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Surface water pollution by pharmaceuticals and an alternative of removal by low-cost adsorbents: A review
Accepted Manuscript Surface water pollution by pharmaceuticals and an alternative of Removal by lowcost adsorbents: a review
Heloise Beatriz Quesada, Aline Takaoka Alves Baptista, Luís Fernando Cusioli, Daiana Seibert, Charleston de Oliveira Bezerra, Rosângela Bergamasco PII:
S0045-6535(19)30225-5
DOI:
10.1016/j.chemosphere.2019.02.009
Reference:
CHEM 23121
To appear in:
Chemosphere
Received Date:
12 November 2018
Accepted Date:
03 February 2019
Please cite this article as: Heloise Beatriz Quesada, Aline Takaoka Alves Baptista, Luís Fernando Cusioli, Daiana Seibert, Charleston de Oliveira Bezerra, Rosângela Bergamasco, Surface water pollution by pharmaceuticals and an alternative of Removal by low-cost adsorbents: a review, Chemosphere (2019), doi: 10.1016/j.chemosphere.2019.02.009
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1
SURFACE WATER POLLUTION BY PHARMACEUTICALS AND
2
AN
3
ADSORBENTS: A REVIEW.
ALTERNATIVE
OF
REMOVAL
BY
LOW-COST
4 5
Heloise Beatriz Quesadaa, Aline Takaoka Alves Baptistaa, Luís Fernando Cusiolia,
6
Daiana Seiberta, Charleston de Oliveira Bezerraa, Rosângela Bergamascoa
7 8
a
9
900, Parana, Brazil. Tel: 55-44-3011-4782, e-mail: [email protected],
State University of Maringa, Department of Chemical Engineering, Maringa 87020-
10
[email protected],
[email protected],
11
[email protected] and [email protected].
[email protected],
12 13
Abstract
14
Micropollutants, also called emerging contaminants, consist of an extensive group of
15
synthetic and natural substances, including pharmaceuticals, personal care products,
16
steroid hormones, and agrochemicals. Currently, the monitoring of residual
17
pharmaceuticals in the environment has been highlighted due to the fact that many of
18
these substances are found in wastewater treatment plants effluents and surface waters,
19
in concentrations ranging from ng L-1 to μg L-1. Most of these compounds are
20
discharged into the environment continuously through domestic sewage treatment
21
systems. In the present work, it is presented an overview of water pollution by these
22
pollutants, as well as a review of the recent literature about the use of low-cost
23
adsorbents for the removal of the main pharmaceuticals found in surface water, focusing
24
on municipal and agroindustrial wastes as precursors. It was possible to observe several
25
examples of high adsorption capacities of these compounds with such materials,
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26
however other aspects must be considered in order to evaluate the real applicability in
27
water and wastewater treatment, such as competition, recyclability and production cost.
28 29
Keywords: Pharmaceuticals. Water pollution. Adsorption. Low-cost adsorbents.
30 31
1. INTRODUCTION
32 33
Over the last decades, the occurrence of micropollutants in the aquatic
34
environment has become a matter of worldwide concern. Micropollutants, also called
35
emerging contaminants, consist of a vast amount of substances of anthropic or natural
36
origin, including pharmaceuticals and personal care products, steroid hormones and
37
agrochemicals. These substances are commonly present in water resources at low
38
concentrations and each substance has a form and mechanism of action, which not only
39
complicate their detection and analysis but also their removal in drinking water and
40
wastewater treatment plants (Bolong et al., 2009; Luo et al., 2014). Another issue is the
41
lack of maximum permissible concentrations of these compounds, and consequently, no
42
or very few precautions and monitoring actions are taken to ensure that these
43
compounds, specifically micro-range pollutants, are not disposed in surface waters.
44
(Bolong et al., 2009).
45
Emerging pollutants are consumed in large amounts every day, and the main
46
characteristic of this group of contaminants is that they do not need to be persistent in
47
the environment to cause negative impacts; their removal or transformation is
48
compensated by their continuous introduction (Petrović et al., 2003). An important fact
49
is that due to their presence in water resources and consequently in drinking water, they
50
can act as human and aquatic organisms endocrine disruptors (Bolong et al., 2009).
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51
Also, it should be taken into account that micropollutants are not found in water
52
resources individually, therefore this mixture can cause synergistic effects, making it
53
more difficult their detection, quantification, and removal (Luo et al., 2014).
54
A large group of chemicals included in emerging contaminants which is poorly
55
taken into account is pharmaceuticals and active ingredients of personal care products
56
(PPCPs). These are used extensively throughout the world, quantities which are often at
57
the same level of agrochemicals (Daughton and Ternes, 1999).
58
Pharmaceuticals have caused great concern because, after their consumption,
59
traces or metabolites are excreted and reach the water resources, either directly or after
60
inefficient treatment (Kümmerer, 2001). Even though the concentrations of
61
pharmaceuticals residues in surface waters are low, their presence and persistence
62
threaten aquatic and terrestrial life, and their effects should not be ignored. Still, there is
63
great difficulty in estimating long-term effects (Asghar et al., 2018; Zuccato et al.,
64
2008). Considering this fact, many studies have proposed tertiary treatments that
65
effectively remove pharmaceuticals from effluent and drinking water. Some techniques
66
evaluated are nanofiltration and reverse osmosis (Garcia-Ivars et al., 2017; Kamrani et
67
al., 2018; Licona et al., 2018), photocatalysis (Dalrymple et al., 2007), ozonization (He
68
et al., 2016; Wang and Bai, 2017) and adsorption (Álvarez-Torrellas et al., 2017; Nam
69
et al., 2014a).
70
Adsorption is considered one of the best alternatives for the removal of organic
71
pollutants, due to its low cost, simplicity of design and ease of operation. Also, during
72
this process, hazardous products are not formed, a situation that can be verified in other
73
treatments (Ahmaruzzaman, 2008). Basically, this process is the accumulation of a
74
pollutant on the surface of a solid (Ali et al., 2012). Besides the removal efficiency of
75
pharmaceuticals and other contaminants, there are a great number of materials that can
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be used as precursors for the adsorbents. The expressive waste generation from
77
agricultural, food and wood industries is an attractive option for the development of the
78
so-called 'low-cost adsorbents' and has encouraged many studies of micropollutants
79
removal by these materials (Reddy et al., 2010).
80
Considering the subjects raised, this review aims to bring the current situation
81
of pharmaceuticals as emerging contaminants of surface water and to detail the
82
adsorption process as an alternative to remove these compounds from water and
83
wastewater.
84 85
2. PHARMACEUTICALS
86 87
Pharmaceuticals are chemicals used to diagnose, treat, change and prevent
88
diseases. The definition is extended to veterinary compounds and can also be applied to
89
illicit drugs (Daughton, 2003; Daughton and Ternes, 1999). A wide variety of human
90
medicines including antibiotics, synthetic hormones, anti-inflammatories, statins, and
91
cytotoxins are produced and consumed, some of them in thousands of tons per year
92
(Boxall, 2004; Metcalfe et al., 2003).
93 94 95 96
Pharmaceuticals differ from other chemical contaminants due to the following characteristics (Putschew and Jekel, 2007): (a) They may be formed by innumerable complex molecules which vary in molecular weight, structure, functionality, and form;
97
(b) They have the capacity to go by cellular membranes and consequently are
98
relatively persistent, once they are not inactivated before reaching the expected
99
therapeutic effect;
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(c) They are polar molecules with more than one ionizable group and their degree of ionization, among other characteristics, depends on the pH of the medium;
102
(d) They are lipophilic and some moderately soluble in water;
103
(e) Drugs such as erythromycin, naproxen, and sulfamethoxazole may persist
104
in the environment for more than one year; others, such as clofibric acid can persist for
105
several years and become biologically active due to accumulation;
106
(f) After administration, the molecules are absorbed in the human body,
107
distributed and subjected to metabolic reactions that can modify their chemical
108
structure.
109 110
2.1 PHARMACEUTICALS CONSUMPTION AND FATE
111 112
The growth rate of financial expenditure per person of pharmaceutical
113
compounds has declined, but their consumption has steadily increased. Due to the
114
development of generic drugs and the production cost decrease, the price of
115
pharmaceuticals became more accessible, which explains the first statement. In
116
addition, increasing demand for treatment of chronic diseases or aging disorders,
117
coupled with economic forces, such as increasing the benefits of health insurance,
118
stimulate drug procurement by the population (Berndt, 2002; Germer and Sinar, 2010).
119
There is a significant difficulty obtaining information about the global
120
consumption of pharmaceuticals, since the administration and number of compounds
121
vary locally, due to different lifestyles and ease of access. Data from Canada indicate
122
that mainly medications prescribed include acetaminophen, acetylsalicylic acid,
123
ibuprofen, naproxen, and carbamazepine (Boxall, 2004; Metcalfe et al., 2003). In
124
European Union, about 3 thousand different substances are used as human medicines,
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125
among them analgesics, anti-inflammatories, contraceptives, antibiotics, beta-blockers,
126
lipid regulators and neuroactive compounds. In Germany in 2001, some of the most
127
commonly used anti-inflammatory drugs were acetylsalicylic acid, with 836 tonnes,
128
paracetamol, 622 tonnes, and ibuprofen, with 345 tonnes (Fent et al., 2006).
129
In 2012, consumption per capita of antihypertensive drugs was the highest in
130
Germany, Hungary and the Czech Republic (575, 543 and 442 doses per thousand
131
people per day, respectively). The increase in sales of medication for the treatment of
132
diabetes was explained by the increase in obesity-related numbers (OECD, 2013). The
133
number of pharmaceuticals consumed influences the effluent load and, consequently,
134
the residual discarded in surface water.
135
Although pharmaceuticals are usually designed with a single mechanism of
136
action and target, they can also have innumerable effects on non-target receptors. In
137
addition, non-target organisms may have receptors and therefore unexpected effects
138
may result from unintended exposure. (Daughton, 2003; Daughton and Ternes, 1999).
139
Concerning
140
inflammation, neurotoxic responses, gametogenic activity and energy status on C.
141
fluminea, a freshwater clam, after exposure to environmentally realistic concentrations
142
of caffeine, ibuprofen, and carbamazepine. It was found that this non-target organism
143
showed concentration-dependent responses related to the mechanism of action of these
144
compounds.
non-target
organisms,
Aguirre-Martínez
et
al.
(2018)
evaluated
145
Currently, the monitoring of residual pharmaceuticals in the environment has
146
been highlighted due to the fact that many of these substances are found in WWTPs
147
effluents and surface waters, in concentrations ranging from ng L-1 to μg L-1 (Bila and
148
Dezotti, 2003). For example, in the studies cited in this review, it was found
149
concentrations from 0.02 ng L-1 to 9.82 μg L-1.
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In general, emerging pollutants are transported through the environment by routes demonstrated in Figure 1.
152
153 154
Figure 1 – Several routes of emerging pollutants in the environment
155 156
More specifically in the case of pharmaceuticals, these compounds are
157
discharged into the environment continuously through domestic sewage treatment
158
systems. Figure 2 schematizes the main routes and fates of the pharmaceuticals in the
159
environment, since their consumption.
160
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161 162
Figure 2 – Routes and fates of pharmaceuticals in the environment
163 164
Pharmaceuticals in their parent form or as metabolites reach aquatic
165
environments through different routes. The main one is by its discard as domestic
166
sewage after its consumption, metabolism in the human body and excretion. That way,
167
they reach WWTPs and may undergo additional transformations and chemical
168
reactions, forming other products, sometimes more toxic and persistent. The literature
169
shows, however, that many of these compounds are not biodegraded in conventional
170
treatment, so they are commonly discharged with treated effluent into rivers, lakes, and
171
estuaries. In addition, veterinary products can get in aquatic systems through manure
172
and subsequent outflow and also through direct application in aquaculture, which makes
173
monitoring a challenging action (Farré et al., 2008; Fent et al., 2006; Rivera-Utrilla et
174
al., 2013).
175
In surface and groundwater, the metabolic compounds can be converted back to
176
their parental form by the action of microorganisms. Further, the WWTP effluent is
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177
formed by a complex mixture, which may have synergistic effects. Some of these
178
synergic compounds are more bioactive than their precursor (Daughton and Ternes,
179
1999; Fent et al., 2006; Rivera-Utrilla et al., 2013).
180
In water resources, biodegradation and photodegradation are two processes of
181
natural attenuation of the pharmaceuticals, which varies with the complexity of the
182
compound. Although these processes are essential, their results are unsatisfactory. In
183
addition, constant discarding of the compounds may lead to toxicological effects, which
184
are still uncertain due to unpredictable synergistic effects (Li, 2014).
185
The environmental concern related to the presence of pharmaceuticals in surface
186
and groundwater is related not only to quantity but also to their persistence and
187
detriments on aquatic life, such as toxicity and the potential effect on endocrine
188
functions. As an example, the steroid hormone 17α-ethinylestradiol, used in
189
contraceptive pills, has a production of approximately 200 kg per year in the European
190
Union and a per capita consumption of 0.84-2.59 µg cap -1 d-1, low values compared to
191
other compounds. However, it is extremely potent and persistent at low concentrations
192
and has an effect on the reproduction of fishes in the concentration of 1-4ng L-1 or
193
smaller (Fent et al., 2006; Johnson et al., 2013). One study concluded that this drug, as
194
well as diclofenac, can induce structural rupture in the kidney and intestine of fish and
195
also change the genes linked to metabolism control (Lyssimachou and Arukwe, 2007;
196
Mehinto et al., 2010).
197
It has been a great challenge in assessing the toxicological effects of
198
pharmaceuticals in surface and groundwater due to their complexity and the occurrence
199
of long-term effects. A possible parameter of toxicological risk analysis that is widely
200
used in current papers is the Hazard Quotient (HQ), expressed as the ratio between the
201
measured environmental concentration and the predicted non-environmental effect
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202
concentration (PNEC) of pharmaceuticals residues. Rivera-Jaimes et al. (2018)
203
calculated the HQ for three trophic levels (fish, algae, and daphnia) for the most
204
commonly found pharmaceuticals in surface water of the city of Cuernavaca, Mexico.
205
The authors concluded that atenolol, diclofenac, gemfibrozil, ibuprofen and salicylic
206
acid were more toxic to fish than to daphnia and algae. Algae were more sensitive to
207
indomethacin, sulfamethoxazole, and trimethoprim, while daphnia was mainly affected
208
by acetaminophen, gemfibrozil, carbamazepine, and naproxen. Furthermore, ibuprofen,
209
sulfamethoxazole, diclofenac, and naproxen had the highest ecotoxicological risks in
210
surface water, with HQ varying from 14.8 to 111. Although widely used, this quotient
211
considers the effect of a single compound, not the effects of the mixture of compounds
212
present in the aquatic environment. Mutiyar et al. (2018), obtained values of HQ related
213
to pharmaceuticals residues found in the Yamuna River (India) lower than 1, i.e., the
214
toxicological risks were insignificant. However, the authors added that because of the
215
above consideration, the actual risk may even be higher than the worst scenario
216
considered in their study. They further stated that individual low concentrations of
217
pharmaceuticals are unlikely to show acute toxic effects, but the chronic effects cannot
218
be neglected. In addition to the ecological effects of pharmaceuticals, it is important to
219
emphasize a possible consequence of the presence of antibiotics in surface water. Their
220
constant presence and contact with aquatic microbiota can lead to the development of
221
resistant bacteria and genes and consequently accelerate the development of resistance
222
to antibiotics in pathogenic bacteria, impairing the treatment of human infections
223
(Sapkota et al., 2008; Taylor et al., 2011).
224 225 226
2.2 PHARMACEUTICALS OCCURRENCE IN SURFACE WATER
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227
The presence of pharmaceuticals in surface water bodies is a global problem,
228
and its concentration varies with location and population consumption. Table 1
229
summarizes some of the most detected compounds in countries of different continents.
