Ecotoxicology and Environmental Safety 151 (2018) 144–152

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Ecotoxicology and Environmental Safety

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

Removal of pharmaceutical pollutants from synthetic wastewater using T

chemically modified biomass of green alga Scenedesmus obliquus
⁎
Mohamed E.M. Ali , Azza M. Abd El-Aty, Mohamed I. Badawy, Rizka K. Ali
Water Pollution Research Department, National Research Centre, 33 El Buhouth St., Dokki, Cairo 12622, Egypt

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

Keywords: Pharmaceutical compounds are considered emerging environmental pollutants that have a potential harmful
Biosorption impact on environment and human health. In this study, the biomass of alga (Scenedesmus obliquus) was mod-
Modified algal biomass ified using alkaline solution, and used for the biosorption of tramadol (TRAM) and other pharmaceuticals. The
Tramadol adsorption kinetics and isotherms were investigated. The obtained results reveal high adsorption capacity of
Kinetics
tramadol over modified algal biomass (MAB) after 45 min with removal percentage of 91%. Pseudo-second order
Isotherm
Toxicity
model was well fitted with the experimental data with correlation coefficient (0.999). Biosorption of tramadol on
modified algal biomass proceeds with Freundlich isotherm model with correlation coefficient (0.942) that
emphasized uptake of TRAM by MAB is driven by chemisorption. FTIR spectra of MAB before and after the
adsorption were analyzed; some IR bands were detected with slight shift and low intensity suggesting their
involving in adsorption. The tramadol biosorption by MAB is a chemical process as confirmed by Dubinin-
Radushkevich. The adsorption of pharmaceutical over MAB is mainly preceded by hydrophilic interactions
between amino and carbonyl groups in pharmaceutical molecules and hydroxyl and carbonyl functional groups
on surface of biosorbent. It was emphasized by disappearance O-H and C-O from biomass IR spectra after ad-
sorption. In matrix of pharmaceutical, the recorded adsorption capacities for CEFA, PARA, IBU, TRAM and CIP
are 68, 58, 42, 42 and 39 mg/g over MAB at natural pH and MAB dose of 0.5 g/L. Furthermore, oxygen uptake
by bacteria was applied for estimate the toxicity of pharmaceutical. The recorded result concluded the efficient
reusability of modified algal biomass for biosorption of pharmaceuticals, as well only the adsorption efficiency
decreased by 4.5% after three runs. Subsequently, the modified algal biomass is a promising reusable adsorbent
for decontamination of wastewater from pharmaceuticals.

1. Introduction
Pharmaceutical compounds are considered emerging environmental
pollutants that have a potential harmful effect on environment and
human health. The contamination of water with pharmaceuticals is
considered as a rising problem due to their non-biodegradability in the
aquatic environment even at low level (Klavarioti et al., 2009). Pre-
vious studies reported that thousands tons of medications are pre-
scribed and consumed annually around the world (Kasprzyk-Hordern
et al., 2009; Merle et al., 2012; Ortiz de García et al., 2013), and large
quantities of them and their metabolites are released into aquatic en-
vironments via manufacturing waste, human or animal excretion,
hospitals or improper disposal runoff (Al-Odaini et al., 2013; Batt et al.,
2008; Besse et al., 2012; Brown et al., 2006; Collado et al., 2014; Escher
et al., 2011). Also, these compounds are discharged directly into was-
tewater throughout various way such as household and consumer
products, disposal of unused or expired medicine in toilets (Lladó et al.,
2016).
Pharmaceutical compounds are hardly to be eliminated by con-
ventional wastewater treatment plants (WWTPs) and transported to
surface waters (González Alonso et al., 2010; Zhou et al., 2010) and
groundwater (Einsiedl et al., 2010). Higher levels of pharmaceuticals
have been detected in developing countries due to the direct discharge
of untreated wastewater from residential area and hospitals into surface
waters (Tran et al., 2014).
Tramadol is a central analgesic whose therapeutic action takes place
on the morphine receiver as a pain control, and it is extensively used
after surgical operations or chronic diseases. About thirty percent of its
concentration is released in the urine (Patel et al., 2009). The psy-
choactive drugs, such as tramadol, doxepin and other derivatives have
significant side effects (anxiety, dementia, paranoia) and possible de-
pendences to drugs. As well, TRAM and other drugs were used by un-
safe manner with medical description in Egypt. In spite of its controlled
utilization, TRAM was detected at high concentration (higher than

⁎
Corresponding author.
E-mail address: alienv81@yahoo.com (M.E.M. Ali).

