Groundwater for Sustainable Development 11 (2020) 100474

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Groundwater for Sustainable Development

journal homepage: http://www.elsevier.com/locate/gsd

Research paper

Simultaneous removal of acetaminophen and ibuprofen from underground

water by an electrocoagulation unit: Operational parameters and kinetics
Mehrdad Negarestani a, Mahsa Motamedi b, Amir Kashtiaray c, Ali Khadir d, *, Mika Sillanpää e, f, g
a
Department of Civil and Environmental Engineering, Iran University of Science and Technology, Tehran, Iran
b
Faculty of Chemical Engineering, Tarbiat Modares University, Tehran, Iran
c
Department of Chemistry, Faculty of Science, Iran University of Science and Technology, Tehran, Iran
d
Young Researcher and Elite Club, Yadegar-e-Imam Khomeini (RAH) Shahre Rey Branch, Islamic Azad University, Tehran, Iran
e
Institute of Research and Development, Duy Tan University, Da Nang, 550000, Viet Nam
f
Faculty of Environment and Chemical Engineering, Duy Tan University, Da Nang, 550000, Viet Nam
g
School of Civil Engineering and Surveying, Faculty of Health, Engineering and Sciences, University of Southern Queensland, West Street, Toowoomba, 4350, QLD,
Australia

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

Keywords: Contamination of water with persistent pharmaceutical compounds has become an increasing concern of the
Electrocoagulation current world, and many studies have been working on the mitigation of such pollution. Groundwater, a crucial
Ibuprofen water source, has been contaminated with pharmaceuticals. In the current study, an electrocoagulation method
Acetaminophen
has been used for the simultaneous removal of two common pharmaceuticals including ibuprofen and acet­
Pharmaceutical
aminophen, for the first time. The process was optimized via the one-at-a-time method. It was found that by
increasing the contact time, the removal efficiency of ibuprofen and acetaminophen reached 50.96% and 22.76%
at electrolysis time of 110 min and pharmaceutical concentration of 40 ppm, respectively. The maximum effi­
ciency was observed at 2 A. Electrode distance of 3 cm was superior to 5 and 6 cm. Optimum values of pH and
agitation speed were seen at 5 and 200 rpm, respectively. To improve efficiency, the double electrocoagulation
stage was considered, and the maximum adsorption efficiency of 78% and 48%, respectively. Produced H2 gas is
one of the other advantages of the electrocoagulation process. Therefore, electrocoagulation can be suggested as
a promising technique to eliminate pharmaceuticals from underground water.

1. Introduction Machiwal et al., 2018). Anthropogenic activities have threatened the

The introduction of pharmaceutical waste into the environment has
threatened humans so long. Inappropriate disposal, manufacturing
waste, and uncontrolled consumption of drugs have resulted in phar­
maceutical pollution in every aspect of the ecosystem (Ahmed, 2017;
Khadir et al., 2020a; Vatovec et al., 2017). The presence and accumu­
lation of biologically active drugs can cause serious harmful effects for
the whole ecosystem. Increasing consumption of Ibuprofen and acet­
aminophen by human beings results in the presence of these drugs in the
surface and groundwater. This presence has received increasing concern
in recent years as these drugs are biologically active compounds with
adverse effects for the environment (Khadir et al., 2020b; Pires et al.,
2019; Rabizadeh et al., 2020).
The importance of groundwater as vital source water for the
ecosystem has been discussed well in the literature (Kubier et al., 2019;
quality of the media as well as its quantity. This could lead to the un­
avoidable fact that groundwater might not be appropriate for the direct
use of humans (Atangana et al., 2018). Detection of pharmaceuticals in
the groundwater has become a serious issue requiring further consid­
erations. In Lagos State, Nigeria, For instance, Ebele et al. (2020) re­
ported that a wide range of pharmaceuticals, including acetaminophen,
ibuprofen, diclofenac, glyburide, naproxen, nicotine, codeine, amoxi­
cillin, tramadol, and gemfibrozil were detected in the groundwater
(Ebele et al., 2020). In the rural agricultural regions, pharmaceuticals
such as acetaminophen, sulfonamides, and fluoroquinolones were
detected (Lee et al., 2019). In irrigated groundwater wells also phar­
maceuticals were observed that the authors accused the wastewater
contribution for groundwater pollution (Kibuye et al., 2019). Several
other scholars, Szymczycha et al. (2020) (Szymczycha et al., 2020), Gao
et al. (2020) (Gao et al., 2020), L. Del Rosario et al. (2014) (Del Rosario

* Corresponding author.
E-mail address: alikhadir.research@gmail.com (A. Khadir).

https://doi.org/10.1016/j.gsd.2020.100474
Received 13 June 2020; Received in revised form 8 August 2020; Accepted 19 August 2020
Available online 22 August 2020
2352-801X/© 2020 Elsevier B.V. All rights reserved.
M. Negarestani et al. Groundwater for Sustainable Development 11 (2020) 100474

