiments pH Contact Time Initial Conc. Dose
6 6 30 2 20
7 6 60 8 5
8 6 120 6 10
9 8 15 6 20
10 8 30 8 15
11 8 60 2 10
12 8 120 4 5
13 10 15 8 10
14 10 30 6 5
15 10 60 4 20
16 10 120 2 15

Table 3 Experiments Designed of Activated Alumina (AA) on Minitab 19

Experiments pH Contact Time Initial Conc. Dose

1 4 15 2 2
2 4 30 4 5
3 4 60 6 10
4 4 120 8 15
5 6 15 4 10
6 6 30 2 15
7 6 60 8 2
8 6 120 6 5
9 8 15 6 15
10 8 30 8 10
11 8 60 2 5
12 8 120 4 2
13 10 15 8 5
14 10 30 6 2
15 10 60 4 15
16 10 120 2 10

3 RESULTS AND DISCUSSION

3.1 MORINGA OLEIFERA SEEDS RESIDUES (MOSR, BIO-ADSORBENT)

Effect of pH

The effect of solution pH on fluoride removal efficiency is illustrated in Figure 1.

 Figure 1 Effect of pH and Contact Time Interaction on Fluoride removal

Figure 1 indicates that high removal efficiencies are obtained at low pH i.e. 4 against higher
range of contact time.
It was also revealed that if pH goes on increasing from 6 to 10, removal efficiency declines
which can be owing to the reason that at high pH, the coordination covalent bond of fluoride
get too weak with functional groups on adsorbents surface. It could also be due to the factor
that high pH, the competition between OH- and fluoride ions increases.
 Figure 2 Effect of Adsorbent Dose and PH interaction on Fluoride removal

The response of pH against dose of biosorbent can be observed in Figure 2. The resulting
removal efficiency against pH and dose shows high fluctuations. The maximum removal
efficiency is observed against pH = However, at the optimum pH, the response of dose is
similar at all the ranges. It shows that the pH has more influence on the overall removal as
compared to dose and pH does not have any effect on the added dose of biosorbent.
 Figure 3 Effect of Initial Concentration and pH interaction on Fluoride removal

As depicted in Figure 3 above, it can be derived that lower pH corresponds higher removal
efficiencies. The increasing fluoride concentration has a reducing effect on the removal
efficiency. Greater fluoride concentration, for adsorption the less active sites are available
and the adsorbent reaches it maximum removal efficiency quickly.
Contact Time

For MOSR, contact time impact on fluoride biosorption was studied by changing contact
time. Figure 4 shows the relationship between contact time, dose Vs removal efficiency
R.E(%).
 Figure 4 Effect of Dose and Contact Time interaction on Fluoride removal

The combined response of contact time and dose against the removal efficiency can be
observed in Figure 4 above. There non-uniformity in the resultant removal efficiency as the
contact time and doses are changed. Better results are obtained at doses between 12-20 g/L
versus the contact time between 50-120 minutes. The statistics show that the dose is time
dependent and it plays of with the variations in time. Relatively higher doses with increased
contact time result in higher removal of fluoride.
 Figure 5 Effect of Initial Concentration and Contact Time interaction on Fluoride removal

At lower initial concentrations and higher contact time, removal efficiencies are observed
to be high as seen from the contour plot in Figure 5 above. The trend replicates as higher
removal efficiencies are also observed at contact time between 60-120 minutes. The
statistics reveal that overall removal is mainly dependent on initial concentration. Since
better results are observed at lower initial concentrations.
 Figure 6 Effect of Contact Time and pH interaction on Fluoride removal

The pH and contact time depicted on contour plot indicates that low pH i.e. 4-5 and contact
time in the range of 60-120 minutes, result in higher removal efficiency. It is evident from
the results that acidic environment i.e. lower pH, suites the removal fluoride. Since
consistently higher removal efficiencies were observed at low pH irrespective of contact
time.
Initial Fluoride Ion Concentration

The impact of concentration (initial) on biosorption of fluoride by using MOSR is shown

in Figure 7
 Figure 7 Effect of Initial Concentration and Dose interaction on Fluoride removal

The removal efficiency plotted against dose and initial concentration depicts those higher
efficiencies are achieved at higher doses and lower initial concentrations. The reason of
better removal efficiencies at higher doses indicates that the biosorbent performs better with
low initial ion concentrations. The dose of biosorbent also affects the removal of fluoride
since moderately higher doses remove the maximum fluoride.