230 231
Table 1 – Occurrence of pharmaceutical in surface water around the world Min Compound
Max
Mean
(ng L-1) (ng L-1) (ng L-1)
Country
Reference
Analgesics and Anti-inflammatories
Acetaminophen
pKa = 9.38
0
9.61
3.18
China
(Yang et al., 2018)
0
200.00
87.30
France
(Celle-Jeanton et al., 2014)
0
1561.00
445.00
India
(Mutiyar et al., 2018)
354.00
508.00
430.00
Mexico
(Rivera-Jaimes et al., 2018)
-
-
89.60
Poland
(Caban et al., 2015)
0
527.00
-
Portugal
(Paíga et al., 2016)
0
69.15
38.18
Portugal
(Pereira et al., 2017)
South-Africa
(Matongo et al., 2015)
-
Diclofenac
1740.00 1296.00
0.03
0.65
0.20
Sweden
(Lindim et al., 2016)
0
9822.00
209.00
UK
(Burns et al., 2018)
0
15.49
3.95
Malaysia
(Praveena et al., 2018)
258.00
352.00
313.00
Mexico
(Rivera-Jaimes et al., 2018)
-
-
40.00
Poland
(Caban et al., 2015)
0
38.00
-
Portugal
(Paíga et al., 2016)
25.13
51.24
33.56
Portugal
(Pereira et al., 2017)
3462.00
49.00
Spain
(Carmona et al., 2014)
0.02
1.49
-
Sweden
(Lindim et al., 2016)
184.00
248.00
231.00
Mexico
(Rivera-Jaimes et al., 2018)
0
2302.00
662.17
India
(Mutiyar et al., 2018)
-
-
55.40
Poland
(Caban et al., 2015)
0
846.00
317.80
South-Africa
(Matongo et al., 2015)
pKa = 4.15
Ibuprofen
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-
6593.00
830.00
Spain
(Carmona et al., 2014)
0
2.21
-
Sweden
(Lindim et al., 2016)
-
-
21.00
USA
(Ferrer and Thurman, 2012)
0.40
86.90
29.51
Portugal
(Pereira et al., 2017)
0.03
1.27
-
Sweden
(Lindim et al., 2016)
834.00
986.00
911.00
Mexico
(Rivera-Jaimes et al., 2018)
-
-
37.70
Poland
(Caban et al., 2015)
0
260.00
-
Portugal
(Paíga et al., 2016)
-
7189.00
278.00
Spain
(Carmona et al., 2014)
0
0.22
-
Sweden
(Lindim et al., 2016)
-
-
95.00
USA
(Ferrer and Thurman, 2012)
pKa = 4.91 Ketoprofen
pKa = 4.45
Naproxen
pKa = 4.15
Antibiotics Erythromycin
pKa = 8.88 Metronidazole
pKa = 2.38
0
6.46
1.31
Bangladesh
(Hossain et al., 2018)
10.20
183.00
55.02
China
(Yang et al., 2018)
32.89
38.80
35.51
Portugal
(Pereira et al., 2017)
0
240.00
60.00
South-Africa
(Matongo et al., 2015)
0.02
0.70
-
Sweden
(Lindim et al., 2016)
0
263.00
-
UK
(Burns et al., 2018)
-
-
137.00
USA
(Ferrer and Thurman, 2012)
0.05
13.51
2.74
Bangladesh
(Hossain et al., 2018)
0
5.10
0.65
China
Asghar et al. (2018)
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Sulfamethoxazole
0
7.24
1.39
Bangladesh
(Hossain et al., 2018)
0
2.50
1.22
China
(Asghar et al., 2018)
2.83
20.80
9.79
China
(Yang et al., 2018)
19.26
114.24
56.19
Malaysia
(Praveena et al., 2018)
108.00
502.00
299.00
Mexico
(Rivera-Jaimes et al., 2018)
0
43.00
-
Portugal
(Paíga et al., 2016)
South-Africa
(Matongo et al., 2015)
0 pKa1 = 1.6; pKa2 = 5.7
Trimethoprim
pKa = 7.12
13
5320.00 2172.00
0
0.14
-
Sweden
(Lindim et al., 2016)
0
33.20
-
UK
(Burns et al., 2018)
0
14.73
-
USA
(Bean et al., 2018)
-
-
320.00
USA
(Ferrer and Thurman, 2012)
0
17.20
3.06
Bangladesh
(Hossain et al., 2018)
0
15.70
2.84
China
(Asghar et al., 2018)
0.40
52.10
12.35
China
(Yang et al., 2018)
34.00
74.00
61.00
Mexico
(Rivera-Jaimes et al., 2018)
0
290.00
58.00
South-Africa
(Matongo et al., 2015)
0.02
0.33
0.10
Sweden
(Lindim et al., 2016)
0
76.00
-
UK
(Burns et al., 2018)
0
2.29
-
USA
(Bean et al., 2018)
Antidepressives
Diazepam
-
-
24.30
China
(Wu et al., 2015)
0
305.00
55.50
India
(Mutiyar et al., 2018)
-
12.00
3.00
Spain
(Huerta-Fontela et al., 2011)
-
-
0.40
China
(Wu et al., 2015)
2.01
19.50
-
Portugal
(Paíga et al., 2016)
pKa = 3.4 Fluoxetine
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pKa = 9.8
14
25.37
25.37
25.37
Portugal
(Pereira et al., 2017)
0
0.01
-
Sweden
(Lindim et al., 2016)
-
-
65.00
USA
(Ferrer and Thurman, 2012)
Antiepileptic
Carbamazepine
pKa = 13.9
0
8.80
1.51
Bangladesh
(Hossain et al., 2018)
0
7.00
1.17
China
(Asghar et al., 2018)
0
3.50
0.44
China
(Yang et al., 2018)
-
-
25.30
China
(Wu et al., 2015)
0
5.80
3.30
France
(Celle-Jeanton et al., 2014)
0
1346.00
412.50
India
(Mutiyar et al., 2018)
8
36.00
19.00
Mexico
(Rivera-Jaimes et al., 2018)
0.02
0.21
-
Sweden
(Lindim et al., 2016)
24.90
214.00
-
Portugal
(Paíga et al., 2016)
0
-
10.90
Portugal
(Pereira et al., 2017)
South-Africa
(Matongo et al., 2015)
130.00
Gabapentin
3240.00 1048.00
-
54.00
13.00
Spain
(Huerta-Fontela et al., 2011)
0.94
9.39
-
USA
(Bean et al., 2018)
-
-
350.00
USA
(Ferrer and Thurman, 2012)
0
195.00
-
UK
(Burns et al., 2018)
0
4.55
-
Sweden
(Lindim et al., 2016)
-
-
54.00
USA
(Ferrer and Thurman, 2012)
pKa1 = 3.68; pK2 = 10.7 Anti-hyperglycemic 0.20
121.40
34.73
China
(Asghar et al., 2018)
0.44
8.40
2.60
Sweden
(Lindim et al., 2016)
45.20
2595.00
677.00
Metformin UK (Burns et al., 2018)
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pKa = 12.4
Beta-blockers
Atenolol
pKa = 9.6
Propanolol
-
900.00
470.00
Spain
(Huerta-Fontela et al., 2011)
4.00
10.00
7.00
Mexico
(Rivera-Jaimes et al., 2018)
-
-
21.70
USA
(Battaglin et al., 2018)
0
13.00
4.90
France
(Celle-Jeanton et al., 2014)
0
100.00
31.12
UK
(Burns et al., 2018)
-
-
166.00
USA
(Ferrer and Thurman, 2012)
0.18
8.47
-
Sweden
(Lindim et al., 2016)
-
270.00
54.00
Spain
(Huerta-Fontela et al., 2011)
0
64.90
11.66
United Kingdom
(Burns et al., 2018)
-
-
53.00
USA
(Ferrer and Thurman, 2012)
pKa = 9.42 Central nervous system (CNS) stimulant
Caffeine
pKa = 14
0
220.00
56.90
China
(Asghar et al., 2018)
18.40
293.00
100.51
China
(Yang et al., 2018)
0
81.00
41.30
France
(Celle-Jeanton et al., 2014)
0
2640.00
977.00
India
(Mutiyar et al., 2018)
16.27
36.00
30.83
Malaysia
(Praveena et al., 2018)
0
332.00
68.60
South-Africa
(Matongo et al., 2015)
-
-
591.77
USA
(Battaglin et al., 2018)
8.05
26.92
-
USA
(Bean et al., 2018)
-
-
220.00
USA
(Ferrer and Thurman, 2012)
Mexico
(Rivera-Jaimes et al., 2018)
Lipid regulators Gemfibrozil
14.00
24.00
20.00
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16
-
3735.00
77.00
Spain
(Carmona et al., 2014)
-
-
95.00
USA
(Ferrer and Thurman, 2012)
pKa = 4.5
232 233
The most detected drug in surface water considering the investigated studies
234
was carbamazepine. This compound is the antiepileptic most commonly found in
235
surface water (Rivera-Utrilla et al., 2013). Burns et al. (2018) detected this substance in
236
10 of the 12 samples collected in Ouse and Foss rivers in the United Kingdom. The
237
constant occurrence of this compound in surface and groundwater was studied by Clara
238
et al. (2004), which found that it is very persistent and is not subject to biodegradation
239
in conventional WWTP.
240
Besides carbamazepine, Burns et al. (2018) observed a high frequency of traces
241
of gabapentin, metformin, and trimethoprim. The authors found that metformin obtained
242
the second highest concentration (6111 ng L-1) in the effluent from a WWTP, only
243
losing to gabapentin (8541 ng L-1); furthermore, it was the compound with the highest
244
annual mean concentration in surface water of two rivers of the city. Metformin,
245
although poorly evaluated by its presence in surface water (present in only three studies
246
of Table 1), has caused concern. Asghar et al. (2018) considered this compound to be
247
one of the most critical of the 33 drugs identified, due to its high concentration in
248
effluents from Wuhan (China) WWTP, which was higher than 100 ng L-1 and to the
249
high occurrence rate in six rivers of the city. Metformin is an antihyperglycemic used in
250
the treatment of diabetes, and the authors justified their critical presence in the country's
251
high number of diabetics.
252
A great frequency of antibiotics could be observed in surface waters. Asghar et
253
al. (2018) found that this group of pharmaceuticals corresponded to 28% of the total
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254
occurrence. Sulfamethoxazole was the second most identified compound in Table 1 and
255
obtained the highest mean, found by Matongo et al. (2015) in Matsunduzi River in
256
South Africa. This compound obtained a high detection frequency among the antibiotics
257
evaluated in Brahmaputra River (Bangladesh) by Hossain et al. (2018), reaching 70%,
258
and was present in all samples collected in the Apatlaco River (Mexico) by Rivera-
259
Jaimes et al. (2018). Generally, the mechanism of sulfamethoxazole is potentiated with
260
trimethoprim, which explains the significant occurrence of this drug in the literature
261
consulted in this study. The maximum concentration of trimethoprim in Table 1 was
262
found by Matongo et al. (2015) of 290 ng L-1. The authors found an even greater
263
concentration of sediment collected in a reservoir in the city, stating that the residence
264
time allowed sorption of the product.
265
Traces of atenolol in aquatic environments are also discussed in the literature.
266
Lindim et al. (2016) have explained that atenolol is not or almost not metabolized in the
267
human body, so it is excreted in the concentrations similar to those consumed. Of all the
268
evaluated pharmaceuticals, this compound obtained the highest concentration found by
269
the authors. Huerta-Fontela et al. (2011) warned that atenolol, besides present in
270
Llobregat River in Spain (mean of 470 ng L-1), is one of the 5 drugs of the 32 evaluated
271
that persists in the water supply after all stages of a conventional DWTP, which shows a
272
great difficulty of removal of the substance.
273
Considering anti-inflammatories, the importance of acetaminophen (or
274
paracetamol) residues in aquatic environments should be emphasized. In Table 1, this
275
compound received the highest concentration among all cited, present in the study of
276
Burns et al. (2018). As a complement, the authors pointed out that acetaminophen
277
obtained the highest concentrations in the influent of all three WWTPs studied, reaching
278
282 319 ng L-1, a condition that, added to the incomplete removal, explains the presence
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18
279
of the drug in Ouse River in all 12 months evaluated. Paíga et al. (2016) reported a
280
similar pattern; the greatest mass load of the influent of two WWTPs was related to
281
paracetamol, also causing the greatest effluent load and higher concentrations along Lis
282
River in Portugal.
283
Caffeine, a central nervous system stimulant, is commonly associated with
284
analgesics and anti-inflammatories in medicine formulations. This fact, coupled with its
285
presence in several consumed beverages worldwide, justifies the frequency of traces of
286
caffeine in surface water. Asghar et al. (2018) found that the highest concentration was
287
related to caffeine, among all the other pharmaceuticals. Also, Celle-Jeanton et al.
288
(2014) concluded that caffeine together with acetaminophen obtained the highest
289
concentrations among the compounds evaluated in the Allier River, justifying the fact
290
by that both are part of the most consumed drugs in France, which beats their
291
biodegradability. Silva et al. (2014) observed that some of the highest concentrations
292
were found in urban spaces, a fact that could be justified by leakages from septic tanks.
293
The authors also highlighted that the sample of which the concentration was less than
294
the limit of detection was collected in a totally uninhabited area, consolidating the
295
concept that caffeine can be a marker of domestic wastewater.
296
The results discussed above justify the importance of complementary treatments
297
to the conventional, both in WWTPs and in DWTTs. One of the possibilities would be
298
the use of adsorption techniques, detailed in the next topic.
299 300
3. ADSORPTION PROCESSES
301 302
Adsorption is a phase transfer process that is widely used to remove substances
303
from the fluid phase (gases or liquids) and transfer to the solid phase (adsorbent
304
particle). It can be observed in different environmental compartments as a natural
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305
process. Regarding water or effluents treatments, the interaction occurs between a solid
306
and a pollutant, such as pharmaceuticals molecules. The pollutant is called adsorbate
307
and the solid is adsorbent. This technique has been used for the efficient removal of a
308
wide variety of contaminants (Ali et al., 2012; Worch, 2012).
309
According to Ho et al., (2000) in practice, adsorption is carried out in batch or
310
fixed bed column containing a certain mass of porous adsorbent. Under these
311
conditions, the effects of mass transfer are inevitable. The complete adsorption
312
sequence comprises three steps:
313 314
Step 1 - Film diffusion (external diffusion): transport of the adsorbate present in the
315
solution to the external surface of the adsorbent.
316
Step 2 - Diffusion of pores (intraparticle diffusion): transport of the adsorbate from the
317
surface of the adsorbent into the pores.
318
Step 3 - Surface reaction: fixation of the adsorbate on the surface of the adsorbent pores.
319 320
It is important to note that the third step is very fast, and the total adsorption rate
321
is determined by film and/or intraparticle diffusion. Also, since these two steps act in
322
series, the slower process characterizes adsorption (Worch, 2012).
323
Adsorption has been shown to be an excellent and promising technique due to its
324
numerous advantages, including low cost, accessibility, efficiency and environmental
325
benignity (Ali et al., 2012). Also, compared to the conventional methods of separation,
326
the advantages include chemical and/or biological sludge minimization, potential
327
adsorbent regeneration potential, no requirement for nutrients addition and the
328
possibility of recovering the adsorbed material if it has an economic value added
329
(Reddy et al., 2010).
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330
The possible materials to be used as adsorbents are various, some examples
331
being: activated carbon of mineral, animal or vegetable origin, ion exchange resin,
332
carbon nanotubes, chitosan, fly ashes and organic resins (Zhu et al., 2017). Besides the
333
efficiency, it is important to analyze the development of adsorbents and application cost,
334
as well as regeneration capacity. From this economic perspective, the term 'low-cost
335
adsorbents' was created. A low-cost adsorbent is defined as a material that requires little
336
processing, is abundant in nature or may be a waste material or by-product from an
337
industry activity (Rafatullah et al., 2010). In the case of the last materials, the economy
338
in the acquisition can offset the cost of processing. For that reason, a cost study is
339
important. Examples of low-cost adsorbents are clays, parts of plants, animals or other
340
materials with high carbon content, such as fruit residues, bark, algae, mosses, hair, and
341
keratin (Ahmaruzzaman, 2008; Rafatullah et al., 2010).
342
The selection of precursors should take into account the following factors:
343
material accessibility, hazardousness, carbon and oxygen content, abrasion resistance,
344
thermal stability, pore diameter, and high adsorption and regeneration capacity (Ali et
345
al., 2012). The textural, structural, morphological and chemical characterizations are
346
indicators of these qualities. Very common analyzes are the Point of Zero Charge
347
(PZC), zeta potential, scanning electron microscopy (SEM), nitrogen physisorption,
348
Fourier transform infrared spectroscopy (FTIR) and X-ray diffraction (XRD).
349 350
3.1 ADSORPTION STUDIES
351 352
In order to evaluate the applicability of adsorption to the removal of
353
contaminants such as pharmaceuticals, a complete study should be performed.
354
Generally, it contains several steps, such as the effect of pH and ionic strength, kinetics,
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355
isotherms, thermodynamics, desorption, and regeneration. These steps can be conducted
356
using either batch or column methods (Tran et al., 2017).
357
In general, three of these studies are the main constituents of the adsorption
358
theory, which have interdependence. The equilibrium study is considered to be the basis
359
of all adsorption models and a precondition for kinetics and dynamics. It assumes that
360
the adsorption capacity is a function of the concentration of the solution. However, the
361
kinetic study assumes that both the adsorption capacity and the concentration are
362
functions of the contact time. The dynamics is based on the two studies and assumes
363
that in addition to being a function of time, the concentration and adsorption capacity
364
are a function of space. This is used when the adsorption is conducted in a fixed bed
365
column (Worch, 2012).
366
Within the studies involving adsorption, it is common to evaluate two
367
parameters: adsorption capacity and percentage of removal. The increase in the
368
percentage of removal is usually proportional to the increase of the mass of the
369
adsorbent due to the greater availability of adsorption sites, however, does not
370
positively affect the adsorption capacity. This happens because once the percentage of
371
removal reaches 100%, the available sites are not saturated, causing an erroneous
372
estimation of the adsorption capacity (Fan et al., 2017).
373 374
3.1.1
Adsorption kinetics
375 376
As explained above, the adsorption kinetics is the basis for further studies.
377
According to Ho (2006), several studies on adsorption of pollutants have been
378
developed to have a better understanding of the mechanisms and to obtain the order of
ACCEPTED MANUSCRIPT
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379
reaction found through kinetics. However, the understanding of the adsorption kinetics
380
is limited by the theoretical complexity of the mechanisms.
