Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 153 (2016) 298–314

Contents lists available at ScienceDirect

Spectrochimica Acta Part A: Molecular and Biomolecular

Spectroscopy
journal homepage: www.elsevier.com/locate/saa

Application of granular activated carbon/MnFe2O4 composite

immobilized on C. glutamicum MTCC 2745 to remove As(III) and As(V):
Kinetic, mechanistic and thermodynamic studies
M.S. Podder ⁎, C.B. Majumder
Department of Chemical Engineering, Indian Institute of Technology, Roorkee, Roorkee 247667, India

a r t i c l e i n f o a b s t r a c t

Article history: The main objective of the present study was to investigate the efficiency of Corynebacterium glutamicum MTCC
Received 16 May 2015 2745 immobilized on granular activated carbon/MnFe2O4 (GAC/MnFe2O4) composite to treat high concentration
Received in revised form 7 July 2015 of arsenic bearing wastewater. Non-linear regression analysis was done for determining the best-fit kinetic
Accepted 11 August 2015
model on the basis of three correlation coefficients and three error functions and also for predicting the param-
Available online 24 August 2015
eters involved in kinetic models. The results showed that Fractal-like mixed 1,2 order model for As(III) and
Keywords:
Brouser–Weron–Sototlongo as well as Fractal-like pseudo second order models for As(V) were proficient to
Arsenic provide realistic description of biosorption/bioaccumulation kinetic. Applicability of mechanistic models in the
Wastewater current study exhibited that the rate governing step in biosorption/bioaccumulation of both As(III) and
Simultaneous biosorption and bioaccumulation As(V) was film diffusion rather than intraparticle diffusion. The evaluated thermodynamic parameters ΔG0,
Kinetic ΔH0 and ΔS0 revealed that biosorption/bioaccumulation of both As(III) and As(V) was feasible, spontaneous
Mechanistic and exothermic under studied conditions.
Thermodynamic © 2015 Elsevier B.V. All rights reserved.

1. Introduction1 maintaining a good quality of fresh water resources, this wastewater

Arsenic is a well-known carcinogen, which is considered as one of
the world's most hazardous chemicals [1]. It is a common naturally
occurring element in nature and is a major pollutant of water bodies.
It can be originated in the earth's crust, marine and ground water as
well as in the organic world. It is mobilized through a combination of
natural processes, such as biological activity, volcanic emissions and
weathering reactions [2,3] other than through a variety of anthropogen-
ic activities including petroleum refining, gold mining, non-ferrous
smelting, electricity generation, treating wood, producing electronic
devices and glass, combustion of fossil fuel in power plants, manufactur-
ing copper and other metals, the usage of arsenical herbicides and
pesticides and producing agricultural fertilizers [4–6]. Copper smelting
creates a huge volume of wastewater containing large amounts of inor-
ganic compounds, such as heavy metals like lead, copper, zinc, iron,
cadmium, bismuth, etc. and highly carcinogenic metalloid like arsenic
species and poses a serious threat towards man and the flora and
fauna of our ecosystem contaminating the natural water tables (ground
water and surface water) in the vicinity. In copper smelting wastewater
concentration of arsenic is as high as 1979 mg/L [7]. With the aim of
⁎ Corresponding author.
E-mail addresses: mou.chem11@gmail.com (M.S. Podder), cbmajumder@gmail.com
(C.B. Majumder).
1
GAC/MnFe2O4 composite (MGAC).
must be treated so that the water can be reverted to the ecosystems.
The anthropogenic discharge of heavy metals makes public health com-
plications because of their toxicity, non-biodegradability and persis-
tence in the environment. Billions of people are affected by lethal
effect of arsenic in Bangladesh and West Bengal in India [2,8,9]. Arsenic
ions exist in ground and surface waters in both organic and inorganic
forms, the inorganic species being the major ones. It may exist both in
+ 3 (Arsenite (As(III))) and + 5 (Arsenate (As(V))) oxidation states
depending on the prevailing pH and redox conditions. As(III) is more
toxic in biological systems than As(V) [10].
Although arsenic is poisonous to animals and plants, inorganic arse-
nic species are robust carcinogenic for humans [11]. The human
poisonousness of arsenic varies from skin lesions to cancer of the lung,
kidney, stomach, liver and brain. Intake of arsenic causes disturbance
of nervous system functions and can lead to death [12]. Because of
these effects, the maximum contaminant level (MCL) of arsenic in
drinking water has been revised to 10 μg/L from 50 μg/L by the World
Health Organization (WHO) in 1993 [13] and the European Commission
in 2003 [14].
Conventional methods for removing As(III) and As(V) ions from
water and wastewater include oxidation/precipitation [15,16], Fe-
electrocoagulation/co-precipitation [17,18], reverse osmosis and
nanofiltration [19,20], ion-exchange resin [21,22], coagulation–
microfiltration [23] and adsorption [9,24]. However few drawbacks of
these methods have been observed, such as operational complexity,

