Chapter 8

A Review on Pharmaceutical Removal

from Aquatic Media by Adsorption:
Understanding the Influential Parameters
and Novel Adsorbents

Ali Khadir, Afsaneh Mollahosseini, Ramin M. A. Tehrani,

and Mehrdad Negarestani

Contents
8.1 I ntroduction 208
8.2 P  harmaceutical Classification 209
8.2.1 Antibiotics (Anti-infectives) 210
8.3 Common Wastewater Treatment Methods 211
8.4 Common Water and Wastewater Treatment Plants 213
8.5 Adsorption Process 219
8.6 Influential Parameters Affecting the Adsorption of Pharmaceuticals 222
8.6.1 Effect of Initial Drug Concentration and Contact Time 223
8.6.2 Effect of Initial pH 225
8.6.3 Effect of Temperature 227
8.6.4 Effect of Adsorbent Dosage 232
8.7 Adsorption Isotherms 233

A. Khadir
Young Researcher and Elite Club, Yadegar-e-Imam Khomeini (RAH) Shahre Rey Branch,
Islamic Azad University, Tehran, Iran
e-mail: [email protected]
A. Mollahosseini (*)
Research Laboratory of Spectroscopy and Micro and Nano Extraction,
Department of Chemistry, Iran University of Science and Technology, Tehran, Iran
e-mail: [email protected]
R. M. A. Tehrani
Department of Chemistry, Yadegar Imam Khomeini (RAH) Shahre Rey Branch, Islamic Azad
University, Tehran, Iran
M. Negarestani
Department of Civil and Environmental Engineering, Iran University of Science
and Technology, Tehran, Iran

© Springer Nature Switzerland AG 2020 207

Inamuddin, A. Asiri (eds.), Sustainable Green Chemical Processes
and their Allied Applications, Nanotechnology in the Life Sciences,
https://doi.org/10.1007/978-3-030-42284-4_8
208 A. Khadir et al.

8.8 A dsorption Kinetics 238

8.9 A  dsorbents for Pharmaceuticals Removal 239
8.9.1 Activated Carbon 239
8.9.2 Graphene-Based materials 242
8.9.3 Chitosan and Its Composites 243
8.9.4 Carbon Nanotube 246
8.9.5 Clay and Zeolite Nanocomposites 248
8.10 Conclusion 252
References 252

8.1 Introduction

There is no doubt that the Industrial Revolution has significantly ameliorated the
life of people globally in every aspect including industrialization and agriculture. In
fact, it is believed that the water supply is the main inevitable parameter for every
society development especially once the world is facing water shortages. The situa-
tion is aggravated while water is polluted by natural sources (soil erosion, decaying
of organic matter) or human activities. Water pollution may be categorized into dif-
ferent groups:
1. Common pollutants
2. Emerging contaminants (micropollutants)
Emerging pollutants are defined as any chemicals that are recently detected in
the environment usually at low concentration and have adverse effects on ecosystem
and human health (Li et al. 2019a). Among various types of micropollutants,
­pharmaceuticals have gained much attention over the last two decades (Khadir et al.
2020). Pharmaceuticals have been produced with the aim of human and animal
treatment; however, these compounds have shown negative effects on the environ-
ment especially for their continuous consumption. Non-steroidal anti-inflammatory
drugs, beta-blockers, antibiotics, neuroleptics, and hormones are the most detected
compounds in the environment (Szymonik et al. 2017). Antibiotics that are used for
treating infections both in people and animals are the most frequently prescribed
pharmaceuticals. In Canada, hypertension drugs and in Germany and United States,
beta-blockers are reported to be the most frequently prescribed drugs (Szymonik
et al. 2017).
Scientists are of firm opinion that the presence of pharmaceutical compounds in
the environment is attributed to the increase in the pharmaceuticals consumption.
Diclofenac as a single drug, for example, its consumption increased from 877 to
940 Mg from 2007 to 2008, respectively (Zhang et al. 2008). In Germany 2001,
some of the most commonly used anti-inflammatory drugs were acetylsalicylic
acid, with 836 tonnes, paracetamol, 622 tonnes, and ibuprofen, with 345 tonnes
(Quesada et al. 2019). It is evident that all of these drugs are not degradable in
human bodies. Hence, many of them are excreted from the body to the environment
8 A Review on Pharmaceutical Removal from Aquatic Media by Adsorption… 209

in an unchanged form or biologically changed structure (Madikizela et al. 2017). An

investigation showed that among 400 households in the UK, 63.2% discarded their
unfinished drugs in household waste and 11.5% discarded them into the toilet or
sink (Bound and Nikolaos 2005). In Germany, it was reported that amounts of up to
16,000 tonnes of pharmaceuticals were disposed of each year from human medical
care (Zhang et al. 2008). Pharmaceuticals are either discarded in the household
waste or excreted from human bodies; they enter the environment, especially
wastewaters.
Literature declared that pharmaceuticals have been widely detected around the
world in water media including influent and effluents wastewater/water treatment
plants, ground water, surface water, and potable water. For instance, ciprofloxacin
hydrochloride and fluoroquinolones were detected in wastewaters in the concentra-
tion of 249–405 ng/L and 0.6–2 μg/L, respectively (Dhiman and Sharma 2019).
Ibuprofen showed the minimum and maximum concentration of 184 and 248 ng/L
in the surface water of Mexico (Rivera-Jaimes et al. 2018). Also, caffeine was
observed in the surface waters of China (Yang et al. 2018a), USA (Bean et al. 2018),
and Malaysia (Praveena et al. 2018). Many researchers believe that the inability of
the conventional wastewater/water treatment plants is one of the significant reasons
of pharmaceutical compounds detection in waters (Greenham et al. 2019; Lee et al.
2019; Reis et al. 2019). So, it is highly necessary to implement an efficient treatment
process to remove these hazardous compounds.
Since now, various treatment methods including nanofiltration, reverse osmosis,
photocatalysis, ozonation, adsorption, ion exchange, and biological processes have
been implemented for drug removal. This review aims to consider the pharmaceuti-
cal pollution and removal in conventional water and wastewater treatment plants
around the world. In addition, the authors attempted to introduce the adsorption
processes as efficient, simple, and promising treatment technique for water and
wastewater purification from pharmaceutical compounds. Accordingly, some of the
basic parameters which strongly influence the whole procedure including contact
time, adsorbent dosage, pharmaceutical concentration, pH, and temperature were
studied. Moreover, this chapter summarized the major works regarding the removal
of pharmaceuticals from water and wastewater using various adsorbents.

8.2 Pharmaceutical Classification

Pharmaceutical compounds have been widely prescribed for illness treatment or

prevention. There are several ways for the classification of pharmaceuticals pro-
posed by various researchers. Generally, pharmaceuticals are categorized into anti-
biotics, beta-blockers and other cardiovascular drugs, cytostatic drugs, drugs
affecting the nervous system, non-steroidal anti-inflammatory drugs, and natural
hormones. Among them, antibiotics are the most important group that in the follow-
ing section they are thoroughly discussed. For further studies about the other drugs,
refer to (Teixeira-Lemos et al. 2019; Ahmed 2017a; Quesada et al. 2019; Li 2014).
210 A. Khadir et al.

8.2.1 Antibiotics (Anti-infectives)

Antibiotics, considered the most significant medical milestone of the twentieth cen-
tury, are pharmaceuticals that are extensively applied to treat bacterial infections in
living creatures by inhibiting or eradicating the growth of microorganism. Antibiotics
own the third rank among the drugs most prescribed for human disease, and in the
case of veterinary medicine, 70% of the consumed drugs are antibiotics (Van
Boeckel et al. 2015; Teixeira-Lemos et al. 2019). In spite of the fact that the devel-
opment of antibiotics has contributed human to have a longer life, the presence of
these compounds in the environment has drawn much attention lately. Based on the
literature, annual consumption of antibiotics is estimated to be between 100,000 and
200,000 tons, and of course consumption rate increased 36% between 2000 and
2010 in 71 countries (Homem and Santos 2011; Klein et al. 2018). Another study
found that Brazil, Russia, India, China, and South Africa are the biggest user of
antibiotics (Gelband and Duse 2011).
Furthermore, global antibiotic use enhanced by 65% between 2000 and 2015
(Klein et al. 2018). In the USA, approximately 23,000 tons antibiotics are con-
sumed annually (Ternes and Joss 2007). In 2013 China was nominated as the global
greatest manufacturer and user of 36 antibiotics (up to 92,700 tons) and released
roughly 53,800 tons antibiotics into the environment (Zhang et al. 2015; Huang
et al. 2019b). Cephalexin, amoxicillin, ofloxacin, tetracycline, and norfloxacin were
the top five antibiotics used in China (Zhang et al. 2015). Reports have revealed than
Turkish people tend to use antibiotics approximately 2–3 times higher than European
countries (Aydin et al. 2019b). According to Al-Faham et al. (2011) and Bin
Abdulhak et al. (2011), 87% and 77% of antibiotics are dispensed without prescrip-
tion in Syria and Saudi Arabia, respectively. Owning to their extensive consump-
tion, contamination of various matrices including water (Wei et al. 2011; Li et al.
2018; Patrolecco et al. 2018; Sabri et al. 2018; Yang et al. 2018b; Danner et al. 2019;
Huang et al. 2019a; Qiu et al. 2019), soil (Song et al. 2016; Zhou et al. 2017; Chen
et al. 2019a; Zeng et al. 2019; Zhao et al. 2019), sediment (Liang et al. 2018; Chen
et al. 2019b; Li et al. 2019c), and even the potable water (Huo et al. 2016; Zeng
et al. 2018) by antibiotics was probable and reported in previous studies. Hospitals
are potential candidates for prevailing antibiotics in the environment, mainly due to
the excretion via urine or feces of the patients. Kümmerer (2001) stated that of total
antibiotics used for human disease, 26% are used in hospitals (Kümmerer 2001). In
Europe, for instance, 20–30% of inpatients receive antibiotic treatment during their
hospitalization (Ansari et al. 2009). The significance of hospital wastewaters is
because they usually have higher concentration of antibiotics than other media
(Pena et al. 2010; Lien et al. 2016; Wang et al. 2018). The presence of antibiotics or
their metabolites in the hospital discharge has been reported in different countries
including Spain (Gros et al. 2013), Italy (Verlicchi et al. 2012), Vietnam (Lien et al.
2016), Norway (Thomas et al. 2007), Romania (Szekeres et al. 2017), Iran (Shokoohi
et al. 2017), Qatar (Al-Maadheed et al. 2019), Oman (Al-Riyami et al. 2018), USA
(Brown et al. 2006), Taiwan (Li and Lin 2015), Sweden (Lindberg et al. 2004),
8 A Review on Pharmaceutical Removal from Aquatic Media by Adsorption… 211

Germany (Ohlsen et al. 2003), China (Wang et al. 2018), Brazil (Santoro et al.
2015), etc. Ciprofloxacin, ofloxacin, clarithromycin, sulfamethoxazole, trime-
thoprim, and metronidazole are the most frequent detected antibiotics in hospital
effluent. Normally, antibiotics concentrations in the hospital effluent are higher in
winter as compared to summer (Verlicchi et al. 2012). Aydin et al. (2019b) investi-
gated the concentration of antibiotics in 16 different hospital effluents. They found
that ciprofloxacin, azithromycin, and clarithromycin owned the greatest concentra-
tion in the hospital discharge. Moreover, the total concentration of antibiotics in
hospital effluents ranged from 21.2 to 4886 ng/L and 497 to 322,735 ng/L in sum-
mer and winter, respectively (Aydin et al. 2019b). Shokoohi et al. (2017) examined
the presence of six common utilized antibiotics (amoxicillin, ciprofloxacin, erythro-
mycin, sulfamethoxazole, imipenem, and cefixime) in wastewater effluent of two
different hospitals in Iran. They found out that in one hospital three antibiotics
including amoxicillin, cefixime, and imipenem with mean concentration of 5.86,
10.85, and 25.53 μg/L, respectively, were identified; however, in the second hospital
none of the mentioned antibiotics was detected (Shokoohi et al. 2017). Hence, for a
proper antibiotic removal, in-situ examination regarding the type and quantity of
these macromolecule compounds must be conducted. The pros of antibiotics in
healthcare centers are undeniable; however, the uncontrolled, immoderate, and mis-
use of antibiotics have engendered to propagation, prevalence, and spread of
antibiotic-­resistant bacteria (ARB) and antibiotic-resistant genes (ARGs) in the
aquatic environment. World Health Organization characterizes antimicrobial resis-
tance as one of the three biggest global public health crises that must be managed
with the utmost urgency (Verlicchi et al. 2015; Yang et al. 2018b). It is estimated
that by 2050, antibiotic resistance (AR) will account for ten million deaths and a
financial burden of approximately US$100 trillion (Sanganyado and Gwenzi 2019).
Unfortunately, many researchers have highlighted hospital effluent as one of the
major sources of antibiotic resistance spread (Le et al. 2016; Varela et al. 2016;
Timraz et al. 2017; Wang et al. 2018).