https://doi.org/10.1016/j.ecoenv.2018.01.012
Received 8 June 2017; Received in revised form 1 January 2018; Accepted 7 January 2018
Available online 12 January 2018
0147-6513/ © 2018 Elsevier Inc. All rights reserved.
M.E.M. Ali et al. Ecotoxicology and Environmental Safety 151 (2018) 144–152

0.2 µg L−1) in various water resources owing to its chemical stability

and non-biodegradability as well as the deficiency of traditional was-
tewater treatment (Rǒa-Gomez and Püttmann, 2012a; Thiebault et al.,
2015). Also, they are found in diverse German surface waters with
various concentrations 25–381 ng L−1 for TRAM) and 35–261 ng L−1
for O-desmethyl tramadol) (Rǒa-Gomez and Püttmann, 2012b), which
might possibly have adverse impacts on marine environment (Painter
et al., 2009). Unfortunately, there is a scarcity of reports demonstrating
the toxicity of long-term exposure of pharmaceuticals and their meta-
bolites. Few studies stated the toxicity of some pharmaceuticals, where
diclofenac showed chronic effect on aquatic organisms for the lowest
observed concentrations (LOC) in treated wastewater effluent con-
centrations (Rǒa-Gomez and Püttmann, 2012b). Also, venlafaxine
showed a time delay in the predator avoidance behavior of fathead
minnows upon chronic exposure of embryos or larvae to low con-
centrations. Recently Stancova et al. (2017), investigated the effects of
sub-lethal or sub-chronic doses of pharmaceutics, including ibuprofen,
diclofenac, and carbamazepine individually, and in mixture, on the
early life stages of tench (Tinca tinca). They found that the tested
pharmaceuticals induced oxidative stress in fish in both exposures.
TRAM is somewhat noxious to aquatic organisms; Daphina magna after
long-term exposure, mostly affecting reproduction parameters (Rǒa-
Gomez and Püttmann, 2012b). Therefore, there is a growing concern to
locate a cost-effective technology for removal of these pharmaceuticals
because there are few attempts for the elimination of these compounds
through different methods; adsorption, advanced oxidation, membrane
filtration, micro-extraction, and electrochemical oxidation (Hollender
et al., 2009; Reungoat et al., 2010; Lee et al., 2012; Lladó et al., 2016).
Moreover, the sorption method is considered superior regarding to Fig. 1. Chemical structure of studied compounds.
other processes for ease of applicability, ease of operation, and sim-
plicity of design and universal in use (Gupta and Saleh et al., 2013) 2. Material and methods
Thus, biosorption can be a hopeful choice method to enhancement
the current decontamination from pharmaceutical wastewater. 2.1. Chemicals
Activated carbon (AC) is a vastly privileged adsorbent due to its
efficient removal for a multiple of noxious pollutants (Gupta et al., Analytical reference compounds namely, Tramadol (TRAM), cefa-
2009; Yadav et al., 2013). Its high cost and the deficiency of re- droxil (CEFA), paracetamol (PARA), ciprofloxacin (CIP) and ibuprofen
generation and/or reuse are the main drawbacks of AC (Marchal et al., (IBU) are supplied from Local Pharma Company, Egypt. They used as
2013). Therefore, economical adsorbents; agricultural wastes, clay received without any further purification (Fig. 1).
materials, biomass, non-living algae, and seafood-processing wastes
were applied for removal of different pollutants (Irem et al., 2013;
Abdel–Aty et al., 2015; Gupta et al., 2015). Green algae are amongst 2.2. Experimental design
low cost adsorbents, they have cellulosic polysaccharides content that
incorporated with high fraction of proteins to form glycoproteins. These 2.2.1. Preparation of modified biosorbent
components have numerous functionalized groups (amino, carboxyl, Micro alga; Scenedesmus obliquus (S. obliquus) a fresh water green
sulphate, and hydroxyl) which have an imperative role in the bio- alga, which was isolated from phytoplankton community of Nile River,
sorption process (Romera et al., 2007). The algal biomass is composed purified and recultivated using BG11 media (Carmichael, 1986). The
of materials with different percent; 53% as protein, 21% as poly- preparation of algal biomass was previously described (Abdel-Aty et al.,
saccharides and 17% as lipids (Laurens et al., 2012). Recently, ad- 2015). The detailed description as following; the cultures were kept at
sorption of pollutants over the algal biomass surface has been in- 24 ± 2 °C on shelves illuminated with daylight fluorescent tubes with
vestigated, i.e., heavy metals (Abdel-Aty et al., 2013; Abd El-Ghafar intensity of 33.8 µE/m2/s. No aeration was provided; the cultures were
et al., 2014), dyes (Hany Abdel Ghafar et al., 2017) aromatic hydro- hand shaken daily to prevent settling and adherence to the flasks.
carbons (Lei et al., 2007) and phenylurea herbicide (Abdel-Aty et al., Cultivation was carried out in sterilized conical flasks. At a maximum
2015). growth, the biomass was harvested by centrifugation at 5000 rpm for
There is no previous data concerning removal of tramadol via ad- 10 min. The biomass was extensively washed with distilled water, dried
sorption. Herein, the modified algal biomass is prepared by treatment at 40 °C (to a constant weight), ground, and sieved into fractions. Then,
algae with solution of 0.1 N NaOH to increase the functional groups dried biomass was modified using alkaline media, herein, a sample of
that play an important role in biosorption process. Alkaline-modified 5 g of dry alga was treated with 50 mL of NaOH solution (mass fraction,
algal biomass will be applied for biosorption of pharmaceutical com- 2%), and magnetically stirred at gentle mixing (150 rpm) at 80 °C for
pounds. The crux objective of study is utilization of modified algal 24 h, then, the alkaline treated sample was then filtered off followed by
biomass for the decontamination of TRAM, and the reusability of bio- washing with deionized water to remove the excess of NaOH. The algal
mass for adsorption of different pharmaceuticals. Moreover, the toxicity biomass was then dried in an oven at 40 °C. HPLC chromatogram for
of raw and treated solution of pharmaceutical mixtures using oxygen separation of different pharmaceutical compounds was illustrated in
uptake by bacteria in activated sludge was examined. Fig. 2.

