Accepted Manuscript

Adsorption of diclofenac sodium from water using oxidized activated carbon

Biswa Nath Bhadra, Pill Won Seo, Sung Hwa Jhung

PII: S1385-8947(16)30593-9
DOI: http://dx.doi.org/10.1016/j.cej.2016.04.143
Reference: CEJ 15149

To appear in: Chemical Engineering Journal

Received Date: 5 April 2016

Revised Date: 27 April 2016
Accepted Date: 28 April 2016

Please cite this article as: B.N. Bhadra, P.W. Seo, S.H. Jhung, Adsorption of diclofenac sodium from water using
oxidized activated carbon, Chemical Engineering Journal (2016), doi: http://dx.doi.org/10.1016/j.cej.2016.04.143

This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers
we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and
review of the resulting proof before it is published in its final form. Please note that during the production process
errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.
Adsorption of diclofenac sodium from water using oxidized

activated carbon

Biswa Nath Bhadra, Pill Won Seo, and Sung Hwa Jhung*

Department of Chemistry and Green-Nano Materials Research Center, Kyungpook

National University, Daegu 702-701, Republic of Korea

*Corresponding Author: Prof. Sung Hwa Jhung

Fax: 82-53-950-6330

E-mail: sung@knu.ac.kr

1
Abstract

Adsorption of diclofenac sodium (DCF) from aqueous solutions using surface-

modified/oxidized activated carbons (OACs) was investigated and compared with that

over virgin activated carbon (AC). The obtained results showed a remarkable increase

(~6 times) in DCF removal over oxidized AC compared to that over a commercial,

unmodified AC, despite the decreased surface area in the OAC. The large increase in

DCF removal may be due to the presence of acidic surface functional groups, which are

created on the AC surface upon oxidation. To understand the role of these acidic

functional groups on the increased adsorption capacity (qt), the concentration of acidic

groups was determined using Boehm titration after oxidation with different quantities of

oxidizing agent. The adsorption capacity of the OAC prepared by treatment with 2.0 M

ammonium persulfate solution (OAC (2.0)) was the highest of the prepared adsorbents.

Therefore, OAC (2.0) was studied in detail by characterizing the material and

investigating the adsorption performances. The effect of pH on the surface charge (zeta

potential) and DCF adsorption capacity of OAC (2.0) was investigated to lead to the

mechanism of DCF adsorption such as hydrogen bonding and electrostatic interactions.

Additionally, the OAC can be recycled for adsorptive removal of DCF by simple solvent

washing. Therefore, the OAC was found to be a promising adsorbent for the removal of

DCF from contaminated water.

Keywords: adsorption; acidic groups; diclofenac sodium; oxidized activated carbon

2
1. Introduction

Contamination of surface water is a growing concern, and contaminants such as

pharmaceuticals and personal care products (PPCPs) are increasingly found in surface

water, even if at low levels. In particular, contamination by PPCPs is increasing as living

standards improve and PPCPs are increasingly used. When surface water becomes

contaminated with these compounds, aquatic life can be harmed, even by trace amounts

[1-4].

The main challenge for the removal of PPCPs from water is their high polarity and

solubility in water. Because of these characteristics, complete removal is impossible in

conventional water treatment plants [5-8]. However, methods for the efficient removal of

such organic pharmaceuticals from wastewater are being developed gradually.

To date, a variety of methods such as photodegradation [9], coagulation–flocculation

[10], biodegradation [11], chlorination [12], ozonation [13], and advanced oxidation

processes (AOPs) [14] have been used to trap or degrade pharmaceutical contaminants

from water. Despite this, alternative methods are sought because, although some of these

degradation methods are efficient (e.g., AOP or ozonation), they have several drawbacks,

i.e., the production of residual toxic by-products [13, 14]. Consequently, adsorption of

contaminants has become a popular method for the removal of organic contaminants

from water, in particular, because these methods are simple, reliable, and cost effective

[15].

Diclofenac sodium (DCF; Scheme 1) is a commonly prescribed analgesic drug, used

to treat, among other conditions, inflammatory disorders and dysmenorrhea. DCF is a

nonsteroidal anti-inflammatory drug [16]. In this paper, DCFA and DCFN represent

3
neutral diclofenac free acid (with –COOH) and the diclofenac anion (deprotonated, i.e.,

with –COO-), respectively. Chronic exposure to DCF has adverse effects for aquatic

animals, but it can also cause hemodynamic changes and thyroid tumors in humans.

Because DCF is common and prescribed in large quantities, it has been detected in both

wastewater and natural water bodies all over the world [10, 17]; therefore, methods for

the removal of DCF from water have attracted much attention. To date, several

adsorbents have been developed that have a high adsorption capacity and efficiency for

the removal of several PPCPs, including DCF [18-21].

Activated carbons (ACs) are well-known conventional adsorbents with many

applications due to their hydrophobicity, surface functionality, pore structure, and high

surface area [22-24]. Furthermore, different functional groups can be generated on the

surfaces of ACs by treatment with acids and bases or by oxidation/reduction reactions

[25-28]. Consequently, ACs, are suitable adsorbents for the removal of hazardous

contaminants from fuel (sulfur- or nitrogen-containing compounds) [25-28] or water (e.g.,

aromatic compounds, drugs, and pesticides) [29, 30]. More importantly, several

carbonaceous adsorbents including multi-walled carbon nanotubes [30, 31], ACs (from

several sources) [32-36], graphite/graphene [37-39] have shown high efficiency in the

removal of DCF from water. Similar to carbon-based adsorbents, zeolites/silicates [40, 41]

and very recently, metal-organic framework-based adsorbents, namely UiO-66s [42] and

cetyltrimethylammonium bromide functionalized ZIF-67 [43], have also been applied to

remove DCF from aqueous solutions. The efficiency of virgin/modified materials in

adsorption mainly depends on the physical/chemical properties of the adsorbates and

their interactions with the adsorbents [21, 44, 45].

