Chemical Engineering Journal 277 (2015) 360–367

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Chemical Engineering Journal

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

A modeling analysis for the assessment of ibuprofen adsorption

mechanism onto activated carbons
P. Iovino a, S. Canzano a, S. Capasso a, A. Erto c,⇑, D. Musmarra b
a
Dipartimento di Scienze e Tecnologie Ambientali, Biologiche e Farmaceutiche, Seconda Università degli Studi di Napoli, Via Vivaldi 43, 81100 Caserta, Italy
b
Dipartimento di Ingegneria Civile, Design, Edilizia e Ambiente, Seconda Università degli Studi di Napoli, Real casa dell’Annunziata, Via Roma 29, 81031 Aversa (CE), Italy
c
Dipartimento di Ingegneria Chimica, dei Materiali e della Produzione Industriale, Università di Napoli Federico II, P.le Tecchio 80, 80125 Napoli, Italy

h i g h l i g h t s g r a p h i c a l a b s t r a c t

 Thermodynamic tests of ibuprofen

adsorption onto activated carbon are
carried out.
 The effect of concentration,
equilibrium pH and temperature is
investigated.
 A speciation analysis of ibuprofen
species is carried out for pH and
temperature.
 A multicomponent Langmuir model is
used for ibuprofen equilibrium
adsorption.
 The proposed model correctly
assesses the effect of the investigated
variables.

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

Article history: This work is an experimental analysis of the adsorption of ibuprofen (IBP) onto a granular activated car-
Received 25 February 2015 bon. Ibuprofen is a NSAID (non-steroidal anti-inflammatory drug) and is now an emerging contaminant
Received in revised form 20 April 2015 of the aquatic environment. The effect of IBP concentration, pH and temperature on the equilibrium
Accepted 21 April 2015
adsorption capacity is investigated through batch tests. The experimental results show that the highest
Available online 29 April 2015
adsorption capacity is observed under acidic pH and high temperature conditions. The combined effect of
pH and temperature on IBP dissociation in water seems to play a major role in determining the IBP
Keywords:
adsorption capacity of the activated carbon. Low pH and high temperature, in fact, reduce the IBP disso-
Ibuprofen
Pharmaceuticals
ciation grade and increase the concentration of the non-ionized IBP species, which is likely to have a
Water treatment higher adsorption capacity with respect to the ionized one. The study puts forward a model to describe
Adsorption the IBP adsorption mechanism considering the variability of the dissociation grade. The model is based on
Activated carbon the multicomponent Langmuir adsorption theory applied to the ionic species in solution. It shows that
Langmuir model the adsorption capacity is strictly dependent on the IBP speciation in solution, allowing for a correct
interpretation of the effects pH and temperature on IBP adsorption capacity. Finally, one of the main goals
of this model is to preserve the exothermicity of the adsorption phenomena despite the trend observed in
the experimental results: the increase in adsorption capacity with temperature appears to be related to a
lower level of IBP dissociation.
Ó 2015 Elsevier B.V. All rights reserved.

⇑ Corresponding author. Tel.: +39 081 7682236; fax: +39 081 5936936.
E-mail address: aleserto@unina.it (A. Erto).

