Received: 29 August 2019 Revised: 30 March 2020 Accepted: 31 May 2020

DOI: 10.1002/ep.13465

REMEDIATION TREATMENT

Experimental study of biosorption of fluoride by immobilized

beads of zeolite NaA and Nostoc sp. (BTA394) using a
continuous flow system

Shraboni Mukherjee1 | Anoar Ali Khan2 | Sanghamitra Barman3 |

Gopinath Halder1

1
Department of Chemical Engineering,
National Institute of Technology Durgapur,
Durgapur, India
2
Department of Chemical Engineering,
Vignan's Foundation for Science, Technology
and Research, Guntur, India
3
Department of Chemical Engineering, Thapar
University, Patiala, India
Correspondence
Gopinath Halder, Department of Chemical
Engineering, National Institute of Technology
Durgapur, Durgapur 713209, India.
Email: gopinath.halder@che.nitdgp.ac.in
Funding information
Department of Biotechnology, Government of
West Bengal, Grant/Award Number: BT (Estt.)
R&D-23/13
Abstract
The current experiment investigated the fluoride sorptive efficacies of immobilized
beads of zeolite NaA and Nostoc sp. (BTA394) from simulated wastewater in column
reactor. Influence of crucial kinetic parameters viz. initial concentration (10, 15, and
20 mg/L), bed height (4, 6, and 8 cm) and flow rate (2, 4, and 6 ml/min) on F− uptake
was examined. Influence of these parameters on breakthrough curves was also deter-
mined. These breakthrough curves were further estimated by Adams–Bohart's and
Thomas models. Spent column was eluted with 0.01 M NaCl, Ca(OH)2, Na2SO4, or
NaOH solution to assess column regeneration efficacy. The Thomas model satisfac-
torily explained the sorption dynamics but Adams–Bohart model could only explicate
preliminary portion of the column sorption mechanism. The exhaustion and break-
through time shortened with increased flow rate, decreased bed height and increased
F− concentration. Safe disposal of spent biosorbents were also performed. From the
results obtained, it can be said that these biosorbents could be used effectively in
treatment of simulated wastewater in continuous flow, although further experiments
are being carried out to assess their defluoridation capabilities for real wastewater in
large-scale operations.

KEYWORDS

biosorption, fluoride, packed bed, safe disposal, simulation

1 | I N T RO DU CT I O N countries.2 Regions affected with groundwater fluoride pollution are

In recent years, rapid urbanization and industrialization have raised
concerns on constant deterioration of the worldwide environment.
Excess F− concentration (>1.5 mg/L) in surface and ground water has
been a major issue among various regions in the world since the past
few decades. Industrialized processes viz. phosphate mining, alumi-
num smelters, fluorinated municipal water discharge into surrounding
lakes, rivers etc, contribute to a major portion of groundwater fluoride
1
contamination. The quality of groundwater is compromised owing to
the presence of several elements, among which, fluoride is one of the
main pollutants of geogenic source in most of the fluoride-affected
characterized by prevalence of various F— borne rocks such as apatite,
fluorite, biotite, fluorapatite etc. found in the water's saturated region,
volcanic-bed rocks, presence of dry conditions and calcium-deficient
sodium bicarbonate-type groundwater.1
Recent reports point out to the fact that millions of people in the
world are affected with endemic fluorosis while many are exposed to
the risk.3 Alteration in the biochemistry and morphology of a living
organism is often a result of prolonged exposure to higher concentra-
tions of fluoride which, in turn, also restricts the ability of an individual
to sustain its position in the ecology.4 In one of the cases,5 it was
detected that accumulation of F− in the foliage of certain hardwood

