sustainability

Review
Waste-Based Adsorbents for the Removal of Phenoxyacetic
Herbicides from Water: A Comprehensive Review
Magdalena Blachnio 1, * , Krzysztof Kusmierek 2 , Andrzej Swiatkowski 2 and Anna Derylo-Marczewska 1

1 Faculty of Chemistry, Maria Curie-Sklodowska University, M. Curie-Sklodowska Sq. 3, 20-031 Lublin, Poland;
anna.derylo-marczewska@mail.umcs.pl
2 Institute of Chemistry, Military University of Technology, gen. S. Kaliskiego St. 2, 00-908 Warszawa, Poland;
krzysztof.kusmierek@wat.edu.pl (K.K.); a.swiatkowski@wp.pl (A.S.)
* Correspondence: magdalena.blachnio@mail.umcs.pl; Tel.: +48-8153-756-37

Abstract: An overview of different adsorbents, based on agricultural and household waste, for
chlorophenoxy herbicides removal from water is presented. Several groups of adsorbents are dis-
cussed, taking into account the modification method used on the initial material and the type of final
product obtained. The adsorbent characteristics and the conditions of the adsorption measurements
are given, and a discussion on the obtained results is presented, along with a theoretical description,
following the application of various equations and models. A group of the most effective adsorbents
is indicated, based on the analysis of the adsorption capacity, towards 2,4-D and/or MCPA, and the
adsorption rate. Some important problems connected with adsorbent utility are discussed, taking
into account economic and ecological aspects. Moreover, the effectiveness of the analyzed materials
is observed through the analysis of its interactions with other components present in real systems.

Keywords: adsorbents based on agricultural waste; adsorbents based on household waste; phenoxy-
acetic herbicides; herbicides removal; herbicides adsorption; herbicides adsorption kinetics

1. Introduction
Citation: Blachnio, M.; Kusmierek, K.; Pesticides are a group of chemical compounds that are used to combat plant diseases,
Swiatkowski, A.; Derylo-Marczewska, remove and destroy weeds, combat pests, and treat seeds. Over the past few decades, there
A. Waste-Based Adsorbents for the has been a constant increase in plant and animal production around the globe, which has
Removal of Phenoxyacetic Herbicides resulted in the growing demand for pesticides. At the global level, in the last decade, a 50%
from Water: A Comprehensive increase in pesticide use compared to the 1990s has been observed. In 2020, the total amount
Review. Sustainability 2023, 15, 16516. of pesticides used in agriculture was on the level of 2.7 million tons of active ingredients,
https://doi.org/10.3390/su152316516 which corresponds to approximately 7.2 million tons of formulated pesticide products.
Academic Editor: Pow Seng Yap
Taking into account the specific target groups, herbicides accounted for the largest share in
the total consumption (52%), followed by fungicides (23%), insecticides (18%), and other
Received: 30 October 2023 pesticides (7%) [1].
Revised: 25 November 2023 The dynamic increase in the use of pesticides poses the risk of water pollution with
Accepted: 1 December 2023 such compounds. This problem is substantial in countries with a high share of agricultural
Published: 3 December 2023
land and those with low water resources, and in countries where surface water is the main
source of drinking water for the inhabitants. According to recent data, on average in the
whole of Europe, 37% of the public water supply comes from surface water [2], while
Copyright: © 2023 by the authors.
in Bulgaria, Ireland, the UK, and Greece it is over 65% [3–7]. The worst situation is in
Licensee MDPI, Basel, Switzerland. Northern Ireland, where the population uses almost exclusively surface water resources for
This article is an open access article consumption purposes [8]. The highest concentrations of pesticides have been found in the
distributed under the terms and runoff of meltwater or flood waters and agrochemical treatments [9]. A natural consequence
conditions of the Creative Commons of the presence of pesticides in surface water is their penetration into groundwater. Since
Attribution (CC BY) license (https:// surface and underground waters are a source of drinking water, they should not contain
creativecommons.org/licenses/by/ harmful substances. However, toxicological and epidemiological studies provide more
4.0/). and more evidence that the quality of some natural water poses a real threat to human

Sustainability 2023, 15, 16516. https://doi.org/10.3390/su152316516 https://www.mdpi.com/journal/sustainability

 Sustainability2023,
Sustainability 2023,15,
15,16516
16516 22 ofof34
34
Sustainability 2023, 15, 16516 2 of 33

moreand
more andmore
moreevidence
evidencethatthatthe
thequality
qualityof
ofsome
somenatural
naturalwater
waterposes
posesaareal
realthreat
threattotohu-
hu-
health.
man Among
manhealth. the
health.Among several
Amongthe thousand
theseveral organic
severalthousand compounds
thousandorganic
organiccompounds identified
compoundsidentified as water
identifiedas pollutants,
aswater
waterpollu-
pollu-
chlorophenoxy
tants, herbicides
tants, chlorophenoxy
chlorophenoxy make a significant
herbicides
herbicides make contribution.
make aa significant
significant This group
contribution.
contribution. of compounds
This
This group of
group is
of com-
com-
widely used to
poundsisiswidely
pounds control
widelyused broadleaf
usedtotocontrol weeds in agricultural
controlbroadleaf
broadleafweeds
weedsin and non-agricultural
inagricultural
agriculturaland areas, while
andnon-agricultural
non-agricultural
2,4-dichlorophenoxyacetic
areas,while
areas, acid (2,4-D) and
while2,4-dichlorophenoxyacetic
2,4-dichlorophenoxyacetic 4-chloro-2-methylphenoxyacetic
acid
acid (2,4-D)and
(2,4-D) acid (MCPA)
and4-chloro-2-methylphenoxyacetic
4-chloro-2-methylphenoxyacetic
are in
acid the top
acid(MCPA) five
(MCPA)are most
arein
inthe often
thetop used
topfive herbicides
fivemost
mostoften in
oftenused the US and
usedherbicides
herbicidesinthe EU
inthe [10,11].
theUSUSand
andthetheEU
EU[10,11].
[10,11].
The chemical
The chemical structures
chemical structures and
structures and the
and themost
the most relevant
most relevant physicochemical
relevant physicochemical properties
physicochemical properties
properties ofofthethe
The of the
chlorophenoxy herbicides used are presented in Table 1.
chlorophenoxyherbicides
chlorophenoxy herbicidesusedusedare
arepresented
presentedin inTable
Table1.1.
Table 1. The
Table structure and physicochemical parameters of 2,4-D and MCPA.
Table 1.1.The
The structure
structure and
and physicochemical
physicochemical parameters
parameters ofof2,4-D
2,4-D and
and MCPA.
MCPA.

Parameter
Parameter
Parameter 2,4-D
2,4-D
2,4-D MCPA
MCPA
MCPA
CASnumber
CAS
CAS number
number 94-75-7
94-75-7
94-75-7 94-74-6
94-74-6
94-74-6
OO OO
OO OO
Chemicalstructure
Chemical
Chemical structure
structure OH
OH OH
OH

ClCl ClCl ClCl CH3 3

CH

Molecularweight
Molecular
Molecular weight
weight mol−1 )−1−1
(g(g (gmol
mol ) ) 221.04
221.04
221.04 200.62
200.62
200.62
Molecular
Molecular size
size
Molecular size (Å) (Å)(Å) 4.88 ××
4.88
4.88 9.49
×9.49
9.49 5.47 ×
5.47
5.47 9.52
××9.52
9.52
Solubility in water at 20 ◦ C (g L−1 )−1−1 0.682 0.825
Solubilityin
Solubility inwater
wateratat20 20°C
°C(g
(gLL ) ) 0.682
0.682 0.825
0.825
Melting point (◦ C) 136–140 108–112
Melting
Melting point
point
Boiling point ( C)◦ (°C)
(°C) 136–140
136–140
160 108–112
108–112
160
Boiling
Boiling pKpoint
point
a (°C)
(°C) 160
160
2.98 160
160
3.14
logpK
K
pK
o/waa 2.37
2.98
2.98 3.25
3.14
3.14
logKKo/w
log o/w 2.37
2.37 3.25
3.25
The permeation of chlorophenoxy herbicides into the body increases the risk of
cancer,The The
such permeation
permeation
as soft-tissue ofchlorophenoxy
of chlorophenoxy
sarcoma, non-Hodgkin’s herbicidesinto
herbicides into thebody
the
lymphoma, bodyincreases
increases
and prostate therisk
the risk
andof of can-
can-
gas-
cer,
cer, such
such asas soft-tissue
soft-tissue sarcoma,
sarcoma, non-Hodgkin’s
non-Hodgkin’s lymphoma,
lymphoma,
tric cancers [12–15]. Other available data indicate correlations between exposure to these and
and prostate
prostate and
and gastric
gastric can-
can-
cers
cers [12–15].
[12–15]. Other
Other available
available data
data indicate
indicate correlations
correlations
herbicides and Parkinson’s disease and birth defects [16]. The toxicity of 2,4-D and MCPA between
between exposure
exposure toto these
these herbi-
herbi-
cides
iscides andParkinson’s
and
evidenced Parkinson’s
by the fact that disease
disease the andandbirthbirthdefects
International defects
Agency [16].for
[16]. The
The toxicityon
toxicity
Research ofofCancer
2,4-Dand
2,4-D and
(IARC) MCPA
MCPA hasisis
evidenced
evidenced
defined them byby the
asthe factthat
fact
possibly that theInternational
the
carcinogenic International
to humans Agency
Agency (Group forResearch
for Research
2B) [17]. on onCancer
For Cancer
this reason, (IARC)
(IARC) both has
has
defined
defined
the Worldthem them
Health asOrganization
as possiblycarcinogenic
possibly carcinogenic
(WHO) and totohumans
humans
the United (Group
(Group States 2B)
2B) [17].For
[17]. Forthis
Environmental thisreason,
reason,both
Protection both
theWorld
the
Agency World Health
(US Health
EPA) Organization
Organization
have (WHO)and
(WHO)
imposed requirements andfor thewater
the United
United StatesEnvironmental
States
intended Environmental
for human consumption, Protection
Protection
Agency
Agency (US
(US EPA)
EPA) have
have imposed
imposed requirements
requirements for
for
specifying that it should not contain more than 0.1 µg L of individual chlorophenoxy water
water − 1 intended
intended for
for human
human consump-
consump-
tion,
herbicides,specifying
tion, specifyingand the that
that it should
it should
total not contain
not contain
concentration should more
more notthanthan
exceed 0.1
0.1 µg µg
0.5 L L
µg of
−1
−1 −
of 1individual
L individual
[18,19]. Such chlorophe-
chlorophe-
rigor-
ousnoxy
noxy herbicides,
herbicides,
standards make and
and the
thethewater total
total concentration
concentration
purification should
should
process notexceed
not
involving exceed
these0.5 0.5 µgL
µg
types L−1−1compounds
of [18,19].Such
[18,19]. Such
rigorousimportant,
rigorous
extremely standardsmake
standards makeathe
from the waterand
water
scientific purification
purification
practical processprocess
point involvingthese
of involving
view. thesetypes typesof ofcom-
com-
pounds
pounds extremelyimportant,
extremely
The techniques important,
used for this from
from aascientific
purpose scientific andpractical
and
are diverse, practical
and depending pointof
point ofonview.
view. the specificity of
Thetechniques
The
the purification techniques
process used
usedthey for
for this
this
are purposeas
purpose
classified are
are diverse,chemical,
diverse,
physical, anddepending
and depending onthe
on
and biological thespecificity
specificity
methods,of of
the
orthe purification
purification
combined ones. process
process
The most they
they areclassified
are
used classified
water asphysical,
as
treatment physical, chemical,
chemical,
techniques andbiological
and
comprise: biological
adsorption methods,
methods,
[20],
orcombined
or combined
membrane ones.The
ones.
filtration The most
[21],most usedwater
used
irradiation water treatment
[22],treatment
photocatalytic techniques
techniques comprise:
comprise:
degradation adsorption
adsorption
[23], thermal [20], [20],
re-
membrane
mediation
membrane [24],filtration
filtration [21],irradiation
electrokinetic
[21], irradiation
coagulation [22],[25],
[22], photocatalytic degradation
oxidation degradation
photocatalytic [26], ozonation [23],
[23], thermal
[27],
thermal chemical reme-
reme-
coagulation–flocculation
diation[24],
diation [24],electrokinetic
electrokinetic [28],coagulation
ion exchange
coagulation [29],
[25],
[25], and biodegradation
oxidation
oxidation [26],ozonation
[26], ozonation [30].[27],
These
[27], techniques
chemical
chemical coag-
coag-
have their advantages[28],
ulation–flocculation
ulation–flocculation andion
[28], drawbacks.
ion exchangeSometimes
exchange [29],and
[29], the latter limits
andbiodegradation
biodegradation theThese
[30].
[30]. usefulness
Thesetechniques of a
techniques
given
havetechnique,
have theiradvantages
their especially
advantages and in technological
anddrawbacks.
drawbacks. Sometimes
Sometimes solutions usedlimits
thelatter
the latter on a the
limits large scale. The
theusefulness
usefulness ofamost
of agiven
given
problematic disadvantages
technique,especially
technique, especiallyin are:
intechnological(i) high
technologicalsolutions cost, (ii)
solutionsused high
usedon energy
onaalarge consumption,
largescale.
scale.The Themost(iii) the
mostproblem- need
problem-
for chemical
atic
atic disadvantages reagents,
disadvantages are: (iv)
are: (i)the
(i) high
high creation
cost,(ii)
cost, ofhigh
(ii) biosolids,
high energy
energy sludge, or new(iii)
consumption,
consumption, harmful
(iii)the
theneed compounds
need forchem-
for chem-
asical
by-products,
ical reagents,(iv)
reagents, (v)
(iv)thethepre-treatment
the creationof
creation stage, (vi)
ofbiosolids,
biosolids, membrane
sludge,
sludge, orornew
newfouling,
harmful
harmful andcompounds
(vii) the need
compounds asasforby-
by-
specific
products,
products, instruments
(v)the
(v) and materials
thepre-treatment
pre-treatment [22,26,30–32].
stage,
stage, (vi)membrane
(vi) membraneAmong the above-mentioned
fouling,
fouling, and(vii)
and (vii)the
theneed
need techniques
forspecific
for specific
for water treatment,
instruments
instruments and adsorption
andmaterials
materials seems to beAmong
[22,26,30–32].
[22,26,30–32]. the most
Among the
the suitable because it istechniques
above-mentioned
above-mentioned characterized
techniques by
forwa-
for wa-
low cost and
tertreatment,
ter low energy
treatment,adsorption consumption;
adsorptionseems seemstotobe moreover,
bethethemost it
mostsuitable is highly
suitablebecause selective and effective.
becauseititisischaracterized
characterizedby There
bylowlow
are various
cost
cost andlow
and groups
low energy
energy ofconsumption;
adsorbents,
consumption; i.e., (i) carbonaceous
moreover,
moreover, ititisishighly
highly materials
selective(commercial
selective andeffective.
and effective. activated
Thereare
There are
carbons, activated
variousgroups
various groupsof carbons
ofadsorbents, from
adsorbents,i.e., solid
i.e.,(i) waste, carbon
(i)carbonaceous
carbonaceousmaterials blacks, carbon
materials(commercial nanotubes,
(commercialactivated graphene,
activatedcar- car-
reduced
bons, graphene
bons,activated
activated oxide,from
carbons
carbons and
fromordered
solidwaste,
solid mesoporous
waste, carbonblacks,
carbon carbons);
blacks, (ii) inorganic
carbon
carbon nanotubes,
nanotubes, materials
graphene,
graphene, (sil-re-
re-
ica gels, activated
ducedgraphene
duced grapheneoxide, alumina,
oxide,and zeolites,
andordered molecular
orderedmesoporous sieves,
mesoporouscarbons); and
carbons);(ii) metal oxides);
(ii)inorganic (iii)
inorganicmaterials advanced
materials(silica (silica
Sustainability 2023, 15, 16516 3 of 33