Figure 8 Effect of Initial Concentration and Contact Time interaction on Fluoride removal
It is visible form the contour plot in Figure 8 above, the lower initial concentrations along
with higher contact times results in higher removal efficiencies which shows that the
biosorbent performs better in the increased contact time low initial concentrations of
fluoride.

Figure 9 Effect of Initial Concentration and pH interaction on Fluoride removal

Figure 9 indicates that removal efficiency is best at low pH and it gradually decreases as
the pH is increased. The response of initial concentration against pH is almost constant i.e.
it results in high efficiencies at low pH.
Adsorbent Dose

Effect of dose on biosorption of fluoride by using MOSR is shown in Figure 10

 Figure 10 Effect of Adsorbent Dose and Contact Time on Fluoride removal

The response of dose of biosorbent is very much irregular against the contact time. The
contour plot shown in Figure 10 indicates that maximum removal efficiency is achieved if
the dose is kept between 12-20 g/L and contact time is 60-120 minutes.

Figure 11 Effect of Initial Concentration and Adsorbent Dose interaction on Fluoride removal

The removal efficiency plotted against dose and initial concentration depicts that higher
efficiencies are achieved at higher doses and lower initial concentrations. Keeping in view
the statistics from the batch studies, it can be established that the relationship of initial
concentration with the performance of biosorbent is inversely proportional.

Figure 12 Effect of Adsorbent Dose and pH interaction on Fluoride removal

Maximum removal efficiencies can be observed at lower pH and lowest removal can be
seen in the pH range of 8 and above. The response of doses is dependent on the pH as
highest efficiencies against all the doses can be seen against lowest pH.
Combined Effect of Parameters

The set of experiments derived from Minitab 19, for batch adsorption studies was evaluated
for parameter against efficiency of removal. Mean of means plotted against the removal
efficiencies for all the parameters including pH, initial concentration, dose and contact time.
Parameters’ combine effect derived from Minitab 19 is summarized in Figure 13 below.
The plot also presents the crux of batch absorption studies and clearly indicates the
optimum values to be used for further investigations.
 Figure 13 Combined Effect of Parameters

Figure 13 points out that optimum value of pH = 4, optimum initial concentration is 2

mg/Optimum contact time is 120 minutes, and the optimum dose is 15 g. These optimum
values were further used in the equilibrium studies.

3.2 ACTIVATED ALUMINA (CHEMICAL ADSORBENT)

pH

At pH 4, 6, 8 and 10 the impact on adsorption capacity for fluoride with changing pH was
determined at. Results are presented in Figure 14
Keeping in view Figure 14, it was discovered that as pH was increased from 4 to 10, the
removal efficiency of fluoride showed a remarkable increase. It was the highest at pH 4
i.e.91% and lowest at pH 10 i.e. 42%.
 Figure 14 Effect of Contact Time and pH interaction on Fluoride removal

Figure 14 indicates that high removal efficiencies are obtained at low pH i.e. 4 against
higher range of contact time.
It was also detected that if pH goes on increasing from 5 to 10, removal efficiency drops
which may be owing to reasons that at high pH, the coordination covalent bond gets too
weak between surface of functional groups of adsorbents and fluoride and. It could also be
due to the factor that high pH, the competition between OH- and fluoride ions increases.
 Figure 15 Effect of Adsorbent Dose and pH interaction on Fluoride removal

The response of pH against dose of adsorbent can be observed in Figure 15. The resulting
removal efficiency against pH and dose shows high fluctuations. The maximum removal
efficiency is observed against pH = However, at the optimum pH, the response of dose is
not similar at all the ranges.

Figure 16 Effect of Initial Concentration and pH interaction on Fluoride removal

As depicted in Figure 16 above, it can be derived that lower pH corresponds higher removal
efficiencies. By increasing fluoride concentration removal efficiency drops. Greater the
fluoride concentration, the less available active sites for adsorption and adsorbent reaches
it maximum removal efficiency quickly.
Contact Time

Adsorption of fluoride by Activated Alumina (AA) was studied by changing contact time.
Figure 17 shows the relationship between contact time, dose Vs removal efficiency R.E(%).