et al., 2014), and N. Gottschall et al. (2011) (Gottschall et al., 2012)
concluded that the presence of pharmaceutical compounds was evident
indicative of potential groundwater contamination. The trace amount of
ibuprofen and acetaminophen has been detected in the waterways of
many areas (Magadini et al., 2020; Yang et al., 2016). The continuous
exposure of the groundwater to pharmaceuticals specially ibuprofen and
acetaminophen is assumed to arise critical health hazards in the up­
coming future.
Implementation of a proper and sustainable treatment method could
be a promising solution for the current pharmaceutical pollution in the
groundwater. Table 1 summarizes the advantages of common methods
for pharmaceutical elimination. Lower quantity of sludge production,
low maintenance, less power requirement, lower cost, and higher
removal efficiency compared to conventional chemical coagulation are
some of the main advantages of the electrocoagulation unit (Moham­
madi et al., 2019). Three consecutive steps are involved in the electro­
coagulation processes: (1) electrochemical reactions (2) flotation (3)
adsorption (Mohammadi et al., 2019). This process creates metal ion
complexes to destabilize colloids drugs in the aqueous solution.
In the case of groundwater, electrocoagulation has been applied for
the removal of almost common groundwater contaminants such as
arsenic (Kobya et al., 2020) and arsenite (Goren et al., 2020), nitrate
(Amarine et al., 2020), perfluoroalkanesulfonic acids (Bao et al., 2020),
phosphates (Castañeda et al., 2020), fluoride (Sandoval et al., 2019),
and chromium (Ali Maitlo et al., 2019). However, few studies have been
reported for the removal of pharmaceutical from groundwater by
electrocoagulation.
In the current study for the first time, simultaneous removal of
acetaminophen (ACT) and ibuprofen (IBU) from groundwater by elec­
trocoagulation technique was investigated. The process was optimized
by considering the effect of operational parameters, including electrol­
ysis time, pH, electrode materials, agitation speed, inter-electrode dis­
tance, and the current on the removal efficiency of the drugs. Moreover,
kinetics models were fitted with experimental data to identify the
adsorption mechanism.
2. Materials and methods
2.1. Chemicals and equipment
The standard drug of ibuprofen and acetaminophen were provided
by Temad Pharmaceutical Company, located in Iran (Fig. 1). The elec­
trodes, aluminum and iron, were supplied by a local market in Tehran,
Iran. Methanol and sodium chloride were purchased from Merck Com­
pany, Germany. To adjust the pH of the solution, NaOH and HCl were
employed, purchased from Merck Company, Germany. All the chemicals
used during the study were of analytical grade and used as received
without further purification. Solutions were prepared using deionized
water.
UV-spectrophotometer model DR6000, HACH LANG (USA) was
utilized for the determination of pharmaceutical concentration. The pH
of the aqueous solution was set by 780 pH Master, Metrohm
(Switzerland).
2.2. Operating conditions

Table 1 Experiments were conducted in an electrocoagulation reactor, with

Advantages of various wastewater treatment processes. iron and aluminum as electrodes (cathode and anode). A system in
Examples Advantages Ref. which simultaneous removal of acetaminophen and ibuprofen occurred
Technologies was consisted of a 1 L breaker and two electrodes connected to a power
Electrocoagulation Fluoride- High removal (Ensano et al.,
supply with adjustable voltage and current. The electrodes distance was
Arsenic efficiency 2019; 3 cm (initially) and for the simplicity of the process the pH was
Well water Easy to operate López-Guzmán considered to be constant at the first step of the reaction. Some operating
Inexpensive et al., 2019) parameters in coagulation process for simultaneous removal of acet­
(there is no need
aminophen and ibuprofen were investigated, including current, inter-
to add chemicals)
No need for any electrode distance, electrode material, agitation speed, and pH. The
subsequent dimensions of electrodes were 10 × 4.1 × 0.1 cm with the effective
treatment surface area of about 33 cm2. To remove the layers’ deposit on the
Membrane filtration Low energy (Fischer et al.,
electrodes, they were washed with HCl solution then rubbed with
Microfiltration consumption 2015; Hube et al.,
Ultra-filtration Low pressure 2020; Kyllönen
sandpapers. Required samples were provided by a university in Tehran,
et al., 2005) Iran. To conduct the experiments, the desired amount of drugs was
Ion exchange Excellent (Levchuk et al., added manually to the sample. Final concentrations of acetaminophen
adsorption 2018; Wang et al., and ibuprofen were determined after each experiment. For acetamino­
selectivity 2020)
phen, the maximum peak was observed at λmax 249 nm in which
Suitable pore size
Regenerable ibuprofen had the negligible absorbance. The maximum peak for
Adsorption Low-cost (Fu and Wang, ibuprofen was recorded at λmax 222 nm. To determine the concentration
Activated adsorbents 2011; Khadir et al., of each pharmaceutical in the mixture solution, the Beer–Lambert’s law
carbon High surface area 2020d; Uddin,
was used. The electrocoagulation removal efficiency was calculated by
Bio-adsorbent High adsorption 2017)
capacity
equation (1):
Chemical Hydroxide Simplicity of Fu and Wang
Cf − Ci
precipitation precipitation process (2011) Removal ​ efficiency ​ (%) = × 100 (1)
Sulfide Inexpensive Ci
precipitation separation
process
Photocatalysis TiO2 High efficiency (Schneider et al.,
Aerobic and Eco friendlyTiO2 2014; You et al.,
anaerobic is an inexpensive 2019)
processes photo catalyst (Bhanot et al.,
and it is non-toxic 2020; Cheng et al.,
Degradation of 2020)
the organic
pollutant
Cost-effective
High COD
removal
Fig. 1. Molecular structure of ibuprofen and acetaminophen.