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M.E.M. Ali et al.
2.3. Preparation of stock solutions
For preparation of stock solution of 200 mg/l of individual phar-
maceutical compound; CEFA, PARA, TRAM, CIP, and IBU, 200 mg of
individual compound was dissolved in 1 l of deionized water by stirring
till complete dissolution.
2.4. Adsorption experiment
The adsorption trials were conducted in batch experiment to de-
termine the optimal condition for removal processes; contact time, so-
lution pH, biosorbent dose and initial concentration of TRAM. To es-
timate the equilibrium time, adsorption trials were conducted on
exactly 50 mL of tramadol solution (50 mg/L) with dose of 0.5 g/L
under dark conditions at invariable temperature for 180 min. The
containers were shaken by shaker (Stuart scientific, UK) at 210 rpm. For
studying the effect of pH on adsorption, pH value of 50 mL of TRAM
solution (50 mg/L) was adjusted with 0.1 M HCl or 0.1 M NaOH solu-
tions to adjust pH from 3 to 11, then biosorbent dose of 0.5 g/L was
introduced. To estimate the effect of biosorbent dose on the TRAM
biosorption rate, different experiments using various doses of MAB
(0.25–1.5 g/L) were conducted at optimal pH (pH 7) and equilibrium
time of 45 min for isotherm study, The effect of original TRAM con-
centrations was examined (25−200 mg/L) adsorption over 0.5 g/L of
alkaline modified algal biomass and neutral pH and equilibrium time of
45 min.
The solution was passed through a syringe filter (PTFE, 0.45 µm).
The residual of tramadol concentration was detected by high perfor-
mance liquid chromatography (HPLC Agilent 1100, USA). The elution
of tramadol using Isocratic elution with phosphoric acid solution (pH 4)
and acetonitrile (60%:40%) with flow rate of 1 mL/min, the column
temperature was kept at 25 °C during analysis. All the experiments were
conducted in triplicate and the mean of the results were used for further
calculations. Blank samples were run under similar experimental con-
ditions but in the absence of adsorbent and did not show a significant
loss of tramadol on the container walls.
The capacity of tramadol by biosorbent (q) is defined as the amount
of tramadol in (mg) bound to one g of biosorbent according to Eq. (1).
(Hammud et al., 2011):
mg ⎞ (Ci − Ce ) × V
q ⎛⎜ ⎟ =
⎝ g ⎠ m (1)
The percentage removal of tramadol was calculated according to Eq.
(2).
(Ci − Ce )
%R = × 100
Ci (2)
Where: m is the biosorbent mass (g). V is tramadol solution volume (L)
in contact with the biosorbent. Ci and Ce are the initial and equilibrium
tramadol concentration (mg/L), respectively.
146
Ecotoxicology and Environmental Safety 151 (2018) 144–152
Fig. 2. HPLC Chromatogram of reference studied
pharmaceutical compounds.
2.5. Characterization of modified biosorbent
Fourier transmittance infrared (FTIR) spectrophotometer (630-
Jasco) was used to determine functional groups on algal surface before
and after tramadol biosorption. Pellets were prepared with 3 mg algal
biomass and 100 mg KBr and whose spectrum was analyzed within the
wavenumber range of 400–4000 cm−1.
2.6. Ecotoxicological test
To evaluate the environmental risk of pharmaceutical, both che-
mical and toxicological analysis should be performed. Chemical de-
tection does not provide information about the toxicity of pharmaceu-
ticals. Oxygen uptake by bacteria in activated sludge can provide a
direct and an appropriate measure of toxicity to complement to che-
mical analysis. Aerated activated sludge spiked with synthetic waste-
water containing pharmaceuticals and treated one will be used for
measurement of oxygen uptake; dissolved oxygen will be measured to
estimate the activity of bacteria and toxicity of wastewater.
3. Results and discussion
3.1. Characterization of alkaline-modified algal biomass by FTIR
FTIR spectra of raw alkaline-modified algal biomass and after the
adsorption process are described in Fig. 3. Notably, the algal biomass is
consists of different biocomponents (Cardoso et al., 2012), many
spectra peaks were detected at different wave number for bare and
tramadol adsorbed-alkaline-modified algal biomass. At 3866 and
3736 cm−1, intense IR bands are remarked for amide N ̶ H stretching
vibration. The broad IR band observed at 3326 cm−1 that is recognized
to O ̶ H stretching vibration and N ̶ H stretching vibration. The peak at
around 2922 cm−1 is related to C-H stretching vibration (Coates, 2000).
At 2369 cm−1, intense IR band noticed that related to stretching vi-
brations of stretching vibration of carboxylic O–H. At 2119 cm−1,
Fig. 3. FTIR spectra for modified algal biomass before and after tramadol adsorption.
M.E.M. Ali et al. Ecotoxicology and Environmental Safety 151 (2018) 144–152