Figure 17 Effect of Adsorbent Dose and contact time interaction on Fluoride removal

The combined response of contact time and dose against the removal efficiency can be
observed in Figure 17 above. There non-uniformity in the resultant removal efficiency as
the contact time and doses are changed. Better results are obtained at doses between 8-10
g/L versus the contact time between 60-100 minutes. The statistics show that the dose is
time dependent and it plays of with the variations in time. Relatively higher doses with
increased contact time result in higher removal of fluoride.
 Figure 18 Effect of Initial Concentration and contact time interaction on Fluoride removal

At lower concentrations and higher contact time, removal efficiencies are noticed to be
high, as seen from the contour plot in Figure 18 above. The trend replicates as higher
removal efficiencies are also observed at contact time between 60-120 minutes. The
statistics reveal that overall removal is mainly dependent on initial concentration. Since
better results are observed at lower initial concentrations irrespective of time.
 Figure 19 Effect of pH and contact time interaction on Fluoride removal

Figure 19 indicates that low pH i.e. 4 and contact time in the range of 60-80 minutes, result
in higher removal efficiency. It is evident from the results that acidic environment i.e. lower
pH, suites the removal fluoride. Since consistently higher removal efficiencies were
observed at low pH irrespective of contact time.
Initial Concentration

The adsorption of fluoride by using Activated Alumina (AA) was observed and results are
given in Figure 20
 Figure 20 Effect of Initial Concentration and Adsorbent Dose interaction on Fluoride removal

The removal efficiency plotted against dose and initial concentration depicts that higher
efficiencies are achieved at higher doses and lower initial concentrations. The reason of
better removal efficiencies at higher doses indicate that the adsorbent performs better with
low initial ion concentrations. The dose of adsorbent also affects the removal of fluoride
since moderately higher doses remove the maximum fluoride.
 Figure 21 Effect of Initial Concentration and Contact Time interaction on Fluoride removal

It is visible form the contour plot in Figure 21 above, the lower initial concentrations along
with lesser contact times results in higher removal efficiencies which shows that the
adsorbent performs better in the increased contact time and low initial concentrations of
fluoride.
 Figure 22 Effect of pH and initial concentration interaction on Fluoride removal

Figure 22 indicates that removal efficiency is best at low pH and it gradually decreases as
the pH is increased. The response of initial concentration against pH is almost constant i.e.
it results in high efficiencies at low pH.
Adsorbent Dose

The adsorption of fluoride by using Activated Alumina (AA) with varying dose is shown
in Figure 23.
 Figure 23 Effect of dose and contact time interaction on Fluoride removal

The response of dose of adsorbent is very much irregular against the contact time. The
contour plot shown in Figure 23 indicates that maximum removal efficiency is achieved if
the dose is kept between 8-10 g/L and contact time is 60-120 minutes.

Figure 24 Effect of Adsorbent Dose and Initial Concentration interaction on Fluoride removal
The removal efficiency plotted against dose and initial concentration depicts that higher
efficiencies are achieved at higher doses and lower initial concentrations. Keeping in view
the statistics from the batch studies, it can be established that the relationship of initial
concentration with the performance of adsorbent is inversely proportional.

Figure 25 Effect of pH and Dose interaction on Fluoride removal

Maximum removal efficiencies can be observed at lower pH and lowest removal can be
seen in the pH range of 8 and above. The response of doses is dependent on the pH as
highest efficiencies against all the doses can be seen against lowest pH.
Combined Effect of Parameters

The set of experiments derived from Minitab 19, for batch adsorption studies was evaluated
for parameter against efficiency of removal. Mean of means plotted against the removal
efficiencies for all the parameters including pH, dose, initial concentration and contact
time.Combine impact of parameters derived from Minitab 19 is summarized in Figure 26
below. The plot also presents the crux of batch absorption studies and clearly indicates the
optimum values to be used for further investigations.
 Figure 26 Combined Effect of Parameters

Figure 26 points out that the optimum pH = 4, optimum contact time is 120 minutes, and
the optimum dose is 10 g and optimum concentration (initial) is 2 mg/L These optimum
values were further used in the equilibrium studies.

