Environmental Science and Pollution Research (2019) 26:4690–4702

https://doi.org/10.1007/s11356-018-3954-2

RESEARCH ARTICLE

Kinetic, equilibrium, and thermodynamic studies on the adsorption

of ciprofloxacin by activated carbon produced from Jerivá
(Syagrus romanzoffiana)
Caroline de Oliveira Carvalho 1 & Daniel Lucas Costa Rodrigues 1 & Éder Cláudio Lima 2 & Cibele Santanna Umpierres 2 &
Diana Fernanda Caicedo Chaguezac 2 & Fernando Machado Machado 1

Received: 22 October 2018 / Accepted: 7 December 2018 / Published online: 18 December 2018
# Springer-Verlag GmbH Germany, part of Springer Nature 2018

Abstract
High specific surface area activated carbon prepared from endocarp of Jerivá (Syagrus romanzoffiana) (ACJ) was used for
ciprofloxacin (CIP) antibiotic removal from aqueous effluents. The activated carbon (AC) was characterized via scanning
electron microscope, Fourier transform infrared spectroscopy, N2 adsorption/desorption, and pH value at the zero-charge point.
Avrami kinetic model was the one that best fit the experimental results in comparison to the pseudo-first-order and pseudo-
second-order kinetic models. The equilibrium data obeyed the Liu isotherm equation, showing a maximum adsorption capacity
of 335.8 mg g−1 at 40 °C. The calculated thermodynamic parameters indicate that the adsorption of CIP was spontaneous and
endothermic at all studied temperatures. Also, the free enthalpy changes (ΔH° = 3.34 kJ mol−1) suggested physical adsorption
between CIP and ACJ. Simulated effluents were utilized to check the potential of the ACJ for wastewater purification. The highly
efficient features enable the activated carbon prepared from endocarp of Jerivá, an attractive carbon adsorbent, to remove
ciprofloxacin from wastewaters.

Keywords Emerging contaminants . Activated carbon . Adsorption . Ciprofloxacin . Nonlinear isotherm fitting . Mesoporous
structure

