Journal of Polymers and the Environment

https://doi.org/10.1007/s10924-020-01746-3

ORIGINAL PAPER

Implication of Greener Biocomposite Bead for Decontamination

of Nickel(II): Column Dynamics Study
Animesh Naskar1,2 · Rajib Majumder3 · Mitrabrata Goswami1 · Saikat Mazumder1 · Samik Maiti4 · Lalitagauri Ray2

© Springer Science+Business Media, LLC, part of Springer Nature 2020

Abstract
The present study reports on the potential of greener Biocomposite designed by living cells of mutated Bacillus sp. inte-
grated passively with alginate to decontaminate Nickel(II) from aqueous medium by continuous column process in order to
ascertain its actual environmental application. The impact of working parameters was investigated, showing better execu-
tion at a low flow rate (4 mL min−1) and highest bed depth (25 cm). The percentage removal was found to be 80.76% at
saturation with a sorption capacity of ~ 54 mg g−1 using an influent concentration of 50 mg ­L−1. The dynamic behaviour of
the processes was well defined by Yoon–Nelson and Thomas kinetic model. Special emphasis was directed to mass transfer
phenomenon using suitable mathematical expressions while different kinetic models have their limitations. The resistance
of mass transfer initially depended on porous diffusion (PD) prior to the proportion of outflow being 3%, ~ 8% and 12% and
subsequent metal removal were controlled by both film mass transfer and PD for Nickel(II) solution 100, 50 and 20 mg ­L−1,
respectively. Biocomposite was characterized by FTIR, SEM-EDXA and elemental analyzer which conveniently ascertained
the interactions of metal to composite through electrostatic, complexation and/or chelation. Nickel(II) was recovered to the
extent of 92% using 0.1 M HCl as eluant in six consecutive cycles. The Biocomposite was also efficient to decontaminate
Nickel(II) from simulated effluent, where breakthrough modeling and mass transfer kinetics revealed a similar trend to the
monometallic solution, thereby ensuring its prospect for industrial practice.

Keywords  Adsorption · Nickel · Biocomposite · Packed bed column · Mass transfer kinetics · Binding mechanism

Introduction

Non-biodegradable, carcinogenic and persistence are the

Electronic supplementary material  The online version of this
article (https​://doi.org/10.1007/s1092​4-020-01746​-3) contains
supplementary material, which is available to authorized users.
* Animesh Naskar
animesh.ftbe@gmail.com
1 require mandatory treatment before discharge into the envi-
Department of Food Technology, Hemnalini Memorial
College of Engineering, Maulana Abul Kalam Azad
University of Technology, Haringhata, West Bengal 741246,
India
2
Department of Food Technology and Biochemical
Engineering, Jadavpur University, Kolkata 700 032, India
3
Department of Biotechnology, School of Life Science
and Biotechnology, Adamas University, Kolkata,
West Bengal 700126, India
4
Department of Mechanical Engineering, Christian College
of Engineering and Technology, Bhilai, Chhattisgarh 490026,
India
most imperative attributes of bivalent Nickel results from
various industries, accountable for the deleterious influences
on the natural ecosystems and human wellbeing [1–3]. This
is also reported that Nickel(II) is a high priority toxic con-
taminant among metal pollutants [1]. Therefore, industrial
effluents bearing higher concentrations of Nickel(II) ions
ronment. Conventional physicochemical techniques used
for metal removal from wastewater are often uneconomi-
cal and emerging few constraints for technical operations
[4]. In this circumstance, biosorption imparting large ben-
efits has been suggested by researchers worldwide as an
effective and financially feasible process for the depletion
of metal ions from aqueous medium [5, 6]. This process
often utilizes low-cost adsorbent mainly of biological origin
[7–9]. Bacterial biomass has obtained a ton of interest in this
regard due to high surface area and exposure of potentially