http://dx.doi.org/10.1016/j.cej.2015.04.097
1385-8947/Ó 2015 Elsevier B.V. All rights reserved.
 P. Iovino et al. / Chemical Engineering Journal 277 (2015) 360–367
1. Introduction
The occurrence of emerging contaminants in the aquatic envi-
ronment is drawing the attention of the scientific community
nowadays. Emerging contaminants include surfactants, pharma-
ceuticals, endocrine disruptors, illicit drugs and many other groups
of compounds, which are still partially regulated or for which the
evidences of toxicity have been collected only recently [1]. In par-
ticular, the presence of pharmaceutical compounds (PhCs) in water
effluents, especially non-steroidal anti-inflammatory drugs
(NSAIDs), is becoming a major concern because they can have
adverse effects on human health and on both terrestrial and aqua-
tic ecosystems, because of chronical exposure even at low concen-
tration [2].
Currently, it is estimated that more than 3000 different PhCs are
used in the European Union and many of them are susceptible to
reach the water cycle. The compound 2-[3-(2-methylpro
pyl)phenyl] propanoic acid, commercially available as ibuprofen
(IBP, CAS number: 15687-27-1), is a widely used NSAID especially
prescribed for the treatment of fever, migraine, muscle aches,
arthritis and tooth aches. It is commonly sold over-the-counter
and several kilotons of IBP are synthesized worldwide every year
[3]. IBP enters the environment via the wastewater from the phar-
maceutical industries, the excrements of medically treated humans
and animals and the disposal of unused medications via the toilet.
As an example, once administered, this compound is only partially
metabolized by the human body and can enter the water cycle
either as unaltered compound or as metabolites or conjugated
compounds, which are excreted mainly through urine and partially
in the feces [2].
When the discharged IBP reaches the wastewater treatment
plants (WWTP), it is subject to a removal procedure by conven-
tional wastewater processing techniques (e.g. biological process)
which could be partially efficient. For this reason, concentrations
of IBP of the order of few lg/L in surface waters located down-
stream the municipal WWTP can be found [2,4].
The fate of any given contaminant in the aquatic environment
depends upon both its physicochemical properties, such as its sol-
ubility in water, Kow (octanol–water partitioning coefficient), Koc
(organic carbon–water partitioning coefficient), etc., and other
environmental characteristics, such as persistence, biodegradabil-
ity, etc., which also influence the transport mechanisms among
phases [4,5]. Natural attenuation phenomena mainly include sorp-
tion on soils or sediments, sunlight photolysis, and other abiotic
transformations (i.e. hydrolysis) [6]. However, a significant persis-
tence grade has been observed for IBP, for which also long-term
biological degradation mechanisms appear to be scarcely active
[7]. Hence, the removal of IBP at its point of source, also including
industrial effluents, is the most effective route for environmental
protection. In this framework, the ionization of the IBP molecule,
as a function of the main thermodynamic parameters (pH, temper-
ature, etc.), should be more accurately considered, as suggested by
several researchers working in this field of investigation [7,8].
Since WWTPs can remove IBP from waters with inadequate effi-
ciency, new research efforts are currently being made to find novel
and efficient treatments to be integrated within the WWTP
schemes. A first line of activities includes the transformation of
IBP into harmless compounds through photocatalysis [9],
Chemical oxidation [10], Fenton processes [7,11], ozonation [12],
sonochemical degradation [13] and cavitation [14]. All these appli-
cations have been put forward only recently and, even if the results
are promising, there is still some uncertainty at the genesis of
degradation compounds and by-products, which should be further
investigated. In order to overcome this drawback and to work out
an effective depuration technology, a second line of investigation
361
refers to the application of adsorption processes, mainly conducted
on either natural materials [15] or activated carbons [16–19].
Adsorption has been widely used for water, groundwater or
wastewater treatment, because it combines good efficiencies with
a reliable and robust process configuration [8,20]. It is a very ver-
satile process that can be used for organic compounds and heavy
metal capture thanks to a wide spectrum of adsorption targets
[21,22,23] as well as for single or multiple contaminations
[20,24]. The wide application of the adsorption process is also
due to the possibility of using different kinds of adsorbents, includ-
ing natural and waste materials either raw or activated
[15,16,21,23].
The identification of the mechanisms that govern the adsorp-
tion phenomena of IBP is of fundamental importance. A correct
approach should take into account the effect of the main thermo-
dynamic parameters (i.e. temperature and pH) and, even if many
efforts have already been made by several authors [17,18,25], some
important parameters, previously mentioned, e.g. ionization,
should be considered simultaneously. In addition, a thorough mod-
eling analysis accounting for the effect of the cited parameters rep-
resents an invaluable tool for the design and optimization of an
adsorption system devoted to the removal of IBP from polluted
water.
The aim of this work is to provide a comprehensive analysis of
IBP adsorption on a commercial granular activated carbon
(Filtrasorb 400) in order to describe the mechanisms that define
the correlation between equilibrium adsorption capacity and the
main process parameters. In particular, some experimental runs
are carried out in model aqueous solutions by analyzing the effect
of IBP concentration, equilibrium pH and temperature on adsorp-
tion capacity.
Finally, a critical interpretation of the experimental results is
provided, based on a modeling analysis of the experimental data
set, which accounts for both IBP ionization phenomena and
adsorption onto activated carbon.
2. Experimental
2.1. Materials
A commercial activated carbon produced starting from a bitu-
minous coal, Filtrasorb 400 (F400), purchased from Calgon
Carbon Corporation, was used in all the experimental runs. A phys-
ical–chemical characterization of the sorbent was carried out,
including B.E.T. surface area, pore size distribution, pHPZC value,
acidic/basic surface functional groups, superficial chemical analy-
sis and proximate analysis [26]. The sorbent is mainly microporous
(with a micropore volume equal to 0.31 cm3 g1) and has a BET
surface area of approximately 1000 m2 g1. The surface is slightly
basic with a pHPZC = 8.5 and a low ash content (about 1.8%). A com-
plete list of its chemical and physical properties is reported in Erto
et al. [27].
An ibuprofen sodium salt of analytical grade with purity higher
than 98% was purchased from Sigma–Aldrich (UK).
2.2. Adsorption procedure
Adsorption working solutions were prepared by dissolving the
ibuprofen sodium salt into deionized water. The initial IBP concen-
tration (C0) used in each adsorption test was 10 mg L1. A variable
amount of activated carbon, 1.0–50 mg, was added to a 50 mL
amber glass bottle with a butyl/PTFE cap (of the type generally
used for head-space analyses). The raw material was gently
crashed and sieved in order to obtained grains in the range 1.0–
362 P. Iovino et al. / Chemical Engineering Journal 277 (2015) 360–367