2
M. Negarestani et al.
where Cf and Ci are the final and initial concentration of the pharma­
ceutical, respectively.
3. Results and discussion
3.1. Electrolysis time
Electrolysis duration is an underlying factor leading to a significant
difference in the removal efficiency. The initial concentrations of
ibuprofen and acetaminophen both were fixed at 40 ppm. Fig. 2 illus­
trates the removal efficiency of ibuprofen and acetaminophen in
different reaction time, ranging from 0 to 180 min. Between electrolysis
duration of 0–110 min, the removal efficiency of acetaminophen
increased and reached approximately 30%. After 110 min, further
duration time did not affect the removal efficiency of acetaminophen.
The trend for the removal efficiency of ibuprofen shows a sharp increase
until the reaction time of 15 min, more increase in the removal effi­
ciency of ibuprofen was observed up to 110 min. The figure shows that
both acetaminophen and ibuprofen have the same trend from 110 min to
180 min. The improvement of efficiency by increasing the electrolysis
time may be attributed to higher coagulant generation by time incre­
ment. The produced amount of metal ions can be calculated by equation
(2):
ItM
m= (2)
FZ
where M is the molar mass of electrode (g/mol), Z and I are valency of
the anode and the current (A), respectively. F is the faraday’s constant
equal to 96,485 C/mol.
Fig. 2b illustrates the mass of coagulant/adsorbent generation at
different time intervals. For instance, the amount of coagulant at 110
Fig. 2. The effect of electrolysis time on the removal of ibuprofen and acet­
aminophen (a), and the mass of coagulant production at different time in­
tervals (b).
3
Groundwater for Sustainable Development 11 (2020) 100474
min is 11 times higher than that of 10 min. Until 110 min, the amount of
coagulant was enough to remove both drugs, while excess reaction time
did not lead to higher removal because the solution reached the required
coagulant, thus more reaction time can be considered as a waste of
energy. Considering a balance between removal efficiency and energy
consumption, 110 min was selected as the optimal electrolysis rime for
the other experiments. Also, the findings demonstrate that ibuprofen
removal was approximately 3 times greater than acetaminophen.
In remediation processes, reaching equilibrium in less time is an
advantage and many scholars have investigated the effect of duration
time. A-Torrellas et al. (2016) studied the removal of the pharmaceutical
compound by adsorption process onto the multi-walled carbon nano­
tubes and the equilibrium was attained within 5 h (Álvarez-Torrellas
et al., 2016). Also, Mestre et al. (2007) reported 120 min as the optimum
contact time to remove the targeted drug by activated carbons (Mestre
et al., 2007). In another study, the process reached the equilibrium state
in 200 min (Coimbra et al., 2019). In comparison to mentioned studies,
an electro duration of 110 min represents electrocoagulation as an
efficient method for the pharmaceutical compounds removal compared
to adsorption process.
3.2. Effect of the current
Electrode current influences the IR-drop and the removal efficiency.
The experiments were done with Al/Al combination and electrolysis
time between 0 and 110 min. Pharmaceuticals concentration was 40
ppm at the initial step of the reactions. Fig. 3 shows the removal effi­
ciency for ibuprofen and acetaminophen by setting the current at 2, 1.3,
and 0.7 A. The removal efficiency increases with the increase of current
for both drugs. At the duration time of 110 min the removal efficiency
obtained 54.51%, 48.44%, and 35.08% for ibuprofen with three
different currents, respectively. In the case of acetaminophen, it was
31.32%, 22.37%, and 17.90%, respectively. The increase in the removal
efficiency with the higher current is due to the higher coagulant and
indeed more active sites for drug removal. In fact, more anode dissoci­
ation and thus more Al ions are generated according to Faraday’s law.
More Al production reacts with more OH− ions to create Al hydroxide,
acting as an adsorbent which is capable of adsorbing/removing the
pharmaceuticals. At higher current, smaller size H2 bubbles with the
larger surface areas are expected which are also effective for drug
elimination. Greater upward flux occurring at high current attributes the
movement of the adsorbate toward coagulant agents, resulting in per­
formance enhancement.
At the reaction time 30 min and current 2 A, the removal efficiency
for ibuprofen was 32.66%, however, for an identical removal efficiency
under current of 0.7 A, electrolysis time of 80 min was required. It
demonstrates by increasing the current density, lower contact time is
needed to achieve a specific removal efficiency. Reducing the required
electrolysis time is another benefit of elevated current as well as higher
removal efficiency. These findings demonstrated that at 2 A, the removal
efficiency of ibuprofen was 1.74 times greater than that of acetamino­
phen. Considering these facts, further experiments were carried out at
current 2 A. Many costs are involved in wastewater treatment processes,
including the cost of electrical energy, electrode materials, and equip­
ment. The consumed amount of energy during the process can be ob­
tained by the following equation (3).
( )
VIT
Energy consumption Wh/ = (3)
L VR
where VR is the effluent volume (L), V is the observed cell voltage (V), I is
the current (A) and T is electrocoagulation time (h). Fig. 3c shows the
energy consumption during ibuprofen and acetaminophen removal. As
expected, higher energy consumption is occurred in elevated current,
and of course it results in better efficiency of the system. It is a must to
make a balance between removal efficiency and energy consumption.
M. Negarestani et al. Groundwater for Sustainable Development 11 (2020) 100474

Fig. 3. Removal efficiency of ibuprofen (a) and acetaminophen (b) in different currents, energy consumption (c) during electrocoagulation process.

Fig. 4. Effect of electrode combination (a), initial pH (b), agitation speed (c) and second-stage electrocoagulation on ibuprofen and acetaminophen removal.

