polymers

Article
Application of Water Hyacinth Biomass (Eichhornia crassipes)
as an Adsorbent for Methylene Blue Dye from Aqueous
Medium: Kinetic and Isothermal Study
Marcelo T. Carneiro 1 , Ana Z. B. Barros 2 , Alan I. S. Morais 2 , André L. F. Carvalho Melo 1 ,
Roosevelt D. S. Bezerra 3 , Josy A. Osajima 2 and Edson C. Silva-Filho 2, *

1 Federal Institute of Piauí, Floriano Campus, Floriano 64808-475, PI, Brazil;

[email protected] (M.T.C.); [email protected] (A.L.F.C.M.)
2 Interdisciplinary Laboratory for Advanced Materials, Teresina 64049-550, PI, Brazil;
[email protected] (A.Z.B.B.); [email protected] (A.I.S.M.); [email protected] (J.A.O.)
3 Federal Institute of Piauí, Teresina-Central Campus, Teresina 64000-040, PI, Brazil; [email protected]
* Correspondence: [email protected]; Tel.: +55-041-(86)-9-9972-0889

Abstract: Water pollution has generated the need to develop technologies to remove industrial
pollutants. Adsorption has been recognized as one of the most effective techniques for effluent
remediation. In this study, parts (stem and leaves) of a problematic aquatic weed, the water hyacinth
(Eichhornia crassipes), were separated to produce a bioadsorbent. The objective was to evaluate the
adsorption of a cationic dye, methylene blue (MB), in an aqueous solution of the biomass from
different parts of the water hyacinth (Eichhornia crassipes) plants. The materials were characterized
through techniques of infrared spectroscopy, scanning electron microscopy, X-ray diffractometry,
Citation: Carneiro, M.T.; Barros,
and thermogravimetric analysis, before and after the material adsorption. Water hyacinth biomasses
A.Z.B.; Morais, A.I.S.; Carvalho Melo,
presented adsorption capacity above 89%, and the kinetics was faster for stem biomass. The kinetic
A.L.F.; Bezerra, R.D.S.; Osajima, J.A.;
study found that the adsorption process is better described by the pseudo-second-order model, and
Silva-Filho, E.C. Application of Water
the adjustments of the isotherm experimental data indicated that both materials are favorable for
Hyacinth Biomass (Eichhornia
crassipes) as an Adsorbent for
adsorption. Therefore, water hyacinth bioadsorbent represents a renewable resource with potential
Methylene Blue Dye from Aqueous for effluent treatment.
Medium: Kinetic and Isothermal
Study. Polymers 2022, 14, 2732. Keywords: water hyacinth; Eichhornia crassipes; bioadsorbent; removal; methylene blue
https://doi.org/10.3390/
polym14132732

Academic Editor: Guozhong Wu

1. Introduction
Received: 13 April 2022 One of the consequences of social growth and development is the generation of large
Accepted: 12 June 2022
amounts of residues from different synthetic compounds. The considerable contamination
Published: 4 July 2022
of effluents has become a severe environmental problem and a serious threat to fauna and
Publisher’s Note: MDPI stays neutral flora, and human beings [1,2]. In recent decades, many industries such as weaving, dyeing,
with regard to jurisdictional claims in papermaking, leather, pharmaceuticals, and chemical production used a significant number
published maps and institutional affil- of dyes in their manufacturing process, leading to the release of hazardous effluents into
iations. drinking water [3], which have caused serious environmental problems [4].
Contamination by new emerging contaminants such as drugs and pharmaceutical
residues [5], heavy metals, textile dyes, pesticides, and surfactants [6] is a major concern,
mainly due to the negative consequences for human and aquatic ecosystem health [7,8].
Copyright: © 2022 by the authors.
Many emerging effluents are proven to cause effects at a biochemical level due to their
Licensee MDPI, Basel, Switzerland.
toxicity, carcinogenicity, and mutagenicity [9]. It is estimated that at least 100,000 of these
This article is an open access article
compounds are produced regularly, equivalent to 200 million tons per year, of which
distributed under the terms and
20–30% can contaminate aquatic environments [10].
conditions of the Creative Commons
For this reason, immediate removal of the methylene blue (MB)dye from water using
Attribution (CC BY) license (https://
creativecommons.org/licenses/by/
appropriate techniques is necessary to protect humans from adverse health effects [11],
4.0/).
mainly due to the limited accessibility of high-quality clean water sources [11,12].

Polymers 2022, 14, 2732. https://doi.org/10.3390/polym14132732 https://www.mdpi.com/journal/polymers

Polymers 2022, 14, 2732 2 of 21

Adsorption has been shown to be one of the most efficient processes due to its flexibil-
ity, efficiency, low cost, and reversibility [6,13].
Research has shown the application of different adsorbents, such as activated car-
bons [10,14], nanoadsorbents [2,5], clays [15], and cellulosic derivatives [6,16], for the
removal of pollutants present in the aquatic environment, have obtained varied adsorp-
tion efficiencies. The use of bioadsorbents–adsorbent materials of natural origin–for the
treatment of effluents is a promising proposal due to their greater adsorption capacities,
the economic aspects (low cost), and their availability in mass [17].
Among the raw materials that can be used to produce bioadsorbents, is water hyacinth
(Eichhornia crassipes). This plant has high proliferation in eutrophic water environments [18]
and is globally recognized as an invasive species that threatens the survival of aquatic
organisms by blocking sunlight and, thus, depriving aquatic life of environmental resources
such as atmospheric oxygen [19].
Therefore, Water hyacinth residue is a possibility to consider for the synthesis of
new adsorbents in the removal of environmental contaminants, in addition to adding
commercial value to the product
This work aimed to analyze the efficiency of MB textile dye removal in aqueous solu-
tions through the adsorption process using water hyacinth (Eichhornia Crassipes) biomass as
bioadsorbent. To verify a useful destination for the expressive amount of this plant, two
bioadsorbents were produced (leaf and stem of the water hyacinth) that were characterized
by Fourier-transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM),
X-ray diffractometry (EDX), and thermogravimetric analysis (TG). The compositions of the
fibrous fractions were determined and the adsorption tests were performed by varying the
pH, time, and concentration of the dye. The experimental tests were adjusted to different
kinetic and isothermal models. Finally, the desorption and reuse processes of the material
were carried out.

2. Materials and Methods

2.1. Materials and Reagents
Methylene blue (C16 H18 SN3 Cl, Dinâmica–Company originating in the country itself -
Brazil), Sodium hydroxide (NaOH, Dynamic, 98%), Hydrochloric acid (HCl, Dynamic, 38%),
Sodium chloride (NaCl, Dynamic, 99%), and Distilled water were provided by the Interdis-
ciplinary Laboratory of Advanced Materials (LIMAV) of the Federal University of Piauí
(UFPI), Teresina, Piauí, Brazil and the company Dinâmica Química Contemporânea LTDA,
Indaiatuba, Brazil with more than 30 years in the market, certified with ISO 9001:2015. All
reagents were analytical grade, and no prior purification was required. The water hyacinth
(Eichhornia crassipes) was obtained from the Matias Augusto Oliveira Matos Environmental
Park, in the city of Teresina (PI), Brazil.