3.3 EQUILIBRIUM STUDIES FOR MOSR ADOSRBENT

Equilibrium data for batch biosorption experiments was analyzed using Freundlich,
Dubinin–Radushkevich (D–R), Langmuir, Tempkin and Flory Huggins isotherms.
The above referred studies were performed separately for MOSR and Activated Alumina
and the results are specified hereunder:

Langmuir Isotherm Model

Langmuir isotherm model was studied to compute MOSR biosorbent efficiency. Figure 27
show that the R2 value for curve is 0.997 which indicates that it fit the Langmuir isotherm.
 1.8
1.6 y = 1.1776x + 0.0077
R² = 0.9977
1.4
1.2
1
Ce/Qe

0.8
0.6
0.4
0.2
0
0 0.5 1 1.5 2 2.5 3
Ce
Slop 1.1776 Intercept 0.0077 Qmax 0.849184783
R2 0.9977 b 152.9350649 RL 0.000130757

Figure 27 Langmuir Isotherm Model

Various constants and parameters calculated for Langmuir Isotherm used for the removal
study of fluoride are presented in above Figure.
‘b’ &‘Qmax’ are constants that are calculated from intercept and slope of the curve. The
value of RL is zero, which indicates that the adsorption is irreversible.
Freundlich Isotherm Model

MOSR biosorbent was studied with Freundlich isotherm model. The resultant curve has
the R2 = 0.957 which indicates that it also suites the Fruendlich isotherm model. Figure 28
shows the Fruendlich Isotherm curve.

-0.05

-0.1
LogQe

-0.15

-0.2
y = -0.1536x - 0.3046
R² = 0.9572
-0.25

-0.3
-1.5 -1.3 -1.1 -0.9 -0.7 -0.5 -0.3
LogCe

Slope 0.0378 Intercept 0.0332 n 26.45502646

Kf 1.07944371 R2 0.3024 -- --
 Figure 28 Fruendlich Isotherm Model

Various constants and parameters calculated for Freundlich Isotherm used for the removal
study of fluoride are presented in above Figure.
‘Kf’ and ‘n’ are constant which are derived from intercept and slope of the curve. The value
of ‘n’ is > 1 that shows the adsorption is homogeneous.
D–R Isotherm Model

D-R isotherm model was evaluated for biosorbent under study. Trendline with R2 = 0.711
indicates that it also fits the model. Figure 29 shows the D-R Isotherm curve.

0
-0.1 y = 3E-08x - 0.5211
-0.2 R² = 0.711

-0.3
LnQe

-0.4
-0.5
-0.6
-0.7
0 2000000 4000000 6000000 8000000 10000000
ɛ2

Slope 7.00E-09 Intercept -0.1368 K 7.00E-03

Qm 0.872144638 E 8.45E+00 R2 0.4929

Figure 29 D-R Isotherm Model

Various constants and parameters calculated for D-R Isotherm used for the removal study
of fluoride are presented in above Figure.
‘Qm’ and ‘K’ are constants that are derived from intercept and slope of curve. ‘E’ value is
positive, that depicts the adsorption is endothermic.
TEMPKIN Model

Temkin isotherm model shows the value of R2 = 0.976 against the MOSR biosorbent
indicating that it does not fit in the Tempkin model. Figure 30 shows the Tempkin Isotherm
curve.
 1
y = -0.1013x + 0.7104
0.8
R² = 0.976

0.6

0.4
Qe

0.2

0
-1 -0.5 0 0.5 1 1.5 2
-0.2

-0.4
LnCe

Slope 0.0311 Intercept 0.8493 R2 0.2955

α 1.037297104 β 0.8493 -- --
Figure 30 Tempkin Isotherm Model

Various constants and parameters calculated for Tempkin Isotherm used for the removal
study of fluoride are presented in above Figure.
β and α are constants that are derived from intercept and slope of the curves.
Flory Huggins

Degree of surface coverage characteristics of the adsorbate on adsorbent and the biosorbent
under study that are described by Flory-Huggins isotherm fits the model on least limit. The
R2 value is 0.987. Figure 31 shows Flory Huggins Isotherm curve.

-0.5

-1
Ln(θ/Co)

-1.5 y = -2.7407x - 5.3936

R² = 0.9873

-2

-2.5

-3
-1.7 -1.5 -1.3 -1.1 -0.9 -0.7 -0.5
Ln(1-θ)
 Slope 2.2832 Intercept 2.5247 R2 0.4571
n 13.782 Kfh 124871.4856 ΔG 5.730367133

Figure 31 Flory Huggins Isotherm

Various constants and parameters calculated for Flory Huggins Isotherm used for the
removal study of fluoride are presented in above Figure.
‘Kfh’ and ‘n’ are constants that are derived from intercept and slope of the curve. ‘ΔG’ is
positive which indicates this model will unfit the experimental data.
Findings of Equilibrium Studies

Adsorption by the biosorbent i.e. MOSR satisfies Langmuir, Fruendlich, Tempkin and
Flory Huggins isotherm models, but it fits best the Langmuir Isotherm with the R2 value
of 0.997.