2.0 mm. Before the adsorption experiments, the sieved material 40

was repeatedly washed with deionized water and the samples
were dried at 40 °C overnight. 35

Adsorption batch tests were conducted at different equilibrium

30
pH (2–10) and temperature (4–34 °C). In particular, the effect of pH
was investigated by adding either HCl (1 M) or NaOH (1 M) to the
25
IBP working solution; the pH was not further altered during the

-1
ω, mg g
experimental run. The samples were stored at constant tempera- 20
ture and periodically shaken until equilibrium was reached.
Preliminary kinetic tests (not reported) allowed estimating the 15
time needed to reach the equilibrium (i.e. 1 week), which was
adopted for all the experimental runs. 10

5
2.3. Analytical methods
0
The analytical measure of total IBP in solution was performed 0 2 4 6 8 10 12
by Gas-Cromatograph coupled with Mass Spectrometry (GC/MS), equilibrium pH
preceded by a solid phase extraction (SPE) step.
The pharmaceuticals were isolated from the water samples by Fig. 1. IBP adsorption capacity onto F400 activated carbon as a function of
equilibrium pH. T = 24 °C; C0 = 10 mg L1; carbon dosage 0.2 mg L1 (10 mg in
means of a reversed-phase cartridge (Oasis HLB 1 cc, Waters).
50 mL); IBP equilibrium concentration 3–9 mg L1.
Each cartridge was pre-conditioned with 3 ml of methanol (analyt-
ical grade, Fluka) followed by 5 ml of ultra-pure water. The sam-
ples were extracted under vacuum at a flow rate of 5 ml/min. 50
After extraction, the cartridges were dried under vacuum for 4°C
10 min. Ibuprofen was eluted with 3 ml of methanol. Extracts were 14°C
24°C
dried under a gentle stream of nitrogen. The final volume extracted 40
34°C
is 100 ll.
The determination of IBP in solution was made with a 7890A
gas chromatograph with a mass spectrometric detector 30
-1
ω, mg g

MSD5975C (Agilent Technologies, USA), equipped with a capillary

column HP-5MS (5% phenylmethylsiloxane) (length: 30 m, internal
diameter: 0.25 mm, film thickness: 0.25 lm). The analytical proce- 20
dure allowed calculating only the total IBP concentration, without
discriminating the contribution of the ionized and non-ionized IBP
species. 10

To assure the accuracy, reliability and reproducibility of the

data collected, all the isotherm tests were repeated in triplicate
0
and only average values were reported. In each replica of test,
0 2 4 6 8 10
the standard deviation in ibuprofen concentration, both in liquid
-1
and on solid, was below 5%. C, mg L

Fig. 2. IBP adsorption isotherms onto F400 activated carbon as a function of

3. Experimental results temperature. Equilibrium pH = 6.8 ± 0.3; C0 = 10 mg L1; Carbon dosage 0.2–1 mg
L1 (10–50 mg in 50 mL).