381
Simplified, the kinetics explains how fast the reaction occurs and still indicates
382
the factors that affect the rate of reaction (Crini and Badot, 2008). Typically, the
383
adsorption equilibrium is not reached instantaneously, as in the case of porous
384
adsorbents. The mass transfer of the solution into the pores inside the particles has
385
resistances, which determine the time required for the equilibrium (Worch, 2012).
386
The adsorption kinetics can be analyzed by mathematical models. The most used
387
models are pseudo-first-order (Ho and McKay, 1999) and pseudo-second-order (Ho and
388
McKay, 1999; Tran et al., 2017). However, the Elovich (Allen and Scaife, 1966; Crini
389
and Badot, 2008) and Intraparticle Diffusion (Weber and Morris, 1963) models have
390
been widely applied.
391 392
3.1.2
Adsorption equilibrium
393 394
The analysis and design of the adsorption process require a study of the
395
equilibrium, which is the most important in the understanding of the process (Vasanth et
396
al., 2007). The adsorption isotherms are equilibrium equations and they are applied to
397
the adsorption process after sufficient time to reach equilibrium at a constant
398
temperature (Kumar, 2007).
399
Since there are a wide variety of equilibrium isotherms to describe the
400
adsorption process, some mathematical models are commonly used to describe
401
equilibrium interactions in a solid-liquid system, such as Langmuir (Langmuir, 1917),
402
Freundlich (Freundlich, 1906), Sips, Tempkin, and Toth (Günay et al., 2007).
403
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3.1.3
23
Adsorption thermodynamics
405 406
Since motion is an intrinsic property of matter and energy is motion-related, it
407
is possible to understand that transformations, whether physical or chemical, are
408
associated with energetic variations. Thermodynamics is part of the physical sciences
409
that evaluates these variations (Nascimento et al., 2014).
410
Information about the adsorption capacity of a material can be obtained through
411
the thermodynamic parameters, such as Gibbs Free Energy (ΔG °), Enthalpy (ΔH °) and
412
Entropy (ΔS°). These are important thermodynamic parameters for the study of the
413
adsorption mechanisms that can confirm the viability, spontaneity and heat exchange
414
for the adsorption process (Zolgharnein et al., 2011).
415 416 417
4. PHARMACEUTICALS ADSORPTION BY LOW-COST ADSORBENTS – A REVIEW ON RECENT LITERATURE
418 419
Many papers have investigated the potential of low-cost adsorbents for the
420
removal of drugs from aqueous solutions. Table 2 was developed taking into account
421
the variety of precursors, mainly municipal and agroindustrial residues.
422 423 424 425
24
426
Table 2 – Adsorption of pharmaceuticals by low-cost adsorbents Chemical Compound
Precursor
Treatment agent
Remov Kinetics
Isotherm
Thermodynamics
Reference
(mg g-1) al (%)
Bamboo
TH
-
-
58
-
-
-
(Solanki and Boyer,
Coconut shell
AC
-
-
94
-
-
-
2017)
-
98
PSO
-
-
AC Acetaminophen
K2CO3, KOH
Cork
pKa = 9.38
qe, max
(Mestre et al., 2014)
AC
-
-
65
PSO
-
-
Cork bark
IN
-
0.99
65
-
-
-
Grape stalk
IN
-
1.74
60
PFO
Langmuir
-
Yohimbe bark
IN
-
31.00
65
-
-
-
(Villaescusa et al., 2011)
ΔG° < 0 Municipal solid
PFO, AC
KOH
180.00
-
wastes
-
ΔH° > 0
(Sumalinog et al., 2018)
PSO ΔS° > 0
Peach stones Atenolol
AC
K2CO3
0.77
80
PSO
Langmuir
-
AC
K2CO3
500.00
-
PSO
Langmuir
-
AC
KOH
555.60
-
PSO
Langmuir
-
AC
-
250.32
-
Elovich
Sips
-
Apple tree branches
Palm kernel shell
(Cabrita et al., 2010) (Marques et al., 2018)
(To et al., 2017)
25
pKa = 9.6
Carbamazepine
Cork
IN
0.37
88
PSO
Freundlich
-
Fish waste
TH
Sewage sludge
(Dordio et al., 2011)
-
27.50
-
-
Sips
-
TH
-
217.40
-
-
Sips
-
Palm kernel shell
AC
-
335.00
-
Elovich
Sips
-
(To et al., 2017)
Peach stones
AC
H3PO4
40.00
-
-
Sips
-
(Torrellas et al., 2015)
(Nielsen et al., 2015)
ΔG° < 0 pKa = 13.9
Rice straw
IN
-
18.00
-
PSO
Freundlich
ΔH° > 0
(Z. Liu et al., 2013)
ΔS° > 0 AC
Grape stalk
pKa = 14
-
98
PSO
-
-
KOH
Cork Caffeine
K2CO3,
(Mestre et al., 2014)
AC
-
-
85
PSO
-
-
IN
-
89.19
75
-
Sips
-
CH
H3PO4
129.56
85
-
Sips
-
AC
H3PO4
395.00
94
-
Sips
-
AC
H3PO4
260.00
-
-
Sips
-
126.00
-
-
Sips
-
Peach stones AC
H3PO4, HNO3
(Portinho et al., 2017)
(Torrellas et al., 2015)
26
ΔG° < 0 Pineapple plant leaves
AC
H3PO4
151.50
-
PSO
Langmuir
ΔH° < 0
(Beltrame et al., 2018)
ΔS° > 0
Diclofenac
Cocoa pod husk
AC
H2SO4
5.53
93
PSO
Freundlich
-
(De Luna et al., 2017)
Coconut shell
AC
-
-
100
-
Freundlich
-
(Nam et al., 2014a)
Olive- waste cakes
AC
H3PO4
38.00
96
PSO
Langmuir
-
(Baccar et al., 2012)
ΔG° > 0 Pine wood
AC
-
0.33
69
PFO
Langmuir
ΔH° > 0 ΔS° < 0 (Lonappan et al., 2018) ΔG° < 0
pKa = 4.15 Pig manure
AC
-
0.95
99
PSO
Freundlich
ΔH° < 0 ΔS° > 0 ΔG° < 0
Ibuprofen
TH
-
5.00
90
PSO
Langmuir
ΔH° < 0 ΔS° > 0
(Chakraborty et al.,
ΔG° < 0
2018)
Aegle marmelos shell
pKa = 4.91
AC
-
12.66
95
PSO
Langmuir
ΔH° < 0 ΔS° > 0
27
AC
150.00
82
PSO
Langmuir
-
KOH
Cork
Cork
K2CO3,
(Mestre et al., 2014)
AC
-
125.00
70
PSO
Langmuir
-
IN
-
0.32
98
PSO
Freundlich
-
(Dordio et al., 2011)
ΔG° < 0 Mung bean husk
AC
-
59.76
99
PSO
Langmuir
ΔH° < 0
(Mondal et al., 2016)
ΔS° < 0 Olive- waste cakes
AC
H3PO4
8.00
Almond shell
AC
H2O2
344.80
79
PSO
Langmuir
-
(Baccar et al., 2012)
PSO
Langmuir
-
(Zbair et al., 2018)
ΔG° < 0 Sulfamethoxazole
Coffee waste
CH
H2SO4
256.95
-
PSO
Langmuir
ΔH° < 0
(Ahsan et al., 2018)
ΔS° < 0 Fish waste
TH
-
17.72
-
Sips
-
(Nielsen and Bandosz,
Sewage sludge
TH
-
79.02
-
Sips
-
2016)
pKa1 = 1.6; pKa2 = 5.7
ΔG° < 0 (Ariful Ahsan et al., Tea leaves
CH
H2SO4
247.29
-
PSO
Temkim
ΔH° < 0 2018) ΔS° < 0
427
IN – in natura, TH – thermal treatment, CH – chemical treatment, AC – activated carbon, PFO – pseudo-first-order, PSO – pseudo-second-order
ACCEPTED MANUSCRIPT
28
428
In Table 2, three classifications of adsorbents were used: in natura (IN),
429
thermically treated (TH) and activated carbon (AC). These treatments can significantly
430
alter the surface properties and pores structure, which is highly related to the uptake of
431
pharmaceuticals molecules. The adsorbents can be used in natura after a simplified
432
washing pretreatment; chemically treated, after contact with chemical solutions for the
433
removal of undesired organic and inorganic matter contained on the surface; and
434
thermally treated, with furnace heating, to increase the surface area breaking the less
435
stable bonds and consequently releasing the volatile fraction of the precursor material
436
(Akhtar et al., 2007).
437
The chemical treatments are used in biomass to improve its adsorption capacity
438
of contaminants and to change the electrical behavior of the surface. The chemical
439
attack is expected to be able to destroy bonds between functional groups and the
440
adsorbent surface. This phenomenon may result in a pore size increase as well as
441
interactions with other functional groups of the contaminant (Módenes et al., 2017). The
442
chemical agents include organic and mineral acids (HCl, HNO3, H2SO4, acetic acid,
443
citric acid, and formic acid), bases and alkali solutions (NaOH, Na2CO3, Ca(OH)2 and
444
CaCl2), oxidizing (H2O2 and K2MnO4), among other compounds (Abdolali et al., 2014).
445
More advanced treatment generates the activated carbon, prepared in a two-
446
stage operation. The first step is the carbonization of the raw material at temperatures
447
below 800ºC in the absence of oxygen. Activation is then carried out with the use of an
448
oxidizing agent (vapor, carbon dioxide or air) at elevated temperatures and sometimes
449
with a catalyst. Activation may be accompanied by chemical or physical treatment
450
(Aygün et al., 2003; Wigmans, 1989). Lately, new methods of activation are being
451
investigated, such as microwave-assisted pyrolysis (Zbair et al., 2018). This method has
452
advantages compared to the conventional two-stage operation, such as more ease of
ACCEPTED MANUSCRIPT
29
453
control, reduced heating time, energy and gas utilization (Yuen and Hameed, 2009).
454
Although the activation process results in the further development of the surface pores,
455
its high cost may become an economic issue, which leads to a greater interest of
456
simplified and efficient treatments of the adsorbents.
457
As expected, it is observed in Table 2 that the higher adsorption capacities are
458
found in activated carbon, followed by chemically or thermally treated adsorbents and,
459
finally, in natura materials. Some works compared different treatments, which allows
460
verifying the influence of each of them on the structure, morphology, and surface loads,
461
characteristics that directly affect the adsorption of drugs. These papers will be
462
highlighted in the discussion of this topic.
463
Portinho et al. (2017), compared three types of adsorbents derived from grape
464
stalk (in natura, chemically treated with phosphoric acid and activated carbon) in the
465
adsorption of caffeine. They observed the above pattern and obtained the maximum qe
466
values of 89.194, 129.56 and 395 mg g-1, respectively. As expected, activated carbon
467
(AC) has a higher surface area and volume of micropores (1009.86 m² g-1 and 0.568 cm³
468
g-1) compared to untreated biomass (6.23 m² g-1 and 0.003 cm³ g-1) and chemically
469
treated (4.21 m² g-1 and 0.002 cm3 g-1). This effect promoted a greater number of sites
470
for adsorption, which implies higher values of qe. Furthermore, the authors emphasized
471
the importance of phosphoric acid addition in the two treatments, which added
472
functional groups to the surface and favored the adsorbate-adsorbent interactions. In this
473
case, the chemical reagent added oxygen groups, which resulted in hydrophilicity to the
474
grape stalk and facilitated the adsorption of polar molecules, such as caffeine.
475
Chakraborty et al. (2018) compared the adsorption capacity of ibuprofen by
476
two adsorbents derived from Aegle marmelos barks: thermally treated and activated
477
with steam. After activation, it was verified that the specific area and pore volume
ACCEPTED MANUSCRIPT
30
478
increased from 4.4 to 308 m² g-1 and from 0.184 to 0.384 cm³ g-1, respectively. This
479
increase not only resulted in the greater removal of ibuprofen but decreased the time
480
required to reach the equilibrium.
481
Regarding the treatments and chemical activations, it is possible to observe the
482
significant occurrence of phosphoric acid (H3PO4) in Table 2. Phosphoric acid is
483
considered to be the most environmentally-friendly reagent when compared to others
484
acids, more corrosive and hazardous, such as nitric acid (HNO3) and sulfuric acid
485
(H2SO4). These also can damage the structure of the adsorbent (Rajapaksha et al.,
486
2016). Benaddi et al. (1998) explained that phosphoric acid promotes the
487
depolymerization of cellulose, dehydration of biopolymers, formation of aromatic rings
488
and elimination of phosphate groups, allowing the increase of the surface area of the
489
adsorbents, besides the addition of functional groups.
490
Potassium hydroxide (KOH) and potassium carbonate (K2CO3) were also
491
frequent reagents in Table 2. Marques et al. (2018) compared the chemical activations
492
by both compounds in apple branches for the adsorption of atenolol. In general, the use
493
of KOH resulted in larger specific areas (maximum of 2472 m² g-1) compared to K2CO3
494
(maximum of 1963 m² g-1). Through scanning electron microscopy, it was observed that
495
the activation with K2CO3 promoted the maintenance of some of the morphological
496
characteristics of the precursor. The authors reported that the activation process with
497
KOH caused more significant destruction of the structure of the AC particles, promoting
498
a more homogeneous particle size distribution of the material. Considering the critical
499
size of the atenolol molecule (0.7 nm), its retention occurs in supermicropores. This fact
500
justified the higher adsorption capacity of adsorbents treated with KOH, which resulted
501
in a higher volume of supermicropores (maximum of 1.19 cm³ g-1).
ACCEPTED MANUSCRIPT
31
502
When it comes to the removal of pharmaceutical compounds from contaminated
503
water, it is important to understand their protonation behavior in aqueous solution. The
504
effect of the pH of the solution on the adsorption processes is important to understand
505
the interaction between the adsorbate and adsorbent since the variation of the pH can
506
promote changes in the superficial charges of adsorbents and influence the protonation
507
of functional groups present in the contaminants (Beltrame et al., 2018). Thus, the pH
508
can affect both the adsorbent surface properties and the nature of the adsorbate, causing
509
different types of mechanisms during the adsorption process (Baccar et al., 2012), and
510
several can be observed in the papers contained in Table 2.
511
The pH of the Point of Zero Charge (pHPZC) of an adsorbent depends on the
512
chemical and electronic properties of the functional groups and is a good indicator for
513
the adsorption process (Song et al., 2010). For a given particle and according to its
514
amphoteric character, it is known that the surface is neutral at pH = pHPZC, negatively
515
charged at pHs higher than pHPZC and positively charged at pHs below pHPZC (Baccar et
516
al., 2012). Regarding pharmaceuticals, these may be weak acids or bases, and their
517
protonation will be based on their pKa values. An acid has the tendency to donate
518
protons, and its dissociation is represented below (Geffertová et al., 2017):
519 HA ⇌H + + A -
520 521 522
Weak acids at pH < pKa are predominantly in their protonated forms (HA),
523
while at pH > pKa they are predominantly in their deprotonated forms (A-). On the
524
contrary, weak bases have the tendency to receive protons, and their ionization occurs
525
as follows (Pardue et al., 2004):
526
ACCEPTED MANUSCRIPT
32
HB + ⇌H + + B
527 528 529
At pH < pKa, weak bases are predominantly in their protonated forms (HB+),
530
while at pH > pKa they are predominantly deprotonated (HB). Briefly, ionizable
531
molecules such as pharmaceuticals may interact with the adsorbent through electrostatic
532
attraction or repulsion, and this interaction varies according to their pKa values (Huerta-
533
Fontela et al., 2011)
534
Exemplifying electrostatic interactions, diclofenac is considered a weak acid
535
since its pKa is around 4.15 (Nam et al., 2014b). According to Nielsen et al. (2015), for
536
hydrophobic compounds, such as diclofenac, adsorption can be largely affected by pH
537
changes, therefore, electrostatic and specific interactions (based on surface polarity,
538
functional groups, organic and inorganic components of the adsorbent) between the
539
contaminant and the surface of the adsorbent particle have an impact on adsorption.
540
Lonappan et al. (2018) verified in their studies that the isoelectric point of pig manure
541
biochar was 2.15 and the adsorption of diclofenac was pH dependent. The maximum
542
removal efficiency of this compound was 99.6% observed at pH 2 (Table 2) and this
543
percentage decreased to 88.8% at pH 12.5. This was justified by the changes in the
544
surface charge and, consequently, the negative surface of the biosorbent repelled by the
545
diclofenac anion.
546
Baccar et al. (2012) in their studies of the biosorbent derived from olive residues
547
(pHPCZ = 5.03) also observed that high pH reduced the uptake of diclofenac and
548
ibuprofen, and this effect was more noticeable when the pH became alkaline. Ibuprofen
549
has pKa = 4.91 and diclofenac pKa = 4.15, both acidic drugs are essentially neutral
550
molecules at pH below the pKa value, however, they acquire a negative charge when
551
the pH is above the pKa value due to the dissociation of molecules of this compound.
ACCEPTED MANUSCRIPT
33
552
Thus, at pH > pHPZC (pH = 8.61), the surface of the adsorbent is negatively charged and
553
a higher proportion of the ionized form of the pharmaceuticals is also charged (pH >
554
pKa), leading to an electrostatic repulsion between adsorbate anions and the surface of
555
the adsorbent and consequently, the removal of pharmaceuticals has decreased.
