Chemical Engineering Research and Design 1 8 0 ( 2 0 2 2 ) 67–78

Contents lists available at ScienceDirect

Chemical Engineering Research and Design

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

Application of araçá fruit husks (Psidium

cattleianum) in the preparation of activated carbon
with FeCl3 for atrazine herbicide adsorption

Joseane S. Lazarotto a,b , Kátia da Boit Martinello c , Jordana Georgin b ,

Dison S.P. Franco a , Matias S. Netto a , Daniel G.A. Piccilli b ,
Luis F.O. Silva d,∗ , Eder C. Lima e , Guilherme L. Dotto a,∗
a Research Group on Adsorptive and Catalytic Process Engineering (ENGEPAC), Federal University of Santa Maria,
Av. Roraima, 1000-7, 97105–900 Santa Maria, RS, Brazil
b Environmental and Sanitary Engineering Department, Federal University of Santa Maria, UFSM, 97105-900,

Santa Maria, Brazil

c Department of Health Sciences, Universidad de la Costa, CUC, Calle 58 # 55-66, Barranquilla, Atlántico, Colombia
d Department of Civil and Environmental, Universidad de la Costa, CUC, Calle 58 # 55–66, Barranquilla, Atlántico,

Colombia
e Institute of Chemistry, Federal University of Rio Grande do Sul, UFRGS, Porto Alegre, RS, Brazil

a r t i c l e i n f o a b s t r a c t

Article history: The residual husks of the edible fruits of Psidium cattleianum were carbonized with FeCl3 as
Received 23 December 2021 an activating agent and used as an adsorbent to remove the toxic herbicide. After the car-
Received in revised form 27 January bonization step, changes in the material’s structure were found. Activated carbon showed
2022 characteristics of microporous materials with a pore volume of 0.280 cm3 g−1 and surface
Accepted 31 January 2022 area of 431 m2 g−1 . Micrographs revealed the emergence of new cavities with a uniform
Available online 9 February 2022 and circular shape. The FTIR spectra showed the disappearance of some bands, remain-
ing bands belonging to functional groups containing carbon, oxygen, and hydrogen. The
Keywords: XRD patterns confirmed the amorphous structure of the material even after the carboniza-
Adsorption tion step, composed of amorphous graphitic carbon. EDS analysis showed that the carbon
Atrazine percentage increased and the oxygen decreased after the carbonization. The experiments
Activated carbon were performed at neutral pH using 1 g L−1 of adsorbent. In equilibrium isotherms, the
Adsorption thermodynamics temperature played a considerable role in the adsorption capacity, increasing from 26.39
Biomass-based adsorbent mg g−1 to 35.67 mg g−1 when the temperature varied from 298 to 328 K. The Liu isotherms
were the ones that best fit the isotherm data. The changes in the adsorption enthalpy were
endothermic (H◦ 129.5 kJ mol−1 ). The general order kinetic model was the most adequate
for kinetic data, presenting the lowest values of the Bayesian Information Criterion. Thus,
activated carbon developed from the residues of the “araça” fruit showed promise in remov-
ing atrazine from aqueous solutions, with the great advantage of its high efficiency under
neutral pH solutions and mild temperatures.
© 2022 Institution of Chemical Engineers. Published by Elsevier Ltd. All rights reserved.

∗
Corresponding authors.
E-mail addresses: [email protected] (L.F.O. Silva), [email protected] (G.L. Dotto).
https://doi.org/10.1016/j.cherd.2022.01.044
0263-8762/© 2022 Institution of Chemical Engineers. Published by Elsevier Ltd. All rights reserved.
68 Chemical Engineering Research and Design 1 8 0 ( 2 0 2 2 ) 67–78

1. Introduction cations and enabling the sustainable economic use of this natural
resource.
In recent decades, the group of emerging contaminants (ECs), which Considering that only the pulp of the P. cattleianum fruit is used
includes pesticides, pharmaceuticals, hormones, hygiene, personal for fresh consumption and the general production of sweets, its husks
care products, and other classes, has received special attention from become a residue. No studies were found using araçá husks as an
the community due to their frequent detection in the environment adsorbent material in the literature. This study aimed to produce acti-
(Irandost et al., 2019; Kowalska et al., 2020; Maletić et al., 2019). vated carbon with FeCl3 for later use as an adsorbent in removing the
Pesticides are considered among the most critical groups of emerg- herbicide atrazine (ATZ) from aqueous solutions, seeking to bring a
ing pollutants due to their bioaccumulation and persistence in the new purpose to this biomass. First, different techniques characterized
environment (Alahabadi and Moussavi, 2017; Khan and Pathak, 2020). the original and carbonaceous materials. Then, the activated carbon
In addition, conventional effluent treatment plants are not able to elim- obtained was used in pH tests, adsorbent dosage, kinetic, isothermal,
inate them, generating environmental problems and putting human and thermodynamic studies.
health at risk (Mahlalela et al., 2021).
Atrazine (6-chloro-N2-ethyl-N4-(propan-2-yl)-1,3,5-triazine-2,4- 2. Materials and methods
diamine) is an herbicide used to control broadleaf weeds and grasses
in corn, wheat, soybean, sorghum, cocoa, sugarcane plantations, 2.1. Chemicals and reagents used
and other cultures (Almeida Lage et al., 2019; Andrade et al., 2019;
Francolino et al., 2021; Tripathi et al., 2021; Zhang et al., 2021). Due to All reagents used in this study were purchased from Merck and
its efficiency is the second most-consumed pesticide globally, reaching
have an analytical purity grade. Iron chloride (FeCl3 ) was used
an annual consumption of around 70,000 to 90,000 tons (Andrade
as an activating agent. HCl and NaOH were utilized to make pH
et al., 2019). However, its extensive use added to its characteristics
adjusts of the solutions. After the pyrolysis process, HCl was
such as low biodegradability, high mobility in the environment, high
water solubility, the long half-life, and high leaching capacity, which also used to extract FeCl3 from the adsorbent material. Ethanol
caused atrazine to be detected in ground and surface water and even (C2 H5 OH) was used to remove extractives present in the sam-
in drinking water at excessive levels (Dangwang Dikdim et al., 2019; ple. The adsorbate investigated in this study was atrazine
Dionne et al., 2021; Gao et al., 2019; Sivarajasekar et al., 2017). (IUPAC: 6-chloro-N2 -ethyl-N4 -(propan-2-yl)-1,3,5-triazine-2,4-
Toxicity studies revealed that atrazine could cause extensive liver diamine; CAS-1912-24-9 Molecular weight 215.685 g mol−1 ;
and kidney damage (de Paiva et al., 2017), genotoxic damage (Andrade Molecular formula C8 H14 ClN5 , see Fig. S1).
et al., 2019), teratogenicity, neurotoxicity, alteration in swimming
behavior (de Albuquerque et al., 2020), and oxidative stress (Singh 2.2. Preparation and characterization of activated
et al., 2018) in fish, in addition to genotoxic and mutagenic effects
carbon with FeCl3
in amphibians, malformations in reptiles and algae growth inhibi-
tion (de Albuquerque et al., 2020). Furthermore, regarding its effects
The fruits of the araçá (Psidium cattleianum) were obtained
on humans, the herbicide can exert a carcinogenic effect and cause
endocrine dysfunction, even at low concentrations (Almeida Lage et al., by rural producers located in the interior of the state of Rio
2019; Dangwang Dikdim et al., 2019; Hu et al., 2021). Thus, develop- Grande do Sul-Brazil. First, the edible part of the pulp was
ing efficient and economical methods for treating water contaminated manually removed, then about 300 g of the residual husks were
with atrazine is extremely important. washed and dried in an oven at 323.15 K for 4 h. Next, the dried
In this sense, it is possible to find in the literature different material was crushed in a knife mill, reaching a particle size
techniques used efficiently in the removal of atrazine from aqueous ≤250 ␮m. Finally, a part of the powder was named PCP (psidium
solutions (Bo et al., 2020; Cao et al., 2021; Ding et al., 2017; Huang cattleyanum peel) and used for the characterization analyses
et al., 2018; Komtchou et al., 2017; Li et al., 2019; McBeath and Graham,
and the activated carbon preparation
2021; Muthusaravanan et al., 2021; Yang et al., 2018). Among these
For activated carbon production, 8 g of PCP were weighed
techniques, adsorption stands out for being a simple, low-cost, and
and mixed with 12 g of FeCl3 (ratio 1:1.5). About 4 mL of deion-
efficient operation at low concentrations (Afolabi et al., 2020; Spaltro
et al., 2021). Another point to be analyzed is the application of activated
ized water was added to the mixture, obtaining a dark-colored
carbon as an adsorbent, which, in addition to presenting favorable paste. This slurry was taken to the oven and dried for 24 h at
characteristics for an adsorbent such as good surface area and poros- 105 ◦ C. The dried material was then pyrolyzed in inert nitrogen
ity, allow the use of residual biomass as plant precursors (Georgin flow (200 mL min−1 ) in a quartz tube using a heating rate of 10
et al., 2021a; Kerkhoff et al., 2021; Salomón et al., 2021; Spessato et al., ◦ C min−1 until the temperature reached 800 ◦ C remaining at