The experimental tests aimed at investigating the effect of tem-

perature and pH on the IBP adsorption capacity of the commercial
activated carbon F400. The experimental conditions were those
typical of polluted waters, in particular the IBP equilibrium con-
centration was in the range of interest of industrial effluent treat-
ment [1,4].
In Fig. 1, the effect of equilibrium pH on the adsorption of IBP
onto F400 activated carbon at constant T = 24 °C is reported.
The results in Fig. 1 clearly show that equilibrium pH affects the
total IBP adsorption capacity (i.e. inclusive of the contribution of
both ionized and non-ionized species). In the investigated pH
range, the total adsorption capacity has a marked monotonic
decreasing trend; the highest value is attained in conjunction with
pH = 2, while an almost 85% reduction occurs at pH = 10.
In Fig. 2, the effect of temperature on IBP adsorption on the
same activated carbon is reported.
Similarly, also in this case the data are reported in terms of total
IBP concentration.
The experimental data show that an increase in temperature in
the range 4–34 °C determines higher total IBP adsorption capaci-
ties. For each temperature level, the adsorption data seem follow-
ing a linear trend; however, even if an asymptotic value of
adsorption capacity is not reached in the investigated conditions,
a slight indication of a non-linear trend at the highest equilibrium
concentration can be observed.
4. Discussion
The experimental analysis was focused on the assessment of the
effect of the main thermodynamic parameters (i.e. temperature
and pH), which are known to have a major influence on both IBP
adsorption onto activated carbon and IBP ionization phenomena
[15,17,18]. An effort was made in order to find a correlation
between these two phenomena and to work out a modeling
description of the entire experimental data set.
As indicated in the previous section, the experimental data
allow evaluating the equilibrium conditions of a solution contain-
ing a given concentration of the total IBP and the amount adsorbed
on the solid. In aqueous solution, the main problem related to the
interpretation of the experimental results concerns the presence of
different chemical species, all potentially adsorbable on the solid
surface. The analytical techniques do not allow discriminating
 P. Iovino et al. / Chemical Engineering Journal 277 (2015) 360–367
the concentrations and the forms in which they are present on the
solid adsorbent. Consequently, as a first step, an analysis of the
equilibrium in the solution, for every experimental point repre-
senting the equilibrium conditions (Figs. 1 and 2) must be carried
out [8].
It is commonly known that weak electrolytes such as IBP coex-
ist in both an ionized and non-ionized form. In the case of IBP,
these correspond to a base (i.e. anionic form [A]) and an acid
(i.e. neutral form [HA]), respectively. The extents of these conju-
gates depend on solution pH and pKa of the acid form as expressed
in the Henderson–Hasselbalch equation, valid for dilute solutions
[28]:
½A 
pH ¼ pKa þ log
½HA
From Eq. (1) it can be easily derived the % of ionization, reported
in the following Eq. (2):
½A  100
% ionization ¼ 100 ¼
½HA þ ½A  1 þ 10ðpKapHÞ
Eq. (2) allows determining [A] and [HA] concentrations for
each experimental point, known pH and temperature (i.e. pKa).
The dependence of temperature on the % of ionization can be
expressed through the pKa dependence on temperature, by a
Van’t Hoff type equation [28]:
d lnðKaÞ DH
¼ 2
dT RT
or
d lnðKaÞ DH
¼ ð4Þ
dð1=TÞ RT
In which Ka is the IBP dissociation constant, DH is the standard
enthalpy change [kJ mol1], T is the absolute temperature [K] and R
is the universal gas constant [kJ mol1 K1].
Under the hypothesis that DH is constant with the temperature,
plotting ln(Ka) versus 1/T results in a linear trend. The DH value
can be determined from the slope of the plot if Ka value at two dif-
ferent temperatures is available. In Table 1, the requested values
are reported (after Meloun et al. [29]).
Either Eqs. (3) or (4) can be used to estimate the IBP dissociation
constant at a different absolute temperature. Starting from the data
reported in Table 1 and using Eq. (4), a value of
DH = 19.17 kJ mol1 was calculated, which allowed determining
Ka values in correspondence of all the temperatures investigated
during adsorption tests, as reported in Table 2.
It is possible to observe that an increase in temperature results
in an increase in pKa, which corresponds to a reduction of the dis-
sociation constant Ka. Consequently, an increase in temperature
determines a lower % ionization of IBP so that the concentration
of the non-ionized species increases.
4.1. Effect of equilibrium pH
The solution pH influences adsorption, as it affects the proper-
ties of both the adsorbent and the adsorbate. In general, the surface
of the activated carbon contains a large number of functional
Table 1
Dissociation constant of IBP (expressed as pKa) as a function of
temperature (after Meloun et al. [29]).
T (°C) pKa
25 4.38
37 4.51
363
Table 2
Dissociation constant of IBP (expressed as pKa) as a function of
temperature calculated by Van’t Hoff Eq. (4).
T (°C) pKa
4 4.13
14 4.25
24 4.37
34 4.48
groups; the type and ionic state of these functional groups and
the mutual interaction with the IBP chemistry in solution may play
a major role in determining its adsorption capacity. The surface
charge of the activated carbons depends on the solution pH and
ð1Þ
its point of zero charge (pHPZC), which is the pH value at which
the net surface charge on carbon surface is zero. For typical ampho-
teric activated carbons, the surface is positively charged at
pH < pHPZC. When pH < pKa or pH > pKa, the IBP is mainly in its
protonated form (i.e. non-ionized) or in its deprotonated form
ð2Þ
(i.e. ionized), respectively. Hence, in both cases, no electrostatic
repulsion between the non-ionized IBP species (neutral) or the ion-
ized species (negative) and the surface is likely to occur.
Conversely, for pH > pHPZC the activated carbon surface is nega-
tively charged. In this case, an electrostatic repulsion between
the surface and the carboxylate IBP anions (i.e. A) is likely to occur
when pH > pKa i.e. when the contribution of the ionized species
increases. Therefore, a depletion of the adsorbed total IBP might
ð3Þ be observed.
The above considerations strengthen the idea that the effect of
pH on IBP adsorption is strictly connected with its % of ionization.
In Fig. 3, the [A] and [HA] fractions of IBP as a function of solu-
tion pH are reported at 24 °C, as calculated by Eq. (2) and with the
pKa data extracted from Table 2.
It is possible to observe that for pH = 2, IBP is almost all in its
non-ionized form (% ionization  0.4%), while for pH higher than
8, IBP is completely dissociated (% of ionization  99.9%).
Moreover, as expected, when pH = pKa the % of ionization is equal
to 50% and [A] = [HA].
As for all PhCs, the ionized and non-ionized forms of IBP have
different properties, which are designed for an optimal absorption
by the human body in terms of both pharmacodynamic and phar-
macokinetic drug action. In particular, the non-ionized form is
commonly considered to have a higher lipophilic character while
the ionized form exhibits the fastest dissolution rate and the great-
est solubility in water [30]. Lipophilicity can be defined as the
1.0
0.8
0.6
Fraction (-)
0.4
[HA]
0.2 [A- ]
0.0
0 2 4 6 8 10 12
pH