4
M. Negarestani et al.
3.3. Effect of inter-electrode distance
The electrode distance has a significant influence on the removal
efficiencies of ibuprofen and acetaminophen. To investigate the effect of
distance on the removal efficiency, electrodes were kept at 3, 5, and 6
cm. Accordingly, the highest removal efficiency of ibuprofen 55.18%
and acetaminophen 30.75% was observed at electrode distance of 3 cm,
however, 6 cm showed the lowest values (35.02% and 20.25%,
respectively). Decreasing the removal efficiency with further distance is
mainly due to the difficulty in the motion of ions in the solution (Khadir
et al., 2020e). Increment of IR-drop by increasing the inter-electrode
distance could negatively affect the whole treatment process via elec­
trocoagulation (Nasrullah et al., 2012). Moreover, energy consumption
was calculated in the examined electrode distances. It was found that
energy consumptions at electrode distances of 3, 5, and 6 cm were 55.2,
59.6, and 69 Wh/L, respectively. Based on the obtained results, the
inter-electrode distance was fixed at 3 cm for further experiments.
3.4. Effect of electrode material
Electrode material plays a huge role in the electrocoagulation pro­
cess because it directly influences the coagulant generation and the
removal efficiency. Because of this, selection of proper materials is of
high importance. In this study, the combinations of Fe and Al were
utilized to examine which one has the best performance. Fig. 4a shows
the removal efficiencies for each pair (anode/cathode) to achieve the
best electrode for removing acetaminophen and ibuprofen. Other pa­
rameters were kept at their optimum values with 110 min duration time
and current 2 A. The maximum removal efficiency for both acetamin­
ophen and ibuprofen was achieved when Al/Al electrode was used, with
42.2% and 98.55%, respectively. From the result, it can be concluded
that the effect of anode material is more significant than the cathode
material because the removal efficiency for both drugs was higher with
Al/Fe combination than Fe/Al. The reason for the higher removal effi­
ciency of Al/Al could be attributed to higher coagulation in the solution.
The same results were obtained when Al electrodes were used for the
removal of COD, using pure Al as an electrode resulted in the removal
efficiency of 97% (Cruz et al., 2019). Similarly, the removal of Reactive
Black 5 improved successfully and reached 99% using Al as electrode
material in 10 min duration (Keyikoglu et al., 2019).
3.5. Effect of pH
In the field of chemistry, pH of the solution is of the primary factor
affecting the nature of the process (Beheshti et al., 2019; Ghenaatgar
et al., 2019). In view of electrocoagulation, pH could affect the surface
charges of the generated coagulant as well as the ionization degree of
pharmaceuticals (Khadir et al., 2020c). The obtained results are depic­
ted in Fig. 4b. For both drugs the maximum removal efficiency was
observed at initial pH value of 5. The figure shows that pH imposed
significant effect on ibuprofen compared to acetaminophen. This
behavior may be attributed to the charges of the drug in the examined
pH value.
pHzpc is the point where the drug has no charge, and in the case of
ibuprofen and acetaminophen, pHzpc is 4.95 and 9.38, respectively
(Nourmoradi et al., 2018). It is indication of the fact that at pH lower
than pHzpc, the compounds are in their non-ionized forms, however, at
pH > pHzpc they own mostly negative charges. In the studied pH range,
acetaminophen is neutral, and it is fair to suggest that its elimination is
because of the physical sorption via coagulant surface. Ibuprofen was
negative at pH 5, and coagulant was positive, favoring to make an
electrostatic attraction. By elevating the pH value, both drug and
adsorbent/coagulant possessed negative charges, resulting in the lower
removal efficiency because of the repulsion forces. Considering these
results, further experiments were conducted at pH 5.
5
Groundwater for Sustainable Development 11 (2020) 100474
3.6. Effect of agitation speed
Agitation speed is of the most important parameter, directly affecting
the rate of the reactions, particularly in systems with particle involve­
ment. In the current investigation, the effect of agitation speed was
tested by changing its value from zero (no agitation) to 600 rpm. The
results are shown in Fig. 4c. The curve demonstrated that by enhancing
the agitation speed from 0 to 600 rpm, the removal efficiencies for
ibuprofen and acetaminophen initially increased very slightly, and then
reduced continuously. Increment in the removal efficiency is due to the
collision of the coagulant and pharmaceuticals with each other,
providing a higher chance of connection. Also, the agitation in the so­
lution could reduce the removal efficiency of the method. It can be
suggested that once the solution is agitated, the molecules of ibuprofen
and acetaminophen were detached from the surface of the coagulant,
lowering the removal efficiency. Under this circumstance, resulting flocs
are encouraged to break-up. Previous literature proves these findings
(Mohammadi et al., 2019; Tezcan Un et al., 2016). D. Sivakumar et al.
(2017) expresses that high agitation speed was not beneficial for the
removal of TOC and COD (Sivakumar et al., 2017). Therefore, agitation
speed of 100 rpm could be nominated as the optimal value.
3.7. Double stage electrocoagulation
In the current study, the operational parameters in the electro­
coagulation process were optimized (electrolysis time 110 min, current
2 A, inter-electrode distance 3 cm, pH 5, agitation speed 100 rpm,
pharmaceutical concentration 40 ppm, and Al/Al combination) and the
removal efficiencies of 59.32% and 33.15% were achieved for ibuprofen
and acetaminophen, respectively. To improve the efficiency of the
process, a double-stage electrocoagulation unit was applied for the
removal of ibuprofen and acetaminophen. The process was conducted
under the previously stated optimum conditions with an agitation speed
of 100 rpm. The results are illustrated in Fig. 4d. It indicates that the
performance of the process enhanced, and it was found that ibuprofen
was removed more than 75% from the solution, and acetaminophen
removal was almost about 50%. G. K. Singh et al. (2019) also reported
that dual stage electrocoagulation process could enhance the applica­
bility of the treatment technique (Singh et al., 2019).
3.8. Kinetic of electrocoagulation
Understanding the kinetics of the adsorption is essential for
designing a reactor for the process. The adsorption mechanism can
determine the underlying mechanism which controls the rate of the
adsorption. Electrocoagulation is almost the same as adsorption whereas
in electrocoagulation instead of using the adsorbent, the coagulant is
produced to remove pharmaceutical compounds. The removed amount
of either ibuprofen or acetaminophen is proportional to the amount of
generated flocs and the remained concentration of ibuprofen or acet­
aminophen at the time t. The first order equation is based on the
assumption that the rate at which vacant sites are filling is proportional
to the number of vacant sites while in second order this rate is propor­
tional to the square of the number of vacant sites.
The kinetic of the study was evaluated based on the first and second-
order kinetic models. equations (4)–(7) are given below:
dCACTt
= k1 CACT (4)
dt
dCACTt
= k2 CACT 2 (5)
dt
Ln ACTt = Ln ACT0 − k1 t (6)
1 1
= + k2 t (7)
ACTt ACT0
M. Negarestani et al. Groundwater for Sustainable Development 11 (2020) 100474