2019). The activating agent is a factor that influences the character- this temperature for 2 h. Finally, the pyrolyzed carbon material
istics of CAs; recent studies have used FeCl3 , showing its low cost was continuously stirred with 10 M HCl for 8 h. This step con-
and lower toxicity compared to other activating agents (Fu et al., sists of extracting FeCl3 from the material. Then, the carbon
2017).
material was thoroughly washed with deionized water and
Psidium cattleianum (Myrtaceae) is a plant native to Brazil (da Costa
further filtrated. This washing process was repeated until the
Amaral et al., 2021; Soliman et al., 2016), which occurs in different
washing waters attained a neutral pH interval (pH 6–8). Next,
regions of the country, such as the northeast and the south, due to
its easy adaptation to different climates. Also, it can be found in sev- the activated carbon was dried at 90 ◦ C for 8 h; the carbon
eral other countries (de Lima et al., 2020; dos Santos Pereira et al., 2018; material was ground to obtain particles ≤149 ␮m. The acti-
Ribeiro et al., 2014). Its fruit is popularly known in Brazil as “araça” vated carbon obtained from the araçá husks was called PCPAC
(da Costa Amaral et al., 2021; Vinholes et al., 2017); the size varies (psidium cattleyanum peel activated carbon); a part was sepa-
from 2.2 cm to 5 cm, presenting an oval shape and weighing less rated for the characterization analysis, and the remainder was
than 20 g (dos Santos Pereira et al., 2018). Local populations appre- used in the ATZ adsorption experiments.
ciate its pulp and are customarily consumed “in natura” or processed
for production in juices, jellies, sweets, and ice cream (Pereira et al., 2.3. Characterization techniques
2020; Zandoná et al., 2020). Currently, there are no Araçá plantations
destined for large-scale trade or industrial applications (Bittencourt
The adsorbent produced and the precursor materials were
et al., 2019). However, the Araçá orchard can produce around 10 tons of
characterized by different techniques described below. First,
fruit per ha, considering the production of 2 kg per plant (dos Santos
Pereira et al., 2018). Therefore, there is great interest in seeking appli- FTIR analysis (Shimadzu Prestige 21, Japan) was used to iden-
 Chemical Engineering Research and Design 1 8 0 ( 2 0 2 2 ) 67–78 69

tify the surface functional groups. The spectra were obtained 2.5. Adsorption equilibrium and thermodynamics
through sequential scans in the 4000–400 cm−1 range, using
the KBr pellets. Next, X-ray diffraction was used to charac- The equilibrium data were accessed using Langmuir
terize the carbon sample (XRD diffractometer, Miniflex 300) (Langmuir, 1918), Freundlich (Freundlich, 1907), and Liu
equipped with Cu K␣ radiation ( = 1.54051 Å). The runs were (Liu et al., 2003). Also, the estimation of the thermodynamic
obtained for 2 ranging from 15◦ to 90◦ at 5◦ /min. Third, scan- parameters of adsorption was carried out as described
ning electron microscopy (SEM) was utilized to observe the elsewhere (Lima et al., 2019b). See Supplementary material.
morphological characteristics of the adsorbent and the precur-
sor material, using a Tescan microscope with magnifications 2.6. Kinetic model
of 500, 1000, and 3000 times. Fourthly, thermogravimetric anal-
ysis (TGA) was carried out to obtain information regarding The kinetic data were fitted using nonlinear pseudo-first-order
the thermal behavior of the samples. These analyses were (PFO) (Lagergren, 1898), pseudo-second-order (PSO) (Ho and
performed using a thermogravimetric analyzer (STA 449 F3 McKay, 1999), and general-order kinetic models (Liu and Shen,
Jupiter, Netzsch), with a heating rate of 10 ◦ C min−1 from 25 ◦ C 2008). See Supplementary material.
to 800 ◦ C under an oxidizing atmosphere (synthetic air) with
a volumetric flow rate of 100 mL min−1 . In addition, differ- 2.7. Statistical evaluation of the models
ential Scanning Calorimetry (DSC) tests were also performed
to verify the thermal degradation profile of the adsorbents The statistical evaluation of the models was performed using
(TA Instruments, DSC-60, USA). Finally, information regard- R2 , R2 adj , SD, and BIC values (see Supplementary material).
ing the textural characterization of the samples was acquired
by isotherms of adsorption–desorption of nitrogen (−196 ◦ C), 3. Results and discussion
using the volumetric analyzer (Micrometrics, ASAP 2020) at a
temperature of −195.85 ◦ C, with a relative pressure (P/P0 ) rang- 3.1. Characterization of carbon-based materials
ing from 0.01 to 0.3. The surface areas of the materials were
estimated based on the BET method, and the total pore vol- EDS analyses of precursor (PCP) and activated carbon (PCPAC)
ume and average pore size were estimated using the Density are shown in Fig. 1. The PCP sample (Fig. 1a) is composed of
Function Theory (DFT). small percentages of calcium (Ca), sulfur (S), and phospho-
rus (F), the remainder being composed of carbon and oxygen,
which is expected since it is plant biomass formed by lignin
and cellulose. After the pyrolysis step, it was found that the
2.4. Atrazine adsorption experiments (ATZ) oxygen decreased from 41.84% to 0 (at least not detected);
as for the carbon, it was found and increased from 55.71%
All adsorption tests were carried out using a thermostatic to 96.37%. In addition to that, traces of Fe from the acti-
shaker (Marconi, MA093, Piracicaba, SP, Brazil) at 170 rotations vation agent were found, which corresponds to 2.89%. The
per minute. At the end of each assay, the samples were cen- elimination of oxygen present in the precursor sample proves
trifuged (Centribio, 80-2B, Brazil) at 4000 rpm for 25 min to that the pyrolysis process was complete since the pyrolysis
separate the liquid from the solid phase. ATZ concentrations process tends to consume the oxygen present on the mate-
in the aqueous phase were measured by a UV–vis spectropho- rial surface (Kerkhoff et al., 2021). Also, according to (Bedia
tometer (mini 1240, Shimadzu) at a wavelength of 222 nm. All et al., 2018), iron-based activating agents favor the degradation
batch contact adsorption experiments were carried out in trip- of the biomass material into volatile compounds, restricting
licate to access the reproducibility of the adsorption system. the formation of tars, thus allowing relatively high carbon
First, an ATZ stock solution was prepared by precisely yields. The small amounts of Cl and Fe found in PCPAC were
dissolving 0.5 g of herbicide in 1000 mL of deionized water attributed to FeCl3 , used as an activating agent. Cl and Fe
(containing methanol 10% V/V). Then, the working solutions have also been reported in other materials that used FeCl3 as
for the adsorption experiments were obtained by serial dilut- an activating agent (Siddique et al., 2020; Xu et al., 2018). In
ing the stock solution. addition, Yu and collaborators (Yu et al., 2020) found a small
In order to evaluate the effect of the initial pH of ATZ solu- amount of Si in samples of carbon prepared from corn stalks.
tion on its adsorption onto activated carbon, five Erlenmeyer The adsorption/desorption isotherms of N2 and PCPAC
flasks containing 50 mL of herbicide solution at a concentra- pore size and distribution are illustrated in Fig. 2, respec-
tion of 20 mg L−1 and adsorbent dosage of 1 g L−1 were used tively. According to the IUPAC classification, the activated
at a pH ranging from 3 to 9. Subsequently, the solutions were carbon presented a microporous structure (type I isotherms),
stirred for 180 min at 298 K. The isothermal and kinetic studies as shown in Fig. 2a (Thommes et al., 2015). The total pore vol-
described below were performed at the ideal pH of the solution ume was 0.280 cm3 g−1 , and the surface area was 431 m2 g−1 .
(pH 7). Marrakchi et al. (2021) obtained a similar area when carboniz-
The isotherm studies were carried out at temperatures of ing seaweed with FeCl3 ; however, most of the works reported
298 to 328 K, changing the Co of ATZ from 5 to 40 mg L−1 with present a surface area above 800 m2 g−1 (Gómez-Avilés et al.,
a contact time of 3 h. 2022; Xu et al., 2019, 2018). According to Fig. 1b, the pore size
Finally, the kinetic studies were conducted at room tem- distribution is located in the micropore region (pore size below
perature (298 K), varying the concentration of ATZ in 5, 10, 2 nm), resulting in an average pore size of 1.231 nm.
and 20 mg L−1 ; samples were collected at intervals of 0, 10, 20, SEM analyzed the morphology of the materials (see Fig. 3).
30, 60, 120, and 180 min. The adsorption capacities at time t Both materials are formed by structures with varied sizes and
(qt ) and the equilibrium (qe ) were determined according to the shapes (Fig. 3A and D); however, after carbonization, it was
batch adsorption equations displayed in the Supplementary possible to observe the appearance of small cavities with uni-
material. form sizes, in the form of circles, randomly distributed over the
70 Chemical Engineering Research and Design 1 8 0 ( 2 0 2 2 ) 67–78

Fig. 1 – EDS standards for the PCP (a) and PCPAC (b).