http://dx.doi.org/10.1016/j.saa.2015.08.022
1386-1425/© 2015 Elsevier B.V. All rights reserved.
 M.S. Podder, C.B. Majumder / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 153 (2016) 298–314
the discarding of the residual metal sludge, high capital and operational
cost, low efficiency and other complications and are not appropriate for
small-scale industries [25,26] which has urged for an alternative
process. So there is an emergent requirement for the improvement of
unique, effective, eco-friendly and cost effective approach for the
remediation of the environmental contaminants.
In recent times the researchers have focused on biofilms in the arena
of bioremediation of heavy metals. The term ‘biofilm’ was invented and
defined by Costerton et al. [27]. Biofilms are mainly clusters of microbial
cells that are attached to a number of various surfaces, such as living
tissues, medical devices, natural aquatic and soil environments or
industrial or portable water piping systems [28,29]. It can be demarcat-
ed as an aggregation of algae, protozoa, bacteria and fungi surrounded
in a matrix including a mixture of polymeric compounds, mainly poly-
saccharides commonly stated as extracellular polymeric substances
(EPS). Microbial community has been observed to be protected from
environmental stresses using biofilms [28,30,31].
Bacteria can create macromolecules, recognized as EPS which is vital
in the development of biofilms [32–34]. ESP mainly consists of
polysaccharides, lipids, proteins, humic substances or nucleic acids
which comprise numerous functional groups for example the phospho-
ric, hydroxyl, amine and carboxyl groups [32,35]. Among various
functions of ESP in biosorption processes, the most important ones are
adhesion to cell surfaces and accumulation of elements from the
environment [35,36]. However, the batch adsorption of contaminants
and probable withdrawing from the reactor are two main difficulties
of biofilm that decrease the efficiency and cause operational prob-
lems [35,37,38]. Thus a supported media for biofilm can be beneficial
to overcome the above difficulties. Numerous natural and synthetic
materials have been employed as supporting materials for bacterial
biofilms. Among the many media, materials with a porous structure
and high adsorption affinity to contaminants and biofilm would be a
proper substitute.
In the heterogeneous systems, the choice of the support is definitely
very vital for the development of a good catalyst and activated carbon
(AC) has been mainly utilized for this purpose since the 1970s [39].
Owing to its high surface area, special surface reactivity and porous
structure, activated carbon, it can efficiently adsorb gases and com-
pounds dispersed or dissolved in liquids [40–43]. In the water treatment
arena, activated carbon is widely utilized as an adsorbent for the
removal of arsenic [24,44]. This adsorbent is highly inert and thermally
stable and it can be utilized over a wide pH range [45] and moreover,
activated carbon can easily be functionalized [46].
MnFe2O4, a familiar soft material, has outstanding chemical stability
and frequently controls the concentration of free metal and organic
matter in water or soil through adsorption reactions [47–49]. GAC is
rich in hydroxyl groups. The hydroxyl groups can offer chemical
reaction sites and adsorb iron and manganese ions to grow MnFe2O4
particles. In this present research the GAC has been used as template,
MnFe2O4 particles have been grown and a composite of GAC and
MnFe2O4 particles has been made. The reason may be that the template
can prevent MnFe2O4 particles from aggregating in adsorption process
and enhance the effective adsorption area, resulting in the highly en-
hancement of adsorption capacity. A similar finding has been found
out for the loading of Fe3O4 on pure wheat straw [50]. The composite
has BET high surface area compared to GAC. GAC can also remove
arsenic, but to increase the adsorption capacity of GAC, it was modified
with MnFe2O4.
Zhang et al. have reported that bimetal oxide magnetic nano-
materials (MnFe2O4 and CoFe2O4) were synthesized and characterized
and used for scavenging of As(III) and As(V) [51]. Parsons et al. reported
the capability of the Fe3O4, Mn3O4, and MnFe2O4 nanophases for scav-
enging As(III) and As(V) from aqueous solutions [52]. Oliveira et al.
have synthesized an activated carbon/iron oxide magnetic composites
for the adsorption of volatile organic compounds such as chloroform,
phenol, chlorobenzene and drimaren red dye from aqueous solution
299
[43]; Zhang et al. have prepared CuFe2O4/activated carbon to adsorb
and catalytically degrade acid orange II [45]; Yang et al. have employed
magnetic Fe3O4/activated carbon nanocomposite particles for the
removal of methylene blue from aqueous solution [53]; Gong et al.
have synthesized magnetic multi-wall carbon nanotube nanocomposite
as adsorbent for the removal of cationic dyes [54].
Corynebacterium glutamicum MTCC 2745 species is of specific
attention due to its high capability for bioremediation. Bacteria can
depollute arsenic wastewater, by accumulation outside the cells and/
or biosorption of the ion on their surface [55] as was defined earlier
for Escherichia coli [56] and Ralstonia eutropha [57]. C. glutamicum
MTCC 2745 does not have an outer membrane, it contains a typical
cell-surface S-layer formed by a protein encoded by cspB [58].
Certainly biosorbents are considerably efficient for scavenging heavy
metals from aqueous phase. Consequently the main aim of the present
investigation was to design a proficient metal ion eliminating system
mediated by immobilized bacterial cells. The removal system of metal
ion designed in the present investigation was called as simultaneous
biosorption and bioaccumulation (SBB) system.
Arsenic removal efficiency of bacteria improves when it is
immobilized on a solid support like GAC [6]. Mondal et al. reported
the bio-removal of arsenic from contaminated water by using
R. eutropha MTCC 2487 and activated carbon in a batch reactor. They
observed simultaneous adsorption bioaccumulation (SABA) when
fresh GAC was used as supporting media for bacterial immobilization
[59]. Mishra et al. has designed the simultaneous biosorption and bioac-
cumulation (SBB) batch system for the removal of Zn(II) ion from liquid
phase. Cedrus deodara sawdust was used as carrier to immobilize Zinc
sequestering bacteria “VMSDCM” accession number HQ108109 [60].
In the present investigation, GAC/MnFe2O4 composite having the
benefits of desired adsorption capacity could be used as an economical
and promising carrier because of its higher porosity, surface area, easy
obtainability and cost efficiency and C. glutamicum MTCC 2745 could
be used for the formation of biofilm due to its arsenic resistance proper-
ty. Finally the immobilized bacterial cells were used to remove a wide
range of arsenic.
The goals of the current research, divided into six parts, were 1) to
characterize the prepared fresh adsorbent (GAC/MnFe2O4 composite)
and adsorbent attached with biofilm before and after metal loading
with SEM-EDX, 2) to examine the influence of contact time in addition
to temperature for removal of As(III) and As(V) from synthetically
prepared copper smelting wastewater, 3) to estimate the kinetics and
mechanism of present biosorption/bioaccumulation process, 4) to
investigate the thermodynamics of biosorption/bioaccumulation pro-
cess to find the mechanism, 5) to study the impact of initial arsenic con-
centration onto the kinetics of biosorption/bioaccumulation and 6) to
explore the effect of temperature onto the kinetics of biosorption/
bioaccumulation.
2. Materials and methods
2.1. Materials
All the chemicals and reagents were of analytical reagent grade and
utilized devoid of additional refinement. Standards, matrix modifier and
wash solutions were prepared by deionised double distilled water. The
stock solutions of As(III) (1000 mg/L) and As(V) (1000 mg/L) were
prepared by dissolving 1.734 g of sodium arsenite (NaAsO2) and
4.16 g of sodium arsenate (Na2HAsO4, 7H2O), purchased from Himedia
Laboratories Pvt. Ltd. Mumbai India, in 1 L of double distilled water,
respectively. All other necessary chemicals used in the experiments,
were purchased from Himedia Laboratories Pvt. Ltd. Mumbai India.
Glassware utilized for experimental purposes was washed in 10% nitric
acid and rinsed with deionised water for removing any probable
interference by other metals.
300 M.S. Podder, C.B. Majumder / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 153 (2016) 298–314
2.2. Microorganism and growth medium
The microorganism utilized was the arsenic-resistant bacterium
C. glutamicum MTCC 2745 (Microbial Type Culture Collection and
Gene Bank (MTCC), Chandigarh, India). Culture media was prepared
as per the guidelines of microbial type cell culture (MTCC). Composition
of growth medium and cultivation conditions are exhibited in Table 1.
2.3. Acclimatization
The revived culture was initially grown in MTCC prescribed growth
media in a 250 mL round bottom flask tightly closed with cotton plug
as follows:
C. glutamicum MTCC 2745 was cultivated in 250 mL flask containing
100 mL of the growth media with As(III) and As(V). The cultures were
acclimatized to As(III) and As(V) individually by exposing the culture
in a series of shake flasks.
The bacterial inoculum was prepared by transferring a loop full of
bacterial culture from the nutrient agar tubes to the flask containing
sterilized growth media, incubated at 30 °C for 24 h with moderate ag-
itation in an incubator cum orbital shaker. Then the acclimatization of
C. glutamicum MTCC 2745 in arsenic environment was carried out as
follows:
After 24 h the synthetic medium in the flask had turned milky
specifying significant bacterial growth in the flask. Appropriate amount
of arsenic (As(III) or As(V)) was added into the flask having 100 mL
sterilized growth media to acquire a concentration of 50 mg/L of arsenic.
Initially the growth of C. glutamicum MTCC 2745 was inhibited and the
growth started after 2 h. After 24 h of incubation at 30 °C, 5 mL of the
arsenic resistant bacterial inoculum was periodically added in a series
of 250 mL flasks containing 100 mL of arsenic containing sterilized
growth media (As(III) or As(V) concentration, 100, 200, 500, 800,
1000, 1200, 1500 and 1800 mg/L) under sterile conditions in a laminar
hood chamber. After 24 h later, another fresh growth media (As(III) or
As(V) concentration, 2000 mg/L) was also inoculated with 5 mL of the
last culture (As(III) or As(V) concentration, 1800 mg/L) to ensure that
the bacteria was already adapted to both As(III) or As(V). For inoculum,
a further sub culturing was performed and all the inoculum transfers
were done in exponential phase (OD value ∼1 at 600 nm).
2.4. Methods
2.4.1. Adsorbent preparation
Granular activated carbon (GAC) was washed systematically with
double distilled water and oven dried at 105 °C for 4 h. 25 g of dried
GAC was added into 500 mL conical flask containing 250 mL of 0.5 M
HCl solution; next was shaken for 4 h at 120 rpm at 25 °C. Then the
mixture was left overnight. The mixture then was filtered to separate
GAC which were repeatedly washed with double distilled water to
provide neural pH. Then the adsorbents were dried at 110 °C for 3 h
for removing moisture, cooled to room temperature and kept in plastic
bags for further use.
GAC/MnFe2O4 composites were prepared by chemical coprecipitation
method with few modifications [61]. In this procedure, a fixed quantity of
acid treated GAC was mixed into 200 mL solution containing dissolved
ferric (III) chloride (FeCl3) (0.05 mol) and manganese (II) chloride
Table 1
Composition of growth medium and cultivation conditions.
Component (g/L) or condition
Beef extract 1.0
Yeast extract 2.0
Peptone 5.0
NaCl 5.0
pH 7.0
Temperature (°C) 30
(MnCl2) (0.025 mol) at room temperature. The amount of acid treated
GAC was fixed for acquiring GAC/MnFe2O4 mass ratios of 2:1. The solution
temperature was raised to 60 °C under energetic magnetic stirring and
then 5 mol/L of NaOH solution was added drop wise to the above mixture
till the pH of the solution attained 11. Thereafter next 1 h agitation was
carried on. Then the suspension was heated in a water bath at 100 °C
for 4 h. After cooling, the prepared composite was constantly washed
with double distilled water for eliminating the contaminations (e.g.,
Na+, Cl−) accompanied with the processes. Next as-prepared composite
was collected from the washed solution by filtering the mixture and
then was oven dried at 110 °C. The reaction ionic equation [62] is as
follows:
Mn2þ þ 2Fe3þ þ 8OH− →MnðOHÞ2 ↓ þ 2FeðOHÞ3 ↓→MnFe2 O4 þ 4H2 O
ð1Þ
MnFe2 O4 þ GAC→GAC–MnFe2 O4 : ð2Þ
2.4.2. Immobilization of microbial cells onto the adsorbent
To immobilize C. glutamicum MTCC 2745 onto the prepared GAC/
MnFe2O4 composite, initially 90 mL culture media was inoculated
with 5 mL of bacterial suspension of C. glutamicum MTCC 2745 from
both As(III) and As(V) acclimatized 24 h old culture. The flasks were
incubated at 30 °C for another 24 h with moderate shaking at
120 rpm. Then immobilization of bacterial cell was performed by adding
weighed amount of prepared GAC/MnFe2O4 composite to the above
suspension containing 24 h old culture. Then the flasks were again incu-
bated at 30 °C for next 24 h with moderate shaking at 120 rpm. Bacterial
cell immobilization was established by observing a small amount of
bacterial treated GAC/MnFe2O4 composite through scanning electron
microscopy.
2.4.3. Characterization
The measurements of SEM were done for observing the surface
morphologies of the GAC/MnFe2O4 composite attached with biofilm
before and after biosorption/bioaccumulation process (SEM; LEO
electron Microscopy, England). The images were taken with an acceler-
ator voltage = 15 kV and an emission current = 100 μA by the Tungsten
filament.
2.4.4. Batch experimental studies and analytical methods
A medium with 1.0 g/L of beef extract and 2.0 g/L of yeast extract,
5.0 g/L of peptone and 5.0 g/L of NaCl was used for the growth of the
microorganism. The media was sterilized at 121 °C for 15 min, cooled
to room temperature, inoculated with bacteria and kept at 30 °C for
24 h with moderate stirring (120 rpm) in an incubator cum orbital
shaker. All biosorption/bioaccumulation experiments were done by
shaking optimum adsorbent dose of 0.9 g/L of the GAC/MnFe2O4
composite with 100 mL of C. glutamicum MTCC 2745 bacterial
suspension as a test solution and required amount of arsenic (As(III)
or As(V)) was supplemented to give final concentration As(III) or
As(V) of requisite concentration, at an optimum initial pH value around
7.0 and at a preferred temperature in an incubator cum orbital shaker
(REMI Laboratory instruments) at 120 rpm. 1.0 N NaOH and 1.0 N HCl
solutions were used to adjust the initial pH of the solution using a digital
pH meter (HACH® India).
To investigate the biosorption/bioaccumulation kinetics, batch ex-
periments were conducted by contacting an optimum adsorbent dose
(0.9 g/L) of the GAC/MnFe2O4 composite with As(III) or As(V) solution
of a fixed concentration (50 mg/L) at a constant temperature (30 °C)
at a range of contact time (5–500 min).
To examine the impact of temperature onto biosorption/bioaccumu-
lation, batch experiments were done by contacting an optimum adsor-
bent dose (0.9 g/L) of the GAC/MnFe2O4 composite with As(III) or
As(V) solution of a fixed concentration (50 mg/L) at an optimum
 M.S. Podder, C.B. Majumder / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 153 (2016) 298–314 301

contact time of 220 min at a range of temperatures (20, 25, 30, 40, 45 The adjusted coefficient of determination ðR2 Þ which generally takes
and 50 °C). into account the number of variables and sample size in the model, is
To study the influence of initial concentration onto the kinetics of deliberated superior to the coefficient of determination (R2), since it
biosorption/bioaccumulation of both As(III) and As(V) by revises the overestimation by R2 [68]. While dealing with small samples,
C. glutamicum MTCC 2745 immobilized on GAC/MnFe2O4 composite, specifically it is more exact than R2.
all batch experiments were performed by agitating 0.9 g/L of GAC/
MnFe2O4 composite with 100 mL of C. glutamicum MTCC 2745 bacterial
suspension as a test solution supplemented with required amount of ar- 3.2. Adsorption kinetic modelling
senic (As(III) or As(V)) to give final concentration As(III) or As(V) of 50,
100, 500, 1000, 1500 and 2000 mg/L at a constant temperature (30 °C). With the purpose of inspecting the dynamic biosorption behaviour
To examine the effect of temperature onto the kinetics of biosorption/ of As(III) and As(V) onto GAC/MnFe2O4 composite i.e., governing the
bioaccumulation of both As(III) and As(V) by C. glutamicum MTCC 2745 current biosorption process mechanisms and the probable rate limiting
immobilized on GAC/MnFe2O4 composite, 0.9 g/L GAC/MnFe2O4 compos- steps, such as mass transport and/or chemical biosorption processes,
ite was added to each round bottom flasks containing 50 mg/L kinetic models have been utilized for fitting the experimental data.
C. glutamicum MTCC 2745 culture media as a test solution of As(III) or Fourteen kinetic models (Table 2) were employed in the current
As(V). Experiments were conducted at three temperatures (30, 40 and research supposing that concentrations on the adsorbent surface are
50 °C) by shaking the flasks. equal to the measured concentrations.
The samples were withdrawn from the flasks through filtration by There are many models for kinetics of biosorption at the interface of
Whatman Filter paper (Cat No 1001 125) (Remi Instruments ltd., solid/solution. Fractional power model (FP), pseudo first order (PFO)
Mumbai India) after fixed contact time for thermodynamic studies as and pseudo second order (PSO) are common empirical models, howev-
well as at predetermined time intervals and then centrifuged at er their major drawback is that they may simply define the kinetics of
10,000 rpm for 10 min for kinetic studies, a portion of filtrate was adsorption at some restrictive situations [69]. Elovich is a two paramet-
diluted with HNO3 solution (10%, v/v). The filtrate was analysed for ric semi-empirical model and fractional power (FP), Ritchie second
determination of arsenic concentration using ThermoFisher Scientific order and exponential (EXP) kinetic models are two parametric empir-
iCE 3000 Series AA graphite furnace atomic absorption (GFAA) ical models to analyse kinetic data at near to equilibrium. As well other
spectrometer (detection limit 20 μg/L). empirical models for instance Avrami, modified pseudo second order
(MPSO) and mixed 1,2 order model (MOE) equations have been recom-
3. Theoretical background mended for modelling the adsorption kinetics at the interface of solid/
solution. These models are mainly three parametric equations.
With the goal of assessing biosorption capacity by mass balance, The prior kinetic models of adsorption at the interface of solid/solution
detailed as the amount of adsorbate molecules adsorbed per unit mass can be generalized by taking into consideration the Fractal-like methodol-
of biosorbent at time t (mg/g) was calculated as follows: ogy i.e., time dependence of adsorption rate coefficient. A physical
significance of the Fractal-like idea has been considered for adsorption
V kinetics onto surfaces of solid that is energetically heterogeneous. The
qt ¼ ðC o −C t Þ : ð3Þ
M Fractal-like study exhibits that the kinetics of adsorption at interface of
the solid/solution in a real system with various kinds of surface sites
The amount of adsorbate molecules adsorbed in terms of percentage and with various affinities for adsorption can be demarcated by a
was calculated as follows: Fractal-like methodology. Based on this study, the history of process can
influence the process besides the achieved rate coefficient of adsorption
ðC o −C t Þ
Re ð%Þ ¼  100 ð4Þ
Co Table 2
Kinetic adsorption models.
where C0 and Ct are arsenic concentrations at time 0 and t (mg/L), Sr. Kinetic model Equation
respectively, V is the volume of the solution (mL) and M is the mass of no.
biosorbent used (g). 1 Fractional power model (FP) qt = kFPtv
2 Pseudo first order model qt = qe(1 − exp(−kPFOt))
3.1. Determining adsorption kinetic parameters by non-linear regression (PFO)
3 Pseudo second order model ðq2 k
qt ¼ 1þðqe PSO
Þt
kPSO tÞ
e
(PSO)
The kinetic parameter sets are computed by non-linear regression
4 Elovich model qt ¼ ð2:3Þ  log ðtþ1 Þ− ð2:3Þ  log ðaE1bE Þ
because of the inherent bias causing after linearization. This offers a bE aE bE bE
nAV
5 Avrami model qt ¼ qe ð1−exp½−ðkAV tÞ Þ
mathematically laborious method to evaluate kinetic parameters utiliz-
6 Modified second order qt ¼ qe f1− ½β þk
1
0 g
ing the original kinetic equation [63–65]. Commonly Gauss–Newton model (MSO)
t 2R 2R