intense IR band noticed that corresponded to stretching vibrations of

C˭C. The noted bands at 1636 and 1542 cm−1 referred to the stretching
vibrations of C˭O and C-N. The IR spectra peak observed at 1419 cm−1
that assigned to bending vibrations of C-H and stretching vibration of C-
O. An intense peak appeared at around 1021 cm−1 is assigned to C ̶ O
stretching vibration. An intense peak appeared at around 548 cm−1 is
assigned to stretching vibration of C-S. FTIR spectra of alkaline-mod-
ified algal biomass observed after the biosorption of tramadol indicated
detected at wave numbers of 3844, 3739, 2917, 2912, 2361, 2100,
1647, 1518, 1016 and 526 cm−1 with some slight shift and low in-
tensity comparing with that of bare MAB. IR bands of 3326 and
1419 cm−1 are completely disappeared, they might involve in the
biosorption process of tramadol. The functional groups of O-H and C-O Fig. 5. Effect of pH on biosorption of tramadol by MAB; time = 45 min, biosorbent dose
which present on algal biomass have a remarkable role in the bio- = 0.5 g/L and tramadol concentration = 50 mg/L.
sorption process, more discussion later.

3.2. Optimization of biosorption of tramadol

Preliminary experiment was conducted for adsorption of TRAM over

unmodified algal biomass; It was found that only 20% removal of
TRAM. But MAB showed more than 95% removal of TRAM. Thus,
different factors that affect the adsorption process were studied as fol-
lowing.