8.3 Common Wastewater Treatment Methods

There are numerous methods that have been proposed in terms of pharmaceutical
removal from various water media in recent years. Generally, wastewater treatment
methods are broadly divided into physical, chemical, and biological processes;
however, some may employ a combination of these processes. Adsorption, ion
exchange, membrane technology, ozonation, irradiation, electrochemical processes,
aerobic and anaerobic microbial degradation are of the most promising and assuring
techniques in terms of pollutant removal. All of these methods have their own
advantages and disadvantages that sometimes may limit their applications in some
cases. Table 8.1 shows the major strengths and drawbacks of different wastewater
treatment methods (Ghenaatgar et al. 2019; Salleh et al. 2011; Carolin et al. 2017;
Ngulube et al. 2017; Wong et al. 2019).
212 A. Khadir et al.

Table 8.1 Comparison of the pros and cons of different wastewater treatment plants
Techniques Pros Cons
Coagulation/  − Cost-effective  − Sludge generation that
flocculation +  − Simple dewatering requires a further process
sedimentation  − Robust process  − Utilization of chemicals
is high
 − High toxicity and TDS
content in sludge
 − pH-dependent system
 − May be expensive due to
the usage of different
chemicals
 − Recycling of chemicals is
not feasible
Membrane − High separation efficiency
   − Very expensive
filtration − Lower space requirement
   − Membrane fouling
− Low energy consumption
   − Complex process
− Enrichment of nitrifying bacteria
   − Concentrated sludge
can reduce fouling in membrane production
bioreactors  − Short life span due to
membrane fouling
 − Membranes must have
excellent chemical and
thermal stability to withstand
high pressures and fluxes
 − High investment cost
Ion exchange − High transformation of
   − Operational cost is high
components  − High cost of resins
− Produces water of high quality
   − Generates large volumes
− Regenerable
  of sludge
Adsorption − Simplicity
   − Incomplete removal
− Easy operation
   − Regeneration may be
− Readily available
  expensive
− High efficiency
   − Desorption
− Regenerable adsorbents
 
− Less sludge production
 
− Utilization of low-cost adsorbents
 
Ozonation − No chemical sludge
  − Extremely short half-life
 
processes − Residual ozone can decompose to
  − High cost
 
oxygen easily − Produces unstable toxic
 
− Does not increase wastewater
  by-products and carcinogenic
volume aromatic amines
− Fast and effective
 
− Can be used in a gaseous state
 
Photochemical − Can effectively eliminate
  − Expensive
 
pollutants − Formation of by-products
 
− No foul odors production
 
(continued)
8 A Review on Pharmaceutical Removal from Aquatic Media by Adsorption… 213

Table 8.1 (continued)

Techniques Pros Cons
Electrochemical  − Low chemical sludge  − Initial investment is high
destruction  − No consumption of chemicals  − Need high electrical
supply
 − High flow rates causing
direct decrease in final
efficiency
Biological − Inexpensive  − Need to be developed
treatment (aerobic − High COD removal  − Incomplete elimination
and anaerobic  − Forms CH4 and H2S
processes)  − Long reaction time and
inflexible

Biological treatment processes utilize a vast variety of microorganisms, mainly

come from human body, to degrade pollutants under aerobic and anaerobic condi-
tions to gain energy for their survival. Simple operation, inexpensiveness, and high
organic matter removal are the significant merits of biological processes. However,
these methods mostly need a large land as well as strict environmental controls
(such as pH, temperature, nutrient, toxic substances, and oxygen). Also, conven-
tional biological methods have proven to be inadequate in terms of pharmaceuticals
removal (Spataro et al. 2019).
Chemical methods are often effective for a wide range of pollutants removal.
Usually, chemical methods use a large number of expensive chemicals and reagents
or electricity which are not always beneficial methods in view of financial supports.
Moreover, advanced oxidation processes are prone to generate secondary pollut-
ants. Beheshti et al. (2019) observed that sulfamethoxazole was completely removed
from the solution by TiO2 and WO3 nanoparticles via photocatalytic degradation;
however, secondary pollutants through oxidation were generated which required
further treatment (Beheshti et al. 2019).
The common adsorption and membrane filtration have been extensively used for
pollutants removal. Adsorption has gained much attention recently because of its
efficiency and simplicity and less generation of sludge. Also, since the process is
physical, no new pollutants are generated (Mollahosseini et al. 2019). Membrane
filtration, including nanofiltration, ultrafiltration, microfiltration, and reverse osmo-
sis is a suitable and efficient treatment method but it must be intended that the
membranes are almost sensitive and may have a short life-span due to the fouling if
it is not controlled preciously (Kaya et al. 2019).

8.4 Common Water and Wastewater Treatment Plants

In any country around the world, water after collecting from an aquatic media is
transferred to water treatment plants (WTPs) to remove contaminants until the
water meets standards for drinking. After the water is consumed in various ways,
214 A. Khadir et al.

Fig. 8.1 Scheme for a conventional wastewater treatment plant having various physical, chemical,
and biological units and processes

including drinking, washing, toilet, shower, etc., wastewater is generated. The gen-
erated wastewater is collected by sanitary sewer networks and sent to the wastewa-
ter treatment plants (WWTPs).
WWTPs generally employ physical, chemical, and biological methods to treat
the wastewater (Fig. 8.1). Firstly, wastewater experiences physical treatment pro-
cesses such as screening and grit trapping to eliminate large, rough, coarse debris,
and particles. These materials are removed by sedimentation tanks allowing the
suspended particles to settle out of wastewater. This process is called primary treat-
ment. According to previous studies, primary treatment could remove lower than
10% of the pharmaceuticals and it is fair to suggest that it is inefficient at removing
pharmaceuticals (Leung et al. 2012).
Then, biological processes are utilized to degrade organic materials to H2O and
CO2 by means of flocculating activated microorganisms. Activated sludge is the
most popular biological treatment process extensively utilized in most of the
WWTPs. This type of treatment was developed by two English researchers, Ardern
and Lockett, in 1914, and since then, it has been implemented on a global scale.
Activated sludge system is comprised of a bioreactor followed by the secondary
sedimentation tank. In the case of carbon, nitrogen and phosphorous removal, the
bioreactor has different compartments with different operational conditions (aero-
bic, anaerobic, and anoxic) (Verlicchi et al. 2013). Finally, the wastewater is disin-
fected to kill pathogenic organisms. In fact, the role of WWTP to minimize the level
of harmful contaminants in reclaimed water is highly concerned.
In terms of pharmaceutical compounds, countless studies have shown that the
present WWTPs are not able to thoroughly remove these hazardous compounds and
therefore they have been detected in effluent of WWTPs, surface water, ground
water, and drinking water samples (Table 8.2). Cosenza et al. (2018) investigated
8 A Review on Pharmaceutical Removal from Aquatic Media by Adsorption… 215

Table 8.2 The concentration of various pharmaceutical compounds in surface water, river, WWTP
influent and effluent, urban effluent, and hospital effluent
Pharmaceuticals Water source Concentration (ng/L)
Atenolol Surface water 7
Surface water 21.7
Surface water 31.12
Acetaminophen Surface water 3.18
Surface water 445
Surface water 430
Surface water 38.18
Surface water 0.20
Surface water 209
Amoxicillin Hospital effluents 900
WWTP influents 9.94 × 103
Ampicillin Industrial effluents 5.8 × 103
Atenolol River 250–600
Bezafibrate WWTP influents 0.3–87
Caffeine Urban effluents 23–776
Surface water 2.9–194
WWTP influents 2448–4865
River 38–250
Carbamazepine WWTP influents 33–1318
Urban effluents 73–729
Surface water 4.5–61
WWTP influents 24–50
River 56–160
Surface water 1.17
Surface water 412.5
Surface water 1048
Cefaclor WWTP influents 6.15 × 103
Cefazolin Industrial effluents 4.2 × 103
Cefotaxime Industrial effluents 4.2 × 103
Cephalexin Hospital effluents 1 × 104
WWTP influents 6.4 × 104
Industrial effluents 3.1 × 103
Ciprofloxacin WWTP influents 27–514
WWTP influents 11–63
Hospital effluents 1.5 × 104
WWTP influents 1.1 × 103
Clofibric acid WWTP influents Nd-82
Liao River 18
(continued)
216 A. Khadir et al.

Table 8.2 (continued)

Pharmaceuticals Water source Concentration (ng/L)
Demethyl diazepam WWTP influents Nd-62
Urban effluents 8.8–127
Surface water 1.1–6.8
WWTP influents 9–13
River 21–98
Surface water 3.95
Surface water 313
Surface water 33.56
Liao River 717
Dilantin Urban effluents 8.8–181
Surface water 1.1–8.9
Enrofloxacin Hospital effluents 100
Erythromycin WWTP influents 9–353
Urban effluents 8.9–294
Surface water 1.8–4.8
Gemfibrozil WWTP influents 181–451
Ibuprofen Liao River 246
Urban effluents 10–137
Surface water 11–38
River 35–270
Surface water 662.17
Ketoprofen Surface water 29.51
Lincomycin WWTP influents 11–629
Hospital effluents 1.7 × 103
Industrial effluents 1.1 × 105
Pharmaceutical Water source Concentration (ng/L)
Metronidazole Industrial effluents 7.8 × 103
Nalidixic acid Industrial effluents 6.7 × 103
Naproxen Urban effluents 20–483
Surface water 1.8–18
River 81–360
Norfloxacin Hospital effluents 200
Ofloxacin WWTP influents 150–1081
Industrial effluents 1.3 × 103
Oxytetracycline Industrial effluents 1.5 × 104
Salicylic acid WWTP influents 433–8036
Liao River 295
Spiramycin WWTP influents 11–129
(continued)
8 A Review on Pharmaceutical Removal from Aquatic Media by Adsorption… 217

Table 8.2 (continued)

Pharmaceuticals Water source Concentration (ng/L)
Sulfadiazine Industrial effluents 353
WWTP influents 46–253
Urban effluents 3.8–407
Surface water 1.7–36
WWTP influents 13–261
River 9–190
Hospital effluents 300
WWTP influents 3 × 103
Industrial effluents 5.8 × 103
Surface water 9.79
Surface water 56.19
Surface water 299
Sulfanilamide Industrial effluents 207
Sulfathiazole Industrial effluents 9.6 × 103
Tetracycline Industrial effluents 1.5 × 103
Urban effluents 10–188
Surface water 3.2–53.
River 11–94
Hospital effluents 300
WWTP influents 4.3 × 103

the occurrence and the behavior of illicit drugs and their metabolites in a conven-
tional WWTP located in Sicily (island of Italy). The following average removal
efficiencies were reported: benzoylecgonine (77.85%), cocaine (92.34%), codeine
(64.75%), and morphine (90.16%).
Al-Maadheed et al. (2019) examined the elimination of eight selected antibiotics
by a domestic wastewater treatment plant built in 1990 Doha, Qatar with a flow rate
of 54,000 m3/d. The WWTP consists of several units and processes, including bar
screen, grit detroiter, elevator, conventional aeration, activated sludge recirculation,
sand filter, and chlorination. The removal efficiencies of clavulanic acid (65.7%),
metronidazole (57.4%), amoxicillin (46.3%), ciprofloxacin (70.5%), tetracycline
(19.2%), penicillin (95.6%), and erythromycin (90.9%) were obtained. More impor-
tantly, they found that concentrations of antibiotics in the influent wastewater were
the same as (or even higher) their concentrations in the effluent water of the main
hospital, indicating that direct disposal of drugs into the sewer system is as impor-
tant as the clinics and hospital effluents as the main source of pharmaceutical com-
pounds spread (Al-Maadheed et al. 2019). They declared that sand filtration could
not remove antibiotics from wastewater.
Three WWTPs in Italy were investigated and it was found that acetaminophen
and ketoprofen were both removed in spite of distinctive in-situ operations (Palli
et al. 2019). However, atenolol removal ranged from medium to excellent based on
the operational parameters in the WWTP. Carbamazepine, diclofenac, and amoxi-
cillin exhibited low removal efficiency and were reluctant to biological oxidation.
218 A. Khadir et al.