Fig. 3. [A ] and [HA] fractions of IBP as a function of solution pH. T = 24 °C.
364 P. Iovino et al. / Chemical Engineering Journal 277 (2015) 360–367
partitioning of a species between a non-aqueous and an aqueous
phase (e.g. partition coefficient in n-octanol/water). It is an impor-
tant factor in the dynamics of separation processes, since it can
exert a significant influence on adsorption phenomena, specifically
when dealing with PhCs [15].
The experimental data reported in Fig. 1 seem to confirm this
correlation. In fact, for pH = 2 the highest IBP adsorption capacity
is observed, which can be associated to the predominant presence
of the non-ionized form (i.e. [HA]) of IBP (cf. Fig. 3).
The main adsorption mechanism of molecules in which an aro-
matic group is present is represented by p–p interactions [31].
However, as observed by Baccar et al. [15], other mechanisms are
likely to be involved in the complex effect of pH on IBP adsorption
capacity. As the pH decreases, the H+ excess determines the simul-
taneous occurrence of hydrogen bonds between carbon and IBP
molecules and a reduction in p–p interaction because of the
diminution of the electron density of the basal planes of the car-
bon. In these conditions, the affinity of carbon for water molecules
is likely to increase, thus determining the formation of surface
complexes, which can partially compete with IBP adsorption
[15,32]. Moreover, the overall positive surface charge leads to
donor–acceptor interactions between the aromatic ring of IBP
(electron acceptor) and the surface carbonyl groups of the acti-
vated carbon (electron donor) [32].
The mutual effect of these mechanisms is likely to explain the
slight increase in the adsorption capacity in correspondence of a
diminution of the pH in the range 2 < pH < 3 and the more evident
increase in the range 3 < pH < 4, where these mechanisms are less
active and the increase in [HA]% from 70% to 96% is the preva-
lent effect.
An increase in pH up to 7.3 determines a significant reduction in
the adsorption capacity associated with a simultaneous increase in
ionized species concentration (which, for pH = 7.3, accounts for
almost 99.7% of the total IBP in solution). In these conditions, the
repulsive effects are slightly active, being pH < pHPZC (cf.
Section 2.1). Hence, the reduction of adsorption capacity can be
attributed to a lower affinity of the ionized IBP species (i.e. A)
towards the activated carbon.
In correspondence to a further pH raise, the physical adsorption
of hydroxyl ions and/or the dissociation of very weakly acidic sur-
face functional groups on the surface of the activated carbon might
occur. As a result, the increasing negative surface charge can deter-
mine some repulsive forces between the adsorbed anionic species
and the anionic surface functional groups, the adsorbed hydroxyl
ions or adjacent adsorbed anionic species.
The results are consistent with the findings of Baccar et al. [15],
Mestre et al. [17] and Mestre et al. [25], even if it is here high-
lighted the absolute necessity to refer the entire discussion to
the equilibrium pH rather than to the corresponding initial value
[8].
4.2. Temperature effect
The analysis of experimental data so far carried out showed the
importance of a correct evaluation of the contributions of IBP spe-
cies present in solution. The analysis of the effect of equilibrium pH
showed that this parameter plays a major role in determining the
chemical equilibria in solution, involving the different IBP species.
Moreover, it was showed that the IBP non-ionized species (i.e. HA)
has a higher adsorption capacity with respect to the ionized one
(i.e. A-), also when repulsive forces involving the activated carbon
surface are scarcely or not at all active (i.e. when pH < pHPZC). At
the same time, the temperature was identified as one of the param-
eters exerting the highest influence on equilibrium species distri-
bution, since pKa values are dependent on temperature even in a
short range such as 4–34 °C (cf. Table 2). All above considered,
the effect of temperature reported in the data of Fig. 2 can be
explained only if the mutual effect of pH and temperature are con-
sidered, stated that the temperature itself has an influence on the
IBP species distribution and on the equilibrium pH. Hence, in order
to address the effect of the temperature on IBP adsorption, the % of
ionization of IBP for all the data reported in Fig. 2, as a function of
both equilibrium pH and temperature, was evaluated. To this aim,