3.2.1. Contact time effect

Fig. 4 illustrated the profile of adsorption capacity of the tramadol
against time over MAB. The results indicated that the adsorption ca-
pacity is progressively improved with time and equilibrium was at-
tained after 45 min with capacity of adsorption of 47 mg/g. This in-
dicated that the MAB is capable of removal a massive concentration of
TRAM in short period. Favourably, the studied modified algal biomass
might be a promising biosorbents for elimination of TRAM from pol-
luted water.
3.2.2. Solution pH effect
Fig. 5 shows the biosorption removal of TRAM over MAB (ad-
sorbent) at various pH values on at experimental condition. It was
noted that the adsorption of TRAM improved with rising pH from 3 to
7, after that, the adsorption capacity was decreased. As well there is no
significant effect on the adsorptive capacity of TRAM in the trial by
increasing pH 5–7. Accordingly, the biosorption mechanism is possibly
hydrophobic relations between functional groups on MAB surface and
TRAM. Where pKa of TRAM is 9, thus the process of adsorption favours
acidic/neutral media. At higher pH, TRAM molecules is negativity
charged and biomass is negativity, thus, the electrostatic repulsion
between adsorbents and TRAM molecules is preannounced leading to
lower biosorption. Therefore, pH has a significant effect on the ad-
sorption process due to its influence on the solubility of pollutant and
Fig. 6. Biosorption of tramadol by different dosages of MAB; time = 45 min, pH = 7 and
tramadol concentration = 50 mg/L.
active functional groups of adsorbent.
3.2.3. Biosorbent dose effect
The tendency of the adsorptive capacity of tramadol versus bio-
sorbent dose is depicted in Fig. 6. Notably, the TRAM biosorption
capability decreased with increasing the biosorbent dose, the biosorp-
tion capability was decreased from 80 mg/g to 11.4 mg/g with raising
dose of biosorbent from 0.25 to 1.5 g/L. Nonetheless, the excess amount
of biosorbent in the solution may lead to agglomeration that diminishes
the adsorption because active sites for biosorption are not completely
occupied (Padmavathy et al., 2016). Based To ensure the utmost re-
moval of tramadol and effective use of modified algal biomass, the dose
of 0.5 g/L was selected.
3.2.4. Effect of tramadol concentration
The profile of the adsorption capacity on MAB with initial TRAM
concentration was shown in Fig. 7. Noticeably, adsorption rate are
improved with increasing initial concentrations. This is owed that
higher concentration of TRAM enhances the transfer of its molecules
from solution to MAB surface that facilitate the interaction between
TRAM and MAB. Thus, TRAM concentration has a noteworthy effect on
the higher MAB adsorption capacity of TRAM.

3.3. Kinetic of biosorption of tramadol

For realizing more data about the adsorption mechanism, different

kinetic models are applied; pseudo-first- or pseudo-second-order reac-
tion (Seen Eq. (3) and Eq. (4))

Fig. 4. Biosorption capacity of MAB profile against time of tramadol; pH = 7, biosorbent k1

Pseudo − first − order:log (qe − q) = logqe − t
dose = 0.5 g/L and tramadol concentration = 50 mg/L. 2.303 (3)