methods or Levenberg–Marquardt based algorithms [66,67] are 7 Ritchie second order model qt ¼ qe f1−½ 1
″ g
1þk2R t
utilized. The biosorption kinetic data of arsenic onto C. glutamicum 8 Exponential kinetic model qt = qe(ln[2.72 − 1.72 exp(−kEXP
′ t)])
MTCC 2745 immobilized on surface of GAC/MnFe2O4 composite were (EXP)
analysed by non-linear curve fitting analysis utilizing professional 9 Mixed 1,2 order model 1−expð−kMOE tÞ
qt ¼ qe 1− f expð−kMOE tÞ
2
(MOE)
graphics software package OriginPro (8.5.1 version) for fitting the 0
10 Fractal-like mixed 1,2 order qe ½1−expð−k1;0 t α Þ
kinetic models. qt ¼ 0
1− f eq expð−k1;0 t α Þ
model (FMOE)
The optimization method requires the selection of a Goodness-of-Fit 11 Fractal-like pseudo first ′ t α))
qt = qe(1 − exp(−kFPFO
Measure (GoFM) with the purpose of valuing the fitting of the kinetics order model (FPFO)
0
12 Fractal-like pseudo second q2 k tα
to the experimental data. In the present research, six GoFM (residual qt ¼ 1þe k0FPSOq α
PSO e t
order (FPSO)
sum of squares (SSE), reduced Chi-square test (reduced χ2), coefficient
13 Fractal-like exponential qt = qe ln[2.72 − 1.72 exp(−k‴Exptα)]
of determination (R2), adjusted R-square ðR2 Þ, R value (R) and Root-MSE (FEXP)
h i
14 Brouser–Weron–Sototlongo α −1=ðnBWS −1Þ
value) were employed for evaluating isotherm parameters utilizing the qt ¼ qe 1−ð1 þ ðnBWS −1Þðτn t
Þ Þ
BWS ;α
model (BWS)
OriginPro software by considering 95% confidence interval.
302 M.S. Podder, C.B. Majumder / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 153 (2016) 298–314
is a function of time (the details of adsorption kinetic modelling are
provided in the Supplementary materials).
3.3. Adsorption mechanistic modelling
The scavenging of adsorbate species from the liquid by the solid
phase is taken place in three successive steps as follows [70–72]. The
three stages tangled in the mechanism of biosorption process are as
follows:
(i) Firstly the adsorbate mass transfer from the aqueous phase onto
the biosorbent surface i.e., film diffusion or surface diffusion
takes place;
(ii) Secondly internal diffusion of adsorbate via either a pore
diffusion model or homogeneous solid phase diffusion model
i.e., particle diffusion occurs; and
(iii) The third stage is the biosorption of adsorbate onto the surface
sites. Due to its very fast in nature, it cannot be considered for
the rate determining step.
So as to know the rate controlling step, the following different
models were applied using the experimental data of kinetic study (the
details of adsorption mechanistic modelling are provided in the
Supplementary materials).
3.4. Adsorption thermodynamic modelling
The entropy and Gibbs free energy parameters should be measured
with the intention of deciding if the processes will happen spontaneous-
ly. Thermodynamic parameters for example ΔG0, ΔH0 and ΔS0 can be
calculated utilizing equilibrium constant while the temperature varies
(the details of adsorption thermodynamic modelling are provided in
the Supplementary materials).
3.5. Adsorption activation energy
The Arrhenius equation to calculate adsorption activation energy is
given as follows [73,74]:
Ea
ln kPSO ¼ − þ lnA:
RT
From the slope of ln kPSO versus 1/T plot, the value of Ea can be
calculated. The magnitude of activation energy may provide knowledge
about the nature of adsorption. Chemical adsorption is definite plus
includes forces much stronger than in physical adsorption. The activa-
tion energy for chemical adsorption is of the same magnitude as the
heat of chemical reactions. There are two types of chemical adsorption
are faced; activated (less regularly) and non-activated. Activated
chemical adsorption refers that the rate differs with temperature
according to finite activation energy (between 8.4 and 83.7 kJ/mol) in
the Arrhenius equation (high Ea). But chemisorption happens quite
fast in some systems, signifying the activation energy is near zero. This
is called non-activated chemisorption [75].
4. Results and discussion
4.1. Effect of contact time
Fig. 1 represents the effect of contact time on the % removal of As(III)
and As(V) using immobilized bacterium. The time important to reach
equilibrium was 220 min for removal of both As(III) and As(V). Further
increase in time, no remarkable improvements was got in eliminating
arsenic. So, 220 min contact time was taken for further biosorption/bio-
accumulation studies.
Fig. 1. Effect of contact time on As(III) and As(V) removal in SBB studies (Co: 50 mg/L; T:
30 °C; pH: 7; M: 0.9 g/L) (error bars represent means ± standard errors from the mean
of duplicate experiments).
From the consequences it is further clear that in all the systems, the
saturation time does not depend on the adsorbate concentration in the
solution. The variation in the rate of removal might be because of the
fact that primarily all sites of adsorbent surfaces attached with biofilm
are easily accessible and also the concentration gradient of adsorbate
is very high. At optimum pH, the fast kinetics of interaction of
adsorbate–adsorbent attached with biofilm might be approved to
raise availability of the active sites of the adsorbent surface attached
with biofilm. Thus the elimination of adsorbate was rapid in the early
stages and slowly lessens with the interval of time till equilibrium in
each case. The decline in elimination of metal ion at the later stage of
the process was because of the lowering of concentration of metal
ions [60]. Thus the curves obtained were single, smooth and continuous
leading to equilibrium and commended the probability of monolayer
coverage of the adsorbate onto the adsorbent surface attached with
biofilm [76].
4.2. Biosorption kinetic studies
ð5Þ
Data on the kinetics of adsorbate uptake is important to recognize
the optimum operating conditions for full scale batch process. As a
non-linearisable kinetic model and with the objective of comparing its
fitting capability to the previous considered models, a non-linear re-
gression analysis was accomplished to the fourteen adsorption kinetic
model. Table 3 shows the values of kinetic constants of all the models
for the biosorption/bioaccumulation of both As(III) and As(V) by
C. glutamicum MTCC 2745 immobilized on surface of GAC/MnFe2O4
composite. The results exhibited that there was no prominent relation-
ship between the kinetic data for both As(III) and As(V) (Fig. 2) with
low correlation coefficients and high error values advising that these
models (fractional power, pseudo first order, Elovich and exponential)
are not appropriate in the current case.
Since the values of correlation coefficients (R, R2 and R2) were almost
similar to each other in the kinetic study, so the best fit model was
mainly determined on the basis of error functions (SSE, reduced χ2
and Root-MSE).
On the basis of the lowest error values SSE (3.56104), reduced χ2
(0.09892) and Root-MSE (0.31451), the superior and perfect fitting of
the experimental outcomes was achieved using Fractal-like mixed 1,2
order (Fig. 2(a)–(b)) for As(III) among all the tested kinetic models.
The analysis of experimental data with Fractal-like mixed 1,2 order
model leads to various consequences such as adsorption rate is
enhanced by improving α, where f2 and k′1,0 have constant values,
 M.S. Podder, C.B. Majumder / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 153 (2016) 298–314 303

Table 3
Kinetic constants of studied models for As(III) and As(V) biosorption/bioaccumulation onto C. glutamicum MTCC 2745 immobilized on surface of GAC/MnFe2O4 composite.

Kinetic models Parameters Values for As(III) Values for As(V)

Fractional power kFP (mg/g min) 24.10939 25.46912

v 0.13204 0.13057
Reduced χ2 10.29217 8.90752
SSE 391.10243 338.48578
R 0.95295 0.96194
R2 0.90811 0.92533
R2 0.90569 0.92336
Root-MSE 3.20814 2.98455
Pseudo first order kPFO (1/min) 0.05776 0.0586
qe(PFO) (mg/g) 49.19755 51.49754
Reduced χ2 4.97144 6.94063
SSE 188.91467 263.74413
R 0.97756 0.97047
R2 0.95561 0.94182
R2 0.95445 0.94028
Root-MSE 2.22967 2.63451
Pseudo second order qe(PSO) (mg/g) 52.26883 54.64374
kPSO (g/mg min) 0.00185 0.00182
Reduced χ2 0.57964 0.79677
SSE 22.02645 30.2771
R 0.99741 0.99665
R2 0.99482 0.99332
R2 0.99469 0.99314
Root-MSE 0.76134 0.89262
Elovich aE (mg/g min) 93.11319 109.93941
bE (g/mg) 0.16391 0.15911
Reduced χ2 6.96123 5.77563
SSE 264.52684 219.47385
R 0.96843 0.97549
R2 0.93785 0.95158
R2 0.93621 0.95031
Root-MSE 2.63841 2.40325
Avrami kAV (1/min) 0.05808 0.05927
qe(Avrami) (mg/g) 50.82907 53.67186
nAV 0.58031 0.53086
Reduced χ2 0.93682 0.6842
SSE 34.66238 25.31546
R 0.99592 0.9972
R2 0.99186 0.99442
R2 0.99142 0.99411
Root-MSE 0.9679 0.82716
Modified second order qe(MSO) (mg/g) 52.28508 54.70328
β2R 1.00634 1.02072
k′2R (1/min) 0.09596 0.09743
Reduced χ2 0.59204 0.78224
SSE 21.90557 28.94301
R 0.99742 0.9968
R2 0.99485 0.99361
R2 0.99458 0.99327
Root-MSE 0.76944 0.88445
Ritchie second order qe(Ritchie) (mg/g) 52.26876 54.64339
k″2R (1/min) 0.09649 0.09928
Reduced χ2 0.57964 0.79677
SSE 22.02645 30.2771
R 0.99741 0.99665
R2 0.99482 0.99332
R2 0.99469 0.99314
Root-MSE 0.76134 0.89262
Exponential kEXP (mg/g min) 2.057292188 2.187552478
qe(EXP) (mg/g) 49.46603 51.77639
Reduced χ2 3.33754 4.74202
SSE 126.82661 180.19661
R 0.98499 0.97992
R2 0.9702 0.96025
R2 0.96942 0.9592
Root-MSE 1.82689 2.17762
Mixed 1,2 order kMOE (1/min) 0.000739696 0.000188491
qe(MOE) (mg/g) 52.07541 54.58995
f2 0.99236 0.9981
Reduced χ2 0.59588 0.81842
SSE 22.04744 30.28138
R 0.99741 0.99665

(continued on next page)

304 M.S. Podder, C.B. Majumder / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 153 (2016) 298–314

Table 3 (continued)

Kinetic models Parameters Values for As(III) Values for As(V)

