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Photocatalytic degradation of pharmaceutical

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Article in Ecotoxicology and Environmental Safety March 2015
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Ecotoxicology and Environmental Safety 121 (2015) 263270

Contents lists available at ScienceDirect

Ecotoxicology and Environmental Safety

journal homepage: www.elsevier.com/locate/ecoenv

Photocatalytic degradation of pharmaceutical wastes by alginate

supported TiO2 nanoparticles in packed bed photo reactor (PBPR)
Santanu Sarkar a, Sudip Chakraborty b, Chiranjib Bhattacharjee a,n
a

Department of Chemical Engineering, Jadavpur University, Kolkata 700032, India

Department of Informatics, Modeling, Electronics and Systems Engineering (D.I.M.E.S.), University of Calabria, Via-P. Bucci, Cubo 42a, 87036 Rende (CS),
Italy
b

art ic l e i nf o

a b s t r a c t

Article history:
Received 29 November 2014
Received in revised form
19 February 2015
Accepted 24 February 2015
Available online 3 March 2015

In recent years deposal of pharmaceutical wastes has become a major problem globally. Therefore, it is
necessary to removes pharmaceutical waste from the municipal as well as industrial efuents before its
discharge. The convectional wastewater and biological treatments are generally failed to separate different drugs from wastewater streams. Thus, heterogeneous photocatalysis process becomes lucrative
method for reduction of detrimental effects of pharmaceutical compounds. The main disadvantage of the
process is the reuse or recycle of photocatalysis is a tedious job. In this work, the degradation of aqueous
solution of chlorhexidine digluconate (CHD), an antibiotic drug, by heterogeneous photocatalysis was
study using supported TiO2 nanoparticle. The major concern of this study is to bring down the limitations
of suspension mode heterogeneous photocatalysis by implementation of immobilized TiO2 with help of
calcium alginate beads. The alginate supported catalyst beads was characterized by scanning electron
microscopy coupled with energy dispersive X-ray spectroscopy (SEM/EDAX) as well as the characteristic
crystalline forms of TiO2 nanoparticle was conrmed by XRD. The degradation efciency of TiO2 impregnated alginate beads (TIAB) was compared with the performance of free TiO2 suspension. Although,
the degradation efciency was reduced considerably using TIAB but the recycle and reuse of catalyst was
increased quite appreciably. The kinetic parameters related to this work have also been measure.
Moreover, to study the susceptibility of the present system photocatalysis of other three drugs ibuprofen
(IBP), atenolol (ATL) and carbamazepine (CBZ) has been carried out using immobilized TiO2. The continuous mode operation in PBPR has ensured the applicability of alginate beads along with TiO2 in
wastewater treatment. The variation of residence time has signicant impact on the performance of
PBPR.
& 2015 Elsevier Inc. All rights reserved.

Keywords:
Photocatalysis
Alginate beads
Pharmaceutical compounds
Packed bed photo reactor

1. Introduction
Wastewaters from pharmaceutical industries and from households contain lots of drugs especially antibiotics are vigorously
entering to water environment. Therefore, threats due to pharmaceutical drugs to the aquatic life as well as all living element
become major concern of research work (Carballa et al., 2004;
Hirsch et al., 1998; Ternes, 1998; Kidd et al., 2007; Lange et al.,
2001; Oaks et al., 2004). For remediation of a disease pharmaceutical drugs are frequently used and thereafter without alternation major part of those medicines enters to the environment
through municipal sewage system. Moreover, sometime medicines
are thrown into environment directly and pharmaceutical wastes
n

Corresponding author.
E-mail addresses: cbhattacharyya@chemical.jdvu.ac.in,
c.bhatta@gmail.com (C. Bhattacharjee).
http://dx.doi.org/10.1016/j.ecoenv.2015.02.035
0147-6513/& 2015 Elsevier Inc. All rights reserved.