similarly to the procedure adopted in the previous section, Eq. (2)
was used with pKa data extracted from Table 2 and the results are
reported in Table 3.
It is possible to observe that an increase in temperature deter-
mines a reduction of the % of dissociation, hence an increase in
the concentration of the non-ionized IBP species (i.e. [HA]). Even
if the differences in the % of dissociation are very low, the effect
on adsorption capacity is marked because the system is highly
dependent also on pH, as reported in the previous section.
Moreover, according to the well-known Le Chatelier’s principle,
the predominant adsorption of the non-ionized IBP species deter-
mines a continuous formation of this species in solution and a con-
sequent consumption of total IBP in solution. This event is likely to
justify the occurrence of a non-negligible adsorption capacity even
when the concentration in solution of the unionized species is very
low. In other words, the adsorption equilibrium between
non-ionized IBP bonded on the carbon surface and the same spe-
cies in solution is largely shifted towards the former, as confirmed
by the adsorption constants calculated by the modeling analysis
reported in the next section.
A comparison between the data reported in Fig. 1 and 2 allows
confirming the simultaneous effect of pH and temperature on the %
of dissociation of IBP and its influence on the IBP adsorption capac-
ity. In fact, an experimental point realized in correspondence of
equilibrium pH = 7.3 and T = 24 °C (from Fig. 1) and an experimen-
tal point realized at equilibrium pH = 7.1 and T = 4 °C (from Fig. 2),
with same IBP equilibrium concentration (8 mg L1), are charac-
terized by the same % of dissociation of IBP, equal to 99.8% (cal-
culated by Fig. 3 and Table 3, respectively). For these points, the
total IBP adsorption capacity resulted almost the same
(x  8 mg g1), thus confirming the high dependence of IBP
adsorption on pH and temperature, through its % of dissociation.
In conclusion, the analysis of experimental data reported allows
concluding that the apparent endothermic adsorption (i.e. increase
of IBP adsorption capacity with temperature) depends on the influ-
ence of the temperature on the chemical equilibria in solution, in
which equilibrium pH plays a major co-role.
4.3. Modeling analysis
The qualitative analysis carried out in the previous sections
pointed out the relevance of IBP speciation in determining the
adsorption capacity of activated carbon at the different experimen-
tal conditions. In fact, for a complete interpretation of experimen-
tal results and in order to understand the effect of the individual
parameters investigated, the starting point is the knowledge of
the contribution of each chemical species at equilibrium in solu-
tion and the amount of total adsorbed IBP. The application of Eq.
(2), coupled with the data reported in Table 2, allowed a punctual
determination of the contributions of the IBP ionized and
Table 3
% of dissociation of IBP in solution as a function of temperature calculated by Eq. (2).
T (°C) % dissociation
4 99.8
14 99.7
24 99.5
34 98.8
 P. Iovino et al. / Chemical Engineering Journal 277 (2015) 360–367
non-ionized forms, in all the investigated experimental conditions.
Subsequently, it is necessary to define an adsorption model, which
is able to correlate the experimental adsorption capacity to the
equilibrium concentrations of the species in solution previously
determined.
The analysis of the IBP adsorption mechanism made in the pre-
vious sections showed that, for pH < pHPZC, the adsorption of IBP
both in its ionized and non-ionized forms mainly occurs by p–p
interactions, while the occurrence of ionic interactions is likely to
be negligible. Differently, when pH > pHPZC, repulsion phenomena
can occur, exerting a significant effect in depleting the adsorption
capacity. Moreover, when the adsorption of both HA and A- species
is possible, it is likely to occur according to a competitive/additive
mechanism.
In this paper, the classical multicomponent Langmuir model [8]
was applied to the quantitative description of IBP adsorption
mechanisms, under the following hypotheses:
– according to the hypotheses of the Langmuir model, adsorption
occurs on active sites with the same energy level. The adsorp-
tion enthalpy and the corresponding Langmuir constant, Ki,
depends on the specific pair of adsorbate-active site, and on
the temperature;
– the value of the Langmuir constant for adsorption reactions, Ki
can be expressed as:
 