materials (inorganic–organic composites, doped materials); and (iv) low-cost materials

(agricultural and household waste-based materials, natural materials, biosorbents, indus-
trial by-products) [33,34]. Due to the low cost of production for most of them, and the
renewability and availability of the raw material, adsorbents based on agricultural and
household waste are considered to be one of the most promising types. Taking into account
these factors, there is no need for the subsequent regeneration and reusability of adsorbents
based on agricultural and household waste. Additionally, the idea on the production of
this type of adsorbents is also a solution for the proper management of agricultural and
household waste. This is extremely important from an economic point of view, because
the regeneration process requires energy or the use of expensive reagents. In general,
agricultural and household waste can be used as adsorbents in the form of unmodified
material, or after physical and/or chemical modification, as modified material, ash, biochar,
or activated carbon. The latter, due to its relatively high efficiency in the purification of
water from organic pollutants, in the near future, may completely replace commercial
activated carbon, which comes from fossil coal and is characterized by a high market price.
Straw, bark, and seed husks from various plants, seeds, and fruit peelings are just a few
examples of renewable and readily available sources of raw material for activated carbon
production. In terms of biochemistry, they mainly consist of biopolymers of cellulose and
other polysaccharides (substances that are a source of elemental carbon), which makes
them a suitable precursor of activated carbon. However, the production of this type of
adsorbent is the most costly compared to other waste-based ones.
In the present paper, an overview of different adsorbents, based on agricultural
and household waste, for chlorophenoxy herbicides removal from water is presented.
The adsorbents were divided into several groups, depending on the applied method of
modification used on the initial material and the type of final product obtained. The
characteristics of the adsorbents, the conditions of the adsorption experiments, and the
results, along with the theoretical models best describing the adsorption process, were
reported. The analysis of the adsorption data, based on the adsorption capacity towards
2,4-D and/or MCPA and the adsorption rate, allowed us to indicate a group of the most
effective adsorbents. The reviewed papers were also evaluated for the presence of studies
that are crucial for the development of new adsorbents, such as: (i) the selectivity of
the adsorbent; (ii) the adsorbent performance in multi-component systems (with heavy
metal ions, antibiotics, phenols, dyes, competitive pesticides or metabolites of degradation,
natural organic matter); (iii) herbicide interactions with adjuvants as integral components
of herbicide formulations; (iv) the regeneration and reusability of the adsorbent; and (v) the
cost balance of adsorbent production (collecting, transporting, and processing of waste)
and the benefits from its use in the water treatment process.
Because many aspects have not been touched on at the preliminary research stage, the
cost effectiveness of the production and applicability of adsorbents based on agricultural
and household waste in the water treatment process is a debatable issue. Nevertheless, the
authors hope the paper facilitates readers in the optimal selection of raw materials, the
modification method particular to a given type of adsorbent, and the adsorption conditions.
The paper also indicates the directions for future research that require development in the
area of new materials dedicated to adsorption applications.

2. Adsorbents Based on Agricultural and Household Waste

The issue of water purification from chlorophenoxy herbicides is related to the selec-
tion of appropriate methods and materials for this purpose, which are effective, economical,
and meet the requirements of “Green chemistry” (maximum reduction in the use and
generation of harmful substances). The method that mostly meets these expectations is the
adsorption of materials based on agricultural and household waste. Due to the biochemical
structure, agricultural and household waste can be used as adsorbents in raw form, or
after physical and/or chemical modifications, or they can be used as a precursor for the
production of activated carbon. The effectiveness of chlorophenoxy herbicide adsorption
Sustainability 2023, 15, 16516 4 of 33

by these types of adsorbents depends on the pollutant concentration, the physicochemical

characteristics of the adsorbent, and the conditions of the adsorption process (solution pH,
temperature, ionic strength, and the accompanying substances in the system). In addition
to the pollutant concentration, the degree of water purification is determined by the affinity
of the herbicide to the adsorbent. Therefore, it is important to select the appropriate raw
material and a method of modification/processing to obtain an effective adsorbent. Evalu-
ation of the adsorption properties of the material is carried out based on the adsorption
capacity and herbicide adsorption rate. Due to the complex composition of water from
natural sources (the presence of other pollutants, i.e., competitive pesticides or metabolites
of degradation, heavy metal ions, phenols, dyes, natural organic matter), it is also advis-
able to assess the selectivity of the adsorbent to a herbicide in multi-component systems
and determine the effectiveness of chlorophenoxy herbicides to adsorption under such
conditions. Commercial herbicide formulations include active substances and adjuvants
that improve the solubility of the preparation, therefore determining the effect of auxiliary
substances on the adsorption yield is equally important. With regard to activated carbon,
the production of which is relatively expensive compared to other waste-based adsorbents,
a study on material regeneration and reusability is recommended. In the final assessment
on the potential use of adsorbents based on agricultural or household waste, it is also
helpful to make use of the cost balance in adsorbent production (collecting, transporting,
and processing of waste) and a list of benefits from the use of adsorbents for the removal
of phenoxyacetic herbicides from water. Special attention has been paid to all these issues
during the browsing of the cited papers.

2.1. Unmodified, Modified Natural Materials and Ashes

The development of adsorbents using agricultural and household waste provides an
interesting alternative to commercial materials intended for environmental applications and
at the same time provides a way for proper waste management. So far, these types of waste
have been disposed of in landfills or by burning in open agricultural fields. Both methods
release greenhouse gases that get into the atmosphere, while field burning is additionally
associated with the destruction of the ecosystem and the risk of the uncontrolled spread
of fire. When considering agricultural and household waste as raw materials for the
preparation of adsorbents, one should emphasize its availability in huge quantities and its
little or no economic value. All this means that more and more studies have been focused on
the transformation of resource waste into useful and functional adsorbents for the removal
of a variety of pollutants from water and wastewater. Excluding waste-based biochars and
activated carbons, the remaining types of adsorbents have been obtained through simple
physical or chemical modifications, several-stage and more complex modifications, as well
as oxidative combustion. There have also been attempts to use unmodified waste materials.
The usefulness of adsorbents in polluted water treatments was closely correlated with
the method used for its preparation (or modification abandonment) and the type of raw
material used.
One such typical agricultural waste is rice husk, which has been tested to remove
phenoxy herbicides from water [35–37]. Deokar et al. described the liquid-phase removal of
2,4-D [35,38] and MCPA [37] using rice husk ash (RHA). The effects of various parameters,
such as the adsorbent dosage, initial concentration, contact time, and particle size of the
RHA, were studied. The adsorption kinetics were studied by applying the PFO, PSO,
and Elovich equations, and the PSO and Elovich kinetic models were found to be the best
models to describe the adsorption. The Langmuir, Freundlich, and Temkin isotherm models
were considered to determine the adsorption capacity and adsorbent affinity. The maximum
adsorption capacity, based on the Langmuir model, was found to be 1.425 mg g−1 for 2,4-D
and 1.681 mg g−1 for MCPA. It was realized that the ash physicochemical parameters, such
as a higher surface area and a smaller silica-to-carbon ratio, favored pollutant adsorption.
In other works [36,39], rice husk waste was reduced to nanosized particles via a
mechanical method and was evaluated for its effective usage as a 2,4-D adsorbent. The
Sustainability 2023, 15, 16516 5 of 33

adsorption isotherms and kinetic models were used to describe the experimental data
and understand the adsorption mechanism. From the results, the PSO model was found
to fit the adsorption best; moreover, the adsorption of 2,4-D onto nanosized rice husk
was the result of a combination of film diffusion and intraparticle diffusion processes.
The Langmuir, Freundlich, Temkin, and DR isotherms were tested, and it was found that
the Langmuir model fitted best with the adsorption data, with the maximum adsorption
capacity of 24.75 mg g−1 (in 2,4-D nanoformulation preparation experiments). In the case
of the batch adsorption experiment, the Freundlich isotherm model was indicated as the
most suitable one, with KF = 8.7 (mg g−1 )(L mg−1 )1/n .
Okumuş et al. [40] investigated the potential of various bio-waste materials, including
apple shell (AS), orange peel (OP), banana peel (BP), and millet waste (MW), as adsor-
bents for the removal of 2,4-D, 2,4-DP (2,4-dichlorophenoxy propanoic acid), and 2,4-DB
(2,4-dichlorophenoxy butyric acid) from aqueous solutions. Batch adsorption experiments
were conducted to study the effect of different operational parameters, such as the pH of
the solution, the contact time, the adsorbent dosage, and the initial herbicide concentra-
tions. The results showed that the optimum pH for the adsorbent was 6–7 and that the
contact time was as short as 60 min for all of the adsorbates. The Langmuir and Freundlich
models were applied to describe the adsorption isotherm, and the data fitted well with
the Langmuir isotherms. The maximum adsorption capacity was obtained for 2,4-D as
OP > MW > BP > AS; 2,4-DP as MW > AS > BP > OP; and 2,4-DB as OP > AS > BP > MW.
A study by Al-Zaben and Mekhamer [41] describes the use of coffee waste to remove
MCPA from aqueous solutions. The effects of contact time, pH, and initial herbicide
concentration were studied. The adsorption kinetics were well described by the PSO kinetic
model, while the equilibrium results were better described by the Langmuir model. The
equilibrium adsorption capacity was found to be 340 mg g−1 , using the Langmuir equation.
Trivedi et al. [42] published a research article that presented data about the use of
cotton plant ash as a cheap adsorbent for the removal of 2,4-D. The BET surface area of
the material was found to be 2 m2 g−1 . The PFO, PSO, and Weber–Morris kinetic models
were applied to the experimental data, and the PSO equation showed the best fit for the
adsorption of 2,4-D. The equilibrium data were analyzed using Freundlich and Langmuir
adsorption isotherms, and these fit well with the Langmuir model. Langmuir’s adsorption
capacity was found to be 0.64 mg g−1 .
The same authors [43] evaluated mustard plant ash as an adsorbent for the removal
of 2,4-D from water. Optimum adsorption conditions were determined as a function of
the adsorbent dose, the initial 2,4-D concentration, the contact time, and the temperature.
Data from the experiments were fitted to various kinetic (PFO and PSO) and isothermal
(Langmuir, Freundlich, and Temkin) models. The PSO kinetic model was found to show
the best fit with the experimental data. The equilibrium data fitted best with the Langmuir
adsorption isotherm, which confirmed the monolayer adsorption (qm = 0.76 mg g−1 ).
Thermodynamic constants indicated the spontaneity, as well as the exothermic nature, and
irreversibility of the 2,4-D adsorption.
The next papers by this research team deal with the investigation of 2,4-D adsorption
by groundnut shell ash [44,45] and wheat straw ash [46]. The first of these works [44]
describes the herbicide adsorption of groundnut shell ash, with a BET surface area of
22 m2 g−1 . Batch adsorption experiments were conducted to study the effect of different
operational parameters, such as the adsorbent dosage, the contact time, and the initial ad-
sorbate concentration, on the adsorption process. The PSO model, as well as the Langmuir
adsorption isotherm model, showed the best fit with the experimental data. The maximum
uptake capacity of the ash was determined as 0.87 mg g−1 . The paper [45] describes the
preparation of three types of adsorbents produced using groundnut shells, namely ash,
biochar, and activated carbon, and their adsorption performance.
Wheat straw ash was characterized and tested as a 2,4-D adsorbent [46]. The BET
surface area of the material was found to be 37 m2 g−1 . The effects of different operational
parameters, such as the adsorbent dose, initial 2,4-D concentration, contact time, and pH,
Sustainability 2023, 15, 16516 6 of 33