Fig. 8.2 The removal efficiency of various drugs in summer and winter

They believed that solid retention time played an important role in the pharmaceuti-
cal removal (Palli et al. 2019).
Kim et al. (2010) reported the presence of clarithromycin, metformin, atenolol,
carbamazepine, and trimethoprim at high concentrations in the effluent of mem-
brane bioreactor WWTP. Furthermore, a sewage treatment plant in Japan was named
as a main source of six anti-cancer agents in its effluent (Azuma et al. 2015). The
presence of various pharmaceuticals in the influent or/and effluent of WWTP in
Adana, Turkey (Daglioglu et al. 2019), Nova Scotia and New Brunswick (Greenham
et al. 2019), Gniewino (Kołecka et al. 2019), 11 cities of China (Yu et al. 2019),
Costa Rica (Causanilles et al. 2017), Durban, South Africa (Faleye et al. 2019),
Rome, Italy (Spataro et al. 2019), and India (Kurasam et al. 2018) has also been
reported.
It has been reported that the removal rate of drugs is dependent on various fac-
tors, including the types and properties of the drugs (solubility, volatility, photodeg-
radation, and biodegradability), the pattern of the drug consumption and its load
during time variations, water consumption rate, geography, climate, and operating
conditions in WWTPs (Tiwari et al. 2017; Kanakaraju et al. 2018). Peng et al.
(2019) stated that in the activated sludge process, pharmaceutical removal occurs
via adsorption, hydrolysis, oxidation, heterotrophic biodegradation, and autotro-
phic biodegradation. The operating conditions generally relate to parameters such
as sludge retention time (SRT), hydraulic retention time (HRT), and pH of the
water. Another report claimed that seasonal variations may be effective in terms of
­pharmaceuticals removal. In this direction, drugs may be categorized into three
distinctive groups as follows (Fig. 8.2) (Castiglioni et al. 2006):
8 A Review on Pharmaceutical Removal from Aquatic Media by Adsorption… 219

1. In summer, higher removal rate was attained including amoxicillin, atenolol,

bezafibrate, and enalapril.
2. There was no difference in removal efficiency in both summer and winter includ-
ing ciprofloxacin, hydrochlorothiazide, and ofloxacin.
3. The third group is of those that the removal efficiency was approximately zero in
both summer and winter.
The higher removal efficiency in summer can be attributed to the influence of the
temperature on the biological processes, the amount of water and drugs consump-
tion and nitrification rate (Wang and Wang 2016). It was formerly proved that with
decreasing the temperature, the nitrification rate and pharmaceutical removal both
decreased (Verlicchi et al. 2013). Moreover, the variations of the drugs concentra-
tion must be intended. Kumar et al. (2019) investigated the seasonal variations of
different drugs in the influent of a WWTP in New Zealand and found that some
compounds only are observed in certain time of the year. Cocaine, for instance, was
only detected in summer and winter. Also, the total concentrations of the studied
drugs were found to be 30–40% higher during summer than winter (Kumar
et al. 2019).
More interestingly, conventional WTPs have reported to be ineffective to remove
pharmaceutical compounds from raw water similar to conventional WWTPs. Reis
et al. (2019) conducted a research regarding occurrence, removal and seasonal vari-
ation of pharmaceuticals in six Brazilian drinking water treatment plants. Table 8.3
shows the concentration of the drugs entering in the WTPs. It can be observed from
Table 8.3 that pharmaceuticals are entered into the WTPs. The authors believed that
the fluctuation of pharmaceuticals among the WTPs was attributed to the area that
raw water was supplied/collected. Table 8.4 summarizes the removal efficiency of
the pharmaceuticals after the treatment. It is evident that some drugs were com-
pletely removed; however, the others are remained in the drinking water and prob-
ably enter the human body. These WTPs employed units and processes such as
primary chlorination, coagulation, flocculation, sedimentation, sand filtration, post-­
chlorination, and dissolved-air flotation that were not suitable enough to remove
pharmaceuticals pollution.
An interesting study was conducted regarding the surface water (including rivers,
lakes, oceans, and aquifers) of the USA (Deo 2014). Figure 8.3 shows the number of
drugs that were detected in the investigated waters. Briefly, of 93 pharmaceuticals
that were observed, 27 antibiotics; 15 antidepressants; 9 antihypertensives; 7 analge-
sics; and 7 anticonvulsants owned the most groups of drugs that were detected.

8.5 Adsorption Process

Adsorption techniques have been extensively applied for the separation of both
organic and inorganic pollutants from various kinds of wastewaters. Adsorption, a
physical phase transfer process, utilizes a solid material as the adsorbent to elimi-
nate pharmaceuticals from the liquid phase. The contaminant in this process is
named adsorbate. In fact, the efficiency of the process is attributed to the interaction
220 A. Khadir et al.

Table 8.3 The concentration of various pharmaceutical compounds entering to six water treatment
plants
Pharmaceuticals WTP1 WTP2 WTP3 WTP4 WTP5 WTP6
Betamethasone <MQL-­ <MDL-­ <MQL-­ <MDL-­ <MQL-­ <MDL-­
6371 4109 11,960 4354 7836 3662
Clarithromycin – <MDL-­ – <MDL-­ – –
168 199
Phenazone – – – – <MDL-33 –
Phenylbutazone <MDL-76 – – – – –
Fenofibrate – – – <MDL-­ <MDL-­ <MDL-­
290 119 1388
Fluconazole <MQL-­ <MQL-­ – <MQL-­ <MQL-­ <MQL-62
1413 583 763 1294
Loratadine <MDL-­ – <MDL-56 <MDL-­ – <MDL-­
123 214 486
Prednisone <MQL-­ <MDL-­ <MQL-2085 <MQL-­ <MQL-­ <MDL-­
1895 2444 2329 8105 855
Atorvastatin <MQL-­ <MDL-­ <MDL-109 <MQL-­ <MQL-­ –
523 455 608 1020
Caffeine – <MDL-­ – – – –
1385
Danofloxacin <MDL-41 <MDL-35 – <MDL-61 <MDL-­ <MDL-23
272
Enoxacin <MDL-­ <MDL-­ – <MDL-­ <MDL-­ –
386 354 257 240
Enrofloxacin – <MDL-64 – <MDL-13 <MDL-71 –
Metformin <MDL-­ – – <MDL-­ – –
203 167
Norfloxacin <MQL-­ <MDL-­ <MDL-89 <MDL-­ <MQL-­ –
156 146 136 285
Ketoprofen <MQL-­ <MQL-­ – <MQL-­ <MQL-­ <MDL-22
300 298 1020 959
Gemfibrozil <MDL-­ <MQL-­ <MDL220 <MDL-­ <MQL-­ <MDL-12
899 475 211 948
Ibuprofen – – – <MDL-­ – –
302

between adsorbent and adsorbate. Generally, adsorption is comprised of three dis-

tinctive steps:
1. Firstly, the adsorbate in the bulk solution must move to the external boundary
layer around the adsorbent which is called film diffusion or external diffusion.
2. Secondly, the adsorbates may be able to enter into the pores of the adsorbent.
This step is pore diffusion.
3. Finally, fixation of the adsorbate on the adsorbent sites via energetic interaction
occurs, named surface reaction.
8 A Review on Pharmaceutical Removal from Aquatic Media by Adsorption… 221

Table 8.4 The removal efficiency of different pharmaceutical compounds after treatment in six
different water treatment plants
Pharmaceuticals WTP1 WTP2 WTP3 WTP4 WTP5 WTP6
Betamethasone 84 ± 23% 70 ± 10% 70 ± 10% 61 ± 34% 75 ± 37% 91 ± 18%
Clarithromycin Na 100%1 Na 100%1 Na Na
Phenazone Na Na Na Na 100 ± 0% Na
Phenylbutazone 100 ± 0% Na Na Na Na Na
Fenofibrate Na Na Na 100%1 100%1 100%1
Fluconazole 59 ± 21% 64 ± 32% Na 48 ± 27% 43 ± 24% 100%1
Loratadine 82 ± 31% Na 100%1 100 ± 0% Na 75 ± 36%
Prednisone 69 ± 25% 60 ± 37% 32 ± 6% 56 ± 38% 45 ± 23% 99 ± 1%
Atorvastatin 57 ± 23% 84 ± 36% 100 ± 0% 55 ± 38% 61 ± 32% Na
Caffeine 100 ± 0% 100%1 Na Na Na Na
Danofloxacin 75 ± 24% 100 ± 0% 100 ± 0% 100 ± 0% 89 ± 22% 100%1
Enoxacin 72 ± 40% 100 ± 0% Na 100 ± 0% 100 ± 0% Na
Enrofloxacin 100 ± 0% 100%1 Na 100%1 96 ± 10% Na
Metformin 100 ± 0% Na Na 100%1 Na Na
Norfloxacin 86 ± 31% 83 ± 20% 100 ± 0% 100 ± 0% 50 ± 29% Na
Gemfibrozil 91 ± 16% 96 ± 9% 100%1 79 ± 12% 59 ± 15% 100%1
Ketoprofen 82 ± 23% 100 ± 0% Na 72 ± 32% 73 ± 38% 100%1
Ibuprofen Na Na Na 100%1 Na Na
Standard deviation not available
1

Fig. 8.3 The number of pharmaceuticals reported to occur in the surface water of the USA
222 A. Khadir et al.

Table 8.5 Comparison between some properties of physical and chemical adsorption
Physical adsorption Chemical adsorption
Multilayer adsorption Monolayer adsorption
Low enthalpy High enthalpy
High entropy Low entropy
Low activation energy High activation energy
Reversible Non-reversible
Low temperatures High temperatures
Weak intermolecular forces like van der Waals Strong covalent bonding involving electron
forces exchange

Fig. 8.4 The schematic

picture to describe the
difference between
physical and chemical
adsorption

It is a generally accepted assumption that the third step is rapid. However, the exter-
nal diffusion and pore diffusion determine the total rate of adsorption kinetic.
Depending on the interaction between adsorbate and adsorbent, the adsorption
can be divided into two types:
1. Physisorption (physical adsorption): When no electron is shared between adsor-
bate and adsorbent, the removal process follows physical sorption. Weak attrac-
tion forces such as hydrophobicity, hydrogen bonding, polarity, static interactions,
π-π interactions, and van der Waals forces are the major responsible of pollutant
removal (Dawood and Sen 2014). Furthermore, low energy, simple desorption,
and multilayer build-up of adsorbate on adsorbent is other properties of
physisorption.
2. Chemisorption (chemical adsorption): Unlike physisorption, chemical adsorp-
tion involves electron sharing (or chemical bond or attraction) and has a high
level of energy. Monolayer is observed in chemisorption and usually desorption
is difficult.
Some of the differences between physisorption and chemisorption are shown in
Table 8.5 (Ngulube et al. 2017). Figure 8.4 shows a scheme for the meaning of
physical and chemical adsorption.

8.6 I nfluential Parameters Affecting the Adsorption

of Pharmaceuticals

To implement the adsorption treatment process for the removal of drugs from aque-
ous media, it is highly important to figure out the effect of parameters on the pro-
cess. Optimization of these parameters leads to attain the maximum efficiency of
8 A Review on Pharmaceutical Removal from Aquatic Media by Adsorption… 223

the process along with minimum cost. In the next section, some of the factors affect-
ing the adsorption of pharmaceuticals are discussed.

8.6.1 Effect of Initial Drug Concentration and Contact Time

The removal efficiency usually depends on the initial pollutant concentration and
enough contact time between adsorbate and adsorbent. As a matter of fact, if the
adsorbent available sites are not completely occupied by the pollutant concentra-
tion, the removal efficiency seems to increase with drugs concentration. On the
other hand, a reduction in removal efficiency can be observed once the adsorbent
sites are saturated and the drugs concentration increases. Generally, removal of
pharmaceuticals increases with an increase in contact time until the equilibrium is
achieved. Once the equilibrium is reached, no significant further uptake of adsor-
bate occurs. Equilibrium state is attained once the rate of adsorption and rate of
desorption becomes equal (Ahmed 2017b).
Khadir et al. (2020) investigated the removal of ibuprofen from aqueous media
by using Luffa fibers/popypyrrple nanocomposite. The authors reported that after
90 min of the reaction, the removal efficiency did not fluctuate and reached a
maximum value of > 60%. Tian et al. (2019) studied the effect of contact time on
the adsorption of terramycin on carbon aerogel and magnetic carbon aerogel. They
observed that at the first 30 min of the reaction adsorption was rapid and then the
adsorption became slow and reached equilibrium after 60 min. Thus, a combination
of rapid/slow trend was seen within the first 60 min (Tian et al. 2019). Duan et al.
(2019) reported the removal of three fluoroquinolone antibiotics using polypyrrole
functionalized Calotropis gigantea fiber. Duan et al. (2019) expressed that within
30 min of the treatment process, more than 75% of enrofloxacin, ciprofloxacin, and
norfloxacin were removed, and the adsorption system reached its equilibrium grad-
ually within 180 min. Similar observations were reported for adsorption of sulfon-
amide antibiotics by amino-functionalized biomass-derived porous carbons (Wang
et al. 2019b), cephalexin antibiotic by activated carbon derived from a single-step
pyrolysis of phosphoric acid-activated chitin (Khanday et al. 2019), fluoroquino-
lone adsorption by chitosan-derived granular hydrogel (Wang et al. 2019a) and tet-
racycline by magnetic graphene oxide (Miao et al. 2019).
Paunovic et al. (2019) studied naproxen removal by microwave functionalized
biochar derived from novel lignocellulosic waste biomass. They noticed that by
increasing the adsorbate concentration from 3.1 to 125.3 ppm, the removal e­ fficiency
decreased. Turk Sekulic et al. (2019a) investigated the adsorption capacity of mul-
tifunctional carbonous adsorbent for drugs adsorption. They observed that the
adsorption capacity increases from 0.499 to 18.981 mg/g for sulfamethoxazole,
from 0.500 to 21.497 mg/g for carbamazepine and from 0.505 to 19.729 mg/g for
ketoprofen when the initial concentration is increased from 1 to 50 ppm (Turk
Sekulic et al. 2019a). A higher driving force at elevated adsorbate concentration was
the main reason for such an increase (Turk Sekulic et al. 2019a).
224 A. Khadir et al.