1 of 13 © 2020 American Institute of Chemical Engineers wileyonlinelibrary.com/journal/ep Environ Prog Sustainable Energy. 2020;39:e13465.
https://doi.org/10.1002/ep.13465
MUKHERJEE ET AL.
trees resulted in reduced photosynthesis and stimulated dark respira-
tion which, in turn, caused a reduction in the carbohydrate availability
6
for growth and seed production. As per reports, exposure to very
low atmospheric F− concentration lowered egg hatchability and fertil-
ity in animals of the future generations as a result of passive exposure
to fluoride. Fluorides can also result in mutations and chromosomal
4
impairment in animal and plant cells and can, therefore, be consid-
ered possible carcinogens. Consumption of water containing fluoride
1.5 mg/L causes diseases such as fluorosis, arthritis, hip fractures,
infertility, osteoporosis and polydipsia. It affects the teeth and skele-
ton, and the accumulation of fluoride over a long period of time can
even lead to changes in the DNA structure.7 Elemental fluorine is
slightly basic when it reacts with water. This is the natural phenomena
for fluoride transfers between water, soils and rocks. Hence, there is a
need to reduce the fluoride content in water using various removal
techniques in order to prevent health hazards. Fluorinated drinking
water might be evidencing for the risk of osteosarcoma (a type of
bone cancer), experimented in male rats. However, no evidence of
cancer-causing potential in female rats was observed. Another serious
issue is renal excretion, which is the major path to eliminate inorganic
fluoride from the body. The effect of fluoride on the renal system
results in exposure of kidney cells as a potential site for acute fluoride
toxicity. Fluoride concentration of 100–380 mg/L can lead to necrosis
of proximal and renal tubules, renal nephritis and dilation of renal
tubules. A further issue of high concentration of fluoride in the gastro-
intestinal system is irritation to the mucous membranes of the stom-
ach lining by combining fluoride and hydrogen ions, resulting in the
formation of hydrogen fluoride. Some of the main health problems
−
associated with F contamination include dental, skeletal, and
nonskeletal fluorosis.8 F− ions, in excess, are known to hinder the
mechanism of proteins, lipids, vitamins, carbohydrates, enzymes etc.
thereby inhibiting their respective roles in body growth and develop-
−
ment. Although the most pronounced impacts of F consumption are
expressed in teeth and bones, it causes the cell membranes by means
of diffusion thereby entering the soft tissues which has antagonistic
effect on the function and metabolism of cells.9-11 The F− concentra-
tion is directly proportional to the concentration of plasma in soft tis-
sues.12 For example, salivary glands play a very important role in
various processes related to oral cavity wherein, the products
secreted by them are vital for various physiological functions.13 F− is
also known to interfere with various enzymatic processes,14,15
wherein often one pathway is inhibited thereby causing more avail-
15
ability of substrate for other pathways. Some of the major conse-
quences to F− exposure include imbalance production between the
antioxidants and ROS which induces oxidative stress and inhibition of
various enzymes thereby leading to a biochemical stress in our bod-
16
ies. Some of the most common examples have been identified in
various cells and soft tissues like the gastrocnemius muscle17 and
brain, liver, heart,16 nervous system,18 blood,11 and osteoblasts.19
Several investigations are being carried out all across the world
in search of an effective wastewater remediation process. 20
Methods like coagulation, membrane separation, precipitation, ion
exchange etc., have been reported to be efficient treatment
2 of 13
techniques.21 However, these techniques have several shortcomings
including investment, maintenance expenses, spent adsorbent regen-
eration challenges, higher density of produced sludge, etc. Among all
such techniques, adsorption is being reportedly one of the best alter-
natives to these for fluoride remediation.2 Biosorption is an emerg-
ing technique of adsorption which involves the use of dead or
inactive materials derived from biological precursors through inert
uptake of contaminants in the cells leading to subsequent binding
onto the vacant sites. Biosorption on packed bed column offers sev-
eral advantages such as simple operation, higher yield of products
and easy scalability from a batch technique. Sorption process in the
liquid phase occurring in the influence of constant flow circum-
stances can be analyzed via breakthrough curves in a continuous
reactor. Dynamics of the sorption column are described by the
breakthrough curves thereby offering relevant information per-
taining to the design and system operation in fixed-bed columns
applied in F− uptake.22-24
Column studies on F− removal by different biosorbents have been
reported, wherein, they have used immobilized Chlorella vulgaris,25
bone char,26 activated carbon of neem leaves,27 activated Vetiveria
zizanioides,28 etc. Defluoridation capabilities of zeolite NaA and Nostoc
sp. (BTA394) in column mode have not been reported yet as per liter-
ature studies. The advantages of using algal biomass as biosorbent for
fluoride sorption have already been discussed by Mukherjee et al.
Naturally occurring 3D crystalline microporous alumina-silicates are
commonly referred to as zeolites,29 often developed by using organic
templates such as alumina-silicate solutions. However, various draw-
backs are related to their production30 like expensive, non-
recyclability, calcinations etc, rice husk has been chosen as the
suitable alternative of precursor material for Si to develop various
forms of A, beta zeolites etc., because of their cheap cost and easy
availability.29
The batch system is effectively applicable only for a short period
of time wherein a much higher quantity of treating material (adsor-
bent) is required for treatment of huge quantity of effluent. Nonethe-
less, in case of continuous studies, the applicability is quite useful
since the operation mode is continuous and controllable.31 ST1 repre-
sents the defluoridation capacities of various biosorbents and bacte-
rial biomass in batch and continuous studies.
Therefore, an attempt has been made to investigate the sorptive
efficiencies of zeolite NaA and Nostoc sp. (BTA394) toward fluoride
uptake from synthetic waste water in a fixed bed column reactor to
ascertain its practical applicability. The effects of parametric condi-
tions like initial feed (F−) concentration (mg/L), flow rate (ml/min) and