were investigated. The experimental data were analyzed using the PFO and PSO kinetic
models, as well as the Freundlich, Langmuir, and Temkin isotherm models. The PSO and
Langmuir models showed the best fit with the experimental data. The adsorption capacity
was found to be 1.89 mg g−1 .
Recently, the adsorption of 2,4-D and ketoprofen by Physalis peruviana fruit residue
functionalized with sulfuric acid was reported by Dhaouadi et al. [47]. Adsorption
isotherms were determined at 298–328 K and pH 2. It was found that the adsorption
of 2,4-D by this biosorbent was multi-anchoring.
Peanut (Arachis hypogaea) skins treated with sulfuric acid were employed as an adsor-
bent for the removal of 2,4-D from aqueous solutions [48]. The results revealed that the
adsorption was favored at acid pH = 2, and the optimal adsorbent dosage was 0.9 g L−1 .
The equilibrium was reached quickly in the first 30 min, and the kinetics were well repre-
sented by the general order model. The Langmuir model was the one that obtained the
best fit with the experimental data. The adsorption capacity of the acid-treated peanut skin
towards 2,4-D was 246.72 mg g−1 .
In another work, wheat husks (Fagopyrum esculentum) modified using a treatment with
H2 SO4 were applied as an adsorbent to remove the 2,4-D herbicide from water [49]. The
kinetics, equilibrium, and thermodynamic behavior, as well as the pH effects and adsorbent
dosage, on the adsorption capacity were investigated. It was found that the Bangham
kinetic model better represented the experimental data, and that the maximum adsorption
capacity was 161.1 mg g−1 at 298 K. The thermodynamic studies indicated spontaneous,
favorable, and exothermic adsorption.
Recently, N-cetylpyridinium-modified tiger nut residue (TNR-CPC) as an adsorbent
was investigated by Kani et al. [50]. The results revealed that the solution pH, adsorbent
dose, temperature, and solution ionic strength affected the adsorptive capacity of TNR-CPC.
The adsorption kinetics followed the PSO model, while the equilibrium data were best
fitted to the Langmuir isotherm equation. The maximum monolayer adsorption capacity at
298 K was 79.3 mg g−1 .
Bartczak et al. [51] studied the use of saw-sedge Cladium mariscus (C. mariscus)
for the adsorption of 2,4-D from aqueous systems. The C. mariscus consisted of carbon
(48%), hydrogen (7%), nitrogen (0.95%), and sulfur (0.4%), and was characterized by a low
surface area (0.6 m2 g−1 ). It was found that the adsorption performance was dependent
on the following parameters: contact time, adsorbent mass, pH, and temperature of the
adsorption system. Maximum adsorption was attained at pH = 3 and T = 25 ◦ C, and
equaled 65.58 mg g−1 . The experimental data corresponded to the pseudo-second-order
kinetic model and the Langmuir isothermal model.
Recently, reports on the development and application of more advanced waste-based
materials with magnetic properties for the removal of 2,4-D were published [52,53]. Accord-
ing to the authors of the paper [52], the forming process of a biomass-MOF composite was
based on the loading of NH2 -MIL-101 (Fe) onto magnetized peanut husk. The adsorption
capacity of the composite for 2,4-D removal was found to be 79.2 mg g−1 according to the
Langmuir isotherm model, while the kinetics were very rapid (attaining equilibrium within
5 min) and followed the PFO and PSO models. The second advanced magnetic material, a
ferrospinel composite [53], was prepared based on activated carbon from lentil residues.
For the synthesis of activated carbon, microwave-assisted K2 CO3 chemical activation was
applied instead of conventional heating, as a faster and more economical method. The
analysis of the 2,4-D adsorption data indicated that the Langmuir model, with the max-
imum adsorption capacity of 400 mg g−1 at 45 ◦ C, and the pseudo-second-order model
were the most suitable models. The magnetic properties of both the MOF and ferrospinel
composites facilitated their separation from a purified medium.
Various unmodified and modified agricultural and household waste materials and
ashes, and their adsorption performance in regard to chlorophenoxy herbicides removal,
are summarized in Table 2. Additionally, the cost–benefit of the given adsorbents was
evaluated based on a comparison between their adsorption capacity towards chlorophe-
Sustainability 2023, 15, 16516 7 of 33

noxy herbicides and the synthesis cost, the impact of their production on the natural
environment (energy consumption, harmfulness of the reagents used, secondary waste),
and their recyclability. Such subjective evaluation is widely accepted and practiced by
many scientists [54,55].
To sum up, due to the variety of materials (i.e., pure agricultural and household waste,
physically or chemically modified materials, ashes, and advanced composite materials),
they show diversity in their biochemical composition, texture, chemical structure, and
surface chemistry. The majority of adsorbents have a non-porous structure and their
ability to bind herbicides from aqueous solutions is closely correlated with the presence
of various functional groups of natural origin, introduced on their surface during the
modification process, or resulting from the oxidation of mineral compounds during raw
material combustion. Ashes are characterized by the lowest adsorption capacity, ranging
from 0.64 to 1.89 mg g−1 and, therefore, their adsorption potential is considered secondary
to other functions they can perform in the economy and agriculture. First of all, the
generation of ash involves the use of waste with low moisture content as feedstock for
industrial boilers or home heating furnaces. Thus, the product obtained is not an end
in itself, but is a consequence of the functioning of the fuel economy. Due to its rich
composition of micronutrients, such as Ca, Mg, K, P, and Si, its high water capacity, and
its carbon sequestration capability, ash is considered a useful addition to soil, improving
its fertility. Moreover, ash after being spread on fields plays a protective role for the
soil, as it adsorbs herbicides. The adsorption is relatively low, but equilibrium is reached
almost instantly.
The adsorption capacities of unmodified, physically modified, and chemically modified
materials are in the range of 22.71–340 mg g−1 , 24.75–76.92 mg g−1 , and 79.3–246.7 mg g−1 ,
respectively. Taking into account the simplicity and low cost of production of these adsor-
bents, or even the possibility of using some waste in an unprocessed form, these results
seem to be promising.
Regarding magnetic composite materials, their adsorption capacities are equal to
79.2–400 mg g−1 . The great advantage of these adsorbents is the ease of their separation,
from the medium subjected to purification, using an external magnet.

Table 2. The results from chlorophenoxy herbicides adsorption studies on unmodified adsorbents,
modified adsorbents, and ashes based on agricultural and household waste.

Adsorption Capacity
(qm ) mg g−1 Isotherm Kinetic Integral
Adsorbent SBET m2 g−1 Ref.
Model Model Cost–Benefit
2,4-D MCPA
Rice husk ash 34 1.425 - L, F, Te PFO, PSO, E Low [35]
Rice husk ash 34 - 1.681 L, F, Te PFO, PSO, E Low [37]
PFO, PSO,
Nanosized rice husk - 24.75 - L, F, Te, DR Medium [36]
W-M
PFO, PSO,
Nanosized rice husk - 76.92 - L, F, Te, DR Medium [39]
W-M
PFO, PSO,
Cotton plant ash 2 0.64 - L, F Low [42]
W-M
Mustard plant ash - 0.76 - L, F, Te PFO, PSO Low [43]
Groundnut shell ash 22 0.87 - L, F, Te PFO, PSO Low [44]
Groundnut shell ash 8 0.87 - L, F, Te PFO, PSO Low [45]
Wheat straw ash 37 1.89 - L, F, Te PFO, PSO Low [46]
Functionalized Physalis
- 233.3 - ITM - High [47]
peruviana biomass
Sustainability 2023, 15, 16516 8 of 33

Table 2. Cont.

Adsorption Capacity
(qm ) mg g−1 Isotherm Kinetic Integral
Adsorbent SBET m2 g−1 Ref.
Model Model Cost–Benefit
2,4-D MCPA
Acid-treated peanut skin - 246.7 - L, F, Te, DR PFO, PSO, E High [48]
Apple shell - 40.08 - L, F Contact time Medium [40]
Orange peel - 22.71 - L, F Contact time Medium [40]
Banana peel - 33.26 - L, F Contact time Medium [40]
Millet waste - 45.45 - L, F Contact time Medium [40]
Coffee wastes - - 340.0 L, F PFO, PSO High [41]
N-cetylpyridinium-
PFO, PSO, E,
modified tiger 0.03 79.3 - L, F, K-C Medium [50]
W-M
nut residue
H2 SO4 -modified
- 161.1 - L, F Ba High [49]
wheat husks
Saw-sedge Cladium
0.6 65.58 - L, F PFO, PSO Medium [51]
mariscus
Biomass-based
71 79.2 - L, F, Te, K-C PFO, PSO Medium [52]
MOF composite
Biomass-based PFO, PSO,
528 400 - L, F High [53]
ferrospinel composite W-M

2.2. Biochars
Biochar is a solid product that can be obtained from the thermal degradation of agri-
cultural and household waste under oxygen-limited conditions (pyrolysis process). Biochar
is generated from the part of biomass that has already been used in human activities and is
problematic for society due to the need for storage and the putrefaction that occurs within
it, which may lead to the uncontrolled emission of greenhouse gases. The physicochemical
properties of biochar greatly depend on various parameters, such as the biomass type,
pyrolysis temperature and duration, pyrolysis procedure, and post-treatment processes. It
is generally assumed that biochar is produced at low temperatures, but in practice a wide
temperature range of 200–800 ◦ C has been used. In the course of biochar production, the
volatile constituents and tar existing in the biomass are emitted and, as a result, a porous
structure in the final product is formed. The development of the porous structure is visible
in the specific increase in the surface area of the biochar by up to several folds compared to
that of ashes. The physicochemical properties of the final product determine its suitability
for specific applications. From the perspective of the utilization of biochar as an adsorbent,
a high capacity towards pollutants, fast adsorption kinetics, and low reversibility of the
adsorption process are the most desirable features. In recent years, several studies in the
scientific literature have dealt with the production of designed biochars suitable for the
adsorption of various organic pollutants, including phenoxyacetic herbicides.
Mandal et al. [56] studied the adsorption process of 2,4-D by biochars produced from
various green wastes, namely tea (TW), oak wood (OW), bamboo (B), and bur cucumber
(BU), at two pyrolytic temperatures (400 and 700 ◦ C). The specific surface area of the
TW, OW, BU, and B biochars was 421.3, 270.7, 475.6, and 2.3 m2 g−1 , respectively. The
experimental data were fitted using the Langmuir and Freundlich isotherm models, as well
as the PFO, PSO, and Elovich kinetic models. The kinetics of the 2,4-D adsorption was best
described by the PSO kinetic model, and the adsorption equilibrium data were successfully
fitted to both the Langmuir and Freundlich equations. The maximum adsorption capacity
was 10.05, 42.67, 26.66, and 28.92 mg g−1 for TW, BU, OW, and B biochars, respectively.
Sustainability 2023, 15, 16516 9 of 33