from the respective industries directly disposed off to the water

bodies (Hirsch et al., 1998; Ternes, 1998; Kidd et al., 2007; HallingSrensen et al., 1998). As a result a gradual growth pharmaceutical
component is observed in water environment. However, it is impossible to separate pharmaceutical compounds i.e. antibiotics,
hormones, steroids, etc. through wastewater treatment and cannot
be degraded by means of biological treatment (Daughton and
Ternes, 1999; Zwiener and Frimmel, 2000). Several groups of researcher have adopted photocatalysis in presence of nanoparticle,
one of the main categories of advanced oxidation process (AOP) to
eliminate detrimental effects of pharmaceutical compounds (Klavarioti et al., 2009).
Heterogeneous photocatalysis in presence of nanoparticle
mainly TiO2 has become a promising pathway for separation of
several micropollutants form wastewater streams (Devipriya and
Yesodharan, 2005; Woo et al., 2009; Zayani et al., 2009; Hsu et al.,
2008; Calza et al., 2006; Sakkas et al., 2007; Zhang et al., 2010; An
et al., 2011; Sarkar et al., 2014a,b). Small size nanoparticle provides

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S. Sarkar et al. / Ecotoxicology and Environmental Safety 121 (2015) 263270

higher surface to volume ratio thus it offers better surface reaction.

Titanium oxide nanoparticle is used frequently due to its strong
oxidizing power, higher photo stability and non-toxic nature
(Gupta and Tripathi, 2011). Many researchers have highlighted
many advantageous sides of photocatalysis in presence of TiO2
nanoparticle although the scale up of heterogeneous photocatalysis process is the main challenging task. The recovery and
reuse of TiO2 nanoparticle at the end of photocatalysis process is
the main obligation of photocatalysis process and eventually it is
very tedious job in practice.
The problem related to the larger scale implementation of
heterogeneous photocatalysis is cumbersome separation and recycling of photo catalyst during the wastewater treatment. This
problem can be obliterated by implementation of immobilization
of TiO2 on solid support. The immobilization is very simple and
easy to execute for immobilization of cells and enzyme (Santos
et al., 2008). However, mentioned method by Santos et al. (2008)
can be adopted to entrap TiO2 nanoparticle. Moreover, it is necessary to develop a cost effective and environment friendly entrapment method so that it can be easily adopted by research
fraternity. Harikumar et al. (2011) described that calcium alginate
was nontoxic, biodegradable, non-immunogenic, water insoluble
and thermally irreversible type of polymer matrix which could
provide better support for immobilization of nanoparticle. Therefore, calcium alginate beads can be used for environment friendly
immobilization of TiO2 nanoparticle and those photo active beads
should be used in wastewater treatment in large scale.
The main goal of this current research work is to develop an
immobilized photocatalytic system to remove pharmaceutical
components from the wastewater. The current research group has
already established that photocatalysis in presence of TiO2 nanoparticle is very much effective in removal of anti-biotic like
chlorhexidine digluconate (CHD) (Das et al., 2014, Sarkar et al.,
2014a,b). Although, the last successful attempt of photocatalytic
degradation of CHD has been done using suspension of photo
catalyst (Das et al., 2014, Sarkar et al., 2014a,b) but it prevails some
limitations which have been described earlier. As per literature
survey, this research work has made the rst attempt to implement immobilized TiO2 using alginate in the eld of pharmaceutical wastewater treatment and at the same time elimination of
disadvantages of suspension mode has been tried so far. Furthermore, a new concept of packed bed photo reactor (PBPR) has been
introduced here in which nanoparticle impregnated alginate beads
have been used as packing material. Introduction of PBPR has been
made to eliminate the major limitation of batch mode during
treatment of large volume of wastewater as PBPR has been operated in continuous mode. Moreover, to ascertain the applicability
of immobilized system as well as PBPR, the present research work
has tried to carry out photocatalytic degradation of different drugs
in continuous mode. Other three pharmaceutical drugs i.e. ibuprofen (IBP), atenolol (ATL) and carbamazepine (CBZ) which have
also some other detrimental effects on environment (Hapeshi
et al., 2010, Georgaki et al., 2014), were also treated with immobilized TiO2 system to check the viability of present treatment
method using PBPR.