bed height (cm) were also studied to obtain the best set of experimen-
tal conditions for fluoride removal in column mode. The experiments
were conducted in a fixed-bed packed column with immobilized beads
of zeolite NaA and Nostoc sp. (BTA394) for analysis of breakthrough
curves of the biosorptive uptake F− ions from aqueous solution. The
present work also involved the application of packed bed modeling to
examine the F− biosorption and diffusion in immobilized beads of zeo-
lite NaA and Nostoc sp. (BTA394). Breakthrough curve data were cor-
related using Adams–Bohart and Thomas models.
3 of 13
2 | EXPERIMENTATION
2.1 | Chemicals
Sodium fluoride (NaF) (>99% purity) was purchased from Merck
(Darmstadt, Germany), which including the other chemicals used were
of analytical grade. Distilled water was collected from the laboratory
set up. Synthetic solutions of fluoride of varying concentrations were
prepared by mixing appropriate quantities of NaF in 1 L distilled
water. Solution pH was maintained in neutral conditions (pH = 7).
2.2 | Preparation of immobilized biosorbents
Pure culture of microalgal species (Nostoc sp. BTA 394) was availed
from IBSD, Manipur, India which is a National facility of Department
of Biotechnology of Government of India in 2009. The isolate was fur-
ther subcultured in batches using BG-11 media. The microalgal
growth pattern was noted for 15 days and the growth curve has been
already discussed in Reference 32. The live biomass was treated with
150 ppm of calcium chloride (CaCl2) according to the process
described by Mukherjee et al.32 Mukherjee et al32 reported that
−
150 ppm of CaCl2 had the most significant effects on F sorption.
Hence, this concentration has been considered in this study as well
for pretreatment of the algal biomass. The algal cells were further
immobilized to form beads for further use as one of the biosorbents in
column study. 1% of Nostoc sp. (BTA394) solution was mixed with 2%
of sodium alginate solution (wt/vol) to maintain a ratio of 1:1. This
was added drop wise with the help of a syringe in 5% of CaCl2 solu-
tion (wt/vol) from a height of approximately 10 cm height. Algal beads
+
of 2 mm were obtained as a result of the Na ions replacement of the
sodium alginate with that of the Ca2+ ions of CaCl2 solution. These
beads were kept overnight in the CaCl2 solution. The immobilized
beads were spherical in shape and their size was measured with the
help of a micrometer screw gauge having accuracy of ±0.01 mm. Each
bead had an average size of 2.03 mm. The other sorbent, zeolite NaA
was developed by hydro-thermal treatment following the technique
of Goyal et al.33 Fumed silica and NaAlO2 (50 and 80 g/L) were mixed
with individual NaOH solutions of concentration 156 g/L and both
these solutions were kept in shaker (BIS 12LX, LAB X, India) at
250 rpm shaking speed with temperature maintaining at 25 ± 2
C.
These samples were taken out at standard intervals (0–72 hr) for
assessing influence of ageing time on crystallization and additional
physical characteristics wherein, surface area and pore volume of the
obtained zeolite was found to increase with ageing.33 The surface
area increased from 54 to 76 m2/g with increasing ageing time (from
24 to 72 hr) which was reportedly higher in comparison to earlier
reports.34 Likewise, pore volume also increased from 0.04 to
3
0.13 cm /g with increasing ageing time. The resultant zeolite units
were centrifuged at 17,000 rpm for 30 min and then washed with dis-
tilled water. Further, these were dried at 110
C in a hot air oven for
about 12 hr. XRD pattern of the synthesized zeolite NaA at different
ageing time have already been discussed in one of our previous
MUKHERJEE ET AL.
experimental investigations.33 The same procedure was followed for
immobilization and storage of the zeolite particles as that of the algal
cells. The resultant zeolite beads were renamed as ZNA and the algal
beads as CNB.
2.3 | Column biosorption experiments
The success of a sorption process depends on its large scale applica-
tion and commercial and economic viability. Therefore, in the present
study, immobilized beads of ZNA and CNB were used as biosorbents
to determine their potentialities in defluoridation in a column reactor.
Previously batch studies have been carried out optimize the paramet-
ric conditions.32 The purpose of this continuous experiment involved
assessment of influence of parameters like flow rate, influent concen-
tration and bed height at various throughput volumes. A schematic
representation of the packed bed reactor is being given in Figure S1.
A glass column of height 24 cm and internal diameter 2.5 cm was
considered to perform the column experiments. The column was
divided into two sections viz. one for the algal sorbent and the other
for the zeolite sorbent. Two sintered dishes of size G4 were placed
equidistant from the top and bottom of the column to act as a base
for the biosorbent materials. The column was wetted with deionized
water in order to establish equilibrium between the water and bio-
sorbents. Prior to packing, both the biosorbents were wetted with
deionized water and then packed into the column. The wetted bio-
sorbents were then packed into the column. On the lower portion of
the column, ZNA were placed on the second sintered dish whereas,
on the upper section, CNB were kept on the first sintered dish. Glass
beads (2 cm) were placed on top of the biosorbent beads in both the
columns to prevent the sorbent beads from floating during the contin-
uous flow. The beads were packed in such a way so that maximum
amount of sorbent materials could be packed devoid of any gaps. F−
solution of pH 7 and concentration was circulated through the beds in
an up-flow direction with the help of a peristaltic pump (RAVEL, India)
at a constant in-flow rate. The experimental studies were performed
at varying influent concentrations (10, 15, and 20 mg/L), bed height
(4, 6, and 8 cm) and flow rate (2, 4, and 6 ml/min). The treated solution
was obtained from column's upper part as shown in Figure 1 at fixed
time intervals. The residual F− concentration of the effluent was quan-
tified by Thermo Scientific Orion Star A214 pH and ISE Benchtop
Meter F− ion selective electrode (India).
The column's breakthrough curve was determined by plotting the
ratio of the Ct/C0 versus time (t) wherein, Ct and C0 refer to effluent
and influent fluoride concentrations, respectively. The column capac-
ity at equilibrium (Qtotal) was calculated using Equation (1).35
t =ð
Q
total
Qtotal = Cads dt ð1Þ
1, 000
t=0
where Cads (mg/L) is change in inlet F− concentration, Q (ml/min)
refers to the flow rate, C0 (mg/L) is the initial F− concentration and Ct
MUKHERJEE ET AL. 4 of 13