Fig. 2 – N2 adsorption–desorption isotherms (a) and desorption pore size distribution (b) for the PCPAC.

surface of the activated carbon (Fig. 3E and F), in the original biomass as a precursor material for activated carbon (Franco
material it is possible to observe the presence of small cracks et al., 2021; Salomón et al., 2021). These behaviors may be
(Fig. 3C and B) which disappear after modification. These mor- related to releasing volatile functional groups during the pyrol-
phological changes were also observed by Siddique et al. (2020) ysis process (Naganathan et al., 2020). The strong FTIR band
when they used FeCl3 as an activating agent for the production at 3448 and 3445 cm−1 , which occurs in both spectra, are
of activated carbon derived from Citrus limetta bark residues. assigned to the biomass (PCP) and activated carbon (PCPAC),
Authors report that the presence of new cavities commonly respectively, can be attributed to NH or OH stretching vibra-
found in activated carbon may be favorable to the adsorption tions (Salomón et al., 2021). The bands located around 2921,
process, as it allows the entry of adsorbent molecules into the 2876 cm−1 (PCP) and 2923 and 2859 cm−1 (PCPAC) may be
adsorbent (Bounaas et al., 2021; Medhat et al., 2021). related to the asymmetrical and symmetrical stretching vibra-
The FTIR spectra can observe the functional groups on the tions of the CH3 and CH2 groups, respectively (Georgin et al.,
carbon precursor and activated carbon surfaces, as shown 2020), these bands are typical of aliphatic compounds. The
in Fig. 4. First, it is possible to observe that some functional band at 1648 (PCP) and 1630 cm−1 (PCPAC) can be attributed
groups disappeared after the pyrolysis process. In addition, to the stretching vibration of C O (Georgin et al., 2021b). The
the remaining bands in PCPAC showed lower intensity. Recent peak at 1562 and 1413 cm−1 (PCP) and 1458 cm−1 (PCPAC)
studies have also observed these two behaviors using residual may be related to the aromatic rings model (Lütke et al., 2019;
 Chemical Engineering Research and Design 1 8 0 ( 2 0 2 2 ) 67–78 71

Fig. 3 – SEM images of precursor material (PCP) (A), (B), and (C) corresponding to the magnifications of 250×, 1000×, and
10k× and activated carbon (PCPAC) (D), (E), and (F), corresponding to the magnifications of 250×, 2k×, and 10K×.

Umpierres et al., 2018; Xu et al., 2019). The FTIR bands at 1380

(PCP) and 1382 cm−1 (PCPAC) are assigned to OH deformation
(Lima et al., 2019a,b). The FTIR bands at 1155 (PCP) and 1158
cm−1 (PCPAC) are assigned to the C-O stretching of secondary
alcohols (Cunha et al., 2020). The FTIR bands at 1034 (PCPAC)
and 1064 cm−1 (PCPAC) are assigned to the stretching of C O of
primary alcohol (Thue et al., 2020). The vibrational band at 619
cm−1 in PCP is attributed to NH2 bending (Lima et al., 2021a).
Although the same bands appear in both PCP and PCPAC, the
intensity of the bands in the activated carbon material is much
lower compared with the original biomass (Cunha et al., 2020;
Lima et al., 2021b).
Fig. 5 shows the X-ray diffraction patterns; it is possible to
notice in both materials a broad diffraction peak at 2 = 12–30◦ ,
typical of amorphous carbon, which can be attributed to the
amorphous nature of the precursor and the carbon activated
(Yagmur et al., 2020). Furthermore, after the pyrolysis pro-
cess, it is possible to observe new diffraction peaks at 2 = 27
and 44◦ , characteristic of crystalline/graphitic carbon (Franco
et al., 2021; Kerkhoff et al., 2021), indicating that there was
a partial reorganization of the carbon after the pyrolysis pro-
cess (Dutournié et al., 2019). Nevertheless, amorphous carbon
materials were the main phase present in the materials. In
general, amorphous materials are as efficient as adsorbents
because they have many voids, which favor the accommoda-
tion of molecules of the adsorbate on the adsorbent surface
(Franco et al., 2021; Georgin et al., 2021b).

Fig. 4 – FT-IR spectra of PCP and PCPAC.

72 Chemical Engineering Research and Design 1 8 0 ( 2 0 2 2 ) 67–78

Fig. 7 – Adsorption isotherm data for the ATZ/PCPAC

system and the Liu model prediction according to the
temperature:  298 K, 308 K, 318 K, 328 K (pH = 7,
Dads = 1 g L−1 , agitation rate = 170 rpm, V = 25 mL).

et al., 2012b). A similar trend has been reported when study-

ing the adsorption of ATZ was worst at low pH and tended to
be improved when reaching pH 7 when employing the carbon
nanotubes as adsorbents (Chen et al., 2008; Tang et al., 2012b).
Thus, the following adsorption experiments were carried out
at deionized water pH values (pH ≈ 6-7).
Fig. 5 – XRD of PCP and PCPAC materials.
3.3. Adsorption isotherms and thermodynamics

The equilibrium data were obtained to evaluate the influence

of temperature on the adsorption of ATZ on PCPAC adsor-
bent. The four curves (Fig. 7) were constructed by varying
the temperature from 298 K to 328 K through five concen-
trations of ATZ. All curves were favorable as the temperature
increased in the system. However, they did not reach a con-
stant value (plateau), which is typical behavior of an L1
isotherm (Machado et al., 2020). Thus, it is possible to say
that atrazine molecules progressively occupied the adsorption
sites on the surface of the adsorbent, but some sites remained
empty (Machado et al., 2020). The highest experimental qe val-
ues increased from 21.71 mg g−1 to 35.67 mg g−1 when the
temperature was raised from 298 K to 328 K, both analyzed at
the highest concentration of ATZ (40 mg L−1 ). This augmenta-
tion in adsorption capacity could be assigned to the decrease
in ATZ solubility and an increase in the ATZ molecule’s mass
Fig. 6 – Effect of the initial solution pH onto the adsorption transfer (Moussavi et al., 2013). Similar behavior was obtained
of ATZ onto the PCPAC (C0 = 20 mg L−1 , T = 298 K, t = 180 by Liu et al. (2015), using biochars derived from agricultural
min, V = 25 mL, and agitation rate = 170 rpm). residues for atrazine removal.
The Liu, Freundlich, and Langmuir isotherm models were
3.2. Effect of pH on ATZ adsorption fitted to the experimental data to interpret the adsorption
equilibrium of this system (Table 1). The quality of the adjust-
The study of the pH of the solution is fundamental in the ments was evaluated using the R2 , R2 adj , SD, and BIC (see
adsorption process, directly influencing the adsorption capac- Supplementary material). Considering the lowest values of SD
ity due to changes in both the adsorbent surface charge and (<0.57 mg g−1 ), R2 > 0.9990, and R2 adj > 0.9984, it was possible
the possibility of the adsorbate gaining or losing a proton to verify that the Liu model obtained a better fit if com-
forming a charged specie in solution (Chabalala et al., 2021). pared to the other isotherm models. In contrast, the Langmuir
Fig. 6 illustrates the effect of this parameter on the uptake of model presented minor favorable fits. In addition, to com-
ATZ in the pH range from 3 to 9, where the highest uptake pare the three models, the Bayesian Information Criterion was
(qexp . 18.34 mg g−1 ) was obtained at pH 7. Considering that employed (Lima et al., 2021b; Lima et al., 2021c) (see Supple-
most of the atrazine in the pH = 7 is found in the neutral form, mentary material). This Statistical tool is decisive to compare
the adsorption is expected to occur due to electrostatic inter- different models. When BIC is >10, the model with the lower
action, hydrogen bonds, n–␲ and/or ␲–␲ interactions (Tang BIC is certainly the best-chosen model. When BIC <2, there
 Chemical Engineering Research and Design 1 8 0 ( 2 0 2 2 ) 67–78 73

the maximum adsorption capacities between the materials.