R2 0.99482 0.99332
R2 0.99454 0.99296
Root-MSE 0.77193 0.90466
Fractal-like mixed 1,2 order qe(FMOE) (mg/g) 21.98568 54.4563
f2 0 0.90666
k′1,0 (1/min)α 0.11922 0.01453
α(FMOE) 0.6454 0.82064
Reduced χ2 0.09892 0.52563
SSE 3.56104 18.92274
R 0.99815 0.99791
R2 0.99631 0.99583
R2 0.996 0.99548
Root-MSE 0.31451 0.725
Fractal-like pseudo first order qe(FPFO) (mg/g) 50.82573 53.66859
k′FPFO (1/min)α 0.19142 0.22288
α(FPFO) 0.5809 0.53123
Reduced χ2 0.93684 0.68421
SSE 34.66312 25.31588
R 0.99592 0.9972
R2 0.99186 0.99442
R2 0.99142 0.99411
Root-MSE 0.96791 0.82717
Fractal-like pseudo second order qe(FPSO) (mg/g) 52.59856 55.98921
k′FPSO (g/mg min)α 0.00205 0.00255
α(FPSO) 0.95692 0.85316
Reduced χ2 0.57297 0.52004
SSE 21.19986 19.24144
R 0.99751 0.99788
R2 0.99502 0.99576
R2 0.99475 0.99553
Root-MSE 0.75695 0.72114
Fractal-like exponential qe(FEXP) (mg/g) 50.80382 53.63717
k″EXP (1/min)α 0.072089307 0.078429109
α(FEXP) 0.66737 0.61139
Reduced χ2 0.90569 0.66432
SSE 33.51062 24.57997
R 0.99606 0.99729
R2 0.99213 0.99458
R2 0.9917 0.99428
Root-MSE 0.95168 0.81506
Brouser–Weron–Sototlongo τnBWS,α (min) 33.32289 10.91125
qe(BWS) (mg/g) 52.44661 55.34186
nBWS 0.588 1.72463
α(BWS) 0.32741 0.76907
Reduced χ2 3.21353 0.52437
SSE 115.68691 18.87715
R 0.98632 0.99792
R2 0.97282 0.99584
R2 0.97055 0.99549

adsorption rate is increased when k′1,0 is increased when α and f2 have
constant values and for α = 1, the Fractal-like rate equation alter to the
corresponding classical form. The rate of adsorption was detected
reliant on rate of agitation and initial concentration of adsorbate
solution. Variations of agitation rate or initial adsorbate concentration
influences instantaneously on both α and k′1,0 parameters in kinetic
models. The value of α is reduced while rate of agitation or initial
adsorbate concentration are raised. k′1,0 is raised by increasing agitation
rate or initial adsorbate concentration.
Whereas for As(V), on the basis of the lowest error values SSE
(18.87715), Brouser–Weron–Sototlongo kinetic model fit well with
the experimental data compared to the other kinetic models, however
based on the lowest error values reduced χ2 (0.52004) and Root-MSE
(0.72114), the better and perfect demonstration of the experimental
results was accomplished using Fractal-like pseudo second order kinetic
model (Fig. 2) among all the well-known kinetic models. Following the
adsorption kinetic data with the Fractal-like pseudo second order model
specifies that the adsorption rate coefficient is a function of time; addi-
tionally the adsorption path on the active site varies with time [77].
Going to the theory behind the best fitting model (i.e., BWS), the
biosorption/bioaccumulation phenomenon of both As(III) and
As(V) onto C. glutamicum MTCC 2745 immobilized on surface of GAC/
MnFe2O4 composite would be ruled by chemisorption interactions
type, illuminating that the rate governing step might be chemical
adsorption including valency forces through exchange or sharing of
electrons between As(III) or As(V) anions and C. glutamicum MTCC
2745 immobilized on surface of GAC/MnFe2O4 composite. Also the
BWS model expresses another remarkable data which is the time
important to adsorb half the maximum amount (τnBWS,α).
As presented in Table 3, with respect to initial arsenic concentration,
33.32289 min and 10.91125 min (the lowest value) were enough to
C. glutamicum MTCC 2745 immobilized on surface of GAC/MnFe2O4
composite to achieve half of the As(III) and As(V) uptake capacities,
respectively, which is significant along with valuable parameter for
calculating the reaction speed.
As for the BSW model itself, it has a good fitting behaviour and more
implicitly, it expresses such quality data (i.e., adsorption capacity
nearest to experimental value, qe(BWS), and the time of half reaction,
 M.S. Podder, C.B. Majumder / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 153 (2016) 298–314
Fig. 2. Kinetic modelling of As(III) and As(V) biosorption/bioaccumulation onto the C. glutamicum MTCC 2745 immobilized on surface of GAC/MnFe2O4 composite (t: 5–500 min; Co: 50
mg/L; M: 0.9 g/L; pH: 7; T: 30 °C) (error bars represent means ± standard errors from the mean of duplicate experiments).
τnBWS,α) which are very esteemed aimed at industrial treatment design
purposes [78].
Based on low error values (SSE, reduced χ2 and Root-MSE) it can be
confirmed that other kinetic models, such as pseudo second order,
Avrami, mixed 1,2 order, modified second order, Ritchie second order,
Fractal-like pseudo first order, Fractal-like pseudo second order and
Fractal-like mixed 1,2 order, Fractal-like exponential and Brouser–
Weron–Sototlongo models also showed good fitting of biosorption/bio-
accumulation kinetic data for both As(III) and As(V) onto C. glutamicum
MTCC 2745 immobilized on surface of GAC/MnFe2O4 composite.
The value of low error values (SSE, reduced χ2 and Root-MSE) for
pseudo second order model forecasts that mechanism of biosorption/
bioaccumulation is chemisorption type.
The Avrami exponent (nAV) (0.58031 for As(III) and 0.53086 for
As(V)) is a fractionary number linked with the probable variations of
the adsorption mechanism that occurs throughout the adsorption
process. In place of following only an integer-kinetic order, the mecha-
nism of adsorption could follow multiple kinetic orders that are altered
throughout the contact of the adsorbate with the adsorbent. nAV is a
resultant of the multiple kinetic order of the adsorption procedure.
It is understood that the mixed 1,2-order rate equation is linear in
the Lagergren coordinates (i.e., it behaves like the first-order equation)
near to the equilibrium and somewhat in the initial portion of the
experiment. Precisely, we may conclude that it contains two linear
segments connected with a curved one. Actually, the second-order
equation shows linear behaviour in the initial portion of the experiment
also, though, the linear section is quite short. On the other hand MOE
may be treated as Langmuir equation for energetically homogeneous
surfaces or as purely empirical equation for energetically heterogeneous
surfaces.
The vital supposition of modified second order model was that a
number of surface sites, nR, are used by each adsorbate. It was supposed
that the pre-adsorbed stage occurred on C. glutamicum MTCC 2745
immobilized on surface of GAC/MnFe2O4 composite adsorption.
The vital supposition of Ritchie second order model was that one
adsorbate was adsorbed onto two surface sites. It was supposed that
the pre-adsorbed stage has not occurred on C. glutamicum MTCC 2745
immobilized on surface of GAC/MnFe2O4 composite adsorption. The
adsorbent surface coverage has been typically presumed to be zero.
In case of Fractal-like models (Fractal-like pseudo first order, Fractal-
like pseudo second order, Fractal-like exponential, Fractal-like mixed
1,2 order) the adsorption rate coefficient is considered a function of
time by using the Fractal-like idea. One of the probable physical
significances of Fractal-like kinetics was that adsorption of As(III) and
As(V) occurred at solid/solution interface. In this approach it was
305
showed that by passing time, various paths for adsorption of As(III)
and As(V) on surface appears.
4.3. Final remarks on biosorption/bioaccumulation kinetic studies
The error values (SSE, reduced χ2 and Root-MSE) for the Fractal-like
mixed 1,2 order kinetic model was better than that observed employing
the other kinetic models for As(III) signifying the rate of adsorption was
dependent on rate of agitation and initial concentration of adsorbate
solution. However on the basis of the acquired error values (SSE), the
Brouser–Weron–Sototlongo kinetic model exhibited the best fit to the
biosorption/bioaccumulation kinetic data of As(V) among all the
models demonstrating a complex mechanism of biosorption/bioaccu-
mulation process. But based on the error values (reduced χ2 and
Root-MSE) it was observed that Fractal-like pseudo second order
ruled in all the possibilities of biosorption/bioaccumulation of
As(V) ion on surface of adsorbent attached with biofilm demonstrating
that the adsorption rate coefficient is a function of time.
It is vital for obtaining the rate at which As(III) or As(V) is biosorbed/
bioaccumulated onto the surface of C. glutamicum MTCC 2745
immobilized on surface of GAC/MnFe2O4 composite that is important
to design fixed bed adsorption column. Using the biosorption/bioaccu-
mulation rate, kinetic constants are estimated to determine the equilib-
rium capacity of adsorbent attached with biofilm and mass transfer
coefficient at various aqueous phase concentrations. Amount of As(III)
or As(V) biosorbed/bioaccumulated onto solid surface is calculated
using the kinetic equation which is important for valuing the concentra-
tion of the aqueous phase in fixed bed column operation. The main
design factors of fixed bed adsorption column, the breakthrough time
as well as the shape of breakthrough curve are reliant on biosorption/
bioaccumulation rate. For the faster biosorption/bioaccumulation rate,
breakpoint time is achieved prior besides the breakthrough curve
shape is steeper.
The descriptive models from the best to worst for As(III) and
As(V) were sorted according to GoFM values and shown Tables S1 and
S2, respectively.
Consequently at this point, the fitting “ambiguity” influenced by the
error values (SSE, reduced χ2 and Root-MSE) was for As(V), because the
error value (SSE) confirmed Brouser–Weron–Sototlongo as best fitting
model (the lowest error values) and error values (reduced χ2 and
Root-MSE) showed that Fractal-like pseudo second order was the best
(the lowest error values). So to overcome this uncertainty, it would be
modest and practical to compare the theoretically assessed qe values
with the experimental ones.
306 M.S. Podder, C.B. Majumder / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 153 (2016) 298–314

Table 5
According to correlation coefficient R2 values the fitness of the
Mechanistic constants of studied models for As(III) and As(V) biosorption/bioaccumula-
models for all kinetic models are almost equivalent to each other. So tion onto C. glutamicum MTCC 2745 immobilized on surface of GAC/MnFe2O4 composite.
on the basis of equivalent adsorption capacity, the orders followed by
Mechanistic models Parameters Values for Values for
the models in decreasing manner are showed in Table 4.
As(III) As(V)