F I G U R E 1 SEM images of (a) CNB − F−, (b) CNB + F−, (c) ZNA − F−, (d) ZNA + F−, and EDX spectra of (e) CNB − F−, (f) CNB + F−, (g) ZNA-
F−, (h) ZNA + F− [Color figure can be viewed at wileyonlinelibrary.com]

Qtotal
(mg/L) refers to the concentration of F− at equilibrium time t. t = total Removal ð%Þ = × 100 ð3Þ
W
refers to the total time required to achieve that maximum removal.
Equation (2) was used to calculate the total quantity of F− ions that
entered the column (W), Volume of bed (BV), rate of biosorbent exhaustion (BER), empty
bed contact time (EBCT) and amount of F− adsorbed in the exhausted
C 0 × Q × te column at service time (qte) (mg/g) were obtained from Equations (4)–
W= ð2Þ
1,000
(7), respectively.

where te (min) refers to the exhaustion time. Volume of effluent

BV = ð4Þ
Volume of biosorbent bed
The percentage of fluoride removal was calculated as follows,
5 of 13 MUKHERJEE ET AL.

Mass of the biosorbent qtotal desorp

BER = ð5Þ qeq desorp = ð9Þ
Treated volume at exhaustion time m

Bed volume
EBCT = ð6Þ Therefore, elution percentage (El%) was calculated from Equa-
Volumetric flow rate
tion (10) where qi represents the remaining amount of undesorbed
Qv te C0 fluoride ions which are not removed by the desorbing solution in
qte = ð7Þ
m mg/g

where te (min) refers to the service time in the exhausted column, C0 qeq desorp
El% = × 100 ð10Þ
qi + qeq desorp
(mg/L) is inlet F− concentration, m (g) indicates mass of biosorbent
and Qv (L/min) refers to effluent flow rate.
Finally, biosorption capability of the biosorption column after
desorption followed by its regeneration was studied using
2.4 | Modeling of column data Equation (11):

An adsorption column is always designed based on the data qReg

obtained from batch scale laboratory tests. Execution of such
adsorption studies is often expensive and prolonged, hence,
upgrading various technical models to antedate altered bed adsorp-
tion remains crucial.
These models will, in turn, help out in clarifying trial information,
characterizing instruments applicable to the process, predicting fluctu-
ations due to diversified working conditions and most prominently,
enhancing the process efficiency in general. Hence, in the current
experiment, Adams–Bohart36 and Thomas models37 were applied to
column data to assess the breakthrough curves and determine typical
column parameters. The experiments were performed in triplicates for
retaining reliability, reproducibility and accurateness of obtained data
and their mean values were applied in further experimentation. These
model parameters and constants were determined from the linear
regression analysis. Suitability of the best model to the sorption sys-
tem was confirmed by evaluation of the correlation coefficients (R2)
values of the models.
2.5 | Continuous mode validation of desorption
and regeneration studies
Reusability of the same sorption column for multiple cycles of
desorption was determined in terms of elution percentage (El%).
This was derived by calculating the maximum time required for
fluoride desorption from the column. Therefore, Equation (8) was
used to calculate the total desorption capacity of the biosorption
column
Reg% = × 100 ð11Þ
q0
where Reg% represents the regeneration percentage of the column
after every desorption-biosorption cycle and qreg and q0 represent
sorption capability of spent biosorbent present in the column after
regeneration and sorption capacity of virgin biosorbents in mg/g,
respectively.
2.6 | Characterization of biosorbents
ZNA and CNB were analyzed to assess their characteristics. A gravi-
metric nitrogen Brunauer–Emmett–Teller (BET) specific surface area
analyser (SMART SORB 92/93 Quantachrome Autosorb-1) was
applied for measurement of specific surface area and micropore vol-
ume of ZNA and CNB. The morphological features and surface tex-
ture of ZNA and CNB were determined by SEM (JEOL JSM 6360,
India). OXFORD Instrument INCAX-sight was used for determination
of elemental compositions of ZNA and CNB before and after F−
uptake by EDX analysis. The samples for both SEM and EDX were
prepared as per the procedure mentioned in literature.32 The pres-
ence of chemical groups on the surfaces of ZNA and CNB were
assessed by Fourier transform infrared (FTIR) spectroscopy by means
of Smart Omni Transmission IS 10 FTIR spectrometer (Thermo Fisher
Scientific, India) in the wavelength range of 4,000–400 cm−1. The
technique was carried out by following the process mentioned in
literature.32