Table 1 – Isotherm parameters estimated for adsorption
of ATZ onto PCPAC. PCPAC had the third-best adsorption capacity (Qmax = 55.85
mg g−1 ), considered intermediate and satisfactory. The great
Temperature (K)
advantage of this material is the high availability of residual
Model 298 308 318 328
Langmuir biomass and its use under natural pH conditions.
Qmax (mg g−1 ) 20.13 27.34 30.19 33.60 The adsorption thermodynamics of the ATZ herbicide onto
KL (L mg−1 ) 23.87 4.695 3.985 3.681 the activated carbon was evaluated using the values of the
R2 0.9730 0.9511 0.9442 0.9725 equilibrium constant (Ke0 ) obtained as described elsewhere
R2 adj 0.9662 0.939 0.9295 0.9656 (Lima et al., 2019a,b), using a best-fit isotherm (Liu and Liu,
SD (mg g−1 ) 1.537 2.278 3.019 2.593
2008). It was possible to calculate the Gibbs free energy change
BIC 8.101 12.82 11.25 14.38
(G◦ ), enthalpy change (H◦ ), and entropy change (S◦ ) using
Freundlich
KF ((mg g−1 ) (mg L−1 )−1/nF ) 15.43 17.74 19.20 21.25 these values of thermodynamic equilibrium constant (Lima
nF (dimensionless) 9.770 6.160 5.902 5.905 et al., 2019a,b). These calculated thermodynamic parameters
R2 0.9997 0.9983 0.9957 0.9881 of adsorption are shown in Table 3. When observing Ke0 it was
R2 adj 0.9997 0.9979 0.9946 0.9852 found that it increased from 3.149.102 to 3.117.105 with the
SD (mg g−1 ) 0.1517 0.4186 0.6206 1.7032 increase in temperature from 298.15 to 328.15 K, indicating
− − −
BIC 19.69 7.509 2.782 9.333
that the temperature favored the adsorption process. The
Liu
Qmax (mg g−1 ) 55.85 55.06 48.67 42.04
G◦ values ranged from −14.29 (298.15 K) to −34.50 (328.15 K),
KL (L mg−1 ) 1.481.10−3 6.962.10−2 0.3243 1.445 showing that the adsorption was spontaneous and favorable.
nL (dimensionless) 0.1453 0.2690 0.3326 0.4598 In addition, the G◦ presented more negative values for
R2 0.9999 0.9999 0.9995 0.9990 the temperature of 328.15 K, indicating that the increase in
R2 adj 0.9999 0.9999 0.9991 0.9984 temperature favored the adsorption process. The obtained
SD (mg g−1 ) 0.005491 0.06743 0.2494 0.5611
− − − −
H◦ value was positive, indicating the endothermic nature of
BIC 59.45 29.35 13.66 3.926
the process, corroborating the isotherm studies. Furthermore,
according to the magnitude of the value (129.5 kJ mol−1 ), it is
is no statistical difference between the two models. For 2 ≤ possible to infer the occurrence of a predominantly physical
BIC < 6, there is a perspective that the model with a lower process (Lima et al., 2021a,b,c). Also, the positive value of S◦
BIC value is the best, and for 6 ≤ BIC < 10, the model with low (0.500 kJ mol−1 K−1 ) indicated the tendency of an increase in
BIC value has a powerful perspective of being the most suit- the level of disorder in the system, assigned to the motion of
able model (Lima et al., 2021b; Lima et al., 2021c). Observing the ATZ molecules during the adsorption process (Franco et al.,
values depicted in Table 1, the Liu isotherm model presented 2021).
the lowest BIC values. Besides that, the BIC values between
Langmuir and Liu were always ≥18.30, and ≥10.87 between 3.4. Adsorption kinetics
Freundlich and Liu. Therefore, the Liu equilibrium model was
the best isotherm model to depict the isotherm of equilibrium The study of kinetic data is highly relevant to the adsorption
for the adsorption of atrazine onto the activated carbon. process, providing information on the time required for the
Table 2 was created to compare the adsorption capacity of system to reach equilibrium, the possibility of applying a given
the developed adsorbent with the adsorption capacity of other adsorbent, the adsorption rate, and the mass transfer parame-
materials reported in the literature for ATZ removal. Although ters (Bonilla-Petriciolet et al., 2019, 2017; Ho and McKay, 1998).
the data were obtained under different experimental con- Hence, the kinetic behavior of ATZ adsorption is shown in
ditions, it is possible to observe a significant difference in Fig. 8.

Table 2 – The maximum adsorption capacity of the ATZ herbicide, qm (mg g−1 ), for different adsorbents in the literature.
Adsorbent pH T (K) C0 (mg L−1 ) SBET (m2 g−1 ) qm (mg g−1 ) Reference

PCPAC 7 298 5–40 431 55.85 This study

Amine-functionalized cellulose sponge coated 2 283 15–35 x 32.06 Nagarajan et al. (2020)
with carbon dots
Zeolite prepared from Egyptian kaolin 7 298 2–10 688 11.86 Jamil et al. (2011)
Organo-beidellites 7 298 10 4.3 0.30 Grundgeiger et al. (2015)
Biochar supported reduced graphene oxide 6 298 10 15.09 72.179 Zhang et al. (2018)
Multi-walled carbon nanotube magnetic 6 298 1–20 162.99 40.16 Tang et al. (2012a,b)
Heat treated kerolite 7.3-7.5 283 1.7–30 224 11 × 10−3 Ureña-Amate et al. (2005)
Surface oxidized multiwalled carbon nanotubes 6-7 298 4.2 167 47.63 Chen et al. (2008)
Nanofibers PAN 10 298 10 x 10.08 Chabalala et al. (2021)
PAN-CD nanofibers crosslinked with citric acid 8 298 10 x 23.53 Chabalala et al. (2021)
Nylon6/polypyrole core–shell nanofibers 10–11 298 200 32.5 2.74 Yang et al. (2015)
Biochar doped with posporous 7 298 2 638.1 26.46 Suo et al. (2019)

Table 3 – Estimated thermodynamics proprieties for adsorption of ATZ onto PCPAC.

T(K) Ke0 G0 (kJ mol−1 ) H0 (kJ mol−1 ) S0 (kJ mol−1 K−1 )

298.15 3.194.102 −14.29

308.15 1.502.104 −24.63
129.5 0.5000
318.15 6.995.104 −29.49
328.15 3.117.105 −34.50
74 Chemical Engineering Research and Design 1 8 0 ( 2 0 2 2 ) 67–78

L−1 of initial concentration of the pesticide. However, when

BIC was employed for 5 mg L−1 of atrazine, the general order
kinetic model presented a BIC of 3.297 concerning PFO, indi-
cating that the general order kinetic model tends to be the
most suitable kinetic model. For 10 mg L−1 of atrazine, there
is no statistical difference between PSO and GO kinetic mod-
els since BIC was <2 (1.844). For 20 mg L−1 of atrazine,
again, there is no significant difference between PSO and
General order since BIC was 1.980. Therefore, based on the
three atrazine concentrations, the general-order kinetic model
seems to be the best model to describe the kinetics of adsorp-
tion of atrazine using the adsorbent (Table 4; Fig. 8).
In order to compare the kinetic models presenting different
constant rates (k), the t1/2 and t0.95 defined as the time required
to attain 50% and 95% of the saturation of the active sites,
respectively, were obtained for each kinetic model. Consider-
ing that the General-order models were the best, it could be
Fig. 8 – Kinetic curves of ATZ adsorption on PCPAC data and
inferred that contact times >105 min will be enough to attain
the general order prediction according to the ATZ initial
the equilibrium.
concentration, where symbols correspond to:  5 mg L−1 of
ATZ, 10 mg L−1 of ATZ, and 20 mg L−1 of ATZ (pH = 7,
Dads = 1 g L−1 , agitation rate = 170 rpm, V = 25 mL). 3.5. Proposal of the adsorption mechanism

Taking into consideration the results obtained from the FT-IR,

Table 4 – Kinetics parameters estimated for the
adsorption of ATZ onto PCPAC. pH of the system, pKa of the atrazine, and the thermodynamic
results is possible to propose the adsorption mechanism. From
Model Atrazine Initial
Concentration (mg L−1 )
the FT-IR results, it was found that the functional groups
such as C C (aromatic rings), C O (carboxylic acid, aldehyde,
50 100 200
ester), and OH (phenol, alcohol, carboxylic acid) are present
Pseudo-first order on the surface of the adsorbent. Furthermore, the adsorption
q1 (mg g−1 ) 11.27 17.86 20.89 was conducted at pH 7, and the pKa of the atrazine is 4.2; it
k1 (min−1 ) 0.07205 0.05100 0.05605
is expected that the atrazine is found at the negative form;
t1/2 (min) 9.620 13.59 12.36
thus, it is expected that adsorption occurs due to the hydro-
t0.95 (min) 41.58 58.71 53.43
R2 0.9987 0.9892 0.9931 gen bonds, ␲–␲ and/or n–␲ interaction (Kerkhoff et al., 2021;
R2 adj 0.9984 0.9870 0.9918 Salomón et al., 2021).
SD (mg g−1 ) 0.1635 0.7482 0.6967
BIC −21.87 −0.5787 −1.577
4. Conclusion
Pseudo-second order
q2 (mg g−1 ) 12.36 20.18 23.43
k2 (g mg−1 min−1 ) 0.008678 0.003283 0.003194 The edible fruit araçá (Psidium cattleianum) peels were success-
t1/2 (min) 8.451 12.93 11.63 fully carbonized with FeCl3 and applied to uptake atrazine
t0.95 (min) 87.03 107.1 102.2 herbicide from an aqueous solution. The isothermal and
R2 0.9937 0.9983 0.9990 kinetic studies were carried out at the natural pH of the
R2 adj 0.9924 0.9980 0.9988
solution (7) for a dosage of 1 g L−1 of adsorbent. The qe ,exp
SD (mg g−1 ) 0.3617 0.2944 0.2693
achieved a maximum value of 35.67 mg g−1 at 328 K. The
BIC −10.75 −13.64 −14.89
General order temperature provided a slight increase in capacity, showing
qg (mg g−1 ) 11.39 19.91 22.39 a good isothermal fit for the Liu model. From a thermody-
kn [(min−1 ).(g mg−1 )n−1 ] 0.05154 0.004319 0.008758 namic point of view, the process was spontaneous, favorable,
n 1.175 1.9087 1.670 and endothermic (H0 129.5 kJ mol−1 ), inferring the occur-
t1/2 (min) 9.333 12.95 11.79 rence of physical interactions. The general order model was
t0.95 (min) 49.61 104.7 91.20
the adequate kinetic model for describing the atrazine adsorp-
R2 0.9994 0.9983 0.9994
R2 adj 0.9991 0.9975 0.9991
tion, presenting the lowest BIC. The results indicate that the
SD (mg g−1 ) 0.1257 0.3268 0.2274 adsorption is controlled by physisorption and occurs due to
BIC −25.17 −11.79 −16.87 electrostatic interactions, hydrogen bonds, ␲–␲ and/or n–␲
interaction. Therefore, the application of araçá fruit residual
biomass has great potential for preparing activated carbon
The kinetic behavior was faster initially, and then the
and subsequent application as an adsorbent to remove the
removal rate was decreased because of the diminution of free
ATZ herbicide. As a suggestion for future work, aiming to use
adsorption sites on the adsorbent surface for the uptake of
this abundant biomass better, other activating agents can be
ATZ molecules until reaching the saturation of the adsorbent
tested, and other emerging pollutants can be removed in aque-
attaining an equilibrium state (Georgin et al., 2021b).
ous media.
The pseudo-first-order, pseudo-second-order, and general
order kinetic models were employed (Table 4). Based on SD
values, it was found that the General-order model presented
Data availability
lower values for initial atrazine concentration of 5 mg L−1
and 20 mg L−1 and the pseudo-second-order model for 10 mg Data will be made available on request.
 Chemical Engineering Research and Design 1 8 0 ( 2 0 2 2 ) 67–78 75