Intraparticle diffusion model kint1 (mg/g 6.8022 7.18405

4.4. Biosorption mechanistic studies
min0.5)
Cint1 (mg/g) 2.23318 2.80345
4.4.1. Intraparticle diffusion model kint2 (mg/g 1.00007 1.08368
Results of intraparticle diffusion model for both As(III) and As(V) are min0.5)
given in Table 5. Fig. 3 identified the multi-linear nature of intraparticle Cint2 (mg/g) 36.35531 37.50988
model. As the plot did not pass through the origin, so intraparticle diffu- R2 1 0.9852 0.97995
sion was not the single rate controlling step. So there were three pro- R2 2 0.99371 0.98981
cesses leading the rate of biosorption/bioaccumulation, however only Determination of rate D1 (cm2/s) 1.24272E−05 1.19323E−05
one was rate controlling in any certain time range. The intraparticle limiting step D2 (cm2/s) 5.89958E−06 5.2782E−06
Dumwald–Wagner model kDW (1/min) 0.01545313 0.01374891
diffusion rate constant kint2 for both As(III) and As(V) was esteemed
R2 0.93049 0.94334
from the slope of the second linear portion (Fig. 3, Table 5). The multi-
Richenberg model R2 0.93283 0.94294
linear curve of the intraparticle model with intercept Cint2 specified
McKay plot kM1 (1/min) 0.0381 0.03547
the fact that both intraparticle diffusion of adsorbate through the
kM2 (1/min) 0.01643 0.01354
mesoporus openings filled with liquid and film/external mass transfer 0.95746 0.94429
R2 1
across the thickness of boundary layer were the rate governing steps 0.8736 0.89072
R2 2
in the biosorption/bioaccumulation of both As(III) and As(V) kinetics
Bangham's model kb (L/g) 27.93324744 28.71054447
onto the surface of C. glutamicum MTCC 2745 immobilized on surface αb 0.43269 0.45925
of GAC/MnFe2O4 composite. The value of intercept Cint obtained R2 0.95137 0.97483
through the model provided the value of thickness of boundary layer Diffusion coefficient Dp (cm2/s) 1.45036E−07 1.47145E−07
of liquid surrounding the adsorbent attached with biofilm [79]. Df (cm2/s) 2.28142E−07 5.28867E−07
The explanation of the haphazard data points detected in Fig. 3 and Diffusivity De (m2/s) 5.56065E−14 4.98E−14
R2 0.93423 0.94331
Table 5 specified that intraparticle mechanistic model had been appro-
priate to cost-effectively and competently express the biosorption/bio-
accumulation of both As(III) and As(V) onto the surface of C. glutamicum
MTCC 2745 immobilized on surface of GAC/MnFe2O4 composite in case. Table 5 displays the computed results of Dumwald–Wagner
model. In the current investigation the linearity of the plots intersected
terms of linear regression coefficient Adjusted R-square ðR2 Þ, ranging the origin of coordinates; consequently film diffusion process was the
between 0.97995 and 0.99371 in both case. Greater value of intercepts rate controlling step.
attained for second linear portion i.e., Cint2 commended that the film
diffusion had played a superior role as the rate governing step [80].
4.4.4. Richenberg model or Boyd plot
4.4.2. Determination of rate limiting step The outcomes of the corresponding model for both As(III) and
The values of the film diffusion coefficient D1 and the pore diffusion As(V) are presented in Table 5 and Fig. 5, respectively. From the plots
coefficient D2 for both As(III) and As(V) are shown in Table 5. The high of Bbt versus t, it was found that the plots had a linear form with a
negative exponential of almost nearest values specified that both pore correlation coefficient Adjusted R-square ðR2 Þ of 0.93283 for As(III)
diffusion and film diffusion had ruled the mechanism of biosorption/ and 0.94294 for As(V) at studied temperature and but did not pass
bioaccumulation for both As(III) and As(V). through origin which had selected the ongoing biosorption/bioaccumu-
lation processes to be governed by film diffusion mechanism.
4.4.3. Dumwald–Wagner model
The plot (Fig. 4) of log (1 − F2) versus t has delivered almost linear 4.4.5. Film diffusion mass transfer rate equation or McKay plot
curves (R2 ≥ 0.93049) for the elimination of both As(III) and As(V) by The values attained for ln(1 − F) as a function of time t, were plotted
C. glutamicum MTCC 2745 immobilized on surface of GAC/MnFe2O4 in Fig. 6 for As(III) and As(V), respectively and the results of the respec-
composite, respectively, but did not pass through the origin demon- tive model for both As(III) and As(V) are exposed in Table 5. The rate
strating that the diffusion of adsorbate into pores of the adsorbent constant of the early rapid process (kM1) was evaluated from the slope
attached with biofilm was not the only rate controlling step in both of the first straight line (Fig. 6). As can be understood from Fig. 6, the

Table 4
Ranking on the basis of equivalent biosorption capacity for kinetic models.

Model qe for As(III) Model qe for As(V)

Fractal-like pseudo second order 52.59856 Fractal-like pseudo second order 55.98921
Brouser–Weron–Sototlongo 52.44661 Brouser–Weron–Sototlongo 55.34186
Modified second order 52.28508 Modified second order 54.70328
Pseudo second order 52.26883 Pseudo second order 54.64374
Ritchie second order 52.26876 Ritchie second order 54.64339
Mixed 1,2 order 52.07541 Mixed 1,2 order 54.58995
Avrami 50.82907 Fractal-like mixed 1,2 order 54.4563
Fractal-like pseudo first order 50.82573 Avrami 53.67186
Fractal-like exponential 50.80382 Fractal-like pseudo first order 53.66859
Exponential 49.46603 Fractal-like exponential 53.63717
Pseudo first order 49.19755 Exponential 51.77639
Fractal-like mixed 1,2 order 21.98568 Pseudo first order 51.49754
 M.S. Podder, C.B. Majumder / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 153 (2016) 298–314 307

Fig. 3. Intraparticle diffusion modelling of As(III) and As(V) biosorption/bioaccumulation onto the C. glutamicum MTCC 2745 immobilized on surface of GAC/MnFe2O4 composite (t: 5–
500 min; Co: 50 mg/L; M: 0.9 g/L; pH: 7.0; T: 30 °C) (error bars represent means ± standard errors from the mean of duplicate experiments).

rate constant of the slow process (kM2) was attained from the slope of
the second linear portion. It is understandable that the early fast process
was ruled by film diffusion. Also the values of kM2 are smaller than the
values of kM1 for both As(III) and As(V). So the attained values of kM2
were evidence of a pore diffusion mechanism in the second stage of
the biosorption/bioaccumulation [81]. The existence of two straight
lines for both As(III) and As(V) stated that two processes i.e., film
diffusion and pore diffusion had involved in these processes.
The plots were approximately linear for both As(III) and As(V), but it
did not return perfect linearity. So pore diffusion was not the rate con-
trolling step. In the current system film diffusion was the rate governing
step.
4.4.6. Bangham's model
The consequences of the respective model for both As(III) and
As(V) are exposed in Table 5 and Fig. 7. The goodness of fit of curve
for Bangham's model was related in terms of correlation coefficient
Adjusted R-square ðR2 Þ. Values of Bangham parameters kb and α are
27.93324744 L/g and 0.43269 for biosorption/bioaccumulation of
As(III) and 28.71054447 L/g and 0.45925 for biosorption/bioaccumula-
tion of As(V) with a correlation coefficients of 0.95137 and 0.97483,
respectively. The double logarithmic plot (Fig. 7 for As(III) and As(V),
respectively) as specified by above equation did not return perfect
linear curves and some data were scattered (R2 ≤ 0.99614) for the scav-
enging of As(III) and As(V) by C. glutamicum MTCC 2745 immobilized
on surface of GAC/MnFe2O4 composite clarifying that the diffusion of
adsorbate within pores of the adsorbent attached with biofilm was not
only the rate controlling step [82], film diffusion also had effect on the
rate controlling step.
4.4.7. Determination of diffusion coefficient
The Dp and Df values for As(III) were 1.45 × 10−7 cm2/s and
2.28 × 10−7 cm2/s, respectively. Likewise these values for As(V) were
1.47 × 10−7 cm2/s and 5.29 × 10−6 cm2/s, respectively (Table 5).
So in the current case pore diffusion was not the only rate governing
step for both As(III) and As(V). For As(III) the value of Df
(1.47 × 10− 7 cm2/s) falls within the range of 10−6 and 10− 8 cm2/s
and for As(V) the Df value (5.29 × 10−6 cm2/s) is also in the range. So
it was observed that the film diffusion had been the rate governing
step for both As(III) and As(V).
Greater value of Df of As(V) than that of As(III) was due to the
presence of As(V) as totally positively charged species and As(III) as
naturally neutral species at the experimental pH. Because of negative
charge of As(V) it was freely transported from the bulk solution to

Fig. 4. Dumwald–Wagner modelling of As(III) and As(V) biosorption/bioaccumulation onto the C. glutamicum MTCC 2745 immobilized on surface of GAC/MnFe2O4 composite (t:
5–500 min; Co: 50 mg/L; M: 0.9 g/L; pH: 7; T: 30 °C) (error bars represent means ± standard errors from the mean of duplicate experiments).
308 M.S. Podder, C.B. Majumder / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 153 (2016) 298–314

Fig. 5. Richenberg modelling of As(III) and As(V) biosorption/bioaccumulation onto the C. glutamicum MTCC 2745 immobilized on surface of GAC/MnFe2O4 composite (t: 5–500 min; Co:
50 mg/L; M: 0.9 g/L; pH: 7; T: 30 °C) (error bars represent means ± standard errors from the mean of duplicate experiments).

generally the positively charged adsorbent surface attached with
biofilm and become biosorbed/bioaccumulated onto the active sites of
adsorbent surface attached with biofilm instead of the interior pores.
4.4.8. Determination of diffusivity
From the slope π2De/r2 of the plot of ln[1/(1 − F2)] versus t (Fig. 8,
Table 5), the value of diffusion coefficient, De as estimated, was detected
to be 5.56 × 10− 14 m2/s and 4.98 × 10− 14 m2/s for As(III) and
As(V) biosorption/bioaccumulation onto C. glutamicum MTCC 2745
immobilized on surface of GAC/MnFe2O4 composite, respectively. For
the current systems, the value of De falls within the range of 10−9 to
10−17 m2/s, so the system was chemisorption system.
4.5. Final remarks on biosorption/bioaccumulation mechanistic studies
The above considered models for biosorption/bioaccumulation of
both As(III) and As(V) specified that two processes i.e., film diffusion
(diffusion of adsorbate through the solution to the external surface of
biosorbent or boundary layer diffusion of adsorbate) and pore diffusion
(diffusion of the adsorbate from the surface film into the pores) were in-
volved in the current biosorption/bioaccumulation processes for both
As(III) and As(V) and pore diffusion was not the only rate controlling
step. Usually film diffusion ruled the rate governing step in both case.
4.6. Effect of temperature
The temperature has two main effects onto the biosorption/bio-
accumulation process. Temperature dependence of the biosorption/
bioaccumulation system advices the biosorption/bioaccumulation
as endothermic or exothermic. Increasing the temperature is well-
known for raising the diffusion rate of the adsorbate, owing to the
decline in the solution viscosity. Also changing the temperature
will change the equilibrium adsorption capacity of the adsorbent
attached with biofilm for a specific adsorbent [83].
The influence of temperature on the elimination efficiency of As(III)
and As(V) was reviewed in the range of 20–50 °C all over the equilibri-
um time. The results of influence of temperature have been shown in
Fig. 9. The favourable temperature for the growth of C. glutamicum
MTCC 2745 is 30 °C according to the guideline of MTCC. The result stated
that the maximum removal was achieved at a temperature of 30 °C in
biosorption/bioaccumulation system. Further increase in temperature
caused in lower elimination efficiency for arsenic removal in
biosorption/bioaccumulation system. This can also be clarified by the
spontaneity and exothermicity of the biosorption/bioaccumulation pro-
cess. This decline in scavenging efficiency might be due to many factors:
the relative rise in the avoidance tendency of the arsenic ions from the
solid adsorbent phase attached with biofilm to the bulk liquid phase;
deactivating surface of adsorbent attached with biofilm or destructing

Fig. 6. McKay plot of As(III) and As(V) biosorption/bioaccumulation onto the C. glutamicum MTCC 2745 immobilized on surface of GAC/MnFe2O4 composite (t: 5–500 min; Co: 50 mg/L; M:
0.9 g/L; pH: 7; T: 30 °C) (error bars represent means ± standard errors from the mean of duplicate experiments).
 M.S. Podder, C.B. Majumder / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 153 (2016) 298–314 309

Fig. 7. Bangham modelling of As(III) and As(V) biosorption/bioaccumulation onto the C. glutamicum MTCC 2745 immobilized on surface of GAC/MnFe2O4 composite (t: 5–500 min; Co: 50
mg/L; M: 0.9 g/L; pH: 7; T: 30 °C) (error bars represent means ± standard errors from the mean of duplicate experiments).