556
However, although many papers justify the pharmaceuticals adsorption by
557
electrostatic interactions, this is not a rule. Portinho et al. (2017) verified that the best
558
caffeine adsorption capacity was obtained at pH 2. Caffeine is a weak base with pKa =
559
14. This implies that at acid pHs the drug is in its protonated form. When analyzing the
560
adsorbents derived from grape stalks by their surface charges, it was observed that the
561
pHPCZ was around 7.5, which shows that at pH 2 the surface of the particles would be
562
positively charged. Therefore, an electrostatic repulsion would occur, which would
563
adversely affect the adsorption process. The authors then justified that better removals
564
at acid pHs were due to non-electrostatic effects, such as, for example, hydrogen bonds
565
between caffeine and grape stalks. Hydrogen bonds occur preferentially when the
566
surface of the adsorbent is positively charged (Sotelo et al., 2012).
567
In short, Moreno-Castilla (2004) cited three possible mechanisms of adsorption
568
of organic compounds, which can be implied to pharmaceuticals: the π–π dispersion
569
interaction, the hydrogen bonding formation, and the electron donor-acceptor complex
570
formation mechanism. These are related to the chemical properties of the adsorbent
571
surface, that can be verified, for example, through the FTIR spectra analysis. In the case
572
of lignocellulosic materials, some functional groups, such as carboxyl, hydroxyl and
573
amides may be related to the process (Dai et al., 2018).
574
Villaescusa et al. (2011) found likely binding sites for acetaminophen on grape
575
stalks surface through the FTIR analysis, such as hydroxyl groups (peak around 3350
576
cm−1), lignin aromatic bonds (1620 cm-1), guayacil unit (1034, 1159 and 1263 cm-1) and
ACCEPTED MANUSCRIPT
34
577
syringil unit (1105 and 1315 cm-1). After adsorption, there was a shift related to the
578
aromatic rings, indicating the possible adsorption site, and then the authors considered
579
that hydrogen bonding and π-stacking interactions with lignin provided the main
580
mechanism for the adsorption of paracetamol in the grape stalk.
581
Zbair et al. (2018) observed by the FTIR spectra of almond shells activated
582
carbon that some peaks were shifted and the intensity changed when loaded with
583
sulfamethoxazole. The authors considered the respective functional groups as the main
584
adsorption sites. The shifted peaks were from 3397 to 3370 cm-1 (Hydroxyl groups),
585
from 1684 to 1596 cm-1 (C=C vibration of aromatic rings), from 1181 to 1051 cm-1 (C-
586
OH) and 640 to 518 cm-1 (C-H deformation). Taking these changes into account, the
587
possible mechanisms were considered to be due to Van der Waals forces or weak
588
electrostatic interaction.
589
Nielsen et al. (2015) found some indications of the adsorption mechanism by
590
analyzing proton binding curves. This analysis showed that their adsorbents developed
591
from sewage sludge and fish waste exhibited basic nature (pHPZC were between 9 and
592
10). After the adsorption of carbamazepine, there was a decrease in basicity on the
593
sludge carbon. Considering the basic nature of the pharmaceutical molecule, this fact
594
could imply that acid-base interactions were not the main adsorption mechanism. A
595
different situation occurred for the fish-derived carbon, and the increase of basicity was
596
related to the dispersive interactions of the aromatic rings of carbamazepine and the
597
exposed amine groups. Also, it was observed that in the adsorbent treated with lower
598
temperatures, there were more changes in the acidity after the adsorption, suggesting
599
chemical interactions, such as the complexation of the pharmaceutical on metal cations.
600
Concerning this aspect, the authors added that higher temperatures lead to higher levels
ACCEPTED MANUSCRIPT
35
601
of aromatization, attracting the aromatic rings of carbamazepine with stronger
602
dispersive forces.
603
Discussing the kinetic models, it is possible to verify the good fit of the pseudo-
604
second-order model in Table 2. As previously mentioned, together with the pseudo-
605
first-order model, this equation is widely applied to kinetic adsorption data. However,
606
due to restricted conditions and application generally, in the first minutes of reaction,
607
the pseudo-first-order model was applied to a few processes.
608
Lonappan et al. (2018) adjusted the linearized pseudo-first, pseudo-second and
609
Elovich models for the kinetic data of diclofenac adsorption on activated carbon of pine
610
wood. Although the pseudo-second-order model obtained a correlation coefficient (R²)
611
of 0.99, the calculated qe value (400 μg g-1) differed significantly from the experimental
612
one (331 μg g-1), a situation that did not occur with the pseudo-first-order-model (qe, calc
613
= 339 µg g-1). Sumalinog et al. (2018) adjusted the linear forms of the pseudo-first and
614
pseudo-second-order equations in kinetic data of paracetamol adsorption in activated
615
carbons derived from municipal solid waste controlled at three different temperatures.
616
In the three curves, the R² coefficients of the two models were satisfactory, varying
617
from 0.986 to 0.999. In addition, the calculated qe values were close. For these reasons,
618
the authors concluded that both models applied to adsorption.
619
In relation to the equilibrium study, the most prominent model in Table 2 was
620
Langmuir, followed by Sips, Freundlich and, finally, Temkin. The occurrence of the
621
Sips model is justified because this is a simplification of Langmuir at high
622
concentrations of adsorbate. To et al. (2017) explained the good fit of both models to
623
the equilibrium data of atenolol and carbamazepine adsorption in palm kernel shell. The
624
fit was analyzed by the sum of the error squares, and this parameter was 0.000001 for
625
Sips, 0.4 for Langmuir and 262.7 for Freundlich. According to the authors, the good fit
ACCEPTED MANUSCRIPT
36
626
of the Langmuir model followed by Sips completed the process understanding,
627
confirming that the pharmaceuticals were adsorbed in a monolayer on the adsorbent
628
surface. Furthermore, the Sips model, which resulted in nF values of 0.81 and 0.37 for
629
carbamazepine and atenolol, respectively, showed that activated carbon has some
630
heterogeneity, which is not as intense as the good fit of Freundlich model would imply.
631
About the effect of temperature, analyzed by thermodynamic parameters, the
632
works cited in Table 2 did not present a pattern. Some showed that the increase in
633
temperature favored the adsorption capacity of pharmaceuticals (Beltrame et al., 2018;
634
Z. Liu et al., 2013; Lonappan et al., 2018; Sumalinog et al., 2018) and others concluded
635
that this effect disfavored the process (Ahsan et al., 2018; Ariful Ahsan et al., 2018;
636
Chakraborty et al., 2018; Lonappan et al., 2018; Mondal et al., 2016). These situations
637
can be justified either by the Gibbs Free Energy (ΔGº) or the Enthalpy values (ΔHº).
638
The Gibbs Free Energy (ΔGº) is related to spontaneity, fundamental for the
639
viability of the process. Sumalinog et al. (2018) observed that the values of this
640
parameter suffered a decrease of 36% with the temperature increase from 303 to 323K.
641
This situation demonstrated the increase of the spontaneity generated by the temperature
642
increase, also favoring the adsorption capacity. The same was also pointed out by
643
Beltrame et al. (2018) and Liu et al. (2013). In contrast, some authors noticed that the
644
higher values of ΔGº occurred with higher temperatures, i.e., there was a decrease in
645
spontaneity, a fact that accompanied the decrease in the adsorption capacity (Ahsan et
646
al., 2018; Ariful Ahsan et al., 2018; Chakraborty et al., 2018; Mondal et al., 2016).
647
It is noteworthy that only one study obtained a positive value for this parameter,
648
indicating a non-spontaneous adsorption. Lonappan et al. (2018) found positive values
649
for the 5 temperatures analyzed in the study of adsorption of diclofenac in pine wood.
650
The authors justified this fact by the energy barrier that could have impeded the process
ACCEPTED MANUSCRIPT
37
651
at the pH used (6.5), since electrostatic forces played an important role in the
652
adsorption, highly pH dependent.
653
Some studies justified the effect of temperature by the enthalpy values. Positive
654
values of ΔH° indicate endothermic reactions, i.e., they absorb heat from the medium
655
and negative values indicate exothermic reactions, i.e., they release heat. Some authors
656
have therefore related the beneficial effect of temperature increase to positive enthalpy
657
values (H. Liu et al., 2013; Sumalinog et al., 2018) and the beneficial effect of
658
decreasing the temperature to negative values of enthalpy (Ahsan et al., 2018; Ariful
659
Ahsan et al., 2018; Chakraborty et al., 2018; Mondal et al., 2016).
660
Another point to be considered in adsorption of pharmaceuticals is the problem
661
of competition. In real water matrices, these compounds are never alone, and the
662
presence of salts and other compounds should be analyzed because they can enhance or
663
inhibit the adsorption capacity (Fernández et al., 2014; Silva et al., 2018). Therefore,
664
there are papers that studied competitive adsorption, by adding two or more
665
pharmaceuticals in aqueous solution or different types of salts. For example, Fernández
666
et al. (2014) studied the competitive effects of sulfamethoxazole and sulfamethazine and
667
observed a reduction of the adsorption capacity when compared to the values related to
668
each compound separately. In the test using separated solutions of 50 mg L-1, the
669
adsorption capacity of sulfamethoxazole and sulfamethazine was 54.2 and 40.1 mg g-1,
670
respectively. When combined the two solutions, the adsorption capacity was reduced to
671
37.2 and 19.0 mg g-1, respectively. In all tests of adsorption competition, it was verified
672
a higher qe for sulfamethoxazole, showing that the adsorbent had more affinity for that
673
compound.
674
Chakraborty et al. (2018) evaluated the competitive effects on the adsorption of
675
ibuprofen and diclofenac and observed that the removal of the first pharmaceutical was
ACCEPTED MANUSCRIPT
38
676
decreased in the presence of the other. This situation was explained by the difference in
677
the molecular structures of the compounds since the molecule of ibuprofen is smaller
678
than that of diclofenac, and the affinity for this compound was higher due to
679
electrostatic interactions.
680
Sotelo et al. (2012) studied competitive adsorption of diclofenac in two
681
aqueous matrices: ultrapure water and a wastewater treatment plant effluent. The
682
authors explained that in this effluent there was a complex mixture of humic acids,
683
inorganic compounds, carbohydrates, and proteins. All these molecules competed with
684
diclofenac for binding sites on the activated carbon surface, and their availability
685
decreased. The experimental data confirmed this statement since the qe decreased from
686
329 mg g-1 to 184 mg g-1 when used the wastewater treatment plant effluent.
687
Despite all the adsorption studies, to evaluate the application of low-cost
688
adsorbents, regeneration must be considered, due to sustainability and economic
689
concerns. Only a few works cited in Table 2 studied this topic. Ariful Ahsan et al.,
690
(2018) performed successive sulfamethoxazole adsorptions, regenerating their modified
691
adsorbent from tea leaves with ethanol. After three cycles, the adsorption capacity was
692
reduced from approximately 90 to 82 mg g-1, and the authors concluded that the
693
material could be used repeatedly for removal of this compound, being an indicator of
694
applicability. Chakraborty et al. (2018) performed four cycles of ibuprofen adsorption,
695
using methanol. Their low-cost adsorbents were regenerated, achieving more than 74%
696
of desorption after the fourth cycle and the qe remained at least 61% of the initial value.
697
Zbair et al. (2018) evaluated five cycles, using ethanol for desorption. The
698
efficiency of sulfamethoxazole removal of their almond shell carbon decreased only
699
7%, and about 89% of the material was recovered. The authors also performed a
700
nitrogen physisorption analysis, observing that the surface specific area and pore
ACCEPTED MANUSCRIPT
39
701
volume decreased from 1274 to 1134 m2 g-1 and from 1.67 to 1.43 m3 g-1, respectively.
702
This data confirmed the deposition of the pharmaceutical molecules on the adsorbent
703
surface.
704
After the cycles or the exhaustion, the adsorbents must be disposed of. The
705
disposal of the loaded adsorbents is fundamental for their safety assessment application
706
(Simeonidis et al., 2017). The spent activated carbon is often incinerated, but there are
707
some alternatives of other uses. Some adsorbents can be used as a component of
708
building materials, such as cement and bricks (Zhou et al., 2019). Another alternative is
709
to use these as fuel in the boilers/incinerators, depending on its heating value, or for the
710
development of fuel-briquettes (Kushwaha et al., 2010).
711
Lastly, since low-cost adsorbents are being discussed, some aspects of costs
712
should be considered. Again, only a few papers cited performed this kind of analysis.
713
Chakraborty et al. (2018) and Zbair et al. (2018) considered the acquisition, size
714
reduction, washing, drying, carbonization, steam activation, reagents and electricity
715
costs for the analysis. It is noteworthy that, in the case of the two works, there were no
716
costs in the acquisition of the precursor materials, since they were residues (wood apple
717
and almond shell). As mentioned, the economy in the acquisition can offset the cost of
718
processing, and there are simplified and complex treatments. Chakraborty et al. (2018)
719
compared two adsorbents, one after simple carbonization and the other after vapor
720
activation. Obviously, activation increased the cost of processing but the adsorption
721
capacity more than doubled. In this case, it must be balanced the efficiency with
722
economic aspects. The cost of the steam activated adsorbent was estimated at $ 3.6/kg, a
723
low value compared to the activated carbon from Zbair et al. (2018) ($27.8/kg).
724
However, the processing used by the last authors were more complex, because of the
725
reagents (H2O2) and nitrogen atmosphere. Also, the adsorption capacity was superior
ACCEPTED MANUSCRIPT
40
726
(344.8 compared to 12.6 mg g-1). For these reasons, costs vs. efficiency should be very
727
carefully analyzed when it comes to applicability.
728
Analyzing Table 2 in general and the discussion about the recyclability and
729
costs, it can be verified the variety of precursors of adsorbent materials for the removal
730
of pharmaceuticals from contaminated water, as well as the variety of treatments in
731
order to improve the adsorption capacity. Furthermore, it was possible to verify the
732
difference in behavior of the adsorbents and the contaminants, which implies the need
733
for complete studies of the process for the possible application in WWTPs and DWTPs.
734 735
CONCLUSION
736 737
Pharmaceuticals are complex molecules that can be persistent in the
738
environment and resistant to conventional treatments of wastewater and drinking water.
739
It is apparent that pharmaceutical compounds are being found in surface water at low
740
and moderate concentrations. However, even in low concentrations, little is known
741
about its long-term effects, considering its influence on aquatic organisms and human
742
health. Recent researches have indicated the toxicological effect of drugs on the organic
743
functions of aquatic organisms in minimal concentrations and some have already been
744
classified as endocrine disrupters.
745
Given the environmental impacts presented, the importance of a complementary
746
treatment to the conventional one which removes efficiently these compounds becomes
747
clear. Adsorption is an alternative to the reduced cost that has been shown to be efficient
748
in the removal of various organic and inorganic compounds and has been investigated
749
for the removal of several pharmaceuticals. The possibility of precursors of adsorbents
750
is wide, and municipal, agricultural and industrial wastes have gained interest and have
ACCEPTED MANUSCRIPT
41
751
been applied as so-called 'low-cost adsorbents'. In recent articles, it was clear the
752
efficiency of these adsorbents, considering the high adsorption capacities and
753
percentage of removal. However, this does not necessarily mean that their application in
754
WWTPs and DWTPs is feasible.
755
The first problem is the reduced number of studies analyzing the removal of
756
pharmaceuticals in real effluents; most studies use solutions prepared in laboratories
757
with ultrapure water. However, in real matrices, these contaminants are never alone and
758
there is competition between different organic and inorganic compounds, which can
759
significantly decrease the adsorption and removal capacity, as observed in some papers.
760
Another factor to consider is the recyclability. There is some difficulty in finding this
761
topic in the recent literature related to the adsorption of pharmaceuticals, which raises
762
doubts about the resistance and durability of the materials studied. In industry, these
763
features are the key to the interest of application. Moreover, for the real interest in so-
764
called ‘low-cost adsorbents’, is the estimation of production investment, a fundamental
765
point that is little discussed, which consequently interfere in the searching for these
766
materials for this purpose. Therefore, considering these issues, it becomes necessary a
767
careful evaluation of the feasibility of transferring the process from laboratory scale to a
768
pilot scale, which is complex and requires complete studies.
769 770
Acknowledgments
771
The authors thank the National Council for Scientific and Technological
772
Development - CNPq and Higher Education Personnel Improvement Coordination e
773
CAPES for financial support.
774 775
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ACCEPTED MANUSCRIPT
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776
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ACCEPTED MANUSCRIPT Highlights
Pharmaceuticals have been found in surface water in μg L-1 to ng L-1. Pharmaceuticals can be persistent in the environment. Adsorption is effective in removing organic and inorganic pollutants from water. Adsorption has been investigated for the removal of several pharmaceuticals. Municipal and agro-industrial wastes can be used as precursors of adsorbents.
