C Journal of

Carbon Research

Review
Comparison of Modified Peels: Natural Peels or Peels-Based
Activated Carbons for the Removal of Several Pollutants Found
in Wastewaters
Athanasia K. Tolkou 1, *, Konstantinos N. Maroulas 1 , Dimitrios Theologis 2 , Ioannis A. Katsoyiannis 2
and George Z. Kyzas 1

1 Hephaestus Laboratory, Department of Chemistry, International Hellenic University,

GR-65404 Kavala, Greece; [email protected] (K.N.M.); [email protected] (G.Z.K.)
2 Laboratory of Chemical and Environmental Technology, Department of Chemistry, Aristotle University of
Thessaloniki, GR-54124 Thessaloniki, Greece; [email protected] (D.T.); [email protected] (I.A.K.)
* Correspondence: [email protected]; Tel.: +30-2510-462-218

Abstract: Wastewater treatment has attracted much attention in recent years as a potential source of
water, and there are some concerns about its safety for human use. Eco-friendly and cost-effective
adsorbent materials were successfully synthesized from several peels, such as orange, banana,
pomegranate, avocado, kiwi, etc., and were used as natural adsorbents or as activated carbons
derived from these peels for water and wastewater treatment. In this review, the latest research
focusing on the effective modification of these peels for the removal of several pollutants found
in wastewaters are summarized and compared, such as pharmaceuticals, dyes, heavy metals, and
anions that are released in waste and have a negative impact on human and animal health. In
this review, focus is given to activated carbon produced from fruit peels. Moreover, fruit peels as
adsorbent materials, without previously being converted to activated carbon, are of limited use in the
recent literature.

Keywords: pharmaceuticals; dyes; chromium; arsenic; fluoride; adsorption; modification

Citation: Tolkou, A.K.; Maroulas,
K.N.; Theologis, D.; Katsoyiannis, I.A.;
Kyzas, G.Z. Comparison of Modified
Peels: Natural Peels or Peels-Based 1. Introduction
Activated Carbons for the Removal of
Several substances in untreated or inadequately treated wastewater are known to be
Several Pollutants Found
toxic to humans, animals, and plants, and consequently have adverse effects on the envi-
in Wastewaters. C 2024, 10, 22.
ronment [1]. Industry is the main source of water pollution, as these industries comprise
https://doi.org/10.3390/c10010022
the tannery, distillery, pulp and paper, textile and dye, food, and metallurgical industries,
Academic Editors: Jorge Bedia and among others [2,3]. Therefore, if these wastes are released into aquatic ecosystems without
Carolina Belver tolerable treatment, they lead to water pollution. Water pollutants can be categorized [1]
Received: 9 February 2024
as organic pollutants, such as, among others, pharmaceuticals and dyes, and inorganic
Revised: 29 February 2024
pollutants such as heavy metals and ions, e.g., fluoride. Therefore, this review focuses on
Accepted: 1 March 2024 these types of pollutants.
Published: 3 March 2024 Particularly, extensive drug use and insufficient management practices have increased
these pollutants’ presence in wastewater and, consequently, in surface and ground water.
These pharmaceutical compounds, despite their beneficial effects at precise concentrations
in the body, cause contrary effects when they are found in water [4,5]. Thus, it is impor-
Copyright: © 2024 by the authors. tant to apply appropriate techniques both for the correct determination of pharmaceutical
Licensee MDPI, Basel, Switzerland.
groups and for their removal. Moreover, the category of organic pollutants also includes
This article is an open access article
the dyes released in wastewater mainly from the textile industries, and consist of very
distributed under the terms and
hazardous compounds that have the potential to be toxic and to cause cancer in humans [6].
conditions of the Creative Commons
Regarding inorganic pollutants, heavy metal ions and metalloids have several harmful ef-
Attribution (CC BY) license (https://
fects on humans and degrade water quality [7]. Among them are chromium (Cr), cadmium
creativecommons.org/licenses/by/
(Cd), mercury (Hg), arsenic (As), lead (Pb), and many others, which can be found in several
4.0/).

C 2024, 10, 22. https://doi.org/10.3390/c10010022 https://www.mdpi.com/journal/carbon

C 2024, 10, 22 2 of 20

places around the world in amounts above the permissible limits for drinking water [8]. In
addition, fluoride is a common pollutant found in a variety of industrial wastewaters [9].
Although fluoride is beneficial to human health at concentrations in the range of 0.7–1.2
mg/L, providing protection against dental caries, at concentrations above the WHO limit
(1.5 mg/L), it has been stated that it causes skeletal and dental fluorosis [9,10].
Adsorption is considered as one of the widely used methods for the removal of organic
and inorganic pollutants from drinking water and industrial wastewater [11]. Currently,
there is a plethora of commercially available adsorbents applied in various treatments, such
as zeolites [12,13], graphene oxide [14–16], chitosan [17], and activated carbon [18,19], or
combinations thereof [5]. Activated carbon is highly effective in removing organic and
inorganic pollutants, and its porous structure and surface functional groups are crucial [20].
However, the economic practicability of activated carbon may be a drawback, despite its
widespread use. Thus, researchers have studied other sources of adsorbents, such as agri-
cultural wastes, used as natural adsorbents [21], that offer an economical and sustainable
solution for several pollutants found in wastewater [22]. Examples of these agricultural
wastes are some shells [23], roots [24], fruit peels [25–27], etc. Particularly, banana peels in
powder form were examined as adsorbents for removing MB dye and pesticides, such as
glyphosate and atrazine [28], or chlorpyrifos by lemon peels [29], from water. In addition,
other kind of peels, such as orange, pomegranate, kiwi, etc., have been found to be effective
for removing several dyes from wastewaters [30,31] and pharmaceuticals [32]. In recent
literature, Artocarpus genus fruit peels were also examined as raw peels or as biomass
for activated carbon production for the removal of various pollutants present in aqueous
streams [33].
Therefore, this review focuses on summarizing and comparing recent trends in sus-
tainable and cost-effective adsorbents using low-cost agricultural wastes, such as modified
peels or activated carbons derived from them, when used as natural adsorbents for the
removal of several pollutants found in wastewater.

2. Biomass-Based Activated Carbons

Activated carbon (AC) adsorption has been shown to be an appropriate method
for removing pollutants from wastewater because of its adaptability, effectiveness, vast
surface area, easy operating method, and economic feasibility [34]. AC’s large specific
surface area and well-formed pore structures facilitate physical adsorption, and the many
oxygen-containing functional groups on the surface of AC supply Brønsted and Lewis
acidic centers. However, developing inexpensive and effective ACs remains a problem.
As a result, recyclable materials such as agro-industrial waste are regarded as the best
manufacturing antecedents [35]. These waste products have greater carbon percentages
and lower percentages of ash [36]. Many studies have investigated the development of low-
cost adsorbents from agricultural wastes in order to eliminate heavy metals, fluoride ions,
pharmaceutical residues, and dyes. Various types of peels, including banana, pomegranate,
orange, cassava, shaddock, potato, etc., have been employed as natural sources for the
production of activated carbon [37–40]. They are a low-cost option for bio-materials that
are, additionally, ecologically friendly.
Physical or chemical activation, or both, represent a common method for preparing
AC. Physical or chemical activation, or both, constitute a common method for preparing
AC. Physical activation involves the carbonization and activation of precursor substances
at high temperatures, utilizing gases such as nitrogen, argon, xenon, CO2 , or steam [41].
Chemical activation is less complicated and produces better results than physical activation;
therefore, it is a preferable option in the case of agricultural waste [37]. The most frequent
activation agents are ZnCl2 , H3 PO4 , and KOH/NaOH; nevertheless, these activating agents
are poisonous and very corrosive. K2 CO3 , which is less hazardous, is a better option [42].
However, chemical activation requires a high amount of oxidizing agents, increasing the
cost, while physical activation is a greener approach [43]. The fabrication of AC requires
a lengthy duration of time and an elevated carbonization temperature, which makes
C 2024, 10, 22 3 of 20

the procedure expensive on a commercial basis. As a result, the cheaper manufacturing

and effective utilization of AC for many purposes remain important challenges [44]. For
economically viable AC generation, minimal activation time and temperature are required.

2.1. Dye Removal

Dye wastewater has grown into a critical issue that stifles quick economic growth,
harms the health of individuals, and negatively impacts the natural world. The majority
of dyes are poisonous organic chemicals with high chemical stability; they are difficult
to break down and have carcinogenic, teratogenic, and mutagenic properties [45]. These
hazardous substances, which leak into subsurface reservoirs from the surface, pollute
groundwater, thus affecting drinking water. As a result, developing innovative AC-based
materials to eliminate them from water is critical.