4
 Oxidation is a well-developed method to create acidic or basic (oxygen containing)

functional groups on the AC/graphene surface [46-48], and oxidized carbonaceous

materials are suitable adsorbents for fuel improvement (adsorptive desulfurization and

denitrogenation) [26-29, 47] and water purification [38, 44] due to their oxygen-

containing functional groups. For example, GO, which has a very low porosity, has been

reported to remove DCF from water; however, a detailed mechanism for the high

adsorption capacity of GO for DCF has not been explored [38], and the adsorption of

PPCPs such as DCF using OAC has not yet been studied.

Of the adsorbents for DCF removal, surface modified/oxidized activated carbon

(OAC) has one of the largest capacities. OAC is an interesting adsorbent because of its

efficiency for DCF removal, easy preparation, low cost, and reusability. Several acidic

groups (carboxylic, phenolic, and lactone) can be produced by the simple oxidation of

commercial AC, and these functional groups may be favorable interaction sites for the

adsorbate. We investigated the comparative adsorption capacities of AC and OACs for

DCF to examine the effect of acidic groups on DCF removal. The acidic functional

groups (AFG) on the activated carbons were quantified by Boehm titration. Furthermore,

a plausible mechanism for the adsorption over OAC is suggested based on the

concentration of acidic groups on the OACs, the effect of pH on the zeta potential of

OAC, and the adsorption of DCF.

2. Materials and methods

2.1 Chemicals

5
 Diclofenac sodium (C14H10Cl2NNaO2) was obtained from Sigma Aldrich. Granular

AC (2–3 mm, practical grade) was purchased from Duksan Pure Chemical Co. Ltd.

Sulfuric acid (H2SO4, 98%) and hydrochloric acid (HCl, 36%) were procured from OCI

Chemicals, and ammonium persulfate ((NH4)2S2O8, 98%), sodium hydroxide (NaOH,

98 %), sodium carbonate (Na2CO3, 98 %), and sodium bicarbonate (NaHCO3, 98 %)

were acquired from Daejung Chemicals & Metals Ltd. All the above mentioned

chemicals were analytical grade and used without any further purification.

2.2 Modification of adsorbents

Chemical modification of the commercial AC was carried out following the method

of Li et al. [46]. To produce different functional groups on the AC surface, AC was

treated with a solution of ammonium persulfate (APS) and sulfuric acid. Initially, APS

solutions with different molar concentrations (0.5, 1.0, 2.0, and 2.5 M) in 1 M H2SO4

were prepared. Oxidative modification was then conducted by adding 1 g of AC to the

previously prepared APS solution (20 mL), and the suspension was mixed for 3 h by

magnetic stirring at 60 °C. After oxidation, the modified ACs were separated by filtration

and washed with de-ionized water to make them neutral. The separated samples were

dried in a vacuum oven at 110 °C for one day and kept in a desiccator until use. The

chemically-modified ACs were designated as OAC (0.5), OAC (1.0), OAC (2.0), and

OAC (2.5) based on the molar concentration of APS in the oxidant solution.

2.3 Characterization of ACs

6
 An X-ray diffractometer (D2 Phaser, Bruker, Germany) with Cu-Kα radiation was

used to analyze the structural characteristics of AC and OACs. The textural properties of

the carbonaceous materials were measured at −196 °C using a surface area and porosity

analyzer (Tristar II 3020, Micromeritics, USA) by nitrogen adsorption/desorption

measurements. All of the adsorbents were evacuated at 150 °C for 12 h before nitrogen

adsorption. The Brunauer-Emmett-Teller (BET) and Langmuir equations were applied to

estimate the BET and Langmuir surface areas, respectively. The adsorbed amounts of

nitrogen (at P/P0 = 0.99) were used to determine the total pore volumes of the studied

samples.

Quantification of the surface functional groups was carried out using Boehm titration

[27]. AC (0.50 g) for analysis was added to each of three separate beakers containing

either NaOH, Na2CO3, or NaHCO3 (50 mL, 0.10 M each), and the mixtures were stirred

magnetically for 24 h at 25 oC. After neutralization, the liquid portions were collected by

filtration, and the amounts of AFGs were calculated by titration of the obtained solution

with standard aqueous HCl (0.10 M) solution. Methyl orange was used as an indicator for

all titrations. A detailed procedure for Boehm titration [27] is summarized in the

Supporting Information. The obtained results are shown in Table 1.

The zeta potential of the modified carbon (OAC (2.0)) was measured at various pH

values using a Zetasizer Nano zs90 instrument. The detailed method of measuring the

zeta potential of OAC (2.0) is described in the Supporting Information. FTIR

spectroscopic analyses were carried out with a Jasco FTIR-4100 (ATR, maximum

resolution: 0.9 cm−1).

7
2.4 Adsorption experiments

DCF solutions for adsorption experiments were prepared from a stock solution of

DCFN (500 mg·L-1, pH: 5.5) in water. Solutions with the desired concentrations (25 to

100 mg·L-1, pH: 5.5) for adsorption over the adsorbents were prepared by successive

dilution of the stock solution. The adsorbents were dried overnight at 100 °C in a vacuum

oven and used for adsorption of DCF from water. Then, adsorbent (5.0 mg) was added to

the DCF solution (25 mL), and the mixtures were shaken with an incubator shaker at a

constant speed (250 rpm) at 25 oC for a set time. After this time, the solutions were

collected by filtration with a syringe filter (polytetrafluoroethylene, hydrophobic, 0.5 µm),

and the residual concentrations of DCF were evaluated by UV spectrometry (at 276 nm,

UV-1800, Shimadzu, Japan). All of the adsorption experiments were repeated three times

to acquire average values, which were reported here. The pseudo-second-order non-linear

kinetic model [49], Langmuir isotherms [49, 50], and separation factor [50] were applied

to investigate the adsorption results. Methods of calculations are described in detail in the

Supporting Information.