K1 (min-1) and K2 (g mg-1 min-1) are the first and second order ki­ Table 2
netics models rate constants, respectively. ACT0 is the initial concen­ Calculated parameters of first order and second order kinetic in different cur­
tration of acetaminophen and ACTt is the concentration of rents for ibuprofen and acetaminophen removal.
acetaminophen at the time t. The above equations were used to study the Pharmaceutical Current (A) First order model Second order model
kinetic behavior of ibuprofen removal by EC with IBUt and IBU0 as the K1 R2 K2 R2
ibuprofen concentration at time t and at the beginning. Integrating
Ibuprofen 2 0.0070 0.7691 0.0003 0.9813
equation (4) resulted in equation (6) in which Ln ACTt has a linear
1.3 0.0006 0.8752 0.0002 0.9587
relation with Ln ACT0 . 0.7 0.0040 0.8802 0.0001 0.9075
To figure out the suitable model which fits best with experimental Acetaminophen 2 0.0030 0.9945 1E-04 0.9976
data, Ln ct and C1t versus time were plotted and Fig. 5 shows these plots, 1.3 0.0020 0.9926 1E-05 0.9966
0.7 0.0015 0.9889 5E-05 0.9927
also the values of the rate constants and regression coefficients were
obtained.
Based on Fig. 5 and Table 2, the second-order can better describe the 3.9. Hydrogen gas production
kinetics of the adsorption both for ibuprofen and acetaminophen. For
ibuprofen, the R2 value for second order and first order was in the range During hydrolysis in the electrocoagulation process for ibuprofen
of (0.9075–0.9813) and (0.7691–0.8802), respectively revealing that and acetaminophen removal, H2 gas is generated at the cathode as the
chemical reactions could be the main mechanism for ibuprofen removal. by-product by equation (8) (Mena et al., 2019):
The experimental results also proved similar observation. As earlier
3
mentioned, ibuprofen tend to be removed via electrostatic attraction. 3H2 O + 3e− → H2 + 3OH − (8)
Surprisingly, acetaminophen resulted in almost very high R2 value both
2
for first order (0.9829–0.9945) and second order (0.9927–09976). Such The evolution of the H2 gases could benefit the efficiency of the
inclination might be attributed to non-ionic nature of the acetamino­ process as well as hydrogen recovery. Deghles and Kurt (2017) sug­
phen under the experimental conditions. K values of the kinetic model gested the utilization of the electrocoagulation as an effective waste­
were also calculated and were summarized in Table 2. By increasing the water treatment technique not only for aqueous decontamination, but
current from 0.7 to 2 A, in all cases the K value also increased which also it can be employed for recovery of hydrogen gas (Deghles, 2017).
demonstrates the faster reaction rate of electrocoagulation in higher Khadir et al. (2019) stated that these gases might be effective for
current values. In the current effect section, the results in 2 A were pollutant removal, and its generation is of high importance (Moham­
absolutely more satisfactory than that of 0.7 A. madi et al., 2019). Equations (9) and (10) are employed to calculated the
In short, it is better to propose the second order model as the best one amount of H2 gas production, and the power content of the collected H2
describing the simultaneous removal of ibuprofen and acetaminophen gas, respectively (Hashim et al., 2019):
by electrocoagulation.

Fig. 5. Kinetic plots of first order and second order models for ibuprofen (a, c) and acetaminophen (b, d) removal.

6
M. Negarestani et al. Groundwater for Sustainable Development 11 (2020) 100474

JAtH molecules could precipitate on the surface of the coagulant, resulting in

Q H2 = (9)
F the pharmaceutical removal. Sweep coagulation might also be effective
for the removal process.
PH2 (kWh) = QH2 × 0.0678 (10)
4. Conclusion
where QH2 (mole) is the amount of H2 produced (mole), J (A/m2) is the
current density of the electrocoagulation process, t (s) is the treatment
In the present study, electrocoagulation technique was utilized as a
time, H (0.5) is the number of hydrogen molecules, and F (96,500) is
green water purification method for the simultaneous elimination of two
Faraday’s constant. Regarding Fig. 6a, an increase in the applied cur­
common pharmaceuticals in water. Accordingly, for the first time,
rent, resulted in higher H2 gas production, and the maximum value was
sample of the groundwater was used and the ibuprofen and acetamin­
0.068 mol at 2 A. Also, the power content (Fig. 6b) of the collected H2
ophen were added to the media manually. The optimization process
gas was found maximum at 2 A (5.79 kWh/m3). Such amount of energy
showed that by increasing the contact time, both ibuprofen and acet­
could be take into account for various other applications. Similar ob­
aminophen removal rate increased until it reached a semi-constant
servations were reported by S. Hashim et al. (2019) (Hashim et al.,
trend. Higher current was favorable in terms of removal efficiency,
2019).
and the maximum removal was observed at 2 A. Al/Al electrode com­
bination was the best choice for the removal. Also, it was demonstrated
3.10. Real wastewater

To extend the application of electrocoagulation unit for the removal

of pharmaceuticals, the experiments were conducted over a real sample,
taken from well water of a university in Tehran, Iran. The main prop­
erties of the real water were as following: COD and BOD = negligible,
pH = 7.12, temperature = 25 ◦ C, EC = 3810 μS/cm, TSS = 3270 mg/g,
total hardness = 1443 mg/L carbonate, Na+ = 657 mg/L, NO−3 = 81 mg/
L. The operational parameters were set at the optimum values found
during the optimization process. The initial ibuprofen and acetamino­
phen concentration were both fixed at 40 ppm. The results exhibited
that ibuprofen removal reached 71% and of acetaminophen it was 32%,
respectively. Such reduction in removal efficiencies are logical and re­
ported in previous literature by many scholars (Ghenaatgar et al., 2019;
Mirjavadi et al., 2019; Piri et al., 2020). The presence of other particles
in wastewaters are the main reason in reducing the removal efficiency of
the technique.

3.11. The mechanism of removal

The current investigation attempted to eliminate ibuprofen and

acetaminophen from water by means of electrocoagulation unit. The
optimization procedure revealed that electrolysis time and current were
the most two important parameters directly influenced the whole per­
formance of the process. The findings exhibited that the generation of
more coagulant is beneficial in terms of pharmaceutical removal, indi­
cating the integral role of the coagulant. Fig. 7 shows a schematic rep­
resentation of ibuprofen and acetaminophen removal by
electrocoagulation unit. At the working pH, ibuprofen is negatively-
Fig. 7. The schematic of the drugs removal by electrocoagulation
charges and tend to be attracted by positively-charged coagulant via (by coagulant).
electrostatic attraction. In addition, ibuprofen and acetaminophen

Fig. 6. The amount of H2 gas production (a), and the power could be obtained by H2 gas (b).

7
M. Negarestani et al. Groundwater for Sustainable Development 11 (2020) 100474

that agitation could have positive and negative effects on the efficiency antibiotic resistance genes in the groundwater. Environ. Int. 136, 105484. https://
doi.org/10.1016/j.envint.2020.105484.
of the process. The double stage electrocoagulation verified the removal
Ghenaatgar, A., Tehrani, M.A., Khadir, A., 2019. Photocatalytic degradation and
efficiencies of 78% and 48% for ibuprofen and acetaminophen, respec­ mineralization of dexamethasone using WO3 and ZrO2 nanoparticles: optimization
tively. The whole process followed second-order rate. In conclusion, of operational parameters and kinetic studies. J. Water Process Eng. 32, 100969.
electrocoagulation could suggest cost-effective opportunities as well as https://doi.org/10.1016/j.jwpe.2019.100969. R.
Goren, A.Y., Kobya, M., Oncel, M.S., 2020. Arsenite removal from groundwater by
high removal efficiency for persistent organic compounds. aerated electrocoagulation reactor with Al ball electrodes: human health risk
assessment. Chemosphere 251, 126363. https://doi.org/10.1016/j.
Declaration of competing interest chemosphere.2020.126363.
Gottschall, N., Topp, E., Metcalfe, C., Edwards, M., Payne, M., Kleywegt, S., Russell, P.,
Lapen, D.R., 2012. Pharmaceutical and personal care products in groundwater,
The authors declare that they have no known competing interests or subsurface drainage, soil, and wheat grain, following a high single application of
personal relationships that could have appeared to influence the work municipal biosolids to a field. Chemosphere 87, 194–203. https://doi.org/10.1016/
j.chemosphere.2011.12.018.
reported in this paper. Hashim, K.S., Al Khaddar, R., Jasim, N., Shaw, A., Phipps, D., Kot, P., Pedrola, M.O.,
Alattabi, A.W., Abdulredha, M., Alawsh, R., 2019. Electrocoagulation as a green
References technology for phosphate removal from river water. Separ. Purif. Technol. 210,
135–144. https://doi.org/10.1016/j.seppur.2018.07.056.
Hube, S., Eskafi, M., Hrafnkelsdóttir, K.F., Bjarnadóttir, B., Bjarnadóttir, M.Á.,
Ahmed, M.J., 2017. Adsorption of quinolone, tetracycline, and penicillin antibiotics from
Axelsdóttir, S., Wu, B., 2020. Direct membrane filtration for wastewater treatment
aqueous solution using activated carbons: Review. Environ. Toxicol. Pharmacol. 50,
and resource recovery: a review. Sci. Total Environ. 710, 136375. https://doi.org/
1–10. https://doi.org/10.1016/j.etap.2017.01.004.
10.1016/j.scitotenv.2019.136375.
Ali Maitlo, H., Kim, K.-H., Yang Park, J., Hwan Kim, J., 2019. Removal mechanism for
Keyikoglu, R., Can, O.T., Aygun, A., Tek, A., 2019. Comparison of the effects of various
chromium (VI) in groundwater with cost-effective iron-air fuel cell
supporting electrolytes on the treatment of a dye solution by electrocoagulation
electrocoagulation. Separ. Purif. Technol. 213, 378–388. https://doi.org/10.1016/j.
process. Colloid Interface Sci. Commun. 33, 100210. https://doi.org/10.1016/j.
seppur.2018.12.058.
colcom.2019.100210.
Álvarez-Torrellas, S., Rodríguez, A., Ovejero, G., García, J., 2016. Comparative
Khadir, A., Mollahosseini, A., Tehrani, R.M.A., Negarestani, M., 2020a. In: Inamuddin,
adsorption performance of ibuprofen and tetracycline from aqueous solution by
Asiri, A. (Eds.), A Review on Pharmaceutical Removal from Aquatic Media by
carbonaceous materials. Chem. Eng. J. 283, 936–947.
Adsorption: Understanding the Influential Parameters and Novel Adsorbents BT -
Amarine, M., Lekhlif, B., Sinan, M., El Rharras, A., Echaabi, J., 2020. Treatment of
Sustainable Green Chemical Processes and Their Allied Applications. Springer
nitrate-rich groundwater using electrocoagulation with aluminum anodes. Groundw.
International Publishing, Cham, pp. 207–265. https://doi.org/10.1007/978-3-030-
Sustain. Dev. 11, 100371. https://doi.org/10.1016/j.gsd.2020.100371.
42284-4_8.
Atangana, A., Atangana, A.B.T.-F.O., 2018. In: Chapter 3 - Groundwater Pollution.
Khadir, A., Motamedi, M., Negarestani, M., Sillanpää, M., Sasani, M., 2020b. Preparation
Academic Press, pp. 49–72. https://doi.org/10.1016/B978-0-12-809670-3.00003-5.
of a nano bio-composite based on cellulosic biomass and conducting polymeric
C. and V.O. with A. to G.-H.
nanoparticles for ibuprofen removal: kinetics, isotherms, and energy site
Bao, J., Yu, W.-J., Liu, Y., Wang, X., Liu, Z.-Q., Duan, Y.-F., 2020. Removal of
distribution. Int. J. Biol. Macromol. https://doi.org/10.1016/j.
perfluoroalkanesulfonic acids (PFSAs) from synthetic and natural groundwater by
ijbiomac.2020.06.095.
electrocoagulation. Chemosphere 248, 125951. https://doi.org/10.1016/j.
Khadir, A., Negarestani, M., Ghiasinejad, H., 2020c. Low-cost sisal fibers/polypyrrole/
chemosphere.2020.125951.
polyaniline biosorbent for sequestration of reactive orange 5 from aqueous solutions.
Beheshti, F., Tehrani, M.A., Khadir, A., 2019. Sulfamethoxazole removal by
J. Environ. Chem. Eng. 8, 103956. https://doi.org/10.1016/j.jece.2020.103956.
photocatalytic degradation utilizing TiO2 and WO3 nanoparticles as catalysts:
Khadir, A., Negarestani, M., Mollahosseini, A., 2020d. Sequestration of a non-steroidal
analysis of various operational parameters. Int. J. Environ. Sci. Technol. https://doi.
anti-inflammatory drug from aquatic media by lignocellulosic material (Luffa
org/10.1007/s13762-019-02212-x. R.
cylindrica) reinforced with polypyrrole: study of parameters, kinetics, and
Bhanot, P., Celin, S.M., Sreekrishnan, T.R., Kalsi, A., Sahai, S.K., Sharma, P., 2020.
equilibrium. J. Environ. Chem. Eng. https://doi.org/10.1016/j.jece.2020.103734,
Application of integrated treatment strategies for explosive industry wastewater—a