Heloise Beatriz Quesada, Aline Takaoka Alves Baptista, Luís Fernando Cusioli, Daiana Seibert, Charleston de Oliveira Bezerra, Rosângela Bergamasco PII:
S0045-6535(19)30225-5
DOI:
10.1016/j.chemosphere.2019.02.009
Reference:
CHEM 23121
To appear in:
Chemosphere
Received Date:
12 November 2018
Accepted Date:
03 February 2019
Please cite this article as: Heloise Beatriz Quesada, Aline Takaoka Alves Baptista, Luís Fernando Cusioli, Daiana Seibert, Charleston de Oliveira Bezerra, Rosângela Bergamasco, Surface water pollution by pharmaceuticals and an alternative of Removal by low-cost adsorbents: a review, Chemosphere (2019), doi: 10.1016/j.chemosphere.2019.02.009
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ACCEPTED MANUSCRIPT
1
1
SURFACE WATER POLLUTION BY PHARMACEUTICALS AND
2
AN
3
ADSORBENTS: A REVIEW.
ALTERNATIVE
OF
REMOVAL
BY
LOW-COST
4 5
Heloise Beatriz Quesadaa, Aline Takaoka Alves Baptistaa, Luís Fernando Cusiolia,
6
Daiana Seiberta, Charleston de Oliveira Bezerraa, Rosângela Bergamascoa
7 8
a
9
900, Parana, Brazil. Tel: 55-44-3011-4782, e-mail: [email protected],
State University of Maringa, Department of Chemical Engineering, Maringa 87020-
10
[email protected],
[email protected],
11
[email protected] and [email protected].
[email protected],
12 13
Abstract
14
Micropollutants, also called emerging contaminants, consist of an extensive group of
15
synthetic and natural substances, including pharmaceuticals, personal care products,
16
steroid hormones, and agrochemicals. Currently, the monitoring of residual
17
pharmaceuticals in the environment has been highlighted due to the fact that many of
18
these substances are found in wastewater treatment plants effluents and surface waters,
19
in concentrations ranging from ng L-1 to μg L-1. Most of these compounds are
20
discharged into the environment continuously through domestic sewage treatment
21
systems. In the present work, it is presented an overview of water pollution by these
22
pollutants, as well as a review of the recent literature about the use of low-cost
23
adsorbents for the removal of the main pharmaceuticals found in surface water, focusing
24
on municipal and agroindustrial wastes as precursors. It was possible to observe several
25
examples of high adsorption capacities of these compounds with such materials,
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2
26
however other aspects must be considered in order to evaluate the real applicability in
27
water and wastewater treatment, such as competition, recyclability and production cost.
28 29
Keywords: Pharmaceuticals. Water pollution. Adsorption. Low-cost adsorbents.
30 31
1. INTRODUCTION
32 33
Over the last decades, the occurrence of micropollutants in the aquatic
34
environment has become a matter of worldwide concern. Micropollutants, also called
35
emerging contaminants, consist of a vast amount of substances of anthropic or natural
36
origin, including pharmaceuticals and personal care products, steroid hormones and
37
agrochemicals. These substances are commonly present in water resources at low
38
concentrations and each substance has a form and mechanism of action, which not only
39
complicate their detection and analysis but also their removal in drinking water and
40
wastewater treatment plants (Bolong et al., 2009; Luo et al., 2014). Another issue is the
41
lack of maximum permissible concentrations of these compounds, and consequently, no
42
or very few precautions and monitoring actions are taken to ensure that these
43
compounds, specifically micro-range pollutants, are not disposed in surface waters.
44
(Bolong et al., 2009).
45
Emerging pollutants are consumed in large amounts every day, and the main
46
characteristic of this group of contaminants is that they do not need to be persistent in
47
the environment to cause negative impacts; their removal or transformation is
48
compensated by their continuous introduction (Petrović et al., 2003). An important fact
49
is that due to their presence in water resources and consequently in drinking water, they
50
can act as human and aquatic organisms endocrine disruptors (Bolong et al., 2009).
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51
Also, it should be taken into account that micropollutants are not found in water
52
resources individually, therefore this mixture can cause synergistic effects, making it
53
more difficult their detection, quantification, and removal (Luo et al., 2014).
54
A large group of chemicals included in emerging contaminants which is poorly
55
taken into account is pharmaceuticals and active ingredients of personal care products
56
(PPCPs). These are used extensively throughout the world, quantities which are often at
57
the same level of agrochemicals (Daughton and Ternes, 1999).
58
Pharmaceuticals have caused great concern because, after their consumption,
59
traces or metabolites are excreted and reach the water resources, either directly or after
60
inefficient treatment (Kümmerer, 2001). Even though the concentrations of
61
pharmaceuticals residues in surface waters are low, their presence and persistence
62
threaten aquatic and terrestrial life, and their effects should not be ignored. Still, there is
63
great difficulty in estimating long-term effects (Asghar et al., 2018; Zuccato et al.,
64
2008). Considering this fact, many studies have proposed tertiary treatments that
65
effectively remove pharmaceuticals from effluent and drinking water. Some techniques
66
evaluated are nanofiltration and reverse osmosis (Garcia-Ivars et al., 2017; Kamrani et
67
al., 2018; Licona et al., 2018), photocatalysis (Dalrymple et al., 2007), ozonization (He
68
et al., 2016; Wang and Bai, 2017) and adsorption (Álvarez-Torrellas et al., 2017; Nam
69
et al., 2014a).
70
Adsorption is considered one of the best alternatives for the removal of organic
71
pollutants, due to its low cost, simplicity of design and ease of operation. Also, during
72
this process, hazardous products are not formed, a situation that can be verified in other
73
treatments (Ahmaruzzaman, 2008). Basically, this process is the accumulation of a
74
pollutant on the surface of a solid (Ali et al., 2012). Besides the removal efficiency of
75
pharmaceuticals and other contaminants, there are a great number of materials that can
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76
be used as precursors for the adsorbents. The expressive waste generation from
77
agricultural, food and wood industries is an attractive option for the development of the
78
so-called 'low-cost adsorbents' and has encouraged many studies of micropollutants
79
removal by these materials (Reddy et al., 2010).
80
Considering the subjects raised, this review aims to bring the current situation
81
of pharmaceuticals as emerging contaminants of surface water and to detail the
82
adsorption process as an alternative to remove these compounds from water and
83
wastewater.
84 85
2. PHARMACEUTICALS
86 87
Pharmaceuticals are chemicals used to diagnose, treat, change and prevent
88
diseases. The definition is extended to veterinary compounds and can also be applied to
89
illicit drugs (Daughton, 2003; Daughton and Ternes, 1999). A wide variety of human
90
medicines including antibiotics, synthetic hormones, anti-inflammatories, statins, and
91
cytotoxins are produced and consumed, some of them in thousands of tons per year
92
(Boxall, 2004; Metcalfe et al., 2003).
93 94 95 96
Pharmaceuticals differ from other chemical contaminants due to the following characteristics (Putschew and Jekel, 2007): (a) They may be formed by innumerable complex molecules which vary in molecular weight, structure, functionality, and form;
97
(b) They have the capacity to go by cellular membranes and consequently are
98
relatively persistent, once they are not inactivated before reaching the expected
99
therapeutic effect;
ACCEPTED MANUSCRIPT 100 101
5
(c) They are polar molecules with more than one ionizable group and their degree of ionization, among other characteristics, depends on the pH of the medium;
102
(d) They are lipophilic and some moderately soluble in water;
103
(e) Drugs such as erythromycin, naproxen, and sulfamethoxazole may persist
104
in the environment for more than one year; others, such as clofibric acid can persist for
105
several years and become biologically active due to accumulation;
106
(f) After administration, the molecules are absorbed in the human body,
107
distributed and subjected to metabolic reactions that can modify their chemical
108
structure.
109 110
2.1 PHARMACEUTICALS CONSUMPTION AND FATE
111 112
The growth rate of financial expenditure per person of pharmaceutical
113
compounds has declined, but their consumption has steadily increased. Due to the
114
development of generic drugs and the production cost decrease, the price of
115
pharmaceuticals became more accessible, which explains the first statement. In
116
addition, increasing demand for treatment of chronic diseases or aging disorders,
117
coupled with economic forces, such as increasing the benefits of health insurance,
118
stimulate drug procurement by the population (Berndt, 2002; Germer and Sinar, 2010).
119
There is a significant difficulty obtaining information about the global
120
consumption of pharmaceuticals, since the administration and number of compounds
121
vary locally, due to different lifestyles and ease of access. Data from Canada indicate
122
that mainly medications prescribed include acetaminophen, acetylsalicylic acid,
123
ibuprofen, naproxen, and carbamazepine (Boxall, 2004; Metcalfe et al., 2003). In
124
European Union, about 3 thousand different substances are used as human medicines,
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125
among them analgesics, anti-inflammatories, contraceptives, antibiotics, beta-blockers,
126
lipid regulators and neuroactive compounds. In Germany in 2001, some of the most
127
commonly used anti-inflammatory drugs were acetylsalicylic acid, with 836 tonnes,
128
paracetamol, 622 tonnes, and ibuprofen, with 345 tonnes (Fent et al., 2006).
129
In 2012, consumption per capita of antihypertensive drugs was the highest in
130
Germany, Hungary and the Czech Republic (575, 543 and 442 doses per thousand
131
people per day, respectively). The increase in sales of medication for the treatment of
132
diabetes was explained by the increase in obesity-related numbers (OECD, 2013). The
133
number of pharmaceuticals consumed influences the effluent load and, consequently,
134
the residual discarded in surface water.
135
Although pharmaceuticals are usually designed with a single mechanism of
136
action and target, they can also have innumerable effects on non-target receptors. In
137
addition, non-target organisms may have receptors and therefore unexpected effects
138
may result from unintended exposure. (Daughton, 2003; Daughton and Ternes, 1999).
139
Concerning
140
inflammation, neurotoxic responses, gametogenic activity and energy status on C.
141
fluminea, a freshwater clam, after exposure to environmentally realistic concentrations
142
of caffeine, ibuprofen, and carbamazepine. It was found that this non-target organism
143
showed concentration-dependent responses related to the mechanism of action of these
144
compounds.
non-target
organisms,
Aguirre-Martínez
et
al.
(2018)
evaluated
145
Currently, the monitoring of residual pharmaceuticals in the environment has
146
been highlighted due to the fact that many of these substances are found in WWTPs
147
effluents and surface waters, in concentrations ranging from ng L-1 to μg L-1 (Bila and
148
Dezotti, 2003). For example, in the studies cited in this review, it was found
149
concentrations from 0.02 ng L-1 to 9.82 μg L-1.
ACCEPTED MANUSCRIPT 150 151
7
In general, emerging pollutants are transported through the environment by routes demonstrated in Figure 1.
152
153 154
Figure 1 – Several routes of emerging pollutants in the environment
155 156
More specifically in the case of pharmaceuticals, these compounds are
157
discharged into the environment continuously through domestic sewage treatment
158
systems. Figure 2 schematizes the main routes and fates of the pharmaceuticals in the
159
environment, since their consumption.
160
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8
161 162
Figure 2 – Routes and fates of pharmaceuticals in the environment
163 164
Pharmaceuticals in their parent form or as metabolites reach aquatic
165
environments through different routes. The main one is by its discard as domestic
166
sewage after its consumption, metabolism in the human body and excretion. That way,
167
they reach WWTPs and may undergo additional transformations and chemical
168
reactions, forming other products, sometimes more toxic and persistent. The literature
169
shows, however, that many of these compounds are not biodegraded in conventional
170
treatment, so they are commonly discharged with treated effluent into rivers, lakes, and
171
estuaries. In addition, veterinary products can get in aquatic systems through manure
172
and subsequent outflow and also through direct application in aquaculture, which makes
173
monitoring a challenging action (Farré et al., 2008; Fent et al., 2006; Rivera-Utrilla et
174
al., 2013).
175
In surface and groundwater, the metabolic compounds can be converted back to
176
their parental form by the action of microorganisms. Further, the WWTP effluent is
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177
formed by a complex mixture, which may have synergistic effects. Some of these
178
synergic compounds are more bioactive than their precursor (Daughton and Ternes,
179
1999; Fent et al., 2006; Rivera-Utrilla et al., 2013).
180
In water resources, biodegradation and photodegradation are two processes of
181
natural attenuation of the pharmaceuticals, which varies with the complexity of the
182
compound. Although these processes are essential, their results are unsatisfactory. In
183
addition, constant discarding of the compounds may lead to toxicological effects, which
184
are still uncertain due to unpredictable synergistic effects (Li, 2014).
185
The environmental concern related to the presence of pharmaceuticals in surface
186
and groundwater is related not only to quantity but also to their persistence and
187
detriments on aquatic life, such as toxicity and the potential effect on endocrine
188
functions. As an example, the steroid hormone 17α-ethinylestradiol, used in
189
contraceptive pills, has a production of approximately 200 kg per year in the European
190
Union and a per capita consumption of 0.84-2.59 µg cap -1 d-1, low values compared to
191
other compounds. However, it is extremely potent and persistent at low concentrations
192
and has an effect on the reproduction of fishes in the concentration of 1-4ng L-1 or
193
smaller (Fent et al., 2006; Johnson et al., 2013). One study concluded that this drug, as
194
well as diclofenac, can induce structural rupture in the kidney and intestine of fish and
195
also change the genes linked to metabolism control (Lyssimachou and Arukwe, 2007;
196
Mehinto et al., 2010).
197
It has been a great challenge in assessing the toxicological effects of
198
pharmaceuticals in surface and groundwater due to their complexity and the occurrence
199
of long-term effects. A possible parameter of toxicological risk analysis that is widely
200
used in current papers is the Hazard Quotient (HQ), expressed as the ratio between the
201
measured environmental concentration and the predicted non-environmental effect
ACCEPTED MANUSCRIPT
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202
concentration (PNEC) of pharmaceuticals residues. Rivera-Jaimes et al. (2018)
203
calculated the HQ for three trophic levels (fish, algae, and daphnia) for the most
204
commonly found pharmaceuticals in surface water of the city of Cuernavaca, Mexico.
205
The authors concluded that atenolol, diclofenac, gemfibrozil, ibuprofen and salicylic
206
acid were more toxic to fish than to daphnia and algae. Algae were more sensitive to
207
indomethacin, sulfamethoxazole, and trimethoprim, while daphnia was mainly affected
208
by acetaminophen, gemfibrozil, carbamazepine, and naproxen. Furthermore, ibuprofen,
209
sulfamethoxazole, diclofenac, and naproxen had the highest ecotoxicological risks in
210
surface water, with HQ varying from 14.8 to 111. Although widely used, this quotient
211
considers the effect of a single compound, not the effects of the mixture of compounds
212
present in the aquatic environment. Mutiyar et al. (2018), obtained values of HQ related
213
to pharmaceuticals residues found in the Yamuna River (India) lower than 1, i.e., the
214
toxicological risks were insignificant. However, the authors added that because of the
215
above consideration, the actual risk may even be higher than the worst scenario
216
considered in their study. They further stated that individual low concentrations of
217
pharmaceuticals are unlikely to show acute toxic effects, but the chronic effects cannot
218
be neglected. In addition to the ecological effects of pharmaceuticals, it is important to
219
emphasize a possible consequence of the presence of antibiotics in surface water. Their
220
constant presence and contact with aquatic microbiota can lead to the development of
221
resistant bacteria and genes and consequently accelerate the development of resistance
222
to antibiotics in pathogenic bacteria, impairing the treatment of human infections
223
(Sapkota et al., 2008; Taylor et al., 2011).
224 225 226
2.2 PHARMACEUTICALS OCCURRENCE IN SURFACE WATER
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227
The presence of pharmaceuticals in surface water bodies is a global problem,
228
and its concentration varies with location and population consumption. Table 1
229
summarizes some of the most detected compounds in countries of different continents.