To determine the effect of solution pH on the adsorption capacity (qt) of OAC (2.0)

for DCF, the pH of the DCF solution (50 mg· L-1) was altered with either aqueous HCl

(0.10 M) or NaOH (0.10 M) solution. The reusability of the OAC (2.0) was evaluated

after the adsorption of DCF for 12 h. The DCF-adsorbed OAC (2.0) (50 mg) was

separated by filtration and washed with deionized water, and then placed into acetone (20

mL) and soaked for 12 h at 25 oC. The soaking was repeated three times for the complete

removal of adsorbed DCF. The detail method of reusability tests were described in the

Supporting Information.

8
3 Results and discussion

3.1 Characterization of the adsorbents

The virgin and oxidized ACs were characterized by XRD diffraction and porosity

analysis (Fig. S1). The powder diffraction patterns of the OACs are shown in Fig. S1a

and are similar to that of the virgin AC, even after the treatment with APS (0.5-2.5 M).

Low-intensity diffraction peaks were observed because of the presence of quartz in the

ACs [27]. The nitrogen adsorption isotherms of the studied adsorbents are shown in Fig.

S1b, and porosity data are summarized in Table S1. The surface areas (both BET and

Langmuir) as well as the total pore volume decreased upon increasing the APS

concentrations used for oxidation.

The total amount and types of functional groups measured by the Boehm titration

method are shown in Table 1. The total amount of AFG on the ACs increased (from

0.212 mmol·g-1 to 0.600 mmol·g-1) on increasing APS concentration to 2 M; however,

further increasing the APS concentration decreased the AFG concentration. The

concentration of phenolic groups showed a similar tendency to that of the total acidic

groups; however, the concentrations of carboxylic or lactonic groups were generally low

and not clearly dependent on the APS concentration.

3.2 Relative adsorption capacities of the adsorbents and adsorption kinetics

Initially, the adsorption performances of AC and the oxidized ACs (OACs) were

tested using a 100 mg·L-1 DCF solution, and the results are shown in Fig. 1. This figure

and Fig. S2 show that the amount DCF adsorbed by the AC and OACs is not dependent

9
on the surface area of the adsorbent. OAC (2.0) showed the highest DCF uptake, despite

the reduction in surface area compared to those of AC and OACs (0.5 and 1.0). In

contrast, OAC (2.5), which had the lowest porosity, showed a much lower qt-value.

Therefore, to understand the reason for the enhancement of DCF adsorption over OACs

(up to 2.0 M APS concentration), further studies were carried out.

To understand the relative performance of the adsorbents, the effect of contact time

on DCF adsorption over AC, OAC (1.0), and OAC (2.0) were checked between 1 to 24 h

at 25 oC. As shown in Fig. 2 (symbols), for the whole adsorption time, performance

increased in the following order: AC < OAC (1.0) < OAC (2.0) and reached equilibrium

within 6 h. The quantity of DCF adsorbed on OAC (1.0) is much greater than that

adsorbed on virgin AC, and the adsorption performance further increased for OAC (2.0),

even though the surface area of OAC (2.0) was low (Table S1). The increasing adsorption

capacity with decreasing surface area suggests that there is a special interaction between

adsorbent and adsorbate.

For a precise comparison of the adsorption kinetics, the pseudo-second-order non-

linear kinetic model [49] was applied. The symbols in the Fig. 2 show the experimental

results obtained from adsorption, and solid lines represent the non-linear plots of the

pseudo-second-order rate equations. Pseudo-second-order rate constants (k2) and

correlation parameters (R2) are summarized in Table 2. On fitting the experimental results

to the pseudo-second-order model, high correlation factors (R2) were obtained. The

kinetic constants indicate that the adsorption of DCF by OACs is about 1.8 times faster

than that by virgin AC, and a similar ordering is found for the adsorption capacities (AC

<< OAC (1.0) < OAC (2.0)). Consequently, the presence of some special interactions

10
between OAC and DCF that increase the adsorption capacity and accelerate the rate

slightly can be inferred.

3.3 Adsorption isotherms

The adsorption of DCF was almost complete after 6 h for all of the tested adsorbents

(Fig. 2). However, the adsorptions of DCF were investigated for extended periods, up to

24 h, to ensure that the system was at equilibrium. Adsorptions isotherms of DCF were

obtained from DCF solution (25–100 mg·L-1, in water) over AC and OAC (2.0), and the

obtained results are shown in Fig. 3a. Langmuir plots were drawn (Fig. 3b) and used to

evaluate the Langmuir parameters: maximum adsorption capacities (Q0), b-values, and

correlation factors (R2), and these are listed in Table 2. Qo for DCF adsorption on AC was

8.3 × 101 mg·g-1, a similar result to those obtained using different ACs [32-35, 42]. Again,

the value of Q0 (4.9 × 102 mg·g-1) for OAC (2.0) demonstrates a noticeable increase in

DCF uptake (~6-times higher than the virgin AC). Table 3 shows the performances of the

reported adsorbents for DCF, and OAC (2.0) can be regarded as one of the most effective

adsorbents for DCF.

The adsorption characteristics of DCF over AC and OAC (2.0) were further

investigated by using “the separation factor” (RL), a dimensionless parameter [50]. The

plots of RL against the initial DCF concentrations for the two adsorbents are shown in Fig.