3.4 EQUILIBRIUM STUDIES FOR ACTIVATED ALUMINA

Using Langmuir, Tempkin, Freundlich, Dubinin–Radushkevich (D–R)and Flory Huggins

isotherm models the equilibrium for biosorption experiments was studied.
Langmuir Isotherm Model

Langmuir isotherm model was utilized for comparing Activated Alumina efficiency.
Figure 32 below that the R2 value for curve is 0.997 which indicates that it fit the Langmuir
isotherm.
 1.8

1.6 y = 1.1776x + 0.0077

R² = 0.9977
1.4

1.2

1
Ce/Qe

0.8

0.6

0.4

0.2

0
0 0.5 1 1.5 2 2.5 3
Ce

Figure 32 Langmuir Isotherm Model

Freundlich Isotherm Model

The Activated Alumina (AA)adsorbent was also studied with the Freundlich isotherm
model. The resultant curve has the R2 = 0.952 which indicates that it also suites the
Fruendlich isotherm model. Figure 33 shows the Fruendlich Isotherm curve.

-0.05

-0.1
LogQe

-0.15

y = -0.1719x - 0.317 -0.2

R² = 0.9525
-0.25

-0.3
-1.6 -1.4 -1.2 -1 -0.8 -0.6 -0.4 -0.2
LogCe
Figure 33 Fruendlich Isotherm Model

D–R Isotherm Model

D-R isotherm model evaluated for the chemical adsorbent under study. The trendline with
R2 = 0.690 indicates that it also fits the model. Figure 34 shows the D-R Isotherm curve.
 0

-0.1

-0.2
y = 3E-08x - 0.5163
-0.3
LnQe

R² = 0.6907
-0.4

-0.5

-0.6

-0.7
0 5000000 10000000 15000000
ɛ2

Figure 34 D-R Isotherm Model

TEMPKIN Model

Temkin isotherm model shows the value of R2 = 0.978 against the Activated Alumina (AA)
adsorbent indicating that it does not fit in the Tempkin model. Figure 35 shows the Tempkin
Isotherm curve.

1
0.9
0.8
0.7
y = -0.1171x + 0.7253
R² = 0.9786 0.6
Qe

0.5
0.4
0.3
0.2
0.1
0
-1.5 -1 -0.5 0 0.5 1 1.5 2
LnCe

Figure 35 Tempkin Isotherm Model

 Flory Huggins

Degree of surface coverage characteristics of the adsorbate on the adsorbent and the
chemical adsorbent as described by Flory-Huggins isotherm shows that it least fits the
model. The R2 value is 0.987. Figure 36 shows Flory Huggins Isotherm curve.

-0.5

-1
Ln(θ/Co)

-1.5 y = -2.7407x - 5.3936

R² = 0.9873

-2

-2.5

-3
-1.7 -1.5 -1.3 -1.1 -0.9 -0.7 -0.5
Ln(1-θ)

Figure 36 Flory Huggins Isotherm

Findings of Equilibrium Studies

Adsorption by the Chemical adsorbent i.e. Activated Alumina (AA) satisfies Langmuir,
Fruendlich, Tempkin and Flory Huggins isotherm models, but it fits best the Langmuir
Isotherm with the R2 value of 0.997.

3.5 KINETICS

Experimental results for understanding the dynamics of biosorption process was

interoperated using Kinetics models. kinetic models used are enlisted below.
i) Pseudo 1storder kinetic model,
ii) Pseudo 2ndorder kinetic model,
Biosorption kinetic represent the fluoride removal rate controlled by residence time of
biosorbent inside the fluoride solution. To investigate prevailing mechanism for
biosorption process we applied kinetic models. The kinetic analysis is also helpful to
determine rate controlling step in biosorption process. Parameters for kinetics are required
for the design of full-scale batch process for the removal of fluoride. Both pseudo 1st&
2ndorder kinetic models were utilized to see uptake extent and for determining the
parameters for biosorption kinetics.
Pseudo 1stOrder Kinetics