2.2. Preparation of Adsorbent Material

The roots of the water hyacinth plants were removed and discarded, and the plants
were washed in running water and left to dry for three days in the open. Then, the stems
and leaves were separated and placed in an oven at 50 ◦ C for 24 h [20]. After the drying
process, they were ground separately and left in an oven at 45 ◦ C for 24 h, and finally,
sieved using a 425 µm particle size sieve.

2.3. Biomass Characterization

The Fourier-transform Infrared Spectroscopy (FTIR) technique was used to determine
which functional groups are present in biomass. The spectra were obtained using a Bruker
spectrophotometer, model Vertex 70, in the ATR configuration. Spectra were obtained with
60 scans in the range of 600 to 4000 cm−1 . The morphology of the materials prepared from
water hyacinth was obtained by scanning electron microscopy (SEM), using a scanning
electron microscope model MEV Tescan®Vega3®LMU®, Sâo Bernardo do Campo, Brazil,
at a voltage acceleration of 30 kv at magnifications of 100× and 500×, to explain the shape
Polymers 2022, 14, 2732 3 of 21

and surface properties of the adsorbent. In addition, X-ray diffraction (XRD) was used
to observe the crystallinity of the biomass before and after adsorption. The analysis was
performed in an X-ray diffractometer (Labx-XRD 600, Shimadzu, Nakagyo-ku, Kyoto,
Japan), using Kα-Cu radiation = 1.5418 Å, in a 2θ range from 5◦ to 75◦ , acceleration voltage
and applied current of 40 kV and 30 mA, respectively. Thermal stability was evaluated
by thermogravimetric analysis (TGA) in a thermal analyzer (DT-60, Shimatzu, Nakagyo-
ku, Kyoto, Japan) using a heating rate of 10 ◦ C/min between 25 and 600 ◦ C, in an inert
nitrogen atmosphere.
The composition of the fibrous fraction of the stem and leaf of the water hyacinth
(Eichhornia crassipes) was performed to determine first the dry matter (DM; method
967.03) and then the fiber fractions (in triplicate), according to the recommendations of
the Association of Official Analytical Chemists [21]. Neutral detergent fiber (NDF) and
acid detergent fiber (ADF) were determined (triplicate) according to the methodology
proposed by Van Soest et al. [22]. Acid detergent lignin (ADL) was obtained from ADF
residue incinerated in an oven at 600 ◦ C for 4 h according to the methodology described
by Van Soest [23]. Cellulose and hemicellulose were calculated from the following
proposal: Hemicellulose = NDF − ADF and Cellulose = ADF − ADL [23].

2.4. Point of Zero Charge (pHpzc )

The methodology consists of determining the pH at which there is a balance of charges
between the surface of the adsorbent and the solution [24]. For this, 20.00-mg samples
of biomass from stems or leaves were added to 20.00 mL of NaCl (0.1 mol·L−1 ), where
the pH was adjusted to correspond to the range from 2 to 12 [6,16]. The pH was adjusted
with two solutions of HCl, one of 1.0 mol·L−1 and one of 0.1 mol·L−1 , as well as two
solutions of NaOH at the same concentrations. The pH reading was performed using a pH
meter [16,25]. The mixtures were left under constant stirring at 140 rpm for 24 h at 25 ◦ C on
a shaker table (model TE-420 INCUBATOR-TECNAL). After the contact time, the solutions
were centrifuged (model NI 1812 Benchtop Centrifuge-INOVA Instruments) for 10 min at
5000 rpm or 4980 rcf, and then the final pH of the solution was measured. The difference
between the initial and final pH was plotted from the data obtained using Equation (1),
identifying the intersection where ∆pH = 0 corresponds to the point of zero charge, which
is pHpzc [25,26].
∆pH = pH0 − pHf (1)

2.5. Influence of pH
The effect of pH on dye adsorption was studied at pH 1, 3, 5, 7, 9, and 11, where
the pH was adjusted with NaOH and HCl solutions. Maintaining the concentration of
300.00 mg·L−1 of the dye, the study was carried out in triplicate at 25 ◦ C [25,27]. The
100.00 mg samples of biomaterials were placed in contact with 20 mL of MB 300.00 mol·L−1
solution. The system was agitated for 48 h. After the contact time, the solutions were
centrifuged and diluted. The new concentrations were determined by reading the aliquots
in a UV-Vis spectrophotometer (Agilent, Santa Clara, CA, USA, Cary 60) using a pre-
established calibration curve.
Finally, the adsorbed amount Qe (mg·g−1 ) and the adsorption efficiency were calcu-
lated according to Equations (2) and (3), respectively [25,28,29].

(Ci − Cf )
Qe = V (2)
m
(Ci − Cf )
R= 100% (3)
Ci
where Ci and Cf represent the initial and final concentrations (mol·L−1 ) of the dye, respec-
tively; m corresponds to the mass of the adsorbent in grams, and V equals the volume in
liters of the dye solution used.
Polymers 2022, 14, 2732 4 of 21

2.6. Adsorption Kinetics

The kinetic adsorption tests were conducted in triplicate, at a temperature of 25 ◦ C
and natural pH of the dye solution (7.01). Initially, 100 mg of leaf or stem biomass were
placed in contact with 20.0 mL of MB solution and kept under constant stirring at 140 rpm
for 4 h [6,25]. After the contact time, aliquots were centrifuged and determined in a UV-Vis
spectrophotometer using the preestablished calibration curve. Finally, the obtained kinetics
were suitable for pseudo-first-order and pseudo-second-order kinetic models.
The linearized form of the pseudo-first-order [30] and pseudo-second-order [31] kinetic
models are expressed in Equations (4) and (5), respectively.


ln qe − qt = ln qe − K1 .t (4)

t 1 t
= + (5)
qt k2 . q2e qe
where qe and qt are the amounts of dye adsorbed (mg·g−1 ) at equilibrium and at time t,
respectively; K1 represents the adsorption constant of the first-order model (min−1 ) and K2
is the constant of the pseudo-second-order kinetic model (mg·g−1 min−1 ) [6,25].

2.7. Adsorption Isotherms

The test was carried out in triplicate at 25 ◦ C, with pH adjusted according to the
best adsorption, in which 100 mg of biosorbent was added to 20 mL of dye in solution,
varying the concentrations between 50 and 1000 mg·L−1 , which were stirred in the best
equilibrium time found in the kinetics experiment [6]. After centrifuging the samples,
measurements were made in a UV–Vis spectrophotometer to calculate the equilibrium
concentrations resulting from the adsorption of each initial dye mass. This was to
investigate which adsorption isotherm model the experimental data fit best (Langmuir
or Freundlich).
Equation (6) expresses the linearized form of the Langmuir equation [32]:

Ceq 1 1
= . Ce + (6)
qe qmax KL .qmax

where qe is the amount of adsorbed species per mass of the bioadsorbent (mg·g−1 ), qmax
is the maximum amount of adsorbed species per mass of the bioadsorbent (mg·g− 1 ),
Ceq represents the equilibrium concentration of the adsorbent (mg·L−1 ), and KL is the
Langmuir adsorption constant related to the chemical balance between adsorbent and
adsorbent (mg·L−1 ) [33].
The linearized form of the Freundlich equation can be observed by Equation (7) [34].