some active sites onto the surface of adsorbent attached with biofilm
because of bond ruptures [84,85] or because of the weakening of
adsorptive forces between the adsorbate species and the active sites of
the adsorbents attached with biofilm and also between the adjacent
molecules of adsorbed phase for high temperatures or movement of
adsorbents attached with biofilm with more speed, consequently,
lower interaction time with the active sites of adsorbents attached
with biofilm was obtainable for them [86,87].
4.7. Biosorption thermodynamic studies
The estimated values of the thermodynamic parameters from the
plot of ln kd versus 1/T (Fig. 10) are shown in Table 6. The equilibrium
constant kd was computed; while the temperature was varied between
20 and 50 °C for both As(III) and As(V). The maximum removal of adsor-
bate was reached at 30 °C in both case. The removal efficiency initially
improved with rising the temperature from 20 to 30 °C. Then it declined
with rising the temperature from 30 to 50 °C. The ΔH0 values achieved
for the biosorption/bioaccumulation of both As(III) and As(V) were
negative because of the exothermic nature of the biosorption/bioaccu-
mulation process. The value achieved for As(V) biosorption/bioaccumu-
lation was more than the value achieved for As(III). A negative value of
ΔG0 stated the spontaneous nature of the biosorption/bioaccumulation
process; though the negative value of ΔS0 offered a reduction in the
randomness at the solid/solution interface during the biosorption/bio-
accumulation process [88]. Higher negative value of ΔG0 at a tempera-
ture of 30 °C, as was achieved in the study, decided more driving force
for biosorption/bioaccumulation at 30 °C [89]. The values of ΔG0
attained in the current investigation were between −22.44 to −23.73
kJ/mol and −24.18 to −25.94 kJ/mol for As(III) and As(V), respectively.
So it stated that the mechanism of current biosorption/bioaccumulation
process had happened via ion exchange and/or surface complexation
mechanism.
4.8. Effect of initial arsenic concentration on biosorption/bioaccumulation
kinetics
To study the influence of initial concentration on kinetic studies, a
series of contact time experiments for both As(III) and As(V) was
carried out at various initial concentrations (50–2000 mg/L) at temper-
ature of 30 °C. Fig. 11 exhibited the contact time essential for both As(III)
and As(V) with initial concentration of 50–1000 mg/L for attaining equi-
librium was 220 min. But for both As(III) and As(V) with higher initial
concentration (N 1000–2000 mg/L), higher equilibrium time of
300 min was needed. As can be decided from Fig. 11, the amount of
the biosorbed/bioaccumulated both As(III) and As(V) onto the surface
of C. glutamicum MTCC 2745 immobilized on surface of GAC/MnFe2O4
composite changed with time and at some point in time attained a

Fig. 8. Diffusivity of As(III) and As(V) biosorption/bioaccumulation onto the C. glutamicum MTCC 2745 immobilized on surface of GAC/MnFe2O4 composite (t: 5–500 min; Co: 50 mg/L; M:
0.7 g/L; pH: 7; T: 30 °C) (error bars represent means ± standard errors from the mean of duplicate experiments).
310 M.S. Podder, C.B. Majumder / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 153 (2016) 298–314

Table 6
Thermodynamic constants for As(III) and As(V) biosorption/bioaccumulation onto
C. glutamicum MTCC 2745 immobilized on surface of GAC/MnFe2O4 composite.

Inorganic form T (K) −ΔG0 (kJ/mol) −ΔH0 (kJ/mol) −ΔS0 (J/mol K)

As(III) 293 22.4364076 23.4674745 0.0015144

298 23.0684935
303 23.7316653
308 23.3466514
313 22.8995923
318 22.741959
323 22.7805001
As(V) 293 24.1788513 26.9236357 0.00653622
298 25.0119506
303 25.9377515
308 25.4166765
313 24.8022939
318 24.6585486
323 24.3643121

Fig. 9. Effect of temperature on As(III) and As(V) removal in SBB studies (Co: 50 mg/L; pH:
7; M: 0.9 g/L; t: 220 min) (error bars represent means ± standard errors from the mean of
duplicate experiments).
constant value beyond which no more As(III) or As(V) was removed
from solution. At the moment the amount of the both As(III) and
As(V) desorbing from the biosorbent was in a state of dynamic equilib-
rium with the amount of the both As(III) and As(V) being biosorbed/
bioaccumulated onto the surface of C. glutamicum MTCC 2745
immobilized on surface of GAC/MnFe2O4 composite. The time essential
for attainment this state of equilibrium is called the equilibrium time.
Thus the rate of biosorption/bioaccumulation declined with time till it
slowly inclined to a plateau because of the constant reduction in the
concentration driving force.
4.9. Determination of initial sorption rate
model can been employed for the whole biosorption/bioaccumulation
process and allowed the chemisorption of both As(III) and As(V) onto
C. glutamicum MTCC 2745 immobilized on surface of GAC/MnFe2O4
composite.
4.10. Effect of temperature on biosorption/bioaccumulation kinetic
Temperature is an important factor leading the biosorption/bioaccu-
mulation process. The influence of temperature onto the of biosorption/
bioaccumulation of both As(III) and As(V) by C. glutamicum MTCC 2745
immobilized on surface of GAC/MnFe2O4 composite was done from 30
to 50 °C at C0 is 50 mg/L and GAC/MnFe2O4 composite loading is
0.9 g/L. A decreasing biosorption rate of both As(III) and As(V) with
increasing temperature from 30 to 50 °C recognized the process to be
exothermic (Fig. 12). This is considered before concerning thermody-
namic parameters in supplementary materials.

From Fig. S1 and Table 7, it is seen that the pseudo second order rate
constants (kPSO) were found to decrease and the initial sorption rates
(h) were understood to raise with higher initial concentration of both
As(III) and As(V). The initial sorption rate was superior for higher initial
As(III) and As(V) concentration as the opposition to uptake both As(III)
and As(V) decreased as the mass transfer driving force improved.
The estimated qe(PSO) values decided just appropriate with the
experimental data and high correlation coefficient (R, R2 and R2 ) and
low error values (SSE, reduced χ2 and Root-MSE) revealed that the
4.11. Biosorption activation energy
Biosorption/bioaccumulation rate constants kPSO of both As(III) and
As(V) were calculated from experimental data at a different tempera-
tures assuming non-linear form of pseudo second order kinetics. Param-
eters of Arrhenius equation were fitted employing these rate constants
for valuing temperature independent rate parameters and biosorption/
bioaccumulation type. A plot of ln kPSO versus 1/T displayed a straight
line with slope − Ea/R (Fig. S2, Table 8). The magnitude of activation

Fig. 10. Thermodynamic modelling of As(III) and As(V) biosorption/bioaccumulation onto the C. glutamicum MTCC 2745 immobilized on surface of GAC/MnFe2O4 composite (T: 20–50 °C;
Co: 50 mg/L; pH: 7.0; M: 0.9 g/L; t: 220 min) (error bars represent means ± standard errors from the mean of duplicate experiments).
 M.S. Podder, C.B. Majumder / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 153 (2016) 298–314 311

Fig. 11. Effect of initial concentration on contact time for As(III) and As(V) biosorption/bioaccumulation onto the C. glutamicum MTCC 2745 immobilized on surface of GAC/MnFe2O4 com-
posite (Co: 50–2000 mg/L; t: 5–500 min; pH: 7.0; M: 0.9 g/L; T: 30 °C) (error bars represent means ± standard errors from the mean of duplicate experiments).

energy for As(III) and As(V) biosorption/bioaccumulation onto again confirmed the manifestation of MnFe2O4 particles onto the acid
C. glutamicum MTCC 2745 immobilized on surface of GAC/MnFe2O4 treated GAC surface as well as biosorption/bioaccumulation of arsenic
composite were 10.77 kJ/mol and 10.41 kJ/mol signifying that both onto the surface of adsorbent attached with biofilm.
the biosorption/bioaccumulation of As(III) and As(V) onto the surface
of the C. glutamicum MTCC 2745 immobilized on surface of GAC/ 5. Conclusions
MnFe2O4 composite was activated chemisorption.
• The present research showed that the C. glutamicum MTCC 2745
4.12. Characterization immobilized on surface of GAC/MnFe2O4 composite was applied
fruitfully for the biosorption/bioaccumulation of both As(III) and
4.12.1. SEM-EDX analysis As(V) from synthetically prepared copper smelting wastewater.
The SEM images of the prepared fresh GAC/MnFe2O4 composite • The optimum contact time and temperature for biosorption/bioac-
(Fig. S3(a)) and As(III) acclimatized C. glutamicum MTCC 2745 cumulation of both As(III) and As(V) were 220 min and 30 °C,
immobilized on surface of GAC/MnFe2O4 composite at stage of unloaded respectively.
and loaded with As(III) (Fig. S3(b)–(c)) and As(V) acclimatized • Contact time required for achievement of equilibrium improved
C. glutamicum MTCC 2745 immobilized on surface of GAC/MnFe2O4 com- with rising concentration, though remained practically unaffected
posite at stage of unloaded and loaded with As(V) (Fig. S3(d)–(e)) were by increasing temperature.
shown. It can be seen from Fig. S3(a), manganese ferrite (MnFe2O4) par- • The rate of biosorption/bioaccumulation of both As(III) and
ticles with several diameters were randomly distributed onto the acid As(V) by C. glutamicum MTCC 2745 immobilized on surface of
treated GAC surface. It is obvious from Fig. S3(b) and Fig. S3(d) that GAC/MnFe2O4 composite decreased with increasing concentration.
most of the active sites of GAC/MnFe2O4 composite were shielded • By applying 14 different kinetic models and utilizing procedure of
because of the formation of biofilm on it [59]. An alteration in surface the nonlinear regression for curve fitting analysis maximizing the
morphology from being smooth to rough and existence of pores indicated correlation coefficient (R, R2, R2 .)nd minimizing the error values
the As(III) and As(V) biosorption/bioaccumulation onto the surface and (SSE, Reduced χ2 and Root-MSE) to estimate optimum parameter
pores of GAC/MnFe2O4 composite providing it a rough texture. The sets, the Fractal-like mixed 1,2 order kinetic model for As(III) and
corresponding EDX spectra of the unloaded and loaded adsorbent at- both Brouser–Weron–Sototlongo as well as Fractal-like pseudo
tached with biofilm was collected and given in Fig. S3(a)–(e). The occur- second order kinetic models for As(V) were found suitable to
rence of iron, manganese and oxygen onto the unloaded composite predict the kinetic of biosorption/bioaccumulation onto GAC/
surface and iron, manganese and oxygen, arsenic on the loaded adsorbent MnFe2O4 composite according to GoFM values.
surface attached with biofilm were exposed evidently. This outcome • The results achieved from different mechanistic models indicated
the controller of film diffusion over pore diffusion.
Table 7 • The effective diffusivity estimated by using Vermeulen's approxi-
Initial sorption rate for As(III) and As(V) biosorption/bioaccumulation onto the mation was indicated that the interaction between arsenic ions
C. glutamicum MTCC 2745 immobilized on surface of GAC/MnFe2O4 composite. (either As(III) or As(V)) and immobilized bacterial cells were
Inorganic form T (K) kPSO (g/mg min) h (mg/g min) chemical in nature.
• The related thermodynamic parameters showed that the
As(III) 50 0.00185 5.054255
100 9.15E−04 9.826596
biosorption/bioaccumulation of both As(III) and As(V) had been a
500 7.54E−04 168.7224 feasible and exothermic process and spontaneous in nature.
1000 6.19E−04 490.0939 • From Arrhenius equation, it was proved that the mechanism of
1500 4.25E−04 573.9969 biosorption/bioaccumulation of As(III) and As(V) by C. glutamicum
2000 3.27E−04 697.0719
MTCC 2745 immobilized on surface of GAC/MnFe2O4 composite
As(V) 50 0.00182 5.434408
100 9.37E−04 11.06475 might be an ion exchange type.
500 8.82E−04 208.3029 • EDX analysis documented the presence of iron and manganese in the
1000 5.94E−04 498.3264 GAC/MnFe2O4 composite and it also established the fact that both
1500 4.24E−04 690.939 As(III) and As(V) was biosorbed/bioaccumulated onto the adsorbent
2000 3.87E−04 918.4216
attached with biofilm.
312 M.S. Podder, C.B. Majumder / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 153 (2016) 298–314

Fig. 12. Effect of temperature on contact time for As(III) and As(V) biosorption onto the C. glutamicum MTCC 2745 immobilized on surface of GAC/MnFe2O4 composite (T: 30–50 °C; t: 5–
500 min; Co: 50 mg/L; pH: 7; M: 0.9 g/L) (error bars represent means ± standard errors from the mean of duplicate experiments).