Declaration of interests Environ. Chem. Eng. 9, 105727,

http://dx.doi.org/10.1016/j.jece.2021.105727.
Chabalala, M.B., Al-Abri, M.Z., Mamba, B.B., Nxumalo, E.N., 2021.
The authors declare that they have no known competing
Mechanistic aspects for the enhanced adsorption of
financial interests or personal relationships that could have
bromophenol blue and atrazine over cyclodextrin modified
appeared to influence the work reported in this paper. polyacrylonitrile nanofiber membranes. Chem. Eng. Res. Des.
169, 19–32, http://dx.doi.org/10.1016/j.cherd.2021.02.010.
Chen, G.C., Shan, X.Q., Wang, Y.S., Pei, Z.G., Shen, X.E., Wen, B.,
Appendix A. Supplementary data Owens, G., 2008. Effects of copper, lead, and cadmium on the
sorption and desorption of atrazine onto and from carbon
nanotubes. Environ. Sci. Technol. 42, 8297–8302,
Supplementary material related to this article can be
http://dx.doi.org/10.1021/es801376w.
found, in the online version, at doi:https://doi.org/10.1016/ Cunha, M.R., Lima, E.C., Lima, D.R., da Silva, R.S., Thue, P.S.,
j.cherd.2022.01.044. Seliem, M.K., Sher, F., dos Reis, G.S., Larsson, S.H., 2020.
Removal of captopril pharmaceutical from synthetic
pharmaceutical-industry wastewaters: use of activated
References carbon derived from Butia catarinensis. J. Environ. Chem. Eng.
8, 104506, http://dx.doi.org/10.1016/j.jece.2020.104506.
da Costa Amaral, S., Roux, D., Caton, F., Rinaudo, M., Barbieri, S.F.,
Afolabi, I.C., Popoola, S.I., Bello, O.S., 2020. Modeling
Meira Silveira, J.L., 2021. Extraction, characterization, and
pseudo-second-order kinetics of orange peel-paracetamol
gelling ability of pectins from araçá (Psidium cattleianum
adsorption process using artificial neural network. Chemom.
Sabine) fruits. Food Hydrocoll. 121, 106845,
Intell. Lab. Syst. 203, 104053,
http://dx.doi.org/10.1016/j.foodhyd.2021.106845.
http://dx.doi.org/10.1016/j.chemolab.2020.104053.
Dangwang Dikdim, J.M., Gong, Y., Noumi, G.B., Sieliechi, J.M.,
Alahabadi, A., Moussavi, G., 2017. Preparation, characterization,
Zhao, X., Ma, N., Yang, M., Tchatchueng, J.B., 2019.
and atrazine adsorption potential of mesoporous
Peroxymonosulfate improved photocatalytic degradation of
carbonate-induced activated biochar (CAB) from Calligonum
atrazine by activated carbon/graphitic carbon nitride
Comosum biomass: parametric experiments and kinetics,
composite under visible light irradiation. Chemosphere 217,
equilibrium and thermodynamic modeling. J. Mol. Liq. 242,
833–842, http://dx.doi.org/10.1016/j.chemosphere.2018.10.177.
40–52, http://dx.doi.org/10.1016/j.molliq.2017.06.116.
de Albuquerque, F.P., de Oliveira, J.L., Moschini-Carlos, V., Fraceto,
Almeida Lage, A.L., Ribeiro, J.M., de Souza-Fagundes, E.M.,
L.F., 2020. An overview of the potential impacts of atrazine in
Brugnera, M.F., Martins, D.C. da S., 2019. Efficient atrazine
aquatic environments: perspectives for tailored solutions
degradation catalyzed by manganese porphyrins:
based on nanotechnology. Sci. Total Environ. 700, 134868,
determination of atrazine degradation products and their
http://dx.doi.org/10.1016/j.scitotenv.2019.134868.
toxicity evaluation by human blood cells test models. J.
de Lima, A.S., Maia, D.V., Haubert, L., Oliveira, T.L., Fiorentini,
Hazard. Mater. 378, 120748,
Â.M., Rombaldi, C.V., da Silva, W.P., 2020. Action mechanism
http://dx.doi.org/10.1016/j.jhazmat.2019.120748.
of araçá (Psidium cattleianum Sabine) hydroalcoholic extract
Andrade, L.L. de, do Espirito Santo Pereira, A., Fernandes Fraceto,
against Staphylococcus aureus. Lwt 119, 108884,
L., Bueno dos Reis Martinez, C., 2019. Can atrazine-loaded
http://dx.doi.org/10.1016/j.lwt.2019.108884.
nanocapsules reduce the toxic effects of this herbicide on the
de Paiva, P.P., Delcorso, M.C., Matheus, V.A., do Nascimento de
fish Prochilodus lineatus? A multibiomarker approach. Sci.
Queiroz, S.C., Collares-Buzato, C.B., Arana, S., 2017. Acute
Total Environ. 663, 548–559,
toxicity of commercial atrazine in Piaractus mesopotamicus:
http://dx.doi.org/10.1016/j.scitotenv.2019.01.380.
histopathological, ultrastructural, molecular, and genotoxic
Bedia, J., Belver, C., Ponce, S., Rodriguez, J.J., Rodriguez, J.J., 2018.
evaluation. Vet. World 10, 1008–1019,
Adsorption of antipyrine by activated carbons from
http://dx.doi.org/10.14202/vetworld.2017.1008-1019.
FeCl3 -activation of Tara gum. Chem. Eng. J. 333, 58–65,
Ding, X., Wang, S., Shen, W., Mu, Y., Wang, L., Chen, H., Zhang, L.,
http://dx.doi.org/10.1016/j.cej.2017.09.161.
2017. Fe@Fe2 O3 promoted electrochemical mineralization of
Bittencourt, G.M., Firmiano, D.M., Fachini, R.P., Lacaz-Ruiz, R.,
atrazine via a triazinon ring-opening mechanism. Water Res.
Fernandes, A.M., Oliveira, A.L., 2019. Application of green
112, 9–18, http://dx.doi.org/10.1016/j.watres.2017.01.024.
technology for the acquisition of extracts of Araçá (Psidium
Dionne, E., Hanson, M.L., Anderson, J.C., Brain, R.A., 2021. Chronic
grandifolium Mart. ex DC.) using supercritical CO2 and
toxicity of technical atrazine to the fathead minnow
pressurized ethanol: characterization and analysis of activity.
(Pimephales promelas) during a full life-cycle exposure and an
J. Food Sci. 84, 1297–1307,
evaluation of the consistency of responses. Sci. Total Environ.
http://dx.doi.org/10.1111/1750-3841.14584.
755, 142589, http://dx.doi.org/10.1016/j.scitotenv.2020.142589.
Bo, L., Kiriarachchi, H.D., Bobb, J.A., Ibrahim, A.A., El-shall, M.S.,
dos Santos Pereira, E., Vinholes, J., Franzon, R.C., Dalmazo, G.,
2020. Preparation, activity, and mechanism of ZnIn2 S4 -based
Vizzotto, M., Nora, L., 2018. Psidium cattleianum fruits: a review
catalysts for photocatalytic degradation of atrazine in
on its composition and bioactivity. Food Chem. 258, 95–103,
aqueous solution. J. Water Process Eng. 36, 101334,
http://dx.doi.org/10.1016/j.foodchem.2018.03.024.
http://dx.doi.org/10.1016/j.jwpe.2020.101334.
Dutournié, P., Bruneau, M., Brendlé, J., Limousy, L., Pluchon, S.,
Bonilla-Petriciolet, A., Mendoza-Castillo, D.I., Reynel-Ávila, H.E.,
2019. Mass transfer modelling in clay-based material:
2017. Adsorption processes for water treatment and
estimation of apparent diffusivity of a molecule of interest.
purification. Adsorpt. Process. Water Treat. Purif., 1–256,
Comptes Rendus Chim. 22, 250–257,
http://dx.doi.org/10.1007/978-3-319-58136-1.
http://dx.doi.org/10.1016/j.crci.2018.10.008.
Bonilla-Petriciolet, A., Mendoza-Castillo, D.I., Dotto, G.L.,
Franco, D.S.P., Georgin, J., Netto, M.S., Allasia, D., Oliveira, M.L.S.,
Duran-Valle, C.J., 2019. Adsorption in water treatment. Chem.
Foletto, E.L., Dotto, G.L., 2021. Highly effective adsorption of
Mol. Sci. Chem. Eng., 1–19.
synthetic phenol effluent by a novel activated carbon
Bounaas, M., Bouguettoucha, A., Chebli, D., Gatica, J.M., Vidal, H.,
prepared from fruit wastes of the Ceiba speciosa forest species.
2021. Role of the wild carob as biosorbent and as precursor of
J. Environ. Chem. Eng. 9, 105927,
a new high-surface-area activated carbon for the adsorption
http://dx.doi.org/10.1016/j.jece.2021.105927.
of methylene blue. Arab. J. Sci. Eng. 46, 325–341,
Francolino, B.Y., Valdes, Y., de Luna, C.A., de França, F.J.L., Moens,
http://dx.doi.org/10.1007/s13369-020-04739-5.
T., dos Santos, G.A.P., 2021. Short-term lethal and sublethal
Cao, Y., Jiang, S., Zhang, Y., Xu, J., Qiu, L., Wang, L., 2021.
atrazine effects on Litoditis marina: towards a nematode
Investigation into adsorption characteristics and mechanism
model for marine toxicity assessment? Ecol. Indic. 126,
of atrazine on nano-MgO modified fallen leaf biochar. J.
76 Chemical Engineering Research and Design 1 8 0 ( 2 0 2 2 ) 67–78