1
ln qe = ln KF + ln Ce (7)
n
where KF is the Freundlich adsorption constant related to the adsorption capacity, 1/n is the
constant related to the surface heterogeneity, qe represents the number of species adsorbed
per mass of the bioadsorbent (mg·g−1 ), and Ce represents the concentration equilibrium of
the adsorbate (mg·L−1 ) [25].

2.8. Material Reuse

The reuse of stem and leaf in the adsorption process was conducted three times:
adsorption, desorption, and reuse. At the first adsorption time, 0.5 g of the biomass was
placed in contact with 100 mL of methylene blue dye at a concentration of 600 mg·L−1
and left under stirring at 130 rpm for 60 min. Aliquots were removed and centrifuged
at 14,000 rpm for 35 s to separate the solid from the supernatant. The second time, the
biomass powders were recovered by filtration with filter paper and washed with methanol
to remove the dye adsorbed on the materials and dried at 40 ◦ C for 12 h. The reuse of the
 left under stirring at 130 rpm for 60 min. Aliquots were removed and centrifuged at 14000
rpm for 35 s to separate the solid from the supernatant. The second time, the biomass
Polymers 2022, 14, 2732 powders were recovered by filtration with filter paper and washed with methanol 5 of 21 to
remove the dye adsorbed on the materials and dried at 40 °C for 12 h. The reuse of the
material was carried out two more times, respecting the entire process described above.
With the UV-Vis
material spectrophotometer,
was carried using
out two more times, the calibration
respecting curve,
the entire aliquots
process were analyzed
described above.
inWith
eachthe
reuse process
UV-Vis [35,36].
spectrophotometer, using the calibration curve, aliquots were analyzed in
each reuse process [35,36].
3. Results
3. Results
3.1. Characterization of Water Hyacinth Biomass
3.1. Characterization of Water Hyacinth Biomass
Figure 1a is the X-ray diffractogram for the studied biomasses. This analysis was used
Figure 1a is the X-ray diffractogram for the studied biomasses. This analysis was
toused
study changes
to study in the
changes crystalline
in the structure
crystalline structureofofbiomass,
biomass, where thepeaks
where the peaksinin
thethe graph
graph
indicate the crystallinity of the material.
indicate the crystallinity of the material.

(a) (b)

(c) (d)

Figure 1. Cont.
 Polymers 2022, 14, 2732 6 of 21
Polymers 2022, 14, x FOR PEER REVIEW 6 of 23

(e) (f)

(g)
Figure 1. 1.
Figure (a)(a)
X-ray diffractograms
X-ray diffractogramsofofthe
thewater
water hyacinth biomass:(a1)
hyacinth biomass: (a1)stem
stemand
and(a2)
(a2)leaf
leafof;of;
(b)(b) FTIR
FTIR
spectra of (b1) stem and (b2) leaf; SEM—micrograph of the water hyacinth parts: (c,d) stem;
spectra of (b1) stem and (b2) leaf; SEM—micrograph of the water hyacinth parts: (c,d) stem; (e,f) leaf.(e,f)
leaf. (g) TG thermogravimetric curves of water hyacinth (g1) stem and (g2) leaf. DTG: water
(g) TG thermogravimetric curves of water hyacinth (g1) stem and (g2) leaf. DTG: water hyacinth
hyacinth (g3) stem and (g4) leaf.
(g3) stem and (g4) leaf.

Cellulose
Cellulose and hemicellulose
and hemicelluloseconstitute
constituteabout
about 65%
65% to 70% of
to 70% oflignocellulosic
lignocellulosicbiomass,
biomass,
including
including water
waterhyacinth
hyacinth[37].
[37].Cellulose
Celluloseisishighly
highly ordered, with 80%
ordered, with 80%ofofcrystalline
crystallineregions.
regions.
In In
Figure
Figure 1 1(a1
(a1and
anda2),
a2),the
thecharacteristic
characteristic peaks at at approximately
approximately2θ 2θ= =15.50 ◦ and
15.50° and ◦
22.12°
22.12
indicate
indicatethethe
crystallinity
crystallinityofofwater
water hyacinth
hyacinthbiomass
biomass[38,39].
[38,39].The
Thesemi-crystalline
semi-crystallineprofile
profileof
theofwater
the water hyacinth
hyacinth is due
is due to the
to the lignin
lignin ininitsitsstructure
structure because
because the
the lignin
ligninisisamorphous,
amorphous,
whilecellulose
while celluloseisispredominantly
predominantly crystalline
crystalline [40]. Other peaks
[40]. Other peaks observed
observedmay mayrefer
refertoto
impurities present in the material, due to the capacity of this plant (water hyacinth)toto
impurities present in the material, due to the capacity of this plant (water hyacinth)
remove
remove inorganicsubstances
inorganic substancesfrom from water
water bodies,
bodies, such
suchas asheavy
heavymetals
metals[37].
[37].
The FTIR spectra of the water hyacinth parts are shown
The FTIR spectra of the water hyacinth parts are shown in Figure in Figure 1b and 1b
display
and bands
display
characteristic of cellulose. The cell wall evidently consists mainly of lignin, hemicellulose,
bands characteristic of cellulose. The cell wall evidently consists mainly of lignin,
and cellulose (among other elements in a smaller proportion), providing functional groups
hemicellulose, and cellulose (among other elements in a smaller proportion), providing
functional groups such as amines, carboxyls, hydroxyls, sulfhydryl, carbonyls, involved
in the removal of pollutants from water [41].
In the range of 3300 cm−1, the band refers to the stretch vibrations v(O-H) present in
the ring and in the side chain [42]. The bands, corresponding to the stretching of the
Polymers 2022, 14, 2732 7 of 21

such as amines, carboxyls, hydroxyls, sulfhydryl, carbonyls, involved in the removal of