3c, and these results confirm the favorable adsorption of DCF over both adsorbents

(because RL< 1). The lower RL value and higher b-value (Table 2) over the OAC (2.0)

than that over AC are in agreement with the more favorable DCF adsorption over OAC

(2.0) than over AC, in accordance with Figs. 2 and 3a.

11
3.4 Adsorption mechanism

Understanding the adsorption mechanism is important, not only to understand the

basics of adsorption but for commercial applications of adsorption technologies. The

surface area of porous adsorbents is the most commonly described factor affecting

adsorption if there are no special interaction sites on the adsorbent surface. However, the

results obtained for the adsorption of DCF by OACs (Figs. 1 and S2) in this study

indicate that the normal dependence on porosity does not apply for OACs, suggesting the

presence of specific interactions between DCF and OAC.

Previous studies have suggested that aromatics compounds, such as DCF, can be

adsorbed to carbonaceous adsorbents, such as carbon nanotubes or grapheme oxide, by π-

π interactions [31, 38]. Moreover, the solubility of DCF is low at pH values less than the

pKa of DCF, i.e., where DCF exists in its neutral form (DCFA). Therefore, adsorption

capacity increased inversely with pH of the solution [35, 36].

To develop a plausible adsorption mechanism, adsorption experiments were carried

out and the zeta potential of OAC (2.0) was measured at different pH values (Fig. 4).

Figure 4a shows the effect of solution pH on the amount of DCF adsorbed on OAC (2.0).

The adsorption capacity at pH values lower than the pKa of DCFA (pH < 4.2) was higher

than that at a pH of 5.5, i.e., the pH condition for adsorption used in this study. On

increasing the pH from 5.5 to 7.0, the capacity decreased, finally becoming negligible at

pH ≥ 8.0. The zeta potential of OAC (2.0) (shown in Fig. 4b) indicates that there is a

negative surface charge on OAC particles over a wide pH range, but surface charge

12
decreases with increasing pH; these results are similar to reported results for other

oxidized carbons [51].

In this study, the solubility of the adsorbate and possible π-π interactions cannot

adequately explain the amount of DCF adsorbed by OAC (2.0), especially considering

the pKa of DCFA (4.2), i.e., qt did not decrease significantly when the pH was greater

than 4.2 even though the solubility of DCF increases significantly on deprotonation. In

addition, the number of π-electrons of DCF and OAC (2.0) does not change with pH.

Therefore, other mechanisms of interaction [20] are required to explain the observed

experimental results in this study.

The amounts of DCF adsorbed by the studied adsorbents, each with different amounts

of AFG (as summarized in Table 1) but at the same pH (5.5), as shown in Figs. 1, 2, and

3, suggest that the degree of adsorption is dependent on the AFG concentration. The

adsorption capacity of OAC (2.0) was nearly constant at pH values ranging from 4.5 to

5.5, but increased slightly at pH values lower than 4 (below the pKa = 4.2 of DCFA), as

shown in Fig. 4a. At low pH, electrostatic interactions may be important for the

adsorption of protonated DCFA onto the negatively charged OAC surface. If electrostatic

interactions are the sole mechanism, the effect of pH on qt (Fig. 4a) should be larger than

that observed; in addition, the adsorption capacity should be very low at pH values

greater than 4.2. Therefore, electrostatic interactions alone cannot explain the observed

adsorption capacities.

OAC has carboxylic (pKa = 4.2), lactonic, and phenolic (pKa = 10.0) groups on the

surface. To identify the AFG responsible for the increase in the DCF adsorption capacity,

the quantity of adsorbed DCF was plotted against the amount of AFGs, as shown in Fig.

13
5. The calculated R2 value for DCF adsorption decreases in the order of phenolic group >

total acidic groups > carboxylic groups (Fig. 5); therefore, phenolic groups are the most

important AFG for adsorption of DCF, but the other groups also contribute to adsorption.

The decreasing value of qt with increasing pH (Fig. 4a) can be explained by the

increasing negative surface charge of adsorbent and number of deprotonated species (-

COO- and –O-) of DCF. Under these conditions, increasing electrostatic repulsion

between negative DCFN and negative species of OAC will occur at high pH.

Considering the polar functional groups present on OAC and in DCF, hydrogen

bonding is a possible mechanism for the adsorption of DCF on OAC; for example,

hydrogen bonding between electronegative species in DCF (such as O and N) and the

phenolic proton (and carboxylic group at pH <4.2) on OAC. Probable directions of

hydrogen bonds formed between Ph-OH (and –COOH) of OAC and DCF are shown in

Scheme 2 for two pH conditions (pH<4.2 and 4.2<pH<10). The phenolic/carboxylic acid

proton can form an attractive interaction with the oxygen atom of the carbonyl and

carboxylate functional groups (protonated or deprotonated) through hydrogen bonding.

Previously, the adsorption of aromatic micropollutants such as DCF over carbonaceous

materials has been explained by the formation of hydrogen bonds [32, 35, 36, 39].

Therefore, we propose that the phenolic and carboxylic acid protons, which are produced

upon oxidation of AC, play a very important role in the adsorption of DCF. Electrostatic

interactions are also important, considering the negative surface charge of OAC and the

presence of charged DCF species (protonated DCFA and DCFN). Plausible adsorption

mechanisms, especially those occurring via formation of hydrogen bonds (and

electrostatic repulsion at pH >10), are shown in Scheme 2 at three different pH conditions.