The initial contaminant concentration also affects the time of the equilibrium
state. Wang et al. (2019a) believed that by increasing the ciprofloxacin and enro-
floxacin concentrations from 10 to 250 mg/L, equilibrium was found to be 30, 60,
and 120 min, respectively. Khanday et al. (2019) also reported similar observations
for cephalexin antibiotic. Hence, to reach a faster equilibrium state the pharmaceu-
ticals concentration would be at minimum. Table 8.6 presented the results of various
studies about the effect of initial pharmaceuticals concentration on adsorption.

Table 8.6 Results obtained from various studies regarding the effect of the initial pharmaceutical
concentrations on the adsorption capacity or the removal efficiency
Initial Adsorption Removal
concentration capacity efficiency
Adsorbent Pharmaceuticals (ppm) (mg/g) (%) Sources
Polyamidoamine/ Clofibric acid 0.05–0.2 – 89–46 Lotfi et al.
silica Diclofenac 0.05–0.2 – 96–55 (2019)
Nanohybrid Ibuprofen 0.05–0.2 – 99–67
Ketoprofen 0.05–0.2 – 98–61
Polypyrrole Enrofloxacin 0–200 0–84 – Duan
functionalized Ciprofloxacin 0–200 0–77 – et al.
Calotropis gigantea Norfloxacin 0–200 0–72 – (2019)
fiber
Functionalized Sulfamethoxazole 1–50 0.49–18.98 – Turk
carbonaceous Carbamazepine 1–50 0.50–21.49 – Sekulic
adsorbent Ketoprofen 1–50 0.50–19.72 – et al.
(2019a)
Amino-­ Sulfadiazine 0–8 0–120 – Khanday
functionalized et al.
porous carbon (2019)
Nanostructured Amoxicillin 60-150 – 92-51 (Abazari
pillar MOF et al.
2019)
Microwave Naproxen 3.1–125.3 7–73 97–23 Paunovic
functionalized et al.
biochar (2019)
Magnetic graphene Chlortetracycline 5–50 20–133 – Miao et al.
oxide (2019)
Activated charcoal Propafenone 0–200 0–172.5 – Zhao et al.
Diphenhydramine 0–200 0–126.7 – (2018)
Propranolol 0–200 0–143.4 –
Thioridazine 0–480 0–338.8 –
Nitrogen-doped Norfloxacin 10–60 91.6–160.2 – Peng et al.
reduced graphene Ketoprofen 10–60 85.4–373.0 – (2018)
oxide/Fe3O4
Chitosan/waste Metamizol 0.25–2.0 1.0–7.6 – Lessa
coffee-grounds Acetylsalicylic 0.25–2.0 1.3–9.9 – et al.
acid 0.25–2.0 1.0–6.3 – (2018))
Acetaminophen 0.25–2.0 1.2–8.2 –
Caffeine
8 A Review on Pharmaceutical Removal from Aquatic Media by Adsorption… 225

8.6.2 Effect of Initial pH

pH is an imperative parameter in adsorption processes since it immensely affects the

surface charge/binding sites of the adsorbent and the ionization degree of the phar-
maceutical compounds (Mirjavadi et al. 2019). For instance, it was proved that the
removal of sulfamethoxazole, carbamazepine, and ketoprofen by a phosphorized
carbonaceous adsorbent was greatly dependent on the operational pH value (Turk
Sekulic et al. 2019a). Similarly, it was claimed that the efficiency of the chitosan-­
based magnetic composite particles in terms of diclofenac sodium and tetracycline
hydrochloride elimination from water was relied on the pH of solution (Zhang et al.
2016b). It seems that pH controls the pharmaceuticals adsorption since it influences
the dominant adsorbent/adsorbate interaction.
The point of zero charge (pHzpc) has been extensively utilized in adsorption stud-
ies for the determination of the mechanism and behavior of the removal pathway. At
pH equal to pHzpc, the surface charge of the material is zero. However, at pHs greater
and lower than pHzpc, the synthesized adsorbent owns negative and positive charge,
respectively (Beheshti et al. 2019). It is fair to suggest that pHs > pHzpc is favorable
for the adsorption of cationic pharmaceuticals. Contrary to this, anionic compounds
are better removed at pHs < pHzpc. Table 8.7 indicates the optimum pH value for the
removal of pharmaceuticals with different adsorbents.
Turk Sekulic et al. (2019b) investigated the removal of ketoprofen by the
phosphorous-­doped microporous carbonous material at various pH values (Fig. 8.5).
It was found that the synthesized carbonous adsorbent had the pHzpc of 4.12. By
increasing the pH value from 2 to 9, the adsorption capacity decreased. The reduc-
tion in adsorption capacity at high pH was attributed to the repulsion force between
the negatively charged adsorbent and the negatively charged adsorbate. At
pH < pHzpc, the adsorption mechanism involved H-bonding and π-π interaction
(Turk Sekulic et al. 2019b).
In another investigation, Reza et al. (2014) employed microwave-assisted acti-
vated bamboo waste as an adsorbent for ibuprofen elimination. It was claimed that
the maximum ibuprofen removal was attained at pH 2-5 (removal efficiency
85.66–97.02%). Ibuprofen is an acidic drug and has the pKa of 4.15, indicating that
at pH higher than 4.15, it acquires a negative charge due to the dissociation of mol-
ecules of this compound. Hence, electrostatic repulsion between adsorbate anions
and the negative surface of the adsorbent led to a reduction in adsorption efficiency
at high pH value (Reza et al. 2014). Similar mechanism was reported by Zhang et al.
(2017a) for adsorption of sulfadiazine by expanded graphite.
Gadipelly et al. (2018) examined the applicability of metal organic framework 5
(MOF5) for the effective adsorption of ciprofloxacin hydrochloride from aqueous
solution over a pH ranged from 3 to 9. They observed that adsorption capacity
increased with the increasing pH and attained a maximum of 87.7 mg/g at pH 5.5,
thereby decreasing on further increment in the pH. Ciprofloxacin hydrochloride
mainly exists as a cation below pH 5.5, an anion above pH 9, and is zwitterion
between pH 5.5 and 9 due to its pKa values of 5.9 and 8.9. MOF5 exhibited a nega-
226 A. Khadir et al.

Table 8.7 The optimum initial pH value for the maximum removal of pharmaceuticals with
different adsorbents
Adsorbent Pharmaceutical Optimum pH Sources
Modified mica and Ibuprofen 4–9 Martín et al.
montmorillonite (2019)
Polyamidoamine/silica Clofibric acid 9 Lotfi et al. (2019)
Nanohybrid Diclofenac
Ibuprofen
Ketoprofen
Multiwalled carbon nanotube Potassium diclofenac 6 Pires et al. (2019)
composite
Phosphorised carbonaceous Sulfamethoxazole 3–5 Turk Sekulic
Carbamazepine No effect et al. (2019a)
Polypyrrole/Calotropis gigantea Enrofloxacin 6 Duan et al.
fiber Ciprofloxacin 8 (2019))
Norfloxacin 8
Powdered zeolites Azithromycin 8 de Sousa et al.
Ofloxacin 6 (2018))
Sulfamethoxazole 2
Magnetic graphene oxide Tetracycline hydrochloride 3.3 Miao et al. (2019)
Oxytetracycline 3.3
Montmorillonite Propranolol 2–9 del Mar Orta
et al. (2019)
Magnetite nanoparticles Acetaminophen 7 Shi et al. (2019)
modified β-cyclodextrin polymer
coupled with KMnO4 oxidation
Goethite Diclofenac 5.23 Zhao et al. (2017)
Activated carbon from spent tea Acetaminophen 3–7 Wong et al.
leaves (2018)
Chitosan/waste coffee-grounds Metamizol 6 Lessa et al.
Acetylsalicylic acid (2018)
Acetaminophen
Caffeine
Polypyrrole functionalized Enrofloxacin 6 Duan et al.
Calotropis gigantea fiber CiprofloxacinNorfloxacin (2019)
Weathered microplastic Oxytetracycline 5 Zhang et al.
polystyrene (2018a)
Magnetic chitosan-g-poly(2-­ Tetracycline 3.3 Lu et al. (2018)
acrylamide-­2-­ Chlorotetracycline
methylpropanesulfonic acid)
Walnut shell-based activated Metronidazole 8 Teixeira et al.
carbon Sulfamethoxazole 5.5 (2019))
Magnetic nanoparticles Levofloxacin 6.5 Al-Jabari et al.
(2019)
Chitosan/waste coffee-grounds Metamizol 6 Lessa et al.
Acetylsalicylic acid (2018)
Acetaminophen
Caffeine
Functional polyaniline/ Meloxicam 2 Dutra et al.
multi-walled carbon nanotube (2018)
8 A Review on Pharmaceutical Removal from Aquatic Media by Adsorption… 227

Fig. 8.5 Fluctuation of the

adsorption capacity toward
ketoprofen removal at
different pH values

tive zeta potential over the studied pH values. Cationic species of the drug were
dominantly removed by the used adsorbent. Electrostatic repulsion force was the
main reason for the reduced adsorption capacity (Gadipelly et al. 2018). However,
in another investigation regarding ciprofloxacin removal by modified waste grape-
fruit peel, it was expressed that ion exchange and π-π interaction were involved in
the adsorption process as well as electrostatic attraction (Fu et al. 2019).

8.6.3 Effect of Temperature

Temperature is another significant factor which mainly influences the nature of the
adsorption process, adsorbate/adsorbent interaction, pharmaceuticals movement,
adsorption rate, and adsorption energy (Li et al. 2019b). Generally, adsorption pro-
cesses are categorized into two different groups: (1) endothermic and (2) exother-
mic. If the adsorption capacity of the synthesized material increases with increasing
temperature then the adsorption is an endothermic. On the other hand, if enhance-
ment of adsorption capacity was observed by lowering the temperature, the process
is exothermic. Table 8.8 shows the results of various studies on the effect of tem-
perature on the pharmaceuticals adsorption by various adsorbents.
Al-Khateeb et al. (2014) studied the removal of the aspirin, acetaminophen, and
caffeine onto graphene nanoplatelets. They inferred that higher adsorption capacity
at lowered temperature may indicate the exothermic nature of the adsorption pro-
cess. The percentage of adsorption of aspirin was decreased from 64.8 to 63.6 and
60.7%, when the solution temperature was raised from 296 to 308, and 323 K,
respectively. For caffeine, the percentage of adsorption decreased from 98.5 to 96.0
and 93.2%. Adsorption of acetaminophen decreased from 90.3 to 84.9 and 79.7%
(Al-Khateeb et al. 2014). Such behavior may be because of the adsorptive forces
reduction between the adsorbent active sites and the pharmaceuticals species.
Table 8.8 The nature of the adsorption process in terms of temperature as well as thermodynamic parameters in each study
228

Adsorbent Pharmaceutical Temperature Process ∆H° ∆S° ∆G° Source

Multi-walled carbon nanotube Potassium diclofenac 25–45 Endothermic 24.71 148.42
−19.52 to Pires et al. (2019)
−22.47
Polypyrrole/multi-walled carbon nanotube Potassium diclofenac 25–45 Endothermic 52.67 246.0 −20.64 to
−25.57
Magnetic graphene oxide Chlortetracycline 283–313 Endothermic 12.3666 46.4173 −0.7406 to Miao et al. (2019)
−2.1331
Tetracycline 283–313 Endothermic 18.9181 67.5944 −0.2735 to
hydrochloride −2.3013
Oxytetracycline 283–313 Endothermic 7.5256 30.0922 −0.9523 to
−1.8551
Commercial organoclay Diclofenac sodium 15–50 Endothermic 112.3 452.6 −16.67 to Maia et al. (2019)
−32.5
Activated carbon Chlorpheniramine 298–308 Endothermic 15.11 75.4 −7.35 to −7.85 (Ali et al. (2019)
Activated carbon Ibuprofen 298–308 Endothermic 18.18 77.16 −4.81 to −5.40
Oxidized activated carbon Chlorpheniramine 298–308 Endothermic 23.52 105.2 −7.82 to −8.58
Oxidized activated carbon Ibuprofen 298–308 Endothermic 22.19 94.92 −6.10 to −6.82
Ethylene diamine to produce basic surface Chlorpheniramine 298–308 Endothermic 18.52 86.1 −7.14 to −7.74
Ethylene diamine to produce basic surface Ibuprofen 298–308 Endothermic 21.20 73.37 −0.66 to −1.35
Ethylamine to produce hydrophobic Chlorpheniramine 298–308 Endothermic 21.41 99.34 −8.19 to −8.88
carbonaceous surface
Ethylamine to produce hydrophobic Ibuprofen 298–308 Endothermic 15.58 61.31 −2.69 to −3.20
carbonaceous surface
Functionalized bean husks Ibuprofen 303–323 96.234 109.111 −26.678 to Bello et al. (2019)
−16.287
Pretreated oat hulls Ciprofloxacin 288–318 Endothermic +17 +163 −29 to −34 Movasaghi et al.
(2019)
A. Khadir et al.
 8

Adsorbent Pharmaceutical Temperature Process ∆H° ∆S° ∆G° Source

Double-oxidized graphene oxide Acetaminophen 283–313 Exothermic −10.84 8.81 −13.36 to Moussavi et al.
−13.64 (2016)
Graphene nanoplatelets Aspirin 296-323 Exothermic −5.42 −13.1 −1.54 Al-Khateeb et al.
Acetaminophen −25.4 −67.3 −5.42 (2014)
Caffeine −46.6 −123.0 −10.2
Amorphous nano-carbon Tetracycline 298–313 Endothermic 52.38 223.39 −14.19 to Wu et al. (2016)
Sulfadiazine 34.94 147.70 −17.54
−9.07 to
−11.28
Sulfamethoxazole 33.43 144.10 −9.51 to
−11.67
A Review on Pharmaceutical Removal from Aquatic Media by Adsorption…
229
230 A. Khadir et al.