pollutants from water [41].
In the range of 3300 cm−1 , the band refers to the stretch vibrations v(O-H) present in the
ring and in the side chain [42]. The bands, corresponding to the stretching of the methylene
groups v(C-H), (CH2 and CH3 ), are located in the region of 3000–2800 cm−1 [26]. The bands
attributed to the symmetric angular deformations δ (CH2 ) and vibrations of asymmetric
elongation ν(C-O-C) of the glycosidic bonds and elongation ν(C-O) are observed at 1423
and 1372 cm−1 , 1160, 1054, and 1113 cm−1 , respectively [6,43,44]. The band at 1249 cm−1
indicates C-O elongation in lignin and hemicellulose [44,45]. The band at 1700 cm−1 either
represents acetyl or uronic ether bonds of carboxylic groups in ferulic acids and p-coumaric
acids, as both acids can be found in lignin [40].
Figure 1 shows the morphological structures of the stem (c and d) and leaf (e and f)
of the water hyacinth at 500× and 100× magnifications, to explain the shape and surface
properties of the adsorbent. Figure 1c and d refers to parts of the stem and displays fibrous
rods with an irregular surface structure with cavities. Figure 1e,f, referring to part of the
water hyacinth leaf, shows nonhomogeneous structures with some cavities, thus justifying
the need to carry out studies with separate parts, since morphology and porosity can
influence the adsorption capacity. The presence of an irregular surface, pores, and surface
fractures of both the water hyacinth leaf and stem indicate the presence of micropores
and a high surface area [46], which are fundamental and important characteristics of
adsorbents [47]. Since these small spaces favor the entry of liquids and adsorption [48].
The analysis of its biosorbent micrograph indicates that the stem in this natural condi-
tion has greater adsorption potential. This was also identified in other studies involving
aquatic macrophytes of different species that exhibit heterogeneous morphology, with
porous with an irregular rough surface full of cavities that provide a perfect state of adsorp-
tion [49,50].
The thermogravimetric curves (TG) of the materials are shown in Figure 1 (g1 and g2)
for the stem and leaf, respectively. The derivative of thermogravimetric curves (DTG) is in
Figure 1 (g3 and g4) for the stem and leaf, respectively. TG and DTG in Figure 1 (g1 and g3)
show that the stem thermal profile can be divided into three stages. The first stage below
260 ◦ C occurs at around 43 ◦ C maximum temperature and is related to loss of adsorbed
water, some dehydration of the cellulose structural units, and loss of volatile compounds.
The second stage between 260 and 400 ◦ C, in which the maximum temperature event occurs
at 307 ◦ C, is probably the thermal decomposition of the material [48], hemicellulose and
the β-(1→4)-glycosidic bonds of cellulose. The third stage, above 400 ◦ C, with a maximum
temperature of 466 ◦ C, probably involves the decomposition of the remaining cellulose and
lignin [51].
Data for leaf material, Figure 1 (g2 and g4) for TG and DTG, respectively, indicate a
similar three-stage stem thermal profile, but with changes in maximum temperature events.
The first stage had a small increase in the maximum temperature of the event to 53 ◦ C,
the second stage had a slight decrease to 301 ◦ C, and in the third stage, the maximum
temperature of the event occurred at 506 ◦ C [52]. Observing the residual mass of the
materials at 600 ◦ C (Figure 1 g1 and g2), the stem showed a residual content higher than
the leaf with 29% and 12%, respectively. A reason for this change may be related to the
slight difference in the concentration of hemicellulose, lignin, and mineral components in
greater quantity in the stem than in the leaf, and this may also be one of the factors for the
ash content formed [53].
Table 1 presents the mean and standard deviation of the composition of the fibrous
fractions of the stem and leaf of the water hyacinth. The water hyacinth stem had a higher
proportion of lignin of 10.88% compared to 8.36% for leaf, as well as cellulose (27.79%
for stem and 20.81% for leaf) and hemicellulose (30.24% for stem and 29.71 % for leaf)
indicating that the leaf can biodegrade faster than the stem [54].
Polymers 2022, 14, 2732 8 of 21

Table 1. Mean and standard deviation (± SD) of fiber fraction composition (triplicate) of stem and
leaf of Eichhornia crassipes (water hyacinth).

Eichhornia crassipes
Fiber Fraction Composition
Stem Leaf
Dry matter-DM (% as fresh matter) 91.63 ± 0.01 91.36 ± 0.02
Neutral detergent fiber (%DM) 68.91 ± 0.38 58.88 ± 0.91
Acid detergent fiber (%DM) 38.67 ± 1.06 29.17 ± 0.42
Acid detergent lignin (%DM) 10.88 ± 1.40 8.36 ± 0.66
Cellulose (%DM) 27.79 ± 0.20 20.81 ± 0.17
Hemicelluloses (%DM) 30.24 ± 0.32 29.71 ± 0.28

The composition of water hyacinth appropriately corresponds to the standard compo-

sition of wet aquatic biomass. According to the literature, it consists mainly of cellulose and
hemicellulose and generally has a low lignin content [55], constituting lignocellulose which
is hygroscopic and has an affinity for water, being able to permeate the noncrystalline
portion of water [56].
Water hyacinth biomass (both leaf and stem) in the form of bioadsorbent is more
relevant, as it contains cellulose, hemicellulose, and lignin in proportional amounts com-
pared to other mostly acquired biomasses, such as rice straw, wood chips, and sugarcane
bagasse [57]. The constituents mentioned above contain the different functional groups,
such as carboxylate, aromatic carboxylate, oxyl, and phenolic hydroxyl groups, which have
good potential for adsorption [58]. The existence of numerous hydroxyl groups in the
cellulose backbone of this aquatic plant is primarily responsible for adsorption, in addition
to having the potential to be chemically modified to improve the adsorption process [19].
The pH is a fundamental parameter in adsorption since it indicates the degree of
distribution of loads in the solution [59]. The point of zero charge (pHpzc ) determines an
index at which a surface tends to become positively or negatively charged as a function
of pH. The adsorption mechanism of organic molecules from dilute aqueous solutions in
carbonaceous materials is known to be a complex interaction between electrostatic, non-
electrostatic, and hydrophobic interactions. These interactions depend on the characteristics
of the adsorbent and the adsorbate, thus emphasizing the importance of pHpzc [60].
Figure 2 illustrates the ∆pH values of the materials, where the points that intercept
∆pH = 0 correspond to the pHpzc . The estimated pHpzc values were approximately 7.4 and
7.6
Polymers 2022, 14, x FOR PEER REVIEW
for the stem and leaf samples, respectively. For the pH values below pHpzc , the surface
9 of 23
charge is positive indicating that there are favored adsorption of anionic species, while
values above pHpzc favor adsorption of cationic species [59,60].

Figure
Figure 2.
2. Representation
RepresentationofofpHpzc forfor
pH pzc
water hyacinth
water stem
hyacinth andand
stem leafleaf
materials.
materials.

3.2. Adsorption Experiments

The behavior of the adsorbed amount as a function of pH was studied by varying the
pH of the MB solution. As illustrated in Figure 3, this variable is very important in its
ability to remove the dye. The obtained results showed that the most effective removal
Polymers 2022, 14, 2732 9 of 21

3.2. Adsorption Experiments

The behavior of the adsorbed amount as a function of pH was studied by varying
the pH of the MB solution. As illustrated in Figure 3, this variable is very important in its
ability to remove the dye. The obtained results showed that the most effective removal
Polymers 2022, 14, x FOR PEER REVIEW 10 of 23
occurred in the range of pH 3 to 11, both for the part of the stem and for the leaf of the
water hyacinth.