2.1.1. Orange, Mandarin, Banana Husks

In a study by Hashem and Amin, ACs from three different peels were prepared under
different drying conditions, by sun or oven [46]. The activation agent was sulfuric acid, and
the removal of methylene blue (MB) was examined. The results showed that all materials
had acidic functional units on their surfaces, making them favorable for cationic dye
adsorption, like MB. Drying fruit peels in an oven prior treatment using H2 SO4 reduced
the total pore area and increased the average pore width. In comparison with the other
fruit peels, AC derived from banana peels had the greatest elimination effectiveness, with a
Qm = 810 mg/g.

2.1.2. Orange Peels AC

Deshmukh et al. evaluated the adsorption of methyl red (MR) onto synthesized
orange peel ACs by chemical activation with ZnCl2 [47]. The key factors influencing the
MR removal effectiveness that were studied were the MR concentration, adsorbent dose,
solution pH, and adsorption temperature. The optimal conditions were found to be 60 min
of contact time in an alkaline environment (pH = 11), while Langmuir demonstrated a
better fit with Qm = 111.11 mg/g, rendering the material capable of eliminating MR from
wastewaters.

2.1.3. Orange Peel/Watermelon Rind AC

The synergetic effect of a mixture of orange peels and watermelon rinds for the fabri-
cation of large-surface-area and effective ACs (OPWRAC) to eliminate crystal violet (CV)
and methylene blue (MB) in wastewaters was examined by Hanafi et al. [48]. Activation
was achieved using the chemical activator ZnCl2 and a microwave oven. The BET equation
revealed 661.3 m2 /g, and an N2 isotherm indicated that the material was composed mainly
of mesopores. The results exhibited that microwave-assisted ZnCl2 activation played a
significant role, providing a great degree of porosity and pore volume. From FT-IR analysis,
it was clear that the adsorption mechanism of OPWRAC towards CV and MB included
electrostatic forces, π–π stacking, pore filling, and H-bonding due to the O-H, C≡C, C=O,
and C-O functional groups of the material. Based to the kinetic and equilibrium findings,
the adsorption of CV and MB occurred by chemisorption. As a result, OPWRAC had a
notable adsorption efficiency for both CV (137.8 mg/g) and MB (200.7 mg/g).

2.1.4. Cactus Fruit Peels AC

Little research has been conducted on the production of AC from cactus peels (ACCP)
according to Akkari et al. [49], who tested ACCP for the removal of the cationic dye Basic
Red 46 (BR46). H3 PO4 was used as the activating agent, since it produces better AC with
non-hazardous properties. The adsorption mechanism involves electrostatic interactions
between ACCP’s negatively charged surface and the dye molecule’s cation at pH = 6. The
results show that the compound had microporosity, with a harsh, uneven surface and a
substantial specific surface area of 1288 m2 /g, making it ideal for BR46 elimination. Finally,
10, x FOR PEER REVIEW 4 of 21

between ACCP’s negatively charged surface and the dye molecule’s cation at pH = 6. The
C 2024, 10, 22 results show that the compound had microporosity, with a harsh, uneven surface and a 4 of 20
substantial specific surface area of 1288 m2/g, making it ideal for BR46 elimination. Finally,
it had an adsorption capacity of 806.38 mg/g, and could be recycled up to four times with
minimal loss ofit efficacy, making it ideal
had an adsorption for cationic
capacity of 806.38dye removal.
mg/g, and could be recycled up to four times with
minimal loss of efficacy, making it ideal for cationic dye removal.
2.1.5. Pineapple Peel AC
2.1.5. Pineapple
Another interesting studyPeel
wasAC conducted by Rosli et al. utilizing pineapple peels
(PiP) [50]. Pineapple Another interesting
peel activated carbonstudy was conducted
(PiPAC) was createdbybyRosli et al. utilizing
a two-stage pineapple peels
pyrolysis
(PiP) [50]. Pineapple peel activated carbon (PiPAC) was
technique, followed by a carbonization step and an activation step. First, the pineapple created by a two-stage pyrolysis
peels (PiP) weretechnique,
carbonized followed
at 700 by°C,aand
carbonization
the char was step and an
soaked activation
with step. being
KOH before First, the pineapple
peels (PiP) ◦ C, and the char was soaked with KOH before being
gasified with CO 2. For the were carbonized
adsorptive at 700Remazol
evaluation, Brilliant Violet (RBV) was used
gasified with
as the model pollutant CO2 .experiments.
in batch For the adsorptive evaluation,
BET analysis showedRemazol Brilliant
that the PiPAC Violet
had (RBV)
a was used
as the model pollutant in batch experiments. BET analysis
surface area of 1160 m /g and mainly consisted of mesopores. Also, because of the chemi-
2 showed that the PiPAC had
a surface area of 1160 m 2 /g and mainly consisted of mesopores. Also, because of the
cal activation process, KOH dissolved in water, producing potassium ions (K2CO3). As a
chemical
result, they entered the activation
gaps that process,
formed on KOH thedissolved
PiP char,in water, producing
penetrating potassium ions (K2 CO3 ).
it and effectively
As a result, they entered the gaps that formed on the PiP char,
increasing the pores. The PFO kinetic model suited the data better than the other models, penetrating it and effectively
and the ideal pHincreasing the pores.
was discovered The
to be pH PFO
= 2,kinetic
with a model suited
Qm = 74.86 the data
mg/g. Lastly,better than the other models,
the material
and the ideal pH was discovered to be
showed excellent regeneration towards RBV for up to three cycles. pH = 2, with a Q m = 74.86 mg/g. Lastly, the material
showed excellent regeneration towards RBV for up
The adsorption mechanism of PiPAC-RBV is presented in Figure 1. As can be ob-to three cycles.
served, PiPAC presentedThe adsorption
hydroxyl mechanism of PiPAC-RBV
(O–H) and carboxyl (C–O)isgroups,
presentedandinfor
Figure 1. As can be observed,
this reason,
PiPAC presented hydroxyl (O–H) and carboxyl (C–O)
there were three possible mechanisms and interactions that could be combined during groups, and for the
this reason, there
were three possible mechanisms and interactions that could be combined during the
adsorption of RBV onto PiPAC, such as:
adsorption of RBV onto PiPAC, such as:
• Hydrogen bonding between the oxygen atom of the dye and the hydroxyl groups of
• Hydrogen bonding between the oxygen atom of the dye and the hydroxyl groups of
the PiPAC;
the PiPAC;
• Electrostatic interactions between the aromatic ring of dye and the oxygen on the
• Electrostatic interactions between the aromatic ring of dye and the oxygen on the
surface of the PiPAC;
surface of the PiPAC;
• π–π interactions between the π–electrons of carbonaceous PiPAC and in the aromatic
• π–π interactions between the π–electrons of carbonaceous PiPAC and in the aromatic
ring of the dye [50].
ring of the dye [50].

Figure 1. SEM images of PiPAC and the possible mechanism of PiPAC–RBV dye [50] (reprinted with
Figure 1. SEM images of PiPAC and the possible mechanism of PiPAC–RBV dye [50] (reprinted
permission).
with permission).
2.1.6. Pomegranate
2.1.6.Peel AC
Pomegranate Peel AC
Surface modification
Surfaceofmodification
activated carbon may also
of activated increase
carbon mayits adsorption
also capability
increase its adsorption capability
for the removal
forofthe
pollutants.
removal ofThis could be This
pollutants. accomplished by chemically by
could be accomplished modifying its modifying its
chemically
surface or by introducing external compounds, thus increasing the quantity of active areas
for adsorption. Thamer et al. introduced AC derived from pomegranate peel (PPAC),
as well as modified PPAC with sulfo-units (S-PPAC) [51]. To produce PPAC, KOH was
 surface or by introducing external compounds, thus increasing the quantity of active areas
for adsorption. Thamer et al. introduced AC derived from pomegranate peel (PPAC), as
C 2024, 10, 22 well as modified PPAC with sulfo-units (S-PPAC) [51]. To produce PPAC, KOH5was of 20
used
as the activating agent along with carbonization. Figure 2 illustrates the production of
PPAC and S-PPAC. The sulfonation of PPAC was achieved by dissolving 5-sulfonate-sa-
licylaldehyde sodium salt
used as the activating and
agent mixing
along with itcarbonization.
with PPAC, Figure
so that2 S-PPAC
illustrateswas
the obtained
productionby co-
of PPAC
valent and S-PPAC.
bonding. The sulfonation
N2 isotherm of PPAC was
and BET analysis achieved
showed that by
bothdissolving
materials5-sulfonate-
had high sur-
salicylaldehyde sodium salt and mixing it with PPAC, so that S-PPAC
face areas: 1180.63 m /g for PPAC and 740.75 m /g for S-PPAC. As the model pollutant,
2 2 was obtained by
covalent bonding. N
crystal violet (CV) was2used. isotherm and BET analysis showed that both materials
The optimal pH was found to be 10, with a 100% removal for had high
surface areas: 1180.63 m2 /g for PPAC and 740.75 m2 /g for S-PPAC. As the model pollutant,
the modified derivative, maintaining a high removal even after 5 cycles. According to the
crystal violet (CV) was used. The optimal pH was found to be 10, with a 100% removal
isotherm data, the Freundlich model was the most suitable for explaining adsorption,
for the modified derivative, maintaining a high removal even after 5 cycles. According to
whereas the Elovich
the isotherm model
data, the was the
Freundlich mostwas
model appropriate for characterizing
the most suitable for explaining adsorption
adsorption,kinet-
ics.whereas
The adsorption mechanism suggested that electrostatic attraction
the Elovich model was the most appropriate for characterizing adsorption was thekinetics.
key driving
factor. However,mechanism
The adsorption the effect of pH evaluation
suggested showedattraction
that electrostatic that pore-filling,
was the keyhydrogen bonding,
driving factor.
andHowever, the effect ofwere
π–π interactions pH evaluation
critical inshowed that pore-filling,
the mechanism hydrogen bonding, and π–π
of adsorption.
interactions were critical in the mechanism of adsorption.