Introduction found in a natural wastewater stream produced by industrial

The emerging contaminants (ECs), such as hormones, medi-
cines and personal care products, flame retardants, plasti-
cizers, surfactants, wood preservatives, disinfectants, laundry
detergents, pesticides, and others, are environmental pollut-
ants of growing concern (Solliec et al. 2016). These ECs were
Responsible editor: Tito Roberto Cadaval Jr
Electronic supplementary material The online version of this article
(https://doi.org/10.1007/s11356-018-3954-2) contains supplementary
material, which is available to authorized users.
* Fernando Machado Machado
fernando.machado@ufpel.edu.br;
fernando.machado@hotmail.com.br
1 Considering that conventional treatments of water and ef-
Technology Development Center, Federal University of Pelotas, 1
Gomes Carneiro St, Pelotas, RS 96010-610, Brazil
2 becomes necessary to apply more specific and efficient
Institute of Chemistry, Federal University of Rio Grande do Sul,
9500 Bento Gonçalves Ave., Postal Box 15003, Porto
Alegre, RS 91501-970, Brazil
and human activities (Solliec et al. 2016; Jauris et al. 2016a).
Many pharmaceutical compounds are produced and con-
sumed worldwide in human and veterinary medicine (Solliec
et al. 2016; Kümmerer 2008). After its consumption, part of
the dosage is eliminated through feces and urine, which even-
tually contaminate water bodies (Jauris et al. 2016a). Among
the classes of pharmaceutical compounds, antibiotics have
been causing environmental impacts because of its persistent
components, which have high water solubility and low de-
gradability (Carmalin et al. 2016; Carmalin et al. 2018).
Ciprofloxacin (CIP) stands out, being an antibiotic used
worldwide for infection treatments (Kümmerer 2008;
Prutthiwanasan et al. 2016). Because of this high consump-
tion, the presence of CIP in water resources is recurrent
(Kümmerer 2008; Prutthiwanasan et al. 2016).
fluents are not able to degrade or eliminate the ECs easily, it
methods (Daoud et al. 2017). Techniques applied for removal
of this type of compound are ozonation, chlorination, reverse
Environ Sci Pollut Res (2019) 26:4690–4702
osmosis, and nanofiltration (Rodriguez-Narvaez et al. 2017).
However, high economic investments are necessary, and these
processes can be challenging to operate, which reduces the
possibilities of using these technologies on an industrial scale
(Rodriguez-Narvaez et al. 2017). Therefore, the adsorption
process has been studied, since it can be applied in low con-
centrations, has a feasible operation, has a low cost of appli-
cation, and can be used in continuous and discontinuous pro-
cesses (Leite et al. 2018; Bergmann and Machado 2015;
Cunha et al. 2018; Umpierres et al. 2018).
The choice of a suitable adsorbent is one of the most critical
parameters for an efficient adsorption process (Bergmann and
Machado 2015). Several carbonaceous materials are used as
adsorbents and, currently, industrial and agricultural wastes
are used to treat effluents, called biosorbents (Leite et al.
2018; Cunha et al. 2018; Umpierres et al. 2018;
Hosseinzadeh and Mohammadi 2015). These materials are
carbon-rich and have a low cost, high availability, low toxic-
ity, and great potential to become activated carbon (AC)
(Hosseinzadeh and Mohammadi 2015).
Authors have effectively applied adsorbents for the adsorp-
tion of the antibiotic CIP. Mao et al. (2016), to improve the
adsorption process, presented a magnetic adsorbent composed
of Fe3O4 and carbon, obtained by hydrothermal synthesis for
CIP adsorption. The results indicated that the adsorbent has
strong magnetism, with an adsorption capacity (Qmax) of
90.1 mg g−1. Langmuir isotherm model best suited the exper-
imental results, with the pseudo-second-order equation accu-
rately describing adsorption kinetics. Sun et al. (2016) dem-
onstrated the production of activated carbons obtained from
two biomass residues from pomelo peel and Arundo donax
Linn, using H3PO4 as the activating agent. The characteriza-
tion results showed that the materials had high porosity and
surface specific area. Also, the adsorption process of CIP onto
an AC followed the Langmuir isotherm model with Qmax of
400 mg g−1, and 244 mg g−1 for AC achieved from Pomelo
peel and Arundo donax Linn. Based on the thermodynamic
parameters, the authors concluded that the adsorption process
on two adsorbents should be physisorption.
Due to its tropical climate, Brazil has a great variety of
fruits, among them, the Jerivá (Syagrus romanzoffiana). This
is a yellow fruit, which measures about 3 cm, originated from
palm trees (see Supplementary Fig. 1). Its external part is
composed of sweet mucilage that mainly serves for feeding
birds (Sun et al. 2016). It is abundant in South America and
produces fruits throughout the year, but has no commercial
application, resulting in an enormous quantity of dry fruits.
For consequence, it acquires a fibrous outer layer that sur-
rounds a rigid endocarp that keeps the almond inside
(Coimbra and Jorge 2011). Although there were researches
to apply the almond as biodiesel (Falasca et al. 2012;
Moreira et al. 2013), no solutions were presented for the res-
idue from the endocarp of the material.
4691
The objective of this study was to evaluate the adsorption
of the ciprofloxacin antibiotic onto high specific surface area
activated carbon produced by the wastes of Jerivá (Syagrus
romanzoffiana). Equilibrium data were analyzed applying
Freundlich, Langmuir, and Liu models. Kinetics experimental
results were evaluated applying the Avrami fractional-order,
and pseudo-first and second-order models. For real applica-
tion objective, the AC produced by the residues of Jerivá was
applied on simulated effluent that was polluted with a combi-
nation of medicine, sugar, and other organic and inorganic
compounds.
The research becomes innovative because there are still no
studies on the use of the fruit as a raw material in the obtain-
ment of AC for applications as an adsorbent, in the removal of
ECs. Such an application enables the treatment of effluent
using renewable source material and which, until then, has
no industrial application.
Materials and Methods
Solutions
The deionized water was utilized during the tests for solution
formulate. Ciprofloxacin antibiotic (CAS, 86393-32-0;
C 17H 18FN 3O 3 MM, 331.347 g mol −1 ; water solubility,
1.70 g L−1 (pH 7), see Supplementary Fig. 2) was furnished
by Pharmanostra (Pelotas, RS, Brazil). The CIP was used
without further purification. This antibiotic is a zwitterionic
compound, which means that it is capable of assuming both
negative and positive charges depending on the pH treatments
(Kümmerer 2008). In this case, CIP has this characteristic in
the range of pH 7.
For adsorption tests, a stock solution of CIP was formulat-
ed by precisely dissolving the antibiotic in deionized water at a
concentration of 1000 mg L−1. Serial dilutions of the stock
solution obtained working solutions of the CIP. The pH regu-
lations of the work solutions were obtained with aliquots of
0.1 mol L−1 HCl and/or NaOH solutions using a pH meter
(Digimed DM 22).
Preparation and characterization of activated carbon
from Jerivá
The fruits of Jerivá (Syagrus romanzoffiana) were obtained by
collecting these fruits in different regions of Pelotas city (RS,
Brazil). After drying the material, the endocarp, material of
interest, was separated, crushed with the aid of a knife milling
machine (Marconi, MA340), oven-dried at approximately
60 °C for 2 h and then sieved until the desired granulometry
was obtained in a sieve with no. 35, receiving Jerivá natural
form (JIN).
4692
For the chemical activation, ZnCl2 was used. The concen-
tration of the activating agent was calculated by relating the
mass of the activating agent to the precursor mass (100 g of
JIN was used), with a ratio of 1:1 (Umpierres et al. 2018). The
mixture formed a uniform dark-colored slurry which was heat-
ed for 40 min at a temperature of 100 °C with constant stirring,
then dehydrated at 150 °C (Kasperiski et al. 2018a). The sam-
ples were carbonized, under N2 flow (200 mL min−1), in an FT
1200-H quartz reactor (Kasperiski et al. 2018a). For the car-
bonization, a temperature of 450 °C was applied, with a
heating rate of 10 °C min−1 and holding at 450 °C for
45 min. In sequence, the material was refluxed with 6.0 M
HCl solution at 90 °C under stirring at 420 rpm for 6 h
(Umpierres et al. 2018; Puchana-Rosero et al. 2016). After
this step, the material was abundantly washed with deionized
water to remove any acid excess until it reaches a neutral pH.
After washing, the material was oven-dried for 24 hours at
110 ± 5 °C. Finally, the obtained solid was sieved in a
53-μm (no. 270, ASTM) sieve to achieve uniform
granulometry. The material produced received the nomencla-
ture of activated carbon of Jerivá (ACJ).
Characterization of activated carbon prepared
from endocarp of Jerivá
Morphological analysis of the obtained ACJ was performed
by scanning electron microscopy (SEM) in JEOL JSM -
6610LV microscope. Voltages of 10 to 20 kV and magnifica-
tion of 2500 to 5000 were used (Kasperiski et al. 2018a).
The porosity and surface specific area analysis measure-
ments were carried out on an Autosorb Quantachrome volu-
metric adsorption analyzer (at − 196.15 °C). For specific sur-
face area and pore size and distribution predictions, multipoint
BET (Brunauer, Emmett and Teller) and BJH (Barret, Joyner,
and Halenda) equation were utilized, respectively (Puchana-
Rosero et al. 2016).
The ACJ was characterized by Fourier transform infrared
(FTIR) spectroscopy. A Shimadzu IR Prestige-21 spectrome-
ter was used to obtain a spectrum with the wavenumber range
between 4000.0 and 400.0 cm−1, with a resolution of 4.0 cm−1
(by 100 cumulative readings) (Prola et al. 2013).
The point of zero charge (pHPZC) of the ACJ was deter-
mined by adding 20.00 mL of 0.050 mol L−1 NaCl with a
previously adjusted initial pH (the initial pH (pHi) values of
the solutions were adjusted from 2.0 to 10.0 by adding
0.10 mol L−1 of NaOH and HCl) to diverse 50.0-mL centri-
fuge tubes containing 50.0 mg of the ACJ, which were quickly
securely capped. The suspensions were shaken (at 150 rpm) in
an acclimatized shaker at 25 °C and allowed to equilibrate for
48 h. The suspensions were then centrifuged for 10 min at
10,000 rpm to separate the ACJ from the aqueous solution.
The pHi of the solutions was carefully measured using the
solutions that had no contact with the solid ACJ; the final
Environ Sci Pollut Res (2019) 26:4690–4702
pH (pHf) values of the supernatant after contact with the solid
were registered. The value of pHPZC is the point where the
curve of pH (pHf − pHi) versus pHi crosses a line equal to zero
(Umpierres et al. 2018).
Adsorption Study
Adsorption studies were performed in triplicate utilizing
the batch adsorption process. In these tests, 30.0 mg of
ACJ was added in 50.0-mL flat-bottomed centrifuge tubes
(Saucier et al. 2017). Solutions of 20.0 mL of the medicine
at pH 7 were added to the vials at concentrations of 200.0
and 400.0 mg L−1 for kinetic studies, and from 100.0 to
900.0 mg L−1 for isotherm experiments. The centrifuge
tubes were shaken (at 150 rpm) for a suitable time (from
1 to 360 min for the kinetic tests, and 24 h for the isotherm
experiments) at different temperatures (15–45 °C). Also,
for isolating the ACJ from the solutions, the tubes were
centrifuged for 5 min at 10,000 rpm in a centrifuge
(Herolab UNICEN H) and subsequently, 1-mL aliquots
were collected and diluted for further concentration read-
ing. The final concentration of CIP remaining in the solu-
tion was estimated by visible spectrophotometry using a
T90 + ultraviolet-visible (UV-VIS) spectrophotometer
(PG Instruments). Absorbance readings were performed
at 272 nm (the maximum wavelength of the CIP).
The amount and the percentage of CIP removal onto by the
ACJ were estimated employing, respectively, Eqs. (1) and (2)
(Saucier et al. 2017; Machado et al. 2016; Kasperiski et al.
2018b):
ðCo −C f Þ
q¼ V ð1Þ
m
ðCo −C f Þ
%Removal ¼ 100  ð2Þ
Co
where q represents the equilibrium adsorption amount of sor-
bate (mg g−1), Co is the initial antibiotic concentration of the
solution (mg L−1), Cf is the CIP concentration (mg L−1) sub-
sequently the removal process, V is the volume of the antibi-
otic solution (L), and m is the ACJ mass (g).
Kinetic and equilibrium models
The Avrami fractional-order, pseudo-first-order, and pseudo-
second-order kinetic models were used for the evaluation of
kinetic data (Saucier et al. 2017; Machado et al. 2016;
Kasperiski et al. 2018b).
The equilibrium data were evaluated utilizing Freundlich,
Langmuir, and Liu adsorption models (Saucier et al. 2017;
Machado et al. 2016; Kasperiski et al. 2018b).
Environ Sci Pollut Res (2019) 26:4690–4702 4693

For particulars of these models, see the Supplementary Results and discussion
Material.
Characterization of the ACJ
Statistical evaluation of the kinetic and isotherm
parameters SEM has demonstrated an extremely robust technique for
characterization of AC adsorbents (Umpierres et al. 2018;
The kinetic and isotherm models were fitted by utilizing a Saucier et al. 2017). This technique was utilized to exam-
nonlinear method applying the nonlinear fitting routines of ine the morphology of the JIN and the ACJ (see Fig. 1).
the software Microcal Origin 2018. Furthermore, the models When in natura (Fig. 1a, b), the material presents a simple,
were evaluated by the standard deviation (SD) of residues, as rough, and rugged surface. On the contrary, it can be ob-
well as by the adjusted determination factor (R2adj) (Machado served that the microstructure of the material is significant-
et al. 2016; Kasperiski et al. 2018b). ly modified after the chemical activation-carbonization.
The Supplementary Material contains the details of the Verifying through Fig. 1c and d, it is possible to detect
statistical evaluation of the kinetic and equilibrium the presence of a vast number of channels and holes, prov-
parameters. ing that the produced ACJ had its morphology altered as a
consequence of the chemical activation with ZnCl 2
Preparation of synthetic hospital effluents (Umpierres et al. 2018; Saucier et al. 2017).
Porosity and specific surface area are two fundamental
For testing the sorption capacity of the ACJ adsorbent for textural characteristics of an adsorbent that influence its
the purification of mixtures of organic and inorganic com- utility and quality for a specific application, particularly
pounds, where the simulation tests were carried out, two for removal of ECs from aqueous effluents (Bergmann
simulated effluents were applied. The synthetic effluents and Machado 2015; Cunha et al. 2018). These character-
with CIP antibiotic, sugar, and eight inorganics and four istics are vital because they are profoundly associated
organic compounds frequently found in hospital wastewa- with the adsorptive capacity of the adsorbent
ters were produced. In Table 1 are demonstrated the com- (Bergmann and Machado 2015; Cunha et al. 2018).
positions, as well as the concentrations of the components Table 2 shows the textural properties of the Jerivá in
of the two effluents. natura and the AC from Jerivá. From this table, it can
be verified that the methodology used in the production
Table 1 The chemical composition of simulated hospital effluents of activated carbon was extraordinarily efficient and
allowed the preparation of an adsorbent with a high spe-
Concentration (mg L−1)
cific surface area (1435 m2 g−1).
Effluent 1 Effluent 2 Other parameters that are utilized for analyzing of
ACJ are the micropore and mesopore volumes. The per-
Pharmaceutical centage of micropores found was 27.9%, and based on
Ciprofloxacin 20.0 40.0 this value, it is seen that the ACJ is mainly a mesopo-
Sugar rous material (Umpierres et al. 2018). This characteristic
Glucose 24.0 40.0 promotes the application of this activated carbon in sorp-
Others organic components tion processes, in which the contaminant penetrates the
Humic acid 8.0 16.0 porous structure of the adsorbents (Cunha et al. 2018;
Urea 8.0 16.0 Umpierres et al. 2018). Based on the morphological
Citric acid 8.0 16.0 (Fig. 1) and textural results (Table 2), it is verified that
Inorganic components AC from Jerivá exhibit excellent characteristics which
Ammonium chloride 16.0 24.0 accredit it for applications such as adsorbent for sorption
Ammonium phosphate 16.0 24.0 of ECs from wastewaters.
Calcium nitrate 8.0 16.0 FTIR spectroscopy was employed to determine the sur-
Magnesium chloride 8.0 16.0 face functional groups of ACJ (see Fig. 2). The absorption
Sodium carbonate 8.0 16.0 band about 3450 cm−1 corresponds to the vibration of OH
Sodium chloride 40.0 56.0 (stretching) bonds of alcohols, phenols, and carboxylic
Sodium dodecyl sulphate 4.0 8.0 acids, thus displaying the presence of Bfree^ hydroxyl
Sodium sulphate 8.0 16.0 groups on the ACJ surface (Prola et al. 2013; Kasperiski
Potassium nitrate 8.0 16.0 et al. 2018a). The band at 3229 cm−1 is credited to the
pH 6.0 6.0 presence of functional group C–H (Smith 1998). The dis-
crete bands at 2905 and 2837 cm −1 are attributed to
4694
Fig. 1 Micrographs of a, b Jerivá in natura, and c, d activated carbon from Jerivá
asymmetric and symmetrical stretches of CH, while the
small peak at approximately 1705 cm−1 is attributed to
the C=O stretching of carboxylic acid (Smith 1998)
(Prola et al. 2013; Umpierres et al. 2018). The peak de-
tected at 1637 cm −1 is attributed to the asymmetric
stretching of carboxylate groups (Smith 1998). The in-
tense and acute peak at approximately 1615 cm−1 shows
the occurrence of existing C=O carbonyl groups in car-
boxylic acids and ketones, and the vibrations around
1600 and 1400 cm −1 refer to the stretching of C=C
bonds of aromatics (Smith 1998). The band around
1200 cm−1 can be attributed to the C–O stretching of
phenol and alcohol (Prola et al. 2013). The band at
1530 cm−1 is assigned to the modes of the aromatic rings
and that at about 1200 cm−1 corresponds to the C–C–O
(stretching) bonds of ketones (Smith 1998). Finally, the
peak at 870 cm−1 represents C–N bonds (Smith 1998).
Table 2 The textural properties of JIN and ACJ
Material Total pore volume t-Plot micropore Mesopore volume
(cm3 g−1) volume (cm3 g−1) (cm3 g−1)
JIN 0.003 – –
ACJ 0.8762 0.2449 0.6313
Environ Sci Pollut Res (2019) 26:4690–4702
Point of zero charge and effect of initial pH
The pH of the adsorbate solution could affect its adsorption
on a solid surface and determines the percentage of distri-
bution of the chemical species of the adsorbate involved in
the adsorption process. The functional groups present on
the adsorbent could be protonated or deprotonated depend-
ing on the pH of adsorbate solution, altering the charge of
an adsorbent. However, there is a pH of the adsorbate so-
lution in which negative and positive charges are equiva-
lent. This value of pH is denominated as pH of the point of
zero charge (pHpzc) is affected by the surface charges pres-
ent on the adsorbent (Sun et al. 2014; Umpierres et al.
2018). The electrostatic mechanism of adsorption is excep-
tionally dependent on the pH of the adsorbate solution
(Prola et al. 2013; Puchana-Rosero et al. 2016). However,
if other mechanisms of adsorption take place, the pH of the
t-Plot micropore Specific surface t-Plot extern. surface
area (m2 g−1) area (m2 g−1) area (m2 g−1)
– 1.89 –
880.7 1435 554.2
Environ Sci Pollut Res (2019) 26:4690–4702 4695

Fig. 2 The infrared spectra of

ACJ adsorbent

adsorbate solution has lower importance (Leite et al. 2018;
Umpierres et al. 2018; Fröhlich et al. 2018).
The pHpzc of ACJ adsorbent was 4.83 (see Fig. 3). Therefore,
at pH values higher than 4.83, the surface charge of the adsorbent
will be negatively charged, and at pH values lower than 4.83, the
surface of the adsorbent will be positively charged.
In Fig. 4, the CIP structures at different pH values are
presented. Using the software Marvin Sketch furnished by
Chemaxon, the pKa values of this antibiotic was determined.
The first pKa is 5.56 and the second pH is 8.77 (see Fig. 4). At
pH 7.0, specie 1 presents 3.48%, specie 2 94.84%, and specie
3 1.63% (see Fig. 4). Therefore, at pH 7, it predominates the
zwitterionic specie (specie 2, see Fig. 4). Studies of pH vary-
ing from 3 to 10 show that the percentage of removal of
ciprofloxacin was practically constant (variations lower than
2%). Therefore, for the further adsorption experiments, the pH
of the solution was set at 7.0 to improve this work.
Adsorption kinetics
For describing the kinetic of adsorption of CIP by ACJ, the
adsorption kinetic models of Avrami fractional-order and
pseudo-first and pseudo-second-order were trained (Lima
et al. 2015; Adebayo et al. 2014; Fröhlich et al. 2018). The

Fig. 3 Effect of pH on ACJ.

Conditions: 20.0 mL of pH-
adjusted NaCl solution of 2 to 10;
ACJ, the mass of ACJ of 50.0 mg;
24 h of contact time, and
temperature, 25 °C
4696 Environ Sci Pollut Res (2019) 26:4690–4702

Fig. 4 The molecular structure of CIP at different pH values. Calculations of the physical-chemical properties of the CIP were made using the Calculator
Plugin of Marvin Sketch 18.23.0

adsorption of CIP onto ACJ as a function of time is exposed in
Fig. 5 as well as their parameters in Table 3. The appropriate-
ness of the models was examined by applying the values of
R2adj (Eq. 9) and SD (Eq. 11). The higher R2adj and the lower
SD values indicate the small discrepancy between experimen-
tal and theoretical q values (Alencar et al. 2012). In the present
study (see Table 3), between the three assessed kinetic models,
Avrami fractional-order obtained the highest R2adj values of
0.9965 and 0.9969 and the lowest SD of 1.818 and
2.437 mg g−1, for initial CIP concentrations of, respectively,
200.0 mg L−1 and 400.0 mg L−1. This indicates that the qt
forecasted by Avrami equation was the closest forecast to
the values of q t found in the adsorption experiments
(Alencar et al. 2012; Adebayo et al. 2014; Thue et al. 2016;
Lima et al. 2016).
The Avrami fractional-order kinetic model has been ef-
fectively applied to elucidate the kinetic processes of many
adsorbates–adsorbents systems (Cunha et al. 2018;
Kasperiski et al. 2018a; Kasperiski et al. 2018b; Thue
et al. 2016; Lima et al. 2016). The nAV of this model con-
sists of a fractional number associated with the potential
changes of the adsorption mechanism, which happens over
the adsorption process (Lima et al. 2015; Lima et al. 2016).
Rather than following just an integer-kinetic order, the
mechanism adsorption can follow many kinetic orders,
which are altered over the interaction of the adsorbent with

Table 3 Adsorption kinetic parameters for CIP antibiotic removal using

ACJ as adsorbents

Co, 200 mg L−1 Co, 400 mg L−1

Pseudo-first-order
qe (mg g−1) 103.9 120.9
k1 (min−1) 0.1616 0.02966
R2adj 0.8512 0.9683
SD (mg g−1) 11.83 7.833
t0.5 (min) 4.289 23.37
t0.95 (min) 18.54 101.0
Pseudo-second-order
qe (mg g−1) 110.4 137.8
k2 (g mg−1 min−1) 2.293 × 10−3 2.653 × 10-4
R2adj 0.9503 0.9929
SD (mg g−1) 6.836 3.710
t0.5 (min) 3.952 27.35
t0.95 (min) 75.09 –
Avrami fractional-order
nAV 0.3759 0.6327
kAV (min−1) 0.09280 0.01982
qe (mg g−1) 118.2 134.7
R2adj 0.9965 0.9969
SD (mg g−1) 1.818 2.437
Fig. 5 Kinetic adsorption curves for CIP of uptake at 25 °C on ACJ. t0.5 (min) 4.065 28.28
Conditions: mass of ACJ of 30.0 mg; pH, 7.0; Co, a 200.0 mg L−1, and t0.95 (min) 199.4 285.8
b 400.0 mg L−1
Environ Sci Pollut Res (2019) 26:4690–4702
the adsorbate (Alencar et al. 2012; Lima et al. 2015). Also,
the nAV is consequential of the several kinetic orders of the
adsorption process (Alencar et al. 2012).
Knowing that the kinetic rate constant of the different ki-
netic equations has different units, impairing its direct com-
parison, t0.5 and t0.95 were obtained to better understand the
kinetics of ciprofloxacin antibiotic onto activated carbon from
Jerivá (Kasperiski et al. 2018a; Cunha et al. 2018). The t0.5
and t0.95, which are the time to achieve 50% and 95% of
adsorption capacity at the saturation (qe), respectively, were
measured by interpolation in the fitting of all the kinetic
models presented in Fig. 5. Considering that the best kinetic
model was the Avrami fractional-order kinetic model, the
values of the time parameters for this model which were t0.5
are 4.065 and 28.28 min for the ACJ utilizing initial CIP
concentrations of 200.0 and 400.0 mg L−1, respectively.
Consequently, the time for achieving the equilibrium was fast,
especially for the concentration of 200 mg L−1. Still, the time
to achieve 95% (t0.95) of the equilibrium (qe) of 199.4 and
285.8 min utilize initial CIP concentrations of, respectively,
200.0 and 400.0 mg L−1. Accordingly, for continuing this
work, the time of contact for the further experiments was set
at 6 h, in order to guarantee that at higher concentrations the
system would attain the equilibrium.
Adsorption equilibrium
To verify the influence of the temperature on the adsorption
process and to report the relationship among the amount of
contaminant retained in the adsorbent and the remaining con-
taminant concentration in the solution, equilibrium tests were
performed. The Langmuir and Freundlich equilibrium
models, as well as the Liu model, were employed (Jauris
et al. 2016a; Puchana-Rosero et al. 2016; Machado et al.
2016; Alencar et al. 2012; Thue et al. 2016; Lima et al.
2016; Umpierres et al. 2018).
The adsorption isotherms of CIP applying ACJ as adsor-
bent were performed applying six temperatures: 15 °C, 25 °C,
30 °C, 35 °C, 40 °C, and 45 °C. Further, the pH of the solution
was set at 7 and the contact time was 6 h with an ACJ mass of
30.0 mg. Figure 6 presents the adsorption isotherms of CIP
antibiotic onto activated carbon from Jerivá at 15 to 45 °C.
Considering the SD and R2Adj, the Liu model was found to
be the greatest equilibrium model for adsorption of CIP anti-
biotic by ACJ (the values presented in Table 4). The Langmuir
and Freundlich SD values ranged from 3.299 to 12.52 and
21.27 to 29.55, respectively. Still, the Langmuir and
Freundlich R2Adj values ranged from 0.9833 to 0.9979 and
0.8784 to 0.9452, respectively. The Liu equilibrium model
(Jauris et al. 2017) presented the lowest SD values, which
ranged from 2.838 to 8.078, and the highest R2Adj values,
which ranged from 0.9942 to 0.9985, which means that the
qi,model fitted for this model was closest to the qi,experimental
4697
gotten into the experimental sorption (Thue et al. 2016;
Lima et al. 2016).
Based on Table 4 and Fig. 6, it is possible to verify that the
adsorption capacity of the ACJ increases with increasing tem-
perature. The variation of this from 15 to 40 °C promoted an
increase of 69.1% in the adsorption capacity of the antibiotic
by ACJ. At 40 °C, the Qmax of CIP antibiotic by ACJ was
found of the 337.8 mg g−1. These values demonstrate that ACJ
is a very good adsorbent for CIP sorption from aqueous solu-
tions. It should be noted that at 45 °C, there was a small drop
in the maximum adsorption capacity. However, the Qmax does
not have a regular pattern with the temperature (Lima et al.
2015). Contrarily, the values of Liu equilibrium constant (Kg)
increased with the increase of the temperature, indicating that
the process of adsorption is endothermic (Lima et al. 2015).
In order to confront the adsorption capacity of activated
carbon produced from Jerivá in the removal of the CIP anti-
biotic from aqueous solutions, in Table 5, a comparison of
sorption capacities CIP adsorbed in diverse adsorbents is pre-
sented (Mao et al. 2016; Sun et al. 2016; Li et al. 2018;
Carabineiro et al. 2012; Yu et al. 2016; Jiang et al. 2013;
Zhu et al. 2015; Cao et al. 2017). As shown in Table 5, the
ACJ exhibited good sorption capacities when compared to
other materials, which include carbon-based nanomaterials
such as carbon nanotubes (Carabineiro et al. 2012; Yu et al.
2016) and graphene (Zhu et al. 2015), materials recognized by
the high adsorption capacity (Bergmann and Machado 2015).
The ACJ presented a higher Qmax among the 11 adsorbents
investigated, which corroborates the excellent capacity of re-
moval of the antibiotic by this adsorbent.
Thermodynamic analysis and mechanism
of adsorption
The following equations determine the thermodynamic data
associated to the adsorption process, such as Gibbs’ free en-
ergy change (ΔG°, kJ mol−1), entropy change (ΔS°, J
mol−1 K−1), and enthalpy change (ΔH°, kJ mol−1):
ΔG° ¼ ΔH ° −TΔS ° ð3Þ
and
ΔG° ¼ −RTLnðKÞ ð4Þ
The combination of Eqs. (3) and (4) gives:
∘
ΔS ΔH 1
∘
LnðKÞ ¼ −  ð5Þ
R R T
where R represents the universal gas constant
(8.314 J K−1 mol−1), T corresponds to the temperature in
Kelvin, and K is the isotherm adsorption constants of
4698 Environ Sci Pollut Res (2019) 26:4690–4702

Fig. 6 Effect of temperature on the adsorption isotherm for CIP onto ACJ at a 15 °C, b 25 °C, c 30 °C, d 35 °C, e 40 °C, and f 45 °C. Conditions: a mass
of ACJ 30.0 mg, contact time of 6 h, and pH 7.0

the isotherm fits (it was considered the K of the model Table 6 exhibits the thermodynamic data of the removal of
of Liu) that should be transformed in liters per mole for CIP antibiotic by ACJ. Predictions of the intercept and slope
being applied in Eq. (5), as earlier suggested (Lima of the linear plot of Ln(K) versus 1/T give, respectively, ΔS°
et al. 2015). and ΔH° values (Lima et al. 2015; Machado et al. 2016). The
Environ Sci Pollut Res (2019) 26:4690–4702 4699

Table 4 Adsorption equilibrium

parameters for the adsorption of 15 °C 25 °C 30 °C 35 °C 40 °C 45 °C
CIP antibiotic adsorption using
ACJ as adsorbents, with 24 h of Langmuir
the contact time KL (L mg−1) 0.09380 0.09302 0.1207 0.1109 0.1320 0.1272
Qmax (mg g−1) 205.8 234.3 262.3 317.7 308.7 287.9
R2adjust 0.9856 0.9979 0.9833 0.9925 0.9853 0.9910
SD (mg g−1) 7.372 3.299 11.05 9.184 12.52 8.614
Freundlich
KF ((mg g−1 (mg L−1)−1/nF) 86.82 87.48 98.29 101.5 103.8 99.87
nF 7.100 6.114 6.068 4.938 5.141 5.451
R2adjust 0.8784 0.9119 0.9387 0.9231 0.9447 0.9452
SD (mg g−1) 21.40 21.53 21.13 29.55 24.24 21.27
Liu
Kg (L mg−1) 0.09051 0.09463 0.09552 0.09978 0.1002 0.1034
Qmax (mg g−1) 198.6 231.2 284.4 328.7 335.8 305.8
nS 1.459 1.101 0.6884 0.8548 0.7076 0.7563
R2adjust 0.9955 0.9985 0.9978 0.9942 0.9959 0.9984
SD (mg g−1) 4.097 2.838 3.987 8.078 6.543 3.594

R2adj and SD values of the linear fit were at least 0.9660 and
8.860 × 10−3 demonstrating that the values of ΔS° and ΔH°
calculated for ACJ adsorbent were reasonably confident.
Negative values of ΔG° suggest that the CIP antibiotic adsorp-
tion by ACJ was a spontaneous and favorable process for all
the evaluated temperatures. The positive values of ΔS° con-
firmed a high preference of CIP molecules on the surface ACJ.
The magnitude of ΔH°, 3.34 kJ mol−1, was consistent with
physisorption of an ACJ with a CIP medicine (Machado et al.
2016; Jauris et al. 2016b, 2017). Also, the ΔH° indicates that
the adsorption followed endothermic processes.
Based on the characteristics of the AC produced and the
ciprofloxacin antibiotic, it can be verified that the pH was a
determining factor for the adsorption efficiency. The pH 7 was
used to evaluate the applicability of AC in real scale. For
adsorption of CIP, this pH range was ideal since the adsorptive
surface is negative; the CIP molecule is zwitterionic
(Kümmerer et al. 2008), that is, both positive and negative,
allowing the adsorption of the compound. The texture proper-
ties of ACJ had an essential impact on CIP adsorption. The
mesoporous structure of this adsorbent (see Table 2) indicates
that it can accommodate many antibiotic molecules.

Table 5 Comparison of the Qmax of CIP applying different material adsorbents. The values were obtained at the best experimental conditions of each
work

Adsorbents CIP concentration Adsorbent Qmax (mg g−1) References

(mg L−1) dosage (mg)

Magnetic carbon composite (Fe3O4/C) 10.0–60.0 20 90.10 Mao et al. 2016

Biochar obtained from used tea leaves 150.0–500.0 200 238.1 Li et al. 2018
AC from Arundo donax Linn 100.0–800.0 100 244.0 Sun et al. 2016
AC from Pomelo peel 100.0–800.0 100 400.0 Sun et al. 2016
Granular AC (commercial) 2.0–60.0 – 217.4 Zhu et al. 2015
AC (commercial) 3.0–30.0 50 231.0 Carabineiro et al. 2012
Carbon-based xerogel 3.0–30.0 50 112.0 Carabineiro et al. 2012
Carbon nanotubes 3.0–30.0 50 135.0 Carabineiro et al. 2012
Oxidized multi-walled carbon nanotubes 10.0–160.0 20 206.0 Yu et al. 2016
Graphene (commercial) 2.0–60.0 – 322.6 Zhu et al. 2015
Birnessite 50.0–1000.0 500 71.00 Jiang et al. 2013
Calotropis gigantea fiber 50.0–250.0 10 168.2 Cao et al. 2017
ACJ 100.0–900.0 30 335.8 The present study
4700 Environ Sci Pollut Res (2019) 26:4690–4702

Table 6 Thermodynamic data for

the removal of CIP antibiotic by 15 °C 25 °C 30 °C 35 °C 40 °C 45 °C
ACJ. Conditions: ACJ mass
30.0 mg, and pH fixed at 7.0 Kg (L mol−1) 2.999 × 104 3.135 × 104 3.165 × 104 3.306 × 104 3.322 × 104 3.425 × 104
ΔG (kJ mol−1) − 24.68 − 25.65 − 26.10 − 26.65 − 27.09 − 27.60
ΔS° (J K−1 mol−1) – 97.28 – – – –
ΔH° (kJ mol−1) – 3.341 – – – –
R2adj – 0.9660 – – – –
SD (mg g−1) – 8.860 × 10−3 – – – –

Moreover, the functional groups present in ACJ struc- Furthermore, the Qmax value of ACJ was compared with
ture (see Fig. 2), as well as those present in the CIP (see several adsorbents, and this adsorbent presents sorption capac-
Fig. 3), also play an essential role in the adsorption pro- ity higher than that found for carbon-based nanomaterials.
cess. Due to the structural characteristics of the ACJ-CIP Three kinetic models were utilized to adjust the adsorption
system, interactions between the delocalized electrons of of antibiotic, and the best fit was the Avrami fractional model
the ACJ basal plane and the free electrons of the CIP when compared to the pseudo-first-order and pseudo-second-
molecule (of the aromatic rings) can occur (Carabineiro order models. Thermodynamic parameters of adsorption were
et al. 2012). The antibiotic molecule has several calculated, and the enthalpy of adsorption suggested that
electron-rich functional groups (a ketone, carboxylic, and
aromatic groups) that can form electron acceptor π-π com-
plexes (Carabineiro et al. 2012). Furthermore, the fluorine
atom bound to the benzene ring of CIP has strong electro-
negativity, so that this ring becomes a strong π electron
acceptor (Yu et al. 2016).

Treatment of simulated effluents

The ACJ was used with an adsorbent for purification of two

synthetic hospital effluents. Figure 7 shows the UV-VIS spec-
tra of the effluents before and after contact treatment with
ACJ. Those spectra were reported with UV-VIS spectropho-
tometer between 190 and 600 nm. The percentage of the mix-
ture of CIP and organic and inorganic compounds removed
from the effluent depends on the area under the absorption
band. The ACJ notably removed 96.19% of effluent 1 and
93.43% of effluent 2. These results indicate that ACJ is an
exciting adsorbent for treatment of hospital effluents.