(C15H12N2O) were purchased from Sigma-Aldrich to prepare the

simulated solutions for experimental purpose. All experiments
were carried out with ultrapure water from Ariums Pro VF (Sartorius Stedim Biotech) of 18.2 M cm resistivity. All other chemicals i.e. sodium alginate, calcium chloride (di-hydrate) were
purchased from Sigma Aldrich Chemical Co., USA.
2.2. Immobilization of TiO2 in calcium alginate beads
The titanium dioxide impregnated beads were prepared by
entrapping TiO2 nanoparticles in the calcium alginate beads. About
100 mL of casting solution was prepared by mixing 4.0 g (4%) of
sodium alginate powder and 1.04.0 g of TiO2 nanoparticle in ultrapure water and stirring until a homogenous solution was
achieved. First, TiO2 nanoparticle was added to 100 ml water and
stirred for 30 min to form homogeneous suspension and then
sodium alginate was introduced in that solution. The mixture
(100 mL) was injected drop wise into 400 mL CaCl2 solution
(0.5 M) using a syringe (10 mL) with a needle (0.8 mm in diameter,
38 mm in length) to form TiO2 impregnated alginate beads (TIAB).
The TIAB were cured in the CaCl2 solution for overnight at room
temperature and then rinsed with ultrapure water for several
times. Prepared TIAB stored in ultrapure water and kept in 4 C for
future use. Blank beads were also prepared by above mentioned
method but without TiO2 addition.
2.3. Adsorption and photocatalysis
The photocatalytic degradation using suspension mode of TiO2
was carried out under articial UV source in a quartz reactor in the
batch mode. The experimental details have been already described
by Das et al. (2014) and Sarkar et al. (2014a) in suspension mode.
The batch study using TIAB was carried out maintaining the favorable conditions similar to the batch study in suspension mode.
The pH and the temperature were maintained at 10.5 and 30 C
and substrate to catalyst ratio (S/C) was xed at 2.5. The irradiation
time for both systems maintained for 1 h. With certain interval
aliquot solution was piped out from the reaction broth to measure
the concentration of antibiotic, CHD. For the adsorption process,
same type of experimental study was carried out as mentioned
above but without UV irradiation. To increase the efcacy of TIAB
and to eliminate the limitations of batch mode operation, the
photocatalysis has been carried out in continuous mode using
Packed Bed Photo Reactor (PBPR). The present mode of operation
has been illustrated schematically in Fig. 1. The residence time ()
and all other physical parameters were selected according to the
best removal condition achieved in batch mode. To maintain
constant temperature during the photocatalysis reaction the reactor is jacketed for the circulation of coolant and to protect UV

2. Experimental
2.1. Chemical and reagents
Titanium dioxide photocatalyst nanopowder AeroxidesP25
(mixture of rutile and anatase, 718467) of particle size 21 nm with
surface area (BET) 3565 m2 g
1 from Sigma-Aldrich, were used as
photo catalysis. Chlorhexidine digluconate solution (20% w/v),
Ibuprofen (CH3H18O2, purity Z 99%), atenolol and carbamazepine

Fig. 1. Schematic representation of PBPR.

S. Sarkar et al. / Ecotoxicology and Environmental Safety 121 (2015) 263270

light, it is covered with quartz glass so that the wavelength of UV

irradiation is unaltered. An articial UVA tube having 365 nm
wavelengths has been used as a source of UV illumination and the
intensity of UV are xed for PBPR. The void fraction of PBPR is 0.37
under fully loaded with TIAB and according to that the ow rate
was kept constant using peristaltic pump to ascertain a xed residence time. The residence time was varied with change of
pharmaceutical drugs and the residence time was a variable
parameter during photocatalysis of individual drug. The experimental study was continued till the outlet concentration of pharmaceutical drug became constant. To study the reusability of TIAB
multiple experimental runs were carried out using same beads.
In case of other three drugs, the photocatalytic degradation was
carried in continuous mode only. The variable process parameters
of the best t were taken from the earlier batch studies, carried
out by other research groups (Hapeshi et al., 2010; Georgaki et al.,
2014) using TiO2 suspension.
2.4. Analytical methods
2.4.1. Characterization of immobilized photo catalyst
The physical appearance of TIAB was white color spherical
particles with average diameter of 3.33 mm. The surface
morphologies of the entrapped catalysts inside alginate matrix
were evaluated by using scanning electron microscopy (SEM) in
combination with energy dispersive X-ray analysis (EDAX). The
X-ray powder diffraction (XRD) pattern for the TIAB was recorded
using Shimadzu XRD-6000 diffractometer using Cu K radiation
(l 1.54 ) operating at 40 kV, 20 mA and scanning rate of
2 min
1. The BET specic surface areas of the TIAB was determined by the N2 adsorptiondesorption method.
2.4.2. Measurement of degradation
The concentration of chlorhexidine digluconate concentration