• C. glutamicum MTCC 2745 immobilized on surface of GAC/MnFe2O4 ka,obs the acquired rate coefficients of adsorption
composite can be employed as a capable biosorbent for removal of kd,obs the acquired rate coefficients of desorption
both As(III) and As(V) from contaminated water sources. kb the Bangham model constant (mL/g L)
kd the adsorption equilibrium constant (L/g)
kDW the Dumwald–Wagner rate constant (1/min)
Nomenclature kEXP the exponential rate coefficient (mg/g v)
aE Elovich coefficient representing the initial adsorption rate kint the intraparticle diffusion rate coefficient (mg/g min0.5)
(mg/g min) kM the film diffusion rate constant (1/min.
bE Elovich coefficient representing desorption constant (g/mg) kMOE the mixed 1,2 order rate coefficient (1/min)
A the frequency factor knBWS,α the reaction constant (1/min)
Bbt a mathematical function of F (F = qt/qe) kPF the fractional power model rate constant (mg/g min)
C0 initial concentration of arsenic in the solution (mg/L) kPFO the pseudo first order rate coefficient (1/min)
Ce equilibrium concentration of arsenic in the solution (mg/L) kPSO the pseudo second order rate coefficient (g/mg min)
Cs the concentration of arsenic onto the adsorbent and in the k′EXP division of kEXP by qe (1/min)
solution (mg/L) k″EXP the Fractal-like exponential rate coefficient (1/min)
Cint the intercept of the intraparticle diffusion plot (mg/g) k′PFO the Fractal-like pseudo first order kinetic rate coefficient
d the thickness of the water film adhered to the adsorbent (cm) (1/min)
D1 film diffusion constant (cm2/s) k′FPFO the Fractal-like pseudo first order kinetic rate coefficient
D2 pore diffusion constant (cm2/s) (1/min)α
De diffusivity (m2/s) k′FPSO is the Fractal-like pseudo second order kinetic rate coefficient
Df film diffusion coefficient (cm2/s) (g/mg min)α.
Dp pore diffusion coefficient (cm2/s) k′PSO multiplication of qe and kPSO (1/min)
Ea the activation energy of adsorption characterizing the distri- k″FPSO multiplication of qe and k′FPSO (1/min)
bution (kJ/mol) M the mass of the adsorbent (dry) (g)
F the adsorption progress (F = qt/qe) m the weight of the adsorbent per litre of solution (g/L)
f2 the involvement of pseudo second order model mb an integer that describes infinite series solution
feq the Langmuir batch equilibrium factor n the number of observations in the experimental study
h the initial adsorption rate (mg/g min) nAV constant corresponding to the mechanism of adsorption
k′1,0 the Fractal-like mixed 1,2 order rate coefficient (1/min)α nBWS a fractional reaction order
k′2R the modified second order rate coefficient (1/min) nR number of surface sites
k″2R the Ritchie second order rate coefficient (1/min) p the number of parameters to be estimated
kAV the Avrami kinetic rate coefficient (1/min) qe the amount of adsorbate adsorbed on the adsorbent surface at
equilibrium (mg/g)
qm the adsorption capacity
qt the amount of adsorbate adsorbed onto the adsorbent surface
Table 8 at time t (mg/g)
Activation energy for As(III) and As(V) biosorption/bioaccumulation onto the qt,,exp the biosorption capacity observed from the batch experiment
C. glutamicum MTCC 2745 immobilized on surface of GAC/MnFe2O4 composite. after time t (mg/g)
Inorganic form T (K) kPSO (g/mg min) Ea (kJ/mol) qt,,model the calculation from the kinetic model corresponding to Ct
r mean radius of adsorbent particle (assumed spherical) (cm)
As(III) 303 0.00185 10.77457
313 0.00216 ra the rate of adsorption
323 0.00241 rd the rate of desorption
As(V) 303 0.00182 10.41594 R the universal gas constant (8.314 J/mol K)
313 0.00212 Re % removal
323 0.00235
t contact time (min)
 M.S. Podder, C.B. Majumder / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 153 (2016) 298–314 313