Wu et al. (2016) studied the removal of tetracycline and sulfamethoxazole anti-

biotics on amorphous nano-carbon at different temperatures. They noticed that by
increasing the temperature from 298 to 313 K, the adsorption capacity toward tetra-
cycline and sulfamethoxazole increased from 79.85 and 96.67 mg/g to 129.54 and
113.56 mg/g, respectively. It can be deduced that the adsorption capacity was higher
at greater temperature (Wu et al. 2016). This phenomenon may be attributed to the
mobility of the pharmaceutical molecules and an increase in the number of available
active sites of the adsorbent. Furthermore, the increased temperature reduces the
thickness and mass transfer resistance of the boundary layer surrounding the
nanoparticles (Xu et al. 2018).
Interestingly, some researches have expressed that the temperature variations
during the adsorption process had no significant effect on the removal efficiency.
Baccar et al. (2012) studied the adsorption of ibuprofen, ketoprofen, naproxen, and
diclofenac onto a low-cost activated carbon, prepared at the laboratory scale from
olive-waste cake. Identical results were also reported regarding ibuprofen adsorp-
tion by powered activated carbon (Mestre et al. 2007) and paracetamol adsorption
by grape stalk (Villaescusa et al. 2011). It is believed that the process was athermic.
One possible explanation of this behavior is that the molecule drugs are well sol-
vated in their aqueous solution.
Aside from the effect of the temperature on the removal efficiency or the adsorp-
tion capacity, temperature results provide more information regarding thermody-
namic parameters such as Gibbs free energy (ΔG°, kJ/mol), enthalpy (ΔH°, kJ/
mol), and entropy (ΔS°, kJ/mol K) and can be determined by the following
equations:

∆G ° = − RT ln K 0

∆G ° = ∆H ° − T ∆S °
∆S ° ∆H °
ln K 0 = −
R RT
T—the system temperature (K)
R—the universal gas constant (8.314 J/mol K)
K0—is the equilibrium constant
ΔG° is related to spontaneity of the adsorption process. ΔH° can possess two
different values that express the adsorption process as an endothermic or e­ xothermic
process if its value is positive or negative, respectively. Also, the type of the adsorp-
tion, physisorption, or chemisorption might be determined by ΔH°. In fact, physical
adsorption has enthalpy lower than 20 kJ/mol; however, chemical adsorption has
the enthalpy ranging from 80 to 400 kJ/mol. Of course, removal processes having
ΔH° values between 20 and 80 kJ/mol are combination of physical/chemical
adsorption.
8 A Review on Pharmaceutical Removal from Aquatic Media by Adsorption… 231

Miao et al. (2019) studied the adsorption of tetracycline using magnetic graphene
oxide at 283, 298, and 313 K and reported that the adsorption capacity was highest
at 313 K and lowest at 283 K. The results exhibited that the values of ΔG° were
negative (spontaneous process) and keep decreasing with increasing temperature.
The positive values of ΔH° implied that the treatment process was endothermic,
favoring at higher temperatures. Moreover, the positive value of ΔS° indicated that
the randomness at the adsorption solid–liquid interface increased during the adsorp-
tion process.
Nasseh et al. (2019) evaluated adsorption thermodynamics of metronidazole on
a new FeNi3/SiO2/CuS magnetic nanocomposite. The corresponding ΔG° values
were from −19.88 to −26.20 kJ/mol for temperatures from 278 to 323 K, respec-
tively. The values of ΔH° and ΔS° were 0.05 kJ/mol and 82.11 J/mol K, respec-
tively. Endothermicity, spontaneity, and feasibility of the adsorption process were
verified by positive enthalpy and negative Gibbs free energy. The positive value of
entropy variations (ΔS°) revealed that the degree of freedom is magnified in the
solid-liquid interface during the adsorption (Nasseh et al. 2019).
Jodeh et al. (2016) studied the thermodynamic parameters of diclofenac adsorp-
tion from aqueous solution using Cyclamen persicum tubers-based activated car-
bon. The values of ΔG° (−3.04 to −1.15 kJ/mol for 288–318 K), ΔH° (−17.45 kJ/
mol), and ΔS° (−50.08 J/mol K) exhibited that the process was exothermic and
spontaneous. From the value of ΔH° which was less than 40 kJ/mol, it is fair to sug-
gest that the adsorption was physical. In another point of view revealing the same
outcome, the absolute magnitude of ΔG° was between 0 and 20 kJ/mol and the
adsorption could be classified as physisorption type (Gereli et al. 2006; Ahmed
2017a). Negative value of ΔS° suggested that diclofenac removal was enthalpy driven.
Sun et al. (2019) examined the adsorption of nitroimidazole antibiotics from
aqueous solutions on self-shaping porous biomass carbon foam pellets derived from
Vallisneria natans waste. Thermodynamic parameters implied an endothermic
adsorption process and indicated that the randomness of adsorbate at the solid-­
liquid interface was increased. Sun et al. (2019) calculated the activation energy of
adsorption process utilizing the formula below proposed by Arrhenius:

Ea
ln K = ln K 0 −
RT
K—pseudo-second-order rate constant (g/mg min)
Ea—the activation energy (kJ/mol)
The activating energy calculated from the experimental data done by Sun et al.
(2019) was 15.33 kJ/mol, indicating that chemical adsorption was involved in the
adsorption processes (Sun et al. 2019). Normally, the activating energy of physical
adsorption is not more than 4.184 kJ/mol due to the weak van der Waals forces
(Duranoğlu et al. 2012).
232 A. Khadir et al.

8.6.4 Effect of Adsorbent Dosage

Adsorbent dosage is a substantial parameter affecting the capacity of an adsorbent

for a given amount of the adsorbent used during pharmaceuticals removal. In gen-
eral, the removal efficiency of pharmaceutical drugs increase with increasing
amount of adsorbent. This positive fact could be attributed to the number and avail-
ability of sorption sites enhancement by increasing adsorbent dosage (Wong
et al. 2018).
Quercus Brantii(Oak) acorn was utilized as an inexpensive material for omis-
sion of two important drugs, acetaminophen and ibuprofen, from water ways
(Nourmoradi et al. 2018). They noticed that the removal efficiency of acetamino-
phen increased from 10.67 to 89.55% by raising adsorbent dosage from 0.5 to 10
g/L. Similar behavior was observed for removal pathway of ibuprofen. The avail-
ability of higher surface area and empty cavities for drugs at higher adsorbent dos-
age were introduced as the main reason for such behavior (Nourmoradi et al. 2018).
It was seen that increasing the adsorbent dosage from a certain value of more than
5.0 g/L, the removal percentage was not changed significantly (Nourmoradi et al.
2018). Ghemit et al. (2019a) tested the elimination of diclofenac and ibuprofen
from aqueous media by organobentonites. They found that with the enhancement
of the adsorbent mass from 10 to 100 mg the adsorbed amount improved with an
increase in adsorbent dose. Similar observations were reported regarding cipro-
floxacin removal by magnetic Fe3O4/red mud-nanoparticles (Fig. 8.6) (Aydin
et al. 2019a).

Fig. 8.6 The figure indicates that by increasing the adsorbent dosage, the removal efficiency con-
tinuously increased. However, the higher adsorption capacity was attained at the lower adsorbent
dosage
8 A Review on Pharmaceutical Removal from Aquatic Media by Adsorption… 233

Wang et al. (2020) attempted to remove low-concentration antibiotics from aque-

ous solution by regenerable Mg(OH)2. They studied the effect of adsorbent dosage
ranging from 0.1 to 1 g/L. The results indicated that the removal rate of ciprofloxa-
cin decreased from 91.1 to 86%, and the adsorption capacity for ciprofloxacin
decreased from 182.1 to 17.19 mg/g by increasing the adsorbent dosage, respec-
tively. Excess usage of adsorbent may increase the overall cost of the operation
along with lowering adsorption capacity and removal efficiency.

8.7 Adsorption Isotherms

Adsorption isotherm models are essential tools for the evaluation of adsorption
behavior via adsorption. In another words, these models are employed to assess the
surface properties of the adsorbents as well as the interaction between adsorbent and
adsorbate. Adsorption isotherms are based on a relationship between the amount of
pharmaceutical adsorbed per unit weight of the adsorbent and the pharmaceutical
concentration at a constant temperature, under equilibrium state.
Accordingly, various models have been used in extensive studies (Syafiuddin
et al. 2018; Neris et al. 2019). Among them, Langmuir, Freundlich, and Temkin
models are the most common models of adsorption in so many studies.
Langmuir model, a theoretical model originally developed to the adsorption of
gases on a solid material, is valid for monolayer adsorption onto a surface contain-
ing a finite number of identical sites. The model is based on the assumptions that
maximum adsorption corresponds to a saturated monolayer of pharmaceuticals
molecules on the adsorbent surface, that the energy of adsorption is constant. Also,
there are no any lateral forces between the adsorbed molecules. The nonlinear
Langmuir isotherm is given as:

qm K L Ce
qe =
1 + K L Ce

qe—the amount of adsorbate adsorbed at equilibrium (mg/g)

qm—the maximum saturated monolayer adsorption capacity of an adsorbent (mg/g)
KL—the constant related to the affinity between adsorbent/adsorbate (L/mg)
Ce—the adsorbate concentration at equilibrium (mg/L)
Since now, four linearized forms of Langmuir equation have been proposed.
They are shown in:

Langmuir − 1( Hanes − Woolf linearization )

Ce Ce 1  Ce 
= +  vs.Ce 
qe qm qm K L  qe 
234 A. Khadir et al.

Langmuir − 2 ( Lineweaver − Burk linearization )

1 1 1 1 1 1 
= +  vs. 
qe qm qm K L Ce  qe Ce 

Langmuir − 3 ( Eadie − Hoffsiee linearization )

1 qe  qe 
qe = qm −  qe vs. 
K L Ce  Ce 

Langmuir − 4 ( Scatchard linearization )

qe q 
= qm K L − K L qe  e vs.qe 
Ce  Ce 

A mathematical expression developed by Webber and Chakkravorti has been used

to test the favorability of the adsorption process:

1
RL =
1 + K L C0

RL—separation factor and dimensionless

C0—initial concentration of pharmaceutical compounds
The Freundlich isotherm, one of the earliest empirical equations, assumes that
the adsorption occurs on a heterogeneous surface, and the amount that is adsorbed
increases infinitely with an increase in concentration. The model cannot describe
the behavior of the adsorption at very low or very high (saturated state) concentrate
of adsorbate. The nonlinear and linear forms of the Freundlich model can be written
as (Piri et al. 2019):

qe = K F Ce1/ n
1
ln qe = ln K F + ln Ce
n

KF—the Freundlich constant (mg/g)/(mg/L)n

n—the Freundlich intensity dimensionless parameter
For the various studies on the application of various adsorbents for pharmaceuti-
cal removal, it was observed that Langmuir model approximately exhibited better
results than Freundlich models (Table 8.9). This means that drugs elimination via
adsorption generally obey Langmuir assumption.
Wu et al. (2019a) studied the competitive adsorption of antibiotic tetracycline and
ciprofloxacin on montmorillonite. They examined Freundlich, Langmuir, Temkin,
and Dubinin-Radushkevich isotherm models. It was found that Langmuir isotherm
model better described the experimental data in single and mixed system. The R2
8 A Review on Pharmaceutical Removal from Aquatic Media by Adsorption… 235

Table 8.9 The best-fitted isotherm and kinetic model for various studies using different adsorbents
for the removal of distinctive pharmaceuticals
Adsorbent Pharmaceuticals Isotherm Kinetic Sources
Modified mica and Ibuprofen Langmuir/ Pseudo Martín et al.
montmorillonite Freundlich second (2019)
order
Polypyrrole/multiwalled Diclofenac Langmuir– Pseudo Martín et al.
carbon nanotube Freundlich second (2019)
order
Polypyrrole/Calotropis Ciprofloxacin Redlich-Peterson Pseudo Duan et al.
gigantea fiber Enrofloxacin second (2019)
order
Powdered zeolites Azithromycin Freundlich Pseudo de Sousa
Ofloxacin second et al. (2018)
Sulfamethoxazole order
Montmorillonite Tetracycline Langmuir Pseudo Wu et al.
Ciprofloxacin second (2019a)
order
Carbon aerogels Terramycin – Pseudo Tian et al.
second (2019)
order
Magnetic graphene oxide Tetracycline Freundlich Pseudo Miao et al.
second (2019))
order
Montmorillonite Propranolol Freundlich/ Pseudo del Mar Orta
Dubinin-­ second et al. (2019)
Radushkevich order
Magnetite nanoparticles Acetaminophen Langmuir Pseudo Shi et al.
modified β-cyclodextrin second (2019)
order
Commercial organoclay Diclofenac Temkin/ Pseudo Maia et al.
sodium Freundlich first (2019)
order
Goethite Diclofenac – Pseudo Zhao et al.
second (2017)
order
Activated carbon from spent Acetaminophen Langmuir Pseudo Wong et al.
tea leaves second (2018)
order
Polyamidoamine/silica Clofibric acid Langmuir Pseudo (Lotfi et al.
Nanohybrid Diclofenac second 2019)
Ibuprofen order
Ketoprofen
Activated charcoal Propafenone Langmuir – Zhao et al.
Diphenhydramine (2018)
Propranolol
Thioridazine
(continued)
236 A. Khadir et al.