230 231
Table 1 – Occurrence of pharmaceutical in surface water around the world Min Compound
Max
Mean
(ng L-1) (ng L-1) (ng L-1)
Country
Reference
Analgesics and Anti-inflammatories
Acetaminophen
pKa = 9.38
0
9.61
3.18
China
(Yang et al., 2018)
0
200.00
87.30
France
(Celle-Jeanton et al., 2014)
0
1561.00
445.00
India
(Mutiyar et al., 2018)
354.00
508.00
430.00
Mexico
(Rivera-Jaimes et al., 2018)
-
-
89.60
Poland
(Caban et al., 2015)
0
527.00
-
Portugal
(Paíga et al., 2016)
0
69.15
38.18
Portugal
(Pereira et al., 2017)
South-Africa
(Matongo et al., 2015)
-
Diclofenac
1740.00 1296.00
0.03
0.65
0.20
Sweden
(Lindim et al., 2016)
0
9822.00
209.00
UK
(Burns et al., 2018)
0
15.49
3.95
Malaysia
(Praveena et al., 2018)
258.00
352.00
313.00
Mexico
(Rivera-Jaimes et al., 2018)
-
-
40.00
Poland
(Caban et al., 2015)
0
38.00
-
Portugal
(Paíga et al., 2016)
25.13
51.24
33.56
Portugal
(Pereira et al., 2017)
3462.00
49.00
Spain
(Carmona et al., 2014)
0.02
1.49
-
Sweden
(Lindim et al., 2016)
184.00
248.00
231.00
Mexico
(Rivera-Jaimes et al., 2018)
0
2302.00
662.17
India
(Mutiyar et al., 2018)
-
-
55.40
Poland
(Caban et al., 2015)
0
846.00
317.80
South-Africa
(Matongo et al., 2015)
pKa = 4.15
Ibuprofen
ACCEPTED MANUSCRIPT
12
-
6593.00
830.00
Spain
(Carmona et al., 2014)
0
2.21
-
Sweden
(Lindim et al., 2016)
-
-
21.00
USA
(Ferrer and Thurman, 2012)
0.40
86.90
29.51
Portugal
(Pereira et al., 2017)
0.03
1.27
-
Sweden
(Lindim et al., 2016)
834.00
986.00
911.00
Mexico
(Rivera-Jaimes et al., 2018)
-
-
37.70
Poland
(Caban et al., 2015)
0
260.00
-
Portugal
(Paíga et al., 2016)
-
7189.00
278.00
Spain
(Carmona et al., 2014)
0
0.22
-
Sweden
(Lindim et al., 2016)
-
-
95.00
USA
(Ferrer and Thurman, 2012)
pKa = 4.91 Ketoprofen
pKa = 4.45
Naproxen
pKa = 4.15
Antibiotics Erythromycin
pKa = 8.88 Metronidazole
pKa = 2.38
0
6.46
1.31
Bangladesh
(Hossain et al., 2018)
10.20
183.00
55.02
China
(Yang et al., 2018)
32.89
38.80
35.51
Portugal
(Pereira et al., 2017)
0
240.00
60.00
South-Africa
(Matongo et al., 2015)
0.02
0.70
-
Sweden
(Lindim et al., 2016)
0
263.00
-
UK
(Burns et al., 2018)
-
-
137.00
USA
(Ferrer and Thurman, 2012)
0.05
13.51
2.74
Bangladesh
(Hossain et al., 2018)
0
5.10
0.65
China
Asghar et al. (2018)
ACCEPTED MANUSCRIPT
Sulfamethoxazole
0
7.24
1.39
Bangladesh
(Hossain et al., 2018)
0
2.50
1.22
China
(Asghar et al., 2018)
2.83
20.80
9.79
China
(Yang et al., 2018)
19.26
114.24
56.19
Malaysia
(Praveena et al., 2018)
108.00
502.00
299.00
Mexico
(Rivera-Jaimes et al., 2018)
0
43.00
-
Portugal
(Paíga et al., 2016)
South-Africa
(Matongo et al., 2015)
0 pKa1 = 1.6; pKa2 = 5.7
Trimethoprim
pKa = 7.12
13
5320.00 2172.00
0
0.14
-
Sweden
(Lindim et al., 2016)
0
33.20
-
UK
(Burns et al., 2018)
0
14.73
-
USA
(Bean et al., 2018)
-
-
320.00
USA
(Ferrer and Thurman, 2012)
0
17.20
3.06
Bangladesh
(Hossain et al., 2018)
0
15.70
2.84
China
(Asghar et al., 2018)
0.40
52.10
12.35
China
(Yang et al., 2018)
34.00
74.00
61.00
Mexico
(Rivera-Jaimes et al., 2018)
0
290.00
58.00
South-Africa
(Matongo et al., 2015)
0.02
0.33
0.10
Sweden
(Lindim et al., 2016)
0
76.00
-
UK
(Burns et al., 2018)
0
2.29
-
USA
(Bean et al., 2018)
Antidepressives
Diazepam
-
-
24.30
China
(Wu et al., 2015)
0
305.00
55.50
India
(Mutiyar et al., 2018)
-
12.00
3.00
Spain
(Huerta-Fontela et al., 2011)
-
-
0.40
China
(Wu et al., 2015)
2.01
19.50
-
Portugal
(Paíga et al., 2016)
pKa = 3.4 Fluoxetine
ACCEPTED MANUSCRIPT
pKa = 9.8
14
25.37
25.37
25.37
Portugal
(Pereira et al., 2017)
0
0.01
-
Sweden
(Lindim et al., 2016)
-
-
65.00
USA
(Ferrer and Thurman, 2012)
Antiepileptic
Carbamazepine
pKa = 13.9
0
8.80
1.51
Bangladesh
(Hossain et al., 2018)
0
7.00
1.17
China
(Asghar et al., 2018)
0
3.50
0.44
China
(Yang et al., 2018)
-
-
25.30
China
(Wu et al., 2015)
0
5.80
3.30
France
(Celle-Jeanton et al., 2014)
0
1346.00
412.50
India
(Mutiyar et al., 2018)
8
36.00
19.00
Mexico
(Rivera-Jaimes et al., 2018)
0.02
0.21
-
Sweden
(Lindim et al., 2016)
24.90
214.00
-
Portugal
(Paíga et al., 2016)
0
-
10.90
Portugal
(Pereira et al., 2017)
South-Africa
(Matongo et al., 2015)
130.00
Gabapentin
3240.00 1048.00
-
54.00
13.00
Spain
(Huerta-Fontela et al., 2011)
0.94
9.39
-
USA
(Bean et al., 2018)
-
-
350.00
USA
(Ferrer and Thurman, 2012)
0
195.00
-
UK
(Burns et al., 2018)
0
4.55
-
Sweden
(Lindim et al., 2016)
-
-
54.00
USA
(Ferrer and Thurman, 2012)
pKa1 = 3.68; pK2 = 10.7 Anti-hyperglycemic 0.20
121.40
34.73
China
(Asghar et al., 2018)
0.44
8.40
2.60
Sweden
(Lindim et al., 2016)
45.20
2595.00
677.00
Metformin UK (Burns et al., 2018)
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15
pKa = 12.4
Beta-blockers
Atenolol
pKa = 9.6
Propanolol
-
900.00
470.00
Spain
(Huerta-Fontela et al., 2011)
4.00
10.00
7.00
Mexico
(Rivera-Jaimes et al., 2018)
-
-
21.70
USA
(Battaglin et al., 2018)
0
13.00
4.90
France
(Celle-Jeanton et al., 2014)
0
100.00
31.12
UK
(Burns et al., 2018)
-
-
166.00
USA
(Ferrer and Thurman, 2012)
0.18
8.47
-
Sweden
(Lindim et al., 2016)
-
270.00
54.00
Spain
(Huerta-Fontela et al., 2011)
0
64.90
11.66
United Kingdom
(Burns et al., 2018)
-
-
53.00
USA
(Ferrer and Thurman, 2012)
pKa = 9.42 Central nervous system (CNS) stimulant
Caffeine
pKa = 14
0
220.00
56.90
China
(Asghar et al., 2018)
18.40
293.00
100.51
China
(Yang et al., 2018)
0
81.00
41.30
France
(Celle-Jeanton et al., 2014)
0
2640.00
977.00
India
(Mutiyar et al., 2018)
16.27
36.00
30.83
Malaysia
(Praveena et al., 2018)
0
332.00
68.60
South-Africa
(Matongo et al., 2015)
-
-
591.77
USA
(Battaglin et al., 2018)
8.05
26.92
-
USA
(Bean et al., 2018)
-
-
220.00
USA
(Ferrer and Thurman, 2012)
Mexico
(Rivera-Jaimes et al., 2018)
Lipid regulators Gemfibrozil
14.00
24.00
20.00
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16
-
3735.00
77.00
Spain
(Carmona et al., 2014)
-
-
95.00
USA
(Ferrer and Thurman, 2012)
pKa = 4.5
232 233
The most detected drug in surface water considering the investigated studies
234
was carbamazepine. This compound is the antiepileptic most commonly found in
235
surface water (Rivera-Utrilla et al., 2013). Burns et al. (2018) detected this substance in
236
10 of the 12 samples collected in Ouse and Foss rivers in the United Kingdom. The
237
constant occurrence of this compound in surface and groundwater was studied by Clara
238
et al. (2004), which found that it is very persistent and is not subject to biodegradation
239
in conventional WWTP.
240
Besides carbamazepine, Burns et al. (2018) observed a high frequency of traces
241
of gabapentin, metformin, and trimethoprim. The authors found that metformin obtained
242
the second highest concentration (6111 ng L-1) in the effluent from a WWTP, only
243
losing to gabapentin (8541 ng L-1); furthermore, it was the compound with the highest
244
annual mean concentration in surface water of two rivers of the city. Metformin,
245
although poorly evaluated by its presence in surface water (present in only three studies
246
of Table 1), has caused concern. Asghar et al. (2018) considered this compound to be
247
one of the most critical of the 33 drugs identified, due to its high concentration in
248
effluents from Wuhan (China) WWTP, which was higher than 100 ng L-1 and to the
249
high occurrence rate in six rivers of the city. Metformin is an antihyperglycemic used in
250
the treatment of diabetes, and the authors justified their critical presence in the country's
251
high number of diabetics.
252
A great frequency of antibiotics could be observed in surface waters. Asghar et
253
al. (2018) found that this group of pharmaceuticals corresponded to 28% of the total
ACCEPTED MANUSCRIPT
17
254
occurrence. Sulfamethoxazole was the second most identified compound in Table 1 and
255
obtained the highest mean, found by Matongo et al. (2015) in Matsunduzi River in
256
South Africa. This compound obtained a high detection frequency among the antibiotics
257
evaluated in Brahmaputra River (Bangladesh) by Hossain et al. (2018), reaching 70%,
258
and was present in all samples collected in the Apatlaco River (Mexico) by Rivera-
259
Jaimes et al. (2018). Generally, the mechanism of sulfamethoxazole is potentiated with
260
trimethoprim, which explains the significant occurrence of this drug in the literature
261
consulted in this study. The maximum concentration of trimethoprim in Table 1 was
262
found by Matongo et al. (2015) of 290 ng L-1. The authors found an even greater
263
concentration of sediment collected in a reservoir in the city, stating that the residence
264
time allowed sorption of the product.
265
Traces of atenolol in aquatic environments are also discussed in the literature.
266
Lindim et al. (2016) have explained that atenolol is not or almost not metabolized in the
267
human body, so it is excreted in the concentrations similar to those consumed. Of all the
268
evaluated pharmaceuticals, this compound obtained the highest concentration found by
269
the authors. Huerta-Fontela et al. (2011) warned that atenolol, besides present in
270
Llobregat River in Spain (mean of 470 ng L-1), is one of the 5 drugs of the 32 evaluated
271
that persists in the water supply after all stages of a conventional DWTP, which shows a
272
great difficulty of removal of the substance.
273
Considering anti-inflammatories, the importance of acetaminophen (or
274
paracetamol) residues in aquatic environments should be emphasized. In Table 1, this
275
compound received the highest concentration among all cited, present in the study of
276
Burns et al. (2018). As a complement, the authors pointed out that acetaminophen
277
obtained the highest concentrations in the influent of all three WWTPs studied, reaching
278
282 319 ng L-1, a condition that, added to the incomplete removal, explains the presence
ACCEPTED MANUSCRIPT
18
279
of the drug in Ouse River in all 12 months evaluated. Paíga et al. (2016) reported a
280
similar pattern; the greatest mass load of the influent of two WWTPs was related to
281
paracetamol, also causing the greatest effluent load and higher concentrations along Lis
282
River in Portugal.
283
Caffeine, a central nervous system stimulant, is commonly associated with
284
analgesics and anti-inflammatories in medicine formulations. This fact, coupled with its
285
presence in several consumed beverages worldwide, justifies the frequency of traces of
286
caffeine in surface water. Asghar et al. (2018) found that the highest concentration was
287
related to caffeine, among all the other pharmaceuticals. Also, Celle-Jeanton et al.
288
(2014) concluded that caffeine together with acetaminophen obtained the highest
289
concentrations among the compounds evaluated in the Allier River, justifying the fact
290
by that both are part of the most consumed drugs in France, which beats their
291
biodegradability. Silva et al. (2014) observed that some of the highest concentrations
292
were found in urban spaces, a fact that could be justified by leakages from septic tanks.
293
The authors also highlighted that the sample of which the concentration was less than
294
the limit of detection was collected in a totally uninhabited area, consolidating the
295
concept that caffeine can be a marker of domestic wastewater.
296
The results discussed above justify the importance of complementary treatments
297
to the conventional, both in WWTPs and in DWTTs. One of the possibilities would be
298
the use of adsorption techniques, detailed in the next topic.
299 300
3. ADSORPTION PROCESSES
301 302
Adsorption is a phase transfer process that is widely used to remove substances
303
from the fluid phase (gases or liquids) and transfer to the solid phase (adsorbent
304
particle). It can be observed in different environmental compartments as a natural
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19
305
process. Regarding water or effluents treatments, the interaction occurs between a solid
306
and a pollutant, such as pharmaceuticals molecules. The pollutant is called adsorbate
307
and the solid is adsorbent. This technique has been used for the efficient removal of a
308
wide variety of contaminants (Ali et al., 2012; Worch, 2012).
309
According to Ho et al., (2000) in practice, adsorption is carried out in batch or
310
fixed bed column containing a certain mass of porous adsorbent. Under these
311
conditions, the effects of mass transfer are inevitable. The complete adsorption
312
sequence comprises three steps:
313 314
Step 1 - Film diffusion (external diffusion): transport of the adsorbate present in the
315
solution to the external surface of the adsorbent.
316
Step 2 - Diffusion of pores (intraparticle diffusion): transport of the adsorbate from the
317
surface of the adsorbent into the pores.
318
Step 3 - Surface reaction: fixation of the adsorbate on the surface of the adsorbent pores.
319 320
It is important to note that the third step is very fast, and the total adsorption rate
321
is determined by film and/or intraparticle diffusion. Also, since these two steps act in
322
series, the slower process characterizes adsorption (Worch, 2012).
323
Adsorption has been shown to be an excellent and promising technique due to its
324
numerous advantages, including low cost, accessibility, efficiency and environmental
325
benignity (Ali et al., 2012). Also, compared to the conventional methods of separation,
326
the advantages include chemical and/or biological sludge minimization, potential
327
adsorbent regeneration potential, no requirement for nutrients addition and the
328
possibility of recovering the adsorbed material if it has an economic value added
329
(Reddy et al., 2010).
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20
330
The possible materials to be used as adsorbents are various, some examples
331
being: activated carbon of mineral, animal or vegetable origin, ion exchange resin,
332
carbon nanotubes, chitosan, fly ashes and organic resins (Zhu et al., 2017). Besides the
333
efficiency, it is important to analyze the development of adsorbents and application cost,
334
as well as regeneration capacity. From this economic perspective, the term 'low-cost
335
adsorbents' was created. A low-cost adsorbent is defined as a material that requires little
336
processing, is abundant in nature or may be a waste material or by-product from an
337
industry activity (Rafatullah et al., 2010). In the case of the last materials, the economy
338
in the acquisition can offset the cost of processing. For that reason, a cost study is
339
important. Examples of low-cost adsorbents are clays, parts of plants, animals or other
340
materials with high carbon content, such as fruit residues, bark, algae, mosses, hair, and
341
keratin (Ahmaruzzaman, 2008; Rafatullah et al., 2010).
342
The selection of precursors should take into account the following factors:
343
material accessibility, hazardousness, carbon and oxygen content, abrasion resistance,
344
thermal stability, pore diameter, and high adsorption and regeneration capacity (Ali et
345
al., 2012). The textural, structural, morphological and chemical characterizations are
346
indicators of these qualities. Very common analyzes are the Point of Zero Charge
347
(PZC), zeta potential, scanning electron microscopy (SEM), nitrogen physisorption,
348
Fourier transform infrared spectroscopy (FTIR) and X-ray diffraction (XRD).
349 350
3.1 ADSORPTION STUDIES
351 352
In order to evaluate the applicability of adsorption to the removal of
353
contaminants such as pharmaceuticals, a complete study should be performed.
354
Generally, it contains several steps, such as the effect of pH and ionic strength, kinetics,
ACCEPTED MANUSCRIPT
21
355
isotherms, thermodynamics, desorption, and regeneration. These steps can be conducted
356
using either batch or column methods (Tran et al., 2017).
357
In general, three of these studies are the main constituents of the adsorption
358
theory, which have interdependence. The equilibrium study is considered to be the basis
359
of all adsorption models and a precondition for kinetics and dynamics. It assumes that
360
the adsorption capacity is a function of the concentration of the solution. However, the
361
kinetic study assumes that both the adsorption capacity and the concentration are
362
functions of the contact time. The dynamics is based on the two studies and assumes
363
that in addition to being a function of time, the concentration and adsorption capacity
364
are a function of space. This is used when the adsorption is conducted in a fixed bed
365
column (Worch, 2012).
366
Within the studies involving adsorption, it is common to evaluate two
367
parameters: adsorption capacity and percentage of removal. The increase in the
368
percentage of removal is usually proportional to the increase of the mass of the
369
adsorbent due to the greater availability of adsorption sites, however, does not
370
positively affect the adsorption capacity. This happens because once the percentage of
371
removal reaches 100%, the available sites are not saturated, causing an erroneous
372
estimation of the adsorption capacity (Fan et al., 2017).
373 374
3.1.1
Adsorption kinetics
375 376
As explained above, the adsorption kinetics is the basis for further studies.
377
According to Ho (2006), several studies on adsorption of pollutants have been
378
developed to have a better understanding of the mechanisms and to obtain the order of
ACCEPTED MANUSCRIPT
22
379
reaction found through kinetics. However, the understanding of the adsorption kinetics
380
is limited by the theoretical complexity of the mechanisms.
381
Simplified, the kinetics explains how fast the reaction occurs and still indicates
382
the factors that affect the rate of reaction (Crini and Badot, 2008). Typically, the
383
adsorption equilibrium is not reached instantaneously, as in the case of porous
384
adsorbents. The mass transfer of the solution into the pores inside the particles has
385
resistances, which determine the time required for the equilibrium (Worch, 2012).