14
3.5 Reusability of OAC (2.0)

The recyclability of adsorbents is an important parameter for commercial applications,

especially for cost-effectiveness. To determine the reusability of OAC (2.0) for DCF

removal, simple solvent washing techniques were applied to recover the adsorbent for the

next use. The regenerated OAC (2.0) was evacuated at each cycle by vacuum drying at

100 °C for 12 h and, then, reused for the adsorption of DCF. The FTIR analysis of the

adsorbent OAC, DCF-adsorbed OAC, DCF, and recycled OAC are compared as shown

in Fig. 6. Similar stretching bands were observed at 740, 1283, 1394, 1449, and 1578 cm-
1
for both DCF and DCF-adsorbed OAC, confirming the presence of adsorbed DCF in

OAC. In contrast, the absence of such a band for the recycled OAC suggests that the used

adsorbent can be regenerated by simple solvent washing. We performed up to 5 cycles of

DCF adsorption on OAC (2.0), and the obtained results are summarized in Fig.7. Even

though the adsorption capacity decreased in the first two runs, steady performances were

obtained from the third run, showing that OAC is a reusable adsorbent for DCF removal

from water. Therefore, OAC can be suggested as a cheap, recyclable, and efficient

adsorbent for the removal of DCF from water.

4 Conclusion

Results obtained from the aqueous-phase adsorption of DCF over AC and OACs led

us to make following conclusions. Firstly, the adsorption capacity over OAC (2.0) is

much greater (~6 times) than that of commercial/virgin AC, and adsorption by OAC (1.0)

and OAC (2.0) was slightly faster than that of the commercial AC. This improved and

15
rapid DCF uptake by OACs may be useful for commercial removal of DCF from spent

water. Secondly, the mechanism for the huge increase in adsorption of DCF on OACs as

compared with virgin AC can be explained by hydrogen bonding and electrostatic

interactions. Furthermore, the best adsorbent, OAC (2.0), was found to be recyclable by

simple water/acetone washing, which was confirmed by FTIR analysis and adsorption

experiments. Considering the huge capacity for adsorption of DCF, low cost, and ready

recyclability of OAC, AC after suitable oxidation may be one of the best adsorbents for

the removal of DCF from water.

Acknowledgement

This research was supported by Basic Science Research Program through the

National Research Foundation of Korea (NRF) grant funded by the Korea government

(MSIP) (grant number: 2013R1A2A2A01007176).

16
References

[1] T. Heberer, Occurrence, fate, and removal of pharmaceutical residues in the aquatic

environment: a review of recent research data. Toxicol. Lett.131 (2002) 5–17.

[2] K. Dutta, M.Y. Lee, W.W.P. Lai, C.H. Lee, A.Y.C. Lin, C.F. Lin, J.G. Lin, Removal

of pharmaceuticals and organic matter from municipal wastewater using two-stage

anaerobic fluidized membrane bioreactor, Bioresour. Technol. 165 (2014) 42–49.

[3] J.L. Zhou, Z.L. Zhang, E. Banks, D. Grover, J.Q. Jiang, Pharmaceutical residues in

wastewater treatment works effluents and their impact on receiving river water. J.

Hazard. Mater. 166 (2009) 655-661.

[4] Y. Luo, W. Guo, H.H. Ngo, L.D. Nghiem, F.I. Hai, J. Zhang, S. Liang, X.C. Wang,

A review on the occurrence of micropollutants in the aquatic environment and their

fate and removal during wastewater treatment, Sci. Total Environ. 473–474 (2014)

619–641.

[5] E.N. Evgenidou, I.K. Konstantinou, D.A. Lambropoulou, Occurrence and removal of

transformation products of PPCPs and illicit drugs in wastewaters: a review, Sci.

Total Environ. 505 (2015) 905–926.

[6] D. Zhang, R.M. Gersberg, W.J. Ng, S.K. Tan, Removal of pharmaceuticals and

personal care products in aquatic plant-based systems: a review, Environ. Pollut. 184

(2014) 620–639.

[7] I. Villaescusa, N. Fiol, J. Poch, A. Bianchi, C. Bazzicalupi, Mechanism of

paracetamol removal by vegetable wastes: the contribution of π– π interactions,

hydrogen bonding and hydrophobic effect, Desalination 270 (2011) 135–142.

17
[8] J.R. Domínguez, T. González, P.E. Palo, M. Cuerda-Correa, Removal of common

pharmaceuticals present in surface waters by Amberlite XAD-7 acrylic-esterresin:

influence of pH and presence of other drugs, Desalination 269 (2011) 231–238.

[9] H.-R. Busar, T. Poiger, M.D. Müller, Occurrence and fate of the pharmaceutical drug

diclofenac in surface waters: rapid photodegradation in a lake, Environ. Sci. Technol.

32 (1998) 3449–3556.

[10] G.R. Boyda, H. Reemtsmaa, D.A. Grimmb, S. Mitrac, Pharmaceuticals and personal

care products (PPCPs) in surface and treated waters of Louisiana, USA and Ontario,

Canada, Sci. Total Environ. 311 (2003) 135–149.

[11] A. Joss, S. Zabczynski, A. Göbel, B. Hoffmann, D. Löffler, C.S. McArdell, T.A.

Ternes, A. Thomsen, H. Siegrist, Biological degradation of pharmaceuticals in

municipal wastewater treatment: proposing a classification scheme, Water Res. 40

(2006) 1686–1696.

[12] G.R. Boyd, S. Zhang, D.A. Grimm, Naproxen removal from water by chlorination

and biofilm processes, Water Res. 39 (2005) 668–676.

[13] S. Esplugas, D.M. Bila, L. Gustavo, T. Krause, M. Dezotti, Ozonation and advanced

oxidation technologies to remove endocrine disrupting chemicals (EDCs) and

pharmaceuticals and personal care products (PPCPs) in water effluents, J. Hazard.

Mater. 149 (2007) 631–642.

[14] M. Klavarioti, D. Mantzavinos, D. Kassinos, Removal of residual pharmaceuticals

from aqueous systems by advanced oxidation processes, Environ. Int. 35 (2009) 402–

417.