t =ð
Q
total
3 | R E S U L T S A N D D I S C U S S I O NS
qtotal desorp = Ce dt ð8Þ
1,000
t=0
3.1 | Proposed mechanism of fluoride biosorption
onto ZNA and CNB beads
where qtotal desorp is the total amount of fluoride ions desorbed from
the column in mg, which was used to determine the optimum fluoride In case of CNB beads, when an exchange mechanism occurs between
desorption at equilibrium (qeq desorp) in mg/g using Equation (9), fluoride and Ca2+ ions, protons (H+) have a great impact on the
MUKHERJEE ET AL.
sorption efficiency of the biosorbent. H+ ions compete with fluoride
ions for getting adhered onto the binding sites of the algal surface.
38,39
According to experimental reports, two protons are adsorbed for
the release of each Ca2+ into the solution. When the algal cells are
2+
treated with Ca , it binds on to the active sites on the surface of the
biosorbent thereby substituting other cations or protons present on
the algal surface. The FTIR spectra confirmed the existence of car-
boxyl, amine and hydroxyl groups on the surface of the algal and zeo-
lite beads which might be considered as substantial binding (sorption)
sites for F− ions. Shifts in NH peaks were observed in the F−-loaded
biosorbents and the decrease in wavenumber suggests the possible
−
interaction of the NH2 groups of the beads with the F ions which is
also confirmed from the FTIR analysis. A slight widening of the NH2
band in the F−-loaded biosorbents was a result of the hydrogen bond-
+ −
ing among protonated amine ( NH3 ) and the fluoride ions (F ).
3.2 | Physical characteristics of ZNA and CNB
Immobilized beads of ZNA and CNB were characterized for the esti-
mation of their physical properties. Table 1 discusses about the vari-
ous characteristics of the prepared biosorbents. Usually, pore volume
often limits the size of the solute molecule that is being sorbed onto
the biosorbent surface and surface area of the biosorbent restricts the
number of adsorbate molecules being adsorbed.
3.3 | SEM–EDX analyses
The electron microscopic images aid in observing the alterations in
−
surface morphology of ZNA and CNB before and after F uptake.
Before fluoride sorption, ZNA and CNB beads had comparatively
smoother surface without much porosity. After sorption, the surface
texture changed drastically with rougher surface and more porosity.
Before analysis, the prepared alginate beads were given an 8 mm thick
palladium coating at a rate of 30 mA for 30 s with the help of an auto
fine coater. The purpose of this coating was to enhance the conduc-
tivity since alginate beads are nonconductive in nature. Following this,
the samples were then dried under infra-red lamp after which it was
used for pictorial analysis under SEM. The chain-like structures of the
CNB beads were clearly visible in the raw beads as can be seen in Fig-
ure 1, whereas, surface of the beads seems less uneven with some
deposits on the surface. These deposits were a result of the adher-
ence of F− ions onto the surface of CNB beads. Similarly, the ZNA
TABLE 1 Physical properties of biosorbents ZNA and CNB
Properties ZNA CNB
Surface area (m2/g) 80.33 3.8153
Total pore volume (cm3/g) 1.15 0.911
Pore size (Å) 533.819 228.633
Micro-pore volume (cm3/g) 0.89 0.65
6 of 13
alginate beads show a rough and bumpy surface. This surface depicts
an overview of the zeolite particles trapped in the alginate network.
However, the surface becomes bumpier after adsorption owing the
deposition of the F− ions.
The adherence of the fluoride ions onto the beads were further
substantiated by EDX analyses as depicted in Figure 1. There was a
notable change in the elemental compositions of both ZNA and CNB
after fluoride sorption. ST3 signifies the EDX study of ZNA and CNB
beads before and after F− uptake. The EDX spectra of the ZNA and
CNB beads and spent ZNA and CNB beads showed a significant pres-
ence of Cl−. This could be indicative of the fact that although the
beads were washed several times with deionized water after synthesis
to remove excess of NaCl, the removal process was not complete.
The beads also depicted expected peak of Ca2+. Carbon and oxygen
were observed to be in the largest proportion, as was expected. Other
elements were detected at trace levels (less than 1 wt%) such as Na,
Mg, and Cl. The wt% of Ca2+ was higher in CNB beads (both raw and
spent) than ZNA beads since the algal biomass was pretreated with
CaCl2 to enhance its sorptive capacity. Further it was observed that
rate of F− uptake by ZNA was higher as compared to CNB beads
which also correlated with the results of this experimental investiga-
tion. Sorption of F− ions will generally be lower in deeper regions of
the ZNA and CNB beads and greater at the top three layers. Sorption
sites that are more available allow for more contact between fluoride
and the sorption sites. If the sorption sites are deeper in the structure
of the beads, these sites will be less accessible and part of the fluoride
ions might stay dissolved, regardless of the fluoride concentration.40
3.4 | FTIR
FTIR spectra determined the functional groups of the immobilized
beads of CNB and ZNA that were responsible for F− uptake. This was
governed by the shifts in peaks and reduction in percentage transmit-
tance of the solid surface's IR spectra after biosorption of fluoride by
CNB and ZNA as visible in Figure S2.
The FTIR spectra confirmed the existence of carboxyl, amine and
hydroxyl groups on the surface of the algal and zeolite beads which
might be considered as substantial binding (sorption) sites for F− ions.
Shifts in NH peaks were observed in the F−-loaded biosorbents and
the decrease in wavenumber suggests the possible interaction of the
NH2 groups of the beads with the F− ions. Since the hydrogen bond-
ing in the hydroxyl groups is relatively stronger than that in amines
hence, the OH stretching bands are broader and more intense than
those of the NH2. A slight widening of the NH2 band in the F−-
loaded biosorbents was a result of the hydrogen bonding among pro-
tonated amine ( NH3+) and the fluoride ions (F−). About 0–2 N H
absorptions are produced by an amide on binding with an amine sub-
ject to its type. The carbonyl (CO) stretching absorption is considered
as a strong IR absorption which is often applicable to determine not
only the structure but also the number of carbonyl groups (presuming
there is no overlapping of peaks) and an estimation of which types.
This group is found in both the immobilized beads. ST2 tabulates the
7 of 13
functional groups found on beads of CNB and ZNA before and after
fluoride biosorption.
3.5 | Column studies
3.5.1 | Influence of fluoride concentration on
breakthrough curves
The F− concentration was differed from 15 to 25 mg/L at a fixed
bed height and flow rate of 3 cm and 2 ml/min to determine its
effects as shown in Figure 2a. At lower concentration, the bed satu-
ration was delayed and also the quantity of fluorinated water treated
was higher. This might be attributed to the generation of a lower
concentration gradient that resulted in a slower transportation
owing decrease in mass transfer coefficient.25 At feed concentration
of 25 mg/L, it was seen that the breakthrough time and exhaustion
time reduced to 40 and 170 min, respectively. When the initial con-
centration is higher, more number of fluoride ions enter into the col-
umn within a given time resulting in rapid saturation of the bed
thereby lowering the breakthrough and exhaustion times. This phe-
nomenon can be attributed to the fact that increase in fluoride
F I G U R E 2 Effects of (a) F− concentration, (b) flow rate, and (c) bed height on breakthrough curves [Color figure can be viewed at
wileyonlinelibrary.com]
MUKHERJEE ET AL.