107642, http://dx.doi.org/10.1016/j.ecolind.2021. Khan, S.H., Pathak, B., 2020. Zinc oxide based photocatalytic
107642. degradation of persistent pesticides: a comprehensive review.
Freundlich, H., 1907. Über die Adsorption in Lösungen. Z. Phys. Environ. Nanotechnol. Monit. Manag. 13, 100290,
Chem. 57U, http://dx.doi.org/10.1515/zpch-1907-5723. http://dx.doi.org/10.1016/j.enmm.2020.100290.
Fu, K., Yue, Q., Gao, B., Wang, Y., Li, Q., 2017. Activated carbon Komtchou, S., Dirany, A., Drogui, P., Robert, D., Lafrance, P., 2017.
from tomato stem by chemical activation with FeCl2 . Colloids Removal of atrazine and its by-products from water using
Surface A Physicochem. Eng. Asp. 529, 842–849, electrochemical advanced oxidation processes. Water Res.
http://dx.doi.org/10.1016/j.colsurfa.2017.06.064. 125, 91–103, http://dx.doi.org/10.1016/j.watres.2017.08.036.
Gao, Y., Jiang, Z., Li, J., Xie, W., Jiang, Q., Bi, M., Zhang, Y., 2019. A Kowalska, K., Maniakova, G., Carotenuto, M., Sacco, O., Vaiano, V.,
comparison of the characteristics and atrazine adsorption Lofrano, G., Rizzo, L., 2020. Removal of carbamazepine,
capacity of co-pyrolysed and mixed biochars generated from diclofenac, and trimethoprim by solar-driven advanced
corn straw and sawdust. Environ. Res. 172, 561–568, oxidation processes in a compound triangular collector based
http://dx.doi.org/10.1016/j.envres.2019.03.010. reactor: a comparison between homogeneous and
Georgin, J., Franco, D., Drumm, F.C.F.C., Grassi, P., Netto, M.S.M.S., heterogeneous processes. Chemosphere 238, 124665,
Allasia, D., Dotto, G.L.G.L., 2020. Powdered biosorbent from the http://dx.doi.org/10.1016/j.chemosphere.2019.124665.
mandacaru cactus (Cereus jamacaru) for discontinuous and Lagergren, S.Y., 1898. Zur Theorie der sogenannten Adsorption.
continuous removal of Basic Fuchsin from aqueous solutions. Langmuir, I., 1918. The adsorption of gases on plane surfaces of
Powder Technol. 364, 584–592, glass, mica, and platinum. J. Am. Chem. Soc. 40, 1361–1403,
http://dx.doi.org/10.1016/j.powtec.2020.01.064. http://dx.doi.org/10.1021/ja02242a004.
Georgin, J., Franco, D.S.P., Netto, M.S., Piccilli, D.G.A., Foletto, E.L., Li, X., Liu, X., Lin, C., Zhang, H., Zhou, Z., Fan, G., Ma, J., 2019.
Dotto, G.L., 2021a. Adsorption investigation of 2,4-D herbicide Cobalt ferrite nanoparticles supported on drinking water
on acid-treated peanut (Arachis hypogaea) skins. Environ. Sci. treatment residuals: an efficient magnetic heterogeneous
Pollut. Res. 28, 36453–36463, catalyst to activate peroxymonosulfate for the degradation of
http://dx.doi.org/10.1007/s11356-021-12813-0. atrazine. Chem. Eng. J. 367, 208–218,
Georgin, J., Yamil, Y.L., Franco, D.S.P., Netto, M.S., Piccilli, D.G.A., http://dx.doi.org/10.1016/j.cej.2019.02.151.
Perondi, D., Silva, L.F.O., Foletto, E.L., Dotto, G.L., 2021b. Lima, D.R., Hosseini-Bandegharaei, A., Thue, P.S., Lima, E.C., de
Development of highly porous activated carbon from Albuquerque, Y.R.T., dos Reis, G.S., Umpierres, C.S., Dias, S.L.P.,
Jacaranda mimosifolia seed pods for remarkable removal of Tran, H.N., 2019a. Efficient acetaminophen removal from
aqueous-phase ketoprofen. J. Environ. Chem. Eng. 9, water and hospital effluents treatment by activated carbons
http://dx.doi.org/10.1016/j.jece.2021.105676. derived from Brazil nutshells. Colloids Surface A
Gómez-Avilés, A., Peñas-Garzón, M., Belver, C., Rodriguez, J.J., Physicochem. Eng. Asp. 583, 123966,
Bedia, J., 2022. Equilibrium, kinetics, and breakthrough curves http://dx.doi.org/10.1016/j.colsurfa.2019.123966.
of acetaminophen adsorption onto activated carbons from Lima, E.C., Hosseini-Bandegharaei, A., Moreno-Piraján, J.C.,
microwave-assisted FeCl3 -activation of lignin. Sep. Purif. Anastopoulos, I., 2019b. A critical review of the estimation of
Technol. 278, http://dx.doi.org/10.1016/j.seppur.2021.119654. the thermodynamic parameters on adsorption equilibria.
Grundgeiger, E., Lim, Y.H., Frost, R.L., Ayoko, G.A., Xi, Y., 2015. Wrong use of equilibrium constant in the Van’t Hoof equation
Applied Clay Science Application of organo-beidellites for the for calculation of thermodynamic parameters of adsorption. J.
adsorption of atrazine. Appl. Clay Sci. 105–106, 252–258, Mol. Liq. 273, 425–434,
http://dx.doi.org/10.1016/j.clay.2015.01.003. http://dx.doi.org/10.1016/j.molliq.2018.10.048.
Ho, Y.S., McKay, G., 1998. Sorption of dye from aqueous solution Lima, D.R., Lima, E.C., Thue, P.S., Dias, S.L.P., Machado, F.M.,
by peat. Chem. Eng. J. 70, 115–124, Seliem, M.K., Sher, F., dos Reis, G.S., Saeb, M.R., Rinklebe, J.,
http://dx.doi.org/10.1016/S0923-0467(98)00076-1. 2021a. Comparison of acidic leaching using a conventional
Ho, Y.S., McKay, G., 1999. Pseudo-second order model for sorption and ultrasound-assisted method for preparation of
processes. Process Biochem. 34, 451–465, magnetic-activated biochar. J. Environ. Chem. Eng. 9, 105865,
http://dx.doi.org/10.1016/S0032-9592(98)00112-5. http://dx.doi.org/10.1016/j.jece.2021.105865.
Hu, N., Xu, Y., Sun, C., Zhu, L., Sun, S., Zhao, Y., Hu, C., 2021. Lima, É.C., Dehghani, M.H., Guleria, A., Sher, F., Karri, R.R., Dotto,
Removal of atrazine in catalytic degradation solutions by G.L., Tran, H.N., 2021b. Adsorption: fundamental aspects and
microalgae Chlorella sp. and evaluation of toxicity of applications of adsorption for effluent treatment. In: Hadi
degradation products via algal growth and photosynthetic Dehghani, M., Karri, R., Lima, E. (Eds.), Green Technologies for
activity. Ecotoxicol. Environ. Saf. 207, 111546, the Defluoridation of Water. Elsevier, pp. 41–88,
http://dx.doi.org/10.1016/j.ecoenv.2020.111546. http://dx.doi.org/10.1016/b978-0-323-85768-0.00004-x.
Huang, Y., Han, C., Liu, Y., Nadagouda, M.N., Machala, L., O’Shea, Lima, E.C., Sher, F., Guleria, A., Saeb, M.R., Anastopoulos, I., Tran,
K.E., Sharma, V.K., Dionysiou, D.D., 2018. Degradation of H.N., Hosseini-Bandegharaei, A., 2021c. Is one performing the
atrazine by ZnxCu1−xFe2 O4 nanomaterial-catalyzed sulfite treatment data of adsorption kinetics correctly? J. Environ.
under UV–vis light irradiation: green strategy to generate Chem. Eng. 9, 104813,
SO4 [rad]−. Appl. Catal. B Environ. 221, 380–392, http://dx.doi.org/10.1016/j.jece.2020.104813.
http://dx.doi.org/10.1016/j.apcatb.2017.09.001. Liu, Y., Liu, Y.J., 2008. Biosorption isotherms, kinetics, and
Irandost, M., Akbarzadeh, R., Pirsaheb, M., Asadi, A., thermodynamics. Sep. Purif. Technol. 61, 229–242,
Mohammadi, P., Sillanpää, M., 2019. Fabrication of highly http://dx.doi.org/10.1016/j.seppur.2007.10.002.
visible active N, S co-doped TiO2 @MoS2 heterojunction with Liu, Y., Shen, L., 2008. A general rate law equation for biosorption.
synergistic effect for photocatalytic degradation of diclofenac: Biochem. Eng. J. 38, 390–394,
mechanisms, modeling and degradation pathway. J. Mol. Liq. http://dx.doi.org/10.1016/j.bej.2007.08.003.
291, 111342, http://dx.doi.org/10.1016/j.molliq.2019.111342. Liu, Y., Xu, H., Yang, S.F., Tay, J.H., 2003. A general model for
Jamil, T.S., Gad-Allah, T.A., Ibrahim, H.S., Saleh, T.S., 2011. biosorption of Cd2+ , Cu2+ , and Zn2+ by aerobic granules. J.
Adsorption and isothermal models of atrazine by zeolite Biotechnol. 102, 233–239,
prepared from Egyptian kaolin. Solid State Sci. 13, 198–203, http://dx.doi.org/10.1016/S0168-1656(03)00030-0.
http://dx.doi.org/10.1016/j.solidstatesciences.2010.11.014. Liu, N., Charrua, A.B., Weng, C.H., Yuan, X., Ding, F., 2015.
Kerkhoff, C.M., Boit Martinello, K. da, Franco, D.S.P., Netto, M.S., Characterization of biochars derived from agriculture wastes
Georgin, J., Foletto, E.L., Piccilli, D.G.A., Silva, L.F.O., Dotto, G.L., and their adsorptive removal of atrazine from aqueous
2021. Adsorption of ketoprofen and paracetamol and solution: a comparative study. Bioresour. Technol. 198, 55–62,
treatment of a synthetic mixture by novel porous carbon http://dx.doi.org/10.1016/j.biortech.2015.08.129.
derived from Butia capitata endocarp. J. Mol. Liq. 339, 117184, Lütke, S.F., Igansi, A.V., Pegoraro, L., Dotto, G.L., Pinto, L.A.A.,
http://dx.doi.org/10.1016/j.molliq.2021.117184. Cadaval, T.R.S., 2019. Preparation of activated carbon from
 Chemical Engineering Research and Design 1 8 0 ( 2 0 2 2 ) 67–78 77