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M.E.M. Ali et al.
Fig. 7. Biosorption of tramadol by MAB as a function tramadol concentrations; time =
45 min, pH = 7 and biosorbent dose = 0.5 g/L.
t 1 1 surface is very fast (Aravindhan et al., 2007). The intra-particle diffu-
Pseudo − second − order: = t+
q qe k2 qe2
Where t is the adsorption time, qe and q, (mg/g) are the adsorbed
amount of tramadol at equilibrium and time t and k1, and k2 are the rate
constants of pseudo-first order and pseudo-second order, respectively.
The kinetics of tramadol adsorption on modified algal biomass de-
picted in Fig. 8(a, b). The experimental qe (exp), and calculated
qe(calculated) value of adsorption capacity, kinetics parameters and cor-
relation coefficient are shown in Table 1. As shown regression coeffi-
cient (R2) for second-order model is higher than that first-order one, as
well the calculated equilibrium adsorption capacity (qe (calculated)) that
extracted from second order is 45.5 mg/g that is close to experimentally
determined qe (exp) (45 mg/g) indicating that the kinetics of TRAM
adsorption by MAB is highly fitted with kinetic model of pseudo-
second-order. Fascinatingly, adsorption of carbamazepine, clofibric
acid, diclofenac, ibuprofen, and ketoprofen on mesoporous silica
obeyed pseudo-second-order (Bui and Choi, 2009). Also, uptake of
tetracycline by multi-walled carbon nanotubes followed the pseudo-
second-order model (Zhang et al., 2011).
Fig. 8. Kinetics of tramadol biosorption on MAB (a) First-order and (b) second-order; pH
= 7, biosorbent dose = 0.5 g/L and tramadol concentration = 50 mg/L.
Ecotoxicology and Environmental Safety 151 (2018) 144–152
Table 1
Kinetics constants of tramadol biosorption by modified algal biomasses.
qe(exp) Pseudo-first-order Pseudo-second-order
(mg/g)
qe(cal) K1 (min−1) R2 qe(cal) K2 (g/ R2
(mg/g) (mg/g) mg min)
45 33.3 0.023 0.996 45.5 0.0027 0.999
3.4. Biosorption mechanisms
The biosorption mechanism is progressed via many step processes;
i) mass transfer of adsorbate from bulk to adsorbent surface, ii) ad-
sorption of adsorbate on adsorbent surface and movement within the
pores of sorbent material (Cheung et al., 2007). The biosorption method
is controlled by first and second step, because adsorptions step on
(4) sion model was applied on the kinetic results. To estimate the transfer
of tramadol from solution to adsorption sites on surface modified algal
biomass, the following expression applied for estimation of intra-par-
ticle diffusion rate;
1
qt = kd t 2 (5)
where kd, in mg/g min1/2, is defined as intra particle diffusion rate
constant. To identify the significance of diffusion in the adsorption
process, the graph plotted between the amount of adsorbed tramadol
(qt) and the square root of time (t1/2). The diagram (Fig. 9) shows a
linear relation. The drawn graph of model does not traverse through the
starting point, thus the adsorption mechanism is intra-particle diffusion
process, but other mechanisms are involved (Arami et al., 2008). The
high correlation coefficients confirmed that the external mass transfer is
well fitted mechanism of tramadol adsorption on algal biomass. The
calculated kd value was found to be 5.29 mg/g min1/2.
3.5. Equilibrium studies
The equilibrium isotherms for tramadol biosorption are applied
obtained data to find the relationship between qe and Ce. Various iso-
thermal models were developed; Langmuir (LH), Freundlich, Dubinin-
Radushkevich (D-R) and Temkin models. Where, LH model deduce the
following; (1) proceeding of biosorption at definite uniform positions
on the biosorbent surface (2) all adsorption sites on surface have con-
stant energy (3) and the capability of independent adsorption of mo-
lecules regardless the occupancy of neighbouring sites.
These models were applied on results of the TRAM biosorption on
MAB biosorbent at equilibrium. The LH model was applied to fit the
adsorption of tramadol on MAB surface and Fig. 10a revealed Langmuir
model. LH model is moderately succeed for ascribing the experimental
data (R2 = 0.88). But mechanism adsorption of TRAM by MAB is not
limited to monolayer adsorption of TRAM on the biomass surface.
Where all available surface sites for adsorption are not alike, thus the
highest biosorption capability (qmax) is 140.25 mg/g and the calculated
Fig. 9. Mass transfer kinetic model of tramadol on MAB surface.
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M.E.M. Ali et al.
Fig. 10. Adsorption isotherms; (a) Langmuir, (b) Freundlich isotherms.
KL value is 0.022 mg/L. Another noteworthy characteristic of the
Langmuir isotherm is dimensionless separation factor (RL) that it can be
articulated in the following expressions;
1 tramadol over MAB.
RL =
1+KL Co
where Co is initial concentration of tramadol (mg/L) and KL is the
Langmuir constant (L/mg). RL values indicate whether the adsorption
process is irreversible (RL = 0), favorable (0 < RL < 1), linear (RL = 1),
irreversible (RL = 0) or unfavorable (RL > 1). In all initial concentra-
tions, the value of RL was ranged from 0.18 to 0.64, indicating a fa-
vorable sorption of tramadol by modified algal biomass.
The isothermal model of Freundlich was used to explain the bio-
sorption on different sites of heterogeneous surface with numerous
adsorption energies (Reddy et al., 2010).
Freundlich isotherm was sat by plotting the values of log qe versus
log Ce, where slope is (1/n) and intercept value is log KF (Fig. 10b). It
was found a good fitting between data and Freundlich model (R2 =
0.94). The biosorption capacity (KF), is 4.82 mg/g, which is equal to qe
at Ce = unity. Freundlich model gave 1/n less unity referring capability
of explaining uptake of tramadol by heterogeneous biosorbents, where
n amounted with 1.68. The obtained correlation coefficient of two
models reveals that Freundlich isotherm model is suitably represented
the tramadol adsorption by algal biosorbent. Moreover, the linearized
Temkin equation is given as follows (Tempkin and Pyzhev, 1940):
qe = BT lnkT + BT lnce
Where BT = RT/b is constant related to heat of sorption (J/mol), T is
the absolute temperature (K), R is the ideal gas constant (8.314 (J/mol),
b is a constant related to the heat of sorption (J/mol) and KT is the
Temkin isotherm constant (l/g). Temkin isotherm equation assumes
that the decrease of adsorption heat of all the molecules on the surface
with covering of molecules due to the adsorbate-adsorbate repulsions
and the adsorption of adsorbate is uniformly distributed and that the
fall in the heat of adsorption is linear rather than logarithmic. Fig. 10a
illustrated the Temkin model, the relation between qe against ln Ce. It is
noticeable that adsorption of tramadol is well fitted with Temkin model
(R2 = 0.941). The BT and KT constants are extracted from the slope and
intercept of Fig. 10a, they are found to be 51.04 and 6.55 J/mol.
Furthermore, the Dubinin-Radushkevich (D-R) isotherm is applied
Ecotoxicology and Environmental Safety 151 (2018) 144–152
Fig. 11. Temkin model (a), Dubinin–Radushkevich isotherm model (b) of biosorption of
(6)
to verify the type of adsorption mechanism (chemical or physical). The
Dubinin-Radushkevich isotherm is linearily expressed as follows:
ln q e = lnqDR −βε 2 (8)
Where (qDR) is the Dubinin-Radushkevich monolayer capacity (mol/g),
(β) is a constant of adsorption energy (mol2/J2), and (ε) is the Polanyi
potential which is related to the equilibrium concentration as follows:
1 ⎞
ε = RTln ⎛1 +
⎜ ⎟
⎝ C e⎠ (9)
The relationship between lnq e and ε2, β and qDR is plotted and
shown is Fig. 11b. The calculated adsorption energy of TRAM is
63.76 KJ/mol indicating for chemical adsorption. D-R model results
revealed the moderately fitting with experimental data at high pollu-
tant concentration (R2 = 0.842).
3.6. Efficiency of modified biomass for adsorption of pharmaceuticals
mixture
The pharmaceuticals present in water and wastewater in mixture,
(7)
their behavior in a mixture is absolutely different and complex. Thus,
the capability of modified algal biomass was tested for biosorption of
pharmaceutical compounds; cefadroxil (CEFA), paracetamol (PARA),
ciprofloxacin (CIP), tramadol (TRAM) and ibuprofen (IBU). Fig. 12a
shows remarkable results for biosorption of a mixture containing five
pharmaceuticals onto modified algal biomass at 45 min of contact time.
The obtained results showed different adsorption behavior of biomass
to different pharmaceutical compounds; where biomass shows the
higher biosorption capacity for CEFA and PARA amounted to 68 and
52 mg/g, respectively. The experimental results tend to moderate ad-
sorption capacity for TRAM, IBU and CIP at the same individual con-
centration (50 ppm). On the contrary, modified biomass is still efficient
for the removal of TRAM in the mixture. This behavior can be eluci-
dated by competitive adsorption. It could be envisaged existence of
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M.E.M. Ali et al. Ecotoxicology and Environmental Safety 151 (2018) 144–152