386
The adsorption kinetics can be analyzed by mathematical models. The most used
387
models are pseudo-first-order (Ho and McKay, 1999) and pseudo-second-order (Ho and
388
McKay, 1999; Tran et al., 2017). However, the Elovich (Allen and Scaife, 1966; Crini
389
and Badot, 2008) and Intraparticle Diffusion (Weber and Morris, 1963) models have
390
been widely applied.
391 392
3.1.2
Adsorption equilibrium
393 394
The analysis and design of the adsorption process require a study of the
395
equilibrium, which is the most important in the understanding of the process (Vasanth et
396
al., 2007). The adsorption isotherms are equilibrium equations and they are applied to
397
the adsorption process after sufficient time to reach equilibrium at a constant
398
temperature (Kumar, 2007).
399
Since there are a wide variety of equilibrium isotherms to describe the
400
adsorption process, some mathematical models are commonly used to describe
401
equilibrium interactions in a solid-liquid system, such as Langmuir (Langmuir, 1917),
402
Freundlich (Freundlich, 1906), Sips, Tempkin, and Toth (Günay et al., 2007).
403
ACCEPTED MANUSCRIPT 404
3.1.3
23
Adsorption thermodynamics
405 406
Since motion is an intrinsic property of matter and energy is motion-related, it
407
is possible to understand that transformations, whether physical or chemical, are
408
associated with energetic variations. Thermodynamics is part of the physical sciences
409
that evaluates these variations (Nascimento et al., 2014).
410
Information about the adsorption capacity of a material can be obtained through
411
the thermodynamic parameters, such as Gibbs Free Energy (ΔG °), Enthalpy (ΔH °) and
412
Entropy (ΔS°). These are important thermodynamic parameters for the study of the
413
adsorption mechanisms that can confirm the viability, spontaneity and heat exchange
414
for the adsorption process (Zolgharnein et al., 2011).
415 416 417
4. PHARMACEUTICALS ADSORPTION BY LOW-COST ADSORBENTS – A REVIEW ON RECENT LITERATURE
418 419
Many papers have investigated the potential of low-cost adsorbents for the
420
removal of drugs from aqueous solutions. Table 2 was developed taking into account
421
the variety of precursors, mainly municipal and agroindustrial residues.
422 423 424 425
24
426
Table 2 – Adsorption of pharmaceuticals by low-cost adsorbents Chemical Compound
Precursor
Treatment agent
Remov Kinetics
Isotherm
Thermodynamics
Reference
(mg g-1) al (%)
Bamboo
TH
-
-
58
-
-
-
(Solanki and Boyer,
Coconut shell
AC
-
-
94
-
-
-
2017)
-
98
PSO
-
-
AC Acetaminophen
K2CO3, KOH
Cork
pKa = 9.38
qe, max
(Mestre et al., 2014)
AC
-
-
65
PSO
-
-
Cork bark
IN
-
0.99
65
-
-
-
Grape stalk
IN
-
1.74
60
PFO
Langmuir
-
Yohimbe bark
IN
-
31.00
65
-
-
-
(Villaescusa et al., 2011)
ΔG° < 0 Municipal solid
PFO, AC
KOH
180.00
-
wastes
-
ΔH° > 0
(Sumalinog et al., 2018)
PSO ΔS° > 0
Peach stones Atenolol
AC
K2CO3
0.77
80
PSO
Langmuir
-
AC
K2CO3
500.00
-
PSO
Langmuir
-
AC
KOH
555.60
-
PSO
Langmuir
-
AC
-
250.32
-
Elovich
Sips
-
Apple tree branches
Palm kernel shell
(Cabrita et al., 2010) (Marques et al., 2018)
(To et al., 2017)
25
pKa = 9.6
Carbamazepine
Cork
IN
0.37
88
PSO
Freundlich
-
Fish waste
TH
Sewage sludge
(Dordio et al., 2011)
-
27.50
-
-
Sips
-
TH
-
217.40
-
-
Sips
-
Palm kernel shell
AC
-
335.00
-
Elovich
Sips
-
(To et al., 2017)
Peach stones
AC
H3PO4
40.00
-
-
Sips
-
(Torrellas et al., 2015)
(Nielsen et al., 2015)
ΔG° < 0 pKa = 13.9
Rice straw
IN
-
18.00
-
PSO
Freundlich
ΔH° > 0
(Z. Liu et al., 2013)
ΔS° > 0 AC
Grape stalk
pKa = 14
-
98
PSO
-
-
KOH
Cork Caffeine
K2CO3,
(Mestre et al., 2014)
AC
-
-
85
PSO
-
-
IN
-
89.19
75
-
Sips
-
CH
H3PO4
129.56
85
-
Sips
-
AC
H3PO4
395.00
94
-
Sips
-
AC
H3PO4
260.00
-
-
Sips
-
126.00
-
-
Sips
-
Peach stones AC
H3PO4, HNO3
(Portinho et al., 2017)
(Torrellas et al., 2015)
26
ΔG° < 0 Pineapple plant leaves
AC
H3PO4
151.50
-
PSO
Langmuir
ΔH° < 0
(Beltrame et al., 2018)
ΔS° > 0
Diclofenac
Cocoa pod husk
AC
H2SO4
5.53
93
PSO
Freundlich
-
(De Luna et al., 2017)
Coconut shell
AC
-
-
100
-
Freundlich
-
(Nam et al., 2014a)
Olive- waste cakes
AC
H3PO4
38.00
96
PSO
Langmuir
-
(Baccar et al., 2012)
ΔG° > 0 Pine wood
AC
-
0.33
69
PFO
Langmuir
ΔH° > 0 ΔS° < 0 (Lonappan et al., 2018) ΔG° < 0
pKa = 4.15 Pig manure
AC
-
0.95
99
PSO
Freundlich
ΔH° < 0 ΔS° > 0 ΔG° < 0
Ibuprofen
TH
-
5.00
90
PSO
Langmuir
ΔH° < 0 ΔS° > 0
(Chakraborty et al.,
ΔG° < 0
2018)
Aegle marmelos shell
pKa = 4.91
AC
-
12.66
95
PSO
Langmuir
ΔH° < 0 ΔS° > 0
27
AC
150.00
82
PSO
Langmuir
-
KOH
Cork
Cork
K2CO3,
(Mestre et al., 2014)
AC
-
125.00
70
PSO
Langmuir
-
IN
-
0.32
98
PSO
Freundlich
-
(Dordio et al., 2011)
ΔG° < 0 Mung bean husk
AC
-
59.76
99
PSO
Langmuir
ΔH° < 0
(Mondal et al., 2016)
ΔS° < 0 Olive- waste cakes
AC
H3PO4
8.00
Almond shell
AC
H2O2
344.80
79
PSO
Langmuir
-
(Baccar et al., 2012)
PSO
Langmuir
-
(Zbair et al., 2018)
ΔG° < 0 Sulfamethoxazole
Coffee waste
CH
H2SO4
256.95
-
PSO
Langmuir
ΔH° < 0
(Ahsan et al., 2018)
ΔS° < 0 Fish waste
TH
-
17.72
-
Sips
-
(Nielsen and Bandosz,
Sewage sludge
TH
-
79.02
-
Sips
-
2016)
pKa1 = 1.6; pKa2 = 5.7
ΔG° < 0 (Ariful Ahsan et al., Tea leaves
CH
H2SO4
247.29
-
PSO
Temkim
ΔH° < 0 2018) ΔS° < 0
427
IN – in natura, TH – thermal treatment, CH – chemical treatment, AC – activated carbon, PFO – pseudo-first-order, PSO – pseudo-second-order
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428
In Table 2, three classifications of adsorbents were used: in natura (IN),
429
thermically treated (TH) and activated carbon (AC). These treatments can significantly
430
alter the surface properties and pores structure, which is highly related to the uptake of
431
pharmaceuticals molecules. The adsorbents can be used in natura after a simplified
432
washing pretreatment; chemically treated, after contact with chemical solutions for the
433
removal of undesired organic and inorganic matter contained on the surface; and
434
thermally treated, with furnace heating, to increase the surface area breaking the less
435
stable bonds and consequently releasing the volatile fraction of the precursor material
436
(Akhtar et al., 2007).
437
The chemical treatments are used in biomass to improve its adsorption capacity
438
of contaminants and to change the electrical behavior of the surface. The chemical
439
attack is expected to be able to destroy bonds between functional groups and the
440
adsorbent surface. This phenomenon may result in a pore size increase as well as
441
interactions with other functional groups of the contaminant (Módenes et al., 2017). The
442
chemical agents include organic and mineral acids (HCl, HNO3, H2SO4, acetic acid,
443
citric acid, and formic acid), bases and alkali solutions (NaOH, Na2CO3, Ca(OH)2 and
444
CaCl2), oxidizing (H2O2 and K2MnO4), among other compounds (Abdolali et al., 2014).
445
More advanced treatment generates the activated carbon, prepared in a two-
446
stage operation. The first step is the carbonization of the raw material at temperatures
447
below 800ºC in the absence of oxygen. Activation is then carried out with the use of an
448
oxidizing agent (vapor, carbon dioxide or air) at elevated temperatures and sometimes
449
with a catalyst. Activation may be accompanied by chemical or physical treatment
450
(Aygün et al., 2003; Wigmans, 1989). Lately, new methods of activation are being
451
investigated, such as microwave-assisted pyrolysis (Zbair et al., 2018). This method has
452
advantages compared to the conventional two-stage operation, such as more ease of
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453
control, reduced heating time, energy and gas utilization (Yuen and Hameed, 2009).
454
Although the activation process results in the further development of the surface pores,
455
its high cost may become an economic issue, which leads to a greater interest of
456
simplified and efficient treatments of the adsorbents.
457
As expected, it is observed in Table 2 that the higher adsorption capacities are
458
found in activated carbon, followed by chemically or thermally treated adsorbents and,
459
finally, in natura materials. Some works compared different treatments, which allows
460
verifying the influence of each of them on the structure, morphology, and surface loads,
461
characteristics that directly affect the adsorption of drugs. These papers will be
462
highlighted in the discussion of this topic.
463
Portinho et al. (2017), compared three types of adsorbents derived from grape
464
stalk (in natura, chemically treated with phosphoric acid and activated carbon) in the
465
adsorption of caffeine. They observed the above pattern and obtained the maximum qe
466
values of 89.194, 129.56 and 395 mg g-1, respectively. As expected, activated carbon
467
(AC) has a higher surface area and volume of micropores (1009.86 m² g-1 and 0.568 cm³
468
g-1) compared to untreated biomass (6.23 m² g-1 and 0.003 cm³ g-1) and chemically
469
treated (4.21 m² g-1 and 0.002 cm3 g-1). This effect promoted a greater number of sites
470
for adsorption, which implies higher values of qe. Furthermore, the authors emphasized
471
the importance of phosphoric acid addition in the two treatments, which added
472
functional groups to the surface and favored the adsorbate-adsorbent interactions. In this
473
case, the chemical reagent added oxygen groups, which resulted in hydrophilicity to the
474
grape stalk and facilitated the adsorption of polar molecules, such as caffeine.
475
Chakraborty et al. (2018) compared the adsorption capacity of ibuprofen by
476
two adsorbents derived from Aegle marmelos barks: thermally treated and activated
477
with steam. After activation, it was verified that the specific area and pore volume
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30
478
increased from 4.4 to 308 m² g-1 and from 0.184 to 0.384 cm³ g-1, respectively. This
479
increase not only resulted in the greater removal of ibuprofen but decreased the time
480
required to reach the equilibrium.
481
Regarding the treatments and chemical activations, it is possible to observe the
482
significant occurrence of phosphoric acid (H3PO4) in Table 2. Phosphoric acid is
483
considered to be the most environmentally-friendly reagent when compared to others
484
acids, more corrosive and hazardous, such as nitric acid (HNO3) and sulfuric acid
485
(H2SO4). These also can damage the structure of the adsorbent (Rajapaksha et al.,
486
2016). Benaddi et al. (1998) explained that phosphoric acid promotes the
487
depolymerization of cellulose, dehydration of biopolymers, formation of aromatic rings
488
and elimination of phosphate groups, allowing the increase of the surface area of the
489
adsorbents, besides the addition of functional groups.
490
Potassium hydroxide (KOH) and potassium carbonate (K2CO3) were also
491
frequent reagents in Table 2. Marques et al. (2018) compared the chemical activations
492
by both compounds in apple branches for the adsorption of atenolol. In general, the use
493
of KOH resulted in larger specific areas (maximum of 2472 m² g-1) compared to K2CO3
494
(maximum of 1963 m² g-1). Through scanning electron microscopy, it was observed that
495
the activation with K2CO3 promoted the maintenance of some of the morphological
496
characteristics of the precursor. The authors reported that the activation process with
497
KOH caused more significant destruction of the structure of the AC particles, promoting
498
a more homogeneous particle size distribution of the material. Considering the critical
499
size of the atenolol molecule (0.7 nm), its retention occurs in supermicropores. This fact
500
justified the higher adsorption capacity of adsorbents treated with KOH, which resulted
501
in a higher volume of supermicropores (maximum of 1.19 cm³ g-1).
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502
When it comes to the removal of pharmaceutical compounds from contaminated
503
water, it is important to understand their protonation behavior in aqueous solution. The
504
effect of the pH of the solution on the adsorption processes is important to understand
505
the interaction between the adsorbate and adsorbent since the variation of the pH can
506
promote changes in the superficial charges of adsorbents and influence the protonation
507
of functional groups present in the contaminants (Beltrame et al., 2018). Thus, the pH
508
can affect both the adsorbent surface properties and the nature of the adsorbate, causing
509
different types of mechanisms during the adsorption process (Baccar et al., 2012), and
510
several can be observed in the papers contained in Table 2.
511
The pH of the Point of Zero Charge (pHPZC) of an adsorbent depends on the
512
chemical and electronic properties of the functional groups and is a good indicator for
513
the adsorption process (Song et al., 2010). For a given particle and according to its
514
amphoteric character, it is known that the surface is neutral at pH = pHPZC, negatively
515
charged at pHs higher than pHPZC and positively charged at pHs below pHPZC (Baccar et
516
al., 2012). Regarding pharmaceuticals, these may be weak acids or bases, and their
517
protonation will be based on their pKa values. An acid has the tendency to donate
518
protons, and its dissociation is represented below (Geffertová et al., 2017):
519 HA ⇌H + + A -
520 521 522
Weak acids at pH < pKa are predominantly in their protonated forms (HA),
523
while at pH > pKa they are predominantly in their deprotonated forms (A-). On the
524
contrary, weak bases have the tendency to receive protons, and their ionization occurs
525
as follows (Pardue et al., 2004):
526
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32
HB + ⇌H + + B
527 528 529
At pH < pKa, weak bases are predominantly in their protonated forms (HB+),
530
while at pH > pKa they are predominantly deprotonated (HB). Briefly, ionizable
531
molecules such as pharmaceuticals may interact with the adsorbent through electrostatic
532
attraction or repulsion, and this interaction varies according to their pKa values (Huerta-
533
Fontela et al., 2011)
534
Exemplifying electrostatic interactions, diclofenac is considered a weak acid
535
since its pKa is around 4.15 (Nam et al., 2014b). According to Nielsen et al. (2015), for
536
hydrophobic compounds, such as diclofenac, adsorption can be largely affected by pH
537
changes, therefore, electrostatic and specific interactions (based on surface polarity,
538
functional groups, organic and inorganic components of the adsorbent) between the
539
contaminant and the surface of the adsorbent particle have an impact on adsorption.
540
Lonappan et al. (2018) verified in their studies that the isoelectric point of pig manure
541
biochar was 2.15 and the adsorption of diclofenac was pH dependent. The maximum
542
removal efficiency of this compound was 99.6% observed at pH 2 (Table 2) and this
543
percentage decreased to 88.8% at pH 12.5. This was justified by the changes in the
544
surface charge and, consequently, the negative surface of the biosorbent repelled by the
545
diclofenac anion.
546
Baccar et al. (2012) in their studies of the biosorbent derived from olive residues
547
(pHPCZ = 5.03) also observed that high pH reduced the uptake of diclofenac and
548
ibuprofen, and this effect was more noticeable when the pH became alkaline. Ibuprofen
549
has pKa = 4.91 and diclofenac pKa = 4.15, both acidic drugs are essentially neutral
550
molecules at pH below the pKa value, however, they acquire a negative charge when
551
the pH is above the pKa value due to the dissociation of molecules of this compound.
ACCEPTED MANUSCRIPT
33
552
Thus, at pH > pHPZC (pH = 8.61), the surface of the adsorbent is negatively charged and
553
a higher proportion of the ionized form of the pharmaceuticals is also charged (pH >
554
pKa), leading to an electrostatic repulsion between adsorbate anions and the surface of
555
the adsorbent and consequently, the removal of pharmaceuticals has decreased.