13
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active different functional groups for the binding of metal
ions [10]. However, instantaneous using free biomass for
large scale applications has downsides to some extent due
to lower recovery limit and loss of biomass quantity [11].
Integration of biomass in diverse, non-toxic and inexpensive
bio-matrices has been proven to be an efficient solution to
achieve reusing facility, good mechanical strength, porosity
as well as upgrading the metal removal proficiency [12, 13].
From an operational viewpoint, biosorption in batch
mode finds few restrictions in the scale-up process on treat-
ing real wastewater. A continuous fixed-bed column system
can be efficient in this regard as an appropriate alternative to
the batch system [14]. The column system offers some ideal
conditions in treating real-time industrial effluent needed
for a practical purpose [15, 16]. It is noteworthy that the
advancement of mathematical modeling regarding the col-
umn framework is undeniably vital for ideal process out-
line and operation since it provides very effective tools on
completely different levels. Besides, the design of fixed-bed
adsorption processes requires an in-depth understanding of
mass transfer in light of process modeling to explore the
rate-limiting step and to facilitate better scaling up of the
processes [17]. Numerous mass transfer models have also
been proposed for the sorption behaviour of various solutes
[18, 19]. The use of empirical model equations in this study
relating to external, internal and global mass transfers has
brought increasing attention to continuous column system
forecasting both qualitative and quantitative measures of
varying coefficients with respect to the percentage of out-
flow. Additionally, these models can monitor the sorption
phenomena of any single solute onto porous materials [20].
This research aimed to explore the mass elimination of
Nickel(II) from aqueous medium utilizing prepared Biocom-
posite through continuous column reactor with special refer-
ence to mass transfer mechanisms appropriate for the indus-
trial requirement. Mass transfer coefficients with respect to
the percentage of outflow was elucidated to determine the
interaction behaviour. The effect of important design param-
eters such as feed flow rate, inlet metal ion concentration,
and column bed height controlling the reactor performance
was investigated as well. In-depth characterization of Bio-
composite and comprehensive adsorption mechanisms were
explored through a Scanning electron microscope (SEM)
equipped with Energy dispersive X-ray analysis (EDXA),
Elemental analyzer and Fourier transform infrared spectros-
copy (FTIR). Furthermore, to ensure the realistic feasibility
of experimental findings, Biocomposite was employed for
the Nickel(II) decontamination from a simulated feed solu-
tion containing auxiliary substances along with target metal.
13
Journal of Polymers and the Environment
Materials and Methods
Chemicals
Nickel chloride (­NiCl2·6H2O) used as adsorbate in this
experiment was obtained from E-Merck, Germany. Micro-
biological media and all the other chemical reagents (ana-
lytical grade) supplied from Hi-media and Merck, India,
respectively.
Microorganism and Yield of Biomass
The mutated bacterial strain, Bacillus cereus ­M116 (MTCC
5521) employed for this study was isolated, identified and
mutated in the laboratory. Initially, the inoculum was pre-
pared by transferring a loop full of pure culture to 50 mL
sterile growth medium (yeast extract, 0.2%; beef extract,
0.1%; peptone, 0.5%; sodium chloride, 0.5%; pH 6.5) in
250 mL Erlenmeyer flask. The flask was then incubated for
24 h under shaking condition (120 rpm) at 30 °C. Afterward,
2% of prepared inoculum was transferred aseptically into
50 mL medium in 250 mL Erlenmeyer flasks followed by
incubated under the same conditions. At the end of incuba-
tion, biomass was harvested by centrifugation (5500 rpm for
10 min, REMI R8C) and washed with double distilled water.
Preparation of Biocomposite Bead
The harvested bacterial biomass was dissolved in sterile dou-
ble distilled water to make a cell suspension (100 mg mL−1).
The bacterial cell suspension was then mixed with sodium
alginate solution in a particular ratio (alginate solution:
biomass suspension = 2:1) to achieve the final alginate con-
centration of 3% and the mixture was extruded into chilled
­CaCl2 (0.5 M) through a hypodermic syringe. The obtained
Biocomposite beads were kept at 4 °C for 2 h before succes-
sive washed with double distilled water. The average diam-
eter of beads (2.1 ± 0.1 mm) was calculated following the
procedure of [21]. The beads were dipped in normal saline
at 4 °C until used in these experiments.
Experimental
A continuous biosorption process was carried out for
Nickel(II) removal on Biocomposite beads in a glass
column having 1.45 cm and 30 cm of internal diameter
­(dcolumn) and height, respectively. The prepared beads were
air-dried before use as packing material in a column. Inlet
silicone tube was connected at the bottom of the vertically
placed packed column via the peristaltic pump to maintain
the desired flow rate. An outlet latex tube was fitted on the
Journal of Polymers and the Environment
top of the column which was connected to another peri-
staltic pump to drag the effluent (Fig. 1). The effluent sam-
ples were collected at regular time intervals and metal ion
concentration was measured using Flame Atomic Absorp-
tion Spectrophotometer (Chemito Technologies Pvt. Ltd,
India, Model No. AA 203, wavelength: 232 nm, slit width:
0.5 nm). The pH of the feed solution was adjusted to 6.0.
To explore the effect of flow rate, bed height and influ-
ent metal ion concentration the experiments were car-
ried out by varying the flow rate (4–8  mL  min –1), bed
height (10–25 cm) and influent metal ion concentration
(20–100 mg ­L–1). Each experiment was conducted in trip-
licate and mean data from the experiments is depicted in
the section of the results and discussion.
Characterization of Biocomposite
Surface morphology of pristine and metal-loaded compos-
ite bead was captured using a Scanning Electron Micro-
scope (JEOL, Model: JSM 6360, UK). Elemental charac-
terization was accomplished by energy dispersive X-ray
analysis equipped with SEM. X-ray elemental mapping
of metal-loaded beads was obtained using this system. To
obtain information about functional groups and their inter-
actions with metal ions, Fourier transform infrared spec-
trophotometer (Shimadzu IR- Prestige-21, Japan) was used
to record the data of pristine and metal-loaded Biocompos-
ite. Drying powder of beads was loaded in the instrument
through KBr disc technique. The data was recorded in the
range of 4000–400 cm–1 with a resolution of 4 cm–1.
Fig. 1  Graphical representation of the column experiment for the
removal of Nickel(II) from its aqueous phase
Regeneration Study
A regeneration study was conducted for six consecutive
cycles. Each cycle was started with adsorption using an influ-
ent Nickel(II) concentration of 100 mg L ­ −1 and followed by
desorption under the optimum bed height and feed flow rate.
0.1 M HCl was used as an eluant to recover the metal ions.
After completion of each cycle, the packed bed column was
thoroughly washed with double distilled water to remove the
rest of the acid in the system and packed further with refreshed
beads, followed by subjecting to the Nickel(II) solution
(100 mg ­L−1) for next cycle.
Theory
The dynamic sorption behavior of metal ions in a fixed bed
column system can be elucidated as a result of effluent time-
concentration profile which is commonly known as a break-
through curve. This curve can be characterized by the normal-
ized ratio of outlet and inlet metal concentration (C/C0) as a
function of time. Besides, different experimental parameters
can also be evaluated for the fixed bed metal sorption process
having crucial importance in the continuous column system
[16, 22].
The volume of effluent ­(Veff) can be determined using the
following equation (Eq. 1):
Veff ,total = Qttotal (1)
where Q denotes the volumetric flow rate (mL m ­ in–1) and
­ttotal represents total flow time (min).
The total fixed bed capacity, ­qtotal (mg) is equal to the
area under the breakthrough curve (A) from the integral of
adsorbed concentrations expressed as C ­ ad (mg ­L–1) for a given
time t (min) and is calculated as follows (Eq. 2):
ttotal
∫
QA Q
qtotal = 1000
= 1000
Cad dt (2)
t0
where, ­Cad can be determined as a consequence of ­C0 – C.
The passing of the total amount of metal through the col-
umn system ­(mtotal) can be estimated by the following expres-
sion (Eq. 3):
Qttotal
mtotal = C0 × 1000
(3)
The percentage of total metal removal (R%) can be deter-
mined from the ratio of the total fixed bed capacity (­ qtotal) to
the quantity of the metal passed through the column as Eq. 4:
qtotal
R% = mtotal
× 100 (4)
13
 Journal of Polymers and the Environment