18
[15] J.L. Sotelo, G. Ovejero, A. Rodríguez, S. Álvarez, J. Galán, J. García, Competitive

adsorption studies of caffeine and diclofenac aqueous solutions by activated carbon.

Chem. Eng. J. 240, 443-453 (2014).

[16] N. Vieno, M. Sillanpää, Fate of diclofenac in municipal wastewater treatment plant -

A review. Environ. Int. 69, 28-39 (2004).

[17] P. Verlicchi, , M.A. Aukidy, E. Zambello, Occurrence of pharmaceutical compounds

in urban wastewater: removal, mass load and environmental risk after a secondary

treatment—a review. Sci. Total Environ. 429, (2012) 123–155.

[18] A. Walcarius, L. Mercier, Mesoporous organosilica adsorbents: nanoengineered

materials for removal of organic and inorganic pollutants, J. Mater. Chem. 20 (2010)

4478–4511.

[19] L.F. Delgado, P. Charles, K. Glucina, C. Morlay, The removal of endocrine

disrupting compounds, pharmaceutically activated compounds and cyanobacterial

toxins during drinking water preparation using activated carbon—A review, Sci.

Total Environ. 435-436 (2012) 509–525.

[20] Z. Hasan, S.H. Jhung, Removal of hazardous organics from water using metal-

organic frameworks (MOFs): Plausible mechanisms for selective adsorptions. J.

Hazard. Mater. 283 (2015) 329–339.

[21] J.M. Dias, M.C.M. Alvim-Ferraz, M.F. Almeida, J. Rivera-Utrilla, M. Sanchez-Polob,

Waste materials for activated carbon preparation and its use in aqueous-phase

treatment: A review, J. Environ. Manage. 85 (2007) 833–846.

19
[22] Z. Yu, S. Peldszus, P.M. Huck, Adsorption characteristics of selected

pharmaceuticals and an endocrine disrupting compound—naproxen, carbamazepine

and nonylphenol—on activated carbon, Water Res. 42, (2008) 2873– 2882.

[23] Z. Yu, S. Peldszus, P.M. Huck, Adsorption of selected pharmaceuticals and an

endocrine disrupting compound by granular activated carbon. 1. adsorption capacity

and kinetics, Environ. Sci. Technol. 43 (2009) 1467–1473.

[24] B.N. Bhadra, K.H. Cho, N.A. Khan, D.-Y. Hong, S.H. Jhung, Liquid-phase

adsorption of aromatics over a metal –organicframework and activated carbon:

effects of hydrophobicity/hydrophilicity of adsorbents and solvent polarity, J. Phys.

Chem. C, 119 (2015) 26620–26627.

[25] X. Feng, X. Ma, N. Li, C. Shang, X. Yanga, X.D. Chen, Adsorption of quinoline

from liquid hydrocarbons on graphite oxide and activated carbons, RSC Adv. 5 (2015)

74684–74691.

[26] B. K. Jung, S.H. Jhung, Adsorptive removal of benzothiophene from model fuel,

using modified activated carbons, in presence of diethylether, Fuel 145 (2015) 249–

255.

[27] X. Han, H. Lin, Y. Zheng, Adsorptive denitrogenation and desulfurization of diesel

using activated carbons oxidized by (NH4)2S2O8 under mild conditions, Can. J. Chem.

Eng. 93 (2015) 538-548.

[28] X. Han, H. Lin, Y. Zheng, The role of oxygen functional groups in the adsorption of

heteroaromatic nitrogen compounds, J. Hazard. Mater. 297 (2015) 217–223.

[29] X. Ren, C. Chen, M. Nagatsu, X. Wang, Carbon nanotubes as adsorbents in

environmental pollution management: A review, Chem. Eng. J. 170 (2011) 395–410.

20
[30] X. Hu, Z. Cheng, Removal of diclofenac from aqueous solution with multi-walled

carbon nanotubes modified by nitric acid, Chin. J. Chem. Eng. 23 (2015) 1551 –1556.

[31] H. Wei, S. Deng, Q. Huang, Y. Nie, B. Wang, J. Huang, G. Yu, Regenerable granular

carbon nanotubes/alumina hybrid adsorbents for diclofenac sodium and

carbamazepine removal from aqueous solution, Water Res. 47 (2013) 4139–4147.

[32] R. Baccar, M. Sarrà, J. Bouzid, M. Feki, P. Blánquez. Removal of pharmaceutical

compounds by activated carbon prepared from agricultural by-product, Chem. Eng. J.

211–212 (2012) 310–317.

[33] M. Antunesa, V.I. Esteves, R. Guégan, J.S. Crespo, A.N. Fernandes, M. Giovanela,

Removal of diclofenac sodium from aqueous solution by Isabel grape bagasse, Chem.

Eng. J. 192 (2012) 114–121.

[34] C. Saucier, M.A. Adebayo, E.C. Lima, R. Cataluna, P.S. Thue, L.D. T. Prola, M.J.

Puchana-Rosero, F. M. Machado, F.A. Pavan, G.L. Dotto, Microwave-assisted

activated carbon from cocoa shell as adsorbent for removal of sodium diclofenac and

nimesulide from aqueous effluents, J. Hazard. Mater. 289 (2015) 18–27.

[35] P. Sathishkumar, M. Arulkumar, V. Ashokkumar, A.R.M. Yusoff, K. Murugesan, T.

Palvannan, Z. Salam, F.N. Ani, T. Hadibarata, Modified phyto-waste Terminalia

catappa fruit shells: a reusable adsorbent for the removal of micropollutant diclofenac,

RSC Adv., 5 (2015) 30950–30962.