556
However, although many papers justify the pharmaceuticals adsorption by
557
electrostatic interactions, this is not a rule. Portinho et al. (2017) verified that the best
558
caffeine adsorption capacity was obtained at pH 2. Caffeine is a weak base with pKa =
559
14. This implies that at acid pHs the drug is in its protonated form. When analyzing the
560
adsorbents derived from grape stalks by their surface charges, it was observed that the
561
pHPCZ was around 7.5, which shows that at pH 2 the surface of the particles would be
562
positively charged. Therefore, an electrostatic repulsion would occur, which would
563
adversely affect the adsorption process. The authors then justified that better removals
564
at acid pHs were due to non-electrostatic effects, such as, for example, hydrogen bonds
565
between caffeine and grape stalks. Hydrogen bonds occur preferentially when the
566
surface of the adsorbent is positively charged (Sotelo et al., 2012).
567
In short, Moreno-Castilla (2004) cited three possible mechanisms of adsorption
568
of organic compounds, which can be implied to pharmaceuticals: the π–π dispersion
569
interaction, the hydrogen bonding formation, and the electron donor-acceptor complex
570
formation mechanism. These are related to the chemical properties of the adsorbent
571
surface, that can be verified, for example, through the FTIR spectra analysis. In the case
572
of lignocellulosic materials, some functional groups, such as carboxyl, hydroxyl and
573
amides may be related to the process (Dai et al., 2018).
574
Villaescusa et al. (2011) found likely binding sites for acetaminophen on grape
575
stalks surface through the FTIR analysis, such as hydroxyl groups (peak around 3350
576
cm−1), lignin aromatic bonds (1620 cm-1), guayacil unit (1034, 1159 and 1263 cm-1) and
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34
577
syringil unit (1105 and 1315 cm-1). After adsorption, there was a shift related to the
578
aromatic rings, indicating the possible adsorption site, and then the authors considered
579
that hydrogen bonding and π-stacking interactions with lignin provided the main
580
mechanism for the adsorption of paracetamol in the grape stalk.
581
Zbair et al. (2018) observed by the FTIR spectra of almond shells activated
582
carbon that some peaks were shifted and the intensity changed when loaded with
583
sulfamethoxazole. The authors considered the respective functional groups as the main
584
adsorption sites. The shifted peaks were from 3397 to 3370 cm-1 (Hydroxyl groups),
585
from 1684 to 1596 cm-1 (C=C vibration of aromatic rings), from 1181 to 1051 cm-1 (C-
586
OH) and 640 to 518 cm-1 (C-H deformation). Taking these changes into account, the
587
possible mechanisms were considered to be due to Van der Waals forces or weak
588
electrostatic interaction.
589
Nielsen et al. (2015) found some indications of the adsorption mechanism by
590
analyzing proton binding curves. This analysis showed that their adsorbents developed
591
from sewage sludge and fish waste exhibited basic nature (pHPZC were between 9 and
592
10). After the adsorption of carbamazepine, there was a decrease in basicity on the
593
sludge carbon. Considering the basic nature of the pharmaceutical molecule, this fact
594
could imply that acid-base interactions were not the main adsorption mechanism. A
595
different situation occurred for the fish-derived carbon, and the increase of basicity was
596
related to the dispersive interactions of the aromatic rings of carbamazepine and the
597
exposed amine groups. Also, it was observed that in the adsorbent treated with lower
598
temperatures, there were more changes in the acidity after the adsorption, suggesting
599
chemical interactions, such as the complexation of the pharmaceutical on metal cations.
600
Concerning this aspect, the authors added that higher temperatures lead to higher levels
ACCEPTED MANUSCRIPT
35
601
of aromatization, attracting the aromatic rings of carbamazepine with stronger
602
dispersive forces.
603
Discussing the kinetic models, it is possible to verify the good fit of the pseudo-
604
second-order model in Table 2. As previously mentioned, together with the pseudo-
605
first-order model, this equation is widely applied to kinetic adsorption data. However,
606
due to restricted conditions and application generally, in the first minutes of reaction,
607
the pseudo-first-order model was applied to a few processes.
608
Lonappan et al. (2018) adjusted the linearized pseudo-first, pseudo-second and
609
Elovich models for the kinetic data of diclofenac adsorption on activated carbon of pine
610
wood. Although the pseudo-second-order model obtained a correlation coefficient (R²)
611
of 0.99, the calculated qe value (400 μg g-1) differed significantly from the experimental
612
one (331 μg g-1), a situation that did not occur with the pseudo-first-order-model (qe, calc
613
= 339 µg g-1). Sumalinog et al. (2018) adjusted the linear forms of the pseudo-first and
614
pseudo-second-order equations in kinetic data of paracetamol adsorption in activated
615
carbons derived from municipal solid waste controlled at three different temperatures.
616
In the three curves, the R² coefficients of the two models were satisfactory, varying
617
from 0.986 to 0.999. In addition, the calculated qe values were close. For these reasons,
618
the authors concluded that both models applied to adsorption.
619
In relation to the equilibrium study, the most prominent model in Table 2 was
620
Langmuir, followed by Sips, Freundlich and, finally, Temkin. The occurrence of the
621
Sips model is justified because this is a simplification of Langmuir at high
622
concentrations of adsorbate. To et al. (2017) explained the good fit of both models to
623
the equilibrium data of atenolol and carbamazepine adsorption in palm kernel shell. The
624
fit was analyzed by the sum of the error squares, and this parameter was 0.000001 for
625
Sips, 0.4 for Langmuir and 262.7 for Freundlich. According to the authors, the good fit
ACCEPTED MANUSCRIPT
36
626
of the Langmuir model followed by Sips completed the process understanding,
627
confirming that the pharmaceuticals were adsorbed in a monolayer on the adsorbent
628
surface. Furthermore, the Sips model, which resulted in nF values of 0.81 and 0.37 for
629
carbamazepine and atenolol, respectively, showed that activated carbon has some
630
heterogeneity, which is not as intense as the good fit of Freundlich model would imply.
631
About the effect of temperature, analyzed by thermodynamic parameters, the
632
works cited in Table 2 did not present a pattern. Some showed that the increase in
633
temperature favored the adsorption capacity of pharmaceuticals (Beltrame et al., 2018;
634
Z. Liu et al., 2013; Lonappan et al., 2018; Sumalinog et al., 2018) and others concluded
635
that this effect disfavored the process (Ahsan et al., 2018; Ariful Ahsan et al., 2018;
636
Chakraborty et al., 2018; Lonappan et al., 2018; Mondal et al., 2016). These situations
637
can be justified either by the Gibbs Free Energy (ΔGº) or the Enthalpy values (ΔHº).
638
The Gibbs Free Energy (ΔGº) is related to spontaneity, fundamental for the
639
viability of the process. Sumalinog et al. (2018) observed that the values of this
640
parameter suffered a decrease of 36% with the temperature increase from 303 to 323K.
641
This situation demonstrated the increase of the spontaneity generated by the temperature
642
increase, also favoring the adsorption capacity. The same was also pointed out by
643
Beltrame et al. (2018) and Liu et al. (2013). In contrast, some authors noticed that the
644
higher values of ΔGº occurred with higher temperatures, i.e., there was a decrease in
645
spontaneity, a fact that accompanied the decrease in the adsorption capacity (Ahsan et
646
al., 2018; Ariful Ahsan et al., 2018; Chakraborty et al., 2018; Mondal et al., 2016).
647
It is noteworthy that only one study obtained a positive value for this parameter,
648
indicating a non-spontaneous adsorption. Lonappan et al. (2018) found positive values
649
for the 5 temperatures analyzed in the study of adsorption of diclofenac in pine wood.
650
The authors justified this fact by the energy barrier that could have impeded the process
ACCEPTED MANUSCRIPT
37
651
at the pH used (6.5), since electrostatic forces played an important role in the
652
adsorption, highly pH dependent.
653
Some studies justified the effect of temperature by the enthalpy values. Positive
654
values of ΔH° indicate endothermic reactions, i.e., they absorb heat from the medium
655
and negative values indicate exothermic reactions, i.e., they release heat. Some authors
656
have therefore related the beneficial effect of temperature increase to positive enthalpy
657
values (H. Liu et al., 2013; Sumalinog et al., 2018) and the beneficial effect of
658
decreasing the temperature to negative values of enthalpy (Ahsan et al., 2018; Ariful
659
Ahsan et al., 2018; Chakraborty et al., 2018; Mondal et al., 2016).
660
Another point to be considered in adsorption of pharmaceuticals is the problem
661
of competition. In real water matrices, these compounds are never alone, and the
662
presence of salts and other compounds should be analyzed because they can enhance or
663
inhibit the adsorption capacity (Fernández et al., 2014; Silva et al., 2018). Therefore,
664
there are papers that studied competitive adsorption, by adding two or more
665
pharmaceuticals in aqueous solution or different types of salts. For example, Fernández
666
et al. (2014) studied the competitive effects of sulfamethoxazole and sulfamethazine and
667
observed a reduction of the adsorption capacity when compared to the values related to
668
each compound separately. In the test using separated solutions of 50 mg L-1, the
669
adsorption capacity of sulfamethoxazole and sulfamethazine was 54.2 and 40.1 mg g-1,
670
respectively. When combined the two solutions, the adsorption capacity was reduced to
671
37.2 and 19.0 mg g-1, respectively. In all tests of adsorption competition, it was verified
672
a higher qe for sulfamethoxazole, showing that the adsorbent had more affinity for that
673
compound.
674
Chakraborty et al. (2018) evaluated the competitive effects on the adsorption of
675
ibuprofen and diclofenac and observed that the removal of the first pharmaceutical was
ACCEPTED MANUSCRIPT
38
676
decreased in the presence of the other. This situation was explained by the difference in
677
the molecular structures of the compounds since the molecule of ibuprofen is smaller
678
than that of diclofenac, and the affinity for this compound was higher due to
679
electrostatic interactions.
680
Sotelo et al. (2012) studied competitive adsorption of diclofenac in two
681
aqueous matrices: ultrapure water and a wastewater treatment plant effluent. The
682
authors explained that in this effluent there was a complex mixture of humic acids,
683
inorganic compounds, carbohydrates, and proteins. All these molecules competed with
684
diclofenac for binding sites on the activated carbon surface, and their availability
685
decreased. The experimental data confirmed this statement since the qe decreased from
686
329 mg g-1 to 184 mg g-1 when used the wastewater treatment plant effluent.
687
Despite all the adsorption studies, to evaluate the application of low-cost
688
adsorbents, regeneration must be considered, due to sustainability and economic
689
concerns. Only a few works cited in Table 2 studied this topic. Ariful Ahsan et al.,
690
(2018) performed successive sulfamethoxazole adsorptions, regenerating their modified
691
adsorbent from tea leaves with ethanol. After three cycles, the adsorption capacity was
692
reduced from approximately 90 to 82 mg g-1, and the authors concluded that the
693
material could be used repeatedly for removal of this compound, being an indicator of
694
applicability. Chakraborty et al. (2018) performed four cycles of ibuprofen adsorption,
695
using methanol. Their low-cost adsorbents were regenerated, achieving more than 74%
696
of desorption after the fourth cycle and the qe remained at least 61% of the initial value.
697
Zbair et al. (2018) evaluated five cycles, using ethanol for desorption. The
698
efficiency of sulfamethoxazole removal of their almond shell carbon decreased only
699
7%, and about 89% of the material was recovered. The authors also performed a
700
nitrogen physisorption analysis, observing that the surface specific area and pore
ACCEPTED MANUSCRIPT
39
701
volume decreased from 1274 to 1134 m2 g-1 and from 1.67 to 1.43 m3 g-1, respectively.
702
This data confirmed the deposition of the pharmaceutical molecules on the adsorbent
703
surface.
704
After the cycles or the exhaustion, the adsorbents must be disposed of. The
705
disposal of the loaded adsorbents is fundamental for their safety assessment application
706
(Simeonidis et al., 2017). The spent activated carbon is often incinerated, but there are
707
some alternatives of other uses. Some adsorbents can be used as a component of
708
building materials, such as cement and bricks (Zhou et al., 2019). Another alternative is
709
to use these as fuel in the boilers/incinerators, depending on its heating value, or for the
710
development of fuel-briquettes (Kushwaha et al., 2010).
711
Lastly, since low-cost adsorbents are being discussed, some aspects of costs
712
should be considered. Again, only a few papers cited performed this kind of analysis.
713
Chakraborty et al. (2018) and Zbair et al. (2018) considered the acquisition, size
714
reduction, washing, drying, carbonization, steam activation, reagents and electricity
715
costs for the analysis. It is noteworthy that, in the case of the two works, there were no
716
costs in the acquisition of the precursor materials, since they were residues (wood apple
717
and almond shell). As mentioned, the economy in the acquisition can offset the cost of
718
processing, and there are simplified and complex treatments. Chakraborty et al. (2018)
719
compared two adsorbents, one after simple carbonization and the other after vapor
720
activation. Obviously, activation increased the cost of processing but the adsorption
721
capacity more than doubled. In this case, it must be balanced the efficiency with
722
economic aspects. The cost of the steam activated adsorbent was estimated at $ 3.6/kg, a
723
low value compared to the activated carbon from Zbair et al. (2018) ($27.8/kg).
724
However, the processing used by the last authors were more complex, because of the
725
reagents (H2O2) and nitrogen atmosphere. Also, the adsorption capacity was superior
ACCEPTED MANUSCRIPT
40
726
(344.8 compared to 12.6 mg g-1). For these reasons, costs vs. efficiency should be very
727
carefully analyzed when it comes to applicability.
728
Analyzing Table 2 in general and the discussion about the recyclability and
729
costs, it can be verified the variety of precursors of adsorbent materials for the removal
730
of pharmaceuticals from contaminated water, as well as the variety of treatments in
731
order to improve the adsorption capacity. Furthermore, it was possible to verify the
732
difference in behavior of the adsorbents and the contaminants, which implies the need
733
for complete studies of the process for the possible application in WWTPs and DWTPs.
734 735
CONCLUSION
736 737
Pharmaceuticals are complex molecules that can be persistent in the
738
environment and resistant to conventional treatments of wastewater and drinking water.
739
It is apparent that pharmaceutical compounds are being found in surface water at low
740
and moderate concentrations. However, even in low concentrations, little is known
741
about its long-term effects, considering its influence on aquatic organisms and human
742
health. Recent researches have indicated the toxicological effect of drugs on the organic
743
functions of aquatic organisms in minimal concentrations and some have already been
744
classified as endocrine disrupters.
745
Given the environmental impacts presented, the importance of a complementary
746
treatment to the conventional one which removes efficiently these compounds becomes
747
clear. Adsorption is an alternative to the reduced cost that has been shown to be efficient
748
in the removal of various organic and inorganic compounds and has been investigated
749
for the removal of several pharmaceuticals. The possibility of precursors of adsorbents
750
is wide, and municipal, agricultural and industrial wastes have gained interest and have
ACCEPTED MANUSCRIPT
41
751
been applied as so-called 'low-cost adsorbents'. In recent articles, it was clear the
752
efficiency of these adsorbents, considering the high adsorption capacities and
753
percentage of removal. However, this does not necessarily mean that their application in
754
WWTPs and DWTPs is feasible.
755
The first problem is the reduced number of studies analyzing the removal of
756
pharmaceuticals in real effluents; most studies use solutions prepared in laboratories
757
with ultrapure water. However, in real matrices, these contaminants are never alone and
758
there is competition between different organic and inorganic compounds, which can
759
significantly decrease the adsorption and removal capacity, as observed in some papers.
760
Another factor to consider is the recyclability. There is some difficulty in finding this
761
topic in the recent literature related to the adsorption of pharmaceuticals, which raises
762
doubts about the resistance and durability of the materials studied. In industry, these
763
features are the key to the interest of application. Moreover, for the real interest in so-
764
called ‘low-cost adsorbents’, is the estimation of production investment, a fundamental
765
point that is little discussed, which consequently interfere in the searching for these
766
materials for this purpose. Therefore, considering these issues, it becomes necessary a
767
careful evaluation of the feasibility of transferring the process from laboratory scale to a
768
pilot scale, which is complex and requires complete studies.
769 770
Acknowledgments
771
The authors thank the National Council for Scientific and Technological
772
Development - CNPq and Higher Education Personnel Improvement Coordination e
773
CAPES for financial support.
774 775
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ACCEPTED MANUSCRIPT
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776
Abdolali, A., Guo, W.S., Ngo, H.H., Chen, S.S., Nguyen, N.C., Tung, K.L., 2014.
777
Typical lignocellulosic wastes and by-products for biosorption process in water
778
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779
https://doi.org/10.1016/j.biortech.2013.12.037
780
Aguirre-Martínez, G. V., André, C., Gagné, F., Martín-Díaz, L.M., 2018. The effects of
781
human drugs in Corbicula fluminea. Assessment of neurotoxicity, inflammation,
782
gametogenic activity, and energy status. Ecotoxicol. Environ. Saf. 148, 652–663.
783
https://doi.org/10.1016/j.ecoenv.2017.09.042
784
Ahmaruzzaman, M., 2008. Adsorption of phenolic compounds on low-cost adsorbents:
785
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ACCEPTED MANUSCRIPT Highlights
Pharmaceuticals have been found in surface water in μg L-1 to ng L-1. Pharmaceuticals can be persistent in the environment. Adsorption is effective in removing organic and inorganic pollutants from water. Adsorption has been investigated for the removal of several pharmaceuticals. Municipal and agro-industrial wastes can be used as precursors of adsorbents.