(a) (b)
Figure 3.
Figure 3. (a)
(a)Relation
Relation between
between thethe amount
amount of adsorbed
of dye dye adsorbed as a function
as a function of (b)
of pH and pHadsorption
and (b) adsorption
efficiency.
efficiency.
Other lignocellulosic materials report that the adsorption of MB by the water hyacinth
plantItisissignificantly
evident that the water
improved hyacinthwhere
in solutions as a the
rawpH material
is greaterforthan
the 2constitution
[46]. The high of
bioadsorbents has natural advantages, such as a spongy structure with
pH may increase the number of negatively charged binding sites, facilitating the removal large cellular gaps,
which
of MB by candry
generate
biomass a significant
surfaces [61].specific
Thissurface area.toInthe
can be due general, the greater
protonation the specific
of carboxyl and
surface area
hydroxyl of the
groups biomass,
present thesurface
on the greaterofthethepore volume,
material (waterwhich can provide
hyacinth) at a pHgreater
lower
adsorption
than pHpzc capacity
(Figure 2), [64]. Its surface
leading to an presents
increase ainslightly
positivemore basicthat
charges character,
repel MB indicating
cations.
that it can adsorb cationic dyes more easily in a certain pH range, but
Considering that the pKa of the MB is 3.8, above this pH value, the cationic species were it also includes some
acidic
the characteristics,
preponderant indicating
MB species thesolutions
in the presence [62].
of different active sites
This behavior on its surface.
as a function of pH This
was
can be
also shownexplained
in MB by the fact that
adsorption S-Pure
studies and L-Pure
in other have adsorption
lignocellulosic materials capacities
[63]. at pHs 3
and 5Finally,
[65]. for both the S-Pure and L-Pure material, the amount of adsorbed dye, from
pH 3Starting
to 11, wasfrom solutions with
statistically equal,a concentration
around 91.87%of±300.0 0.17mg∙L −1 allows observation of the
for stem and 94.68% ± 0.01 for
adsorption
leaf (Figure 3).kinetics
As theofadsorption
the system, in favorable
was which theand dyehad
removal rates were
little variation fastpH
from during the
3 values,
initial
we chosecontact
to use time.
the Stem
natural andpHleaf biomass
(without pH removed
control)approximately
of the MB solution 50.42 (7.01)
mg∙g for
−1 ± 0.15
the
following
(90.8%) and tests, because
46.88 mg∙g−1the process
± 0.25 is easier
(89.9%) to optimize,
of the without
total adsorbate, the need forThe
respectively. pH amount
control,
reducing
adsorbedcosts. increased rapidly over time, until the system reached equilibrium in
It is evident60that
approximately min,theafter
water hyacinth
which thereaswasa raw material for
no significant the constitution
change of bioadsor-
in concentration, both
bents
for stemhas natural
and leaf, advantages,
indicatingsuch as a spongy
a rapid structure
interaction, whichwithislarge cellular gaps,
an extremely which
favorable
can generate
parameter a significant
(Figure 4). specific surface area. In general, the greater the specific surface
area of the biomass, the greater the pore volume, which can provide greater adsorption
capacity [64]. Its surface presents a slightly more basic character, indicating that it can
adsorb cationic dyes more easily in a certain pH range, but it also includes some acidic
characteristics, indicating the presence of different active sites on its surface. This can be
explained by the fact that S-Pure and L-Pure have adsorption capacities at pHs 3 and 5 [65].
Starting from solutions with a concentration of 300.0 mg·L−1 allows observation of the
adsorption kinetics of the system, in which the dye removal rates were fast during the initial
contact time. Stem and leaf biomass removed approximately 50.42 mg·g−1 ± 0.15 (90.8%)
and 46.88 mg·g−1 ± 0.25 (89.9%) of the total adsorbate, respectively. The amount adsorbed
increased rapidly over time, until the system reached equilibrium in approximately 60 min,
 can be explained by the fact that S-Pure and L-Pure have adsorption capacities at pHs 3
and 5 [65].
Starting from solutions with a concentration of 300.0 mg∙L−1 allows observation of the
adsorption kinetics of the system, in which the dye removal rates were fast during the
initial contact time. Stem and leaf biomass removed approximately 50.42 mg∙g−1 ± 0.15
Polymers 2022, 14, 2732 10 of 21
(90.8%) and 46.88 mg∙g−1 ± 0.25 (89.9%) of the total adsorbate, respectively. The amount
adsorbed increased rapidly over time, until the system reached equilibrium in
approximately 60 min, after which there was no significant change in concentration, both
for
afterstem
whichand leaf,was
there indicating a rapid
no significant interaction,
change which is an
in concentration, extremely
both for stem favorable
and leaf,
parameter
indicating a(Figure 4).
rapid interaction, which is an extremely favorable parameter (Figure 4).

22, 14, x FOR PEER REVIEW 11 of 23

(a) (b)
Figure 4. (a) Time isotherm for MB removal by water hyacinth stem and leaf biomass and (b)
adsorption efficiency.
Figure 4. (a) Time isotherm for MB removal by water hyacinth stem and leaf biomass and (b) adsorp-
tion efficiency.
From the data obtained (Figure 4), the adjustments of the pseudo-first-order and
pseudo-second-order From the were
models data obtained (Figure
calculated 4), the
to observe adjustments
which of the
is the most pseudo-first-order
appropriate to and
pseudo-second-order models were calculated to observe which
describe the mechanism of MB adsorption in the studied biomaterials (Figure 5). The is the most appropriate
to parameters
calculated kinetic describe the are
mechanism
shown inofTable
MB adsorption
2. in the studied biomaterials (Figure 5). The
calculated kinetic parameters are shown in Table 2.

Figure 5. Adjustment
Figureto5.the kinetic model
Adjustment for themodel
to the kinetic stem:for
(a)thepseudo-first- and (b) pseudo-second-
stem: (a) pseudo-first- and (b) pseudo-second-order
order for the MB for
in contact with the biomass. For the leaf: (c) pseudo-first- and (d) and
the MB in contact with the biomass. For the leaf: (c) pseudo-first- pseudo-second-
(d) pseudo-second-order
order for the MB in
forcontact
the MB with the biomass.
in contact with the biomass.

Table 2. Constant of the kinetic models of the stem and leaf of water hyacinth (Eichhornia Crassipes)
in the adsorption of the methylene blue cationic dye.

Pseudo-First-Order Pseudo-Second-Order
Polymers 2022, 14, 2732 11 of 21

Table 2. Constant of the kinetic models of the stem and leaf of water hyacinth (Eichhornia Crassipes) in
the adsorption of the methylene blue cationic dye.

Pseudo-First-Order Pseudo-Second-Order
qe K1 qe K2
Adsorbent Error R2 Error R2
(mg·g−1 ) (min−1 ) (mg·g−1 ) (mg·g−1 min−1 )
Stem 06.29 0.0016 0.11028 0.24042 50.42 0.0811 0.00566 0.99996
Leaf 11.16 0.0027 0.11048 0.52553 46.88 0.0141 0.00565 0.99996
qe amount of dye adsorbed at equilibrium (mg·g−1 );
K1 adsorption constant of the first-order model (min−1 ); K2
s-order model constant (mg·g−1 min−1 ), and R2 linearity coefficient.