265

in the reaction mixtures was determined using spectrophotometer

at 275 nm. The details of identication have been elaborately described in the recent publication by the same research group (Das
et al., 2014; Sarkar et al., 2014a). To validate the concentration
measurements and for the identication of product pattern, RPHPLC system (Cyber Lab, Millbury, USA) with Zorbax SB Phenyl
column (4.8  250 mm2, 5 mm, Agilent, USA) was used. The details
of HPLC analysis and the chromatogram from HPLC were described
earlier (Das et al., 2014) and chromatogram ensured the generation of by-product. To characterize the degraded by-products from
CHD, the mass spectra analysis was done in Quadrapole-TOF Micromass Spectrometer (Waters Co., USA). The details of chromatogram and mass spectroscopy had been indicated in the experimental research work by the present research group (Das et al.,
2014).
The residue of other three drugs and identication & measurement of degraded by-products from ATL, IBP and CBZ were
carried out according to the principles that described by Hapeshi
et al. (2010) and Georgaki et al. (2014) respectively. In all three
cases HPLC (Perkin Elmer, Series 200) was used with essential C18
column for IBP and ATL and Hypersil BDS C8 column for CBZ
(250 mm  4 mm  5 m).
The removal percentage of pharmaceutical components has
been calculated during the whole study using Eq. (1).

Ct
% Removal of pharmaceutical component = 1
100%
C

(1)

where, Ct is the concentration of any drug at any time t and C0 is

corresponding value at t 0.

Fig. 2. (a) Photograph of TIAB and (b) and (C) SEM images at different magnications, (d) EDXA spectra of a single TIAB congaing 4% alginate beads and 2% TiO2 nanoparticles
by weight.

266

S. Sarkar et al. / Ecotoxicology and Environmental Safety 121 (2015) 263270

3. Results and discussions

3.1. Characterization of TIAB
The formation of nano-TiO2 impregnated bead (Fig. 2a) was
conrmed by SEM with EDXA and XRD patterns. TiO2 nanoparticles were entrapped in a polymeric matrix to study its activity
towards the photo catalytic degradation of antibiotic drugs. Calcium alginate was used as the solid support in this research topic.
Calcium alginate beads in diluted acidic and alkaline solutions
were mechanically stable. SEM analysis was carried out to conrm
the presence of nanoparticles, and its distribution pattern in
polymeric matrix. A representative SEM image (Fig. 2b and c)
shows that most of the particles are well distributed. The quantitative compositional analysis of the TiO2 nanoparticle entrapped
beads was carried out using EDXA spectroscopy measurements.
The spectra conrm the presence of TiO2 in the structure. The
spectra were recorded from a single bead which was produced
from casting solution containing 4% alginate and 2% TiO2 nanoparticles by weight. From the measurements, it was ensured that
the each bead consisted of an average 6.21% Ti, 18.14% O2, 15.43%
Ca, 9.83% Na and 47.28% Cl2 and the EDXA spectrum has been
shown in Fig. 2(d). EDXA analysis showed minimum level of impurities were present inside the alginate beads. The characterization by XRD evidenced the amorphous nature of the TIAB.
Therefore, it was difcult to identify the crystalline phases of TiO2.
Under reduce scanning velocity two phases of TiO2, anatase and
rutile phases were observed. The BET surface area of the same
TIAB was measured to be 21.43 m2 g
1.
3.2. Effect of alginate to catalyst (A/C) ratio
The main process parameter of the current system is alginate to
catalyst ratio as all other parameters are kept same with the
parametric values from the earlier study (Das et al., 2014). It refers
that at S/C ratio (substrate to catalyst ratio) 2.5, pH of 10.5, temperature of 30 C and UV intensity of 80 W/cm2 the removal
percentage of CHD reached its steady state value after 1 h. To study
the effect of alginate to catalyst (A/C) ratio, it was varied in four
different ways from ratio 0.5 to 4.0 and the effect has been clearly
indicated in Fig. 3 though so many trial experiments were conducted with the variation of A/C ratio. Fig. 3 reveals that with
decrease of A/C ratio adsorption efciency of the system decreases
for the current system. With increase of A/C ratio concentration of
nanoparticle inside alginate matrix was decreased, therefore more

Fig. 3. Effects of A/C ratio on both adsorptions an photocatalysis process and the
interdependency between adsorption and photocatalysis.

porous vacant sites were available on outer surface of beads to

adsorb the substrate molecules. Thus, higher adsorption was observed for lower catalyst concentration. TiO2 nanoparticles were
entrapped inside porous matrix of beads therefore; during photocatalysis a different observation was identied. Both at lower
and higher value of A/C ratio photocatalytic activity were reduced.
Lower value of A/C ratio refers higher catalyst concentration and
higher catalyst concentration causes problem for UV penetration
(Das et al., 2014; Sarkar et al., 2014a). As a result at lower value of
A/C ratio photocatalytic degradation of CHD was reduced. But at
higher A/C ratio, available active site on alginate beads for photocatalytic reaction was not sufcient. Moreover, at similar situation TiO2 distribution on surface of the alginate beads was inadequate which referred poor amount of active sites was available
for photocatalysis. Larger value of A/C refers higher concentration
of alginate present in TIAB and as a result the opacity of the alginate beads increases which causes lower UV penetration
through alginate surface to reach the active site of the TiO2 nanoparticle. Therefore, at that particular ratio it was impossible to
degrade CHD completely by photocatalysis. On the contrary the
residual amount of CHD after adsorption process could be degraded completely by photocatalysis using alginate beads with A/C
ratio of 2. However, for this type of reaction A/C ratio played the
major role for percentage removal of pharmaceutical component
and it should be optimized to achieve better removal of the pollutants from the system.
Minute observation on Fig. 3 could reveal that at lower value of
A/C ratio during the photocatalysis same percentage of CHD was
removed. This was due to at lower value of such ratio the distributions of TiO2 on the upper surface of TIAB was similar and at
same time the difculty of UV penetration through alginate beads
reduced to some extent.
From the above discussion, it may be concluded that A/C ratio
should be maintained in such way that both the stability and the
catalytic activity of TIBA can reach their optimum value. Then only
TIBA can be reused several times without losing catalytic activity
in photocatalytic wastewater treatment.
3.3. Adsorption and photocatalysis of CHD
Simultaneous adsorption and photocatalysis process was carried out at 30 C and pH of 10.5 with S/C of 2.5 in batch mode.
Those process parameters have been chosen from the previous
study (Das et al., 2014) carried out using TiO2 suspension to
evaluate the comparison between suspension and immobilized
mode of operations. Moreover, at that parametric condition maximum removal of CHD was possible. After 1 h adsorption process,
photocatalysis was carried out for 1 h to nd out the removal efciency of photocatalysis alone. From Fig. 3 it has been observed
that under same operating condition and maintaining A/C ratio at
2, the maximum number of CHD molecules have been adsorbed on
the surface of the TIAB and after that left amount of CHD has been
degraded with help of photocatalysis reaction. This observation
can be justied with help of porous structure of TIAB. As it has
already been mentioned that TIAB offered higher BET surface area
therefore CHD was adsorbed inside the porous matrix of alginate
beads. As a consequence free molecule of CHD was not available
for photocatalytic degradation. The main advantage of this process
with the help of TIAB almost all molecules of the pharmaceutical
component (CHD) can be removed within 2 h. Though, in current
process adsorption played the major role to remove pharmaceutical waste from the system. Therefore, to understand efcacy of
TIAB, the fresh pharmaceutical component was continually fed to
the system for photocatalytic degradation. In later part of the
present article it would be understandable that the extent of adsorption on photocatalytic degradation using TIAB.

S. Sarkar et al. / Ecotoxicology and Environmental Safety 121 (2015) 263270

267

3.4. Adsorption and reaction kinetics

In the present study two types of kinetics are involved, one is
adsorption kinetics and other is reaction kinetics during photocatalysis. Both are necessary to understand the direction and extent of the removal process. First adsorption of target molecule
takes place on TIAB surface and then photocatalytic degradation of
that molecule occurs. Here, CHD was adsorbed on TIAB surface and
simultaneously it was disappeared from the system due photocatalytic reaction.
The phenomenon of adsorption of a substrate on any adsorbent
can be explained through isotherms. For the liquidsolid adsorption the amount of adsorbate absorbs on the solid adsorbent surface is the function of concentration of adsorbate at constant
temperature. In the present study TIAB is absorbent and CHD is
absorbate. Though, different types of isotherm have already been
developed; among those Langmuir isotherms is quite popular to
describe the adsorption phenomenon on the solid surface. Moreover, this was developed considering that adsorbate was inert to
active surface without no phase change and single molecule could
occupy one active site thus mono layer formation took place. In
this study, the experimental adsorption data has been well tted
with Langmuir isotherm than all other isotherms, which can be
expressed mathematically using Eq. (2) (Stumn and Morgan, 1996)
and in the isotherm study, initial CHD concentration was the
variable parameter, whereas the others were kept constant.

C0
C0
1
=
+
qequ
qmaxKCHDG
qmax

(2)

where, qequ is the amount of CHD adsorbed at equilibrium per

gram of TIAB, C0 initial equilibrium concentration of CHD (main
driving force), qmax is the maximum amount of CHD adsorbed at
equilibrium per gram of TIAB; KCHD adsorption rate constant (g
1).
The tted curve of C0 vs C0/qequ has linearity with the correlation
coefcient of 0.897 that has been shown in Fig. 4(a). The value
qmax and KCHD have been obtained as 0.286 and 0.035 g
1
respectively from the same plot.
The heterogeneous photocatalysis reactions generally follow
pseudo rst order reaction kinetics (Sarkar et al., 2014b). A good
agreement between theoretical pseudo rst order kinetic model
and experimental observation has been observed and that can be
expressed using Eq. (3).

rphoto
=

dC
= kCt
dt

(3)

where, rphoto
and k is pseudo st order reaction rate and rate
constant respectively. The above equation can be written after
integrating with boundary condition

Ct
ln = kt
C0

(4)

Initial concentration of pharmaceutical waste (CHD) is represented as C0. The rate constant values can be calculated from
the slope of the plot of
ln(Ct/C0) vs time From Fig. 4(b) the value
of rate constant (k) was calculated as 0.0555 min
1.
3.5. Comparison between suspension and entrapment mode
The present research group already observed in suspension
mode maximum 30% CHD was removed due to adsorption and up
to 70% removal was possible during photocatalytic degradation
(Das et al., 2014) at earlier specied condition. In that case photocatalysis was predominant for removal of CHD. Although at same
parametric condition, in the present study, the adsorption process
on TIAB played the major contribution (79%) for removal of CHD

Fig. 4. Measurement of
(b) photocatalysis of CHD.

kinetics

parameters

for

(a)

adsorption

and

from the system. Moreover, with combination of both adsorption

and photocatalysis could remove 99% of present antibiotic form
the reaction mixture. Therefore, in batch study adsorption played
the important role for the removal of pharmaceutical component,
CHD from the simulated solution.
3.6. Photocatalytic degradation using PBPR
In PBPR, TIAB was used as packing material. In the center of the
packed column UV source was there. The sufcient time was
provided for photocatalytic degradation. The operating parameters
were chosen from the batch studies which were performed by
several researchers (Das et al., 2014; Hapeshi et al., 2010; Georgaki
et al., 2014). During all experimental observation A/C ratio of 2 was
maintained. The photocatalytic degradation of several pharmaceutical drugs has been carried out using PBPR and experimental
observation has been represented clearly in the current context.
3.6.1. Degradation of CHD in PBPR
In the earlier batch study in suspension mode the present research group (Das et al., 2014) has revealed that maximum percentage of CHD can be removed at S/C ratio of 2.5, pH 10.5 and
ambient temperature (30 C). In the present case same parametric
condition has been maintained during the photocatalytic degradation in PBPR and outlet concentration of CHD has been
measured to calculate its removal percentage with time which has
been plotted in Fig. 5(a). At the initial stage almost 99% removal
has been observed for 60 min residence time but as the time

268

S. Sarkar et al. / Ecotoxicology and Environmental Safety 121 (2015) 263270

Fig. 5. Percentage removal of different pharmaceutical drugs using TIAB in PBPR at specied conditions.

progress the removal percentage has decreased gradually. In the

connection with that it should be noted, the treated simulated
waste water rst came out from PBPR after 60 min from the start
of removal process. This observation may be explained with the
help of earlier batch study. According to Fig. 3 initially maximum
removals of CHD was possible with help of surface adsorption on
TIAB but as the time progress active sites present in porous matrix
of alginate beads were getting occupied by CHD molecules.
Therefore, effective adsorption was reduced after some time and at
that time only photocatalysis became the predominant factor to
remove pharmaceutical components. Moreover, the substrate
molecules were also available to take part in photocatalysis. It has
also been observed from Fig. 5(a) that removal percentage of CHD
reached to its steady state value after some time. Though, in
continuous mode only 55% steady state removal of CHD was
possible using TIAB in PBPR whereas nearly 70% removal was
achieved (Das et al., 2014) using TiO2 suspension in batch mode.
This contradictory behavior was observed as in suspension mode
all TiO2 nanoparticles were freely available for photocatalysis but
in case of alginate beads catalyst particles were in entrapped
condition. Thus, all nanoparticles could not take part in such reaction. Moreover, lower UV penetration through the alginate surface was one of the major drawbacks of the system and beads
were placed around the UV source in multi-layered condition,
which also caused lower light penetration through TIABs which
were far away from UV light.
3.6.2. Degradation of other drugs
To establish the applicability of PBPR for photocatalytic degradation of pharmaceutical wastes, three other pharmaceutical

components namely ATL, IBP and CBZ were degraded using TIAB in
continuous mode. The removal percentage of those three components has been shown in Fig. 5(b)(d). For all the cases temperature, pH and S/C ratio was maintained at 25 C, 7 and 0.04
respectively. The parametric conditions for ATL was taken as described by Hapeshi et al. (2010) and for other two, it was opted
from the research work Georgaki et al. (2014). The most interesting think is that Hapeshi et al. (2010) and Georgaki et al. (2014)
was experimented with lower value of substrate concentration
such that it could replicate the environmental pollution load due
to those drugs. It has been observed from their studies that at
mentioned condition ATL, IBP and CBZ can be removed up to 85%,
99% and 99% after 60 min, 20 min and 40 min respectively in
suspension mode of operation. For all cases initial concentration
was kept constant at 10 mg/L. In the current study, the continuous
mode of operation has been preformed considering the residence
time is equal to the time after which the maximum removal percentage was obtained by Hapeshi et al. (2010) and Georgaki et al.
(2014) in batch mode. In the present system the steady state
percentage of removal was achieved 58%, 85% and 80% for ATL, IBP
and CBZ when residence times were 60 min, 20 min and 40 min
respectively and those values were much lesser than suspension
mode. The similar observation was observed in case of CHD.
Therefore, similar type of explanation prevails for the removal of
ATL, IBP and CBZ using TIAB.
From the above discussion it is clear that TIAB as well as PBPR
has failed to achieve maximum percentage of removal of pharmaceutical components from the simulated solution. Though, one
thing is conrmed that an appreciable amount of drugs can be
removed by such type of continuous mode of photocatalysis

S. Sarkar et al. / Ecotoxicology and Environmental Safety 121 (2015) 263270

269

degradation process for pharmaceutical wastewater treatment.

The obtained results showed that the efciency decreases from
99% to 85%. This is likely due to the fouling of porous surface TIAB
as well as the catalyst surface and loss of catalyst due to repeated
acid wash.

4. Conclusions

Fig. 6. The recycling efciency of TIAB in continuous mode during CHD removal.

process and therefore, large volume of wastewater can be treated

by the present system. Moreover, TIBA also ensures the reduction
of loss of valuable photocatalyst and its contamination. Accordingly, the reusability of nanoparticle in immobilized condition has
been studied here.
3.6.3. Effect of residence time in PBPR
Residence time () is the time period that spends by a molecule
in a system. Higher residence time refers longer staying and vice
versa. To understand the effect of on the performance of PBPR,
has been decreased from the value of residence time in batch
mode operation (Das et al., 2014, Hapeshi et al., 2010; Georgaki
et al., 2014) for each drug i.e. CHD, ATL, IBP and CBZ. The has
been varied in three different ways for each antibiotic and results
have been plotted in Fig. 5. It has been observed that at a specied
condition with decrease of the removal percentage of any drug
has decreased very rapidly. This was happened during removal of
any pharmaceutical components because lower value of provided short time period of adsorption and photocatalysis as well. A
sufcient amount time is required to come in contact between
catalyst and target molecule. Thus, in case PBPR higher value of
residence time is favorable though it is not possible to increase
that value innitely. Moreover, higher loading concentration of
pharmaceutical components in waste efuents leads to increase
residence time because at that particular condition more time is
required for adsorption and photocatalytic degradation. At larger
value of , the inlet and outlet ow rate of reactor becomes lower
hence the volume of wastewater which can be handled by PBPR
per unit time also reduces at a particular condition. The liquid
chandelling capacity by a PBPR can be kept constant at higher
residence time; the volume of the reactor should be increased
accordingly which is not feasible in practice. Therefore, the residence time should be maintained in such a way that the removal
percentage of pharmaceutical component can reach to desired
value and at the same time the PBPR can handle large volume of
pharmaceutical wastewater.
3.7. Recycling of photocatalyst
TIAB can be recycled effectively which makes the process cost
effective. To study the reusability, the catalyst was recycled ve
times in continuous mode of operation using PBPR during degradation of CHD and degradation efciency was recorded which
had been plotted in Fig. 6. At optimized conditions for photocatalysis the degradation of CHD were determined, the catalyst
was recovered by giving mild acid water wash and again used in

The above study is very much important considering the aspects of recycling and reuse of TiO2 nanoparticles in continuous
mode operation. After suspension mode study, A/C ratio is the
most important parameter which is needed to be optimized for
entrapment mode photocatalysis. TIAB can efciently remove the
pharmaceutical components from the reaction mixture though the
reduction of antibiotic activity is less signicant. The uses of alginate beads as immobilization of photo catalysts show some
difculty, mainly lower degradation efciency when compared
with suspension mode photocatalysis. But with the help of PBPR
appreciable percentage of pharmaceutical drugs can be removed
and large amount of wastewater can be treated using such system.
The residence time has signicant effect on the performance of
PBPR and at higher value of it produces better efciency of PBPR.
Finally, TIAB can be reused without losing its effectiveness for at
least ve cycles in PBPR which is main advantage to make the
process more cost effective over the suspension mode of photocatalysis. Some necessary modications should be incorporated to
enhance the photocatalytic performance of alginate beads. Then
only this methodology can be viable for large scale pharmaceutical
wastewater treatment.

Acknowledgement
The work reported in this article is part of an Indo-Bulgarian
project (vide sanction letter no. INT/BULGARIP-09/2012), funded
by Department of Science & Technology (Government of India).
Accordingly, the contributions of DST (India) are gratefully
acknowledged.

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