103734.
critical review. J. Water Process Eng. 35, 101232. https://doi.org/10.1016/j.
Khadir, A., Negarestani, M., Motamedi, M., 2020e. Optimization of an electrocoagulation
jwpe.2020.101232.
unit for purification of ibuprofen from drinking water: effect of conditions and
Castañeda, L.F., Coreño, O., Nava, J.L., 2020. Simultaneous elimination of hydrated
linear/non-linear isotherm study. Separ. Sci. Technol. https://doi.org/10.1080/
silica, arsenic and phosphates from real groundwater by electrocoagulation using a
01496395.2020.1770795.
cascade-shaped up-flow reactor. Electrochim. Acta 331, 135365. https://doi.org/
Kibuye, F.A., Gall, H.E., Elkin, K.R., Ayers, B., Veith, T.L., Miller, M., Jacob, S.,
10.1016/j.electacta.2019.135365.
Hayden, K.R., Watson, J.E., Elliott, H.A., 2019. Fate of pharmaceuticals in a spray-
Cheng, H.-H., Narindri, B., Chu, H., Whang, L.-M., 2020. Recent advancement on
irrigation system: from wastewater to groundwater. Sci. Total Environ. 654,
biological technologies and strategies for resource recovery from swine wastewater.
197–208. https://doi.org/10.1016/j.scitotenv.2018.10.442.
Bioresour. Technol. 303, 122861. https://doi.org/10.1016/j.biortech.2020.122861.
Kobya, M., Soltani, R.D.C., Omwene, P.I., Khataee, A., 2020. A review on
Coimbra, R.N., Calisto, V., Ferreira, C.I.A., Esteves, V.I., Otero, M., 2019. Removal of
decontamination of arsenic-contained water by electrocoagulation: reactor
pharmaceuticals from municipal wastewater by adsorption onto pyrolyzed pulp mill
configurations and operating cost along with removal mechanisms. Environ.
sludge. Arab. J. Chem. 12, 3611–3620. https://doi.org/10.1016/j.
Technol. Innov. 17, 100519. https://doi.org/10.1016/j.eti.2019.100519.
arabjc.2015.12.001.
Kubier, A., Wilkin, R.T., Pichler, T., 2019. Cadmium in soils and groundwater: a review.
Cruz, K.D., Francisco, J.T.J., Mellendrez, K.J.M., Pineda, J.M.F., 2019.
Appl. Geochem. 108, 104388. https://doi.org/10.1016/j.apgeochem.2019.104388.
Electrocoagulation treatment of swine slaughterhouse wastewater: effect of
Kyllönen, H.M., Pirkonen, P., Nyström, M., 2005. Membrane filtration enhanced by
electrode material. E3S Web Conf 117. https://doi.org/10.1051/e3sconf/
ultrasound: a review. Desalination 181, 319–335. https://doi.org/10.1016/j.
201911700020.
desal.2005.06.003.
Deghles, A., 2017. Hydrogen Gas Production from Tannery Wastewater by
Lee, H.-J., Kim, K.Y., Hamm, S.-Y., Kim, M., Kim, H.K., Oh, J.-E., 2019. Occurrence and
Electrocoagulation of a Continuous Mode with Simultaneous Pollutants Removal,
distribution of pharmaceutical and personal care products, artificial sweeteners, and
vol. 10, pp. 40–51.
pesticides in groundwater from an agricultural area in Korea. Sci. Total Environ.
Del Rosario, K.L., Mitra, S., Humphrey, C.P., O’Driscoll, M.A., 2014. Detection of
659, 168–176. https://doi.org/10.1016/j.scitotenv.2018.12.258.
pharmaceuticals and other personal care products in groundwater beneath and
Levchuk, I., Rueda Márquez, J.J., Sillanpää, M., 2018. Removal of natural organic matter
adjacent to onsite wastewater treatment systems in a coastal plain shallow aquifer.
(NOM) from water by ion exchange – a review. Chemosphere 192, 90–104. https://
Sci. Total Environ. 487, 216–223. https://doi.org/10.1016/j.scitotenv.2014.03.135.
doi.org/10.1016/j.chemosphere.2017.10.101.
Ebele, A.J., Oluseyi, T., Drage, D.S., Harrad, S., Abou-Elwafa Abdallah, M., 2020.
López-Guzmán, M., Alarcón-Herrera, M.T., Irigoyen-Campuzano, J.R., Torres-
Occurrence, seasonal variation and human exposure to pharmaceuticals and
Castañón, L.A., Reynoso-Cuevas, L., 2019. Simultaneous removal of fluoride and
personal care products in surface water, groundwater and drinking water in Lagos
arsenic from well water by electrocoagulation. Sci. Total Environ. 678, 181–187.
State, Nigeria. Emerg. Contam. 6, 124–132. https://doi.org/10.1016/j.
https://doi.org/10.1016/j.scitotenv.2019.04.400.
emcon.2020.02.004.
Machiwal, D., Jha, M.K., Singh, V.P., Mohan, C., 2018. Assessment and mapping of
Ensano, B.M.B., Borea, L., Naddeo, V., Belgiorno, V., de Luna, M.D.G., Balakrishnan, M.,
groundwater vulnerability to pollution: current status and challenges. Earth Sci. Rev.
Ballesteros, F.C., 2019. Applicability of the electrocoagulation process in treating
185, 901–927. https://doi.org/10.1016/j.earscirev.2018.08.009.
real municipal wastewater containing pharmaceutical active compounds. J. Hazard
Magadini, D.L., Goes, J.I., Ortiz, S., Lipscomb, J., Pitiranggon, M., Yan, B., 2020.
Mater. 361, 367–373. https://doi.org/10.1016/j.jhazmat.2018.07.093.
Assessing the sorption of pharmaceuticals to microplastics through in-situ
Fischer, K., Grimm, M., Meyers, J., Dietrich, C., Gläser, R., Schulze, A., 2015. Photoactive
experiments in New York City waterways. Sci. Total Environ. https://doi.org/
microfiltration membranes via directed synthesis of TiO2 nanoparticles on the
10.1016/j.scitotenv.2020.138766.
polymer surface for removal of drugs from water. J. Membr. Sci. 478, 49–57. https://
Mena, V.F., Betancor-Abreu, A., González, S., Delgado, S., Souto, R.M., Santana, J.J.,
doi.org/10.1016/j.memsci.2015.01.009.
2019. Fluoride removal from natural volcanic underground water by an
Fu, F., Wang, Q., 2011. Removal of heavy metal ions from wastewaters: a review.
electrocoagulation process: parametric and cost evaluations. J. Environ. Manag. 246,
J. Environ. Manag. 92, 407–418.
472–483. https://doi.org/10.1016/j.jenvman.2019.05.147.
Gao, F.-Z., Zou, H.-Y., Wu, D.-L., Chen, S., He, L.-Y., Zhang, M., Bai, H., Ying, G.-G., 2020.
Swine farming elevated the proliferation of Acinetobacter with the prevalence of