Figure 2. 2.
Figure Preparation
Preparation and surface
and surface modification
modification of PPAC
of PPAC [51] (no[51] (nopermission
special special permission isreuse).
is required to required to
reuse).
Table 1 summarizes the described modified activated carbons from peels for dye
removal,
Table 1providing
summarizes the major experimental
the described conditions
modified used. As
activated depicted,
carbons fromin alkalic
peels condi-
for dye re-
tions, the maximum removal capacities were achieved in most of the cases, and the removal
moval, providing the major experimental conditions used. As depicted, in alkalic condi-
rates reached up to 100% by using only 0.5 g/L of S-PPAC material.
tions, the maximum removal capacities were achieved in most of the cases, and the re-
moval
Tablerates reached
1. Modified up tocarbons
activated 100% by using
from peels only
for dye0.5 g/L of S-PPAC material.
removal.

TableModification
1. Modified activated carbons from
Initialpeels for dye removal.
Dosage
Contact Adsorption
Material Peels Dye pH Conc. Time Capacity R% Ref.
Agent (g/L)
Modification Initial Conc.(mg/L)
Dosage (min)
Contact (mg/g)
Adsorption
MaterialBOS Peels Banana Dye
H2 SO4
pH
MB 9 1000 1 Time 1140 Capacity
810.00
R %[46] Ref.
Agent (mg/L) (g/L) (min) (mg/g) 81
BOS OPAC Banana Orange
H2SO4 ZnCl
MB 2 9MR 11
1000 100 1 1 1140 60 111.11
810.00 93 81 [47] [46]

OPACOPWRAC Orange/watermelon
Orange ZnCl2 ZnCl
MR 2 11CV 10
100 20 1 1 60 35 137
111.11 91 93 [48] [47]
Orange/wa-
OPWRAC Orange/watermelon ZnCl2 MB 200 200 1 35 200.00 94 [48]
OPWRAC ZnCl2 CV 10 20 1 35 137 91 [48]
termelon
C 2024, 10, 22 6 of 20

C 2024, 10, x FOR PEER REVIEW 6 of

Table 1. Cont.

Initial Contact Adsorption

Modification
Orange/wa- Dosage
Material Peels
OPWRAC ZnClDye
2 MBpH 200 Conc. 200 1 Time 35 Capacity R%
200.00 Ref. 94 [48]
Agent
termelon (g/L)
(mg/L) (min) (mg/g)
ACCP ACCP
Cactus Cactus
H3 PO4 H3PO 4
BR46 BR466 6 20–1000
20–1000 1 1 180 180 806.38 806.38
90 [49] 90 [49]
PiPAC Pineapple KOH/CO2 RBV 2 100 1 360 74.86 72 [50]
PiPAC Pineapple KOH/CO2 RBV 2 100 1 360 74.86 72 [50]
Pomegran-
S-PPAC S-PPAC
Pomegranate KOH KOHCV CV10 10 300 300 0.5 0.5 210 210 785.53 785.53
100 [51] 100 [51]
ate

2.2. Pharmaceuticals
2.2. Pharmaceuticals Removal Removal
PharmaceuticalsPharmaceuticals are anand
are an important important
quicklyand quickly
rising rising
group of group of organic
organic pollutants d
pollutants
distinguished by their regular and frequent use. Compared to some other organic pollutants, pollutan
tinguished by their regular and frequent use. Compared to some other organic
they survive inthey survive world
the natural in the natural world for period
for an extended an extended period
of time, and ofmaytime, and may accumulate
accumulate at
extremely tiny amounts (in the µg/L and
extremely tiny amounts (in the µg/L and ng/L range) [52]. ng/L range) [52].

2.2.1. Jackfruit Peels AC

2.2.1. Jackfruit Peels AC
Magesh et al. used jackfruit peels (JFP) to synthesize AC and eliminate ciprofloxacin
Magesh et al.
from an aqueous environment used
[53]. The jackfruit
JFP werepeels (JFP)into
made to synthesize AC and eliminate
a pair of adsorbent ciprofloxac
materials.
The first was made by treating it with H3 PO4 and converting it into activated carbon, and materia
from an aqueous environment [53]. The JFP were made into a pair of adsorbent
the second was The first was
prepared by made by JFP
grafting treating it with
activated H3POwith
carbon 4 and converting it into activated carbon, an
ZnO (ZJFP) via a sonication
method. The modified AC had a fascinating removal of 99.8%carbon
the second was prepared by grafting JFP activated with ZnO
at optimal (ZJFP) via a son
conditions,
which included pH = 6 at a dosage of 0.3 g/L. The kinetic data prove that the adsorption condition
cation method. The modified AC had a fascinating removal of 99.8% at optimal
which included pH = 6 at a dosage of 0.3 g/L. The kinetic data prove that the adsorption pr
procedure consisted of chemisorption, and that ZJFP better fit the Freundlich isotherm
cedure consisted of chemisorption, and that ZJFP better fit the Freundlich isotherm mod
model, indicating double-layer adsorption. Figure 3 presents the SEM images before and
indicating double-layer adsorption. Figure 3 presents the SEM images before and after a
after adsorption.
sorption.

Figure 3. (a) FESEM analysis of JFP before adsorption; (b) FESEM analysis of JFP after adsorptio
Figure 3. (a) FESEM analysis of JFP before adsorption; (b) FESEM analysis of JFP after adsorption;
(c) FESEM analysis of ZJFP before adsorption; (d) FESEM analysis of ZJFP after adsorption [5
(c) FESEM analysis of ZJFP before adsorption; (d) FESEM analysis of ZJFP after adsorption [53]
(reprinted with permission).
(reprinted with permission).
2.2.2. Pomegranate Peels AC
C 2024, 10, 22 7 of 20