Pseudo 1storder kinetic equation defines the linear driving force concept
(Langergren,1898):

(3.1)

qe is metal ion amount sorbed at equilibrium onto biosorbent (mg per gram), k1is pseudo
1storder biosorption rate constant (g per mgperhour), qt is metal ion amount sorbedat time
t onto biosorbent (mg per gram) and t is time (hour). By having definite integral at initial
conditions at t = 0, qt = 0 and at t = t, qt = qtthe integrated form is shown as Eq. (1). Linear
form used for estimation of qe and k1 from intercept and slope of plot t vs. natural log of
(qe-qt). 1storder kinetics do not presents whole biosorption process but only accounts for
sorption sites

(3.2)
Figures 37 & 38 present linear plot for pseudo 1st order model for fluoride biosorption on
MOSR &AA respectively. The R2 value in case of MOSR and AA are 0.9589 and 0.9361
respectively for pseudo first order kinetics.
 Pseudo 1st Order (MOSR)
0
-0.2
-0.4
-0.6
Log(Qe-Qt)

-0.8 y = -0.0048x - 1.2764

-1 R² = 0.9589

-1.2
-1.4
-1.6
-1.8
-2
0 20 40 60 80 100 120 140
Time (min)

Figure 37 Pseudo 1st Order Kinetic Model for Fluoride Biosorption on MOSR

Pseudo 1st Order (AA)

0
-0.2
-0.4
-0.6
Log(Qe-Qt)

-0.8 y = -0.0043x - 1.3366

-1 R² = 0.9361
-1.2
-1.4
-1.6
-1.8
-2
0 20 40 60 80 100 120 140
Time (min)

Figure 38 Pseudo 1st Order Kinetic Model for Fluoride Biosorption on Activated Alumina (AA)

Pseudo Second Order Kinetics

The assumption that act as base for Pseudo 2nd order equation is that 2nd order
chemisorption mechanism is being followed by biosorption which is applicable for total
time of biosorption and the rate controlling step prevails. The pseudo 2nd order kinetic is
consistent with linear driving force concept (Ho & McKay, 1999):
 (3.3)
qe is metal ion amount sorbedat equilibrium onto biosorbent (mg per gram), k2 is rate
constant of pseudo 2nd order biosorption (g per mg per hour), qt is metal ion amount
sorbedat time t onto biosorbent (mg per gram) and t is time (hour). Linear form of pseudo
2ndorder after having definite integral for t = 0, forqt = 0 and for t = t ,qt = qt boundary
conditions is given in equation Eq. (4). For estimation of k2 & qe from the intercept and
slope of plot of t &t/qt the equation is used.

(3.4)
Figures 39 & 40 present linear plot for pseudo 2nd order kinetic model for biosorption of
fluoride on MOSR and AA respectively. The R2 value in case of MOSR and AA are 0.9886
and 0.9931 respectively for pseudo 2nd order kinetics which indicates that adsorption of
fluoride on MOSR & AA follows pseudo second order kinetics.

Pseudo 2nd Order (MOSR)

2500

2000

1500
T/Qt

y = 13.89x + 646.16
R² = 0.9886
1000

500

0
0 20 40 60 80 100 120 140
Time (min)

Figure 39 Pseudo 2nd Order Kinetic Model for Fluoride Biosorption onto MOSR
 Pseudo 2nd Order
3000

2500

2000
T/Qt

1500 y = 16.273x + 583.75

R² = 0.9931
1000

500

0
0 20 40 60 80 100 120 140
Time (min)

Figure 40 Pseudo 2nd Order Kinetic Model for Fluoride Biosorption onto Activated Alumina (AA)

3.6 COST ANALYSIS

The cost for biosorbent and chemical adsorbent has been analyzed based on prevailing
market rate of chemicals used in the treatment process. The cost analysis for treatment of
one liter of water is given hereunder:
Cost of Chemicals

MOSR
The cost of MOSR= PKR 2,000/ kg
Per gram cost of MOSR = PKR 2/g
Optimum dose of biosorbent for treatment = 15g/ L
Therefore,
Cost of MOSR for 15g of biosorbent = 15*2 = PKR 30
ACTIVATED ALUMINA (AA)
The cost of AA= PKR 15,000/ 500 g
Per gram cost of AA = PKR 30/g
Optimum dose of AA for treatment = 10g/ L
Therefore,
Cost of MOSR for 5 g of AA= 30*10 = PKR 300
4 CONCLUSIONS AND RECOMMENDATIONS