8
M. Negarestani et al.
Mestre, A.S., Pires, J., Nogueira, J.M.F., Carvalho, A.P., 2007. Activated carbons for the
adsorption of ibuprofen. Carbon N. Y. 45, 1979–1988. https://doi.org/10.1016/j.
carbon.2007.06.005.
Mirjavadi, E.S., Tehrani, M.A., Khadir, A., 2019. Effective adsorption of zinc on magnetic
nanocomposite of Fe3O4/zeolite/cellulose nanofibers: kinetic, equilibrium, and
thermodynamic study. Environ. Sci. Pollut. Res. https://doi.org/10.1007/s11356-
019-06165-z. R.
Mohammadi, A., Khadir, A., Tehrani, R.M.A., 2019. Optimization of nitrogen removal
from an anaerobic digester effluent by electrocoagulation process. J. Environ. Chem.
Eng. https://doi.org/10.1016/j.jece.2019.103195.
Nasrullah, M., Singh, L., Wahid, Z.A., 2012. Treatment of sewage by electrocoagulation
and the effect of high current density. Energy Environ. Eng. J.
Nourmoradi, H., Moghadam, K.F., Jafari, A., Kamarehie, B., 2018. Removal of
acetaminophen and ibuprofen from aqueous solutions by activated carbon derived
from Quercus Brantii (Oak) acorn as a low-cost biosorbent. J. Environ. Chem. Eng. 6,
6807–6815. https://doi.org/10.1016/j.jece.2018.10.047.
Pires, B.C., do Nascimento, T.A., Dutra, F.V.A., Borges, K.B., 2019. Removal of a non-
steroidal anti-inflammatory by adsorption on polypyrrole/multiwalled carbon
nanotube composite—study of kinetics and equilibrium in aqueous medium.
Colloids Surfaces A Physicochem. Eng. Asp. 578, 123583. https://doi.org/10.1016/j.
colsurfa.2019.123583.
Piri, F., Mollahosseini, A., Khadir, A., Milani Hosseini, M., 2020. Synthesis of a novel
magnetic zeolite–hydroxyapatite adsorbent via microwave-assisted method for
protein adsorption via magnetic solid-phase extraction. J. Iran. Chem. Soc. https://
doi.org/10.1007/s13738-020-01883-5.
Rabizadeh, H., Feizbakhsh, A., Panahi, H.A., Konoz, E., 2020. A convenient synthesis of
NiO-CuS/molecularly imprinted polymer nanocomposites with highly enhanced
adsorption activity and selectivity for removal of Letrozole. Polym. Technol. Mater.
59, 619–629. https://doi.org/10.1080/25740881.2019.1669658.
Sandoval, M.A., Fuentes, R., Nava, J.L., Coreño, O., Li, Y., Hernández, J.H., 2019.
Simultaneous removal of fluoride and arsenic from groundwater by
electrocoagulation using a filter-press flow reactor with a three-cell stack. Separ.
Purif. Technol. 208, 208–216. https://doi.org/10.1016/j.seppur.2018.02.018.
Groundwater for Sustainable Development 11 (2020) 100474
Schneider, J., Matsuoka, M., Takeuchi, M., Zhang, J., Horiuchi, Y., Anpo, M.,
Bahnemann, D.W., 2014. Understanding TiO2 photocatalysis: mechanisms and
materials. Chem. Rev. 114, 9919–9986. https://doi.org/10.1021/cr5001892.
Singh, G.K., Singh, N.B., Shukla, S.P., Markandeya, 2019. Remediation of COD and color
from textile wastewater using dual stage electrocoagulation process. SN Appl. Sci. 1,
1000. https://doi.org/10.1007/s42452-019-1046-7.
Sivakumar, D., Shankar, D., Mohana, M., 2017. REMOVAL OF TOC AND COD FROM
MUNICIPAL SOLID WASTE LEACHATE USING ALUMINIUM ELECTRODE IN
ELECTROCOAGULATION.
Szymczycha, B., Borecka, M., Białk-Bielińska, A., Siedlewicz, G., Pazdro, K., 2020.
Submarine groundwater discharge as a source of pharmaceutical and caffeine
residues in coastal ecosystem: bay of Puck, southern Baltic Sea case study. Sci. Total
Environ. 713, 136522. https://doi.org/10.1016/j.scitotenv.2020.136522.
Tezcan Un, U., Topal, S., Ates, F., 2016. Electrocoagulation of tissue paper wastewater
and an evaluation of sludge for pyrolysis. Desalin. Water Treat. 57, 28724–28733.
Uddin, M.K., 2017. A review on the adsorption of heavy metals by clay minerals, with
special focus on the past decade. Chem. Eng. J. 308, 438–462. https://doi.org/
10.1016/j.cej.2016.09.029.
Vatovec, C., Van Wagoner, E., Evans, C., 2017. Investigating sources of pharmaceutical
pollution: survey of over-the-counter and prescription medication purchasing, use,
and disposal practices among university students. J. Environ. Manag. 198, 348–352.
https://doi.org/10.1016/j.jenvman.2017.04.101.
Wang, Q., Sang, H., Chen, L., Wu, Y., Wei, Y., 2020. Selective separation of Pd(II)
through ion exchange and oxidation-reduction with hexacyanoferrates from high-
level liquid waste. Separ. Purif. Technol. 231, 115932. https://doi.org/10.1016/j.
seppur.2019.115932.
Yang, G.C.C., Huang, S.C., Wang, C.L., Jen, Y.S., 2016. Degradation of phthalate esters
and acetaminophen in river sediments using the electrokinetic process integrated
with a novel Fenton-like process catalyzed by nanoscale schwertmannite.
Chemosphere. https://doi.org/10.1016/j.chemosphere.2016.04.119.
You, J., Guo, Y., Guo, R., Liu, X., 2019. A review of visible light-active photocatalysts for
water disinfection: features and prospects. Chem. Eng. J. 373, 624–641. https://doi.
org/10.1016/j.cej.2019.05.071.