Figure 5 demonstrates that the experimental data were adjusted to the pseudo-second-
order model, both for the systems using the leaf adsorbent and the stem, which obtained lin-
earity coefficients R2 = 0.99996 (Figure 5b,d). This model assumes that the rate-determining
step depends on the physicochemical interactions between the adsorbate and the adsorbent
surface groups, thus indicating a chemisorption process [66,67].
Polymers 2022, 14, x FOR PEER REVIEW The analysis can also be interpreted when comparing the amount of adsorbed 12 of 23 dye
(qe ) and the reaction rate constant (K) of the stem and leaf biomasses by pseudo-first- and
second-order models (Table 2) [68]. The pseudo-second-order values present better results
than the pseudo-first-order.
second-order models (Table 2) [68]. The pseudo-second-order values present better results
Several
than the authors found results adjusted to the pseudo-second-order model using bioad-
pseudo-first-order.
sorbents. For example,
Several authors Jahangiri
found results et al. [67]to
adjusted worked on Pb(II) lead removal
the pseudo-second-order modelfromusingaqueous
bioadsorbents.
solutions and wastewater using water hyacinth (Eichhornia crassipes) roots. The from
For example, Jahangiri et al. [67] worked on Pb(II) lead removal kinetic data
aqueous
indicatedsolutions andadsorption
that Pb(II) wastewaterfollowed
using water thehyacinth (Eichhornia crassipes)
pseudo-second-order modelroots.
withThe a reaction
kinetic data indicated that Pb(II) −
adsorption
1 − 1 followed the pseudo-second-order
rate constant (K) of 0.0127 (mg·g min ). The kinetics data for the pseudo-second-order model
with
model a reaction
suggestrate constant
that (K) of 0.0127
chemisorptions (mg.g
were the.min
−1 −1). The kinetics data for the pseudo-
rate-limiting step in the adsorption process.
second-order
The research by Prasad et al. [46] found that Eichhorniathe
model suggest that chemisorptions were rate-limiting
crassipes step in biosorbent
is an excellent the
adsorption process. The research by Prasad et al. [46] found that Eichhornia crassipes is an
for industrial effluent treatment. The authors also observed the adsorption kinetic with
excellent biosorbent for industrial effluent treatment. The authors also observed the
a correlation coefficient R2 = 0.99, very close to 1, showing that the pseudo-second-order
adsorption kinetic with a correlation coefficient R2 = 0.99, very close to 1, showing that the
model was better than the pseudo-first-order model.
pseudo-second-order model was better than the pseudo-first-order model.
The adsorption isotherm represents the equilibrium relationship between the amount
The adsorption isotherm represents the equilibrium relationship between the
of material adsorbed
amount of material and theand
adsorbed concentration in the fluid
the concentration in thephase
fluid at a constant
phase temperature.
at a constant
Many isotherm equations exist to adjust the experimental data, and
temperature. Many isotherm equations exist to adjust the experimental data, and among among the most used
are the equations proposed by Langmuir and Freundlich, due
the most used are the equations proposed by Langmuir and Freundlich, due to theirto their ability to predict the
behavior of experimental data [32,34].
ability to predict the behavior of experimental data [32,34].
Plottingthe
Plotting thevalues
values obtained,
obtained, the the experimental
experimental isotherms
isotherms of theof theare
dye dye are shown
shown in in
Figure6.6.
Figure

Figure
Figure6.6.MB
MBadsorption
adsorptionisotherm for for
isotherm water hyacinth
water stemstem
hyacinth and leaf
andbiomass.
leaf biomass.

The downward concave adsorption isotherm indicates a strongly favorable isotherm

that leads to greater adsorption capacity [69]. When analyzing the adsorption isotherm in
Figure 6, the plotted curves illustrate that the adsorption for both stem and water hyacinth
leaf biomass is favorable, indicating that the adsorption process occurs even at low
 Polymers 2022, 14, 2732 12 of 21

The downward concave adsorption isotherm indicates a strongly favorable isotherm

that leads to greater adsorption capacity [69]. When analyzing the adsorption isotherm
in Figure 6, the plotted curves illustrate that the adsorption for both stem and water
hyacinth leaf biomass is favorable, indicating that the adsorption process occurs even at
low concentrations.
Polymers 2022, 14, x FOR PEER REVIEW By linearizing the obtained data, it was possible to adjust the experimental data13toofthe
23
Langmuir and Freundlich models for stem (Figure 7a,b) and leaf (Figure 7c,d) biosorbents.
The isothermal parameters are in Table 3.

Figure
Figure 7.
7. Linearized isothermofof(a)(a)
Linearized isotherm Langmuir
Langmuir andand (b) Freundlich
(b) Freundlich for thefor the adsorption
adsorption of stem
of stem biomass;
biomass;
linearizedlinearized concentration
concentration isotherm
isotherm of of (c) and
(c) Langmuir Langmuir and (d) for
(d) Freundlich Freundlich for leaf
leaf biomass biomass
adsorption.
adsorption.
Table 3. Constant of the isothermal models of the stem and leaf of water hyacinth (Eichhornia Crassipes)
Table
in the 3. Constantofofthe
adsorption thecationic
isothermal models ofblue.
dye methylene the stem and leaf of water hyacinth (Eichhornia
Crassipes) in the adsorption of the cationic dye methylene blue.
Langmuir Freundlich
Langmuir Freundlich
qmax KL KF
Adsorbent qmax KL Error R22 1/n KF Error R22
Adsorbent (mg·g−1 ) (mg·L−1 ) Error R 1/n (mg·g−1 ) Error R
(mg.g−1) (mg.L−1) (mg.g−1)
Stem 153.84 0.024 0.025 0.9935 1.700 6.724 0.236 0.9264
Stem 153.84 0.024 0.025 0.9935 1.700 6.724 0.236 0.9264
Leaf 153.84 0.017 0.047 0.9848 1.828 6.881 0.210 0.9383
Leaf 153.84 0.017 0.047 0.9848 1.828 6.881 0.210 0.9383
−1
(mg·g (mg.g
qqmax : maximum amount
: maximum
max amountofofspecies adsorbed
species per mass
adsorbed of bioadsorbent
per mass of bioadsorbent ); 1/n:−1constant related torelated
); 1/n: constant surface
heterogeneity;
to surface K L : Langmuir adsorption constant at chemical equilibrium between adsorbate
heterogeneity; KL: Langmuir adsorption constant at chemical equilibrium between and adsorbent
(mg·L−1 ); KF : Freundlich adsorption constant related to adsorption capacity and R2 linearity coefficient.
adsorbate and adsorbent (mg.L−1); KF: Freundlich adsorption constant related to adsorption capacity
and R2 linearity coefficient. 2
The data fit better the Langmuir model, with R linearity value closer to 1 for both stem
and leaf of the water hyacinth, as shown in Figure 7a,c, respectively. This model assumes
The data fit better the Langmuir model, with R2 linearity value closer to 1 for both
that the solid surface is homogeneous and restricted to monolayers, characterizing a fixed
stem and leaf of the water hyacinth, as shown in Figure 7a,c, respectively. This model
number of active binding sites with the same affinity as MB. However, the experimental
assumes
data has athat
goodthe solid
fit for surface ismodel
the Freundlich homogeneous
(Figure 7b,d), and restricted
which tointeractions
considers monolayers,on
characterizing a fixed number of active binding sites with the same affinity
heterogeneous multilayer surfaces with different affinities and interaction energies between as MB.
However,
MB and the theactive
experimental data
sites on the has aof
surface good fit forand
the stem theleaf.
Freundlich model
This model also(Figure 7b,d),
predicts that
which considers interactions on heterogeneous
2 multilayer surfaces with
the adsorption process is favorable, as the R linearity value was close to 1 for both the different
affinities and interaction energies between MB and the active sites on the surface of the
stem and leaf. This model also predicts that the adsorption process is favorable, as the R²
linearity value was close to 1 for both the stem and leaf [70]. The Langmuir model was
observed in other adsorption studies using water hyacinth biomass [71].
Polymers 2022, 14, 2732 13 of 21

stem and leaf [70]. The Langmuir model was observed in other adsorption studies using
water hyacinth biomass [71].
Corroborating our results, Kulkarni et al. [72] performed isothermal tests using water
hyacinth root powder to remove Congo red dye in batch operation and in a continuous
packed bed, whose values described the best result for Langmuir, where the maximum
adoption capacity was 93.82 mg·g−1 .
Jahangiri et al. [67] performed isothermal tests using water hyacinth (Eichhornia cras-
sipes) roots to remove lead from aqueous solutions and wastewater. The values described
the best result for Langmuir (R2 = 0.986), and the maximum adsorption capacity was
50 mg·g−1 Pb(II) of dry roots.
Observing the results in Table 3, the maximum adsorption capacity of MB was approx-
imately 153.84 mg·g−1 for stem and leaf biomass in a solution of an initial concentration of
1000 mg·L−1 , which demonstrates the potential of stem and leaf to remove this dye in an
aqueous medium. The value of the Freundlich constant was not evaluated, because the
Langmuir data were better.