A carbonized chestnut shell was used for the removal of 2,4-D from water [57]. The
surface area of the carbonized adsorbent was 280.4 m2 g−1 . The adsorption equilibrium
was achieved in 250 min, and the kinetics followed the PFO model. The experimental
data were modeled using the Langmuir, Freundlich, Temkin, and Dubinin–Radushkevich
equations. The Temkin isotherm model represented the adsorption phenomenon very well,
at all the temperatures studied (at 35, 45, and 55 ◦ C). Langmuir’s maximum adsorption of
2,4-D was 0.93 mg g−1 .
Biochars generated from corncobs, bamboo, wood chips, and rice straw were tested as
adsorbents for the removal of 2,4-D from aqueous solutions [58]. Various pyrolysis condi-
tions, including the pyrolysis time and temperature (400–700 ◦ C), were investigated. The
highest BET surface area was 389 m2 g−1 (700 ◦ C) for the wood chips biochar, 510 m2 g−1
(700 ◦ C) for the bamboo biochar, 128 m2 g−1 (500 ◦ C) for the rice straw biochar, and
2.3 m2 g−1 (600 ◦ C) for the corncobs biochar. The Freundlich KF adsorption parameters
were 8.72, 19.5, 1.23, and 1.06 (mg g−1 )(L mg−1 )1/n , respectively.
The corncob biochar was synthesized at 600 ◦ C for 4 h, as a low-cost adsorbent for the
removal of 2,4-D from water [59]. The specific surface area of the biochar was 298 m2 g−1 .
It was found that the pH was a key factor for 2,4-D removal by the corncob biochar. The
experimental adsorption data followed the PSO model and the Langmuir isotherm, with a
maximum adsorption capacity of 37.40 mg g−1 .
A study by Essandoh et al. [60] describes the preparation of biochar from switchgrass
(Panicum virgatum). The BET surface area of the biochar was found to be 1.1 m2 g−1 . Kinetic
and adsorption isotherm studies for 2,4-D and MCPA were conducted. The PSO model was
superior to the PFO kinetic model for both 2,4-D and MCPA. The adsorption isotherms were
described by the Freundlich, Langmuir, Toth, and Redlich–Peterson models. In general,
all the theoretical isotherm equations provided reasonable fits with the experimental data;
however, the highest overall regression coefficients belonged to the data fitted to the
Freundlich model (in the case of 2,4-D) and the Redlich–Peterson model (in the case of
MCPA). The maximum adsorption capacity for 2,4-D and MCPA was 134 mg g−1 and
50 mg g−1 , respectively.
A series of biochars were produced from softwood shavings (WS), pig manure
(PM), and sewage sludge (SS), under various conditions (with an initial heating rate
of 25 ◦ C min−1 up to 200 ◦ C, 350 ◦ C, and 500 ◦ C, maintained for 4 h) [61]. The specific
surface area ranged from 4 to 347 m2 g−1 for the WS, from 2 to 27 m2 g−1 for the PM, and
11 to 43 m2 g−1 for the SS. The biochars were examined as potential adsorbents for the
removal of 2,4-D, MCPA, 2,4-DB (4-(2,4-dichlorophenoxy)-butanoic acid), and triclosan
(5-chloro-2-(2,4-dichlorophenoxy)phenol) from an aqueous solution. The Freundlich model
fitted the adsorption isotherm of the biochars very well. The results revealed that the
adsorption increased in the order: 2,4-D < MCPA < 2,4-DB < triclosan.
Biochars produced by slow pyrolysis from a mixture of about 80% birchwood
(Betula sp.) and 20% Norway spruce wood (Picea abies) were tested in batch [62] and
column [63] studies. The wood-based biochar was additionally modified by a heat treat-
ment and by an iron salts treatment [62]. The BET surface area of the untreated biochar,
heated biochar, and biochar treated with iron salts was 74, 116, and 59 m2 g−1 , respec-
tively. These materials were used for the adsorptive removal of five pesticides, including
bentazone, chlorpyrifos, diuron, glyphosate, and MCPA, from aqueous solutions. The
experimental data were modelled using the Freundlich isotherm model, and the KF values
decreased in the order: diuron > chlorpyrifos > MCPA > bentazone > glyphosate. The
results showed that heat treatment increased the adsorption of bentazone and MCPA, while
iron salts treatment increased the adsorption of glyphosate.
The Liu research group [64] studied the adsorption performance of hydrochars (HCs)
prepared by the hydrothermal carbonization (HTC) of lettuce waste (LHC), taro waste (THC),
and watermelon peel (WHC) in low-temperature conditions (180–240 ◦ C). The determined
adsorption capacities of the HCs were hydrochar precursor and HTC temperature depen-
dent. The greatest capacities of LHC180 (88.4 mg g−1 ), THC180 (90.2 mg g−1 ), and WHC240
Sustainability 2023, 15, 16516 10 of 33

(88.4 mg g−1 ) for 2,4-D removal were achieved at HTC temperatures of 180, 180, and 240 ◦ C,
respectively. It was found that such hydrochar properties as a well-developed surface area
with small mesopores, low aromaticity, and a high amount of C–O functional groups, favored
herbicide adsorption via intensive partitioning and/or chemisorption. The pseudo-second-
order model fitted the 2,4-D adsorption data better than the pseudo-first-order model.
A series of biochars based on water lettuce (WL), water hyacinth (WH), wheat bran
(WB), pinewood sawdust (PS), and oak tree wood biomass (OTW), was fabricated via
pyrolysis at 500 ◦ C [65]. The adsorption performance was found to be in the following
order: PS (62.53%) > OTW (53.24%) > WB (46.56%) > WH (33.54%) > WL (28.25%).
Ma et al. [66] and Almahri et al. [67] studied spent coffee ground biochars as adsorbents
for the removal of 2,4-D from aqueous solutions. Ma et al. [66] obtained the char via low-
temperature pyrolysis (300 ◦ C) and impregnation with H3 PO4 as a pre-treatment stage.
The best kinetic and isotherm fits were found for the Elovich and Freundlich equations,
respectively. It was shown that the adsorption efficiency diminishes with a rising pH, and
the highest efficiency was achieved at a pH of 2. The maximum adsorption capacity of
biochar was reported as 323.76 mg g−1 . The thermodynamic studies pointed out that the
adsorption process was exothermic. Almahri et al. [67] synthetized biochar by biomass
pyrolysis at 700 ◦ C in a neutral atmosphere, followed by the transfer to a steam atmosphere.
The surface area and pore volume of the biochar reached 422.4 m2 g−1 and 0.46 cm2 g−1 ,
respectively. The results showed that the adsorption behavior was significantly impacted
by changes in the solution pH. The pH value of 6 was indicated as the most beneficial to the
adsorption process (qm = 276.3 mg g−1 ). The thermodynamic parameters were determined
and revealed that the process was endothermic, chemisorptive, and spontaneous. The
adsorption process was best fitted to the Langmuir isotherm model and the pseudo-second-
order kinetic model.
In the subsequent works [68,69], the adsorption of 2,4-D by rice husk biochar from
synthetic wastewater and drainage water was studied. Of the various operating parameters,
the initial adsorbate concentration and adsorbent dosage were indicated as those that had
the greatest impact on the adsorption capacity. The highest efficiency of biochar in 2,4-D
removal was achieved at a pH of 5.5, a contact time of 80 min, a temperature of 60 ◦ C,
an adsorbent dose of 0.2 g, and an initial solution concentration of 60 mg L−1 . The PFO
and PSO kinetic models, as well as the Langmuir, Freundlich, Langmuir–Freundlich, and
Redlich–Peterson isotherms, were tested. The pseudo-first-order model and Freundlich
equations were chosen as those that best described the adsorption process. The maximum
adsorption capacity of 2,4-D by rice husk biochar equaled 246 mg g−1 . Regarding ther-
modynamics, the adsorption process was exothermic and spontaneous. The adsorption
potential of the biochar was also evaluated with other materials, e.g., granular activated
carbon (GAC) and multi-walled carbon nanotubes (MWCNTs). The maximum adsorption
capacities of the chars were lower than the GAC, but higher than the MWCNTs. However,
in terms of the herbicide removal dynamics, the adsorption process required the longest
time to reach an equilibrium state.
A study by Zhu et al. [70] describes the effect of various modifications of corn stalk
biochar (BC) on the adsorption properties of the obtained materials. The applied modifica-
tions involved activation of the BC with potassium carbonate (KBC), followed by surface
oxidation (OKBC), surface amination (NKBC), loading nano-zero valent iron (nZVI@KBC),
and loading nano-iron oxyhydroxide (nHIO@KBC), respectively. The biochars exhibited
the following order towards 2,4-D adsorption capacity: NKBC > KBC > OKBC > BC >
nHIO@KBC > nZVI@KBC. It was shown that a well-developed specific surface area of
the adsorbent was not the only factor determining the adsorption capacity. The surface
properties of the adsorbent, such as the polarity, hydrophobicity, and surface functional
groups, are equally important factors. The activation of the biochar structure with potas-
sium carbonate, surface amination, or surface oxidation, made it more suitable for 2,4-D
adsorption in comparison with unmodified char, while the surface loading of nanometal
and nanometal oxyhydroxide made the biochar worse regarding its adsorbency.
Sustainability 2023, 15, 16516 11 of 33

Kearns et al. [71,72] tested the usefulness of biochars generated from updraft gasifiers,
under conditions of simultaneous co-pyrolysis thermal air activation (CPTA), on the ad-
sorption of 2,4-D and simazine from surface water containing dissolved organic matter.
Cherry pits, Jatropha press-cake waste, sugarcane bagasse pellets, pecan shells, bamboo,
pine, eucalyptus, and longan wood, were used as raw materials. Enhanced adsorption
capabilities of the as-received chars by about one order of magnitude, compared to con-
ventional anoxic pyrolysis (CAP) biochars, were observed. Applying a high-temperature
synthesis mode combined with CPTA conditions resulted in biochars with a specific surface
area and mesopore surface area of 330 and 110 m2 g−1 , respectively. Such characteristics
of the final product were related to the thermochemical widening of the pores and/or the
removal of the pyrolysis tars from its structure. Increasing the pyrolysis temperature or
process duration during the biochar synthesis procedure, conducted by using a horizontal
drum kiln, increased the 2,4-D adsorption capacity of the biochar, whereas the type of
feedstock did not affect it.
The removal of 2,4-D and carbofuran from water by biochars obtained from agricul-
tural by-products, i.e., rice husk (RH), corn stover (CS), corncob (CC), and sorghum stems
(SS), was studied as a function of pH [73]. It was shown that the greatest efficiency in
herbicide removal was obtained at pH = 6. The equilibrium adsorption capacities of these
biochars for 2,4-D were found to be 0.64, 0.76, 0.81, and 0.71 mg g−1 for RH, CS, CC, and
SS, respectively.
Evaluation of the impact of the physicochemical properties of a high-temperature
wheat straw biochar on its adsorption behavior related to various pesticides (2,4-D, MCPA,
metolachlor, carbaryl, and carbofuran) was the research theme of Ćwielag-Piasecka
˛ et al. [74].
The obtained adsorbent was characterized by a surface area of 237.39 m2 g−1 . The adsorp-
tion affinity of the biochar to the pesticides decreased in the order: carbofuran > carbaryl >
metolachlor > 2,4-D > MCPA. The relatively low adsorption capability of the biochar for
chlorophenoxy acids was ascribed to the electrostatic attraction between the herbicides
and the polar functional groups on the BC surface, or to a nonspecific interaction with the
adsorbate. Hydrophobic interaction was postulated as the main mechanism of pesticide
adsorption by the BC.
Lü et al. [75] tested the use of rice straw biochars made by slow pyrolysis at 200 ◦ C
(RS200), 350 ◦ C (RS350), and 500 ◦ C (RS500), for the regulation on the release and leaching
of acetochlor and 2,4-D in soils. Part of the research concerned the equilibrium adsorption
of herbicides by biochars differentiated in structure (SBET = 2.1, 20.6, and 128 m2 g−1 ,
respectively), the elemental composition, and ash residue. The Freundlich KF adsorption
parameters for the adsorption of 2,4-D were 0.206, 4.48 and 3.24 (mg−1 )(L mg−1 )1/n by
RS200, RS350, and RS500 biochars, respectively. The lower adsorption capacity of RS500
than RS350, despite its more developed surface area, was explained by the high content of
stable minerals (ash), accounting for nearly one-half of the mass of the sample.
Trivedi et al. [42,45,46] used the cotton plant biochar (SBET = 109 m2 g−1 ), groundnut
shells biochar (SBET = 43 m2 g−1 ), and wheat straw biochar (SBET = 96 m2 g−1 ), for the
removal of 2,4-D. The experimental adsorption data for the studied biochars followed the
PSO model and the Langmuir isotherm, with a qm that equaled 3.93, 3.02, and 2.02 mg g−1 .
Table 3 shows some of the adsorption capacities of the biochars reported in the literature.
Most of the pristine biochars synthetized through pyrolysis under a neutral atmo-
sphere are characterized by a relatively small surface area (~1–400 m2 g−1 ), an undeveloped
pores structure, and a limited amount of surface functional groups. Only a few biochars
have a more extensive network of internal pores, translating into surface areas in the
range of 400–523 m2 g−1 . However, the more developed pores’ structure in a solid does
not always guarantee its ability to adsorb chlorophenoxy acids from aqueous solutions.
There are also biochars with a poor pores’ structure that exhibit relatively high adsorption
capacities for these pollutants. Noteworthy are the hydrochars whose adsorption capacity
towards 2,4-D results mainly from the surface chemistry of the solid and to a lesser extent
from its porosity. It has been found that the greater the aromaticity, the oxygen-containing
Sustainability 2023, 15, 16516 12 of 33

surface functional groups (e.g., phenolic, carboxyl, hydroxyls), and the lower the content of
ash in the biochar, improves its adsorption ability. These solid features, in turn, depend
on various factors, such as the type of raw material, the synthesis parameters, the furnace
characteristics, and the post-synthesis treatments.
To enhance the applicability of biochars in removing chlorophenoxy herbicides from
aqueous solutions, they were subjected to structural activation or surface modification.
Structural activation was carried out using: (i) specialized equipment, e.g., an updraft
gasifier working under conditions of simultaneous co-pyrolysis and thermal air activation,
(ii) gases, or (iii) chemicals. Regarding surface modification of biochars, the processes
of amination and oxidation brought satisfactory results. In our opinion, the structural
activation of biochar using a steam atmosphere or potassium carbonate leads to a change
in the classification of the final product from biochar to activated carbon, but they have
been left in this subsection based on the nomenclature given by the researchers.
Some biochars exhibit adsorption capacities comparable to waste-based activated
carbons (see the subsection below), but their production is low cost and does not use
harmful chemicals, so it can be concluded that these materials are competitors to activated
carbons in regard to the adsorption techniques for removing phenoxyacetic herbicides from
water and wastewater.
In the case of those biochars that show relatively low adsorption capacity towards
herbicides, they may be suitable materials for the prevention of herbicide leaking and
mobility in soil profiles if they are applied as a soil amendment. Moreover, biochars have
great potential for the improvement of soil properties, such as increasing the pH, nutrient
availability, and water retention. These filter materials could be applied in farm fields, as
well as in agricultural ditches, drainage systems, and places accidentally contaminated
with chlorophenoxy herbicides. Mitigating climate change is the secondary environmental
benefit of biochar soil amendment associated with carbon sequestration.

