Journal of Industrial and Engineering Chemistry 20 (2014) 979–987

Contents lists available at SciVerse ScienceDirect

Journal of Industrial and Engineering Chemistry

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

Removal of pharmaceutical and personal care products (PPCPs)

pollutants from water by novel TiO2–Coconut Shell Powder (TCNSP)
composite
Majeda Khraisheh a,*, Jongkyu Kim b, Luiza Campos b, Ala’a H. Al-Muhtaseb c,
Alaa Al-Hawari d, Mohammad Al Ghouti e, Gavin M. Walker f,g
a
Department of Chemical Engineering, Qatar University, P.O. Box 2713, Doha, Qatar
b
Department of Civil, Environmental and Geomatic Engineering, University College London, WC1E 6BT, UK
c
Petroleum and Chemical Engineering Department, Faculty of Engineering, Sultan Qaboos University, Muscat, Oman
d
Department of Civil Engineering, Qatar University, P.O. Box 2713, Doha, Qatar
e
Department of Environmental and Biological Sciences, Qatar University, P.O. Box 2713, Doha, Qatar
f
School of Chemistry and Chemical Engineering, Queen’s University Belfast, Belfast BT9 5AG, Northern Ireland, UK
g
Materials Surface Science Institute, Department of Chemical and Environmental Sciences, University of Limerick, Ireland

A R T I C L E I N F O A B S T R A C T

Article history: Photocatlytic removal of three pharmaceutical and personal care products pollutants using novel TiO2–
Received 3 February 2013 Coconut Shell Powder (TCNSP) composite was investigated. The photocatalytic degradation rate of PPCPs
Accepted 23 June 2013 generally increased with increasing light intensity and dissolved oxygen concentration. The degradation
Available online 29 June 2013
rate decreased with increasing initial concentration of PPCPs. The PPCPs concentration decreased
substantially under irradiation of UVC when used in conjunction with the TCNSP composite. A number of
Keywords: composite/radiation types and intensities were tested. The concentration rate decrease trend was as:
Pharmaceutical and personal care products
UVC/TCNSP > UVA/TCNSP > UVC > UVA. Under the UVC/TCNP combination, 99% removal was achieved
Photocatalytic degradation
compared to 30% for TiO2.
TiO2
Coconut Shell Powder ß 2013 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights
Recycling performance reserved.

1. Introduction typically at a concentration of hundreds of nano grams per liter to

Recently, pharmaceuticals and personal care products (PPCPs)
have been frequently detected in wastewater treatment plant
effluents, surface, ground and drinking water [1,2] and classified as
emerging pollutants [3]. PPCPs are produced with long shelf life to
meet the customer’s demand, which makes PPCPs persistent in the
environment [4].
The most prominent entry route for PPCPs into the aquatic
environment is the release from water and wastewater treatment
plants (WWTPs). This is due to a large proportion of medication
taken by patients passes through their body unmodified and
travels via urine and feces to the wastewater [5]. The sludge
produced in WWTPs is commonly applied in agricultural fields as a
soil amendment; the occurrence of pharmaceuticals, in soils, with
low sorption affinity can contribute to the contamination of
adjacent surface and ground waters through run-off and infiltra-
tion. PPCPs have been found in WWTP effluents around the world
* Corresponding author. Tel.: +974 33166752.
E-mail address: m.Khraisheh@qu.edu.qa (M. Khraisheh).
micrograms-per-liter range [6].
Among those PPCPs carbamazepine, clofibric acid and triclosan
were detected at a high frequency [6]. Carbamazepine
(C15H12N2O), a worldwide used antiepileptic drug, is typically
prescribed for treatment of seizure disorders, chronic pain, and for
psychopharmacotherapy [7]. The globally consumed volume of
carbamazepine is estimated to be 1014 t/yr [8]. Studies in Europe
and North America have shown that carbamazepine is one of the
most frequently detected chemicals in WWTP and in river water
[7,9,10].
On the other hand, clofibric acid is an active metabolite of
clofibrate, etofibrate and etofyllinclofibrate, mainly used in the
form of ethyl ester (clofibrate) as a blood lipid regulator and was
identified as refractory contaminant in several investigations of
municipal sewage influents [10]. This compound is resistant under
anoxic and aerobic conditions in biodegradation studies. In
laboratory experiments using soil columns, clofibric acid did not
show any signification sorption, leaching almost through the soil
column without retardation [3,10].
Triclosan is a lipophilic and phenolic compound. This com-
pound becomes a widespread contaminant in human body and