3.3. Characterization of Water Hyacinth Biomass after Adsorption

Characterizations of the materials after adsorption were carried out to understand
how adsorption affects the studied materials. After adsorption, the XRD results show an
increase in amorphous regions, with the disappearance and reduction of intense peaks
from 2θ = 40◦ (Figure 8 (a2 and b2)), both for the stem and leaf material, which may indicate
that diffusion of the adsorbate to the internal local sites changed its structure. Furthermore,
after adsorption of the cationic dye, the intense peak of the stems decreased compared to
that of the leaves. Thus, it can be concluded that the amount adsorbed by the stems is
greater than the leaves [73].
Note that after MB adsorption, the intensity also changed in the 3300 cm−1 band in
both spectra, which may indicate the interaction of adsorbent and adsorbate (Figure 8 (c2
and d2)). This corroborates the XRD results, in which an increase in amorphous regions was
observed. This is because this region is completely amorphous, giving access to adsorbed
molecules to penetrate the surface of the material [74]. In this context, the negative surface
also charges, referring to the O-H phenolic groups, facilitating adsorption by electrostatic
attraction with MB, a cationic dye [75].
Furthermore, two characteristic bands of MB appear at 1487 and 1604 cm−1 represent-
ing the vibration of elongation C=C and bond C=N in aromatic rings, respectively [76]. The
FTIR spectrum of leaves and stems loaded with MB shows that the bands are displaced
from their position, and the intensities change. These results indicate the establishment of
interactions between MB dye molecules and the functional groups of leaves and stems [73].
Regarding the results of thermal analysis after adsorption, TG and DTG (Figure 8
(e1–e4)) indicate that the thermal profile of the stem and leaf remained in three stages. The
first mass loss event with maximum temperature for the S-Pure material of 43 ◦ C (Figure 1
g3) changed to 48 ◦ C after adsorption in S-Ads (Figure 8 (e3)); the second event for S-Pure
at 307 ◦ C changed to 318 ◦ C after adsorption in S-Ads; and the third event for S-Pure from
466 ◦ C changed to 527 ◦ C after adsorption in S-Ads.
Similarly, there were some changes in the mass loss events for the L-Pure material.
The first event with a maximum temperature of 53 ◦ C (Figure 1 (g4)) changed to 48 ◦ C
after adsorption in L-Ads (Figure 8 (e4)); the second event for L-Pure at 301 ◦ C changed
to 319 ◦ C after adsorption in S-Ads, and the third event for L-Pure at 506 ◦ C changed to
477 ◦ C after adsorption in L-Ads.
Thus, this may indicate the interaction of the dye with the water hyacinth, as corrobo-
rated by the FTIR and XRD results. Finally, after adsorption, there was a total degradation
of leaf biomass at approximately 550 ◦ C and less than 5% residue for the stem at maximum
temperature. This can be explained by the alteration of the material structure due to MB
adsorption, leaving the structure more amorphous, as shown in XRD, and thus reducing its
degradation temperature.
14, x FOR Polymers
PEER REVIEW
2022, 14, 2732 15 of 23 14 of 21

Figure 8. X-ray
Figure 8. X-ray diffractograms of diffractograms
water hyacinth ofstem:
water (a1)
hyacinth stem:
before (a1) before(a2)
adsorption, adsorption, (a2) after adsorption;
after adsorption;
and leaf:(b1) beforeand leaf:(b1) before
adsorption, (b2) adsorption, (b2) after
after adsorption; adsorption;
FTIR of waterFTIR of water
hyacinth: hyacinth:
stem: stem: (c1) before
(c1) before
adsorption, (c2) after adsorption; and leaf: (d1) before adsorption, (d2) after adsorption; TG of waterTG of water
adsorption, (c2) after adsorption; and leaf: (d1) before adsorption, (d2) after adsorption;
hyacinth: (e1) stemhyacinth:
and (e2)(e1)leafstem
afterand (e2) leaf after
adsorption. DTG adsorption.
of water DTG of water
hyacinth: (e3)hyacinth:
stem and (e3) stem
(e4) and (e4) leaf
leaf
after adsorption. after adsorption.

3.4. Material Reuse

Note that after MB adsorption, the intensity also changed in the 3300 cm−1 band in
The study of MB desorption with stem and leaf bioadsorbents is important for the
both spectra, which may indicate the interaction of adsorbent and adsorbate (Figure 8 (c2
material to be reused again in the adsorption process [36,77]. The adsorption, desorp-
and d2)). This corroborates the XRD
tion, and reuse results, (first,
experiments in which an increase
second, and thirdintimes)
amorphous regions and de-
were performed
was observed. This is because this region is completely amorphous, giving
scribed in the methodology. In Figure 9, adsorption of MB from the stem biomass access to was
adsorbed molecules101.42 tomg − 1
penetrate
·g ± 0.48, theand
surface
biomass ofleaf
thewas
material −
89.83 mg[74].
·g ±1 In0.60.
thisAfter
context, the the ma-
desorption,
negative surface also
terialcharges, referring
was reused for the to thetime,
first O-Handphenolic groups,capacities
the adsorption facilitating adsorption
of stem-2 and leaf-2 were
by electrostatic attraction with MB, a cationic dye [75].
Furthermore, two characteristic bands of MB appear at 1487 and 1604 cm−1
representing the vibration of elongation C=C and bond C=N in aromatic rings,
respectively [76]. The FTIR spectrum of leaves and stems loaded with MB shows that the
 Polymers 2022, 14, 2732 15 of 21

78.97 mg·g−1 ± 0.67 (80%) and 65.98 mg·g−1 ± 0.98 (65%), respectively, verifying there is a
slight decrease in the adsorption capacity when compared to the previous adsorption. For
the second reuse of materials, the adsorption values continued to decrease for stem-3 and
leaf-3, being 56.57 mg·g−1 ± 1.77 (64%) and 48.43 mg·g−1 ± 0.77 (56%), respectively. From 17 of 23
Polymers 2022, 14, x FOR PEER REVIEW
the two evaluated cycles, the stem showed higher levels of adsorption than the leaf, but
significantly lower retention of the initial levels of adsorption.

Figure 9.9.Material
Figure Materialadsorption:
adsorption:leafleaf
andand
stem; reusereuse
stem; 1: leaf-2 and stem-2;
1: leaf-2 reuse 2:reuse
and stem-2; leaf-32:
and stem-3.
leaf-3 and stem-3.