Table 3. The results from chlorophenoxy herbicides adsorption studies on biochars.

Adsorption Capacity
Adsorbent SBET m2 g−1 (qm ) mg g−1 Isotherm Kinetic Integral
Ref.
Model Model Cost–Benefit
2,4-D MCPA
PFO, PSO,
Cotton plant biochar 109 3.93 - L, F Low [42]
W-M
Groundnut shell biochar 43 3.02 - L, F, Te PFO, PSO Low [45]
Wheat straw biochar 96 2.02 - L, F, Te PFO, PSO Low [46]
Tea waste biochar 421 10.05 - L, F PFO, PSO, E Low [56]
Oak wood biochar 271 26.66 - L, F PFO, PSO, E Medium [56]
Bamboo biochar 476 28.92 - L, F PFO, PSO, E Medium [56]
Bur cucumber biochar 2.3 42.67 - L, F PFO, PSO, E Medium [56]
PFO, PSO,
Carbonized chestnut shell 280 0.93 - L, F, Te, DR Low [57]
W-M
Corncob biochar 298 37.40 - L, F PFO, PSO Medium [59]
Switchgrass biochar 1.10 134 50 L, F, To, DR PFO, PSO High [60]
Lettuce waste hydrochar
6.28 88.4 - - PFO, PSO Medium [64]
(LHC180 )
Lettuce waste hydrochar
6.90 80.0 - - - Medium [64]
(LHC200 )
Lettuce waste hydrochar
6.47 80.9 - - - Medium [64]
(LHC220 )
Sustainability 2023, 15, 16516 13 of 33

Table 3. Cont.

Adsorption Capacity
Adsorbent SBET m2 g−1 (qm ) mg g−1 Isotherm Kinetic Integral
Ref.
Model Model Cost–Benefit
2,4-D MCPA
Lettuce waste hydrochar
3.67 77.4 - - - Medium [64]
(LHC240 )
Taro waste hydrochar
9.23 90.2 - - - Medium [64]
(THC180 )
Taro waste hydrochar
2.51 35.5 - - - Medium [64]
(THC200 )
Taro waste hydrochar
3.12 47.5 - - - Medium [64]
(THC220 )
Taro waste hydrochar
0.68 33.6 - - - Medium [64]
(THC240 )
Watermelon peel
3.29 45.7 - - - Medium [64]
hydrochar (WHC180 )
Watermelon peel
5.82 59.7 - - - Medium [64]
hydrochar (WHC200 )
Watermelon peel
8.45 64.0 - - - Medium [64]
hydrochar (WHC220 )
Watermelon peel
5.99 88.4 - - - Medium [64]
hydrochar (WHC240 )
Coffee ground biochar 82 323.76 - L, F PFO, PSO, E High [66]
Water lettuce biochar - 84.79 - L - Medium [65]
Water hyacinth biochar - 100.62 - L - High [65]
Wheat bran biochar - 139.69 - L - High [65]
Pinewood sawdust
- 187.60 - L - High [65]
biochar
Oak tree wood biochar - 159.69 - L - High [65]
L, F, Te, DR, J, PFO, PSO, E,
Coffee ground biochar 422.4 276.3 - High [67]
K, Hi, S IDM, A
Rice husk biochar 320 246 - L, F, L-F, R-P PFO, PSO High [68,69]
Corn stalk biochar (BC) 523 8.54 - L, F - Low [70]
Modified corn stalk
680 19.8 - L, F - Low [70]
biochar (KBC)
Modified corn stalk
290 12.87 - L, F - Low [70]
biochar (OKBC)
Modified corn stalk
691 22.84 - L, F - Medium [70]
biochar (NKBC)
Modified corn stalk
179 3.03 - L, F - Low [70]
biochar (nZVI@KBC)
Modified corn stalk
272 6.53 - L, F - Low [70]
biochar (nHIO@KBC)
Rice husk biochar - 0.64 - - - Low [73]
Corn stover biochar - 0.76 - - - Low [73]
Corncob biochar - 0.81 - - - Low [73]
Sorghum stem biochar - 0.71 - - - Low [73]
Sustainability 2023, 15, 16516 14 of 33

2.3. Activated Carbons

Activated carbons are another group of adsorbents that can be obtained from agri-
cultural and household waste and used for the removal of phenoxyacetic herbicides from
water. Activated carbon synthesis involves two main stages: the carbonization of the raw
material at temperatures below 800 ◦ C in an inert atmosphere and the activation of the
carbonized product (char). The latter stage is carried out by physical and/or chemical acti-
vation. Physical activation is based on the char treatment, with oxidizing gases at elevated
temperatures. During this process, the char is partially gasified leading to the development
of the internal surface of the solid. Chemical activation is based on the mixing of the raw
material with a chemical reagent, i.e., oxidizing acid, salt solution, or alkali followed by
heat treatment. The mechanism of chemical activation depends on the activating agent
used and, in some cases, is very complex. Depending on the type of raw material, the
activating agent, and the conditions of carbonization and activation processes, activated
carbons may be characterized by various pore structures, surface chemistry, and adsorption
properties towards specific pollutants.
The agricultural and household waste-based activated carbons presented in this sub-
section, as potential adsorbents for the water treatment of phenoxyacetic herbicides, were
divided into groups depending on the type of activation process used. Among the physical
activating agents, steam (ST) and carbon dioxide (CD) are the most popular; however,
mixtures of these agents and microwave radiation (MV) are occasionally used. In one
case, the activation process followed the self-activation mode, where various gases like
CO, CH4 , H2 , CO2 , and H2 O, emitted during the biomass pyrolysis, were activating agents.
Regarding chemical activation, the leading activating agents were zinc chloride (ZnCl2 ),
followed by potassium hydroxide (KOH), orthophosphoric acid (H3 PO4 ), sulfuric acid
(H2 SO4 ), a combination of different chemical activating agents (H2 SO4 and KOH; KOH
and Fe3 O4 ), or a combination of chemical and physical activating agents (KOH and CO2 ).

2.3.1. Activated Carbons Based on Physical Activation

Activated carbon produced from Lagenaria vulgaris shell by thermo-chemical carboniza-
tion and steam activation was applied to the removal of 2,4-D from aqueous solutions
by Bojić et al. [76]. The BET of the as-prepared AC was found to be 665 m2 g−1 . The
equilibrium data were fitted to the Langmuir, Freundlich, Sips, and Brouers–Sotolongo
models, and the maximum adsorption capacity was 333.3 mg g−1 . The thermodynamic
data showed that the adsorption was endothermic, spontaneous, and physical.
Brito et al. [77] evaluated the removal efficiency of 2,4-D from water by three ACs from
agricultural biomass waste. These materials were prepared using the one-step carboniza-
tion/physical activation route, using steam at 800 ◦ C under an argon atmosphere, from
sugarcane bagasse, coconut shell, and endocarp from babassu coconut. The BET surface
areas of the ACs were 547, 991, and 1068 m2 g−1 , respectively. The adsorption process for
2,4-D was investigated using the Langmuir, Freundlich, Redlich–Peterson, Temkin, and
Dubinin–Radushkevich isotherm models. The results revealed that the Langmuir and R-P
equations best described the adsorption process. The adsorption kinetics were described
well by the PSO model, and the thermodynamic data indicated the spontaneous nature of
the adsorption process.
Amiri et al. [78] investigated the potential of activated carbon derived from canola
stalk as an adsorbent for 2,4-D removal from water. The AC was synthesized via the
physical activation of the canola stalk biochar by steam, and its BET surface area was
556.8 m2 g−1 . According to the authors, the maximum amount of 2,4-D removal was
achieved as 135.8 mg g−1 under a pH of 2 and an initial herbicide concentration of
150 mg g−1 . The particle diffusion model was the best-fitting kinetic model for the
2,4-D adsorption.
Mandal et al. [56] studied the adsorption process for 2,4-D using activated carbon
produced from tea biochar, through activation with steam. The specific surface area of the
material was 576 m2 g−1 . The herbicide adsorption followed the PSO kinetic model, and
Sustainability 2023, 15, 16516 15 of 33

the adsorption equilibrium data were successfully fitted to the Langmuir equation, with a
maximum adsorption capacity of 58.8 mg g−1 .
Orduz et al. [79] investigated the 2,4-D adsorption by activated carbon from peanut
shells (steam activation, SBET = 1240 m2 g−1 ) in aqueous and organic solvents. The pollutant
desorption kinetics and the application of the AC as a filler in a solid-phase extraction
procedure (SPE) were presented. It was stated that the pollutant affinity towards the
AC was higher in aqueous solvents than in organic ones (acetonitrile and methanol),
with q = 549 mg g−1 (F). The 2,4-D desorption process was the most effective in methanol
(regarding the pollutant amount and desorption rate); mini columns filled with AC were
characterized by high reuse capacity.
Cansado et al. [80] obtained activated carbons based on Tectona grandis tree sawdust us-
ing physical activation with carbon dioxide at 973 K and different activation times, e.g., 360
and 480 min for Teak-7360 and Teak-7480, respectively. The adsorbents were characterized
by high values for the specific surface area (787 and 910 m2 g−1 ) and were applied for
the removal of MCPA during the liquid phase. The adsorption capacity of Teak-7360 and
Teak-7480 was found to be 212.7 and 313 mg g−1 , respectively. The herbicide adsorption
experimental data were optimized using the Langmuir and Freundlich equations.
The same gaseous activating agent in the production of activated carbons, based
on wood waste from Angola, was used by Tchikuala et al. [81]. The activation time and
carbon precursor were variable synthesis factors. It was stated that the values of MCPA
adsorption (85–295 mg g−1 ) correlated with the degree of development of the activated
carbons’ specific surface area (603–838 m2 g−1 ).
Blachnio et al. [82] used pistachio shells for the preparation of activated carbons
through physical activation using carbon dioxide; steam and carbon dioxide; and carbon
dioxide and microwave radiation. The obtained activated carbons were characterized
by high values for the specific surface area (556–685 m2 g−1 ) and were utilized for the
removal of the model organic pollutants from the single- and multi-component systems.
The adsorption capacities for MCPA removal were equal to 314–288.9 mg g−1 (the general
Langmuir isotherm model). A slight effect of the crystal violet presence on the MCPA
adsorption and the inverse of this was noticed as a result of the adsorption by different
types of pores. For similar herbicides (MCPA and 2,4-D), strong competition in the capacity
and adsorption rate was observed.
The paper [83] describes the results from the conversion of soybean residues via
one-step microwave irradiation (SBET = 1696 m2 g−1 ) and its application for the removal of
2,4-D from aqueous solutions. The equilibrium uptake was analyzed using the Langmuir,
Freundlich, and Temkin isotherms, with the Freundlich equation indicated as the best
one (q = 253.17 mg g−1 ). In addition to the adsorptive properties, the adsorbent showed
antibacterial and antifungal activity.
Gurav et al. [65] fabricated a self-activated carbon from Pinus taeda wood by utilizing
gases released during the biomass pyrolysis process. The as-received adsorbent with a
well-developed surface area (SBET = 1450 m2 g−1 ) was applied for 2,4-D removal during
the aqueous phase. At pH = 2, the maximum adsorption capacity reached 471.70 mg g−1
(the Langmuir model). The adsorption kinetics obeyed the pseudo-second-order model.
The effect of natural organic matter and salinity on 2,4-D removal was also tested. The
reusability studies on self-activated carbon revealed outstanding performance in up to
seven adsorption–regeneration cycles.

2.3.2. Activated Carbons Based on Chemical Activation

Activated carbon from sesame seeds was prepared by ZnCl2 activation and its adsorp-
tion capacity for 2,4-D in aqueous solutions was investigated [84]. The effect of varying
parameters (pH, temperature, adsorbent dose, and contact time) was also studied. The ad-
sorption kinetics followed the PSO kinetic model. The Freundlich and DR models described
the adsorption at equilibrium well.
Sustainability 2023, 15, 16516 16 of 33