The void fraction of the column (ω) can be calculated from Adams–Bohart model is based on the fact that the sorp-
the volume of water eluted out of the column after the beads tion rate is exclusively proportional to the concentration of
of the packed bed are saturated with water (W) (Eq. 5) and metal ions used as well as the residual capacity of the sorb-
total volume of effective column ­(Wh), can be expressed by ent. This model was considered to demonstrate the initial
the following equation (Eq. 6). part of the breakthrough curves [25]. The mathematical
W
equation can be expressed as follows (Eq. 9):
𝜔= Wh (5) ( )
C H
ln = kAB C0 t − kAB N0 (9)
With C0 F

where ­kAB represents the kinetic constant (L ­min–1 mg–1),

2
𝜋dcolumn H
Wh = (6)
4
­ –1),
­N0 is the concentration at the level of saturation (mg L
–1
where ­dcolumn is the internal diameter of the column and H F and H are the flow rate (mL m ­ in ) and the bed depth of
is effective bed height. column (cm), respectively.

Model Analysis of the Breakthrough Curve

Operational process variables should be optimized for the col-
umn system since it determines the efficient removal of solute.
Additionally, the rational significance of the column experi-
ment requires a better investigation of breakthrough curves
and delineates adsorption behavior in dynamic mode with dif-
ferent scientific models such as Thomas, Adams–Bohart and
Yoon–Nelson model [23, 24]. The Thomas model is a standout
amongst the broad and customarily utilized models as a part of
the packed column which is useful for forecasting the break-
through curves. This model is affordable with no external and
internal dispersion limits. Additionally, the model depends on
Langmuir energy of adsorption–desorption and the rate of the
process is related to the driving force of second-order revers-
ible reaction kinetics.
The mathematical equation for the Thomas model is given
as (Eq. 7):
[( ) ] system at irregular intervals of time [20].
C0 k qw
ln − 1 = Th 0 − kTh C0 t (7)
C Q
Mass Transfer Kinetics
Mass transfer phenomena can be defined as the transfer of
mass from high to low concentration. This expression is
often utilized as a part of designing for physical processes.
Mass transfer behaviour typically incorporates the ensuing
steps such as film mass transfer (FMT), intra-particle diffu-
sion (PD) and immediate binding of the solute to acceptor
destinations with a strong affinity [26]. However, the imme-
diate attachment has no massive impact on the resistance of
mass transfer. The resistance of mass transfer is exclusively
controlled by either film mass transfer or pore diffusion, or
on both. The accompanying condition (Eq. 10) has been uti-
lized for the most part to depict the reduction of solute in
aqueous solution. The mass balance equation (Eq. 11) sup-
ports the fact while monitoring the concentration of sorbate
entrance into the column and the concentration leaving the
NA = − kL f × S × (C − C∗ )
[ ]
(10)