concentration also increased the fluoride concentration gradient
along with decreasing the mass-transfer interface. As a result,
increase in ionic concentration the time required for sorption of a
certain amount of fluoride ions reduced due to their overcrowding
effect on the surface of the beads. The availability of the biosorbents
for biosorption reduces with increase in fluoride ion concentration
as compared to the mass of fluoride ions.41 Therefore, the excess
ions which could not be bound leave the column unadsorbed which,
in turn, reduces the uptake capacity of the column. As stated above,
increasing fluoride concentration in the inlet aqueous solution
affects both breakthrough and exhaustion time. Therefore, it can be
stated that the mass diffusion process is influence by the ionic pres-
sure gradient. Hence, higher fluoride concentration requires a higher
amount of driving force with maximum mass-transfer and higher
concentration gradient. For every increase in ionic concentration,
there has been a decrease in mass-transfer or diffusion coefficient at
the interface which led to alteration in concentration gradient and
slower movement of adsorbate from liquid–solid interface to the
pores present on the beads. Also, it can be said that over-crowding
of fluoride ions have lowered the chances of surface interaction at
an earlier phase causing both faster breakthrough time and exhaus-
tion time.
MUKHERJEE ET AL.
3.5.2 | Influence of feed flow rate on
breakthrough curves
−
In order to investigate the influence of flow rate on F uptake, bed
height and F− concentration were kept fixed at 3 cm and 25 mg/L
while varying feed flow rate at 2, 4, and 6 ml/min. Figure 2b repre-
sents the impact of flow rate on the breakthrough curves. Results
indicated that the column's performance was most efficient at the
lowest flow rate of 2 ml/min and the rate of sorptive uptake of fluo-
ride was quite higher at low flow rate. As can be seen from the figure,
with increasing inlet flow, the column reached its saturation point
faster followed by les amount of treated aqueous solution. This is
indicative of the accessibility to the active sites on ZNA and CNB for
adherence of the fluoride ions. However, with time, the rate slows
down due to steady possession of those binding sites thereby lower-
ing the F− uptake capacity of the column. The exhaustion and break-
through times decreased on increasing the flow rate flow rate (2–
6 ml/min) as a result of which, slope of breakthrough curves were
found to be steeper and mass transfer zone shortened. As per stud-
ies,25,41 residence time of the fluorinated solution in column at high
flow rates will not be sufficient to establish equilibrium. Hence, most
of the ions leave the column unadsorbed, thereby resulting in poor
biosorption rates. This also caused an early exhaustion and break-
through time which became the main cause of shortened mass trans-
fer zone and steep breakthrough curves. The column's performance
was best at 2 ml/min. Therefore, the flow rate of 2 ml/min was
maintained for further studies.
At higher flow rate, the optimum time required for external mass
transfer decreases which results in premature saturation of the col-
umn with lesser removal. Further, at lower flow rate, intraparticle dif-
fusion becomes predominant, hence, keeping the column suitable for
fluoride removal for longer time period. Several experimental studies
have reported that removal percentage is higher for a particular set of
batch study whereas the same adsorbent-adsorbate particles tend to
42
contradict when subjected to a continuous mode of operation.
3.5.3 | Influence of bed height on breakthrough
curves
The column sorption experiments were performed at fixed feed con-
centration and flow rate of 25 mg/L and 2 ml/min, respectively, to
evaluate the influence of bed height (2, 3, and 4 cm) on fluoride
−
uptake. Figure 2 depicts the impact of bed height on F biosorption
by ZNA and CNB. It was observed that increase in bed height from 2
to 4 cm resulted in increased exhaustion and breakthrough times,
which is owing the higher superficial area and increase in the availabil-
ity of binding sites for the fluoride ions. The mass transfer zone is also
broadened as a result of increasing bed height. Increased prominence
of breakthrough curve with increased bed height was observed owing
43
the availability of broadened mass transfer interface. As per reports,
increasing sorbent volume in column enhances the predominance of
8 of 13
diffusive mass-transfer over axial dispersion of sorbate. Axial disper-
sion is supposed to be the governing mechanism for mass transfer at
lower bed height. Since the time for the F− ions is not sufficient for
diffusion through the entire sorbent bed, this results in shortened
breakthrough time which are consistent with other reported works.43-
46
Therefore, the bed height of 4 cm was considered as optimum for
column sorption of fluoride by ZNA and CNB. It can further be noted
that the breakthrough curve tends to be more prominent with every
increase in bed height due to availability of greater mass-transfer
interface. Also it has been reported that increase in adsorbent in
adsorbent volume in a column suggests that the probability of diffu-
sive mass-transfer generally is predominant over axial dispersion of
adsorbate.42 Hence, in reference to previous studies, it can be con-
cluded that greater contaminant removal from aqueous solution is
achievable with higher bed height which will provide maximum active
sites for adhesion of the adsorbate on to adsorbent.
A tabular representation comparing the defluoridation capabilities
of zeolite NaA and Nostoc sp. (BTA 394) with that of other reported
adsorbents has been presented in Table 2.
3.5.4 | Modeling of breakthrough curves
Efficient analysis of breakthrough curves by various mathematical
models depend on several factors like effectual prediction of the
breakthrough curves, evaluation of the influence of each distinctive
variable and mathematical convenience on the sorption process.
Therefore, the pattern of the rate of sorptive uptake of fluoride by
ZNA and CNB was investigated by applying Adams–Bohart36 and
Thomas models37 for extrapolation of breakthrough curves along with
determining individual factors of the column.
As per literature review, these two models are the most common
and extensively applied methods in column performance theory. The-
oretically, the Thomas model is appropriate for estimation of bio-
sorption process wherein internal and external diffusion resistances
are very small.46 This model is best fitting for lower flow rate, longer
bed height, and higher inlet concentration. This model discusses
adsorption performance in the continuous column in the form of
effluent outlet concentration versus time. The Adams–Bohart model
helps in understanding the prediction for saturation concentration of
adsorbate. The Adams–Bohart model further helps in predicting the
adsorption capacity of the adsorbent and also helps in determining ini-
tial part of the break through curve.51-55 Thomas model works better
when the initial concentration is relatively higher and the flow rate is
considerably lower. Assumption of the type of sorption isotherm is
the main difference between the Thomas and Bohart–Adams models,
wherein the former considers a Langmuir isotherm and the latter
takes into consideration a rectangular (irreversible) isotherm. In the
present experimental investigation, the results obtained for each
model were different and Thomas model provided the most suitable
results in case of fluoride biosorption. The column data were
processed using Microsoft Excel 2013 program.
9 of 13 MUKHERJEE ET AL.