[36] S. Larous, A.-H. Meniai, Adsorption of Diclofenac from aqueous solution using

activated carbon prepared from olive stones, Int. J. Hydrogen Energy, 2016, in press,

doi:10.1016/j.ijhydene.2016.01.096.

21
[37] M.D. Vedenyapina, D.A. Borisova, A.P. Simakova, L.P. Proshina, A.A. Vedenyapin,

Adsorption of diclofenac sodium from aqueous solutions on expanded graphite, Solid

Fuel Chem. 47 (2013) 59–63.

[38] S.-W. Nam, C. Jung, H. Li, M. Yu, J.R.V. Flora, L.K. Boateng, N. Her, K.-D. Zoh, Y.

Yoon, Adsorption characteristics of diclofenac and sulfamethoxazole to graphene

oxide in aqueous solution, Chemosphere 136 (2015) 20–26.

[39] I.M. Jauris, C.F. Matos, C. Saucier, E.C. Lima, A.J.G. Zarbin, S.B. Fagan, F.M.

Machado I. Zanella, Adsorption of sodium diclofenac on graphene: a combined

experimental and theoretical study, Phys . Chem. Chem. Phys. 18 (2016) 1526- 1536.

[40] D. Krajisnik, A. Dakovic, M. Milojevic, E. Malenovic, M. Kragovic, D.B.

Bogdanovic, V. Dondur, J. Milic, Properties of diclofenac sodium sorption onto

natural zeolite modified with cetylpyridinium chloride, Colloids Surf., B 83 (2011)

165–172

[41] N. Suriyanon, P. Punyapalakul, C. Ngamcharussrivichai, Mechanistic study of

diclofenac and carbamazepine adsorption on functionalized silica-based porous

materials, Chem. Eng. J. 214 (2013) 208–218.

[42] Z. Hasan, N.A. Khan, S.H. Jhung, Adsorptive removal of diclofenac sodium from

water with Zr-based metal–organic frameworks, Chem. Eng. J. 284, (2016) 1406–

1413.

[43] K.-Y. A. Lin, H. Yang and W.-D. Lee, Enhanced removal of diclofenac from water

using a zeolitic imidazole framework functionalized with cetyltrimethylammonium

bromide (CTAB), RSC Adv., 5 (2015) 81330–81340.

22
[44] B. Pan, B.S. Xing, Adsorption mechanisms of organic chemicals on carbon

nanotubes, Environ. Sci. Technol. 42 (2008) 9005 –9013.

[45] S.-W. Nam, D.-J. Choi, S.-K. Kim, N. Her, K.-D. Zoh, Adsorption characteristics of

selected hydrophilic and hydrophobic micropollutants in water using activated

carbon, J. Hazard. Mater. 270 (2014) 144–152.

[46] N. Li, X. Ma, Q. Zha, K. Kim, Y. Chen, C. Song, Maximizing the number of oxygen-

containing functional groups on activated carbon by using ammonium persulfate and

improving the temperature-programmed desorption characterization of carbon

surface chemistry, Carbon 49 (2011) 5002 –5013.

[47] N. Li, J. Zhu, X. Ma, Q. Zha, C. Song, Tailoring of surface oxygen-containing

functional groups and their effect on adsorptive denitrogenation of liquid

hydrocarbons over activated carbon, AIChE J., 59 (2013) 1236–1244.

[48] J. Shen, Y. Hu, M. Shi, X. Lu, C. Qin, C. Li, M. Ye, Fast and facile preparation of

graphene oxide and reduced grapheme oxide nanoplatelets, Chem. Mater. 21 (2009)

3514–3520.

[49] Z. Hasan, J. Jeon, S.H. Jhung, Adsorptive removal of naproxen and clofibric acid

from water using metal-organic frameworks, J. Hazard. Mater. 209 (2012) 151–157.

[50] N.A. Khan, Z. Hasan, K.S. Min, S.-M. Paek, S.H. Jhung, Facile introduction of Cu+

on activated carbon at ambient conditions and adsorption of benzothiophene over

Cu+/activated carbon, Fuel Process. Technol. 100 (2012) 49-54.

[51] V. Strelko Jr., D.J. Malik, M. Streat, Characterisation of the surface of oxidised

carbon adsorbents, Carbon 40 (2002) 95-104.

23
Table 1. Concentrations of acidic functional groups of AC and OACs determined by

Boehm titration.

Acidic group (mmol·g-1)

Adsorbents
Carboxylic Lactonic Phenolic Total

AC 0.212 0.0 0 0.212

OAC (0.5) 0.143 0.040 0.245 0.428

OAC (1.0) 0.240 0.010 0.290 0.540

OAC (2.0) 0.260 0.020 0.320 0.600

OAC (2.5) 0.267 0.026 0.285 0.578

24
Table 2. Kinetic constants and Langmuir parameters (Q0 and b-values) for adsorptions of

DCF from water onto AC and OACs.

Adsorbents Kinetic parameters Langmuir parameters

-1 -1 2 2
k2 (g ·mg h ) R Q0 (mg·g-1) b (mg·L-1) R
-3 1 -2
AC 6.6×10 0.998 8.3×10 4.4×10 0.999
-2
OAC (1.0) 1.1×10 0.998 — — —
-2 2 -1
OAC (2.0) 1.2×10 0.997 4.9×10 1.2×10 0.998