where the ­kTh (L ­min–1 mg–1) represents the constant of

QC = Q × (C − 𝛿C) − kL f × S × (C − C∗ )
[ ]
Thomas model, q­ o (mg g­ –1) addresses the maximum sorp- (11)
tion capacity, t is the time (min), W is the mass of adsorbent
used (g), Q and C ­ in–1) and
­ 0 are the influent flow rate (mL m where, ­NA represents the amount of the solute (A) trans-
initial metal concentration (mg L –1
­ ), respectively. C is the ported per unit time (mg h­ –1), ­[kL]f stands for film mass
metal ion concentration of effluent (mg ­L–1). transfer coefficient (­ h–1), (C − C*) represents the driving
The conception of Yoon and Nelson model is listed in the force (mg ­L–1) and the surface area of biomass is symbol-
column study of lead adsorption on Lentil Husk done by Basu ized by S ­(m2). The magnitude of ­[kL]f can be evaluated
et al. [15]. The model equation can be written as (Eq. 8): from the plotting of ­NA versus (C − C*). C and Q are the
concentration of the sorbate (mg ­L−1) and flow rate (L ­h−1),
respectively.
( )
C
ln = kYN t − 𝜏kYN (8) To assess the film mass transfer by utilizing Eq. 11 can
C0 − C
be expressed as (Eq. 12):
where the Yoon–Nelson model rate constant is symbolized
by ­kYN (L ­min–1) and τ represents time (min) required for −
𝛿C [ ]
= kL f ×
S
× (C − C∗ ) (12)
50% sorbate breakthrough. 𝛿t 𝛿V
where V is the volume of the treated water (L).

13
Journal of Polymers and the Environment

Now consider a situation where C* ≪ C and the surface (t) in Eq. 16 provides a straight-line intercept at B with 1/β
of interfacial liquid–solid S/V = a(m2). Thereby Eq. 13 is the as the slope. The Eq. 17 is now suitable to derive the value
resultant outcome by integrating the Eq. 12 from C = C0 to of variable ­[kLa]g by following the proportion of outflow (­ Cs/
C = Cs, from V = 0 to V = V and from t = 0 to t = t. C0 ratio) since the index B and β were verified.
( ) The variable intraparticle diffusion factor ­([kLa]d) ­(h−1)
C0 is mathematically calculated by the difference between the
(13)
[ ]
ln = kL a f × t
Cs global and film mass transfer factor. This may be written in
the equation (Eq. 18):
where, ­C0 and ­Cs are the concentration of the sorbate (mg
­L−1) enter into the column and depart from the column,
[ ] [ ] [ ]
kL a d = kL a g − kL a f (18)
respectively.[kLa]f represents the film mass transfer coeffi-
cient ­(h−1) and t is the accumulative time of feeding solution
into the column (h). Statistical Analysis
The correlation plot of ln(C0/Cs) versus t provides a
constant value of [­ kLa]f. However, the varying degree of All the results were articulated as mean data of triplicate
­[kLa]f should be reasonable for a continuous column system, experiments while considering the p-value is less than 0.05.
since progressive increment of influent passed through the The magnitude of the regression coefficient and Chi-square
column. were obtained using Origin 8.0.
For that reason, the scientific condition (Eq. 14) has been
created in light of the fact, relating to external and global
mass transfer [26].
Results and Discussion
kL a f = kL a g × e−𝛽q
[ ] [ ]
(14)
Electron Microscopic Observation and Elemental
−1
where ­[kLa]g stands for global mass transfer coefficient ­(h ), Analyses
q the is the amount of the metal ions adsorbed onto Biocom-
posite beads (mg g­ −1) and β represents the affinity parameter Surface morphology can be extensively analyzed by scan-
between sorbate–sorbent (g ­h−1 mg−1). ning electron microscopy. Pristine composite displayed
By substituting Eq. 14 into Eq. 13 yields the following highly uneven surface characteristics over a large surface
continuous equation (Eq. 15): area and assumed a fibrillar arrangement upon the matrix
available for metal attachment (Fig. 2a). Noticeable changes
occurred as a result of interaction with Nickel(II) (Fig. 2b),
( )
C0
= kL a g × e−𝛽q × t (15)
[ ]
ln
Cs which became smooth and more regular highlighted at a
higher magnification image (Fig. 2d). Quantitative analy-
It is now acceptable for a continuous column system to sis of various atoms was performed in area profile mode
determine the variation of ­[kLa]g as a result of the quantita- through energy dispersive X-ray analysis and Elemental
tive relation between ­C0/Cs vs. t. For efficient model devel- mapping, where the signals of Nickel(II) were noted on
opment observing the C ­ s after the passing point is an imper- the metal-laden bead in EDXA profile (Fig. 2f), which was
ative task in this regard. However, prior to obtaining the indeed confirmed by mapping of target metal. Mapping
variable ­[kLa]g, there is a necessity to check the parameter β results revealed the spatial allocation of Nickel(II) on the
as constant. The fixed value of β can be established by exam- surface of metal adsorbed composite (Fig. 2c).
ining the experimental results in light of linear regression. A
numerical derivation of Eq. 15 may confer the straight-line
FTIR study for Determination of Surface
equation which can be written as follows (Eq. 16) [20, 26]:
Functionality of Biocomposite
1
q=B+ × ln t (16) To explore the active functional groups of prepared Bio-
𝛽
composite responsible for target metal binding, the FTIR
With study was accomplished and the resultant data are depicted
([ ] ) { ( )}
C
in Fig. 3. The newly appeared, disappeared and changes in
ln kL a g − ln ln C0 peak profile were more clearly summarized in Table 1. The
B=
s (17)
𝛽 findings revealed that the hydroxyl, carboxyl, amide, and
methyl groups of the composite were mainly responsible for
where B is the potential mass transfer index relating to the the rapid binding of Nickel(II) ions through complexation or
driving force of mass transfer (mg ­g−1). A plot of q versus ln chelation and electrostatic interaction [13, 27].

13
 Journal of Polymers and the Environment

Fig. 2  SEM micrographs of bio-

composite: a pristine, b metal
treated, d magnified image of
the selected area. c Metal map-
ping of the selected area. EDX
analysis e pristine biocomposite
and f metal treated biocom-
posite

Void Fraction Effect of Bed Height on Nickel(II) Removal

The void fraction of the fixed-bed column was found to The variation of packed bed height ranging from 10 to
be 0.12 as assuming Biocomposite beads are spherical 25 cm on the column system was investigated for initial
and uniform in size. Nickel(II) ion concentration of 50 mg ­L–1 with a constant

13
Journal of Polymers and the Environment

to be 20, 70, and 150 min for 10, 18 and 25 cm bed height,
respectively (Fig. 4a). This performance may be attributed
to the availability of more number of active sites and an
increase in the surface area for metal attachments [28, 29].
Alongside, highest bed depth facilitates longer residence
time to contact the Biocomposite bead resulting to improve
in metal removal (Mishra et al. 2016). Raiza et al. interpreted
this fact in light of the mass transfer phenomenon in which
diffusion prevails in the mass transfer over axial dispersion
with an increment of bed depth [30]. Hence, the highest bed
height (25 cm) was chosen for the subsequent experiments.

Effect of Inlet Flow Rate on Nickel(II) Removal

Flow rate is a fundamental parameter for the implemen-

Fig. 3  FTIR spectra of pristine and metal treated biocomposite
flow of 4 mL min–1 and corresponding results are illustrated
in Table 2. The steady increment of Nickel(II) sorption per-
centage was observed from 43.88 to 80.76% with a rise in
bed height from 10 to 25 cm. Breakthrough time was found
tation of biosorption techniques, notably for continuous
treatment of hazardous elements on industrial large scale
effluent. In this way, the impact of the influent flow rate on
sorption of Nickel(II) by Biocomposite beads was inves-
tigated by varying the flow rate while maintaining a con-
stant inlet Nickel(II) ion concentration (50 mg ­L−1) and
bed depth (25 cm). The obtained results are presented in

Table 1  FTIR peak assignment of pristine and Nickel(II) laden biocomposite

Pristine biomass Nickel(II) loaded biocom- Peak assignment References
­(cm–1) posite ­(cm–1)

3433.08* 3409.94 O−H stretching [41]

– 2929.69± C−H stretching [42]
2129.86± –  −C=C stretching [43]
1633.61 1631.88 Asymmetric vibration [44]
peak of COO− 
1406.02* 1419.52 Symmetric vibration [44]
peak of COO− 
1325.01* 1332.73 C−O−C [45]
1247.87* 1240.15 Amide III [46]
1082.00 1085.85 complex stretching vibrations of glycopeptides and carbohydrates or P–O–C [47]
1027.99 1027.99 links of the organic phosphate groups and P–O vibration of (C–PO32−)
moiety

*Chages in peak profile after Nickel(II) treatment

±
 Appearance/disappearance of peak after Nickel(II) treatment

Table 2  Breakthrough curve C0 (mg ­L–1) Q (mL H (cm) A (mg ­min–1 ­L–1) qtotal (mg) mtotal (mg) R (%)
parameters corresponding to ­min–1)
bed height, flow rate, and inlet
metal concentration 50 4 10 10533.58 42.13 96.00 43.88
50 4 18 16036.62 64.14 96.00 66.81
50 4 25 19382.87 77.53 96.00 80.76
50 6 25 16497.98 98.98 144.00 68.73
50 8 25 11787.99 94.30 192.00 49.11
20 4 25 8255.75 33.02 38.40 85.98
100 4 25 30661.54 122.64 192.00 63.87

13

Fig. 4  Effect of a bed height, b flow rate and c initial metal ion concentration on Nickel(II) ion sorption by biocomposite in continuous packed
bed column
Fig. 4b and calculated parameters are depicted in Table 2.
This could be shown that a lower flow rate (4 mL min–1)
provided more sorption efficiency (80.76%) and higher
breakthrough time (~ 150 min). This trend may be related
to the residence time of the Nickel(II) solution within the
column. At lower flow rate, contact time between metal
ions and active sites around or inside the Biocomposite
beads was much higher, facilitating the removal of more
Nickel(II) ions. Moreover, enough time rendered the metal
13
Journal of Polymers and the Environment
ions to be diffused into the pores of the beads through
intra-particle diffusion [31]. In contrast, with the increase
in flow rate (8 mL min–1), the nature of the breakthrough
curve became steeper. The metal ions leave the column
before achieving an equilibrium state. Moreover, a high
flow rate decreased the contact time between sorbate and
sorbent owing to reduce diffusion coefficient as well as
Nickel(II) removal [32, 33]. Therefore the lower flow rate
was to be selected for the rest of the studies.
Journal of Polymers and the Environment

Effect of Inlet Metal Concentration
To explore the potential impact of the initial concentration
of metal ions, column experiments were conducted by vary-
ing the influent concentration (20–100 mg ­L−1) under the
previously optimized bed height and flow rate of the system.
The results are illustrated in Fig. 4c and relevant parameters
are summarized in Table 2. Notably, the breakthrough time
became shorter to ~ 50 min from 190 min with an increase
in metal ion concentration from 20 to 100 mg L ­ −1, respec-
tively, leading to alteration of the pattern of the breakthrough
curve. This fact may be accounted for an additional quantity
of metal ions passed through the fixed-bed per unit time
attributing the faster saturation of the Biocomposite beads,
thereby reducing the breakthrough time. The percentage
removal of metal ions also reduced from 80.76% to merely
64% with rising in feed concentration. A similar influence of
intel concentration on the removal of zinc by dual surface-
modified biomass was reported by Saravanan et al. [34].
Better clarification leads to rising in driving force due to an
increase in concentration gradient facilitating potential mass
transfer from the aqueous phase to a solid phase, thereby
exhausting the sites more quickly [35, 36].
Model Analysis of Column Breakthrough Curves
Three different models were utilized to explain the kinetics
of the present study. First, the conception of Adams–Bohart
model was considered to evaluate the experimental data.
The respective model constants were calculated using lin-
ear regression analysis and the results are summarised in
Table 3. The resultant magnitude of ­kAB decreased with
an increase in initial Nickel(II) concentration as well as
the feed flow rate. These outcomes demonstrate that exter-
nal mass transfer might be dominated in the initial part of
the Nickel(II) removal process. Additionally, there was an
indication regarding the influent flow rate which should be
lower during the column operation [23]. Secondly, the rela-
tive constants and coefficients of the Thomas model were
also obtained using linear regression analysis. The value of
­kTH decreased and the value of ­q0 increased as rising flow
rate depicted in Table 4. These findings may be related to
the higher driving force due to high Nickel(II) ion concentra-
tion in the system, thereby increasing the ­q0 value [15]. The
model also revealed a better correlation with experimental
data ­(R2 ranging from 0.85 to 0.92), suggesting the perti-
nence of this model in describing the sorption phenomenon.
Thirdly, one more basic hypothetical model postulated by
Yoon–Nelson was employed to explore the breakthrough
behavior for such column experiments and the value of ­kYN
and τ were determined from linear regression analysis, uti-
lizing the appropriate model equation (Table 5). The results
demonstrated that the 50% breakthrough time (τ) declined
with increasing the flow rate as well as Nickel(II) ion con-
centration due to the rapid saturation of the column bed.
Moreover, the magnitude of the regression coefficient varied
from 0.86 to 0.92 addressed the validity of this model for the
present system [24].
Mass Transfer Kinetics of the Column Process
A step forward investigation for the determination of mass
transfer resistance can be an effective means for designing
a packed bed column reactor in chemical engineering prob-
lems [37]. However, the detailed analysis of the experimental
data using the above three kinetic models has its limitations.
For instance, Adams–Bohart model proposed the dispersion
of metal ions caused by mass transfer resistance was negligi-
ble. Thomas model did not have any axial dispersion still, it
could not be used to determine the resistance of mass trans-
fer. To meet the problems, the mass transfer models postu-
lated by Fulazzaky, [20] are ready to distinguish between
the mechanics of external and internal mass transfer for the
Table 4  Calculated parameters from Thomas model
Flow rate Concentra- KTh q0 R2
(mL ­min−1) tion (mg ­L−1) (mL ­min–1 mg–1) (mg ­g–1)
4 20 6.12 × 10–2 23.04 0.9287
50 2.49 × 10–2 53.98 0.8938
100 8.56 × 10–3 90.01 0.8563
6 50 1.97 × 10–2 70.54 0.8788
8 50 1.43 × 10–2 101.14 0.8637

Table 3  Calculated coefficients from Adam–Bohart model Table 5  Obtained results from Yoon–Nelson model
2
Flow rate Concentra- KAB N0 R Flow rate (mL Concentration kYN τ R2
(mL ­min−1) tion (mg ­L−1) (L m
­ in–1 mg–1) (mg ­L–1) ­min−1) (mg ­L−1) (L ­min–1) (min)

4 20 5.22 × 10–4 1651.48 0.8953 4 20 1.22 × 10–2 459.15 0.9288

50 2.15 × 10–4 3890.14 0.8396 50 1.24 × 10–2 429.19 0.8959
100 6.39 × 10–5 7697.47 0.7704 100 8.56 × 10–3 358.95 0.8663
6 50 1.52 × 10–4 5694.29 0.7795 6 50 9.16 × 10–3 374.70 0.8708
8 50 8.44 × 10–5 5651.17 0.7122 8 50 7.15 × 10–3 263.46 0.8437

13

sorption of single sorbate, which is foremost importance in
the continuous column process. The global mass transfer
phenomena combine, transporting a solute from the aqueous
phase to film zone (film mass transfer, FMT) and subsequent
diffusion towards sorbent pores, known as porous diffusion
(PD). Experimental results show that the B values and β
values varied with the concentration of Nickel(II) ions in
the column system (Table S1, supplementary data), as the
concentration gradient was the significant factor to diagnose
the above processes differently.
The diverse rate of global mass transfer (GMT) was rep-
resented by the variation of [­ kLa]g values in Fig. 5a. This
could be shown that the value of ­[kLa]g diminished rapidly
at the very beginning of the process corresponding to the C
­ s/
Fig. 5  Variation of a global mass transfer coefficients, b film mass transfer coefficients and c porous mass transfer coefficients
13
Journal of Polymers and the Environment
C0 ratio of ~ 8%. This may be related to the fast interaction
affinity of metal ions towards active binding sites of Biocom-
posite, thereby immediate decreasing signal was noted [26,
37]. Afterward, the rate was decreased gradually towards a
steady-state of GMT due to the inhabiting of Nickel(II) ions
to accessible sites. The detail clarification of data illustrates
that the magnitudes of ­[kLa]g remained 0.7039, 0.5023 and
0.4161 min−1 for influent metal ion concentration of 20, 50
and 100 mg ­L−1, respectively while ­Cs/C0 ratio resulted in
merely 12%. In subsequent process, the declination of ­[kLa]g
value exhibited to 0.0618, 0.0516 and 0.0488 min−1at around
80% ratio of C
­ s/C0. However, the initial phase involved in the
quick fixation of metal ions on active binding sites was not
responsible for mass transfer resistance. Suggestively, the
Journal of Polymers and the Environment
mass transfer resistance in this phase was controlled either
by film diffusion or intra-particle diffusion or both the pro-
cesses [20].
The rate of FMT represented as [­ kLa]f was varied with
increasing ­Cs/C0 ratio. The relevant results are depicted in
Fig. 5b. As observed, the peak of [­ kLa]f decreased sharply at
the very beginning with a ­Cs/C0 ratio of 3% for 100 mg ­L−1
and almost 12% and ~ 8% for 20 and 50 mg L ­ −1 metal ion
concentration, respectively. This phenomenon can be illus-
trated by the fact that enhanced accessibility to large surface
area and more active binding sites on the Biocomposite ren-
dered the initial phase of Nickel(II) sorption very swift [20,
26]. Therefore, FMT was not responsible for the resistance
of mass transfer for that phase of metal sorption on sorbate.
Further increase in ­Cs/C0 ratio, control of mass transfer was
feasible as the value of ­[kLa]f decreased progressively till the
end. Consequently, the surface of composite beads seems
to be covered by a thin film layer of the Nickel(II) ions as
evident from SEM analysis.
Pore diffusion coefficients (­ [kLa]d) were also evaluated
from the above-mentioned equation (Eq. 18). The resultant
data as displayed in Fig. 5c shows the initial convex nature
of the graph at 3% and ~ 8% and 12% C ­ s/C0 ratio for 100 mg
­L−1 and 50 and 20 mg ­L−1, respectively. It may be consid-
ered that the resistance of mass transfer was reliant on PD to
an early stage. This is because metal ions took a long time
to arrive at deeper acceptor sites within pores compared to
its forceful movement from the bulk aqueous solution to the
film zone. After that, a gradual descend was observed with
an increase in ­Cs/C0 ratio. This curvature revealed a similar
declining trend as observed for ­[KLa]g and ­[kLa]f. Hence, this
can be articulated that both FMT and PD were responsible
for the resistance of mass transfer at later stages [20, 26, 37].
Regeneration Study
Reusing experiments was accounted for not only to recover
the sorbed metal but also focused on economic develop-
ment [16]. In this context, the desorption step was consid-
ered prior to forward the Biocomposite beads into the next
cycle. 0.1 M HCl proved to be a superior eluant that was
used for this purpose. The results reveal that five repetitive
adsorption–desorption cycles could be conducted with an
adequate metal removal efficiency of prepared Biocompos-
ite (Fig. 6). Nickel(II) was also recovered to the extent of
∼92% during six cycles. However, as increasing the num-
ber of cycles, the metal sorption efficiency of Biocomposite
was reduced to some extent. This decreasing performance
may be related to the decomposition of active binding sites
present on the composite surface due to prolonged acid treat-
ment as reported by the researchers [1, 38]. However, the
principles followed here were proficient utilization of eco-
friendly resources with compatible regeneration properties,
Fig. 6  Reusing efficiency of biocomposite for the removal of
Nickel(II) in continuous packed bed column: ± SD shown by the error
bar
finding beyond 92% in metal recovery even after six con-
secutive cycles.
Treatment of Simulated Wastewater
by Biocomposite
Nickel plating industrial wastewaters not only contains
Nickel(II) but also have a mixture of other heavy metals
like chromium, zinc, copper along with hazardous ani-
ons such as sulfate, chloride, and cations. However, the
Nickel(II) concentration in the discharging effluent var-
ies from industry to industry [39, 40]. In this experiment,
simulated effluent composed by Nickel(II) with auxiliary
contaminants shown in Table S2 (supplementary data) was
considered as a feed solution in the column experiment. The
resultant data revealed a sorption capacity of 77.53 mg g−1
at the point of saturation with the percentage removal of
75.08%. Satisfactory performance of prepared Biocompos-
ite was established for removing Nickel(II) since the mag-
nitude of hindrance exerted by auxiliary contaminants in
the feed solution was found to be rather insignificant. The
experimental kinetic data were analyzed in accordance with
Adam-Bohart, Thomas and Yoon-Nelson models. The calcu-
lated parameters are represented in Table S3 (supplementary
data), establishing the pertinence of both Thomas and Yoon-
Nelson models. Furthermore, the results of mass transfer
kinetics show that porous diffusion was responsible for the
resistance of mass transfer in the initial phase (~ 7% of C­ s/
C0 ratio) and the subsequent process was controlled by both
film transfer and pore diffusion (Fig. 7). The results were in
greater corroboration with the outcomes of the monome-
tallic system. The performance of this packed bed column
13