TABLE 2 Comparison of the defluoridation capabilities of adsorbents with that of ZNA + CNB

Adsorption Flow rate Initial F− conc. Mathematical

Adsorbent capacity (ml/min) (mg/L) Bed height model References
Activated alumina 1,450 mg/kg 20 2.8 10 cm One-dimensional 47
MnO2-coated tamarind fruit 1,990 mg/kg – 2 15 Thomas 48
shell
Rice husk activated carbon 13 mg/g 1 18 2 g/L (sorbent Thomas 49
dose)
Corn cob activated carbon 9.3 mg/g 1 13 2 g/L (sorbent Thomas 49
dose)
Kanuma mud 1.558 mg/g 5 20 10 cm BDST 50
Immobilized Chlorella – 5 10 6 cm Yoon-Nelson 25
vulgaris
ZNA + CKB 34.2 2 20 4 cm Thomas Present
study

F I G U R E 3 Estimation of (a) F− concentration, (b) flow rate, and (c) bed height using Adams–Bohart model [Color figure can be viewed at
wileyonlinelibrary.com]

3.5.5 | Adams–Bohart model
The Adams–Bohart model, established by Bohart and Adams,36 takes
into consideration the surface reaction theory which presumes that equi-
librium is not attained instantaneously and focuses on assessment of fac-
tors like kinetic constant KAB and maximum adsorption capacity N0,
hence, the rate of biosorption is directly proportional to the sorption
capacity which still remains on the sorbent. This model was the first to
describe the crucial equations that define the relationship of Ct/C0 with
respect to t in a continuous arrangement and also defines initial part of
the breakthrough curve. The parameters N0 and KAB are determined
using a quasi-chemical kinetic rate expression using Equation (12),
MUKHERJEE ET AL. 10 of 13

   
Ct Z for explaining column efficiency and simultaneous extrapolation of
ln = K AB C0 t− K AB N0 ð12Þ
C0 F breakthrough curves.37 The basic assumptions of this model comprise:
(a) minor axial and radial diffusion in packed-bed column; (b) pseudo
where C0 and Ct refer to the influent and effluent fluoride concentra- second-order reversible rate kinetics is obeyed by the driving force;
tions (mg/L), F indicates the linear velocity (cm/min), N0 (mg/L) and KAB (c) the sorption process follows the Langmuir isotherm for equilibrium;
(L mg/min) refer to sorption capacity of bed and Adams–Bohart model (d) fixed column void fraction; (e) constant physical characteristics of
rate constant, respectively, t gives the time (min) and Z indicates height the biomass in solid and liquid phases, respectively; (f) isobaric and
of column bed (cm). Linear velocity can be calculated by dividing flow isothermal process environments, and (g) insignificant external resis-
rate with column's cross-sectional area. The slope and intercept of ln(Ct/ tance and intraparticle diffusion throughout the mass transfer
C0) against time (t) plot give the values of N0 and KAB, respectively, as procedures.55
visible from Figure 3. The results are tabulated in Table 3. This model is applicable particularly in the lack of internal and
The kinetic constant (KAB) was observed to increase with external diffusion limitations. Equation (13) gives the linearized from
increased flow rate and decrease with rise in initial fluoride concentra- of the Thomas model,
tion and bed height as visible from Table 3, which suggests that entire
 
kinetic system was occupied by external mass transfer in the initial C0 K Th × q0 × W
ln −1 = −K Th × C0 × t ð13Þ
stages of the column biosorption study. Since the correlation coeffi- Ct Q

cient values found in this model were lower than that of the Thomas
model, it fails to satisfactorily explain the breakthrough curves of the
experimental data.
3.5.6 | Thomas model
Thomas model is a broadly acceptable and efficient model that is
applied for interpretation of the data acquired from column studies
where C0 (mg/L) and Ct (mg/L) refer to influent and effluent fluoride
concentrations, KTh (ml/min/mg) is the Thomas rate constant, q0 (mg/
g) refers to equilibrium fluoride uptake per gram of ZNA and CNB,
respectively, W (g) indicates the mass of biosorbents used, Q (ml/min)
indicates flow rate and t (min) refers to the flow time. The values of
KTh and q0 are obtained from intercept and slope of the linearized plot
of ln[(C0/Ct) − 1] against time (t). KTh and q0 values were obtained by
fitting column data to this model. The linear regression analysis was

TABLE 3 Adams–Bohart parameters and Thomas model parameters at altered conditions for F− uptake onto ZNA + CNB