black wattle bark waste and its application for phenol Siddique, A., Nayak, A.K., Singh, J., 2020. Synthesis of
adsorption. J. Environ. Chem. Eng. 7, 103396, FeCl3 -activated carbon derived from waste Citrus limetta peels
http://dx.doi.org/10.1016/j.jece.2019.103396. for removal of fluoride: an eco-friendly approach for the
Machado, L.M.M.M., Lütke, S.F., Perondi, D., Godinho, M., Oliveira, treatment of groundwater and bio-waste collectively.
M.L.S.S., Collazzo, G.C., Dotto, G.L., 2020. Treatment of Groundw. Sustain. Dev. 10, 100339,
effluents containing 2-chlorophenol by adsorption onto http://dx.doi.org/10.1016/j.gsd.2020.100339.
chemically and physically activated biochars. J. Environ. Singh, N.B., Nagpal, G., Agrawal, S., Rachna, 2018. Water
Chem. Eng. 8, 104473, purification by using adsorbents: a review. Environ. Technol.
http://dx.doi.org/10.1016/j.jece.2020.104473. Innov. 11, 187–240, http://dx.doi.org/10.1016/j.eti.2018.05.006.
Mahlalela, L.C., Casado, C., Marugán, J., Septien, S., Ndlovu, T., Sivarajasekar, N., Balasubramani, K., Mohanraj, N., Prakash
Dlamini, L.N., 2021. Coupling biological and photocatalytic Maran, J., Sivamani, S., Ajmal Koya, P., Karthik, V., 2017.
treatment of atrazine and tebuthiuron in aqueous solution. J. Fixed-bed adsorption of atrazine onto microwave irradiated
Water Process Eng. 40, Aegle marmelos Correa fruit shell: statistical optimization,
http://dx.doi.org/10.1016/j.jwpe.2021.101918. process design and breakthrough modeling. J. Mol. Liq. 241,
Maletić, M., Vukčević, M., Kalijadis, A., Janković-Častvan, I., 823–830, http://dx.doi.org/10.1016/j.molliq.2017.06.064.
Dapčević, A., Laušević, Z., Laušević, M., 2019. Hydrothermal Soliman, F.M., Fathy, M.M., Salama, M.M., Saber, F.R., 2016.
synthesis of TiO2 /carbon composites and their application for Comparative study of the volatile oil content and
removal of organic pollutants. Arab. J. Chem. 12, 4388–4397, antimicrobial activity of Psidium guajava L. and Psidium
http://dx.doi.org/10.1016/j.arabjc.2016.06.020. cattleianum Sabine leaves. Bull. Fac. Pharm. Cairo Univ. 54,
Marrakchi, F., Fazeli Zafar, F., Wei, M., Wang, S., 2021. Cross-linked 219–225, http://dx.doi.org/10.1016/j.bfopcu.2016.06.003.
FeCl3 -activated seaweed carbon/MCM-41/alginate hydrogel Spaltro, A., Pila, M.N., Colasurdo, D.D., Noseda Grau, E., Román,
composite for effective biosorption of bisphenol A plasticizer G., Simonetti, S., Ruiz, D.L., 2021. Removal of paracetamol
and basic dye from aqueous solution. Bioresour. Technol. 331, from aqueous solution by activated carbon and silica.
125046, http://dx.doi.org/10.1016/j.biortech.2021.125046. Experimental and computational study. J. Contam. Hydrol.
McBeath, S.T., Graham, N.J.D., 2021. Simultaneous 236, 103739, http://dx.doi.org/10.1016/j.jconhyd.2020.103739.
electrochemical oxidation and ferrate generation for the Spessato, L., Bedin, K.C., Cazetta, A.L., Souza, I.P.A.F., Duarte, V.A.,
treatment of atrazine: a novel process for water treatment Crespo, L.H.S., Silva, M.C., Pontes, R.M., Almeida, V.C., 2019.
applications. J. Hazard. Mater. 411, 125167, KOH-super activated carbon from biomass waste: insights
http://dx.doi.org/10.1016/j.jhazmat.2021.125167. into the paracetamol adsorption mechanism and thermal
Medhat, A., El-Maghrabi, H.H., Abdelghany, A., Abdel Menem, regeneration cycles. J. Hazard. Mater. 371, 499–505,
N.M., Raynaud, P., Moustafa, Y.M., Elsayed, M.A., Nada, A.A., http://dx.doi.org/10.1016/j.jhazmat.2019.02.102.
2021. Efficiently activated carbons from corn cob for Suo, F., You, X., Ma, Y., Li, Y., 2019. Rapid removal of triazine
methylene blue adsorption. Appl. Surf. Sci. Adv. 3, 100037, pesticides by P doped biochar and the adsorption mechanism.
http://dx.doi.org/10.1016/j.apsadv.2020.100037. Chemosphere 235, 918–925,
Moussavi, G., Alahabadi, A., Yaghmaeian, K., Eskandari, M., 2013. http://dx.doi.org/10.1016/j.chemosphere.2019.06.158.
Preparation, characterization, and adsorption potential of the Tang, W., Zeng, G., Gong, J., Liu, Y., Wang, X., 2012a. Simultaneous
NH4 Cl-induced activated carbon for the removal of adsorption of atrazine and Cu(II) from wastewater by
amoxicillin antibiotic from water. Chem. Eng. J. 217, 119–128, magnetic multi-walled carbon nanotube. Chem. Eng. J.
http://dx.doi.org/10.1016/j.cej.2012.11.069. 211–212, 470–478, http://dx.doi.org/10.1016/j.cej.2012.09.102.
Muthusaravanan, S., Balasubramani, K., Suresh, R., Ganesh, R.S., Tang, Y., Luo, S., Teng, Y., Liu, C., Xu, X., Zhang, X., Chen, L., 2012b.
Sivarajasekar, N., Arul, H., Rambabu, K., Bharath, G., Efficient removal of herbicide 2,4-dichlorophenoxyacetic acid
Sathishkumar, V.E., Murthy, A.P., Banat, F., 2021. Adsorptive from water using Ag/reduced graphene oxide co-decorated
removal of noxious atrazine using graphene oxide TiO2 nanotube arrays. J. Hazard. Mater. 241–242, 323–330,
nanosheets: insights to process optimization, equilibrium, http://dx.doi.org/10.1016/j.jhazmat.2012.09.050.
kinetics, and density functional theory calculations. Environ. Thommes, M., Kaneko, K., Neimark, A.V., Olivier, J.P.,
Res. 200, 111428, Rodriguez-Reinoso, F., Rouquerol, J., Sing, K.S.W., 2015.
http://dx.doi.org/10.1016/j.envres.2021.111428. Physisorption of gases, with special reference to the
Naganathan, K.K., Faizal, A.N.M., Zaini, M.A.A., Ali, A., 2020. evaluation of surface area and pore size distribution (IUPAC
Adsorptive removal of bisphenol a from aqueous solution Technical Report). Pure Appl. Chem. 87, 1051–1069,
using activated carbon from coffee residue. Mater. Today Proc. http://dx.doi.org/10.1515/pac-2014-1117.
47, 1307–1312, http://dx.doi.org/10.1016/j.matpr.2021.02.802. Thue, P.S., Umpierres, C.S., Lima, E.C., Lima, D.R., Machado, F.M.,
Nagarajan, D., Varada, O.M., Venkatanarasimhan, S., 2020. Carbon dos Reis, G.S., da Silva, R.S., Pavan, F.A., Tran, H.N., 2020.
dots coated on amine-functionalized cellulose sponge for the Single-step pyrolysis for producing magnetic activated carbon
adsorption of the toxic herbicide atrazine. Mater. Today Proc. from tucumã (Astrocaryum aculeatum) seed and nickel(II)
47, 790–799, http://dx.doi.org/10.1016/j.matpr.2020.08. chloride and zinc(II) chloride. Application for removal of
071. nicotinamide and propanolol. J. Hazard. Mater. 398, 122903,
Pereira, E. dos S., Vinholes, J.R., Camargo, T.M., Nora, F.R., Crizel, http://dx.doi.org/10.1016/j.jhazmat.2020.122903.
R.L., Chaves, F., Nora, L., Vizzotto, M., 2020. Characterization of Tripathi, P., Yadav, R., Das, P., Singh, A., Singh, R.P., Kandasamy, P.,
araçá fruits (Psidium cattleianum Sabine): phenolic Kalra, A., Khare, P., 2021. Endophytic bacterium CIMAP-A7
composition, antioxidant activity, and inhibition of ␣-amylase mediated amelioration of atrazine induced phyto-toxicity in
and ␣-glucosidase. Food Biosci. 37, 100665, Andrographis paniculata. Environ. Pollut. 287, 117635,
http://dx.doi.org/10.1016/j.fbio.2020.100665. http://dx.doi.org/10.1016/j.envpol.2021.117635.
Ribeiro, A.B., Chisté, R.C., Freitas, M., Da Silva, A.F., Visentainer, Umpierres, C.S., Thue, P.S., Lima, E.C., Reis, G.S. do, de Brum,
J.V., Fernandes, E., 2014. Psidium cattleianum fruit extracts are I.A.S., Alencar, W.S. d., Dias, S.L.P., Dotto, G.L., 2018.
efficient in vitro scavengers of physiologically relevant Microwave-activated carbons from tucumã (Astrocaryum
reactive oxygen and nitrogen species. Food Chem. 165, aculeatum) seed for efficient removal of 2-nitrophenol from
140–148, http://dx.doi.org/10.1016/j.foodchem.2014.05.079. aqueous solutions. Environ. Technol. (United Kingdom) 39,
Salomón, Y.L.D.O., Georgin, J., Franco, D.S.P., Netto, M.S., Piccilli, 1173–1187, http://dx.doi.org/10.1080/09593330.2017.1323957.
D.G.A., Foletto, E.L., Oliveira, L.F.S., Dotto, G.L., 2021. Ureña-Amate, M.D., Socías-Viciana, M., González-Pradas, E., Saifi,
High-performance removal of 2,4-dichlorophenoxyacetic acid M., 2005. Effects of ionic strength and temperature on
herbicide in water using activated carbon derived from Queen adsorption of atrazine by a heat treated kerolite.
palm fruit endocarp (Syagrus romanzoffiana). J. Environ. Chem. Chemosphere 59, 69–74,
Eng. 9, http://dx.doi.org/10.1016/j.jece.2020.104911. http://dx.doi.org/10.1016/j.chemosphere.2004.09.098.
78 Chemical Engineering Research and Design 1 8 0 ( 2 0 2 2 ) 67–78