Conclusions

In this study, endocarp of Jerivá (Syagrus romanzoffiana) was

successfully utilized as a precursor material for producing
activated carbon. The produced adsorbent displayed a high
surface area, up to 1435 m2 g−1, and predominantly mesopo-
rous structure. The obtained activated carbon was applied with
an adsorbent to remove CIP from aqueous solutions and
showed high Qmax of the antibiotic. The Liu isotherm model
best explains the isothermal data of CIP onto the activated
carbon from Jerivá, when compared to the Langmuir and
Freundlich equilibrium equations. The Qmax value of cipro-
floxacin is 335.8 mg g−1 at 40 °C. Fig. 7 Spectra of synthetic hospital effluents. a Effluent 1, and b effluent 2
Environ Sci Pollut Res (2019) 26:4690–4702
adsorption was an endothermic process. Also, the magnitude
of enthalpy indicates physisorption between activated carbon
and antibiotic. For treatment of synthetic hospital effluents,
the ACJ showed up the excellent performance for removing
at least 93.43% of the mix of antibiotic, sugar, and four organ-
ic and eight inorganic compounds. Finally, it can be concluded
that the AC from the Jerivá has excellent potential, due to it
being easy to obtain and its high adsorption capacity, which
claims its application as an adsorbent to remove other emer-
gent contaminants from wastewaters.
Acknowledgments We are grateful to Centro de Microscopia Eletrônica
da Zona Sul (CEME SUL–FURG) for the use of the SEM microscope.
We are also grateful to Chemaxon for giving us an academic research
license for the Marvin Sketch software, Version 18.23.0, (http://www.
chemaxon.com), 2018, used for molecule physical-chemical properties.
Funding information This study received financial support from the
Coordenação de Aperfeiçoamento de Pessoal de Nível Superior
(CAPES), Fundação de Amparo à Pesquisa do Estado do Rio Grande
do Sul (FAPERGS, Process 17/2551-0001074-4), and National Council
for Scientific and Technological Development (CNPq, Brazil).
References
Adebayo MA, Prola LDT, Lima EC, Puchana-Rosero MJ, Cataluña R,
Saucier C, Umpierres CS, Vaghetti JCP, da Silva LG, Ruggiero R
(2014) Adsorption of Procion Blue MX-R dye from aqueous solu-
tions by lignin chemically modified with aluminium and manga-
nese. J Hazard Mater 268:43–50. https://doi.org/10.1016/j.jhazmat.
2014.01.005
Alencar WS, Lima EC, Royer B, dos Santos BD, Calvete T, da Silva EA,
Alves CN (2012) Application of aqai stalks as biosorbents for the
removal of the dye Procion Blue MX-R from aqueous solution. Sep
Sci Technol 47:513–526. https://doi.org/10.1080/01496395.2011.
616568
Bergmann CP, Machado FM (2015) Carbon nanomaterials as adsorbents
for environmental and biological applications. Springer, Berlin.
https://doi.org/10.1007/978-3-319-18875-1
Cao E, Duan W, Zheng Y (2017) Oriented growth of poly(m-
phenylenediamine) on Calotropis gigantea fiber for rapid adsorption
of ciprofloxacin. Chemosphere 171:223–230. https://doi.org/10.
1016/j.chemosphere.2016.12.087
Carabineiro SAC, Thavorn-Amornsri T, Pereira MFR, Serp P, Figueiredo
JL (2012) Comparison between activated carbon, carbon xerogel
and carbon nanotubes for the adsorption of the antibiotic ciproflox-
acin. Catal Today 186:29–34. https://doi.org/10.1016/j.cattod.2011.
08.020
Carmalin SA, Lima EC (2018) Removal of emerging contaminants from
the environment by adsorption. Ecotoxicol Environ Saf 150:1–17.
https://doi.org/10.1016/j.ecoenv.2017.12.026
Carmalin SA, Lima EC, Allaudeen N, Rajan S (2016) Application of
graphene based materials for adsorption of pharmaceutical traces
from water and wastewater—a review. Desalin Water Treat 57:
27573–27586. https://doi.org/10.1080/19443994.2016.1172989
Coimbra MC, Jorge N (2011) Proximate composition of guariroba
(Syagrus oleracea), Jerivá (Syagrus romanzoffiana) and macaúba
(Acrocomia aculeata) palm fruits. Food Res Int 44:2139–2142.
https://doi.org/10.1016/j.foodres.2011.03.032
4701
Cunha MR, Lima EC, Cimirro NFGM, Thue PS, Dias SLP, Gelesky MA,
Dotto GL, Dos Reis GS, Pavan FA (2018) Conversion of Eragrostis
plana Nees leaves to activated carbon by microwave-assisted pyrol-
ysis for the removal of organic emerging contaminants from aque-
ous solutions. Environ Sci Pollut Res 25:23315–23327. https://doi.
org/10.1007/s11356-018-2439-7
Daoud F, Pelzer D, Zuehlke S, Spiteller M, Kayser O (2017) Ozone
pretreatment of process wastewater generated in the course of fluo-
roquinolone production. Chemosphere 185:953–963. https://doi.
org/10.1016/j.chemosphere.2017.07.040
Falasca SL, Del Fresno CM, Ulberich A (2012) Possibilities for growing
queen palm (Syagrus romanzoffiana) in Argentina as a biodiesel
producer under semi-arid climate conditions. Int J Hydrogen Energ
37:14843–14848. https://doi.org/10.1016/j.ijhydene.2011.12.092
Fröhlich AC, Reis G, Pavan FA, Lima EC, Foletto EL, Dotto GL (2018)
Improvement of activated carbon characteristics by sonication and
its application for pharmaceutical contaminants adsorption. Environ
Sci Pollut Res 25:24713–24725. https://doi.org/10.1007/s11356-
018-2525-x
Hosseinzadeh H, Mohammadi S (2015) Quince seed mucilage magnetic
nanocomposites as novel bioadsorbents for efficient removal of cat-
ionic dyes from aqueous solutions. Carbohydr Polym 134:213–221.
https://doi.org/10.1016/j.carbpol.2015.08.008
Jauris IM, Matos CF, Saucier C, Lima EC, Zarbin AJG, Fagan SB,
Machado FM, Zanella I (2016a) Adsorption of sodium diclofenac
on graphene: a combined experimental and theoretical study. Phys
Chem Chem Phys 18:1526–1536. https://doi.org/10.1039/
C5CP05940B
Jauris IM, Fagan SB, Adebayo MA, Machado FM (2016b) Adsorption of
acridine orange and methylene blue synthetic dyes and anthracene on
single-wall carbon nanotubes: a first principle approach. Comput Theor
Chem 1076:42–50. https://doi.org/10.1016/j.comptc.2015.11.021
Jauris IM, Matos CF, Zarbin AJG, Umpierres CS, Saucier C, Lima EC,
Fagan SB, Zanella I, Machado FM (2017) Adsorption of anti-
inflammatory nimesulide by graphene materials: a combined theo-
retical and experimental study. Phys Chem Chem Phys 19:22099–
22110. https://doi.org/10.1039/c7cp04272h