Fig. 12. adsorption capacities of different pharmaceutical compounds over modified

biomass (a), reusability of MAB for adsorption of pharmaceutical compounds (b).
specific functional groups interaction among CEFA, and PARA which
stimulate the adsorption of two compounds on surface of biomass ra-
ther than other three ones. At pH 7.8 (natural pH of solution), CEFA
(pKa = 3.45, 7.03, 9.6) showed the highest removal rates, followed by
PARA (pKa = 9.5), due to their higher pKa values, compared to that of
IBU (pKa = 4.91) and CIP (pKa = 6.2). CIP and IBU compounds are
willingly deprotonated to be negatively charged. Consequently, it leads
less favorable adsorption on biomass while CEFA.
As well, the results of adsorption of the studied pharmaceuticals on
biomass indicated that they proscribed via adsorption process by hy-
drophilic interactions between amino and carbonyl groups in pharma-
ceutical molecules and hydroxyl and carbonyl functional groups on
surface of modified algal biomass, it was emphasized by disappearance
Fig. 13. Oxygen uptake rate by bacteria in activated sludge in different media (a)
pharmaceutical mixtures (b) treated one by adsorption on MAB.
O–H and C–O from biomass IR spectra after adsorption. To confirm the
feasibility of modified biomass as promising adsorbent for pharma-
ceuticals compounds, the reusability of biomass of adsorption for dif-
ferent pharmaceuticals is assessed. Fig. 12b shows the biosorption ca-
pacity of mixture of pharmaceutical compounds after three successive
runs. The obtained revealed a slight decrease of adsorption removal of
pharmaceutical mixture over biomass after three successive runs. The
modified algal biomass shows a high potential in reusability in ad-
sorption of pharmaceutical compound from water.

Table 2
Comparison between the adsorption capacities of biomass materials for pharmaceutical compounds.

Adsorbent Pollutants Maximum capacity (qm), (mg/g) Reference

Carbopal APa Tramadol 84 Rúa-Gómez et al. (2012)