C 2024, 10, x FOR PEER REVIEW 2.2.2. Pomegranate Peels AC 7 of 21

The removal of carbamazepine was examined by Al-Ghoul et al. by employing acti-

vated carbon from pomegranate peels (AC-PGPs) [54]. Pomegranate peels were converted
to AC byTheheating
removal andof carbamazepine
using NaOH as wasanexamined
activatingbyagent,
Al-Ghoul
and et
theal.final
by employing acti-charac-
product was
vated carbon from pomegranate peels (AC-PGPs) [54]. Pomegranate peels were
terized. The adsorption behavior of carbamazepine was studied with batch experiments by converted
to AC by the
evaluating heating andof
effects using
pH, NaOH as an activating
temperature, contact agent, and initial
time, and the final product was char-
concentration. FT-IR and
acterized. The adsorption behavior of carbamazepine was studied with batch experiments
pH experiments validated that the driving forces for adsorption were hydrophobic and
by evaluating the effects of pH, temperature, contact time, and initial concentration. FT-
π–π interactions, while the kinetic data demonstrated that the procedure was chemisorp-
IR and pH experiments validated that the driving forces for adsorption were hydrophobic
tion.
andLastly, the findings
π–π interactions, showed
while that,data
the kinetic afterdemonstrated
1 h of contact time,
that AC-PGPswas
the procedure could eradicate
chemi-
upsorption.
to 96.5%Lastly,
of the pollutant, rendering it a considerable candidate for an adsorbent
the findings showed that, after 1 h of contact time, AC-PGPs could erad- of
pharmaceuticals.
icate up to 96.5% of the pollutant, rendering it a considerable candidate for an adsorbent
of pharmaceuticals.
2.2.3. Plantain Peels AC
2.2.3.
In Plantain
a study Peels AC et al., plantain peels were used to synthesize AC (PPAC), and
by Dada
were impregnated
In a study bywith
DadaZnOet al.,inplantain
order to eliminate
peels chloroquine
were used [55].
to synthesize ACThe activation
(PPAC), and was
were impregnated with ZnO in order to eliminate chloroquine [55]. The
performed chemically by utilizing H3 PO4 , and the grafting was carried out by Zn(NO3 )2 activation was
performed
along chemically byIn
with calcination. utilizing
this way,H3PO 4, and
the the grafting
obtained was carried
product exhibitedout low
by Zn(NO
ratios3)2of ash,
moisture, and volatile components, leading to a surface area of 273.4 m /g,mois-
along with calcination. In this way, the obtained product exhibited low ratios of ash,
2 according
to ture,
Saer’s andmethod.
volatile components,
Based on FT-IR leadingand
to a pH
surface
effect of 273.4 m2/g,
areaevaluation, according
the adsorptionto Saer’s
involved
method. Based on FT-IR and pH effect evaluation, the adsorption involved electrostatic
electrostatic attraction, while SEM revealed the pore-filling with images before and after
attraction, while SEM revealed the pore-filling with images before and after adsorption.
adsorption. The optimal conditions were found to be an initial concentration of 10 ppm at
The optimal conditions were found to be an initial concentration of 10 ppm at a 1 g/L
a 1dosage
g/L dosage
and 313and 313 K, showing
K, showing a 78.89% aefficiency.
78.89% efficiency.

2.2.4. Mangosteen
2.2.4. MangosteenPeel
Peel AC
AC
Ciprofloxacin
Ciprofloxacinisisaa fluoroquinolone antibiotic
fluoroquinolone antibiotic that
that hashas
been been extensively
extensively utilized
utilized for thefor the
remediation of both human and animal infections in the past
remediation of both human and animal infections in the past few years. Its presence few years. Its presence
in in
wastewaters
wastewatersisisharmful
harmful to thethe ecosystem.
ecosystem.Tran Tran
et et
al. al. suggested
suggested theof
the use use of adsorbent-based
adsorbent-based
ACAC from
frommangosteen
mangosteen peels [56]. ZnCl
peels [56]. ZnCl 2 was
2 was selected
selected for for
the the activation,
activation, creating
creating a greata great
number
number of of voids
voids andand a surface
a surface areaofof
area 419.85mm
419.85 2 /g,
2/g, thus increasing the porosity and re-
thus increasing the porosity and removal
of moval of the pollutant.
the pollutant. The adsorption
The adsorption data showed
data showed a spontaneous,
a spontaneous, endothermic,physical,
endothermic, physi- and
cal, and chemical adsorption, achieving a 98% removal at pH 6 and
chemical adsorption, achieving a 98% removal at pH 6 and an initial concentration of an initial concentration
50 of 50 ppm.
ppm. The The effect
effect of pH
of pH revealed
revealed that
that thethedriving
drivingforce
force for
for the
the adsorption
adsorptionwas waselectro-
electrostatic
static attraction. Furthermore, as shown in Figure 4, regarding the SEM images, there was
attraction. Furthermore, as shown in Figure 4, regarding the SEM images, there was an
an obvious difference in the surfaces of MP and ACMP, with the second being smoother.
obvious difference in the surfaces of MP and ACMP, with the second being smoother.

Figure
Figure 4. 4.
SEMSEMimage
imageof
of the
the MP
MP (A)
(A)and
andACMP
ACMP(B)(B)
[56] (no(no
[56] special permission
special is required
permission to reuse).
is required to reuse).

2.2.5.
2.2.5. DilleniaIndica
Dillenia Indica Peels
Peels AC
AC
Fadzailetetal.
Fadzail al.examined
examined the
theremoval
removalofof
naproxen using
naproxen usingactivated carbon
activated from Dillenia
carbon from Dillenia
Indica peels (DI-AC), activating them chemically with H 3PO4 [57]. FT-IR and effect of pH
Indica peels (DI-AC), activating them chemically with H3 PO4 [57]. FT-IR and effect of
pHanalysis exhibited that the adsorption was conducted with electrostatic as well as π–π
analysis exhibited that the adsorption was conducted with electrostatic as well as
electron donor–acceptor interactions. The results better fit the Langmuir and Temkin iso-
π–π electron donor–acceptor interactions. The results better fit the Langmuir and Temkin
therms, and a pseudo-second order model was used for kinetic analysis. The data indicate
isotherms, and a pseudo-second order model was used for kinetic analysis. The data
indicate that sorption occurred as a monolayer and was governed by a chemisorption
procedure. However, the time required for equilibrium was very long (480 min), and the
 C 2024, 10, x FOR PEER REVIEW 8 of 21

C 2024, 10, 22 8 of 20

that sorption occurred as a monolayer and was governed by a chemisorption procedure.

However, the time required for equilibrium was very long (480 min), and the Qm was only
Q10.76
m was only
mg/g. 10.76
From themg/g. Frompresented
SEM images the SEMinimages presented
Figure 5, in Figure
it is noteworthy 5, itthe
that that is noteworthy
raw that
that the raw
material had amaterial had aFurthermore,
rough surface. rough surface.thereFurthermore, there wereonnothepores
were no pores discernible discernible on
surface
of the
the raw material
surface (Figure
of the raw 5a) in (Figure
material comparison to the
5a) in activated carbon
comparison to the prepared
activatedincarbon
this prepared
instudy
this (Figure 5b).
study (Figure 5b).

Figure 5. SEM images for (a) raw material; (b) activated carbon at magnification of x500 [57] (re-
Figure 5. SEM images for (a) raw material; (b) activated carbon at magnification of ×500 [57]
printed with permission).
(reprinted with permission).
2.2.6. Banana Peels as AC
2.2.6. Banana Peels as AC
Recently, banana peels were applied for the purpose of producing activated carbon
as a Recently, banana for
tentative adsorbent peels
the were
removalapplied for the purpose
of pharmaceuticals, of producing
specifically amoxicillinactivated
and carbon
ascarbamazepine,
a tentative adsorbent for theThe
from wastewater. removal of pharmaceuticals,
activation of carbon was conducted specifically amoxicillin and
using phos-
phoric acid (H3POfrom
carbamazepine, 4), and carbonizationThe
wastewater. occurred at 350 of
activation °C,carbon
450 °C, was
and 550 °C [58]. For
conducted the phosphoric
using
produced
acid (H3 PO BPAC,
), the optimum
and conditions
carbonization were found
occurred at to be◦aC,
350 pH450
of 5,◦ C,
a dosage
and of 1.2◦ C
550 g/L,
[58]. For the
4
a contact time of 120 min, and an initial concentration of the pollutants’ mixture of 25 mg/L
produced BPAC, the optimum conditions were found to be a pH of 5, a dosage of 1.2 g/L, a
at 25 °C. The maximum adsorption capacities for BPAC were found to be 393.70 mg/g for
contact timeremoval
amoxicillin of 120 and min, and mg/g
338.98 an initial concentration of the pollutants’ mixture of 25 mg/L
for carbamazepine.
◦
at 25 ΙnC.Table
The 2,maximum adsorption capacities
the modified activated carbons fromfor BPAC
peels were found to removal
for pharmaceuticals be 393.70 mg/g for
amoxicillin
are tabulated,removal and 338.98
and as shown, mg/g
pH 6 was for carbamazepine.
applied in many studies reviewed in this manu-
InThe
script. Table 2, material
ZJFP the modified activated
exhibited carbons
the maximum fromcapacities
removal peels forand pharmaceuticals
rates using only removal are
0.3 g/L.
tabulated, and as shown, pH 6 was applied in many studies reviewed in this manuscript.
The ZJFP material exhibited the maximum removal capacities and rates using only 0.3 g/L.
Table 2. Modified activated carbons from peels for pharmaceuticals removal.

Table 2. Modified activated carbons Adsorption

Modification Initialfrom
Conc.peels
Dosage forContact
pharmaceuticals
Time removal.
Material Peels Pharmaceutical pH Capacity R % Ref.
Agent (mg/L) (g/L) (min)
(mg/g)
Initial Contact Adsorption
ZJFP
Material Jackfruit
Peels H3Modification
PO4 Ciprofloxacin 6
Pharmaceutical pH 50 Conc.0.3 Dosage
120 70.12
Time 99.8 [53]
Capacity R% Ref.
AC-PGPs Pomegranate NaOH Agent Carbamazepine 6.7 20 8 (g/L)
60
(mg/L) (min)- 98 [54]
(mg/g)
PPAC-
ZJFP Plantain
Jackfruit H3POH 4 3 PO4 Chloroquine 7.02
Ciprofloxacin 6 10 50 1 120
0.3 12050.5 78.8 [55]
70.12 99.8 [53]
ZnO
AC-PGPs Pomegranate NaOH Carbamazepine 6.7 20 8 60 - 98 [54]
ACMP Mangosteen ZnCl2 Ciprofloxacin 6 50 3 60 29.78 98 [56]
PPAC-ZnO Plantain H3 PO4 Chloroquine 7.02 10 1 120 50.5 78.8 [55]
ACMPDI-AC Dillenia Indica
Mangosteen H3PO4ZnCl Naproxen 5
Ciprofloxacin 6 - 500.4 480
3 10.76
60 -
29.78 [57] 98 [56]
2
BPAC
DI-AC BananaIndica H3POH
Dillenia 4
PO Amoxicillin
Naproxen 5 5 25 - 1.2 120
0.4 393.70
480 82.3 [58]
10.76 - [57]
3 4
BPACBPAC Banana
Banana H3POH 4 Carbamazepine
3 PO4 Amoxicillin5 5 25 251.2 120
1.2 338.98
120 81.5 [58]
393.70 82.3 [58]
BPAC Banana H3 PO4 Carbamazepine 5 25 1.2 120 338.98 81.5 [58]
2.3. Heavy Metals Removal
With the flow of time, and in tandem with population expansion and rise in industry,
2.3. Heavy Metals Removal
there has been a jump in the quantity of industrial waste which may pollute the natural
With the flow of time, and in tandem with population expansion and rise in industry,
there has been a jump in the quantity of industrial waste which may pollute the natural
world. Water contamination caused by waste consisting of heavy metals is detrimental for
human health [59].

2.3.1. Pea Peel AC

To face the threat of As (III) and As (V), Sahu et al. suggested the use of magnetized
carbon-based adsorbents with AC derived from pea peels [60]. The activation was phys-
ically carried out by pyrolysis at 500 ◦ C (MPAC-500) and 600 ◦ C (MPAC-600), with the
latter having the better results. The evaluation was conducted with batch experiments,
C 2024, 10, 22 9 of 20

and the parameters that were tested were sorbent dose, initial pollutant concentration,
temperature, and contact time. BET analysis exhibited that MPAC-600 had 214.04 m2 /g
and was a meso-macroporous material. The active sites available on the surface of the
adsorbent were responsible for the mechanism of As adsorption. Groups such as -OH,
aromatic amines, -CO, -NO2 , COO− , and -C-N were present on the surface of the material
before adsorption, and almost similar compounds were found following As adsorption.
The cation As was drawn to the anion COO− on the compound’s surface via electrostatic
attraction. Surprisingly, the removal by of As (III) was exothermic, while the removal of
As(V) was an endothermic procedure. The optimal adsorption conditions for both were
found to be pH = 7 and a contact time of 300 min, for an adsorption capacity of 1.33 and
0.80 for As (III) and As (V), respectively.

2.3.2. Navel Orange Peel AC

Xiao et al. prepared a glycine functionalized activated carbon derived from navel
orange peel (NOP), and chose Gd (III) as the model pollutant [61]. The activation of
NOPs/Glycine occurred chemically, with H3 PO4 and heating up to 500 ◦ C. According to
the BET results, grafting with glycine increased the specific surface area by almost 50%,
up to 1523 m2 /g. Glycine addition also considerably increased activated carbon’s Gd(III)
adsorption ability, with a removal efficiency of 99% at pH = 7. The adsorption isotherms
were compatible with the Langmuir isotherm model, and the material had an optimal
adsorption capacity of roughly 48.5 mg/g.

2.3.3. Orange Peels-TiO2 Modified AC

Modifying AC with functional groups can significantly enhance its adsorptive effi-
ciency. Neisan et al. produced AC using orange peel (OP) and studied its removal efficiency
for Cu (II) [62]. The activation was achieved with pyrolysis and CO2 , and they grafted
TiO2 nanoparticles onto OP by mixing them in DI water and sonication. This modification
increased the surface area, and increased the adsorption capacity to 13.34 mg/g. The
kinetics indicated that the optimum contact time was 216 min to reach equilibrium, and the
C 2024, 10, x FOR PEER REVIEW adsorption process was chemisorption. As shown in Figure 6, the adsorbents OP-TiO10 2 and
of 21
DS-TiO2 after their modification with TiO2 NPs presented aggregates on the surfaces of the
particles, while in the unmodified materials, they displayed smoother surfaces.

Figure 6. SEM images of (A) AC-OP, (B) OP-TiO2, (C) AC-DS, and (D) DS-TiO2 [62] (reprinted with
Figure 6. SEM images of (A) AC-OP, (B) OP-TiO2 , (C) AC-DS, and (D) DS-TiO2 [62] (reprinted
permission).
with permission).

2.3.4. Pea Peel AC

In a study by Sahlabji et al., pea peel AC was synthesized with the chemical activating
agent ZnCl2 in order to eliminate hexavalent chromium [63]. Chemical activation resulted
in an outstanding 1299 m2/g and a dense porous matrix consisting of micropores, as shown
by BET analysis. The increased number of pores, along with the abundant active sites, as
confirmed by FT-IR, provided the material with an adsorption capacity of 480 mg/g at a
C 2024, 10, 22 10 of 20

2.3.4. Pea Peel AC

In a study by Sahlabji et al., pea peel AC was synthesized with the chemical activating
agent ZnCl2 in order to eliminate hexavalent chromium [63]. Chemical activation resulted
in an outstanding 1299 m2 /g and a dense porous matrix consisting of micropores, as shown
by BET analysis. The increased number of pores, along with the abundant active sites, as
confirmed by FT-IR, provided the material with an adsorption capacity of 480 mg/g at a
dosage of 0.75 g/L. The kinetic and isotherm data exhibited that the adsorption process
consisted of chemisorption together with intra-particle diffusion. A possible adsorption
mechanism may have involved electrostatic interactions between Cr (VI) and the hydroxyl
groups of the adsorbent.

2.3.5. Banana Peel AC

Ramutshatsha-Makhwedzha et al. used a composite material comprising chitosan,
Al2 O3 , and AC derived from banana peels [64]. Chemical activation with KOH and H2 SO4
was carried out so as to acquire a higher surface and porosity, according to the literature.
BET analysis showed that the adsorbent had a surface area of 140.4 m2 /g, while SEM
and TEM revealed the binding microstructure morphology. The composite’s adsorptive
capabilities were evaluated with Cd (II) and Pb (II), some of the tests investigating the
effects of pH, contact time, and adsorbent mass. The driving force for the adsorption
of these heavy metals was electrostatic attraction, in agreement with the kinetics, which
revealed that the process consisted of chemisorption.
According to the results shown in Table 3, all the applied materials showed very high
removal rates, except for As removal. In detail, an adsorption capacity of 480.5 mg/g
was found in the case of Cr(VI) by applying only 0.75 g/L of pea peel AC, but for As
removal, the relative capacities were found to be only 0.8 mg/g and 1.3 mg/g for As(V)
and As(II), respectively. It is worth noting that the initial concentration used in each case
was different (400 mg/L and 0.5 mg/L for Cr(VI) and As, respectively), which also affected
the adsorption capacity. The % removal rates were nearly 100 in the majority of them.

Table 3. Modified activated carbons from peels for removal of heavy metals.

Initial Contact Adsorption

Modification Heavy Dosage
Material Peels pH Conc. Time Capacity R% Ref.
Agent Metal (g/L)
(mg/L) (min) (mg/g)
MPAC-600 Pea Pyrolysis As(III) 7 0.5 3.0 300 1.33 87.6 [60]
MPAC-600 Pea Pyrolysis As(V) 7 0.5 2.5 300 0.80 99.7 [60]
NOPAC-Gly-60 Navel orange H3 PO4 Gd (III) 7 50 0.6 90 48.5 99 [61]
OP-TiO2 Orange Pyrolysis-CO2 Cu (II) 5 24.6 4.9 216 13.34 99.9 [62]
AC Pea ZnCl2 Cr (VI) 1.55 400 0.75 180 480.05 99.5 [63]
BPAC-Al3 O2 @chitosan Banana H2 SO4 /KOH Cd(II) 6 20 5.0 40 46.9 99.9 [64]
BPAC-Al3 O2 @chitosan Banana H2 SO4 /KOH Pb(II) 6 20 5.0 40 57.1 99.9 [64]

2.4. Fluoride Removal

2.4.1. Sweet Lime Peel AC
Fluoride is a prominent hazardous contaminant found in both surface and groundwa-
ter. Siddique et al. faced this particular problem by utilizing sweet lime (Citrus limetta)
to synthesize AC [65]. The activation was carried out physically via pyrolysis at two
different temperatures, and the material with the highest treatment temperature (500 ◦ C)
showed the better results. The pHZPC experiments revealed that the composites had more
acid-active groups, making them ideal for anionic pollutant removal, while the increase in
carbonization temperature came along with an increase in pHZPC . Particularly, the pHZPC
of AC-CLP250 , carbonized at 250 ◦ C, was found to be 2.17, while the relative AC-CLP500 ,
carbonized at 500 ◦ C, provided a pHPZC value of 4.61, as Siddique et al. proved in their
study. The adsorption data revealed that the favorable pH was 6.6 at a 1 g/L dosage and
240 min contact time, and isotherm studies showed that the Langmuir model fit better,
C 2024, 10, 22 11 of 20

indicating a multilayer adsorption process. Finally, the mechanism of adsorption involved

electrostatic attraction, since pH < pHZPC .

2.4.2. Banana Peel AC

A study by Getachew revealed the option of removing fluoride using H2 SO4 -activated
banana peel AC [66]. The adsorption effectiveness was shown to be affected by working
variables such as adsorbent dosage, contact duration, pH, and starting fluoride concentra-
tion. When applied to a real water specimen, the removal effectiveness ranged from 80 to
84%. With regard to the amount of time and adsorbent needed, banana peel AC seemed
to have the slowest kinetics of all materials that were studied. At the optimal pH = 6.6,
the exterior of the adsorbent was strongly protonated in the acidic media, and additional
fluoride ions may have been adsorbed to the surface. In other words, the increased fluoride
sorption rate in acidic media was due to a large coulombic force of attraction between the
positively charged surface and the fluoride anion.

2.4.3. Pea Peel AC

Sahu et al. examined the removal of fluoride from an aqueous solution by both batch
and column experiments with activated carbon derived from pea peels, activated by FeCl3
and pyrolysis [60]. The efficiency of MPPAC-500 was evaluated by the study of the effects
of temperature, kinetics, and pH, and the material was characterized. In batch research,
5 mg/L starting fluoride concentration at a pH = 7, 4 g/L dosage and 420 min of exposure
C 2024, 10, x FOR PEER REVIEW 12 of 21
resulted in 99% fluoride elimination. The Freundlich isotherm model was preferred in
the adsorption investigation, revealing a mono-layer adsorption process. The pseudo-
second-order kinetic model accurately characterized fluoride accumulation, showing that
chemisorption was preferred.
chemisorption was preferred.Thermodynamic
Thermodynamiccharacteristics
characteristicsrevealed
revealed that
that thethe adsorp-
adsorption
tion reaction
reaction was endothermic
was endothermic and spontaneous.
and spontaneous. A possible
A possible adsorption
adsorption mechanismmechanism
is shown inis
shown
Figure 7inbelow.
Figure 7 below.

Figure 7. Possible adsorption mechanism of fluoride on MPPAC-500 [60] (no special permission is
Figure 7. Possible adsorption mechanism of fluoride on MPPAC-500 [60] (no special permission is
required to
required to reuse).
reuse).

In Table 4, the experimental conditions used for fluoride removal using activated
In Table 4, the experimental conditions used for fluoride removal using activated car-
carbons derived from fruit peels are shown.
bons derived from fruit peels are shown.
From the data presented, is clear that the chemical activation of AC is a far better
option regarding the efficiency of the adsorbents. During the activation process, these
Table 4. Modified activated carbons from peels for fluoride removal.
agents induced a material with an increased porosity and a higher number of pores,
Modification Initial Conc.
as mentioned in previous studies.Dosage
However, Contact
every Time
chemicalAdsorption
modification agent can be
Material Peels pH R % Ref.
Agentspecialized based on what (mg/L) properties are the most
(g/L) (min)appropriate for(mg/g)
Capacity each material. For
AC-CLP500 Lime instance, ZnCl
Pyrolysis 6.6 2 presented5–30denser and1 larger pores,
240as confirmed9.70
by SEM images
94.8 of the
[65]
Banana-
Banana H2SO4 2 10 96 780 0.39 85 [66]
AC
MPPAC-
Lime FeCl3 7 5 4 420 4.71 99 [60]
500
C 2024, 10, 22 12 of 20

aforementioned AC materials, while H3 PO4 showed higher specific surface areas, according
to BET analysis. Nevertheless, these details affected the adsorption capacity and the kinetics
of the process, leading to huge differences even with the same precursor materials.

Table 4. Modified activated carbons from peels for fluoride removal.

Initial Contact Adsorption

Modification Dosage
Material Peels pH Conc. Time Capacity R% Ref.
Agent (g/L)
(mg/L) (min) (mg/g)
AC-CLP500 Lime Pyrolysis 6.6 5–30 1 240 9.70 94.8 [65]
Banana-AC Banana H2 SO4 2 10 96 780 0.39 85 [66]
MPPAC-500 Lime FeCl3 7 5 4 420 4.71 99 [60]

Grafting AC with other functional groups or linking it with a polymer appeared to have
a positive outcome. These extra units can enhance the adsorption efficiency significantly,
either by increasing the adsorption capacity or by making the composite available for the
adsorption of different types of pollutants. Another interesting finding is that there is not
extensive research in the field of fluoride removal by AC derived from peels, with only
three research articles available in the past years.

3. Peels as Natural Adsorbents

Fruit peels as adsorbent materials, without previously being converted to activated
carbon, have been used in the recent literature, but not in a large volume of publications.
In particular, it has been found that they are extensively used mainly for the removal of
heavy metals and dyes from wastewater, but there are no extensive reports on this type of
agricultural waste in terms of pharmaceuticals or fluoride ions. A reference is made below
to the relevant literature, and the research presented is classified according to the use of
peels for the removal of organic and inorganic pollutants.

3.1. Organic Pollutant Removal

3.1.1. Pharmaceuticals Removal
In the study of Bouallegue et al. [67], a biosorbent from pomegranate peels (PG) was
produced for the removal of sulfasalazine (SSZ), a pharmaceutical used to treat diseases
such as rheumatoid arthritis and Crohn’s disease. According to the results, maximum
removal (100%) was achieved at pH 4.8, with 50 mg/L as the initial concentration of SSZ and
an adsorbent dose of 0.5 g/L within 60 min. The Langmuir model was found, according
to isotherm models, to best describe the adsorption process, suggesting a monolayer,
homogeneous surface. In addition, Elovich and intra-particle models recommended more
than one mechanism taking place in the adsorption process. Thermodynamics exhibited
a spontaneous and endothermic process. Therefore, pomegranate peels appear to be an
auspicious adsorbent for the treatment of pharmaceutical wastewater [67].
Furthermore, banana peel (BP) was studied to remove acetylsalicylic acid (ASA), an
analgesic and anti-inflammatory drug in aqueous solution [68]. The results exhibited
that BP had a satisfactory maximum adsorption capacity of 2.29 mg/g, according to the
Langmuir model. pH 3.0 was found to be more efficient in removing ASA, but in this
study, pH 7.0 was chosen for further experiments, as it is the value used in water treatment
plants in Brazil [68]. A dosage of 1.5 g of adsorbent was the optimum applied to achieve a
maximum removal of around 48% at only 15 min of contact time. After this time, a decrease
in the drug adsorption was observed, probably due to the desorption of ASA from the BP
during agitation and due to the weak interactions between the drug and the banana peel.

3.1.2. Dye Removal

Regarding dye removal by natural fruit peels, recent studies are summarized as
follows. Particularly, banana peels were used to remove 75.3% of Congo Red by using an
C 2024, 10, 22 13 of 20

initial concentration of 20 mg/L and by applying 18.8 g/L of adsorbent at pH 10 for 90 min
as the contact time. According to kinetics, the best model found to fit the experimental
results was the pseudo-second order. Isotherm data showed an adsorption capacity of
1.727 mg/g, according to the Langmuir model, at 313 K [69].
Moreover, Ahmed et al. [70] used 2.0 g/L of orange peels to remove 86.7% of 50 mg/L
crystal violet. A pH of 8.0 was used, and at 303 K, the Langmuir model was best fitted to the
results presenting a Qmax = 138.9 mg/g. Equilibrium was reached at 70 min, and according
to kinetics, the adsorption was better described by the pseudo-second order model.
Very recently, banana, orange, and pomegranate peels were applied as natural adsor-
bents for the removal of both anionic and cationic dyes from wastewater [25]. A descriptive
and comparative report is made in this study, and the results show that these peels are
very efficient materials for all the dye categories studied. Specifically, Reactive Red 120
(RR120), Reactive Black 5 (RB5), and Remazol Brilliant Blue R (RBBR) as anionic dyes, as
well as cationic Methylene Blue (MB), were examined. The results showed that, for anionic
dyes, 5.0–6.0 g/L of banana or orange peels was sufficient to remove more than 90% of
anionic dyes at pH 2.0, and for cationic MB dye, 4.0 g/L was adequate to achieve 98%
removal at pH 9.0. Pomegranate peels were efficient mainly for cationic dye. Finally, this
study demonstrates the viability of reusing the banana, orange, and pomegranate peel
adsorbents for eight, four, and five cycles, showing a gradual reduction of around 50% in
their effectiveness [25].
Recently, pristine kiwi peel (KP) and nitric acid-modified kiwi peel (NA-KP) were
produced as adsorbents and examined for the removal of cationic dyes from wastewater [30]
as malachite green (MG). According to the results, the adsorption process of MG onto both
KP and NA-KP fit better to the pseudo-second-order kinetic model, but according to
isotherms, the adsorption onto KP followed the Langmuir model, while the adsorption
process of MG onto NA-KP followed the Freundlich isotherm model. In addition, the
Langmuir maximum adsorption capacity for NA-KP was 580.61 mg/g, and for KP, it was
297.15 mg/g. This significant difference in the adsorption capacity of NA-KP compared to
KP can be attributed to the increase in functional groups after HNO3 modification.
In Table 5, the experimental conditions used for the removal of pharmaceuticals and
dyes from wastewater are tabulated.

Table 5. Modified fruit peels for organic pollutant removal.

Initial Contact Adsorption

Modification Organic Dosage
Material Peels pH Conc. Time Capacity R% Ref.
Agent Pollutant (g/L)
(mg/L) (min) (mg/g)
PG Pomegranate Untreated Sulfasalazine 4.8 50 0.5 60 64.04 100 [67]
BP Banana Untreated Acetylsalicylic acid 7.0 100 1.5 15 2.29 48 [68]
BP Banana Untreated Congo Red 10.0 20 18.8 90 1.73 75 [69]
OP Orange Untreated Crystal Violet 8.0 50 2.0 70 138.90 87 [70]
BP Banana Untreated Anionic dyes 2.0 300 5.0 90 58.1 100 [25]
OP Orange Untreated Anionic dyes 2.0 300 6.0 90 40.1 92 [25]
PP Pomegranate Untreated Methylene Blue 9.0 300 6.0 90 98.1 98 [25]
KP Kiwi Untreated Malachite green - 50 0.05 - 297.15 - [30]
NA-KP Kiwi HNO3 Malachite green - 50 0.05 - 580.61 - [30]

3.2. Inorganic Pollytants Removal

3.2.1. Heavy Metals Removal
Acrylonitrile-grafted banana peels have been used for the removal of chromium [71].
Graft copolymerization is used for improving the thermal, chemical, mechanical, and
hydrogel properties while preserving their intrinsic characteristics. This intricate process
involves grafting diverse monomers onto the backbones of naturally occurring polymers,
a procedure induced through the application of chemical initiators. In the realm of water
purification, cellulose emerges as a particularly cost-effective adsorbent for extracting
metallic ions. Renowned as one of the planet’s most abundant natural and renewable
polymers, cellulose is highly esteemed due to its economic feasibility and widespread
 C 2024, 10, 22 14 of 20

availability for adsorption purposes. The intricate cellulose structure is delineated by

the formation of b-(1,4)-glycosidic linkages of the D-glucose unit, featuring a repeating
unit with three hydroxyl groups. Various industrial sectors discharge heavy metal ions
C 2024, 10, x FOR PEER REVIEW and impurities into effluents, where cellulose-based graft copolymers come into play for 15 of 21
effective removal. Previous research, as documented in publications, has explored the
grafting of cellulose with monomers like acrylic acid, acrylonitrile, and methyl methacrylate.
These modifications have been shown to significantly enhance the adsorption capacities
forNumerous
heavy metals research endeavors
[72]. Chemically have agricultural
treated explored the use of both
adsorbents untreated
considerably and chemi-
improve
cally treatedcapacities
adsorption banana compared
peels forto extracting
their untreatedtoxic heavy metal
counterparts [73]. ions from water and
wastewater. In a research
Numerous recent work, rawhave
endeavors banana peels
explored the initially treated
use of both untreatedwithandacid, alkali, and
chemically
treated banana peels for extracting toxic heavy metal ions from water and
bleaching agents such as NaClO3 and H2O2 are investigated, following their functionaliza- wastewater. In a
recent work, raw banana peels initially treated with acid, alkali, and bleaching
tion by acrylonitrile. The grafted banana peels (GBPs) that were produced served a crucial agents such
as NaClO3 and H2 O2 are investigated, following their functionalization by acrylonitrile.
role as adsorbents for extracting Cr(VI) from water. The increased adsorption capacity
The grafted banana peels (GBPs) that were produced served a crucial role as adsorbents for
observed in chemically treated banana peels can be ascribed to the removal of lignin and
extracting Cr(VI) from water. The increased adsorption capacity observed in chemically
pectin,
treatedwhich
bananaarepeels
viscous
can becompounds.
ascribed to theFurthermore,
removal of ligninthe introduction
and pectin, which of the
are acrylonitrile
viscous
side chain into the cellulosic framework played a pivotal role in augmenting
compounds. Furthermore, the introduction of the acrylonitrile side chain into the cellulosic its interaction
with the molecules
framework playedbeing adsorbed
a pivotal [73]. As shown
role in augmenting in Figure with
its interaction 8, according to SEM
the molecules images,
being
lignin, pectin,
adsorbed and
[73]. Asother
shown viscous compounds
in Figure 8, according cause
to SEM theimages,
fibers tolignin,
stick pectin,
together and(Figure
other 8A),
butviscous
they compounds
are removed cause the fibers
during to stick treatment
chemical together (Figure 8A),8B).
(Figure but they
The are removed
surface became
during chemical treatment (Figure 8B). The surface became smoother after
smoother after the adsorption of Cr(VI) due to the fact that the pores and caves were oc- the adsorption
of Cr(VI)
cupied due to (Figure
by Cr(VI) the fact that the pores and caves were occupied by Cr(VI) (Figure 8E,F).
8E,F).

Figure 8. (A) SEM image of raw banana peel. (B) Bleached banana peel. (C) Acrylonitrile grafted
Figure 8. (A) SEM image of raw banana peel. (B) Bleached banana peel. (C) Acrylonitrile grafted
banana peel. (D) GBPs before adsorption. (E,F) GBPs after Cr(VI) adsorption [73].
banana peel. (D) GBPs before adsorption. (E,F) GBPs after Cr(VI) adsorption [73].

Moreover,
Moreover,dragonfruit and passion
dragonfruit and passionfruit
fruithave
have been
been extensively
extensively studied.
studied. The cellular
The cellular
composition of these agricultural materials primarily comprises tannin, lignin, and
composition of these agricultural materials primarily comprises tannin, lignin, and cellu- cellulose,
presenting
lose, presenting significant potential
significant for thefor
potential absorption of heavyofmetal
the absorption heavyions [74].ions
metal Sulfuric
[74].acid
Sulfuric
(H SO ) is used as a modification agent in fruit peels for the removal of heavy
acid (H2SO4) is used as a modification agent in fruit peels for the removal of heavy metals.
2 4 metals.
These adsorbents, after the adsorption of Cu(II), were darker than they were prior to
These adsorbents, after the adsorption of Cu(II), were darker than they were prior to any
any treatment.
treatment.
Copper, a heavy metal frequently found in industrial effluents, poses toxicity to living
Copper, necessitating
organisms, a heavy metal frequently
effective found
wastewater in industrial
treatment effluents,
measures. poses toxicity
The adsorption processto liv-
ing organisms, necessitating effective wastewater treatment measures. The adsorption
process has been a focal point of extensive research aimed at addressing wastewater issues
across multiple industries. There are a few conventional technologies for the retrieval of
metals from wastewater, but the researchers have turned their attention to low-cost ad-
sorbents such as fruit peels [74].
C 2024, 10, 22 15 of 20