25
Table 3. Maximum adsorption capacities (Q0) of some studied adsorbents and OAC (2.0) for the adsorption of DCF from water.
SABET Q0 Reference
Entry Adsorbents Interaction mechanism
(m2·g-1)* (mg·g-1)**
1 CNT/HNO3 190 24 — [30]
2 CNT/Al2O3 237 27 π-π interaction and van der Waals forces [31]
3 AC from agricultural by-product 793 56 H-bonding and/or van der Waals forces [32]
4 Grape bagasse 2 77 Electrostatic [33]
5 AC from cocoa shell 619 63 Electrostatic/polar [34]
6 AC from Terminalia catappa 514 91 H-bonding [35]
7 AC from olive stones 84 11 H-bonding [36]
8 Expanded graphite 600-900 330 Hydrophobicity and energetically uniform [37]
carbon surface
9 GO — 500 Hydrophobic and π-π interaction [38]
10 rGO 98 cm2 g-1 59.67 Electrostatic and H-bonding [39]
11 Mercapto-functionalized hexagonal 912 80 Electrostatic and H-bonding [40]
mesoporous silicate
12 Zeolite modified with 68.6 160 Electrostatic and hydrophobic [41]
cetylpyridiumchloride
13 Commercial AC 870 76 Electrostatic [42]

14 UiO-66 1082 189 Electrostatic [43]

15 18%SO3-UiO-66 910 263 Acid–base
16 CTAB-ZIF-67 817 54.31 Electrostatic
17 Commercial AC 1016 83 Electrostatic This work
18 OAC (2.0) 704 487 Electrostatic and H-bonding This work
2 ‒1
*BET surface area of adsorbents (m ·g ), ** Maximum adsorption capacity (mg·g‒1)

26
 O

Cl ONa
H
N

Cl

Scheme 1. Molecular structure of diclofenac sodium.

27
 Cl
Cl Cl
Cl Cl
Cl Cl
Cl
NH2+ Cl δ+
N H1+x Nδ+ H1+x
NH2+ Nδ+ H1+x O
Cl
N Cl
H2+ Cl
O
O
O
HO HO O
HO O O
O H
O repulsion
O
H H Phenolic O
H H H
O O O O
Phenolic O
O
O Carboxylate
O
Carboxylic Carboxylic

4.2<pH<10.0 H-bond

pH<4.2 H-bond

Cl

NH

Cl O

repulsion
O

O phenolate carboxylate
O

pH>10.0

Scheme 2. Plausible mechanisms for adsorption of DCF over OAC (electrostatic

interactions between negative surface charge and positive DCF (at low pH) or negative

DCF (at high pH) were omitted for clarity).

28
 300

200
-1
qt, mg.g

100

0
AC OAC (0.5) OAC (1.0) OAC (2.0) OAC (2.5)

Adsorbents
Fig. 1. Adsorption of DCF over AC and OACs. Condition: 0.005 g of adsorbents in 25

mL solution (100 mg·L-1), 12 h at 25 oC.

29
 400

OAC (2.0)
300
OAC (1.0)
-1

200
qt, mg.g

100
AC

0
0 5 10 15 20 25
Time, h

Fig. 2. Effect of contact time on DCF adsorption over AC and OACs. Condition: 0.005 g

of adsorbents in 25 mL solution (100 mg·L-1), 1-24 h at 25 oC.

30
 400 1.5
(a) (b)
OAC (2.0) 1.2 AC
300
0.9
-1
qe, mg.g

200

Ce/qe
0.6

100 AC 0.3
OAC (2.0)
0 0.0
0 20 40 60 80 100 0 20 40 60 80 100
Ce, ppm Ce, ppm

0.6
(c)

0.4
AC
RL

0.2
OAC (2.0)

0.0
20 40 60 80 100 120
Ci, ppm

Fig. 3. (a)Adsorption isotherms (b) Langmuir plots and (c) effects of initial

concentrations on RL values for adsorption of DCF from water over AC and OAC (2.0).

Condition: 0.005 g of adsorbents in 25 mL solution (25-100 mg·L-1), 24 h at 25 oC.

31
 250
(a)
200

150
-1
q24 h, mg.g

100

50

2 3 4 5 6 7 8 9 10
pH of DCF solution

0 (b)
-10
Zeta potential (mV)

-20

-30

-40

-50
2 4 6 8 10 12 14
pH
Fig. 4. Effect of pH on (a) DCF adsorption over OAC (2.0) and (b) zeta potential of OAC

(2.0). The adsorptions were carried from 50 mg·L-1 DCF solutions at 25 oC for 24 h.

32
 350
Carboxylic Total acidic groups
300
R2 = 0.807 Phenolic
-1
qt, mg.g

250
R2 = 0.991 R2 = 0.968

200

150
0.1 0.2 0.3 0.4 0.5 0.6
-1
Amount of acidic groups (mmol.g )

Fig. 5. Effects of concentrations of acidic groups on DCF adsorption on OACs (0.5, 1.0

and 2.0).

33
 Recycled OAC

1394
Transmittance (%) DCF 1578

DCF-adsorbed OAC
740

OAC 1449 1283

3000 2500 2000 1500 1000

-1
Wavenumber (cm )

Fig. 6. FTIR spectra of OAC (2.0), DCF-adsorbed OAC (2.0), DCF and recycled OAC

(2.0).

34
 300

200
-1
qt, mg.g

100

0
1 2 3 4 5
Number of cycles

Fig. 7. Reusability of OAC (2.0) for the adsorption of DCF (100 mg· L-1, 24 h) after

solvent washing.

35
Graph Abstract

Adsorption of diclifenac sodium over

oxidized activated carbons (OACs)
Cl Cl
Cl
Cl Cl
Cl
NH2+ NH2 + NH2+

HO HO
O HO O O

H
H H H
O O O O

O
O

36
Research highlights

► Removal of diclofenac sodium (DCF) was done using oxidized activated carbons.
► Oxidized activated carbon (OAC) showed huge uptake of DCF (~ 6 times of AC).
►Adsorption mechanism was explained with H-bond and electrostatic interactions.
►Phenolic functonal groups were the most important in the adsorption of DCF.
► OACs are useful adsorbents because they are cheap, recyclable and highly efficient.

37