1226-086X/$ – see front matter ß 2013 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.jiec.2013.06.032
980 M. Khraisheh et al. / Journal of Industrial and Engineering Chemistry 20 (2014) 979–987
environment because of its lipophilic characteristics. It has a wide-
spread use in a variety of consumer products including toothpaste,
deodorant, soaps, polymer and fibers [11]. Triclosan is not acutely
toxic to mammals but in vitro studies indicated that at low
concentrations of triclosan may disturb metabolic systems and
hormone homeostasis [12,13].
Different treatment methods have been reported such as
coagulation–flocculation [14], biodegradation [15], biofiltration
[16], ozonation [17], chemical precipitation [18] and adsorption
[1]. However, it is reported that these conventional treatments
such removed a maximum of 25% of PPCPs [19].
In recent years, heterogeneous photocatalysis gained increased
attention owing to its widespread environmental application and
potential to remove aqueous pollutants [20]. This process is active,
low in cost, non-toxic, and chemically stable over a wide pH range
[21]. Practically, the commercial TiO2 nanopowder is the most
active photocatalyst used in wastewater treatment. Several routes
have been explored to prepare TiO2 supported photocatalysts on a
variety of supports such activated carbon and carbon precursor.
Coconut shell is a particularly interesting raw material as precursor
of carbon due to the excellent natural structure and low ash
content [22]. In addition, it is a waste product from the agriculture
and food processing operations with little or no economic value
and their disposal is not only costly but may also cause
environmental issues [23].
In this study, the photocatalytic activity of the novel TiO2–
Coconut Shell Powder (TCNSP) composite for the photodegrada-
tion of three PPCPs pollutants is investigated under UVC (254 nm)
and black light blue UVA (365 nm) irradiation. Effect of various
process parameters such as initial concentration of PPCPs; TCNSP
loading; light intensity; dissolved oxygen, and pH were also
studied as well as recycling performance. The physicochemical
properties of the prepared TiO2–Coconut Shell Powder (TCNSP)
composite have been fully characterized and reported previously
[24].
2. Materials and methods
2.1. Synthesis of TiO2–Coconut Shell Powder (TCNSP) composite
All the chemicals used in this work were of analytical grade. The
water used in the preparation of all the solutions was obtained
from an Ondeo water purification system (Cambridge, UK).
Coconut Shell Powder was used as the main raw material in the
production of TCNSP. The TCNSP was purchased from Sri Lanka via
a Korean based company (Wooil E.R.S. Co. Ltd., Korea). Composi-
tion analysis on the material showed that it contained 58.0%
holocellulose (of which 45.0% cellulose and 13.0% hemicellulose),
39% lignin and the rest water.
Novel TCNSP composite was synthesized by coating raw CNSP
(particle size of 0.4–0.2 mm) with TiO2 via acid-catalyzed sol–gel
method [25]. The TCNSP composites were prepared using the
procedure described in [24]. The granulation process and the
production of the TCNSP composite pellets along with the physical
and chemical characterization are reported by the authors
elsewhere [24].
2.2. PPCPs samples preparation
Carbamazepine, clofibric acid and triclosan powders were
obtained from Sigma (UK), and were used without further
purification. Table 1 summarizes the main chemical structure of
the three model materials used in this study. 50 mg of target
sample was dissolved into 50 ml of HPLC grade methanol (SK
Chemical, Korea). The sample was stirred for 24 h to ensure a
complete dissolution [26] and then stored at 4 8C. The sample
solutions for all photocatalysis reaction experiments were
prepared by adding ultra-pure water with the stock solution to
achieve the desired concentration levels.
2.3. Fixed bed reactor
The photocatalytic reaction of PPCPs was conducted in a fixed
bed photocatalytic reactor coupled with circulative flow mode
(Fig. 1). Two types of UV light sources were used in this study,
TUV11W germicidal UVC lamp (Philips, Holland) providing a
principal output at 254 nm and a black light blue UVA lamp
(Philips, Holland) with a principal output at 365 nm. All parts of
reactor were made from stainless steel in order to enhance the
refracted light intensity and repress organic compound attach-
ment on the surface of the reactor. The temperature of the system
was maintained constant at approximately 25 8C by a cooling
water-bath surrounding the reservoir. Full design details of the
reactor set up are given in [24].
2.4. Photocatalytic reaction experiment
The photocatalytic reaction experiments were carried out by
mixing 10–50 mg/L selected PPCPs solution with the appropriate
amount of TCNSP composite in the range of 60–140 g/L. The
resulting mixture was loaded in the photocatalytic reaction
reactor. The experimental set up for the adsorption and photo-
catalytic reaction (Fig. 1) consists of a batch scale reactor with
water pump for keeping a recirculation regime. In order to induce
satisfactory mixing of the solution, a magnetic stirrer was used in
the reservoir tank of 4 L volume and a device was equipped for
withdrawal of samples. Total volume of the withdrawn sample was
less than 2% (by volume) of the circulated solution. Experiments
were carried out using a total working volume of 3 L and a
recirculation flow rate of 0.1 L/min by a solution circulation pump
(FM 1.30TT, Han-il pump Co. Ltd. Korea), which led to a residence
time of 10 s in the absorbed and irradiated reactor The temperature
of the system was maintained constant at approximately 25 8C by
using a cooling water-bath surrounding the reservoir.
The solution was then irradiated using the UVC or UVA lamps
for 60 min as appropriate. During the photocatalytic reaction
experiments, the temperature was maintained at 25 8C and oxygen
was continuously supplied into the reaction mixture. 5 mL of
PPCPs samples were drawn to measure the absorbance at regular
10 min intervals. The absorbance of the PPCPs samples were
measured with a UV–visible spectrophotometer (Shimadzu UV-
1601, Japan) at the following absorbance maxima: 227 nm, 284
and 218 for clofibric acid, carbamazepine and triclosan respective-
ly. The pH of the solution was adjusted ranging from pH 3 to 11 by
H2SO4 and NaOH to the desired value throughout the experiments.
All experiments were carried out in triplicates. Four different kinds
of materials were tested for their ability to remove the model
chemical compounds. Those included: pure TiO2 pellets, CNSP
pellets, commercial TiO2 bead, and commercial granular activated
carbon, GAC.
3. Results and discussion
3.1. Photocatalytic degradation of PPCPs on TCNSP composite
3.1.1. Effect of initial concentration of PPCPs
It is important from both mechanistic and application point of
view to study the dependence of photocatalytic reaction rate on
the PPCPs concentration. Hence the influence of PPCPs concentra-
tion on the degradation rate was studied at different concentra-
tions varying from 10 to 50 mg/L under a UVC irradiation. Fig. 2
shows the degradation rates of carbamazepine, clofibric acid and
 M. Khraisheh et al. / Journal of Industrial and Engineering Chemistry 20 (2014) 979–987 981

Table 1
Chemical formulas, molecular weight, structure and octanol–water partition coefficients (log Kow) of PPCPs compounds.

Compound Chemical formula MW (g/mol) CAS No. log Kow Structure

Carbamazepine C15H12N2O 236.27 298-46-4 2.45

Clofibric acid C10H11CIO3 214.65 882-09-7 2.88

Triclosan C12H7Cl3O2 289.54 3380-34-5 4.76

triclosan. It can be seen that the degradation rate constant
increased as the initial concentration decreased for all materials
tested due to more organic substrates being adsorbed on the
surface of TCNSP in higher initial concentrations. The generation of
hydroxyl radicals is reduced as a result since there are only fewer
active sites for adsorption of hydroxyl ions and generation of
hydroxyl radicals [27,28]. Furthermore, for higher PPCPs solution
concentrations, the photons created from UV light are intercepted
by the PPCP compounds in solution before they reach the TCNSP
surface. Accordingly, the absorption of photons by the TCNSP
reduces and consequently the efficiency of TCNSP photocatalysis
removal decreases [29]. The generation of intermediates during
the photocatalytic reaction affects the rate constant of its parent
compounds. Within sorption processes higher initial concentra-
tions may yield higher concentrations of adsorbed intermediates,
which affect the overall rate [30].
3.1.2. Effect of TCNSP loading
The effect of different loading of TCNSP composite on the
photocatalytic degradation for the three PPCPs was examined in
the range of 60–140 g/L. Fig. 3 shows the variation of degradation
of pseudo-first order rate constant with different TCNSP composite
loading amount. The rate constants increased from 0.017, 0.026
and 0.034 min1 at 60 g/L TCNSP composite to 0.044, 0.051 and
0.061 min1 at 140 g/L TCNSP composite for carbamazepine,
clofibric acid and triclosan, respectively. As clearly seen, all the
rate constant k1 increased with the increasing TCNSP loading and
k1 was approached up to a certain value at high dosage for these
three PPCP compounds. This is possibly due to the increase in the
total surface area of TCNSP composite; specifically this increased
the number of active sites that are available for the adsorption and
photocatalytic reactions as the loading amount of TCNSP
composite increased [29]. In general, an unlimited increase in

Fig. 1. Schematic diagram of the fixed bed photocatalytic reactor coupled with circulative flow mode.
982 M. Khraisheh et al. / Journal of Industrial and Engineering Chemistry 20 (2014) 979–987

0.06
(a)
50 0.05
10mg/L

Rate constant k1(min-1)

20mg/L
Initial concentration (mg/L)

40 0.04
30mg/L
40mg/L
30 0.03
50mg/L

20 0.02

10 0.01
Carbamazepine Clofibric acid Triclosan

0 0
0 10 20 30 40 50 60 40 60 80 100 120 140
Time(min) TCNSP concentration (g/L)

Fig. 3. Effect of TCNSP composite dosage on the photocatalytic degradation rate

(b) constant of PPCPs (Initial concentration of PPCPs = 30 mg/L, pH = 7.0, irradiation
time = 60 min, oxygenconcentration = 24 mg/L, UVC intensity = 10.5 mW/cm2,
50 T = 25 8C).
10mg/L
Initial concentration (mg/L)

20mg/L
40
30mg/L the three target compounds under sole UVA light were negligibly
30 40mg/L small at 0.001, 0.002 and 0.001 min1 for carbamazepine, clofibric
50mg/L
acid and triclosan, respectively. However, UVC light had slightly
20
higher rate constant of 0.003, 0.004 and 0.003 min1 for
carbamazepine, clofibric acid and triclosan, respectively, compar-
ing with UVA light in the absence of TCNSP composite. This is due
10
to a greater number of photons from a small fraction of 254 nm and
photonic energy [32]. In addition, rate constant in the present of
0 TCNSP composite was significantly increased to 0.025, 0.035 and
0 10 20 30 40 50 60
0.045 min1 at UVA and 0.042, 0.049 and 0.059 min1 at UVC for
Time(min) three target compounds. This may be due to a higher adsorption
efficiency of TCNSP composite and hydroxyl radicals (OH) which
(c) were generated from UV light source with titanium dioxide on the
surface of TCNSP composite contributing to the reaction. This
60 result agrees with the study conducted by Yang et al. [29] who
10mg/L
found that in the presence of titanium dioxide with UVA and/or
Initial concentration (mg/L)

50 20mg/L
UVC radiation, much faster degradation of paracetamol occurred
40
30mg/L compared to reactions without titanium dioxide and radiation
40mg/L only.
30 50mg/L
3.1.4. Effect of light intensity
20 Fig. 5 shows the relationship between the photocatalytic
degradation rates with the light intensity of three PPCPs. The
10 degradation rate of PPCPs was significantly increased with
increasing light intensity. For carbamazepine, the degradation
0
rate increased from 52% at 4.2 mW/cm2 light intensity to 93% at
0 10 20 30 40 50 60
10.5 mW/cm2 light intensity. Degradation rate of both clofibric
Time(min)
acid and triclosan also rose from 60% and 65% to 95% and 97%,
Fig. 2. Effect of initial concentration of PPCPs on the photocatalytic degradation: (a) respectively. This finding suggests that the UV irradiation
carbamazepine; (b) clofibric acid; (c) triclosan (TCNSP composite generates the photons required for the electron transfer from
concentration = 120 g/L, pH = 7.0, irradiation time = 60 min, oxygen the valence band to the conduction band of a TCNSP composite. It
concentration = 24 mg/L, UVC intensity = 10.5 mW/cm2, T = 25 8C). also indicates that the energy of a photon is related to its
wavelength and the overall energy input to a photocatalytic
photocatalyst does not reach an improved effect on the photo- process is depending on light intensity [27].
catalytic degradation. Therefore an optimum loading amount of
photocatalyst is undoubtedly one of the critical design parameters 3.1.5. Effect of dissolved oxygen
for photocatalytic degradation system in any practical application Fig. 6 shows an addition of oxygen varying from 6 mg/L to
[31]. 24 mg/L increased the photocatalytic degradation rate constant of
CBZ up to more than 1.6 times higher, corresponding to the
3.1.3. Effect of irradiation source reaction rate constant changing from 0.025 to 0.042 min1. For
Degradation reaction rates of the three PPCPs were plotted as a clofibric acid and triclosan, the rate constant also increased from
function of irradiation source in Fig. 4. Measured degradation rate 0.032 and 0.038 to 0.049 and 0.059 min1, respectively, with
constants (k1) of three target compounds followed the trend of increasing oxygen concentration. This indicates that introducing
UVC/TCNSP > UVA/TCNSP > UVC > UVA. Overall, rate constant of oxygen into the reaction system effectively suppress electron–hole
 M. Khraisheh et al. / Journal of Industrial and Engineering Chemistry 20 (2014) 979–987 983

0.06
(a) (a)
1.0
0.05
Rate constant k1(min-1)

0.9
0.04 0.8
0.7
0.03
0.6

C/Co
0.5
0.02
0.4 4.2 /

0.01 0.3 6.3 /

0.2 8.4 /
0 0.1 10.5 /
UVA UVA-TCNSP UVC UVC-TCNSP
0.0
0 10 20 30 40 50 60
(b) Irradiation time (min)

0.06
1.0
(b)
0.05 0.9
Rate constant k1(min -1)

0.8
0.04
0.7

0.03 0.6

C/Co
0.5
0.02 0.4
4.2 /
0.3
6.3 /
0.01
0.2
8.4 /
0.1 10.5 /
0
UVA UVA-TCNSP UVC UVC-TCNSP 0.0
0 10 20 30 40 50 60
Irradiation time (min)
(c)
0.06

1.0
(c)
0.05
0.9
Rate constant k1(min-1)

0.8
0.04
0.7

0.03 0.6
C/Co

0.5
0.02 0.4
4.2 /
0.3
0.01 6.3 /
0.2
8.4 /
0.1
0 10.5 /
UVA UVA-TCNSP UVC UVC-TCNSP 0.0
0 10 20 30 40 50 60
Fig. 4. Reaction rate constant k1 (min1) for photolysis and photocatalysis of PPCPs: Irradiation time (min)
(a) carbamazepine; (b) clofibric acid; (c) triclosan under UVA, UVA with TCNSP, UVC
and UVC with TCNSP (initial concentration of PPCPs = 30 mg/L, TCNSP composite Fig. 5. Effect of the light intensity on photocatalytic degradation of PPCPs: (a)
concentration = 120 g/L, pH = 7.0, irradiation time = 60 min, oxygen carbamazepine; (b) clofibric acid; (c) triclosan (initial concentration of
concentration = 24 mg/L, T = 25 8C). PPCPs = 30 mg/L, TCNSP composite concentration = 120 g/L, pH = 7.0, irradiation
time = 60 min, oxygen concentration = 24 mg/L, T = 25 8C).
recombination as oxygen consumes conduction band electrons,
hereby increasing hydroxyl radical concentration and allowing
valence band holes to directly and indirectly oxidize PPCPs [29,33]. strongly affected by the pH of the reaction solution. This is because
In addition, oxygen can serve as an electron acceptor and create of pH is a complex parameter and it has amphoteric behavior [35].
oxidative species such as the superoxide radical. The superoxide In order to identify the effect of pH on the photocatalytic reaction
radicals react with hydrogen ions to produce hydroxyl radical. of TCNSP composite during PPCPs degradation, initial pH levels
Hence, though enhancing hydroxyl radical-PPCPs oxidation, were varied within a range of 3–11. The selection of very low pH
superoxide can indirectly degrade PPCPs [29]. levels was due to the consideration of possible effect of the pKa of
three target compounds. The pH value of the three PPCPs solution
3.1.6. Effect of pH has a dominant influence on the photocatalytic process for a
Degradation of pollutants occurs predominantly either at the variety of reasons, including the TiO2 surface charge state, the flat-
surface of TiO2 or within few monolayers around the photo- band potential, and the dissociation of the three PPCPs, which are
catalytic surface [34]. Therefore, adsorption on the surface of all strongly pH dependent. The initial pH of 30 mg/L carbamaze-
photocatalyst is very important and photocatalytic reaction is pine, clofibric acid and triclosan was 7.0 and it was adjusted to
984 M. Khraisheh et al. / Journal of Industrial and Engineering Chemistry 20 (2014) 979–987

0.07
Carbamazepine Clof ibic acid Triclosan (a)
0.06 1.2 pH 3
Rate constant k1 (min -1)

0.05 1 pH 5
pH 7
0.04 0.8
pH 9

C/Co
0.03 0.6 pH 11

0.02 0.4

0.01
0.2

0
0
6 12 24
0 10 20 30 40 50 60
Oxygen concentration (mg/L)
Time(min)

Fig. 6. Effect of oxygen concentration on photocatalytic degradation rate constants

of three PPCPs (initial concentration of PPCPs = 30 mg/L, TCNSP composite
concentration = 120 g/L, pH = 7.0, irradiation time = 60 min, UVC (b)
intensity = 10.5 mW/cm2, T = 25 8C).
1.2
pH 3
1 pH 5
acidic or alkaline conditions by adding the appropriate amount of pH 7
HCl or NaOH solutions, respectively. Fig. 7 depicts the relationship 0.8 pH 9
between the rate constants with the initial pH values of three

C/Co
pH 11
PPCPs solutions. It can be seen that the three selected compounds 0.6

have different change trends in the pH values range of 3–11.

0.4

3.1.6.1. Triclosan removal. As seen in Fig. 8a, the rate constant 0.2
gradually decreased with increasing pH value reaching a value of
0.027 min1 at pH 11. In terms of triclosan removal efficiency, it 0
was over 96% between pH 3 and 7 and decreased to about 79% at 0 10 20 30 40 50 60

pH 11. This phenomenon may be due to the dissociation of the Time(min)

triclosan molecule. The dissociation coefficient of triclosan is
8.14(pKa) and more than 50% of the triclosan is expected to be
(c)
deprotonated when pH value is higher than pKa (Behera et al. [26]).
1
Generally, functional groups on the surface of hydrated TiO2 pH3
include TiOH2+, TiOH and TiO since hydroxyl groups on the
pH5
surface of TiO2 can gain or lose a proton depending on pH [29] as 0.8
pH7
shown below:
0.6 pH9
TiðOHÞ2 þ ! > TiOH þ Hþ (1)
C/Co

pH11
0.4
TiOH ! > TiO þ Hþ (2)
0.2
where pKa1 = 4.5 and pKa2 = 8 for Degussa P25. The pH of the point
of zero charge, pHpzc, can be calculated from half of the sum of pKa1
0
0 10 20 30 40 50 60
0.09 Time(min )
Triclosan
0.08
Clof ibric acid Fig. 8. Effect of initial solution pH of (a) triclosan; (b) clofibric acid; (c)
0.07 Carbamazepine carbamazepine (initial concentration of PPCPs = 30 mg/L, TCNSP composite
Rate constant k1 (min-1)

concentration = 120 g/L, irradiation time = 60 min, oxygen concentration = 24 mg/

0.06 L, UVC intensity = 10.5 mW/cm2, T = 25 8C).

0.05
and pKa2: pHpzc = 6.25 [29]. The surface of titanium dioxide shows
0.04
a net positive charge as pH decrease below the pHpzc and the
0.03 negative charged surface dominates as pH increases above pHpzc
0.02
[29]. Therefore, the adsorption capacity is reduced when adsorp-
tion occurs in basic pH due the repulsive force works between the
0.01 deprotonated triclosan and the negatively charged TCNSP com-
0 posite surface, whereas adsorption occurs in neutral and acidic pH,
2 3 4 5 6 7 8 9 10 11 12 the net charge on TCNSP composite surface is positively charged
pH and triclosan is non-deprotonated. Consequently, the repulsive
force interactions were reduced and adsorption efficiency was
Fig. 7. Effect of pH values on the photocatalytic degradation rate constant of PPCPs
(initial concentration of PPCPs = 30 mg/L, TCNSP composite concentration = 120 g/ enhanced. It is also consistent with the found of Behera et al. [26]
L, irradiation time = 60 min, oxygen concentration = 24 mg/L, UVC that activated carbon adsorption rate for triclosan degradation
intensity = 10.5 mW/cm2, T = 25 8C). experiments a dramatically decrease in the pH range from 3 to 10.
 M. Khraisheh et al. / Journal of Industrial and Engineering Chemistry 20 (2014) 979–987
3.1.6.2. Clofibric acid removal. The tendency of clofibric acid was
shown almost the same as that of triclosan. However the rate
constant dramatically decreased while pH value increased
(Fig. 8b). That is, the rate constants decreased from 0.082 min1
at pH value 3 to reach the bottom 0.027 min1 at pH value 11
(Fig. 7). Clofibric acid is a weak electrolyte (pKa 3.6) and so its
ionization is strongly dependent of pH. The clofibric acid removal
was complete for pH value 3, where the neutral form of clofibric
acid is dominant. On the other hand, increasing pH value to 11
leaded to considerable decreased removal efficiency by the TCNSP
composite. At this pH value only around 58% of the initial clofibric
acid was removed. This was probably due to the charge in the
molecular of clofibric acid and particle structure of TCNSP
composite, respectively. As previously observed for triclosan,
depending on the pH of point of zero charge (pHpzc) the TCNSP
composite (hydrated TiO2) could be neutral or positively charged
for solution pH < pHpzc, and negatively charged for pH > pHpzc
since the acid functionalities would dissociate releasing protons
into the medium and leaving a negatively charged surface on the
TCNSP composite [36]. Therefore, the removal efficiency decreased
when the pH was increased for values below the pHpzc, indicating a
weaker interaction of the TCNSP composite surface with the anion
form of clofibric acid. This is in agreement with Yang et al. [28],
who observed two sulfa pharmaceuticals, sulfachlorpyridazine
(pKa1  2.0  0.3) and sulfisoxazole (pKa1  1.5  0.3) had high rate
constants in low pH value range. They found that two sulfa
compounds are difficult to be protonated in weak acidic solution
(pH  3.0), so these neutral molecules can be adsorbed easily onto the
positively charged titanium dioxide surface below the point of zero
charge.
3.1.6.3. Carbamazepine removal. The degradation rate constants of
carbamazepine were not significantly affected by pH value. As seen
in Fig. 7, rate constant of carbamazepine exhibited totally different
trend from the two former compounds, and the rate constants
were kept almost up linearly from 0.05 min1 at pH 3 to
0.049 min1 at pH 11. Fig. 8c shows the effect of initial solution
pH value of carbamazepine. After 60 min of irradiation, the
removal efficiencies were achieved as 94.4%, 92.2% and 89.2% for
pH value 3.0, 7.0 and 11.0, respectively.
The degradation trend shown in Fig. 8c was probably due to it
has larger size and lack of functional groups capable of undergoing
ionization (pKa 13.94), it could be easily adsorption on the surface
of TCNSP composite. In the adsorption and photocatalysis process
using TCNSP composite, pH could affect the rate of adsorption on
the surface of TCNSP composite when positive surface favored the
100
90
80
Removal efficiency (%)
70
60
50
40
30
20
10 TCNSP pure TiO2 CNSP
0 hole pairs, commercial TiO2 beads will be the better photocatalyst
0 60 120 180 240
Reaction time (min)
Fig. 9. Comparison of carbamazepine removal efficiency at five different kinds of
solids (initial concentration of carbamazepine = 10 mg/L, solids
concentration = 120 g/L, pH = 7.0, irradiation time = 360 min, oxygen
2
concentration = 24 mg/L, UVC intensity = 10.5 mW/cm , T = 25 8C).
985
migration of photo-produced electrons and suppress electron–
hole recombination, hence, the rate of removal (function as
adsorption) increased. On the other hand, negative charge on the
surface of TCNSP composite enhanced the reaction of OH radical
production from H2O/OH and titanium dioxide, thus, the removal
rate (function as photocatalytic degradation) also increased [31].
Therefore, the effect of pH on both TCNSP composite adsorption
and photocatalytic degradation was investigated.
3.2. Performance comparison
In order to compare the removal efficiency of TCNSP composite
with four different kinds of solids (i.e. pure TiO2 pellets, CNSP
pellet, commercial TiO2 beads and commercial granular activated
carbon, GAC) on photocatalytic degradation, one model PPCP
compound (carbamazepine) was used. Fig. 9 shows the perfor-
mance of TCNSP composite with four different types of solids for
removal of carbamazepine.
At 60 min irradiation, commercial GAC and TCNSP composite
shows around 90% and 99% of removal efficiency, whereas,
commercial TiO2 beads, pure TiO2 pellets, CNSP pellets showed
around 30% removal efficiency of carbamazepine. The result
showed that commercial GAC and TCNSP composite had higher
removal efficiency than the three other solids. Commercial GAC
had slightly higher removal efficiency than TCNSP composite in the
first 5 min and 10 min and remained nearly constant from 60 min
to 360 min. It indicates that the surface area of commercial area is
larger than that of TCNSP composite. Consequently, the target
compound became quickly adsorbed into the GAC particles and
pores of GAC became saturated by target compounds. For this
reason, the ability of GAC adsorption became remarkable
decreased; it is shown that the removal efficiency of TCNSP
composite surpassed that of commercial GAC after 20 min reaction
time. This can be explained that the adsorption and photocatalysis
of TCNSP composite worked as absorbent and photocatalyst.
With pure TiO2 pellets, CNSP pellets and commercial TiO2
beads, carbamazepine removed around 35%, 42% and 39%,
respectively, during 90 min reaction time. After 120 min irradia-
tion, the removal with commercial TiO2 beads was increased
dramatically only compared with pure TiO2 and CNSP pellets and
reached at around 75% removal efficiency at 360 min irradiation. It
is well known that photocatalytic degradation using TiO2, the
photolysis and photocatalysis can be achieved by direct reaction
with photons generated by UV irradiation, and/or by indirect
reaction with OH radicals generated by the reaction between H2O/
OH ion and TiO2. Thus, with commercial TiO2 beads used as
photocatalyst the removal of carbamazepine was higher than with
pure TiO2 and CNSP pellets, although the surface area of
commercial TiO2 beads has smaller than two solids. The high
photocatalytic degradation of commercial TiO2 beads in compari-
son to pure TiO2 which prepared in this research can be explained
by its slow recombination rate of electron/hole. The commercial
TiO2 bead consists of 70% of anatase crystallite phase and 30% of
rutile crystallite phase; thus, the anatase with rutile combination
promotes charge pair separation and prohibits recombination [10].
On the other hand, since there is only anatase crystallite phase in
pure TiO2 pellets, a fast interfacial electron-transfer to hole is
occurred. Therefore, this suggests that the adsorption/desorption
GAC TiO2 bead of the PPCPs is slow in comparison to the formation of electron/
300 360 because it has longer lifetimes for recombination of electrons and
holes [10].
In summary, the enhanced removal efficiency of TCNSP
composite can be explained that TCNSP composite has surface
area which can absorb the target compound effectively and
photocatalytic ability to generate a strong oxidant such as OH
986 M. Khraisheh et al. / Journal of Industrial and Engineering Chemistry 20 (2014) 979–987
Fig. 10. Recycling test for removal of carbamazepine with five different kinds of
solids (initial concentration of carbamazepine = 10 mg/L, solids
concentration = 120 g/L, pH = 7.0, irradiation time = 60 min, oxygen
concentration = 24 mg/L, UVC intensity = 10.5 mW/cm2, T = 25 8C).
radical. It is suggested that the adsorbable ability of TCNSP
composite is more effective than that of photocatalysis in terms of
removing the PPCPs in water. Liu et al. [35] has also justified that
suitable adsorption capacity is crucial for high photocatalytic
degradation.
3.3. Recycling performance
Recycling tests of the reactions for adsorption and photo-
catalytic activity with TCNSP composite, commercial GAC, pure
TiO2, CNSP and commercial TiO2 beads were carried out, as shown
in Fig. 10. After the first 60 min removal reaction, the solids were
separated and reused for further runs without any treatment. The
results in Fig. 10 show that TCNSP composites were easily recycled,
around 80% of carbamazepine removal was maintained after five
runs, while removal efficiency of commercial GAC was decreased
dramatically and significant deactivation occurred; only approxi-
mately 40% of carbamazepine could be removed after five runs.
After the 10th reuse of GAC the adsorption reaction plateau at 4%
removal efficiency. Therefore it can be assumed that GAC reaches
the break-point after the 9th reuse for removal reaction. It can be
speculated that TiO2 which is contained in TCNSP composite goes
through photocatalytic reaction and removes adsorbed target
compounds on TCNSP composite surface. Therefore adsorption
reaction of TCNSP composite occurs continuously and removal
efficiency can be maintained at a high level. On the other hand,
commercial GAC only has an adsorption capability which limits its
ability to remove target compound and hence commercial GAC
reaches its break-point faster than TCNSP composite. Fig. 10 also
shows that pure TiO2 has 49% reduction in its removal efficiency
after its first use however after the 10th reuse of the same pure
TiO2 showed only 12% reduction in its removal efficiency. In case of
CNSP it showed initial removal efficiency of 39% which reduced to
approximately 3% from the 8th reuse of the same CNSP. This result
shows that pure TiO2 offers better removal efficiency compared to
CNSP as explained above for TCNSP and GAC. Commercial TiO2
beads showed 32% removal efficiency in its first use, 29% after 5th
reuse and 20% even after the 11th reuse. Therefore, this result
suggests that carbamazepine may have been photocatalytic
degraded rather than adsorbed. Although commercial TiO2 beads
demonstrated lower initial removal efficiency compared to the
other solids, it showed consistent removal efficiency which makes
it favorable for continuous reuse.
4. Conclusions
Photocatalytic degradation performance of TiO2–Coconut Shell
Powder (TCNSP) composite for the removal of three pharmaceuti-
cal and personal care products (PPCPs) was investigated in this
study. The photocatalytic reaction rate of PPCPs decreased with
increasing initial concentration of PPCPs, but increased with
increasing light intensity, TCNSP concentration and dissolve
oxygen concentration. The removal trends were UVC/
TCNSP > UVA/TCNSP > UVC > UVA. The pH has dominant influ-
ence on the UV/TCNSP composite process. In comparison test,
TCNSP composite and commercial GAC showed 99% and 90%
removal efficiency, respectively. On the other hand, commercial
TiO2 beads, pure TiO2 pellets and CNSP pellets showed around 30%
removal efficiency. Results also showed that TCNSP composites
were easily reused and 80% carbamazepine removal still main-
taining after five runs, while removal efficiency of other adsorbent
decreased dramatically and significant deactivation occurred.
Acknowledgment
The authors would like to acknowledge the support of QNRF
NPRP 09-328-2-122. The authors were also grateful to Kangwon
National University of Korea for support of production equip-
ment’s.
References
[1] Z. Hasan, J. Jeon, S.H. Jhung, Journal of Hazardous Materials 209–210 (2012) 151–
157.
[2] T. Heberer, Toxicology Letters 131 (2002) 5–17.
[3] H. Tungudomwongsa, J. Leckie, T. Mill, Journal of Advanced Oxidation Technolo-
gies 9 (2006) 59–64.
[4] S.M. Rivera-Jiménez, A.J. Hernández-Maldonado, Microporous and Mesoporous
Materials 116 (2008) 246–252.
[5] T.A. Ternes, J. Stuber, N. Herrmann, D. McDowell, A. Ried, M. Kampmann, B. Teiser,
Water Research 37 (2003) 1976–1982.
[6] O.A.H. Jones, N. Voulvoulis, J.N. Lester, Water Research 36 (2002) 5013–5022.
[7] D. Vogna, R. Marotta, R. Andreozzi, A. Napolitano, M. d’Ischia, Chemosphere 54
(2004) 497–505.
[8] Y. Zhang, S. Geißen, C. Gal, Chemosphere 73 (2008) 1151–1161.
[9] R. Andreozzi, M. Raffaels, P. Nicklas, Chemosphere 50 (2002) 1319–1330.
[10] T.E. Doll, F.H. Frimmel, Water Research 39 (2005) 403–411.
[11] M. Adolfsson-Erici, M. Pettersson, J. Parkkonen, J. Sturve, Chemosphere 46 (2002)
1485–1489.
[12] A.G. Schuur, F.F. Legger, M.E. van Meeteren, M.J.H. Moonen, I. van Leeuwen-Bol, A.
Bergman, Chemical Research in Toxicology 11 (1998) 1075–1081.
[13] L.Q. Wang, C.N. Falany, M.O. James, Drug Metabolism and Disposition 32 (2004)
1162–1169.
[14] G.R. Boyda, H. Reemtsmaa, D.A. Grimmb, S. Mitrac, Science of the Total Environ-
ment 311 (2003) 135–149.
[15] A. Joss, S. Zabczynski, A. Göbel, B. Hoffmannc, D. Löffler, C.S. McArdell, T.A. Ternes,
A. Thomsen, H. Siegrist, Water Research 40 (2006) 1686–1696.
[16] V. Matamorosa, C. Ariasb, H. Brixb, J.M. Bayonaa, Water Research 43 (2009)
55–62.
[17] T.A. Ternes, J. Stüber, N. Herrmann, D. McDowell, A. Ried, M. Kampmann, B. Teiser,
Water Research 37 (2003) 1976–1982.
[18] A. Lindstrom, I.J. Buerge, T. Poiger, P.A. Bergqvist, M.D. Muller, H.R. Buser,
Environmental Science & Technology 36 (2002) 2322–2329.
[19] P. Westerhoff, Southwest Hydrology 2 (2003) 18–19.
[20] S. Valencia, F. Catano, L. Rios, G. Restrepo, J. Marı́n, Applied Catalysis B: Environ-
mental 104 (2011) 300–304.
[21] M. Nieto-Suárez, G. Palmisano, M.L. Ferrer, M. Concepción Gutiérrez, S. Yurdakal,
V. Augugliaro, M. Pagliaro, F. del Monte, Journal of Materials Chemistry 19 (2009)
2070–2075.
[22] W. Su, L. Zhou, Y.P. Zhou, Carbon 41 (2003) 861–863.
[23] M.A. Al-Ghouti, J. Li, Y. Salameh, N. Al-Laqtah, G.M. Walker, M.N.M. Ahmad,
Journal of Hazardous Materials 176 (2010) 510–520.
[24] M. Khraisheh, J. Kim, L. Campos, G.M. Walker, A.H. Al-Muhtaseb, Environmental
Engineering Science (2013) (in press).
[25] Y. Li, S. Zhang, Q. Yu, W. Yin, Applied Surface Science 253 (2007) 9254–9258.
[26] S.K. Behera, S.Y. Oh, H.S. Park, Journal of Hazardous Materials 179 (2010)
684–691.
 M. Khraisheh et al. / Journal of Industrial and Engineering Chemistry 20 (2014) 979–987
[27] M.A. Behnajady, N. Modirshahla, R. Hamzavi, Journal of Hazardous Materials B
133 (2006) 226–232.
[28] H. Yang, G. Li, Y. Gao, J. Fu, Catalysis Today 153 (2010) 200–207.
[29] L. Yang, L.E. Yu, M.B. Ray, Water Research 42 (2008) 3480–3488.
[30] G.M. Walker, L.R. Weatherley, Process Biochemistry 32 (1997) 327–335.
[31] W.K. Choy, W. Chu, Industrial & Engineering Chemistry Research 44 (2005) 8184–
8189.
[32] X.V. Dooslaer, K. Demeestere, P.M. Heynderick, H.V. Langenhove, J. Dewulf,
Applied Catalysis B: Environmental 101 (2011) 540–547.
987
[33] N. Daneshvar, M. Rabbani, N. Modirshahla, M.A. Behnajady, Journal of Photo-
chemistry and Photobiology A: Chemistry 168 (2004) 39–45.
[34] R.A. Damodar, T. Swaminathan, Chemical Engineering Journal 144 (2008)
59–66.
[35] S.X. Liu, X.Y. Chen, A. Chen, Journal of Hazardous Materials 143 (2007)
257–263.
[36] J.A. Menendez-Diaz, I. Martin-Gullon, in: T.J. Bandosz (Ed.), Activated Carbon
Surfaces in Environmental Remediation, vol. 7, Elsevier, Academic Press, New
York, 2006.