has been a focal point of extensive research aimed at addressing wastewater issues across
multiple industries. There are a few conventional technologies for the retrieval of metals
from wastewater, but the researchers have turned their attention to low-cost adsorbents
such as fruit peels [74].
The carboxylate group present at the active site exhibits a strong adsorption capacity
for Cu2+ ions. Consequently, the fruit peel adsorbents possess a higher number of metal-
binding active sites and more negatively charged surfaces. This characteristic enhances the
retention of Cu2+ ions on the surface, resulting in a higher percentage of Cu(II) removal.
However, the adsorption mechanism for metal ions is influenced by various factors, in-
cluding the solution’s pH and binding characteristics. In this research, the adsorption of
Cu(II) was elucidated by considering the pH effect and employing FT-IR-based characteri-
zation techniques. These analyses supported the binding of Cu2+ ions on fruit peels, where
functional groups electrostatically interact with Cu2+ and Cu(OH)2 . At higher pH values,
copper hydroxides were precipitated on the surface of the peels [74].
In a recent study, orange peel waste (POP) was effectively examined for its ability to
remove Mn(II) and Co(II) ions from water [75]. For Co(II) ions, the addition of 0.2 g/L
of POP at an initial concentration of 250 mg/L at pH 6.05 was found to be effective, with
100 min as the contact time. In the case of Mn(II) ions, an initial concentration of 200 mg/L
was used by adding 0.2 g/L of the adsorbent at a lower pH of 5.42. The maximum
adsorption capacities were found for Co(II) 25.91 mg/g and for Mn(II) 25.25 mg/g at 318 K.
Furthermore, the pseudo-second-order model better fit the experimental data for both
Co(II) and Mn(II) ions [75].

3.2.2. Fluoride Removal

One of the main waste products in tropical areas is banana peels. Regarding the
removal of fluoride from this waste, there is no information. This has led scientists to
investigate the adsorption of F− using banana peels [76]. The maximum adsorption of
fluoride occurs at pH 6.0 (<pHZPC ); thus, F− is more attached to the surface of banana
peels having been chemically treated with Ca2+ . To determine the types of functional
groups included in banana peels, the FTIR spectra were acquired. Many peaks were
visible in the FTIR spectra, suggesting that the adsorbent is complex. –OH stretching,
C–H stretching of alkane, C–H and C=O stretching of carboxylic acid or ester, COO–anion
stretching, OH bending, C–O stretching of ester or ether, and N–H deformation of amines
were the explanations given for bands that appeared at 3905.88–3258, 2928.13, 2856.01, 1734,
1631, 1393.45, 1269.11, and 1116.24–624.66 cm−1 , respectively. Among these, hydroxyl and
carboxylic groups were crucial in the elimination of fluoride ions [76].
Furthermore, banana peels were modified by zirconium (IV), and the Zr(IV)-loaded
saponified banana peels appeared to be an excellent substitute [77] for fluoride removal.
Sorbents have recently been developed using rare earth metal oxides and hydroxides, such
as zirconium. When it comes to species that contain oxygen donors, the zirconium (IV)
cation exhibits strong electrostatic and coordination affinity. Additionally, Zr(IV)-modified
adsorbents are non-toxic to humans and have a low leaching rate. In these conditions,
pomegranate peel has been modified with Zr(IV) to improve its adsorption performance.
Peels are often saponified—that is, treated with a basic solution—prior to Zr(IV) loading. By
breaking the ester bonds and obtaining additional carboxyl and hydroxyl groups for Zr(IV)
loading, this pretreatment (saponification) will be helpful in increasing the adsorption
capacity [78].
Low adsorption occurs at pH < 2 because the combination of F− ions and H+ ions
in solution forms weakly ionizable hydrofluoric acid, which reduces the availability of
F− ions for adsorption. The greatest fluoride adsorption onto Zr(IV)-SBP is observed at a
pH of about 3. When Zr(IV)-SBP is protonated at this pH, the coordinated hydroxyl ligand
in the coordination sphere of the loaded Zr(IV) interacts with the fluoride anion through
coulombic interaction, leading to fluoride adsorption and the release of water. Fluoride
anions and hydroxyl ligands exchange ligands to produce a net reaction. As the pH rises,
C 2024, 10, 22 16 of 20

the fluoride adsorption gradually decreases, possibly as a result of competition between

the increased concentration of hydroxyl ions and fluoride ions [77].
In Table 6, the experimental conditions used for the removal of heavy metals and
fluoride ions from wastewater are summarized.

Table 6. Modified fruit peels for removal of inorganic pollutants.

Initial Adsorption
Heavy Dosage Contact
Material Peels Modification Agent pH Conc. Capacity R% Ref.
Metal (g/L) Time (min)
(mg/L) (mg/g)
Acrylonitrile grafted Acrylonitrile
Banana Cr(VI) 3 400 4 120 6.17 99.7 [73]
banana peels (grafting)
H2 SO4 treated Dragon fruit H2 SO4 Cu(II) 4 100 0.25 180 92.59 99.2
dragon/passion fruit [74]
peels Passion fruit H2 SO4 Cu(II) 4 100 0.25 180 121.95 99.6
Mn(II) 5 200 0.2 100 25.25
Orange peels Orange NaOH and CaCl2 [75]
Co(II) 6 250 0.2 100 25.91
Ca-impregnated
Banana Ca2+ F− 6 10 1 180 39.5 99 [76]
banana peel dust
Zr (IV) loaded
Banana ZrOCl2 8H2 O F− 3 10 2 300 36.02 99 [77]
banana peels

4. Conclusions
In this review, focus is given to recent trends involving using low-cost agricultural
wastes as adsorbents, such as modified peels and even the natural adsorbents or activated
carbons derived from them, for the removal of several pollutants found in wastewater.
Among them, pharmaceuticals dyes, heavy metals, and ions such as fluoride have been
selected as pollutants in order to present and compare the efficiency of the application of
low-cost agricultural wastes as adsorbents.
Activated carbon derived from peels appeared to be an effective solution. Biomass-
based activated carbons present high removal efficiency, and for some kinds of pollutants,
even reach 99.9% rates using only a small dosage; i.e., the pea peel AC examined for
the removal of Cr(VI), which exhibited a very high adsorption capacity (480.5 mg/g) by
applying only 0.75 g/L.
Moreover, fruit peels as adsorbent materials, without previously being converted to
activated carbon, have not been extensively used in the recent literature for pharmaceuticals
or fluoride ions, but have been used mainly for the removal of heavy metals and dyes from
wastewater. Therefore, it is concluded that research should be focused on more applications
of these natural sorbents from peels in wastewater treatment in order to reduce the cost of
the whole process. A significant difference in the adsorption capacity of nitric acid-modified
kiwi fruit peels (i.e., NA-KP) compared to unmodified kiwi peels (KPs) for the removal of
cationic dyes was found (580.61 and 297.15 mg/g, respectively), and this can be attributed
to the increase in functional groups after modification.
Overall, mainly banana peels, and then orange and pomegranate peels, were found to
be the most common agricultural wastes applied as natural peels or peel-based activated
carbons for the removal of the specific pollutants examined in this review.

Author Contributions: Conceptualization, A.K.T., K.N.M., D.T., I.A.K. and G.Z.K.; methodology,
A.K.T., K.N.M., D.T., I.A.K. and G.Z.K.; validation, A.K.T., I.A.K. and G.Z.K.; formal analysis, A.K.T.,
K.N.M., D.T., I.A.K. and G.Z.K.; investigation, A.K.T., K.N.M., D.T., I.A.K. and G.Z.K.; resources,
A.K.T., K.N.M., D.T., I.A.K. and G.Z.K.; data curation, A.K.T., K.N.M. and D.T.; writing—original
draft preparation, A.K.T., K.N.M. and D.T.; writing—review and editing, A.K.T., K.N.M., D.T., I.A.K.
and G.Z.K.; visualization, A.K.T., K.N.M., D.T., I.A.K. and G.Z.K.; supervision, A.K.T., I.A.K. and
G.Z.K. 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.
C 2024, 10, 22 17 of 20

Data Availability Statement: All data analyzed during this study are included in this published article.
Acknowledgments: We acknowledge support of this work by the project “Advanced Nanostructured
Materials for Sustainable Growth: Green Energy Production/Storage, Energy Saving and Environ-
mental Remediation” (TAEDR-0535821), which is implemented under the action “Flagship actions in
interdisciplinary scientific fields with a special focus on the productive fabric” (ID 16618), Greece
2.0—National Recovery and Resilience Fund and funded by European Union NextGenerationEU.
Conflicts of Interest: The authors declare no conflicts of interest.

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