Corroborating our research, Guo, Liang, and Tian [78] studied the heavy metal ions
The adsorption capacity of dyes by bioadsorbents decreases slightly after
removal from aqueous solutions by adsorption using modified orange peel as an adsorbent.
regeneration, as 100% desorption or destruction of adsorbed dyes does not occur during
The authors observed that after the reuse experiments, the adsorption efficiencies decreased
regeneration [79]. However, for the
after the first adsorption-desorption commercial
cycle, maintainingapplication of water
the adsorption hyacinth,
of around 78% andit may not
be
75%necessary to regenerate and reuse the biosorbent if the cost of such processes exceeds
of the materials.
the cost
The adsorption capacityWater
of replacement. hyacinth
of dyes could bedecreases
by bioadsorbents easily substituted
slightly aftersince the material is
regeneration,
low costdesorption
as 100% and readily availableofasadsorbed
or destruction biological
dyeswaste
does not[80]. Furthermore,
occur the remaining
during regeneration [79]. ash
However, for the commercial application of water hyacinth, it may not be
can be used in landfills and in the production of fire bricks, building blocks, and other necessary
to regenerate
building and reuse
materials [81],the biosorbent
thus completingif thewaste
cost of such processes exceeds the cost of
recycling.
replacement. Water hyacinth could be easily substituted since the material is low cost
Despite the efficient use of water hyacinth for the decontamination of pollutants
and readily available as biological waste [80]. Furthermore, the remaining ash can be
future research should be carried out with the application of carbonization and activation
used in landfills and in the production of fire bricks, building blocks, and other building
of the material
materials to extend
[81], thus completingthe waste
reuse recycling.
of this biomass in several cycles, aiming to combat the
deficiency
Despite the efficient use of water pollutants
of ineffective removal of hyacinth forwithin limited reuse cycles
the decontamination and the use or
of pollutants,
valorization
future researchofshould
the water hyacinth.
be carried out with the application of carbonization and activation
of the material to extend the reuse of this biomass in several cycles, aiming to combat the
deficiency
3.5. of ineffective
Comparative Profile removal of pollutants within limited reuse cycles and the use or
valorization of the water hyacinth.
To evaluate the development behavior of the new adsorbent proposed in this
research, a comparison
3.5. Comparative Profile study was performed between the leaf and stem biomass of the
waterTo hyacinth and
evaluate the other adsorbents
development reported
behavior of the new in previous
adsorbent studies
proposed (Table
in this 4). Notably
research,
water hyacinth biomass has excellent adsorption capacity for MB
a comparison study was performed between the leaf and stem biomass of the water hyacinthdye and a fast
adsorption process, as
and other adsorbents it reaches
reported equilibrium
in previous in about
studies (Table an
4). hour, standing
Notably, water out in relation to
hyacinth
biomass
other has excellent adsorption
bioadsorbents found in thecapacity
recentfor MB dye and a fast adsorption process, as it
literature.
reaches equilibrium in about an hour, standing out in relation to other bioadsorbents found
in the recent
Table literature.
4. Comparison of the maximum adsorption of methylene blue by the bioadsorbent produced
from the leaf and stem of water hyacinth with various adsorbents.

Adsorbent qmax (mg.g−1) References

Cotton gin rubbish dust 112.6 [82]
Corn cob 405.22 [83]
Polymers 2022, 14, 2732 16 of 21

Table 4. Comparison of the maximum adsorption of methylene blue by the bioadsorbent produced
from the leaf and stem of water hyacinth with various adsorbents.

Adsorbent qmax (mg·g−1 ) References

Cotton gin rubbish dust 112.6 [82]
Corn cob 405.22 [83]
Bread nutshell 409.00 [84]
Terminalia catappa (Indian almond) husks 88.62 [85]
White pine sawdust 87 [86]
Soy husk 169.90 [87]
Punica granatum bark 10.7296 [88]
Brown algae Sargassum muticum 9.55 [89]
Rice straw 20.38 [90]
Streptomyces fradiae biomass 59.63 [91]
Pitaya peels 190.30 [92]
Pomegranate peels 200.0 [93]
Syringa vulgaris leaf powder 188.2 [94]
Weeds 41,67 [95]
Cucumis sativus bark 20.1410 [96]
Walnut shell powder 142.85 [97]
Water hyacinth stem 50.42 This study
Water hyacinth leaf 46.88 This study

4. Conclusions and Future Prospects

The results obtained allow us to conclude that the water hyacinth (Eichhornia crassipes)
biomass has a microcrystalline profile due to the presence of lignin in its constitution,
by XRD analysis. The analysis of the FTIR spectra of the water hyacinth parts indicated
the presence of characteristic bands of cellulose and lignin. Regarding the morphological
structures, the biomass presented irregular structures, thus demonstrating heterogeneity
on the surface. The thermogravimetric curves (TG) show that the stem achieved a higher
residual content than the leaf, which may be related to hemicellulose, lignin, and mineral
components that are present in greater quantity in the stem.
The adsorption data better fit the pseudo-second-order model for the sorption kinetics
of MB, with 90.8% and 89.9% removal for the stem and leaf biomass, respectively, in contact
time of up to 60 min. The maximum adsorption occurred at natural pH. The equilibrium
studies elucidated by the isotherm of both bioadsorbents that the adsorption is favorable
and that the data better fit the Langmuir model, indicating active binding sites with the
same affinity as MB.
However, in the process of desorption and reuse of the material, with each reuse, the
materials gradually decrease the adsorption capacity, with the stem showing higher levels
of adsorption in relation to the leaf.
Nevertheless, it is possible to affirm that the application of the water hyacinth bioad-
sorbent is a renewable, potentially efficient, economical resource and can be used for
the removal of industrial effluents via an adsorption process, with the purpose of also
mitigating the aquatic pollution caused by its uncontrolled growth.
Polymers 2022, 14, 2732 17 of 21

Author Contributions: Conceptualization: M.T.C., A.Z.B.B., A.I.S.M. and A.L.F.C.M.; methodology:

M.T.C., A.Z.B.B., A.I.S.M. and A.L.F.C.M.; software: M.T.C., A.Z.B.B., A.I.S.M. and A.L.F.C.M.;
validation: M.T.C., A.Z.B.B., A.I.S.M. and A.L.F.C.M.; investigation: M.T.C., A.I.S.M. and R.D.S.B.;
resources: J.A.O. and E.C.S.-F.; data curation: M.T.C., A.I.S.M. and R.D.S.B.; writing—original draft
preparation: M.T.C., A.I.S.M. and R.D.S.B.; writing—review and editing: M.T.C., A.I.S.M., R.D.S.B.,
J.A.O. and E.C.S.-F.; visualization: R.D.S.B., J.A.O. and E.C.S.-F.; supervision: J.A.O. and E.C.S.-F.;
project administration: J.A.O. and E.C.S.-F.; funding acquisition: J.A.O. and E.C.S.-F. All authors have
read and agreed to the published version of the manuscript.
Funding: This research received no external funding.
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Acknowledgments: The authors thank the Coordination Support in Higher Education (CAPES),
the National Council for Scientific and Technological Development (CNPq), and the Foundation of
Support to Research of Piauí (FAPEPI) for financial support. The Federal University of Piauí (UFPI)
and the Federal Institute of Piauí (IFPI) provided the research conditions.
Conflicts of Interest: The authors declare no conflict of interest.

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