Table 8.9 (continued)

Adsorbent Pharmaceuticals Isotherm Kinetic Sources
Functionalized carbonaceous Sulfamethoxazole Langmuir Pseudo Turk Sekulic
adsorbent Carbamazepine second et al. (2019a)
Ketoprofen order
Microwave functionalized Naproxen Langmuir Pseudo Paunovic
biochar derived from second et al. (2019)
lignocellulosic waste biomass order
Fe3O4@SiO2/SiCRG Metoprolol Langmuir/Toth – Soares et al.
(2016)
Activated carbon of babassu Acetylsalicylic Sips Pseudo Hoppen et al.
coconut mesocarp acid second (2019)
order
Iron oxide-mesoporous silica Acetylsalicylic Langmuir – Teo et al.
MCM-41 acid (2016)
Metal-organic frameworks Acetic acid Freundlich Pseudo Zhang et al.
second (2016a)
order
Activated carbons Acetaminophen Langmuir – Rey-Mafull
et al. (2014)
Activated carbon prepared Paracetamol Langmuir Pseudo George Nche
from rice husk second et al. (2017)
order
Single walled carbon Amoxicillin Langmuir Pseudo Balarak et al.
nanotubes second (2016)
order
Multi-walled carbon nanotubes Ciprofloxacin Dubinin-­ Pseudo Yu et al.
with different oxygen contents Radushkevich second (2016)
order
Magnetic multi-walled carbon Amoxicillin Langmuir – Fazelirad
nanotube et al. (2015)
Graphene oxide Tetracycline Langmuir Pseudo Gao et al.
second (2012)
order
Magnetic chitosan-g-poly(2-­ Tetracycline Langmuir Pseudo Lu et al.
acrylamide-­2-­ Chlorotetracycline second (2018)
methylpropanesulfonic acid) order
Pretreated oat hulls Ciprofloxacin Freundlich Pseudo Movasaghi
second et al. (2019)
order
A novel core-shell-structure Sulfamethoxazole Freundlich Pseudo Pamphile
activated carbon second et al. (2019)
order
Auricularia-based magnetic Langmuir Pseudo Xie et al.
porous carbon second (2019)
order
Nitrogen-functionalized Carbamazepine Langmuir Pseudo Prarat et al.
carbon Clofibric acid Freundlich second (2019)
Oxytetracycline Freundlich order
8 A Review on Pharmaceutical Removal from Aquatic Media by Adsorption… 237

value, the maximum saturated monolayer adsorption capacity, and experimental

maximum adsorption capacity for tetracycline were 0.99, 1.06, and 1.00 mmol/g,
respectively. Freundlich isotherm was also reported in the literature. It was remarked
that tetracycline removal by magnetic graphene oxide was well-­described by the
Freundlich model than Langmuir model (Miao et al. 2019). It seems that the type of
adsorbent is important for the determination of the best isotherm model.
Moreover, some researches have expressed more than one isotherm as the best
model describing the removal process. Martin et al. (2019), for instance, believed
that omission of ibuprofen from aqueous media by montmorillonite is fitted well
with both Freundlich and Langmuir equations since they revealed high R2 values
(greater than 0.999). Maia et al. (2019) showed that the removal pathway of diclof-
enac sodium by commercial organoclay was governed by Freundlich at 15 and
30 °C; however, at 50 °C Temkin was more practical in adsorption process descrip-
tion. Chemisorption was assumed as the main removal mechanism.
Dubinin-Radushkevich model was also employed in some studies. Dubinin-­
Radushkevich, a semiempirical temperature-dependent model, is based on the fact
that adsorption mechanism is pore filling, following Gaussian energy distribution
onto heterogeneous surfaces. Dubinin-Radushkevich isotherm is expressed as follows:
2
qe = qDR e − KDR ε

The linear form of the presented model is:

ln qe = − K DR ε 2 + ln qDR

 1 
ε = RT ln  1 + 
 Ce 

qDR—the adsorption capacity (mg/g)

KDR—is a constant related to the sorption energy (mol2/kJ2)
ε—the Polanyi potential
R—the gas constant (8.314)
Yu et al. (2016) employed multi-walled carbon nanotubes with different oxygen
contents for ciprofloxacin removal. They stated that Dubinin-Radushkevich and
Langmuir model were revealed as the best model for describing the adsorption
­process (Yu et al. 2016). Also, they calculated the average free energy of adsorption
by using the below formula.

1
E=
2 K DR

E—the average (mean) adsorption energy (kJ/mol)

Yu et al. (2016) believed that the removal process was chemisorption since the
adsorption energy was in the range of 20–40 kJ/mol. Generally, physical adsorption
238 A. Khadir et al.

exists in the adsorption process at the adsorption energy of lower than 8 kJ/mol, while
chemical adsorption such as ion exchange owns the adsorption energy of 8–16 kJ/
mol (Tahir and Rauf 2006). In a similar study concerning diclofenac sodium removal
by commercial organoclay, the adsorption energy at 30 and 50 °C was found to be
8.53 and 10.96 kJ/mol, suggesting a chemical adsorption process (Maia et al. 2019).

8.8 Adsorption Kinetics

For the implementation of an industrial scale adsorption unit, it is necessary to

reveal the controlling mechanism for the pollutant removal by means of kinetics
models. The adsorption kinetics exhibit the rate of adsorbate attachment to the sur-
face of the adsorbent. Many models have been suggested to find the best order of the
reaction in order to design an optimum treatment unit. Accordingly, Lagergren
pseudo-first-order model and Lagergren pseudo-second-order model are the two
most studied models in countless studies.
The Lagergren pseudo-first-order kinetic rate equation is based on the premise
that the adsorption rate is corresponding to the difference between the adsorbed
amount and the equilibrium adsorption capacity and can be written as follows:

dqt
= K1 ( qe − qt )
dt

K1—the rate constant of the pseudo first-order model (min−1)

Integrating the equation for boundary conditions (t = 0, qt = 0 and t = t, qe = qt)
leads to the following linear equation:

 Kt 
ln ( qe − qt ) = ln qe − K1t  Or log ( qe − qt ) = log qe − 1 
 2.303 

which can be rearranged in a nonlinearized form:

(
qt = qe 1 − e K1t )
The differential equation of Lagergren pseudo-second-order model is generally
known and described as:

dqt
= K 2 ( qe − qt )
2

dt

K2—the rate constant of the pseudo second-order model (g/mg min)

The integration of this equation for the boundary conditions (t = 0, qt = 0 and
t = t, qe = qt) gives the formula below:
8 A Review on Pharmaceutical Removal from Aquatic Media by Adsorption… 239

qe2 Kt
qt =
1 + qe t

Equation below can be rearranged to obtain the linear form:

t 1 t
= 2
+
qt Kqe qe

Table 8.9 exhibits the best fitting model for the removal of pharmaceutical com-
pounds by various types of adsorbents. As can be observed from Table 8.9,
adsorption kinetics of almost all of the pharmaceuticals is nicely described by
pseudo second order. For instance, Tian et al. (2019) used carbon aerogel to
remove antibiotics (Tian et al. 2019). They expressed that the adsorption kinetics
was satisfactory followed by pseudo second order and adsorption process was
mainly based on the chemical adsorption with the assistance of physical adsorp-
tion. Lotfi et al. (2019) believed that pseudo second order was more suitable than
pseudo first order and intraparticle diffusion to expound the kinetics of clofibric
acid, diclofenac, ibuprofen, and ketoprofen by polyamidoamine/silica nanohy-
brid. Other studies complying pseudo second order are listed in Table 8.9. These
evidences propose that the adsorption of pharmaceuticals is chiefly governed by
chemisorption via exchanging or sharing electrons between adsorbate and
adsorbent.

8.9 Adsorbents for Pharmaceuticals Removal

To date, so many adsorbents with various advantages and disadvantages have been
proposed for removal of pollutants. In this review, the following materials are con-
sidered since they are approximately famous and extensively employed in countless
studies.

8.9.1 Activated Carbon

Among many materials that have been suggested for adsorption processes, activated
carbon owing to its large specific surface, its micropore structure, unique surface
chemistry, tunable pore structure, good thermostability at high temperatures in inert
or reduction atmospheres, low acid-base reactivity and high adsorption capacity
offers a great potential for the removal of pharmaceutical compounds (Ao et al.
2018). Table 8.10 shows several studies used different activated carbon for pharma-
ceutical removal as well as the maximum adsorption capacity. Figure 8.7 shows a
simple procedure for production of activated carbon.
240 A. Khadir et al.

Table 8.10 The utilization of different activated carbon for the removal of various pharmaceutical
compounds
Adsorption
capacity
Adsorbents Origin Pharmaceuticals (mg/g) Sources
Commercial activated – Diclofenac 50 Varga et al.
carbon Naproxen 80 (2019)
Pulverized activated – Diclofenac 320 Varga et al.
carbon Naproxen 280 (2019)
Powdered activated Vegetable Carbamazepine 242 Delgado et al.
carbon Sildenafil citrate 341 (2019)
Activated carbon – Ibuprofen 160 Bahamon and
Naproxen Diclofenac 241 Vega (2017)
188
NiFe2O4/activated Vegetable Ibuprofen 261.35 Fröhlich et al.
carbon Ketoprofen 97.75 (2019)
Activated carbon with Shell of Aegle Ibuprofen 12.7 Chakraborty
steam preparation Marmelos et al. (2018)
Thermally activated Bovine bone Ibuprofen 56.8 Cazetta et al.
carbon preparation (2016)
Chemically activated Sisal (Agave Ibuprofen Iopamidol 325 Mestre et al.
high grade sisalana) 1097 (2019)
nanoporous carbons residues
biomass
Surface functionalized Date palm Chlorpheniramine 455 Ali et al. (2019)
activated carbons leaflets
A novel core-shell-­ A coal power Sulfamethoxazole 95.5 Pamphile et al.
structure activated plant (2019)
carbon
Activated carbon-­ Waste tires Ciprofloxacin 93 Mogolodi
decorated Danofloxacin 99 Dimpe and
polyacrylonitrile Enrofloxacin 112 Nomngongo
nanofibers (2019)
Auricularia-based Auricularia Tetracycline 397.25 Xie et al. (2019)
magnetic porous
carbon
Ultrafine magnetic – Carbamazepine 62.7 Shan et al.
biochar tetracycline 94.2 (2016)
Ultrafine magnetic – Carbamazepine 135.1 Shan et al.
Activated carbon tetracycline 45.3 (2016)
Nitrogen-­ Pomelo peel Carbamazepine 216.2 Prarat et al.
functionalized carbon waste Clofibric acid 19.4 (2019)
Oxytetracycline 64.9
Activated carbon Bamboo Ciprofloxacin 615 Wang et al.
(2015)
8 A Review on Pharmaceutical Removal from Aquatic Media by Adsorption… 241

Fig. 8.7 It shows that the production of the activated carbon is constituted of four steps that the
most important ones are impregnation and activation

Varga et al. (2019) employed commercial activated carbon for pharmaceutical

adsorption. In their studies, the experimental maximal adsorption capacity of 50 and
80 mg/g was found for diclofenac and naproxen, respectively. Furthermore, they
pulverized and sieved activated carbon through a 0.1 mm mesh size and reach the
adsorption capacity of 320 and 280 mg/g for diclofenac and naproxen, respectively.
Availability of the pores of granules was one of the main factors influencing adsorp-
tion (Varga et al. 2019). Delgado et al. (2019) reported that powdered active carbon
is more effective that granular active carbon for pharmaceuticals removal since it
has greater surface area with the value of 1328 m2/g and 956 m2/g, respectively.
Also, micro-grain activated carbon, characterized by having a particle size of
200–600 μm (between PAC (<100 μm) and GAC (>800 μm)), was utilized for drug
removal (Alves et al. 2018).
Magnetic adsorbents have recently been proposed in adsorption process due to
their easy separation and better adsorption performance (Mollahosseini et al. 2019).
Fröhlich et al. (2019) stated NiFe2O4/activated carbon composite as a promising
magnetic adsorbent for elimination of ibuprofen and ketoprofen pharmaceuticals
from water. The highest adsorption capacity according to Sips model was found to
be 261.35 for ibuprofen and 97.75 for ketoprofen with initial concentration of
0–100 ppm. Also, auricularia-based magnetic porous carbon was developed by Xie
242 A. Khadir et al.

et al. (2019) via facile simultaneous activation and magnetization strategy. They
attained the surface area and adsorption capacity of 823.2 m2/g and 397.25 mg/g for
tetracycline, respectively. The interaction mainly involved π-π interaction, hydrogen
bond, and electrostatic attraction. Furthermore, Jiang et al. (2019) prepared separa-
ble mesoporous-activated carbons from brown coal with Fe3O4.
Moreover, ball milling is another technique to prepare materials with greater
adsorption capacity. Accordingly, Shan et al. (2016) reported an ultrafine magnetic
biochar and activated carbon for pharmaceutical adsorption. The biochar/Fe3O4 had
the greatest adsorption capacity of 62.7 mg/g for carbamazepine and 94.2 mg/g for
tetracycline, while values obtained for activated carbon/Fe3O4 were 135.1 mg/g for
carbamazepine and 45.3 mg/g for tetracycline, respectively. Similar observations
were also reported by Wang et al. (2011).