Hydraffin XC30-Aa Tramadol 76 Rúa-Gómez et al. (2012)
Hydraffin XC30-Bb Tramadol 85 Rúa-Gómez et al. (2012)
Norit SAE Supera Tramadol 87 Rúa-Gómez et al. (2012)
Potassium carbonate -cork waste Ibuprofen 416.7 Mestre et al. (2007)
H3PO4-Olive stones Ibuprofen 160.9 Mansouri et al. (2015)
CO2-Olive stones Ibuprofen 282.6 Mansouri et al. (2015)
ZnCl2-Waste apricot Naproxen 106.4 Onal et al. (2007)
Potassium carbonate-Cork powder Ibuprofen 145.2 Mestre et al. (2009)
Steam-Cork powder Ibuprofen 378.1 Mestre et al. (2009)
H2SO4 treated-Mugwort leaves Ibuprofen 16.95 Dubey et al. (2010)
H3PO4-Olive waste Ibuprofen 12.6 Baccar et al. (2012)
H3PO4-Olive waste Naproxen 39.5 Baccar et al. (2012)
H3PO4-Olive waste Ketoprofen 24.7 Baccar et al. (2012)
H3PO4-Olive waste Diclofanac 56.2 Baccar et al. (2012)
H3PO4-Peach stones Ibuprofen 141.2 Alvarez-Torrellas et al. (2016)
Steam treated-Mung bean husk Ibuprofen 62.5 Mondal et al. (2016b)
H2SO4-Olive stones Diclofanac 11.01 Larous and Meniai (2016)
NaOH-Parthenium weed Ibuprofen 3.8 Mondal et al. (2016a)
H3PO4-Peach stones Diclofanac 200 Torrellas et al. (2015)
H2SO4-Bone char Ibuprofen 56.78 Cazetta et al. (2016)
ZnCl-Cyclamen tubers Diclofanac 22.22 Jodeh et al. (2016)
NaOH-Pine chip Diclofanac 372 Jung et al. (2015)
NaOH-Pine chip Naproxen 290 Jung et al. (2015)
NaOH-Pine chip Ibuprofen 311 Jung et al. (2015)
NaOH-algal biomass Tramadol 140.25 The current work

150
M.E.M. Ali et al.
3.7. Comparative study for adsorption of pharmaceutical compounds on
biomass
It is exigent to compare the current experimental results with pre-
vious reported work because adsorption rate was noticed differently
according to biomass source, modification and type of pollutant. Some
previous results for adsorption of pharmaceutical compounds over
carbonaceous biomass material are illustrated in Table 2. As seen
Table 2, the obtained pharmaceutical maximum adsorption capacity
(qm) is comparable with previous studies.
3.8. Ecotoxicological test
Results in Fig. 13 show the oxygen uptake rate by organism in
different media; control, wastewaters of pharmaceutical mixture of
125 mg/L, and mixture of 250 mg/L, and treated solution of both
pharmaceutical mixtures after adsorption over modified algal biomass.
Comparison with control domestic wastewater, it worthy noted that
wastewater containing pharmaceutical mixture showed a drastic de-
crease of dissolved oxygen by 91%, and 95% (Seen Fig. 13a) for was-
tewaters of pharmaceutical mixture of 125 mg/L, and mixture of
250 mg/L (Seen Fig. 13b), respectively. It is indicated that high toxicity
of studied pharmaceutical wastewaters to bacteria in activated sludge.
Meanwhile, dissolved oxygen in treated pharmaceutical mixtures after
adsorption over MAB is not slightly decreased, that revealed low toxi-
city of treated solution of pharmaceutical mixtures.
4. Conclusions
The adsorption of tramadol by MAB biosorbent was investigated for
applicability of low cost biomass for removal of pollutants from aqu-
eous media. The Adsorption results of tramadol demonstrated that the
high removal was found at neutral pH. TRAM biosorption was best
described pseudo-second-order kinetic model rather than by pseudo-
first-order. The qe(cal) using pseudo-second-order kinetic model was si-
milar to qe(exp). Adsorption of TRAM by MAB biosorbents was well fitted
by Langmuir isotherms rather than the other studied isotherm model
that exhibited a maximum adsorption capacity 140.25 mg/g highest
correlation coefficient (0.942). In addition, Dubinin-Radushkevich in-
dicates that the biosorption of tramadol by MAB is a chemical process.
The obtained results of revealed that adsorption of pharmaceutical over
modified biosorbent is mainly ensued by hydrophilic interactions be-
tween amino and carbonyl groups in pharmaceutical molecules and
hydroxyl and carbonyl functional groups on surface of modified algal
biomass, it was confirmed by disappearance O–H and C–O from bio-
mass IR spectra after adsorption. Obtainable results reflected that the
algal biomass has a high potential in reusability for adsorption of
pharmaceuticals compound from wastewater. Depending on the results
the ecotoxicological test is very important to determine the efficiency of
modified biomass for adsorption of pharmaceutical mixture. Based on
the obtained results, modified algal biomass could be applied is as a
promising alternative reusable sorbent for the removal of pharmaceu-
ticals from wastewater.
Acknowledgment
The authors are grateful to National Research Centre, Egypt, for
financial support of research work.
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