CONCLUSIONS

The present study yields following conclusions:

i) Optimum combination of parameters obtained after batch adsorption studies for
MOSR comes out to be pH value of 4, contact time 120 minutes, initial
concentration of 2 mg/L and adsorbent dose of 15 g/L.
ii) Optimum combination of parameters obtained after batch adsorption studies for
Activated Alumina (AA) comes out to be pH value of 4, contact time 120 minutes,
initial concentration of 2 mg/L and adsorbent dose of 10 g/L.
iii) The equilibrium studies indicate that the Fluoride adsorption onto MOSR and
Activated Alumina best fits the Langmuir Isotherm with R2 values 0.997& 0.991
respectively.
iv) The maximum fluoride removal efficiency that can be achieved from MOSR and
Activated Alumina are 87% and 91% respectively.
v) In order to obtain same removal efficiency from MOSR and Activated Alumina,
more dose of MOSR is required as compared to Activated Alumina.
vi) Adsorption of fluoride could be fitted-well with a pseudo 2ndorder model and
follows Langmuir isotherm model as kinetic studies revealed.
vii) Treatment cost through MOSR is PKR 30/ liter while it is PKR 300 in case of AA.
RECOMMENDATIONS

Below are the recommendations:

i) Focus of study was to evaluate the optimum conditions for adsorption process by
employing two different adsorbents in a Batch Process. A similar study may be
conducted based on Continuous Adsorption Process.
ii) Cilantro can be used in combination with activated alumina to evaluate the
combined optimum conditions for adsorption process and the removal efficiency
that can be achieved by the combination of two adsorbents,
iii) Moringa Oleifera Seeds Residue may be used to study the removal of other
contaminants as well.
Funding

Not Applicable
Conflict of Interest
The authors declare that they have no conflict of interest.

Ethics approval

Not Applicable

Consent to participate

Not Applicable

Consent for publication

I, on the behalf of all the authors give consent for the publication of this work.

Availability of data and material

The open source dataset is used and presented in this study. The raw data supporting the
conclusive remarks of this article will be made accessible by the writers, without any objection.

Code availability

Not Applicable
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Table Click here to access/download;Table;Tables referred in
manuscript-JER.docx

Table. 1

Classification Item
pH meter (Method: EPA-9040-B)
Ion Selective Electrode (ISE) for Fluoride with
Analytical temperature probe
Jar Test Apparatus

Filtering Apparatus
Non-Analytical Oven
Grinder

Table. 2

Experiments pH Contact Time Initial Conc. Dose

1 4 15 2 5

2 4 30 4 10

3 4 60 6 15

4 4 120 8 20

5 6 15 4 15

6 6 30 2 20

7 6 60 8 5

8 6 120 6 10

9 8 15 6 20

10 8 30 8 15

11 8 60 2 10

12 8 120 4 5

13 10 15 8 10

14 10 30 6 5

15 10 60 4 20

16 10 120 2 15
Table. 3

Experiments pH Contact Time Initial Conc. Dose

1 4 15 2 2

2 4 30 4 5

3 4 60 6 10

4 4 120 8 15

5 6 15 4 10

6 6 30 2 15

7 6 60 8 2

8 6 120 6 5

9 8 15 6 15

10 8 30 8 10

11 8 60 2 5

12 8 120 4 2

13 10 15 8 5

14 10 30 6 2

15 10 60 4 15

16 10 120 2 10
Figure Click here to access/download;Figure;Figures referred in
manuscript-JER.docx