8.9.2 Graphene-Based materials

Graphene, a one-atom-thick and two-dimensional (2D) layer of sp2-bonded carbon

with a molecule bond length of 0.142 nm and an interplanar spacing of 0.123 nm,
has gained many researchers attention due to its significant properties such as excel-
lent mechanical, electrical, thermal, optical properties, and very high specific sur-
face area (Al-Khateeb et al. 2014; Iannazzo et al. 2018).
Graphene atoms are able to contact with pollutant molecules from both sides that
is favorable for adsorption processes. However, surface hydrophobicity and easy
agglomeration in aqueous solution are the main limitations of graphene that neces-
sitate the modification of this material (Li et al. 2019b). Zhu et al. (2015) studied the
removal of ciprofloxacin by graphene and found that the maximum adsorption
capacity of 322.6 mg/g was achieved at pH 4 and equilibrium time of 0.05 h. The
removal process followed Langmuir and pseudo second order assumptions.
Graphene oxide (GO) and reduced graphene oxide (rGO) are of two main deriva-
tions of graphene. rGO is obtained from GO reduction. GO was employed for
removal of sulfamethoxazole, ciprofloxacin, levofloxacin, and tetracycline that
revealed the maximum adsorption capacity of 240, 379, 256.6, and 313 mg/g,
respectively (Çalışkan and Göktürk 2010; Gao et al. 2012; Dong et al. 2016).
The combination of magnetic nanoparticles and graphene has recently attracted
great interest. It has been proven that the introduction of Fe3O4 nanoparticles in gra-
phene structure results in better performance. It was observed that the adsorption
capacity of graphene/Fe3O4 (423 mg/g) was 1.35 times higher than graphene
(313 mg/g) for tetracycline removal (Zhang et al. 2017b). In another study, magneti-
cally separable Fe/Cu bimetallic nanoparticles were supported by GO for removal of
pharmaceuticals compound (Tabrizian et al. 2019). Figure 8.8 shows the adsorption
procedure and SEM images of the prepared materials. Under the optimum conditions
(pH 6.5, contact time 0.25 h, adsorbent dosage 0.25 g/L), the maximum adsorption
capacity of 201.9 mg/g was achieved, following Freundlich isotherm equation.
8 A Review on Pharmaceutical Removal from Aquatic Media by Adsorption… 243

Fig. 8.8 The SEM images of F/Cu and Fe/Cu-graphene oxide composite. Reprinted with
­permission of Elsevier from (Tabrizian et al. 2019)

The utilization of the magnetic graphene-based adsorbents was further studied

by the researchers. In paper manufacturing, textile printing, photographic, and
leather processing industries, thiourea dioxide has been widely employed as a
strong reductant. Yang et al. (2017) used thiourea dioxide/reduced magnetic gra-
phene oxide for the decontamination of tetracycline. They observed the maximum
adsorption capacity of 1233 mg/g under pH 4, and adsorbent dosage 0.07 g/L. The
removal process was governed by pseudo second-order and Langmuir models.
Results indicated that higher temperature favored pharmaceutical adsorption, sup-
porting that the adsorption was spontaneous and endothermic. Also, the presence of
NaCl as the ionic strength in the solution facilitated the adsorption process, and the
optimum adsorption capacity was obtained when the NaCl concentration was higher
than 0.001 M.

8.9.3 Chitosan and Its Composites

Chitosan, composed of randomly distributed (1–4)-linked 2-amino-2-deoxy-β-d-

glucopyranose units, is the second most abundant naturally available biopolymer,
and has high affinity to adsorb different pollutants from aqueous solution. Properties
such as low price and abundance, antibacterial property, non-toxicity, biocompati-
bility, biodegradability, macromolecular structure, hydrophilicity, cationicity,
active sites, and high adsorption capability have made it as a suitable alternative
(Vakili et al. 2019). Chitosan can be obtained by simple deacetylation of chitin as
shown in Fig. 8.9. Since chitosan has high contents of amino and hydroxy func-
tional groups, electrostatic interaction, ion exchange, chelation, and ion pair forma-
tion might be introduced as the main adsorption mechanisms. Table 8.11 reveals
244 A. Khadir et al.

Fig. 8.9 It shows the procedure of chitosan from shrimps, crab, and shell wastes. Briefly, chitosan
is obtained from the deacetylation of chitin

the utilization of chitosan and its composites for the removal of various
pharmaceuticals.
However, separation of powdery chitosan from water requires high-speed cen-
trifugation, which limits its large-scale applications. Liang et al. (2019) developed a
magnetic composite based on amine-functionalized chitosan and magnetic nanopar-
ticles to remove diclofenac sodium from water (Liang et al. 2019). TEM results
revealed that the adsorbent had the mean diameter of 25 nm. The maximum adsor-
bent capacity of 469.48 mg/g was attained and the removal process was governed
by Langmuir and pseudo second-order models. It was observed that hydrogen bond-
ing was an important removal pathway.
Sometimes raw biopolymers including chitosan do not have an acceptable per-
formance for particular pollutants unless they are modified. In this direction, chito-
san/biochar hydrogel beads composite was employed for drug removal (Afzal et al.
2018). Figure 8.10 shows the SEM image of biochar before modification (a) and
8 A Review on Pharmaceutical Removal from Aquatic Media by Adsorption… 245

Table 8.11 The utilization of chitosan and its composites for the removal of various
pharmaceutical compounds
Adsorption
Adsorbents Pharmaceuticals capacity (mg/g) Sources
Magnetic amine-functionalized Diclofenac sodium 469.48 Liang et al.
chitosan (2019)
Magnetic activated carbon/chitosan Ciprofloxacin 90.10 Danalıoğlu et al.
Erythromycin 178.57 (2017)
Amoxicillin 526.31
Chitosan/biochar hydrogel beads Ciprofloxacin 36.72 Afzal et al.
(2018)
Chitosan derived granular hydrogel Ciprofloxacin 267.7 Wang et al.
Enrofloxacin 387.7 (2019a)
Chitosan/waste coffee-grounds Acetylsalicylic acid 9.92 Lessa et al.
Acetaminophen 7.52 (2018)
Caffeine 8.21
Chitosan–ethylene glycol hydrogel Perfluorooctanoic 1275.9 Long et al.
acid (2019)
ZnFe2O4/chitosan Diclofenac 188 dos Santos et al.
(2019)
Bilayer amino-functionalized Diclofenac 444.44 Hu et al. (2019)
cellulose nanocrystals/chitosan
Magnetic genipin-cross-linked Tetracycline 473.28 Liu et al. (2019)
chitosan/graphene oxide-SO3H

Fig. 8.10 The SEM images of biochar and chitosan/biochar composite. Reprinted with permis-
sion of Elsevier from (Afzal et al. 2018)

after modification with chitosan (b). It is obvious that various pores and sites are
formed after modification which is beneficial in terms of pollutant removal. The
maximum uptake capacity of 36.72 mg/g for ciprofloxacin was achieved thorough
π-π electron donor-acceptor interaction, hydrogen bonding, and hydrophobic inter-
action at pH 3.
In view of environmental decontamination and protection, chitosan-based wastes
have also been suggested. Waste coffee-grounds, for instance, remained after coffee
dripping that need large quantity of oxygen for full decomposition. Lessa et al.
246 A. Khadir et al.

(2018), for the first time, utilized chitosan/waste coffee-grounds composite for
pharmaceutical adsorption. Besides the fact that the synthesized adsorbent exhib-
ited a suitable performance and it was cost-effective and eco-friendly, the mechani-
cal properties of chitosan were enhanced after modification. Formerly, the
application of chitosan was limited because of its low mechanical strength and
deformation (Crini 2006).
Chitosan has low stability at strong pH changes that impede the applications of this
material. To overcome this issue as well as mechanical problems, crosslinking, impreg-
nation, and grafting techniques were suggested by the researchers. Glutaraldehyde,
epichlorohydrin, ethylene glycol diglycidyl ether, and tripolyphosphate are the well-
known cross-linking agents. dos Santos et al. (2019) used zinc ferrite as the core mate-
rial and chitosan as the external layer by means of glutaraldehyde.

8.9.4 Carbon Nanotube

Carbon nanotubes (CNTs) have gained considerably high attention since its inven-
tion by Iijima in 1991. CNTs possess unique properties such as high surface area,
porous structure, hydrophobic nature, tunable surface chemistry, thermal and chem-
ical stability and mechanical properties make CNTs as a distinctive material for
water purification (Anjum et al. 2019). They consist of one or more graphene sheets
wrapped around themselves to form a cylindrical shape with a length of more than
20 μm and a radius of less than 100 nanometer (Fiyadh et al. 2019). Depending on
the side walls configuration, CNTs have two types: single-walled carbon nanotubes
(SWCNTs, contain one graphene sheet) and multi-walled carbon nanotubes
(MWCNTs, contain more than one graphene sheet). Figure 8.11 illustrates the
SWCNTs and MWCNTs.
Since now, various pharmaceuticals compounds have been removed by CNTs
especially with MWCNTs (Table 8.12). Ncibi and Sillanpää (2017) compared the
removal of carbamazepine and dorzolamide from aqueous solutions using mesoporous-­
activated carbons and MWCNTs. They found that for both drugs MWCNTs exhibited
higher adsorption capacity of 224.6 and 78.8 mg/g, respectively. Also, MWCNTs had
better performance than bentonite clay, zeolite, rice straw, Fe3O4 nanoparticles, sew-
age sludge/fish waste, and activated carbons from potato peels.
Similar to chitosan and activated carbon, CNTs were also integrated with mag-
netic nanoparticles. Bhatia et al. (2019) conducted a research to compare the
­applicability of MWCNTs and MWCNTs/Fe3O4 nanocomposite. They reported
that the adsorption capacity of 671 and 1234 mg/g for MWCNT and MWCNT/
Fe3O4 was found for isonicotinic acid removal, respectively. In fact, the authors
proved that the presence of magnetic particles in the nanocomposite not only pro-
vides a better situation for separation of the spent adsorbent but also increases the
adsorption capacity.
In recent years, the modification of CNTs with conducting polymers has been
conducted in several investigations. Pires et al. (2019) formed composite named
8 A Review on Pharmaceutical Removal from Aquatic Media by Adsorption… 247

Fig. 8.11 The structure of single-walled carbon nanotubes and multi-walled carbon nanotubes

polypyrrole/MWCNTs for the removal of a non-steroidal anti-inflammatory drug.

Some features of polypyrrole such as low cost, environmental stability, non-toxic
nature, and facile synthesis via chemical and electrochemical methods make it
stands out among the other conducting polymers. The BET analysis proved that
the surface area of MWCNTs increased from 277.5 to 541.2 m2/g after the addi-
tion of polypyrrole. In the case of adsorption capacity, the polypyrrole/MWCNTs
(229.39 mg/g) revealed a higher value than pristine MWCNTs (59.67 mg/g).
In a similar study concerning CNTs modification with conducting polymers,
Dutra et al. (2018) used functional polyaniline/multi-walled carbon nanotube com-
posite for pharmaceutical elimination. Maximum meloxicam removal was achieved
at pH 2 and contact time 6 min. Interestingly, Avelar Dutra et al. (2017) also did
another research for removal of meloxicam by polyaniline-deposited cellulose fiber
composite and reported that the highest adsorption capacity was arrived at 4 min of
contact time. It is fair to suggest that polyaniline may lead to a rapid adsorption.
Metal-organic frameworks (MOFs), known as coordination polymers and a class
of highly ordered porous crystalline hybrid material, were also used for CNTs mod-
ification with the aim of greater CNTs application. Xiong et al. (2018) proposed
multi-walled carbon nanotube functionalized MIL-53(Fe) as a new adsorbent for
tetracycline antibiotics removal. BET analysis showed that the surface area of pris-
tine MIL-53 (Fe) and MWCNTs was 52.18 and 136.99 m2/g, respectively; however,
of MWCNTs/MIL-53 (Fe) it was 60.17 m2/g. The results showed that adsorption
capacity of MWCNTs/MIL-53 (Fe) for tetracycline antibiotics was at least 1.2
times higher than single MWCNTs. In addition, π–π interaction between adsorbent
and adsorbate played an important role in the adsorption process.
248 A. Khadir et al.