Adams–Bohart parameters

C0 (mg/L) Z (cm) v (ml/min) KAB [ml/(min mg)] × 10−4 N0 (mg/L) × 10−5 R2

15 6 2.0 9.16 3.8 0.9063
20 6 2.0 8.4 4.24 0.9172
25 6 2.0 6.6 5.43 0.9760
15 6 2.0 6.4 3.79 0.9028
15 6 4.0 6.0 5.89 0.9015
15 6 6.0 2.0 10.95 0.9019
15 4 2.0 8.0 9.29 0.9087
15 6 2.0 4.0 3.89 0.9113
15 8 2.0 2.68 2.74 0.9334
Thomas model parameters
C 0 (mg/L) W (g) Q (ml/min) K Th [ml/(min mg)] × 10−4 q 0 (mg/g) × 10−5 R2
15 4.2 2.0 11.56 2.67 0.9778
20 4.2 2.0 9.57 2.54 0.9726
25 4.2 2.0 8.3 2.28 0.9606
15 4.2 2.0 11.92 2.83 0.9206
15 4.2 4.0 12.04 1.37 0.9203
15 4.2 6.0 11.52 1.26 0.9220
15 2.8 2.0 12.48 2.49 0.9171
15 4.2 2.0 12.04 2.71 0.9222
15 5.6 2.0 13.6 6.65 0.9198
11 of 13
used to calculate the relative constants and determined coefficients
which are tabulated in Table 3.
The Thomas model provided more suitable fit to column data at
the varying flow rates studied with R2 > 0.94 which pointed out
toward the internal and external diffusions being not the rate limiting
step.46 Increase in flow rate also increased the rate constant which
pointed toward a decrease in the mass transport resistance. There-
fore, it can be said that the difference in fluoride concentration among
the biosorbents and aqueous solution served as the main driving force
for biosorption.46 The evaluation of experimental points and predicted
curves as per Thomas model has been depicted in Figure 4. ST4 pre-
sents the mathematical description of the column parameters.
3.5.7 | Continuous mode validation of desorption
and regeneration studies
Desorption of the fluoride-loaded biosorbent beads was carried out
with 0.1 M Ca(OH)2 after the column was saturated with fluoride ions
followed by regeneration with 0.1 NaOH. It was observed that the
desorbed biosorbent beads were able to separate the fluoride ions
F I G U R E 4 Estimation of (a) F− concentration, (b) flow rate, and (c) bed height using Thomas model [Color figure can be viewed at
wileyonlinelibrary.com]
MUKHERJEE ET AL.
from the influent up to three cycles with a regeneration percentage of
34.88% following which a change in the shape of the breakthrough
curve was observed as is evident in Figure 5. Regeneration of the col-
umn bed aided in maintaining the reusable cycles for multiple times
by neutralizing the solid surface from excess of H+ ions with OH− ions
which made fluoride ion adhesion possible. Further, the alginate beads
promoted in maintenance of the stability of the biosorbent beads for
multiple cycles.
3.6 | Disposal of F−-loaded biosorbents
Safe disposal of contaminant-loaded biosorbent is extremely com-
mended as this governs its overall effect on the environment. Com-
plete removal of F− ions from the spent biosorbent is suggested since
there might be leaching of F− ions into the soil which, in turn, contrib-
utes toward environmental pollution. Various methods on safe dis-
posal of spent biosorbents have been reported by Robarts and
Zohary.56 According to one of the disposal methods, the fluoride-
loaded CNB and ZNA beads were oven-dried at at 60
C oven and
incinerated at 200
C. Ten grams of the incinerated ash was dissolved
MUKHERJEE ET AL.
F I G U R E 5 Desorption–adsorption cycle of fluoride removal
[Color figure can be viewed at wileyonlinelibrary.com]
in 25 ml of deionized water which was persistently agitated for
24 hr.32 The filtrate obtained was analyzed and no leaching of F− ions
was found which was also confirmed by the XRD analyses of the
spent biosorbent beads as depicted in Figure S3. XRD helped in deter-
mining the mineral phase that produces stable compound in fluoride
which prevents the fluoride from being leached.
4 | C O N CL U S I O N S
The biosorbents prepared by immobilization of zeolite NaA and Nos-
toc sp. (BTA394) has proved to be a promising tool for fluoride
removal from aqueous solution. The biosorbents demonstrated equiv-
alent performance under the influence of differing bed height, influent
concentration and flow rate in a packed bed reactor. Results suggest
that initial F− concentration, bed height and flow rate had significant
effects on the shape of breakthrough curves and biosorption of fluo-
ride by the biosorbents namely ZNA and CNB. Optimal conditions for
maximum biosorption capacity of 34.2 mg/g were achieved at F− con-
centration of 20 mg/L at a 4 cm bed height and 2 ml/min flow rate
with a maximum removal of 88%. Column data were well explained
with Thomas model over Adams–Bohart model. The biosorbents were
able to survive and maintain their biosorptive capacity for multiple
cycles of desorption–adsorption. This is indicative of the mechanical
strength of the biosorbents which supported ionic stressed condition
for longer period of service time. The study also suggested disposal of
the fluoride-loaded biosorbents to prevent any further contamination.
Hence, it can be concluded that the biosorbents could be used as
alternatives for fluoride removal due to environmentally benign nature
and could be used for application at larger scale with further
modifications.
ACKNOWLEDGMENT
GNH and SM are thankful to Department of Biotechnology, Govern-
ment of West Bengal vide project grant BT (Estt.) R&D-23/13.
12 of 13
OR CID
Anoar Ali Khan https://orcid.org/0000-0001-9274-3837
Gopinath Halder https://orcid.org/0000-0002-2050-9109
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SUPPORTING INF ORMATION
Additional supporting information may be found online in the
Supporting Information section at the end of this article.
How to cite this article: Mukherjee S, Khan AA, Barman S,
Halder G. Experimental study of biosorption of fluoride by
immobilized beads of zeolite NaA and Nostoc sp. (BTA394)
using a continuous flow system. Environ Prog Sustainable
Energy. 2020;39:e13465. https://doi.org/10.1002/ep.13465