Fig. 1

Fig. 2
Fig. 3

Fig. 4

Fig. 5
Fig. 6
Fig. 7

Fig. 8
Fig. 9

Fig. 10
Fig. 11

Fig. 12
Fig. 13

Fig. 14
Fig. 15

Fig. 16
Fig. 17

Fig. 18
Fig. 19

Fig. 20
Fig. 21

Fig. 22
Fig. 23

Fig. 24
Fig. 25

Fig. 26
Fig. 27

1.8

1.6 y = 1.1776x + 0.0077

R² = 0.9977
1.4

1.2

1
Ce/Qe

0.8

0.6

0.4

0.2

0
0 0.5 1 1.5 2 2.5 3
Ce

Slop 1.1776 Intercept 0.0077 Qmax 0.849184783

R2 0.9977 b 152.9350649 RL 0.000130757

Fig. 28

-0.05

-0.1
LogQe

-0.15

-0.2
y = -0.1536x - 0.3046
R² = 0.9572
-0.25

-0.3
-1.5 -1.3 -1.1 -0.9 -0.7 -0.5 -0.3
LogCe

Slope 0.0378 Intercept 0.0332 n 26.45502646

Kf 1.07944371 R2 0.3024 -- --
Fig. 29

0
-0.1 y = 3E-08x - 0.5211
-0.2 R² = 0.711

-0.3
LnQe

-0.4
-0.5
-0.6
-0.7
0 2000000 4000000 6000000 8000000 10000000
ɛ2

Slope 7.00E-09 Intercept -0.1368 K 7.00E-03

Qm 0.872144638 E 8.45E+00 R2 0.4929

Fig. 30

1
y = -0.1013x + 0.7104
0.8
R² = 0.976
0.6

0.4
Qe

0.2

0
-1 -0.5 0 0.5 1 1.5 2
-0.2

-0.4
LnCe

Slope 0.0311 Intercept 0.8493 R2 0.2955

α 1.037297104 β 0.8493 -- --
Fig. 31

-0.5

-1
Ln(θ/Co)

-1.5 y = -2.7407x - 5.3936

R² = 0.9873

-2

-2.5

-3
-1.7 -1.5 -1.3 -1.1 -0.9 -0.7 -0.5
Ln(1-θ)

Slope 2.2832 Intercept 2.5247 R2 0.4571

n 13.782 Kfh 124871.4856 ΔG 5.730367133

Fig. 32

1.8

1.6 y = 1.1776x + 0.0077

R² = 0.9977
1.4

1.2

1
Ce/Qe

0.8

0.6

0.4

0.2

0
0 0.5 1 1.5 2 2.5 3
Ce
Fig. 33

-0.05

-0.1
LogQe

-0.15

y = -0.1719x - 0.317 -0.2

R² = 0.9525
-0.25

-0.3
-1.6 -1.4 -1.2 -1 -0.8 -0.6 -0.4 -0.2
LogCe

Fig. 34

-0.1

-0.2
y = 3E-08x - 0.5163
-0.3
LnQe

R² = 0.6907
-0.4

-0.5

-0.6

-0.7
0 5000000 10000000 15000000
ɛ2
Fig. 35

1
0.9
0.8
0.7
y = -0.1171x + 0.7253
R² = 0.9786 0.6
Qe

0.5
0.4
0.3
0.2
0.1
0
-1.5 -1 -0.5 0 0.5 1 1.5 2
LnCe

Fig. 36

-0.5

-1
Ln(θ/Co)

-1.5 y = -2.7407x - 5.3936

R² = 0.9873

-2

-2.5

-3
-1.7 -1.5 -1.3 -1.1 -0.9 -0.7 -0.5
Ln(1-θ)
Fig. 37

Pseudo 1st Order (MOSR)

0
-0.2
-0.4
-0.6
Log(Qe-Qt)

-0.8 y = -0.0048x - 1.2764

-1 R² = 0.9589

-1.2
-1.4
-1.6
-1.8
-2
0 20 40 60 80 100 120 140
Time (min)

Fig. 38

Pseudo 1st Order (AA)

0
-0.2
-0.4
-0.6
Log(Qe-Qt)

-0.8 y = -0.0043x - 1.3366

-1 R² = 0.9361
-1.2
-1.4
-1.6
-1.8
-2
0 20 40 60 80 100 120 140
Time (min)
Fig. 39

Pseudo 2nd Order (MOSR)

2500

2000

1500
T/Qt

y = 13.89x + 646.16
R² = 0.9886
1000

500

0
0 20 40 60 80 100 120 140
Time (min)

Fig. 40

Pseudo 2nd Order

3000

2500

2000
T/Qt

1500 y = 16.273x + 583.75

R² = 0.9931
1000

500

0
0 20 40 60 80 100 120 140
Time (min)
Declaration of Interest Statement

Removal of Fluoride from Drinking Water Using Different

Adsorbents

Conflict of Interest

The authors declare that they have no conflict of interest.