In a study by Angin and Ilci [85], activated carbon was prepared from olive-waste
cake by chemical activation using ZnCl2 and used for 2,4-D removal. The results revealed
that the adsorption kinetics and adsorption isotherms were described well by the PSO
kinetic model and the Langmuir isotherm equation, respectively. The maximum adsorption
capacity, based on the Langmuir model, was found to be 129.9 mg g−1 . The thermodynamic
data indicated that the adsorption process was feasible, spontaneous, and exothermic.
The removal of 2,4-D from water using AC prepared from queen palm endocarp
(Syagrus romanzoffiana) by pyrolysis with ZnCl2 activation was also reported [86]. In
that investigation, the influence of the initial pH, the adsorbent dose, the initial 2,4-D
concentration, and the temperature on the adsorption was evaluated. The adsorption
kinetic study indicated that the process reached equilibrium at 180 min and followed the
PSO model. The equilibrium data were analyzed using the Langmuir, Freundlich, Temkin,
and Dubinin–Radushkevich isotherm equations. The results showed that the adsorption
isotherms were well described by the Langmuir equilibrium isotherm equation, and the
calculated monolayer adsorption capacity was 367.8 mg g−1 . The thermodynamic data
indicated that the adsorption process was spontaneous and endothermic.
A recent study by Angın and Güneş [87] describes the preparation of activated carbon
from orange (Citrus sinensis L.) pulp by chemical activation with zinc chloride. The AC was
characterized and then used as an adsorbent for 2,4-D removal from an aqueous solution.
The effects of the adsorbent dosage, the contact time, the initial concentration of 2,4-D, the
temperature, and the pH, on the adsorption were studied. The PSO, PFO, and intra-particle
diffusion kinetic models were tested with the experimental data, and the PSO kinetics
model was the best fit for the adsorption of 2,4-D by the orange pulp-derived AC. The
experimental data were analyzed by the Langmuir, Freundlich, Temkin, and Dubinin–
Radushkevich isotherm models. The equilibrium data fitted well with the Langmuir model,
with a maximum adsorption capacity of 71.9 mg g−1 . The thermodynamic parameters
indicated feasible, spontaneous, and exothermic adsorption.
Boumaraf et al. [88] reported the synthesis, characterization, and applicability of acti-
vated carbon from Elaeagnus angustifolia seeds using ZnCl2 activation. The influence of the
operating parameters (solid dose, contact time, stirring speed, and pH) on 2,4-D adsorption
was investigated. The adsorption process was spontaneous and exothermic, and obeyed
the Langmuir and the pseudo-second-order models. The maximum adsorption capacity
equaled 189 mg g−1 . Satisfactory results from the application of AC for the elimination of
2,4-D from environmental waters (Algerian dam waters) synthetically polluted with 2,4-D
were obtained (efficiency of 96%).
The same chemical activating agent (zinc chloride) was used to develop mushroom
residues-based activated carbons for the removal of 2,4-D [89]. The differentiation in the
pyrolysis temperature (400 and 500 ◦ C) resulted in various values of SBET of the adsor-
bents (1067 and 799 m2 g−1 ) and of the adsorption capacity for the herbicide (105.4 and
118.2 mg g−1 , respectively). The maximum adsorption capacity of carbon pyrolyzed in
higher temperatures equaled 241.7 mg g−1 (pH = 4). The adsorption data were best de-
scribed using the Langmuir and the linear driving force (LDF) models. It was shown that
the use of the adsorbent resulted in a high degree of herbicide removal (70%) from the river
water solution and, after the regeneration process, it was retained with high efficiency until
the ninth cycle of reuse.
The elimination of 2,4-D and MCPA from an aqueous solution by activated carbons
from rice straw in a batch system was investigated [90]. The ACs were prepared by
chemical activation with ZnCl2 and H3 PO4 , and their surface area was 771 and 613 m2 g−1 ,
respectively. The adsorption kinetics was described well by the PSO model, while the
adsorption isotherms were well fitted to the Langmuir model. The adsorption capacity of
both the ACs for MCPA removal was greater than for 2,4-D.
Activated carbon from an oil palm trunk was fabricated via a chemical activation route
using H3 PO4 to test its ability to remove 2,4-D from aqueous solutions [91]. The effects of
the pH, the temperature, the initial adsorbate concentration, and the contact time, on the
Sustainability 2023, 15, 16516 17 of 33

adsorption process were investigated. The highest removal efficiency was obtained at pH 2.
The adsorption efficiency decreased as the temperature increased. The Langmuir isotherm
model and the PSO kinetic model showed a better correlation with the experimental data.
The monolayer maximum adsorption capacity was found to be 420.4 mg g−1 at 25 ◦ C.
The activated carbon prepared from peanut shells by chemical activation with H3 PO4
was tested as an adsorbent for 2,4-D removal from water [92]. Adsorption experiments for
2,4-D removal were performed via a batch system, in which the effects of the initial 2,4-D
concentration, the adsorbent dose, the contact time, the pH, and the temperature were
studied. Moreover, the influence of the simultaneous presence of inorganic salts and humic
acid on the adsorption process was also investigated. The kinetic results yielded well to the
PSO model. The adsorption equilibrium was best fitted to the Langmuir model, and the
maximum adsorption capacity of the AC for 2,4-D removal was 281.2 mg g−1 at 30 ◦ C.
Mesoporous activated carbon derived from Peltophorum pterocarpum pods was ob-
tained by Samanth et al. [93] through chemical activation with H3 PO4 , followed by low-
temperature carbonization. The surface area of the adsorbent was found to be 1078 m2 g−1
and its adsorption capacity for 2,4-D removal was 255.1 mg g−1 . The adsorption data were
fitted using the Langmuir and pseudo-second-order models. The values on the adsorption
energy and thermodynamic functions revealed physisorption and exothermicity.
Naboulsi et al. [94] generated activated carbon from Ritama-Monosperma (L.) Boiss
powder through carbonization at 500 ◦ C and activation with H3 PO4 . The influence of
various experimental parameters (pH, temperature, adsorbate dose) on the equilibrium,
kinetics, and thermodynamics of 2,4-D and 2,4,5-T adsorption from a bicomponent solution
was evaluated. A maximum adsorption capacity of 69.44 mg g−1 was found for 2,4-D and
13.81 mg g−1 for 2,4,5-T. The Freundlich and the pseudo-second-order kinetic equations
were indicated as working well for the theoretical description of the adsorption process.
A paper by Doczekalska et al. [95] reports the efficient removal of 2,4-D and MCPA
during an aqueous phase, using activated carbons derived from various lignocellulosic
materials. In that investigation, the ACs were prepared from willow, miscanthus, flax, and
hemp shives, via KOH activation. The adsorption was pH-dependent, and the removal of
both herbicides decreased with an increase in the initial pH of the solution. The adsorption
kinetics of both herbicides was better represented by the PSO model, while the equilibrium
data followed the Langmuir isotherm.
Trivedi et al. [45] proposed activated carbon synthesis from groundnut shells via
chemical activation with KOH. The as-received AC was characterized by SBET = 709 m2 g−1
and an adsorption capacity for 2,4-D removal of 250 mg g−1 .
Activated carbon obtained by KOH activation of the biochar, obtained as a result of the
pyrolysis of safflower press cake, was prepared and tested as an adsorbent for the removal
of 2,4-D from aqueous solutions [96]. The effects of the initial pH value, the adsorbent
dosage, the initial concentration, the contact time, and the temperature were evaluated.
The results showed that the PSO model was more compatible with the experimental
kinetic data and that the Langmuir isotherm model provided a better correlation for the
adsorption of 2,4-D. The maximum adsorption capacity was found to be 344.8 mg g−1 at
318 K. The thermodynamic studies revealed that the adsorption process was spontaneous
and endothermic.
Koyuncu et al. [97], Rambabu et al. [98], and Pandiarajan et al. [99] prepared activated
carbons from capsicum industrial processing pulp, date palm coir, and orange peel, respec-
tively, via single-step KOH-catalyzed pyrolysis. The first research group demonstrated that
the isotherm data were described well by the Langmuir isotherm model, and the maximum
adsorption capacity for 2,4-D removal was 385 mg g−1 . The date palm coir-based activated
carbon [98] was characterized by a flaky morphology, a well-graphitized porous structure
(947 m2 g−1 ), and oxygen-rich surface moieties. The Langmuir and the pseudo-second-
order models best described the equilibrium (with qm = 50.3 mg g−1 ) and the kinetics
of the adsorption process. An evaluation of the costs of the adsorbent production and
regeneration was made, and cyclic reusability tests were also conducted. Pandiarajan’s
Sustainability 2023, 15, 16516 18 of 33

group extended an adsorption study to other chlorophenoxy acid herbicides (2,4-DP, MCPA,
2,4,5-T, MCPP). The Langmuir model fitted all the herbicide adsorption isotherms very
well. The results showed that the adsorption increased in the order: 2,4-DP < 2,4,5-T <
MCPA < 2,4-D < MCPP. The pseudo-second-order kinetic model was indicated as the one
with the highest fitting quality to the experimental data for all the adsorption systems.
Tefera and Tulu [100] tested activated carbon prepared from wheat straw treated with
sulfuric acid and potassium hydroxide for the removal of 2,4-D from aqueous solutions. The
removal efficiency of 2,4-D was evaluated using varying parameters, such as the adsorbent
dose, temperature, pH, and contact time. It was observed that the adsorption efficiency of
the herbicide increased with the increasing temperature, contact time, and adsorbent dose,
and decreased with an increase in the solution pH. The equilibrium data were analyzed
using the Langmuir and Freundlich isotherms and the Langmuir model best described the
experimental data.
Herrera-García et al. [101] prepared activated carbon from agricultural waste made
of yam peel (Dioscorea rotundata) by chemical activation with KOH. The as-prepared AC
was chemically modified using magnetite nanoparticles. Both the ACs were characterized
and tested as adsorbents for the removal of 2,4-D from aqueous solutions. The effects of
the solution pH, the initial concentrations of 2,4-D, and the temperature, were investigated.
The PFO, PSO, Elovich, and Webber–Morris kinetic equations, as well as the Langmuir,
Freundlich, and Elovich isotherms, were used for the description of the experimental
data. The results showed that the adsorption kinetics and isotherms were better described
through the PSO and Freundlich models, respectively. Langmuir’s maximum adsorption
capacity values at 25 ◦ C were 99.0 and 86.2 mg g−1 for non-modified and Fe3 O4 -modified
ACs, respectively.
Salman in the paper [102] dealt with the optimization of the conditions of activated
carbon preparation from palm oil fronds using the physiochemical activation method
(KOH and CO2 as activating agents), and its application for the removal of various types
of pesticides (e.g., bentazon, carbofuran, and 2,4-D). Of the variable synthesis parameters
(activation time and chemical impregnation ratios KOH/biochar, activation temperature),
the latter one was found to have the greatest effect on the activated carbon yield in regard
to pesticides adsorption. The surface area of the activated carbon, prepared under optimum
conditions, equaled 1237 m2 g−1 . The optimizing analysis of variance was carried out using
the response surface methodology (RSM).
Table 4 presents a compilation of the results of various activated carbons in the removal
of 2,4-D and MCPA and their adsorption capacity.
The collected adsorption results showed that activated carbons derived from agricul-
tural and household waste were very good adsorbents for the removal of chlorophenoxy
herbicides from an aqueous solution. The adsorption capacities of activated carbons to-
wards 2,4-D and MCPA were in the range of 1.015–592.7 mg g−1 and 85–546.7 mg g−1 ,
respectively. The observed differences resulted mainly from the degree of development
of the porous structure of the solids, the chemical characteristics of the surface, and the
experimental conditions of the adsorption process. The high surface area of activated car-
bon, the basic nature of its surface, and the acidic conditions of the adsorption experiment
favored chlorophenoxy herbicides adsorption. In general, the adsorption capacities of
the activated carbons were very high when compared with other waste-based adsorbents,
i.e., unmodified/modified materials, ashes, and biochars. Additionally, their adsorption
capacities were not inferior to commercial activated carbons derived from fossil coals,
for which the values of the parameter qm towards 2,4-D and MCPA were in the range
of 8.11–555.5 mg g−1 and 105.3–599.9 mg g−1 , respectively [33]. A significant share of
micropores in the pores’ structure caused the overall adsorption rate to be pore volume
diffusion-dependent.
Sustainability 2023, 15, 16516 19 of 33

Table 4. The results from chlorophenoxy herbicides adsorption studies on activated carbons produced
from agricultural and household waste.

Adsorption Capacity
Adsorbent/ (qm ), mg g−1 Isotherm Kinetic Integral
SBET m2 g−1 Ref.
Activating Agent Model Model Cost–Benefit
2,4-D MCPA
AC from tea waste/ST 576 58.8 - L, F PFO, PSO, E Low [56]
AC from Pinus taeda
1450 471.7 - L, F, Te PFO, PSO, E High [65]
wood/self-activation
AC from Lagenaria vulgaris
665 333.3 - L, F, S PFO, PSO High [76]
shell/ST
AC from sugarcane L, F, R-P,
547 153.9 - PFO, PSO, E Medium [77]
bagasse/ST Te, DR
L, F, R-P,
AC from coconut shell/ST 991 233.0 - PFO, PSO, E High [77]
Te, DR
AC from endocarp from L, F, R-P,
1068 235.5 - PFO, PSO, E High [77]
babassu coconut/ST Te, DR
AC from canola stalk/ST 556.8 135.8 - - PFO, PSO, E Medium [78]
AC from peanut shells/ST 1240 549 - F PFO High [79]
AC from Tectona grandis
tree sawdust 787 - 212.7 L, F - High [80]
(Teak-7360)/CD
AC from Tectona grandis
tree sawdust 910 - 313 L, F - High [80]
(Teak-7480)/CD
AC from Njiliti wood
603 - 85 - - Low [81]
waste/CD
AC from Candeia wood
838 - 295 - - High [81]
waste/CD
AC from Tchitiotidi wood
741 - 220 - - High [81]
waste/CD
AC from Nuati wood
801 - 245 - - High [81]
waste/CD
AC from pistachio PFO, PSO, E,
556 453.4 314 GL High [82]
shell/CD m-exp, MOE
AC from pistachio PFO, PSO, E,
669 288.9 GL High [82]
shell/ST; CD m-exp, MOE
AC from pistachio PFO, PSO, E,
685 286.9 GL High [82]
shell/CD; MV m-exp, MOE
AC from Soybean
1696 253.2 - L, F, Te - High [83]
waste/MV
AC from sesame
- 166.7 - L, F, Te, DR PFO, PSO, E Medium [84]
seed/ZnCl2
AC from olive-waste
1418 129.9 - L, F PFO, PSO Medium [85]
cake/ZnCl2
AC from queen palm
782 367.8 - L, F, Te, DR PFO, PSO High [86]
endocarp/ZnCl2
AC from orange PFO, PSO,
1779 71.9 - L, F, Te, DR Low [87]
pulp/ZnCl2 W-M
AC from Elaeagnus
1109 189 - L, F, Te PFO, PSO Medium [88]
angustifolia seeds/ZnCl2
Sustainability 2023, 15, 16516 20 of 33

Table 4. Cont.