DGi
K i ¼ exp
RT
where DGi is the free Gibbs’ energy of the corresponding adsorption
reaction;
- the experimental adsorption capacity is the sum of the contri-
butions of both IBP species present in solution.
The adopted multicomponent Langmuir model correlates the
total amount of adsorbed IBP (deriving from experimental data)
with the solution equilibrium concentrations of the two IBP species
(deriving from data analysis):
K HA ½HA þ K A ½A 
x ¼ xHA þ xA ¼ xmax
1 þ K HA ½HA þ K A ½A 
where xHA and xA are the partial adsorption capacities; K HA and
K A are the Langmuir constants for the IBP species HA and A,
respectively, and xmax represents the maximum adsorption capac-
ity of total IBP as an intrinsic characteristic of the carbon, which can
be assumed as constant with temperature [8,20].
The model reported in the Eq. (6) was applied to the data
reported in Fig. 1 in which the total IBP adsorption capacity was
assessed for different pH values and, consequently, in experimental
conditions covering the entire range of the % of dissociation (i. e.
0–100%). In this way, the different adsorption capacity of the
IBP species HA and A can be correctly modeled. Following this
path, it is possible to estimate the Langmuir constants K HA and
K A and xmax (Table 4).
From the data reported in Table 4, the corresponding values of
the Gibb’s free energy DGHA = 2.137101 kJ mol1 and
1
DGA ¼ 2:489 kJ mol can be calculated, using Eq. (5).
Consequently, the constants K HA and K A can be calculated in
Table 4
Regression parameters of Langmuir multicomponent adsorption model (Eq. (6)).
2
Mean Std. error R
xmax, mmol g1 1.86101 1.531102 0.901
K HA , L mmol1 5.723103 3.387103
K A , L mmol1 2.739 3.636
365
correspondence of all the investigated temperatures and the total
IBP adsorption capacity can be modeled by applying the Eq. (6).
In Fig. 4, the comparison between experimental (xexp) and model
(xmod) total IBP adsorption capacity (experimental data taken from
Figs. 1 and 2) is reported, in the form of a parity plot.
A very good matching between experimental and model data
can be observed for all the investigated temperatures, even if a
slight deviation is present for data at 34 °C and for those at highest
adsorption capacity.
In addition, the contributions of the single IBP species to the
total adsorption capacity can be determined by the Langmuir mul-
ticomponent model, expressed by the following Eq. (7):
K HA ½HA
xHA ¼ xmax
1 þ K HA ½HA þ K A ½A 
K A ½A 
xA ¼ xmax ð7Þ
1 þ K HA ½HA þ K A ½A 
In Fig. 5, the modeling adsorption isotherms of the HA and A
species at different temperatures are reported, expressed as corre-
spondence of the equilibrium concentration (calculated by Eq. (2)
applied to the experimental data reported in Fig. 2) and model
adsorption capacity (determined by Eq. (7), using the adsorption
constants reported in Table 4.
The application of the Langmuir model to IBP adsorption data
confirmed that the HA species has the largely highest adsorption
capacity, with respect to the A species. However, the most inter-
ð5Þ
esting result is represented by the trends of the curves reported in
both Fig. 5A and B. In fact, in both the cases, the partial adsorption
capacity increases for lower temperatures, in line with the
expected (from theory) exothermicity of adsorption phenomena.
In conclusion, IBP adsorption is an exothermic phenomenon and
the apparent endothermic behavior showed in Fig. 2 is the result
of equilibrium dynamics coupled with single IBP species adsorp-
tion capacity, the IBP dissociation grade playing a major role.
5. Conclusions
ð6Þ
The adsorption of Ibuprofen (IBP), a non-steroidal
anti-inflammatory drug, onto a granular activated carbon was
experimentally investigated. Batch adsorption tests were carried
out in order to analyze the effect of IBP concentration, equilibrium
pH and temperature.
50
4°C
14°C
24°C
40
34°C
-1
30
ωmod, mg g
20
10
0
0 10 20 30 40 50
ωexp, mg g-1
Fig. 4. Comparison between experimental and model (Langmuir multicomponent)
adsorption capacity of total IBP on F400 activated carbon.
366 P. Iovino et al. / Chemical Engineering Journal 277 (2015) 360–367