Jiang W-T, Chang P-H, Wang Y-S, Tsai Y, Jean J-S, Li Z, Krukowski K
(2013) Removal of ciprofloxacin from water by birnessite. J Hazard
Mater 250-251:362–369. https://doi.org/10.1016/j.jhazmat.2013.02.015
Kasperiski FM, Lima EC, Umpierres CS, dos Reis GS, Thue PS, Lima
DR, Dias SLP, Saucier C, da Costa JB (2018a) Production of porous
activated carbons from Caesalpinia ferrea seed pod wastes: highly
efficient removal of Captopril from aqueous solutions. J Clean Prod
197:919–929. https://doi.org/10.1016/j.jclepro.2018.06.146
Kasperiski FM, Lima EC, Reis GS, Da Costa JB, Dotto GL, Dias SLP,
Cunha MR, Pavan F, Correa CS (2018b) Preparation of CTAB-
functionalized Aqai Stalk and its efficient application as adsorbent
for the removal of Direct Blue 15 and Direct Red 23 dyes from
aqueous media. Chem Eng Commun 205:1520–1536. https://doi.
org/10.1080/00986445.2018.1458028
Kümmerer K (2008) Pharmaceuticals in the environment: sources, fate,
effects, and risks. Springer, Berlin. https://doi.org/10.1007/978-3-
540-74664-5
Leite AB, Saucier C, Lima EC, dos Reis GS, Umpierres CS, Mello BL,
Shirmardi M, Dias SLP, Sampaio CH (2018) Activated carbons
from avocado seed: optimization and application for removal several
emerging organic compounds. Environ Sci Pollut Res 25:7647–
7661. https://doi.org/10.1007/s11356-017-1105-9
Li J, Yu G, Pan L, Li C, You F, Xie S, Wang Y, Ma J, Shang X (2018) Study
of ciprofloxacin removal by biochar obtained from used tea leaves. J
Environ Sci 73:20–30. https://doi.org/10.1016/j.jes.2017.12.024
Lima EC, Adebayo MA, Machado FM (2015) Chapter 3 — kinetic and
equilibrium models of adsorption in Carbon nanomaterials as adsor-
bents for environmental and biological applications, Bergmann CP,
4702
Machado FM editors, Springer pp.71-84. https://doi.org/10.1007/
978-3-319-18875-1_3
Lima EC, Cestari AR, Adebayo MA (2016) Comments on the paper: a
critical review of the applicability of Avrami fractional kinetic equa-
tion in adsorption-based water treatment studies. Desalin Water Treat
57:19566–19571. https://doi.org/10.1080/19443994.2015.1095129
Machado FM, Carmalin SA, Lima EC, Dias SLP, Prola LDT, Saucier C,
Jauris IM, Zanella I, Fagan SB (2016) Adsorption of Alizarin Red S
Dye by carbon nanotubes: an experimental and theoretical investi-
gation. J Phys Chem C 120:18296–18306. https://doi.org/10.1021/
acs.jpcc.6b03884
Mao H, Wang S, Lin J-Y, Wang Z, Ren J (2016) Modification of a
magnetic carbon composite for ciprofloxacin adsorption. J Environ
Sci 49:179–188. https://doi.org/10.1016/j.jes.2016.05.048
Moreira MAC, Arrúa MEP, Antunes AC, Fiuza TER, Costa BJ, Neto
WPH, Antunes SRM (2013) Characterization of Syagrus
romanzoffiana oil aiming at biodiesel production. Ind Crop Prod
48:57–60. https://doi.org/10.1016/j.indcrop.2013.04.006
Prola LDT, Machado FM, Bergmann CP, de Souza FE, Gally CR, Lima
EC, Adebayo MA, Dias SLP, Calvete T (2013) Adsorption of Direct
Blue 53 dye from aqueous solutions by multi-walled carbon nano-
tubes and activated carbon. J Environ Manag 130:166–175. https://
doi.org/10.1016/j.jenvman.2013.09.003
Prutthiwanasan B, Phechkrajang C, Suntornsuk L (2016) Fluorescent
labelling of ciprofloxacin and norfloxacin and its application for
residues analysis in surface water. Talanta 159:74–79. https://doi.
org/10.1016/j.talanta.2016.05.080
Puchana-Rosero MJ, Adebayo MA, Lima EC, Machado FM, Thue PS,
Vaghetti JCP, Umpierres CS, Gutterres M (2016) Microwave-
assisted activated carbon obtained from the sludge of tannery-
treatment effluent plant for removal of leather dyes. Colloids Surf
A: Physicochem Eng Aspects 504:105–115. https://doi.org/10.
1016/j.colsurfa.2016.05.059
Rodriguez-Narvaez OM, Peralta-Hernandez JM, Goonetilleke A,
Bandala ER (2017) Treatment technologies for emerging contami-
nants in water: a review. Chem Eng J 323:361–380. https://doi.org/
10.1016/j.cej.2017.04.106
Environ Sci Pollut Res (2019) 26:4690–4702
Saucier C, Karthickeyan P, Ranjithkumar V, Lima EC, dos Reis GS, de
Brum IAS (2017) Efficient removal of amoxicillin and paracetamol
from aqueous solutions using magnetic activated carbon. Environ
Sci Pollut Res 24(6):5918–5932. https://doi.org/10.1007/s11356-
016-8304-7
Smith BC (1998) Infrared Spectral interpretation: a systematic approach:
CRC Press. York, New
Solliec M, Roy-Lachapelle A, Gasser M-O, Coté C, Généreux M, Sauvé
S (2016) Fractionation and analysis of veterinary antibiotics and
their related degradation products in agricultural soils and drainage
waters following swine manure amendment. Sci Total Environ 543:
524–535. https://doi.org/10.1016/j.scitotenv.2015.11.061
Sun Y, Yue Q, Gao B, Gao Y, Xu X, Li Q, Wang Y (2014) Adsorption and
co-sorption of ciprofloxacin and Ni(II) on activated carbon-
mechanism study. J Taiwan Inst Chem Eng 45:681–688. https://
doi.org/10.1016/j.jtice.2013.05.013
Sun Y, Li H, Li G, Gao B, Yue Q, Li X (2016) Characterization and
ciprofloxacin adsorption properties of activated carbons prepared
from biomass wastes by H3PO4 activation. Bioresour Technol 217:
239–244. https://doi.org/10.1016/j.biortech.2016.03.047
Thue PS, Adebayo MA, Lima EC, Sieliechi JM, Machado FM, Dotto GL,
Vaghetti JCP, Dias SLP (2016) Preparation, characterization and
application of microwave-assisted activated carbons from wood
chips for removal of phenol from aqueous solution. J Mol Liq
223:1067–1080. https://doi.org/10.1016/j.molliq.2016.09.032
Umpierres CS, Thue PS, Lima EC, dos Reis GS, de Brum IAS, de
Alencar WS, Dias SLP, Dotto GL (2018) Microwave-activated car-
bons from tucumã (Astrocaryum aculeatum) seed for efficient re-
moval of 2-nitrophenol from aqueous solutions. Environ Technol
39:1173–1187. https://doi.org/10.1080/09593330.2017.1323957
Yu F, Sun S, Han S, Zheng J, Ma J (2016) Adsorption removal of cipro-
floxacin by multi-walled carbon nanotubes with different oxygen
contents from aqueous solutions. Chem Eng J 285:588–595.
https://doi.org/10.1016/j.cej.2015.10.039
Zhu X, Tsang DCW, Chen F, Li S, Yang X (2015) Ciprofloxacin adsorp-
tion on graphene and granular activated carbon: kinetics, isotherms,
and effects of solution chemistry. Environ Technol 36:3094–3102.
https://doi.org/10.1080/09593330.2015.1054316