Fig. 7  Study on mass transfer kinetics for the removal of Nickel(II)
from simulated wastewater in a continuous packed bed column
system proved its prospect in treating real-time large scale
industrial effluent.
Conclusions
The present study inferences the successful employment of
eco-friendly Biocomposite bead prepared from the mutated
bacterial cell with alginate for removing Nickel(II) from
monometallic as well as simulated wastewater in a packed-
bed column reactor. The results observed are only based on
specific settings of the experiments. Maximum adsorption
(~ 54 mg g−1) on a 50 mg ­L−1 metal solution was observed
within the highest bed depth of 25 cm and a low flow rate of
4 mL min−1. Analysis of Breakthrough curves with differ-
ent kinetic models established pertinence of Yoon–Nelson
model and Thomas model in characterizing the adsorption
pattern in continuous mode. Principal interest focused on the
evaluation of fractional mass transfer kinetics in the superior
way as to scale up the process to an actual industrial column.
The developed mass transfer models employed in this study
are facile to assess the relationship between global, external
and internal mass transfer, attributing both qualitative and
quantitative measures of varying mass transfer coefficients
with respect to the percentage of outflow. Accordingly, the
resistance of mass transfer in the initial stage was controlled
by porous diffusion prior to the proportion of outflow of
3%, ~ 8% and 12%, followed by both film mass transfer and
porous diffusion for 100, 50 and 20 mg L ­ −1, respectively.
Hydroxyl, carboxyl, amide and methyl groups of compos-
ite played a key role in the binding of Nickel(II) through
complexation or chelation, and electrostatic interaction as
indicated by FTIR analyses. Desorption was successful and
13
Journal of Polymers and the Environment
Nickel(II) was recovered more than 92% during six cycles.
This developed Biocomposite was also applied in treating
the simulated wastewater, addressing its immense potential
to remove Nickel(II) from real wastewater. Hence, this study
speaks new insight into mass transfer mechanisms and sca-
lar enhancement of wastewater treatment. Future directions
may also take into account addressing problems with actual
industrial effluents comprising of multiple pollutants and
needs thorough investigations for the applications of this
technology.
Acknowledgements  Authors gratefully acknowledge to University
Grants Commission (UGC), Government of India for providing the
research fund.
Compliance with Ethical Standards 
Conflict of interest  There is no conflict of interest on behalf of all au-
thors.
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