30 30
A B 4°C
14°C
25 25
24°C
34°C
20 20
ωHA, mg g-1

ωA-, mg g-1
15 15

10 10
4°C
14°C
5 24°C 5
34°C
0 0
0.00 0.02 0.04 0.06 0.08 0.10 0.12 0.14 0.16 0 2 4 6 8 10
-1 - -1
[HA], mg L [A ], mg L

Fig. 5. Adsorption isotherms of HA (A) and A (B) IBP species as a function of temperature, as determined by speciation analysis (Eq. (2)) and Langmuir multicomponent
model (Eq. (7)).

Experimental results showed that the equilibrium pH exerts a
major effect on the total IBP adsorption capacity and the highest
value is verified in correspondence of pH = 2. The temperature
effect is equally marked and the experimental results showed that
an increase in temperature determines a significant increase in
total IBP adsorption capacity.
The analysis of the experimental data was focused on the effect
of these parameters (i.e. equilibrium pH and temperature) on the
dissociation grade of IBP in solution, which gives rise to the simul-
taneous presence of an ionized (i.e. [A]) and non-ionized (i.e.
[HA]) form of IBP. The analysis of the results showed that the
non-ionized species has the highest adsorption capacity. Hence,
an overall increase in the adsorption capacity is observed in corre-
spondence of a decreasing of the IBP dissociation grade, which
occurs at lower pH and higher temperature. In addition, the effect
of pH is also related to the pHPZC of the activated carbon. In fact,
when the IBP dissociation is high and the solution pH is higher
than pHPZC, the repulsion between the negatively charged acti-
vated carbon surface and the anionic IBP species significantly
reduces the total IBP adsorption capacity.
The analysis of the experimental data was coupled with a mod-
eling analysis based on the application of the Langmuir multicom-
ponent model to the entire experimental data set.
The model allows a very good description of the effect of the
investigated variables, providing for a reliable description of IBP
adsorption mechanisms. A competitive/additive mechanism can
be likely assumed and the total IBP adsorption capacity confirmed
to be directly related to the IBP species concentrations.
Finally, the model allows the evaluation of the contribution of
each IBP species to the total adsorption capacity showing that,
despite the layout of the experimental results, for both the species,
the adsorption is exothermic and the IBP dissociation grade plays
the major role.
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