Adsorption Capacity
Adsorbent/ (qm ), mg g−1 Isotherm Kinetic Integral
SBET m2 g−1 Ref.
Activating Agent Model Model Cost–Benefit
2,4-D MCPA
AC from mushroom
1067 105.4 - L, F, R-P LDF Medium [89]
residues (AC400)/ZnCl2
AC from mushroom
799 241.7 - L, F, R-P LDF High [89]
residues (AC500)/ZnCl2
AC from rice straw/ZnCl2 771 280.7 329.0 L, F, P-R PFO, PSO High [90]
AC from rice
613 271.8 329.0 L, F, P-R PFO, PSO High [90]
straw/H3 PO4
AC from oil palm
1657 420.4 - L,F PFO, PSO High [91]
trunk/H3 PO4
AC from peanut PFO, PSO,
458.2 281.2 - L, F, Te High [92]
shell/H3 PO4 W-M
AC from P. pterocarpum
1078 255.1 - L PSO High [93]
pods/H3 PO4
AC from R.-M. (L.) Boiss PFO, PSO,
- 69.4 - F Low [94]
powder/H3 PO4 IDM
AC from willow/KOH 1280 510.5 484.4 L, F PFO, PSO High [95]
AC from
1420 569.5 537.1 L, F PFO, PSO High [95]
miscanthus/KOH
AC from flax shives/KOH 1587 592.7 546.7 L, F PFO, PSO High [95]
AC from hemp
1324 540.5 493.5 L, F PFO, PSO High [95]
shives/KOH
AC from groundnut
709 250.0 - L, F, Te PFO, PSO High [45]
shell/KOH
AC from biochar/KOH 1277 344.8 - L, F, Te, DR PFO, PSO High [96]
AC from capsicum
1564 385 - L,F - High [97]
pulp/KOH
AC from date palm
947 53 - L, F, Te E, PFO, PSO Low [98]
coir/KOH
AC from orange E, IDM, L, F,
592 515.5 416.7 PFO, PSO High [99]
peel/KOH Te, DR
AC from wheat
- 1.015 - L,F Contact time Low [100]
straw/H2 SO4 ; KOH
AC from yam peels/KOH 715 99.0 - L, F, E PFO, PSO, E Low [101]
AC from yam
325 86.2 - L, F, E PFO, PSO, E Low [101]
peels/KOH; Fe3 O4

3. Mechanism of Adsorption
Adsorption of chlorophenoxy herbicides by the different adsorbents, based on agri-
cultural and household waste, is the result of various specific and nonspecific interactions.
The adsorption mechanism of the same compound may change depending on the different
properties of the adsorbent. The same situation occurs, for example, with a change in pH
because the pH of the solution affects both the degree of dissociation and ionization of
the adsorbate molecules, as well as the charge that will be present on the surface of the
adsorbent. Thus, depending on the pH of the solution, adsorption can occur via electrostatic
interactions (attractive or repulsive) between the adsorbate and the adsorbent.
Sustainability 2023, 15, 16516 21 of 33

The most typical and important forces driving adsorption by biochars and activated car-
bons include π-π interactions, electrostatic attraction and repulsion, hydrophobic interactions,
covalent bonding and hydrogen bonding interactions between the herbicide molecules and
the adsorbent surface functional groups. A significant share of the micro- or small mesopores
in16516
Sustainability 2023, 15, the structure of these materials causes the adsorption to proceed mainly through the 21 of 3
pore-filling mechanism. Figure 1a presents possible supramolecular systems created during
the adsorption of the 2,4-D molecule on the exemplary biochar [66]. Impregnation of the
raw material determined
with H3 PO4the at the pre-treatment
occurrence stageinteractions
of typical of synthesis determined
between the occurrence
the adsorbate and the adsor
of typical interactions between the adsorbate and the adsorbent, as well
bent, as well as specific ones resulting from the activating agent used as specific onesmetaphos
(i.e., with
resulting fromphate
the activating
groups). The high value of the maximum adsorption capacity for this of
agent used (i.e., with metaphosphate groups). The high value biochar to
the maximumwardsadsorption capacity
2,4-D (323.76 mgforg−1this biochar
) at pH towards
= 2 and T = 3182,4-D (323.76
K was found.mg g−1 ) at pH =
Additionally, 2 morpho
the
and T = 318 Klogical
was found. Additionally, the morphological structure of the used adsorbent
structure of the used adsorbent and the herbicide adsorption isotherms are illus
and the herbicide
tratedadsorption isotherms
in Figure 1b–d, are illustrated in Figure 1b–d, respectively.
respectively.

Figure 1.interactions
Figure 1. The possible The possibleininteractions in the 2,4-D
the 2,4-D adsorptive adsorptive
process usingprocess using coffee
coffee ground charground
(a). SEMchar (a).
SEM images
images of the adsorbent of the
(b,c). Theadsorbent
herbicide(b,c). The herbicide
adsorption adsorption
isotherms isotherms
on the biochar (d)on the biochar
Reprinted (d) Re-
with
printed with permission from Ref. [66]. Copyright 2023, copyright Elsevier.
permission from Ref. [66]. Copyright 2023, copyright Elsevier.

Regarding unmodified and modified natural materials and ashes, the mechanism o
the 2,4-D or MCPA adsorption must be considered individually in conjunction with the
unique (individual) physicochemical properties of the adsorbent. According to the au
thors of some works [35–37,39], the adsorption of chlorophenoxy herbicides by rice husk
with a positive surface charge, follows a chemical ion-exchange mechanism or occurs via
Sustainability 2023, 15, 16516 22 of 33

Regarding unmodified and modified natural materials and ashes, the mechanism
of the 2,4-D or MCPA adsorption must be considered individually in conjunction with
the unique (individual) physicochemical properties of the adsorbent. According to the
authors of some works [35–37,39], the adsorption of chlorophenoxy herbicides by rice
husks with a positive surface charge, follows a chemical ion-exchange mechanism or occurs
via a chemical process (involving valency force sharing). Chemical reactions (through free
electron pairs of surface functional groups, e.g., carbonyl, amide, ether), cation–dipole
interactions (due to the occurrence of hydroxyl, amine, and amide groups), as well as
hydrogen bonds are proposed for the adsorption of 2,4-D by saw-sedge Cladium mariscus
(C. mariscus). In turn, for bio-waste materials, such as apple shell, orange peel, banana peel,
and millet residue, the discussed process results from molecular interactions (when the
molecular form of the pesticide occurs) and repulsive electrostatic interactions (at a solution
pH where both the adsorbent surface moieties, i.e., carboxyl and sulphate, and 2,4-D are
negatively charged) [40]. Al-Zaben and Mekhamer [41] reported no relationship between
the MCPA removal efficiency and the pH solution using coffee waste as the adsorbent. The
existence of an electrostatic interaction was excluded in this system, and the responsibility
for the adsorption was assigned to the hydrogen bonds between the OH moieties on the
adsorbent surface and the acidic group of the adsorbate molecules.
According to the authors of papers [47–49], the oxidation of various biomass
(Physalis peruviana fruit, Arachis hypogaea skins and wheat husks) with sulfuric acid
resulted in oxygenated functionalities on their surface, which participated in the adsorp-
tion of the chlorophenoxy herbicides via electrostatic forces, hydrogen bonding, and
van der Waals forces. The authors of the latter paper [49] also indicated halogen bonds
and π–π interactions as responsible for adsorption. Noteworthy is the relatively high
adsorption efficiency of acid-modified wheat husks, with the capacity of 161.1 mg g−1
(pH = 2, T = 298 K). For this reason, the possible supramolecular systems of this ad-
sorbent with the 2,4-D molecule (Figure 2a), along with the morphological structure
of the adsorbent (Figure 2b–d), and the equilibrium isotherms at various experimental
temperatures (Figure 2e), are presented.
The modification of tiger nut residue using N-cetylpyridinium [50] resulted in obtain-
ing the adsorbent, which interacted with 2,4-D through electrostatic attraction, hydrogen
bonding, and triggered π-π stacking. Trivedi’s comprehensive research [42–46] on ashes
originating from various waste materials showed a close relationship between their chem-
ical composition and the mechanism of the chlorophenoxy herbicides adsorption. The
presence of metallic oxides (CaO, K2 O) in ash, which in water take the form of metal-
lic hydroxides, resulted in electrostatic repulsion forces between them and adsorbate
anions. In turn, for Al2 O3 , which constitutes positive centers on the adsorbent surface,
the triggering of attractive electrostatic interactions was observed. Thus, the mineral
composition of ash determines the mechanism and effectiveness of the adsorption process.
For hydrochars (HCs), the mechanism of the 2,4-D adsorption via intensive partitioning
and/or chemisorption was postulated [64]. Regarding the interactions of pollutants with
more advanced magnetic waste-based materials [52,53] with various functional groups
(hydroxyl, amine, carboxyl), the hydrogen bonding, electrostatic complexation, and π-π
mechanisms were suggested. Moreover, some of these interactions were additionally
enhanced by the occurrence of iron. The high efficiency of the ferrospinel composite
(FLPWAC) [53] (qm = 400 mg g−1 , T = 318 K) was found. The possible supramolecu-
lar adsorbate–adsorbent systems (Figure 3a), the morphological structure of the adsor-
bent (Figure 3b–f), and the equilibrium isotherms at various experimental temperatures
(Figure 3g), are presented.
Sustainability 2023, 15, 16516 23 of 34

Sustainability 2023, 15, 16516 23 of 33

Figure 2. The
Figure possible
2. The possibleinteractions
interactions in
in the 2,4-Dadsorptive
the 2,4-D adsorptive process
process usingusing acid-modified
acid-modified wheatwheat
huskshusks
(a).(a).
SEM SEMimages
imagesofofthe
the adsorbent (magnitudes:
adsorbent (magnitudes: (b)(b) ×500,
×500, (c) (c) ×1000,
×1000, (d) ×(d) ×3000),
3000), (b–d).
(b–d). Equilibrium
Equilibrium
isotherms
isotherms of of
thethe
2,4-D
2,4-Dadsorption
adsorption by modified
modifiedwheat
wheat husks
husks (pH(pH
= 2)= (e)
2) Reprinted
(e) Reprinted
with with permission
permission
from Ref.
from [49].
Ref. Copyright
[49]. Copyright2021,
2021, copyright Elsevier.
copyright Elsevier.

The modification of tiger nut residue using N-cetylpyridinium [50] resulted in ob-
taining the adsorbent, which interacted with 2,4-D through electrostatic attraction, hydro-
gen bonding, and triggered π-π stacking. Trivedi’s comprehensive research [42–46] on
ashes originating from various waste materials showed a close relationship between their
chemical composition and the mechanism of the chlorophenoxy herbicides adsorption.
Sustainability 2023, 15, 16516 25 of 34

Sustainability 2023, 15, 16516 24 of 33

Figure 3. 3.
Figure TheThepossible
possibleinteractions
interactions ininthe
the 2,4-D
2,4-D adsorptive
adsorptive process
process using using the ferrospinel
the ferrospinel composite composite
(a).
(a).SEM
SEMimages
images of adsorbent
of the the adsorbent at different
at different expansionexpansion
ratios (b–f).ratios (b–f).
Langmuir Langmuir
plots plots
of the 2,4-D of the 2,4-D
adsorption
adsorption on the composite
on the composite (g).
(g). Reprinted Reprinted
with with
permission frompermission from Ref.
Ref. [53]. Copyright [53].
2020, Copyright
copyright 2020, copy-
Elsevier.
right Elsevier.
Summing up, the variety of types of adsorbents and their different characteristics trans-
late into
Summing a multitude
up, the of variety
mechanisms leading
of types oftoadsorbents
the adsorption andoftheir
chlorophenoxy
different herbicides.
characteristics
translate into a multitude of mechanisms leading to the adsorption of chlorophenoxy
herbicides.
Sustainability 2023, 15, 16516 25 of 33