t(1/2) the time necessary for falling the adsorbate concentration to [17] H.K. Hansen, P. Nu˜nez, R. Grandon, Electrocoagulation as a remediation tool for
wastewaters containing arsenic, Miner. Eng. 19 (2006) 521–524.
half the initial concentration (s) [18] C.A. Basha, S.J. Selvi, E. Ramasamyc, Removal of arsenic and sulphate from the
tα a Fractal time copper smelting industrial effluent, Chem. Eng. J. 141 (2008) 89–98.
T the absolute temperature (K) [19] T. Urase, J.-I. Oh, K. Yamamoto, Effect of pH on rejection of different species of
arsenic by nanofiltration, Desalination 117 (1998) 11–18.
ueq relative equilibrium uptake [20] K. Kŏsuti'c, L. Furaˇc, L. Sipos, B. Kunst, Removal of arsenic and pesticides from drink-
v adjustment parameter ing water by nanofiltration membranes, Sep. Purif. Technol. 42 (2) (2005) 137–144.
V the volume of the solution (mL) [21] E.O. Kartinen, J.C. Martin, An overview of arsenic removal processes, Desalination
103 (1995) 79–88.
[22] K. Vaaramaa, J. Lehto, Removal of metals and anions from drinking water by ion
Greek symbols exchange, Desalination 155 (2) (2003) 157–170.
α the Fractal time exponent [23] B. Han, T. Runnells, J. Zimbron, R. Wickramasinghe, Arsenic removal from drinking
water by flocculation and microfiltration, Desalination 145 (2002) 293–298.
αb Bangham model constant
[24] P. Mondal, C. Balomajumder, B. Mohanty, A laboratory study for the treatment of
θ the adsorbent surface coverage at pre-adsorbed stage, arsenic, iron, and manganese bearing ground water using Fe3+ impregnated
(θ = qt/qe) dimensionless activated carbon: effects of shaking time, pH and temperature, J. Hazard. Mater.
θ0 the adsorbent surface coverage at time t, (θ0 = q0/qe) 144 (2007) 420–426.
[25] J.W. Patterson, Industrial Wastewater Treatment Technology, 2nd ed. Butterworths,
dimensionless USA, 1985.
θe the relative surface coverage at equilibrium [26] M. Tuzen, A. Sarı, D. Mendil, O.D. Uluozlu, M. Soylak, Mehmet Dogan, Characteriza-
τ1/2 half-reaction time (min) tion of biosorption process of As(III) on green algae Ulothrix cylindricum, J. Hazard.
Mater. 165 (2009) 566–572.
τnBWS,α the time required for adsorbing half the maximum amount [27] J.W. Costerton, G.G. Geesey, K.J. Cheng, How bacteria stick, Sci. Am. 238 (1978)
ΔG0 Gibbs free energy change (kJ/mol) 86–95.
ΔH0 enthalpy change (kJ/mol) [28] H.C. Flemming, J. Wingender, Relevance of microbial extracellular polymeric sub-
stances (EPSs)—part I: structural and ecological aspects, Water Sci. Technol. 43
ΔS0 entropy change (J/mol K) (2001) 1–8.
[29] R.M. Donlan, Biofilms: microbial life on surfaces, Emerg. Infect. Dis. 8 (2002)
Acknowledgement 881–890.
[30] R. Singh, D. Paul, R.K. Jain, Biofilms: implications in bioremediation, Trends
Microbiol. 14 (2006) 389–397.
Our thanks to the Indian Institute of Technology, Roorkee for provid- [31] F. Ahimou, M.J. Semmens, G. Haugstad, P.J. Novak, Effect of protein, polysaccharide,
ing necessary facilities and to the Ministry of Human Resource Develop- and oxygen concentration profiles on biofilm cohesiveness, Appl. Environ.
Microbiol. 73 (2007) 2905–2910.
ment, Government of India for financial support. [32] C. Quintelas, B. Fernandes, J. Castro, H. Figueiredo, T. Tavares, Biosorption of Cr(VI)
by a Bacillus coagulans biofilm supported on granular activated carbon (GAC),
Appendix A. Supplementary data Chem. Eng. J. 136 (2008) 195–203.
[33] C. Quintelas, B. Fonseca, B. Silva, H. Figueiredo, T. Tavares, Treatment of
chromium(VI) solutions in a pilot-scale bioreactor through a biofilm of Arthrobacter
Supplementary data to this article can be found online at http://dx. viscosus supported on GAC, Bioresour. Technol. 100 (2009) 220–226.
doi.org/10.1016/j.saa.2015.08.022. [34] S. Comte, G. Guibaud, M. Baudu, Biosorption properties of extracellular polymeric
substances (EPS) towards Cd, Cu and Pb for different pH values, J. Hazard. Mater.
151 (2008) 185–193.
References [35] K.E. Eboigbodin, C.A. Biggs, Characterization of the extracellular polymeric
substances produced by Escherichia coli using infrared spectroscopic, proteomic,
[1] USEPA, National Primary Drinking Water Regulations: Arsenic and Clarifications to and aggregation studies, Biomacromolecules 9 (2008) 686–695.
Compliance and New Source Contaminants Monitoring, Federal Register, CFR Parts [36] W. Wang, W. Wang, X. Zhang, D. Wang, Adsorption of p-chlorophenol by biofilm
9, 402001 141–142. components, Water Res. 36 (2002) 551–560.
[2] P.L. Smedley, D.G. Kinniburgh, A review of the source, behaviour and distribution of [37] S. Lameiras, C. Quintelas, T. Tavares, Biosorption of Cr (VI) using a bacterial biofilm
arsenic in natural waters, Appl. Geochem. 17 (2002) 517–568. supported on granular activated carbon and on zeolite, Bioresour. Technol. 99
[3] B.K. Biswas, J.I.K. Inoue, K.N. Ghimire, H. Harada, K. Ohto, H. Kawakita, Adsorptive re- (2008) 801.
moval of As(V) and As(III) from water by a Zr(IV)-loaded orange waste gel, J. Haz- [38] C. Quintelas, Z. Rocha, B. Silva, B. Fonseca, H. Figueiredo, T. Tavares, Biosorptive per-
ard. Mater. 154 (2008) 1066–1074. formance of an Escherichia coli biofilm supported on zeolite NaY for the removal of
[4] M.J. Haron, W.M.Z.W. Yunus, N.L. Yong, S. Tokunaga, Sorption of arsenate and arse- Cr(VI), Cd(II), Fe(III) and Ni(II), Chem. Eng. J. 152 (2009) 110–115.
nite anions by iron(III)–poly(hydroxamic acid) complex, Chemosphere 39 (1999) [39] F.R. Reinoso, The role of carbon materials in heterogeneous catalysis, Carbon 36
2459–2466. (1998) 159–175.
[5] D.C. Adriano, Trace Elements in Terrestrial Environments, Biogeochemistry, [40] G.L. Culp, R.L. Culp, New Concepts in Water Purification, Reinhold, New York, 1974.
Bioavailability and Risks of Metals, Springer–Verlag, New York, 2001. [41] D.M. Ruthven, Principles of Adsorption and Adsorption Processes, Wiley, New York,
[6] P. Mondal, C.B. Majumder, B. Mohanty, Laboratory based approaches for arsenic 1984.
remediation from contaminated water: recent developments, J. Hazard. Mater. [42] K.P. Gadkaree, Carbon honeycomb structures for adsorption applications, Carbon 36
137 (2006) 464–479. (1998) 981–989.
[7] C.A. Basha, N.S. Bhadrinarayana, N. Anantharaman, K.M.M.S. Begum, Heavy metal [43] L.C.A. Oliveira, R.V.R.A. Rios, J.D. Fabris, V.K. Garg, K. Sapag, R.M. Lago, Activated
removal from copper smelting effluent using electrochemical cylindrical flow carbon/iron oxide magnetic composites for the adsorption of contaminants in
reactor, J. Hazard. Mater. 152 (2008) 71–78. water, Carbon 40 (2002) 2177–2183.
[8] J.F. Ferguson, J. Gavis, A review of the arsenic cycle in nature waters, Water Res. 6 [44] P. Mondal, C.B. Majumder, B. Mohanty, Effects of adsorbent dose, its particle size and
(1972) 1259–1274. initial arsenic concentration on the removal of arsenic, iron and manganese from
[9] D. Mohan, C.U. Pittman Jr., Arsenic removal from water/wastewater using simulated ground water by Fe3+ impregnated activated carbon, J. Hazard. Mater.
adsorbents—a critical review, J. Hazard. Mater. 142 (2007) 1–53. 150 (2008) 695–702.
[10] H. Yamamuchi, B.A. Fowler, Toxicity and metabolism of inorganic and methylated [45] G.S. Zhang, J.H. Qu, H.J. Liu, A.T. Cooper, R.C. Wu, CuFe2O4/activated carbon compos-
arsenicals, in: J.O. Nriagu (Ed.), Arsenic in the Environment Part II. Human Health ite: a novel magnetic adsorbent for the removal of acid orange II and catalytic regen-
and Ecosystem Effects, Wiley, New York 1994, pp. 35–53. eration, Chemosphere 68 (2007) 1058–1066.
[11] J.C. Ng, Environmental contamination of arsenic and its toxicological impact on [46] J.W. Shim, S.J. Park, S.K. Ryu, Effect of modification with HNO3 and NaOH on metals
humans, Environ. Chem. 2 (2005) 146–160. adsorption by pitch-based activated carbon fiber, Carbon 39 (2001) 1635–1642.
[12] V.M. Boddu, K. Abburi, J.L. Talbott, E.D. Smith, R. Haasch, Removal of As(III) and [47] C.A. Backes, R.G. McLaren, A.W. Rate, R.S. Swift, Kinetics of cadmium and cobalt de-
As(V) from aqueous medium using chitosan-coated biosorbent, Water Res. 42 sorption from iron and manganese oxides, Soil Sci. Soc. Am. J. 59 (1995) 778–785.
(2008) 633–642. [48] M. Muroi, R. Street, P.G. McCormick, Magnetic properties of ultrafine MnFe2O4 pow-
[13] WHO, Guidelines for Drinking Water Quality, World Health Organization, Geneva, ders prepared by mechanochemical processing, Phys. Rev. B Condens. Matter 63
1993 41. (2001) 184414–184420.
[14] European Commission Directive, 98/83/EC, Related with Drinking Water Quality [49] R. Wu, J. Qu, Removal of water-soluble azo dye by the magnetic material MnFe2O4, J.
Intended for Human Consumption, Brussels, Belgium, 1998. Chem. Technol. Biotechnol. 80 (2005) 20–27.
[15] T. Nishimura, Y. Umetsu, Oxidative precipitation of arsenic(III) with manganese(II) [50] Y. Tian, M. Wu, X. Lin, P. Huang, Y. Huang, Synthesis of magnetic wheat straw for
and iron(II) in dilute acidic solution by ozone, Hydrometallurgy 62 (2001) 83–92. arsenic adsorption, J. Hazard. Mater. 193 (2011) 10–16.
[16] O.X. Leupin, S.J. Hug, Oxidation and removal of arsenic(III) from aerated groundwa- [51] S. Zhang, H. Niu, Y. Cai, X. Zhao, Y. Shi, Arsenite and arsenate adsorption on
ter by filtration through sand and zero-valent iron, Water Res. 39 (9) (2005) coprecipitated bimetal oxide magnetic nanomaterials: MnFe2O4 and CoFe2O4,
1729–1740. Chem. Eng. J. 158 (2010) 599–607.
314 M.S. Podder, C.B. Majumder / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 153 (2016) 298–314
[52] J.G. Parsons, M.L. Lopez, J.R. Peralta-Videa, J.L. Gardea-Torresdey, Determination of
arsenic(III) and arsenic(V) binding to microwave assisted hydrothermal syntheti-
cally prepared Fe3O4, Mn3O4, and MnFe2O4 nanoadsorbents, Microchem. J. 91
(2009) 100–106.
[53] N. Yang, S.M. Zhu, D. Zhang, S. Xu, Synthesis and properties of magnetic Fe3O4-
activated carbon nanocomposite particles for dye removal, Mater. Lett. 62 (2008)
645–647.
[54] J.L. Gong, B. Wang, G.M. Zeng, C.P. Yang, C.G. Niu, Q.Y. Niu, W.J. Zhou, Y. Liang, Re-
moval of cationic dyes from aqueous solution using magnetic multi-wall carbon
nanotube nanocomposite as adsorbent, J. Hazard. Mater. 164 (2009) 1517–1522.
[55] L.M. Mateos, E. Ordóñez, M. Letek, J.A. Gil, Corynebacterium glutamicum as a model
bacterium for the bioremediation of arsenic, Int. Microbiol. 9 (2006) 207–215.
[56] P. Kotrba, L. Dolecková, V. de Lorenzo, T. Ruml, Enhanced bioaccumulation of heavy
metal ions by bacterial cells due to surface display of short metal binding peptides,
Appl. Environ. Microbiol. 65 (1999) 1092–1098.
[57] M. Valls, S. Atrian, V. de Lorenzo, L.A. Fernández, Engineering a mouse metallothio-
nein on the cell surface of Ralstonia eutropha CH34 for immobilization of heavy
metals in soil, Nat. Biotechnol. 18 (2000) 661–665.
[58] J.L. Peyret, N. Bayan, G. Joliff, T. Gulik-Krzywicki, L. Mathieu, E. Schechter, G. Leblon,
Characterization of the cspB gene encoding PS2, an ordered surface-layer protein in
Corynebacterium glutamicum, Mol. Microbiol. 9 (1993) 97–109.
[59] P. Mondal, C.B. Majumder, B. Mohanty, Treatment of arsenic contaminated water in
a batch reactor by using Ralstonia eutropha MTCC 2487 and granular activated
carbon, J. Hazard. Mater. 153 (2008) 588–599.
[60] V. Mishra, C.B. Majumder, V.K. Agarwal, Zn(II) ion biosorption onto surface of
eucalyptus leaf biomass: isotherm, kinetic, and mechanistic modeling, Clean Soil
Air Water 38 (2010) 1062–1073.
[61] L. Shao, Z. Ren, G. Zhang, L. Chen, Facile synthesis, characterization of a MnFe2O4/ac-
tivated carbon magnetic composite and its effectiveness in tetracycline removal,
Mater. Chem. Phys. 135 (2012) 16–24.
[62] Z. Bianfang, T. Guide, Y. Zonglin, W. Zhenbiao, Y. Qingfen, C. Jianpo, Synthesis of
magnetic manganese ferrite, J. Wuhan Univ. Technol. Mater. Sci. Ed. 22 (2007)
514–517.
[63] A.R. Khan, I.R. Al-Waheab, A. Al-Haddad, A generalized equation for adsorption
isotherms for multi-component organic pollutants in dilute aqueous solution,
Environ. Technol. 17 (1996) 13–23.
[64] M.C. Ncibi, Applicability of some statistical tools to predict optimum adsorption iso-
therm after linear and non-linear regression analysis, J. Hazard. Mater. 153 (2008)
207–212.
[65] M. Hadi, G. McKay, M.R. Samarghandi, A. Maleki, M.S. Aminabad, Prediction of
optimum adsorption isotherm: comparison of chi-square and log-likelihood
statistics, Desalin. Water Treat. 49 (2012) 81–94.
[66] T.F. Edgar, D.M. Himmelblau, Optimization of Chemical Processes, McGraw-Hill,
New York, 1989.
[67] O.T. Hanna, O.C. Sandall, Computational Methods in Chemical Engineering, Prentice-
Hall International, New Jersey, 1995.
[68] M.J. Warrens, On similarity coefficients for 2 × 2 tables and correction for chance,
Psychometrika 73 (2008) 487–502.
[69] M. Haerifar, S. Azizian, An exponential kinetic model for adsorption at solid/solution
interface, Chem. Eng. J. 215–216 (2013) 65–71.
[70] G. McKay, M.S. Otterburn, A.G. Sweeny, Surface mass transfer process during colour
removal from effluents using silica, Water Res. 15 (1981) 321–331.
[71] T.S. Singh, K.K. Pant, Kinetics and mass transfer studies on the adsorption of arsenic
onto activated alumina and iron oxide impregnated activated alumina, Water Qual.
Res. J. Can. 41 (2006) 147–156.
[72] Y.S. Al-Degs, M.I. El-Barghouthi, A.H. El-Sheikh, G.M. Walker, Effect of solution pH,
ionic strength, and temperature on adsorption behavior of reactive dyes on activat-
ed carbon, Dyes Pigments 77 (2008) 16–23.
[73] J. Guo, A.C. Lua, Textural and chemical characteristics of activated carbon prepared
from oil–palm stone with H2SO4 and KOH impregnation, Microporous Mesoporous
Mater. 32 (1999) 111–117.
[74] R. Rakhshaee, M. Giahi, A. Pourahmad, Studying effect of cell wall's carboxyl–
carboxylate ratio change of Lemna minor to remove heavy metals from aqueous
solution, J. Hazard. Mater. 163 (2009) 165–173.
[75] J.M. Smith, Chemical Engineering Kinetics, 3rd ed. McGraw-Hill, New York, 1981
310–322.
[76] D. Ranjan, M. Talat, S.H. Hasan, Biosorption of arsenic from aqueous solution using
agricultural residue ‘rice polish’, J. Hazard. Mater. 166 (2009) 1050–1059.
[77] M. Haerifar, S. Azizian, Fractal-like adsorption kinetics at the solid/solution interface,
J. Phys. Chem. C 116 (2012) 13111–13119.
[78] M.C. Ncibi, R. Ranguin, M.J. Pintor, V. Jeanne-Rose, M. Sillanpää, S. Gaspard, Prepara-
tion and characterization of chemically activated carbons derived from Mediterra-
nean Posidonia oceanica (L.) fibres, J. Anal. Appl. Pyrolysis 109 (2014) 205–214.
[79] D. Kavitha, C. Namasivayam, Experimental and kinetic studies on methylene blue
adsorption by coir pith carbon, Bioresour. Technol. 98 (2007) 14–21.
[80] S. Rengaraj, J.-W. Yeon, Y. Kim, Y. Jung, Y.-K. Ha, W.-H. Kim, Adsorption characteris-
tics of Cu(II) onto ion exchange resins 252H and 1500H: kinetics, isotherms and
error analysis, J. Hazard. Mater. 143 (2007) 469–477.
[81] G. Atun, G. Hisarli, Adsorption of carminic acid, a dye onto glass powder, Chem. Eng.
J. 95 (2003) 241–249.
[82] W.J. Weber Jr., J.C. Morris, Intraparticle diffusion during the sorption of surfactants
onto activated carbon, J. Sanit. Eng. Div. Am. Soc. Civ. Eng. 89 (1963) 53–61.
[83] L. Nouri, I. Ghodbane, O. Hamdaoui, M. Chiha, Batch sorption dynamics and
equilibrium for the removal of cadmium ions from aqueous phase using wheat
bran, J. Hazard. Mater. 149 (2007) 115–125.
[84] A.K. Meena, G.K. Mishra, P.K. Rai, C. Rajagopal, P.N. Nagar, Removal of heavy metal
ions from aqueous solutions using carbon aerogel as an adsorbent, J. Hazard.
Mater. 122 (2005) 161–170.
[85] J. Romero-Gonźalez, J.R. Peralta-Videa, E. Rodríguez, S.L. Ramirez, J.L. Gardea-
Torresdey, Determination of thermodynamic parameters of Cr(VI) adsorption
from aqueous solution onto Agave lechuguilla biomass, J. Chem. Thermodyn. 37
(2005) 343–347.
[86] K.P. Yadav, B.S. Tyagi, Fly-ash for the treatment of Cd-rich effluent, Environ. Technol.
Lett. 8 (1987) 225–234.
[87] P. Roy, N.K. Mondal, K. Das, Modeling of the adsorptive removal of arsenic: a
statistical approach, J. Environ. Chem. Eng. 2 (2014) 585–597.
[88] W.S.W. Ngah, M.A.K.M. Hanafiah, Adsorption of copper on rubber (Hevea
brasiliensis) leaf powder: kinetics, equilibrium and thermodynamic studies,
Biochem. Eng. J. 39 (2008) 521–530.
[89] G. Crini, P.-M. Badot, Application of chitosan, a natural aminopolysaccharide, for dye
removal from aqueous solutions by adsorption processes using batch studies: a
review of recent literature, Prog. Polym. Sci. 33 (2008) 399–447.