Table 8.12 The utilization of carbon nanotubes and its composites for the removal of various
pharmaceutical compounds
Adsorption
Adsorbents Pharmaceuticals capacity (mg/g) Sources
Multiwalled carbon Carbamazepine 224.6 Ncibi and
nanotubes Dorzolamide 78.8 Sillanpää
(2017)
Single walled carbon Carbamazepine 130 Lerman et al.
nanotube (2013)
Multiwalled carbon Carbamazepine 441.4 Oleszczuk et al.
nanotubes (10–20 nm outer (2009)
diameters)
Multiwalled carbon Isonicotinic acid 671 Bhatia et al.
nanotubes (2019)
Multiwalled carbon Isonicotinic acid 1234
nanotubes/Fe3O4
Multiwalled carbon Ciprofloxacin 200 Yu et al. (2016)
nanotubes
Carbon dot magnetic carbon Carbamazepine 65 Deng et al.
nanotubes (2019)
Functional polyaniline/ Meloxicam 221.2 Dutra et al.
multiwalled carbon nanotube (2018)
Multiwalled carbon nanotube Potassium diclofenac 59.67 Pires et al.
Polypyrrole/multiwalled Potassium diclofenac 229.39 (2019)
carbon nanotube
Multi-walled carbon nanotube Tetracycline 364.37 Xiong et al.
functionalized MIL-53(Fe) Oxytetracycline 325.59 (2018)
chlortetracycline 180.68
Single-walled Oxytetracycline 554 Ncibi and
Carbon nanotube Ciprofloxacin 721 Sillanpää
Double-walled carbon Oxytetracycline 507 (2015)
nanotube Ciprofloxacin 605
Multi-walled carbon nanotube Oxytetracycline 391
Ciprofloxacin 475
Multiwall carbon nanotubes Sulfamethoxazole 3.03 Wang et al.
(2017)

8.9.5 Clay and Zeolite Nanocomposites

Clay, a small fine-grained natural particle on the surface of the earth (<2 μm), is
mainly composed of silica, alumina, water, and weathered rock having different
layered structures (Uddin 2017). Kaolinite, montmorillonite, and bentonite are the
main types of clay minerals. The popularity of clay minerals is because of their
inexpensiveness, accessibility, vast effective area, mechanical strength, high swell-
ing capacity, layered structure, harmlessness, and ion exchange capability. Ions H+,
K+, Na+, Ca2+, Mg2+, NH+4, Cl−, SO2− 4
, PO3−
4
, and NO3− are usually found on the
surface of the clay (Ngulube et al. 2017). Commonly, pollutant elimination by clay-­
based adsorbents is eventuated by the contribution of the surface of the adsorbent,
8 A Review on Pharmaceutical Removal from Aquatic Media by Adsorption… 249

the edge of the plates and the available active sites situated between the layers (Chen
et al. 2016).
Waste-based materials have gained much attention recently because they are
readily available and reuse of them is profitable in terms of clean environment.
Ashiq et al. (2019) tried to remove ciprofloxacin from water ways by developing a
composite based on the municipal solid waste biochar/bentonite. They reported the
maximum adsorption capacity of 190 mg/g, which was approximately 40% higher
than raw biochar. They proposed the following equations for ciprofloxacin removal
at acidic conditions:

H + + R NH → R NH +2

R − NH +2 + M − → RNH 2 M

R— the group represented of ciprofloxacin

M—bentonite group
In another study, norfloxacin removal was studied by attapulgite-biochar com-
posites derived from potato stem and natural attapulgite (Li et al. 2017). Figure 8.12
shows the synthesis procedure and SEM images of the prepared material. Batch
sorption experiment indicated that the maximum adsorption capacity of attapulgite-­
biochar composites (5.24 mg/g) was 1.68 times higher than pristine biochar, so
modification process was successful. It is believed that the attapulgite particles on
the biochar surface served as available vacant sorption sites and interacted with the
drug through electrostatic interactions. In addition, norfloxacin was studied by
montmorillonite-biochar and had the adsorption capacity of 25.53 mg/g (Zhang
et al. 2018b). Higher capacity of montmorillonite-biochar than attapulgite-biochar
may be attributed to N2 adsorption-desorption analysis. Montmorillonite/biochar
has the surface area and pore volume of 112.6 m2/g and 0.604 cm3/g; however of
attapulgite-biochar they were 90.40 m2/g and 0.1225 cm3/g, respectively. Also,
montmorillonite itself was employed for propranolol adsorption (del Mar et al. 2019).
Some researchers have focused on montmorillonitemodification to increase the
applicability of these materials for a wider range of pollutant removal. Hydroxyapatite
(Ca10(OH)2(PO4)6), similar to inorganic components of the bone matrix and the
teeth, has been used for pollutants adsorption. Accordingly, hydroxyapatite/clay
was synthesized with the aim of tetracycline removal (Ersan et al. 2015).
Hydroxyapatite/clay showed the surface area of 43.07 m2/g and total pore volume
of 0.33 cm3/g with the maximum adsorption capacity of 76.02 mg/g which was
higher than similar studies with various adsorbents like montmorillonite (54 mg/g)
and kaolinite (4.32 mg/g) (Figueroa et al. 2004; Li et al. 2010).
Zeolites are environmentally microporous compatible crystalline alumino-­
silicates in a tetrahedral structure, which are linked together by oxygen atoms. The
pores of the molecular size are between 0.5 and 1.2 nm. Zeolites are widely used in
water/wastewater treatment due to their properties such as low cost, availability,
cation exchange capability, high degree of hydration/dehydration, low density, and
good crystal stability (Wen et al. 2018). Concerning the ratio of the silica to alumi-
num ratio (Si/Al ratio), the low-silica and high-silica zeolites are prepared with Si/
250 A. Khadir et al.

Fig. 8.12 (a) The synthesis procedure of clay/biochar composite production and (b) the SEM
images of the prepared materials. Reprinted with permission of Elsevier from (Li et al. 2017)

Al lower than 2 and up to several thousands, respectively (Jiang et al. 2018). There
are 194 unique zeolite frameworks and over 40 naturally occurring zeolites
(Ozekmekci et al. 2015).
Researches on the synthesis of magnetic nanoparticles based on zeolite have
been undertaken. Natural zeolite and natural zeolite coated with magnetic Fe3O4
nanoparticles were investigated in terms of cephalexin removal (Mohseni-Bandpi
et al. 2016). Zeolite/Fe3O4 (24.9 mg/g) was found to have a higher adsorption capac-
ity than pristine natural zeolite (14.1 mg/g). It was observed that the adsorption
process was non-spontaneous and exothermic, following Langmuir and pseudo
second-order models. In comparison with other adsorbents for cephalexin adsorp-
tion, zeolite/Fe3O4 revealed satisfactory results. For instance, activated carbon, ben-
tonite, activated carbon nanoparticles, and MnO2-coated zeolite showed the
maximum adsorption capacity of 17.361 mg/g (Al-Khalisy et al. 2010), 10.384 mg/g
(Al-Khalisy et al. 2010), 7.080 mg/g (Pouretedal and Sadegh 2014), and 24.5 mg/g
(Samarghandi et al. 2015), respectively.
In another study, natural clinoptilolite zeolite was treated by mechanochemistry
(Chen et al. 2019c). In fact, mechanochemistry is a facile free-solvent method to change
the physical and chemical properties of the material without the need of special tools or
reagents (Majano et al. 2014). The procedure was initiated by milling the humic acid
and natural clinoptilolite zeolite in a planetary ball mill at room temperature. The maxi-
mum adsorption capacity of 47.68 mg/g was attained. Table 8.13 shows the usage of
clay, zeolite, and their composites for the removal of various pharmaceutical compounds.
8 A Review on Pharmaceutical Removal from Aquatic Media by Adsorption… 251

Table 8.13 The utilization of clay, zeolite, and their composites for removal of various
pharmaceutical compounds
Adsorption
Adsorbents Pharmaceuticals capacity (mg/g) Sources
Magnetic polymer clay Atenolol 15.6 Arya and Philip
Ciprofloxacin 39.1 (2016)
Gemfibrozil 24.8
Montmorillonite Tetracycline 1 mmol/g Wu et al. (2019a)
ciprofloxacin 1.01 mmol/g
Clay/biochar Norfloxacin 5.24 Li et al. (2017)
Montmorillonite-biochar Norfloxacin 25.53 Zhang et al.
(2018b)
Municipal solid waste derived Ciprofloxacin 190 Ashiq et al. (2019)
biochar/bentonite clay
Fe-pillared montmorillonite Levofloxacin 48.61 Liu et al. (2015)
Nanotube structured halloysite Niprofloxacin 21.7 Duan et al. (2018)
Hydroxyapatite/clay Tetracycline 76.02 Ersan et al. (2015)
Organobentonites Diclofenac 600.6 Ghemit et al.
Ibuprofen 194.9 (2019b)
2:1 layered non-swelling clay Tetracycline 32 Chang et al. (2012)
mineral illite
Na-montmorillonite Tetracycline 0.92 mmol/g Wu et al. (2019b)
Commercial organoclay Diclofenac sodium 0.133 Mol/g Maia et al. (2019)
Montmorillonite Ciprofloxacin Up to 330 Roca Jalil et al.
(2015)
Palygorskite/montmorillonite Bisphenol A 77.3 mg/kg Berhane et al.
ciprofloxacin 107,000 mg/kg (2016))
Mechanochemistry treated Levofloxacin 47.68 Chen et al. (2019c)
zeolite
Zeolite-hydroxyapatite-activated Tetracycline 244.63 Khanday and
oil palm ash Hameed (2018)
NaY zeolite from wheat straws Doxycycline 269.75 Ali and Ahmed
ash (2017)
Struvite loaded zeolite Tetracycline 197.53 mmol/kg Wang et al.
(2019c)
Natural zeolite Cephalexin 16.1 Samarghandi et al.
Zeolite coated with manganese 24.5 (2015)
oxide nanoparticles
Natural zeolite Cephalexin 16.1 Mohseni-Bandpi
Natural zeolite/Fe3O4 24.9 et al. (2016)
Natural clinoptilolite Apramycin 0.089 Saadi et al. (2019)
Natural clinoptilolite/triton 0.091
X-100 0.092
Natural clinoptilolite/tween 80
252 A. Khadir et al.

8.10 Conclusion

Pharmaceutical compounds are complex biological persistent substances that have

been employed for the treatment of humans and animals. However, excessive con-
sumption of drugs has consequently led to the presence and detection of these haz-
ardous substances in water media including surface water, ground water, and potable
water at low and moderate concentrations. Most of the conventional WWTPs that
consist of preliminary, primary, and secondary treatments are not capable of com-
plete removal of all pharmaceuticals. Similar observation was reported for WTPs.
The fluctuation of the drug concentration in a year, temperature, pH, and type of the
pharmaceutical were among the most parameters that affected the final efficiency.
Many studies have revealed that conventional WWTPs are the main entry point of
pharmaceutical compounds to the environment.
In this review, the authors have described the recent works on adsorption processes
regarding pharmaceutical compound removal. In the first part, the influential parame-
ters including contact time, initial pharmaceutical concentration, pH, adsorbent dos-
age, and temperature affecting the adsorbent/adsorbate interaction were discussed. It
seems that pH was the most important factor since it affects the surface charge/binding
sites of the adsorbent and the ionization degree of the pharmaceutical compounds.
Thermodynamic parameters exhibited that the adsorption process was endothermic,
suggesting that higher temperature is favored for pharmaceuticals removal. Furthermore,
it was seen that the Langmuir model was better to describe the equilibrium data, which
indicated homogenous monolayer coverage of drugs on the adsorbent surface. Also,
the kinetics data were well described by pseudo-­second-­order model which confirmed
the chemisorption nature of the adsorption process in many studies.
This review presented the most used adsorbents such as activated carbon,
graphene-­based adsorbents, chitosan, carbon nanotubes, clay, and zeolites in the
removal of drugs from aqueous media. Intending the faults in the pristine materials,
many studies focused on the modification of the raw material with the aim of higher
applicability. Results proved that the modification processes were almost successful
in terms of pharmaceutical removal with higher adsorption capacity. Magnetic
nanoparticles were highly used in the prepared composites since its easy and facile
separation after completion of the treatment process.
Still, the prepared composites own intrinsic disadvantages like low adsorption
capacity, experimental-based usage, hard synthesis procedure with hazardous
chemicals, and expensive that may hinder the utilization of the adsorbents. In fact,
more work is necessary to resolve these issues and gaps in future studies.

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