4. Effect of Co-Substances on Chlorophenoxy Herbicides Adsorption by

Waste-Based Adsorbents
Environmental waters are complex biological systems, containing several compounds
of natural and anthropogenic origin, so research on the assessment of the impact of various
co-substances on chlorophenoxy herbicide removal by waste-based adsorbents is enor-
mously important. This issue has been addressed in only a few papers out of all the ones
cited. The studies concerned the co-existence of mineral salts, organic matter, dyes, and
other herbicides, but there was no information on the co-existence of adjuvants, which are
auxiliary substances in commercial formulations of herbicide preparations.
Fatombi et al. [92] and Almahri [67] reported that 2,4-D removal efficiency by activated
carbon and biochar in the presence of NaCl, CaCl2 , and humic acid (HA) decreased, wherein
the influence of CaCl2 was lower than NaCl. Such a difference was explained by the higher
polarizability effect of the Ca2+ ion and the lower thickness of the double layer in the solid
with the participation of this ion. The adsorption capacities were found to be 281.22, 86.12,
160.32, and 154.96 mg g–1 for adsorption of 2,4-D only, and with the co-existence of NaCl,
CaCl2 , and HA, respectively. It was also noticed that an increase in the salt concentration
negatively affected herbicide adsorption, due to a higher dissociation degree of the 2,4-D
molecules and the forming of pairs between the salt cations and herbicide anions. The
slighter impact of CaCl2 on 2,4-D adsorption was related to the screening effect of the
negative charge of 2,4-D by the formation of complexes based on intermolecular bridges
(R–COO—-Ca2+ —-OOC–R).
A similar trend in the influence of the presence of natural organic matter on 2,4-D
adsorption by AC was also noticed by Gurav’s research group [65]. Here, the adsorption
capacities equaled 491.76 and 466.73 mg g–1 for 2,4-D adsorbed from single- and bicompo-
nent solutions, respectively. However, the effect of salinity on 2,4-D removal was reversed
compared to that observed by Fatombi et al. [92]. The occurrence of NaCl in water in
a certain concentration range (1–4 g L–1 ) slightly enhanced the 2,4-D adsorption (from
493.86 to 496.39 mg g–1 ), but a further increase in salt concentration caused a decrease in
adsorption (to 489.08 mg g–1 ). The enhancement of the adsorption with the rise in the
ionic strength of the solution was connected with the screening effect of the carbon surface
charge by NaCl.
In the paper [82], the effect of competing substances was analyzed for MCPA adsorp-
tion by two activated carbons, differentiated in terms of their porous structure and surface
functionality. A slight effect of crystal violet co-existence on the MCPA adsorption was
revealed, which was explained by the affinity of both pollutants to different adsorption
sites. The large dye molecules were adsorbed in the mesopores, while the small MCPA ones
were mainly located in the micropores. Thus, the authors stated that the adsorption of both
compounds was mostly independent. However, a significant influence of the competing
substance was observed when in the solution there were two substances belonging to the
same group of herbicides (MCPA and 2,4-D). Here, a decrease in MCPA adsorption with
the co-existing substance was a consequence of the occupation of the same adsorption sites
(qm equals 314 and 144.43 mg g–1 for the MCPA adsorbed from single- and bicomponent
solutions, respectively). Relatively similar physicochemical properties and structures of
the herbicides caused strong competition between each other in the adsorption process
by activated carbon. It was also noticed that 2,4-D showed greater affinity to the carbon
surface than MCPA due to the greater adsorption strength, which favored keeping 2,4-D in
the adsorption active sites or replacing it after MCPA desorption. The adsorption capac-
ities were found to be 242.58 and 144.43 mg g–1 for 2,4-D and MCPA adsorbed from the
bicomponent solution, respectively.
Naboulsi et al. [94] studied the competition effect on the adsorption of 2,4-D and
2,4,5-T by waste-based ACs. The maximum adsorption capacity of 69.44 mg g–1 for 2,4-D
and 13.81 mg g–1 for 2,4,5-T for the bicomponent system was determined. The application
of density functional theory (DFT) enabled the identification of 2,4-D as a more selective
Sustainability 2023, 15, 16516 26 of 33

pollutant due to the greater reactivity of its molecules (more active sites, either nucleophilic
or electrophilic in nature).
A higher selectivity of the biomass-MOF composite towards 2,4-D compared to tetracy-
cline (antibiotic) in binary systems was also observed [52]. Such behavior by the adsorbent
was attributed to the relatively smaller size of the herbicide, which reduced the steric hin-
drance. However, it was found that an increase in the adsorbent dose reduced the adsorption
efficiency due to grains agglomeration (limiting accessibility to the surface area).
In the paper [69], promising results from 2,4-D adsorption studies on biochar in multi-
component systems were presented. A 100% biochar performance for pollutants from
drainage water and 96.8% from simulated one-component wastewater was noted. This was
due to the synergistic effect of the coexisting cations and anions in the drainage water on
herbicide adsorption.
The 2,4-D removal in the range of 86.5–95.6% by biochar from real water (river effluent,
drinking water, and wastewater) was achieved by Almahri et al. [67]. Only slightly worse
results on 2,4-D removal efficiencies (72–76.30%) by sulfuric acid-treated peanut skins and
wheat husks were found in the treatment of synthetic wastewater, consisting of a mixture
of 2,4-D, atrazine, NaCl, KCl, or the simulated effluent from two Brazilian rivers [48,49].
The studies on various co-existing substances and their impact on the chlorophenoxy
herbicides adsorption by waste-based adsorbents showed the complexity of the interactions
between the components of adsorption systems and highlighted the significance of taking
them into account in the development and optimization of new adsorbents for environmen-
tal applications. However, taking into account the complex composition of natural water
for a better understanding of the interactions between other co-substances, herbicides, and
adsorbents, further research in this direction is required.

5. Regeneration and Reusability of Waste-Based Activated Carbons

The evaluation of the recycling and reuse potential of waste-based ACs is another
crucial factor in determining the implementation of these materials for adsorption applica-
tions. This is related to cost reduction for new adsorbents and actions to prevent possible
secondary pollution of the environment with herbicides and other co-adsorbates, as a
result of their leaching due to environmental factors from used activated carbon deposits at
storage sites. The proper management of spent adsorbents seems to be such an important
issue that many research groups have initiated studies in this direction. Generally, chem-
ical, thermal, physical, and biological methods are used to regenerate activated carbons.
Regarding the regeneration of waste-based activated carbons with adsorbed chlorophe-
noxy herbicides, the commonly used chemical method was based on the desorption of the
adsorbate using NaOH solution as an eluent [50,65,84,86,89,92,93,98], and less frequently
using other specific solvents or solutions, such as acetone [78], ethanol [78], water [78,98],
and NaCl. The performance of this method depended on the interactions between the
herbicide–activated carbon and between the herbicide–regenerating chemical agent. The
adsorption efficiency of the regenerated adsorbent usually decreased with the number of
adsorption–desorption cycles (maximum number of cycles 3–5), but some adsorbents could
be reused even 7–9 times, with the maintenance of the adsorption effectiveness close to the
initial use [65,86,89,98]. The decrease in the adsorption capacity in the following regenera-
tion stages resulted from various factors: (i) the decrease in the surface sites’ adsorption
potential, (ii) steric effects, (iii) the disintegration of the pore structure, and (iv) the inability
of the herbicide to desorb from the carbon structure. Of the solvents, e.g., acetone, ethanol,
and water, the first one appeared to be the superior agent for AC regeneration. The thermal
method of regeneration was applied by Bojić et al. [76] and Herrera-García et al. [101],
with 49–60% keeping their initial adsorption capacities after five cycles. More satisfying
results (70–79% initial efficiency) were obtained for the physical method of regeneration
using a microwave heating oven. All these findings showed that ACs successfully passed
the regeneration and reusability tests. However, for the application of adsorbents on an
industrial scale, it is advisable to perform additional adsorption studies within a column or
Sustainability 2023, 15, 16516 27 of 33

a continuous flow system (fluidized-bed column) for the treatment of water polluted with
chlorophenoxy herbicides.
Research in the field of regeneration and reusability of adsorbents makes economic
and practical sense if a given material shows high adsorption capacity towards pollutants.
Therefore, this issue has been described in only a few papers devoted to materials other
than activated carbon. More precisely, they concerned coffee waste-based biochar and
acid-modified wheat husk, with adsorption capacities for 2,4-D of 276.3 and 161.1 mg g–1 ,
respectively [49,67]. As in the case of many active carbons, the best results (retaining
45–84% removal efficiency after five cycles of adsorption–desorption) were obtained using
sodium hydroxide as a desorbing agent. Nitric acid, calcium chloride, hydrochloric acid,
ethylenediamine tetraacetic acid (EDTA), and ultrasonic cleaning with alcohol, were found
not to be effective enough in the desorption of pollutants from biochars [67,70]. There
were also materials that were treated with NaOH after use, but their subsequent efficiency
was negligible. An example of such a material is a peanut husk-based MOF composite
with magnetic properties [52]. Nevertheless, the regeneration process used allowed the
recovery and reuse of the adsorbate, while the adsorbent disposed into soil acted as organic
amendment due to the slow release of its major elements (i.e., Fe, C, N, and O).

6. Cost of Production of Waste-Based Activated Carbons

A review of the relevant literature revealed the selectivity and satisfying adsorption
capability of waste-based activated carbons towards chlorophenoxy herbicides in model
experiments both in single-component and multi-component systems. Importantly, these
adsorbents could be regenerated using simple methods, which enables multiple use at
a high level of efficiency. Another issue to analyze is the cost effectiveness of waste-
based AC production compared to commercial materials. In a paper from 2022 [97], the
authors estimated the production cost of a Capsicum pulp-based AC at approximately
USD 1.75 per kg (summing up the costs of the raw material transport; the reagents, namely
nitrogen gas, KOH, and hydrochloric acid; and the media, namely power, water), which is
lower than that for commercial ACs, e.g., USD 2–5 per kg. In other works from 2021, the
fabrication of ACs from mushroom residues [89] and date palm coir waste [98] was assessed
to be USD 2.39 per kg (the total costs of reagents, namely nitrogen gas, hydrochloric acid,
and zinc chloride; and media, namely power) and USD 3 per kg (the total costs of the capital
expenses, namely the installation equipment, land, buildings, service; and the operating
ones, namely the precursor collection, water, electricity, and labor), respectively. According
to [98], the cost of commercial activated carbon may even reach USD 15 per kg. Actually,
only a few cited works contained cost estimations, but based on the available data, the
undertaking to expand the production of these adsorbents from a laboratory scale to an
industrial one seems to be economically viable. Moreover, this project is in line with the
trend of sustainable waste management, which is beneficial for the natural environment.

7. Conclusions
This paper presents a wide range of agricultural and household wastes as low-cost
alternative adsorbents for the removal of two common herbicides, 2,4-D and MCPA, from
water. The characteristics of the adsorbents, the conditions of the adsorption experiments
and their results, and the theoretical models that best describe the adsorption process have
been reported. Based on the available literature, mainly from the last decade, the use of
waste materials as low-cost adsorbents, both in their original form and after modification,
mainly in the form of waste-based biochar and activated carbon, was shown to be very
attractive. Such adsorbents are not only effective, but are also very interesting from an
economic point of view. The use of waste itself as an adsorbent reduces the cost of waste
disposal and, thus, promotes environmental protection, and the low cost of these materials
means that they can be disposed of after use without costly regeneration. However, the
problems concerning the regeneration and reusability of waste-based activated carbons
and the costs involved have been discussed. The waste materials presented in this paper
Sustainability 2023, 15, 16516 28 of 33

showed a satisfactory affinity with 2,4-D and MCPA, and since they are relatively low-
or no-cost, readily available, and easily modified, e.g., by pyrolysis and activation, their
use as alternative adsorbents seems very interesting and promising. The development
of adsorbents using agricultural and household waste offers an interesting alternative to
commercial materials for environmental applications and at the same time offers a way
forward for proper waste management.
At the same time, it should be added that the presented review on the use of adsorbents
based on waste materials for water purification, also showed the need to intensify the
research towards extending it to more complex systems corresponding to real ones. Only a
few studies concern this problem, while water and sewage contain many toxic substances
with very diverse properties, originating from various sources, including those used as
pesticide additives. The aim of adsorption techniques is to remove substances to the highest
possible extent, which is difficult to achieve in such complex systems, in which a large
part of the components may compete for access to the adsorption centers. Therefore, an
important direction of future research is the analysis of adsorption in model and real multi-
component systems. Taking into account the diversity of the physicochemical properties of
the toxic substances present in water and sewage, including the molecular size, hydrophobic
or hydrophilic nature, and molecular form, it is also necessary to analyze materials or
systems of materials with a different porosity and chemical nature of the surface in order
to achieve the maximum possible level of purification. On the other hand, in many cases
the selective adsorbents should be applied; thus, also the studies concerning the mutual
interactions between the adsorbates in complex systems, which can decrease the adsorption
effectiveness of a given substance, are of great importance.

Author Contributions: Conceptualization, M.B., K.K., A.S. and A.D.-M.; data curation, M.B. and
K.K.; visualization, M.B. and K.K.; formal analysis, K.K., A.S. and A.D.-M.; supervision, K.K., A.S.
and A.D.-M.; writing—original draft, M.B., K.K. and A.S.; writing—review and editing, K.K., A.S.
and A.D.-M. 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: Informed consent was obtained from all subjects involved in the study.
Data Availability Statement: The data are available from the corresponding author.
Conflicts of Interest: The authors declare no conflict of interest.

Abbreviations

AC Activated carbon
A Avrami kinetic model
Ba Bangham kinetic model
DR Dubinin–Radushkevich isotherm
E Elovich isotherm model
F Freundlich isotherm model
GL The generalized Langmuir isotherm
Hi Hill isotherm model
IDM Intraparticle diffusion model
ITM Theoretical adsorption model
J Jovanovic equilibrium model
K Khan equilibrium model
K-C Koble–Corrigan equilibrium model q
mg 1
ki Intraparticle diffusion rate in W-M kinetic model, g min
k1 The rate constant for the PFO kinetic model, min − 1

k2 The rate constant for the PSO kinetic model, g mg−1 min−1
Sustainability 2023, 15, 16516 29 of 33

L Langmuir isotherm
LDF Linear driving force kinetic model
L-F Langmuir–Freundlich isotherm
m-exp Multi-exponential kinetic equation
MOE Mixed-order equation
PFO Pseudo-first-order kinetic model/equation (PFOE)
PSO Pseudo-second-order kinetic model/equation (PSOE)
qm The maximum adsorption capacity, mg g−1
R-P Redlich–Peterson isotherm
S Sips isotherm
Te Temkin isotherm
To Toth isotherm
W-M Weber–Morris kinetic model

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