Vinholes, J., Lemos, G., Lia Barbieri, R., Franzon, R.C., Vizzotto, M., adsorption and photo-degradation. Chem. Eng. J. 352, 581–589,
2017. In vitro assessment of the antihyperglycemic and http://dx.doi.org/10.1016/j.cej.2018.07.058.
antioxidant properties of araçá, butiá and pitanga. Food Yu, Y., An, Q., Jin, L., Luo, N., Li, Z., Jiang, J., 2020. Unraveling
Biosci. 19, 92–100, http://dx.doi.org/10.1016/j.fbio.2017.06.005. sorption of Cr(VI) from aqueous solution by FeCl3 and
Xu, Z., Zhang, T., Yuan, Z., Zhang, D., Sun, Z., Huang, Y.X., Chen, ZnCl2 -modified corn stalks biochar: implicit mechanism and
W., Tian, D., Deng, H., Zhou, Y., 2018. Fabrication of cotton application. Bioresour. Technol. 297,
textile waste-based magnetic activated carbon using FeCl3 http://dx.doi.org/10.1016/j.biortech.2019.122466.
activation by the Box-Behnken design: optimization and Zandoná, G.P., Bagatini, L., Woloszyn, N., de Souza Cardoso, J.,
characteristics. RSC Adv. 8, 38081–38090, Hoffmann, J.F., Moroni, L.S., Stefanello, F.M., Junges, A.,
http://dx.doi.org/10.1039/c8ra06253f. Rombaldi, C.V., 2020. Extraction and characterization of
Xu, Z., Sun, Z., Zhou, Y., Chen, W., Zhang, T., Huang, Y., Zhang, D., phytochemical compounds from araçazeiro (Psidium
2019. Insights into the pyrolysis behavior and adsorption cattleianum) leaf: putative antioxidant and antimicrobial
properties of activated carbon from waste cotton textiles by properties. Food Res. Int. 137, 109573,
FeCl3 -activation. Colloids Surfaces A Physicochem. Eng. Asp. http://dx.doi.org/10.1016/j.foodres.2020.109573.
582, 123934, http://dx.doi.org/10.1016/j.colsurfa.2019.123934. Zhang, Y., Cao, B., Zhao, L., Sun, L., Gao, Y., Li, J., Yang, F., 2018.
Yagmur, E., Gokce, Y., Tekin, S., Semerci, N.I., Aktas, Z., 2020. Biochar-supported reduced graphene oxide composite for
Characteristics and comparison of activated carbons prepared adsorption and coadsorption of atrazine and lead ions. Appl.
from oleaster (Elaeagnus angustifolia L.) fruit using KOH and Surf. Sci. 427, 147–155,
ZnCl2 . Fuel 267, 117232, http://dx.doi.org/10.1016/j.apsusc.2017.07.237.
http://dx.doi.org/10.1016/j.fuel.2020.117232. Zhang, X., Li, Y., Wu, M., Pang, Y., Hao, Z., Hu, M., Qiu, R., Chen, Z.,
Yang, B.Y., Cao, Y., Qi, F.F., Li, X.Q., Xu, Q., 2015. Atrazine 2021. Enhanced adsorption of tetracycline by an iron and
adsorption removal with nylon6/polypyrrole core-shell manganese oxides loaded biochar: kinetics, mechanism and
nanofibers mat: possible mechanism and characteristics. column adsorption. Bioresour. Technol. 320, 124264,
Nanoscale Res. Lett. 10, http://dx.doi.org/10.1016/j.biortech.2020.124264.
http://dx.doi.org/10.1186/s11671-015-0903-6.
Yang, Y., Deng, Q., Yan, W., Jing, C., Zhang, Y., 2018. Comparative
study of glyphosate removal on goethite and magnetite: