ChemBioEng Reviews - 2023 - Somashekara - Sequestration of Contaminants From Wastewater A Review of Adsorption Processes

Sequestration of Contaminants from Wastewater: A Review
of Adsorption Processes
Divyashree Somashekara[1], Lavanya Mulky[2],*
Abstract
Adsorption has widespread applications in separa- compounds along with non-biodegradable contami-
tion processes, particularly aiming at environmental nants from industrial wastewater. The separation
decontamination owing to its economic and highly techniques have emerged with greater efficiency in
efficient outcomes. This literature studies various eliminating specific pollutants in terms of discharge
isotherm models concerning adsorption which is legislation. Such methods have been reviewed here-
accompanied by information related to the mechan- by in this document based on literature published
ism of the adsorption process, which is a crucial lately. Concerning the process of adsorption, this re-
aspect of the system design. Many modification view elucidates the adsorption isotherms, kinetic
techniques bring about a significant enhancement models, breakthrough curve modelling, thermody-
in the working capacity. The build-up of industrial namic concepts, and the regeneration of the support
activities causes a spike in the dispersion of toxic required in batch or continuous reactors.
Keywords: Adsorption, Isotherm, Kinetics, Mechanism, Modelling, Regeneration
Received: October 25, 2022; revised: February 16, 2023; accepted: June 05, 2023
DOI: 10.1002/cben.202200050
This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium,
provided the original work is properly cited.
1 Introduction stances has been in the limelight as the chemical industries

generate massive amounts of wastewater regularly, which usu-
Human beings are confronted with two primary challenges ally finds its way into the open surroundings and gives birth to
worldwide, namely scarcity of clean water and its pollution. undesired influences on human vitality and aquatic habitats
The groundwater and surface water getting contaminated is the due to its multi colours and severe toxicity level [7]. All the bio-
root cause of this paucity, whereas the basic sources remain to logical, chemical, and physical treatment techniques are imple-
be natural and anthropogenic [1]. The sustainability of life on mented to facilitate the elimination of heavy metals as well as
Earth requires water as a fundamental requirement. The urban dyes found in the wastewater. Out of the myriad of decontami-
activities spanning industries, the agricultural sector, the health nation methods, adsorption stands out because of the availabil-
domains, and so on, produce a considerable quantity of micro- ity of various adsorbents, simplicity of preparation, easy han-
pollutants, thereby affecting the aqueous life [2]. The domains dling, minimal operational expense, high efficiency, fast
that have caught the attention of researchers in recent times kinetics, extensive applicability, non-secondary contamination,
are environmental pollution and the extensive use of pharma- and easy regeneration capacity of the adsorbents [8]. As the
ceutical compounds [3]. Compounds that affect the initial extent of adsorption is measured by suitable adsorbents for
water quality ranging from bacteria to industrial discharges specific components, it is necessary to completely interpret the
result in the formation of wastewater upon its encounter with physicochemical aspects of adsorbents and the mechanisms
water bodies. Various reports suggest that a range of pollutants
are present in the wastewater from refinery like heavy metals,
hydrocarbons, and phenol which induces serious damage to —————
the human body when released untreated [4]. The organic pol- [1]
Dr. Divyashree Somashekara
lutants being considered are dyes, volatile organic compounds, Department of Biotechnology, Manipal Institute of Technology,
and pesticides whereas metals and disinfectant by-products Manipal Academy of Higher Education, Karnataka, India.
(DBP) such as bromide come within inorganic toxins [5]. [2]
Dr. Lavanya Mulky https://orcid.org/0000-0002-7331-4209
Worldwide, dyes are produced annually in thousands of tons. (lavanya.m@manipal.edu)
Specifically, the annual industrial production of dye corre- Department of Chemical Engineering, Manipal Institute of Tech-
sponds to ~7 · 105 tons [6]. Eliminating these harmful sub- nology, Manipal Academy of Higher Education, Karnataka, India.
www.ChemBioEngRev.de ª 2023 The Authors. ChemBioEng Reviews published by Wiley-VCH GmbH ChemBioEng Rev. 2023, 10, No. 4, 491–509 491
21969744, 2023, 4, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/cben.202200050, Wiley Online Library on [23/01/2024]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
associated [9]. The textural properties and the location of
active sites influence the adsorption mechanism [10]. The
method of adsorption is based on the settling of the impurity
over the surface of the adsorbent or among its voids. As the ad-
sorbent plays a crucial role throughout this mechanism, various
substances have been studied as they have a probable role as ef-
ficient adsorbents. The most regarded among these adsorbents
happens to be the application of activated carbon (AC). The
property that makes AC the desired adsorbent in the treatment
of wastewater is the extensive surface area, leading to remark-
able adsorption abilities covering a wide spectrum of toxins.
On the other hand, its high cost imposes a hurdle in its exten-
sive use and urged numerous other materials to be studied as
an alternate source of adsorbents. This write-up has methodi-
cally reviewed the kinds of adsorbents and adsorbates, simulat-
ed methods, and adsorption mechanisms and isotherms.
This review gives a basis of adsorption and highlights a theo- Figure 1. Schematic representation of the interaction between
retical description of the phenomenon under contemplation. the components in a ternary system.
The paper deals with common industrial contaminants crit-
ically showing the possible adsorbent that can be used for the remains in contact with the surface utilizing physical forces
development of adsorption and presenting some of the state- during physisorption and through the different properties of
of-the-art literature on it. Owing to today’s application of bonds holding the adsorbate and adsorbent together in case of
adsorption science in industry, and in environmental manage- chemisorption [16]. Among these, the former is recognized to
ment. The relationship between adsorbent and contaminant be reversible, meanwhile the latter remains irreversible owing
and the adsorption theory is focussed. Current perspectives to its chemical bonds. The aspect of recycling or regeneration
pertaining to challenges are discussed and illustrated. of the adsorbent materials is a major benefit which brings
about economic viability [17].
Depending on the mode of the operation, the process is fur-
2 Adsorption Process ther categorized as static adsorption and dynamic adsorption.
Even known as batch adsorption, static adsorption takes place
Adsorption is a separation process by which adsorbate is inside a closed system having the exact quantity of adsorbent
attached to the adsorbent surface in an aqueous medium by being contacted with a fixed quantity of adsorbate solution,
any form of attractive force (hydrogen bonding, van Der Waals, whereas dynamic adsorption happens under open-system con-
or hydrophobic bonding) or chemisorption [11]. The adsorp- ditions where adsorbate solution incessantly flows past a col-
tion process is regarded as a favoured process over others, to umn filled with the adsorbent [18].
seize the organic components out of the water bodies. Regard-
less, the physicochemical properties of adsorbents would
impact the applicability and also the attainment of high values 3 Different Contaminants of Concern
of desired parameters during the process [12]. When consid-
ered with a low-cost adsorbent, the simple operating system 3.1 Heavy Metal Contamination
can make its implementation attractive for numerous systems
[13]. Adsorption can be performed with a lot of adsorbents The effluents from industry consist of different organic and
and comprises a covalent bond developing among the adsorb- inorganic pollutants, which include heavy metals that could
ate and adsorbent that is reversible to a considerable extent probably be toxic and/or carcinogenic thus proving dangerous
[14]. to humans and other living beings. The ones of major concern
A schematic model of the adsorption process indicating the here are Pb, Zn, Cu, As, Cd, Cr, Ni, and Hg [19]. The risks
three associated components and their interactions have been imposed by the heavy metals being exposed to nature have a
depicted in Fig. 1. The attraction in the middle of the adsorbent connection with toxicity as well as bioaccumulation in living
and the adsorbate acts as the driving force in the process of beings or even the food chain given their biological non-
adsorption generally in a ternary system. Simultaneously, the degradable property. The toxicity of these heavy metals endan-
affinities existing among the adsorbate and the solution, the gers life forms and thus compels their removal to prevent dam-
adsorbent and the solution, and the toxic components also age to the environment [20]. The variety of paints imple-
have a significant contribution to adsorption [15]. Adsorption mented in the painting process in the graphics domain brings
deals with the separation of components present at the juncture along remains of heavy metals and the cleansing of printing de-
of two distinct phases which could be liquid-liquid, gas-liquid, vices dissolves the majority of these components and passes
gas-solid, and liquid-solid. The two classifications of adsorp- them with the effluents. The graphic industry is commonly
tion happen to be physisorption and chemisorption, which found in urban areas and the sewage network is the most prob-
holds upon the basis of the nature of bonds between the adsor- able destination of its effluents degrading the quality of river
bate and the adsorbent. The adsorbate is the one which water flowing through the cities [21].
The issues arising out of pollution caused by heavy metals threat caused by the presence of these emerging compounds
can be brought down by implementing strategies like precipita- in aquatic sources [30].
tion, ultra-filtration, or electro-deposition alongside different
techniques, but the drawback of high cost and ineffectiveness
in low concentrations exists. Here, adsorption is regarded as an 3.4 Nuclear Industry – Contamination
effectual, cheap and environment considerate technique having
great scope for discarding, recovery and recycling of heavy Among all the longest-lived radio nuclides, uranium (U(VI)) is
metals [22, 23] upon the combination with appropriate desorp- known to impose serious health issues on humans, specifically
tion stages acts as a solution to the issue of sludge disposal at comparatively higher concentrations due to its toxic and
[24]. radioactive properties. The activities taking place in the nuclear
industry, copper mining industry, etc. cause uranium to enter
the water streams. Cancer-causing effects of uranium have been
3.2 Surfactant Contamination well established, and its uptake can result in health damages,
particularly in the liver and kidney and eventually leading to
The compound which finds its use in a myriad of industrial death. According to the standards set by the World Health
and domestic applications is a surfactant. Because of their Organization, the permissible limit of U(VI) strength in water
extensive use in detergent formulation, they are now seen as is 0.05 mg L–1. Such strict rules have initiated the upcoming of
one of the most general types of contaminants in wastewater. several methodologies for its separation from wastewater aris-
Surfactants are divided into four groups depending on their ing out of nuclear industries and mining processes [31].
surface charge, anionic, cationic, non-ionic and amphoteric
(zwitterionic). Both anionic and non-ionic surfactants deliver
harmful effects due to acute toxicity. However, the non-ionic 4 Parameters Influencing Adsorption
ones display higher toxicity as compared to their anionic coun-
terparts [25]. The use of surfactants has been a usual practice Several factors including surface morphology, thickness, the
and has seen a rise from the 1980s, emerging from 1.7 million porosity of adsorbent alongside adsorbate charge, diameter and
tons in 1984 and 9.3 million tons in 1995 [166] to a massive their contact duration drastically influence adsorption [32].
15.93 million tons in 2014 and a probable figure of 24.19 to be Some of the factors are depicted in Fig. 2.
used in 2022 [26]. The worldwide production of surfactants is
above 10 million tons per annum and many daily-use products
contain surfactant formulations [27]. Membrane treatment 4.1 pH
and other physical, chemical, and biological techniques are
deployed for the separation of surfactants in wastewater. A solution’s pH is a prime factor in adsorption as it triggers
Choosing the best treatment method for this process depends electrostatic attractions or repulsions amongst the dye molecule
on numerous factors like influent and effluent quality, the envi- and dendrimer-related adsorbent, based on the nature of the
ronmental footprint, treatment expenses and energy usage dye (cationic/anionic) and/or the solution pH [33]. The pH has
[28]. a direct impact on the metal solubility such that a rise in pH
registers a dip in the solubility because of the generation of
less-soluble metal hydroxides and oxides arising out of the che-
3.3 Pharmaceuticals – Contamination lating activity of the ions on the cations, thereby turning the
Pharmaceutical industries are working on

the manufacture of healthcare commod-
ities, vitamins, vaccines, hormones,
growth parameters, proteins, antibiotics,
cosmetic products, cell cultures and so
on. Similar to other industries, the waste
generated by them is discharged as efflu-
ents (liquid waste), termed ‘pharmaceuti-
cal effluent’, which is a mixture of phar-
maceutically active compounds in low
concentration, by-products, heavy metals,
chemicals, micro-organisms, and cell cul-
tures associated to this process. The threat
caused to the environment by more and
more of its use and input to the aquatic
environment is becoming severe [29]. The
lack of proper knowledge about the actual
consequences on both environment and
human health is an added reason for the Figure 2. Schematic representation of parameters that influence adsorption.
metal soluble in solution which is required for its adsorption. sites on the adsorbent surface. With the duration of adsorption,
Also, extremely low pH figures indicate a higher concentration the sites which were available turn saturated ultimately reach-
of H+ free ions in the solution, in the ion exchange action of ing an equilibrium state [44].
the zeolite, improving the clash among the H ions and the met-
al getting adsorbed, causing their damage (Wang and Peng
[70]). The adsorption of anionic dyes rises with dropping pH 4.5 Temperature
values and behaves vice-versa in the case of cationic dyes
[34, 35]. A rise in the temperature leads to a rise in the removal
strength, which supports the point that the elimination meth-
ods were impulsive, attainable, and endothermic in nature, and
4.2 Adsorbent Dosage can be further stated by the active sites of adsorbent available
in addition to the expansion of the pores and surface area at
The ideal adsorbent dosage affects the quantity of adsorbed elevated temperatures [45]. With respect to the thermodynamic
adsorbate and is thus a key parameter. The surface area keeps properties and their temperature-related behavior, suggests that
on increasing with the escalating adsorbent dosage, and know- the adsorption reaction is enhanced by decreasing temperature,
ing an optimal dosage is essential to avoid excess consumption while the desorption reaction can be favored by increasing the
[36]. Various research teams have studied the influence of temperature [46].
adsorbent dosage on dye or metal removal by adjusting the
adsorbent dosage concentration [37–39]. The MB removal per-
centage is dependent on adsorbent dosage in the case of the 5 Adsorbents
three studied materials (BMB, Biochar, and CO2 biochar). The
trend depicting rising adsorbent dosage brought about a rise in The adsorbent is considered very crucial and is the base of the
percentage separation of MB which is credited to the large adsorption process. The ones used in treating water should not
aggregate of adsorption sites [40]. The adsorbent dosage upon just have good adsorption efficiency, cost-effectiveness and
its increase also increases the percentage of dye removal along- eco-friendly properties, but even the properties of simple sepa-
side. Towards the beginning, this increase was seen to be rapid ration and reproducibility. Currently, different adsorbents are
which decelerated as the dose was extracted. The explanation coming with their unique properties, which allow them to be
for this phenomenon is that the adsorbate is more conveniently used in their actual structure or a modified version to separate
accessible at a smaller adsorbent dose and hence the removal numerous organic or inorganic contaminants from wastewater
for every unit weight of adsorbent is larger too. However, with [47]. The main benefit of these cheaper alternatives is that no
an increase in the adsorbent dose, there is a reduced corre- regeneration is required because of their excessive availability
sponding uprush of adsorption, arising out of the various sites [48]. The broad classification of the adsorbents is given in
staying unsaturated through the adsorption. This could be due Fig. 3.
to the fact that there exists rapid superficial adsorption over the
adsorbent surface at a higher adsorption amount, and this pro-
duces a lower solute concentration as compared to when the
adsorbent dose is the lowest [41].
4.3 Particle Size
The adsorption ability steps up with a decreasing adsorbent

particle dimension due to the expanding surface area.
Although, a scenario where adsorbate is unable to penetrate
some of the interior pores may arise, mostly when their dimen- Figure 3. Broad classification of adsorbents found in the litera-
sions are huge. The smaller-sized particle has easier access to ture [49].
all the pores [42]. The influence of the adsorbent particle di-
mension over the adsorption kinetics had remarkable signifi-
cance. The rate constant (k) associated with the adsorption by 5.1 Nano Adsorbents
the adsorbent showed a dropping trend with rising particle
dimension, highlighting the impact of specific surface area over Nanotechnology presents novel approaches for the water treat-
the rate of adsorption [43]. ment processes in practice by taking some control over the size,
shape, and functionality of the materials [50]. There are adsor-
bents-based n nanoparticles (NPs), which possess a huge, fixed
4.4 Contact Time surface area, which brings about an adsorption rate noticeably
greater than the earlier ones. Nanomaterials owing to their
In the initial stage, adsorption occurs at a rapid rate and their exclusive properties like free surface energy, nano-size the sur-
capacities witness a quick rise at the beginning of the experi- face volume ratio, catalytic, magnetic, and optical properties
ment as a result of a large amount of unoccupied adsorption have gained the attention of the scientific community for the
removal of toxic pollutants [51]. These also have an excellent use thermal stability, great mechanical strength, great adsorption
in cleansing processes, along with being more active and quicker ability and manageable morphology [56].
in eliminating inorganic pollutants like denser metals and organ-
ic contaminants. Adding to the expense of adsorption devices,
the increased efficiency of this technique turns it feasible to exe- 5.3 Activated Carbon
cute other complicated methodologies for wastewater treatment.
The ones that are studied more commonly are: The earliest recognized adsorbents are the activated carbons
Nano adsorbents related to carbon (carbon nanotubes (ACs). They come with a highly porous configuration having a
(CNTs)), nano adsorbents depending on metals, polymeric huge inner surface area varying from 500 to 2000 m2g–1 and as
nano adsorbents, and Zeolites [167]. In recent years, to de- an impact has good adsorption capacities for several substan-
crease the cost of synthesis, wastes with silicon and aluminum ces. It has found its use in separating a range of pollutants con-
have been used for zeolite synthesis, which has developed as a taining organic and inorganic components from the liquid or
research hotspot [52]. gaseous state. They are found in several forms as displayed in
Nanomaterials can be remade without compromising much Fig. 4: powdered activated carbon (PAC), and specifically, gran-
(6–10 %) on their initial performance. Also, the selectivity of ular activated carbon (GAC). Among them, PAC consists of
nanomaterials for a particular contaminant among the co-ex- fine particles, smaller than 0.2 mm in diameter, and hence
isting and competing ions serves as a direction to explore [53]. exhibits large external surface area and small diffusional resis-
The nature of carbon has drawn the attention of researchers tance. This results in a high rate of adsorption. On the other
in recent times as the morphological, physical and chemical hand, GAC is made of larger carbon particles measuring up to
properties associated with it are good to consider. Alongside, 5 mm in diameter, accompanied by smaller external surface
adjusting the surface of carbon spheres or introducing a coat- areas in comparison with PAC.
ing of nanoparticles over it would improve its functionality and The activated carbon gets attracted by organic compounds
agreement, which finally ends with applications in several fields and has oxygenated functional groups present over the com-
[54]. Graphene oxide (GO) is considered a possible 2D compo- plete surface, which attracts the attention of organic pollutants
nent having a huge area. Examples like hydroxyl (-OH), car- [58]. Different residues like industrial activity ash, rice husks,
boxylic acid (-COOH), and epoxide groups indicate vast varia- coconuts, residual sludge, peat, with more, are being put to use
ble functionalities, which are crucial in imparting various for the making of activated carbon [59]. Activated carbon has a
advantages to the GO surface for widespread uses. Although lot of characteristics to offer including a definite surface area,
adsorption happens easily on the GO surface, the extension to high porosity and pore volume, and changeable surface charac-
practical implementations has not been possible due to the teristics with respect to morphology and functional groups. Its
severe deposition of GO in the solution in terms of its excessive applications have been widespread, inclusive of water treat-
hydrophilicity. Various surface manipulations have been tested ment. It is procured by the thermochemical transformation of
to allow recycling of GO and enhance adsorption ability along organic materials at elevated temperatures and void of oxygen.
with its potential to deal with this drawback. Magnetic gra- The factors like the raw material, production methodology, and
phene oxide is a composite component made of graphene constraints have all portrayed a vital part in enhancing its
oxide along with a magnetic component like iron oxide. The adsorption efficiency [60].
nano adsorbents based on phosphorene-oxide are being sug- The activated charcoal usually adsorbs the inhibitors much
gested for the concurrent elimination of very harmful inorganic more effectively than the polymer resin adsorbents, and it is
species like As(III) and As(V) from water. They
display some typical benefits like: i) adsorption
mechanism through surface complexation of the
inner portion of the sphere, ii) good adsorption ef-
ficiency in addition to moderate oxidation degree,
and iii) large recovery owing to easy treatment
techniques using alkaline eluents. Hence, these
become highly probable options for future control
and corrective methodologies for arsenic pollution
in water [46].
5.2 Carbon-based Adsorbents
The materials out of carbon are either finely

crushed or rather large non-metallic solid ones
having a major portion filled by carbon including
activated carbon/biochar (AC/BC), carbon nano-
tubes (CNTs) and graphene (GN) analogues, etc.
Additionally, they are known for the added benefit Figure 4. A schematic flowchart representing different types of activated car-
of greater area, ample pore layout, commendable bon [57].
further complicated as well as expensive to recover them from of the ample surface functional groups and excessive adsorp-
activated charcoals than from polymer resin adsorbents. As action efficiency [66]. In recent times, hyper cross-linked poly-
tivated charcoals are not apt for recovering the inhibitors, the mers (HCPs) are known to be effective organic polymer-based
separation of the inhibitors from lignocellulosic biomass hy- adsorbents which can be used for wastewater treatment. Due to
drolysates with polymeric resin adsorbents is being considered the hydrophobic characteristics of HCPs arising out of rich ar-
[61]. AC for commercial purposes is generally obtained from omatic systems in their skeletons, they can very well eliminate
carbon-based materials like coal, peat, petroleum coke, etc. The oleophilic-hydrophobic pollutants with its base being hydro-
major disadvantage associated is their costly reactivation proc- phobic interaction, van der Waals interaction and p–p interac-
esses as well as greater regeneration energies that occasionally tion amidst the target pollutant molecules and adsorbents.
cause decay in the case of solid adsorbents post several cycles. Although, when HCPs are subjected to hydrophilic or water-
soluble toxins like metal iron, water-soluble dye and antibiotics,
the adsorption capability is significantly diminished [67].
5.4 Polymers
The natural and synthetic types of polymers find an application 5.5 Clay
as adsorbents. The polymeric adsorbents bring along their
advantages and limitations too. Their main advantage lies in Clay has a final negative charge giving it vital cation adsorption
their easy modification to attain selectivity/affinity for certain and cation exchange characteristics. Its arrangement and the
pollutant types based on different chemical alteration methods. aqueous part’s pH decide the onset of adsorption and other
While the prominent drawback remains its price as it is rela- exchange characteristics of the clay. Clay being implemented in
tively expensive to synthesize as compared to other adsorbent environmental applications is known for the adsorption of
classes [62]. Synthetic polymers are seen extensively in the dangerous contaminants like transition metals, and organic mi-
retrieval of natural polyphenols because of their selectivity, effi- cro-pollutants (example: biocides, dyes) in wastewater. Still, the
ciency, regenerative ability, minimal cost, chemical inertia, and affinity of clay towards phosphate adsorption is quite low. Allo-
minimal toxicity [63]. Cellulose acts as a biodegradable, non- phane is an exception as it has various environmental uses
meltable and renewable polymer that is also insoluble in a owing to its reaction seen with harmful anions. The reasons
majority of the solvents because of its hydrogen bonds and behind the high retention capacity for anions are the small par-
crystalline properties. Natural cellulose has smaller adsorption ticle size, great area occupied on the surface and the aluminol
strength unlike modified cellulose, and this can be improved by groups found on the surface [168]. Over decades, the adsorbent
manipulation using chemicals. This can be used as an adsor- employed to eliminate heavy metals, and dyes in aqueous solu-
bent, but cellulose is also modified due to its low adsorption tions are natural and synthetic clays. Over the past few years,
capacity of the former one. Cellulose itself and many of its shedding natural clays into low-dimensional nanosheets or
products do not affect the environment as they come back to nanotubes for making multifunctional clay-based adsorbents is
the natural carbon cycle through a simple decay with decom- gaining a lot of importance. Because of the complicated porous
posers. They also have a typical physicochemical property of structure having a large specific surface area, the internal, as
having great sorption power, thus turning them into a perfect well as external surfaces of clays, get to deal with dissolved spe-
adsorbent in their natural and modified forms [169]. cies. In the case of many clay minerals with negative surface
Cyclodextrin polymers function as effectual adsorbents for charges, the factor causing this is the isomorphic substitution
the rapid adsorption of heavy metal ions from the environment in the tetrahedral sheets (Al3+ for Si4+) and/or in the octahedral
[64]. The coordination polymers (CPs) are being considered sheets (Mg2+ for Al3+), and cationic contaminants will be at-
more for its empty channel, composition distinction optimum tracted. The ones that occur naturally like Ca2+, Mg2+, and Na+
structural diversity and different dimensions and configura- are found in between or over the surface to adjust the charge,
tions. This makes it suitable to be used for catalysis, gas storage making the clay instilled with an ion-exchange capacity to
and delivery. Specifically, in comparison, CP is advantageous manage the pollutant [68].
due to its easier attainment of functionalization and diverse With respect to the adsorption properties of the clay mineral,
preparation methods along with being the best adsorbent for surface modifications have been considered as depicted in Fig. 5
separating metal ions. The low chemical stability, low adsorp- as they permit the coalescence of new materials and as a result,
tion ability and meagre selectivity of many CPs become a hur- the introduction of new areas of usage. Their preparation can be
dle in their application in aqueous solutions. This makes the made possible with sol-gel synthesis at room temperature,
method of improvisation of material performance key to its co-precipitation, and microwave-aided blend with numerous
application [65]. Being a polysaccharide derived from sesbania molecules. The functional groups which are found on interlayer
seeds, sesbania gum (SG) is organic, chemically non-reactive, clay mineral surfaces play an important role, and the mentioned
non-toxic, cost-effective and seamlessly available. Considerably, organic functional groups are enabled to provoke certain interac-
the plentiful hydroxyl groups present on the SG surface’ pro- tivities with adsorbate molecules. Various environmental, biolog-
vides versatile probabilities for covalent functionalization. It is ical, and catalytic activities need the synthesis of functional clays
being widely studied as a side substrate in numerous cases to be greatly dissolvable in an aqueous medium and capable to
including adsorption, catalysis, flocculation, textiles, pigments, bond with required substrates (adsorbates) [22].
and cosmetics. Specifically, SG has been identified to be a suit-
able adsorbent for combating environmental pollution because
Figure 5. Progress in
Clay related adsorbents
from natural clay to
nano-clay composite.
5.6 Industrial Waste nology and a cost-effective culture substrate can be used
because of the lesser production expenses of fungal biomass.
Some of the wastes generated by the industries are being used Also, biosorption is an expanding method which managed to
in the form of adsorbents for the adsorption of ions and organ- surpass the imperfections of selectivity in conventional adsorp-
ics in wastewater [69]. This use of waste is becoming popular tion processes. Meanwhile, bio-adsorption is also known to
because of its easy availability, minimal cost, and good mechan- have some unfavorable factors associated with it. The first of
ical and chemical resistance. This application is in line with the them is that adsorption is a slow process, followed by the other
concept of green chemistry and also with the booming environ- is that the pH has an effect on this process. Also, the functional
mental regulations enforced to prevent improper disposal prac- groups and surface features in fungal organisms show an effect
tices [70]. The reuse and recycling of industrial garbage have on adsorption. Moreover, some additional factors also altered
been explained through the circular economy, sustainable de- the adsorption process, namely competitive salt and ion con-
velopment, along with green engineering techniques. The fate, centration. In addition to this, the biomasses could restrict the
transportation, and transfer of disposed of graphite impurity in adsorption column easily [74]. Among biosorbents, Chitosan
soil, water and air components because i) environmental prob- has some disadvantages in terms of being soluble in low pH as
lems acting as the absorber and carrier of harmful compounds, it does not adsorb Cr (total) at small pH levels. This happens
ii) acute health issues like graphitizes because of unwanted due to reason that the active site (amine group) in Chitosan
graphite exposure, and iii) social disturbance as the dense goes through protonation and its adsorption ability gets
graphite dust obstructs visibility [71]. Mechanically activated affected by anions in water [75]. Tab. 1 lists the Adsorption effi-
fly ashes can be employed as an adsorbent for separating a few ciencies of various adsorbents.
heavy metals namely, Cu(II), Mn(II), Ni(II), Pb(II), and Zn(II)
from aqueous solutions. The adsorption ability of fly ash can
be varied by enhancing the surface activity with mechanical 6 Qualities of Good Adsorbents
activation [72].
The salient characteristics of an adsorbent in any application
are its capacity, selectivity, reconstructibility, kinetics, compati-
5.7 Natural Adsorbents bility, and expense [92]. Along with this, an excellent adsorbent
must also possess the following characteristics. Fig. 6 illustrates
The natural biomasses being used as adsorbent is grabbing
more and more attention because of their biodegradability, bio-
compatibility, and renewability [73].
Biosorbents are the category of adsorbents obtained from
biomass and related materials which do not take part in any
thermochemical breakdown prior to being used. The important
aspect of biosorbents is their retention ability towards the
actual composition of the source material. In terms of biomass,
the degrading of components starts at a temperature greater
than 300 C. Although, material processed below this tempera-
ture is also considered a biosorbent. Further, even without hav-
ing an extremely large surface area, the numerous functional
groups provide it with the ability of dye uptake through various
physicochemical interaction mechanisms [62].
Biosorption implements a few biological materials such as
chitosan, yeasts, fungi, chitin, and bacteria in order to separate
toxins in the mixture using chelation and complexation. Con-
sidered alongside the conventional ion exchange resins and
commercial AC, the biosorption materials show an improved
selectivity in addition to the toxin quantity brought down to
the ppb range. Biosorption is an ideal technique to eliminate
contaminants at a very minimal price. It also has an added
advantage of a high elimination rate specifically for extremely Figure 6. Schematic representation of qualities of good adsor-
toxic wastewater. Further, an easier path of fermentation tech- bents.
Table 1. Adsorption efficiencies of various adsorbents from the literature. account the build-up of a chemical
bond, either ionic or covalent, be-
Efficiency [%] Adsorbate Adsorbent Ref. tween the adsorbent and the adsorb-
ate, accompanied by an enormous
99.95 Methylene blue (MB) and Magnetic silicate@Fe3O4 [68]
cationic yellow (CY) exothermic enthalpy and induces a
modification in the electronic con-
70 Yellow dye Natural clay [76] figuration of the adsorbate as well as
100 Carbendazim Bentonite clay [77] the adsorbent. Whereas physisorp-
tion has weaker forces involved like
92 Cd Natural clay [78] Van der Waals and polar interac-
100 and 93 MB dye and methylene orange Industrial carpet waste [79] tions, being associated with a rela-
tively smaller enthalpy causes some
99.17 Azodye Industrial waste [80] agitation in the electronic structure
90 Cationic dye Ceramic adsorbents prepared from [81] of the compounds associated [97].
industrial waste Considering physisorption, the drop
sticks onto the surface because of
82.7 As Slag material [82]
Van der Waals’s force of attraction,
88.7 Industrial toxic dye Moringa seeds [83] surface roughness or hydrophobici-
ty. This accumulation takes place
97 mixed dyes Industrial microbial waste [84]
over the surface in a mono-layer or
97 MB Rice straw [85] multi-layer form based on process
96.6 Heavy metals Organic-inorganic hybrid of [86]
characteristics. In the case of the
poly(acrylic acid-acrylonitrile)/ monolayer build-up, the solute
attapulgite, P(A-N)/AT nanocomposites builds up in the form of a single layer
with one molecule depth, and in the
94.85 and 92.78 Pb Mango seeds cover with kernel, and [87] multilayer one, the solute accumu-
jamun seeds cover with kernel
lates in multiple layers comprising
99 Cr, Cu, Pb, and Hg Activated carbon and biochar, and [88] changing chemical bonds and physi-
nanomaterials cal forces in several layers. And the
86.7 Cd(II) ions Chitosan composite [89]
multilayer accumulation will give
higher adsorption quantities, but
98.71 U(VI) Brown algae [90] owing to the number of bonds asso-
85 Heavy metal Desiccated coconut [91] ciated, the pores are required to be
sufficiently big to adjust the bond
lengths [98].
the qualities of good adsorbents: (1) good reusability, (2) dis-
tinct pore structure to enable rapid interaction between adsorb-
ate and adsorbent, (3) high thermal stability, (4) high surface 8 Adsorption Isotherm
area [93], (5) reversibility of adsorption, and (6) easy renew-
ability [94]. The mechanism concerning the adsorption of natural and syn-
Appropriate functional groups have to be chosen as adsorp- thetic adsorbents has been revisited in terms of thermodynam-
tion spots for strong adsorption forces like primary, secondary ic, equilibrium, and kinetic studies. The isotherm models
and tertiary amines for interactions among the ions. Alongside, explaining the adsorption equilibrium were studied on the ba-
a certain amount of overall adsorption sites and decent adsorb- sis of several isotherm models. Depending on the assumptions
ent accessibility is necessary for the dyes. Thus, an adsorbent that these patterns are derived, it could be estimated whether
must have a plausible amount of adsorption sites for every unit the adsorption processes turn out to be homogeneous or het-
of surface area [95]. The adsorbents are generally in granular erogeneous, or if an amalgam of both took place on the surface.
form having dimensions from 0.5 mm to 12 mm, and they Additionally, they also suggest if the process happened favor-
should not provide a high-pressure drop or even get taken ably, unfavorably, chemically, or physically [99]. The isotherms
away with a stream flow. Their shape and size should remain are vital in explaining the interactions among adsorbent and
intact amidst handling, and they should have a larger surface adsorbate that are useful in understanding the process [100].
area per unit mass along with too many pores [96]. Adsorption isotherms are affected by: adsorbent properties,
adsorption cycles and desorption differ adsorbent properties
likely because of the gradually developing changes in the pore
7 Mechanism of Adsorption structure, origin and preparation technique, in addition to tem-
perature and relative humidity of the gaseous stream [170].
Based on the factors governing the activities at the solid surface Along with the ongoing adsorption process, the desorption
and the adsorbate, adsorption is categorized into chemisorption and adsorption rate will acquire a similar stage with time,
and physisorption. Among these, chemisorption takes into which indicates that the kinetic model and adsorption isotherm
are usually made to adjust with the adsorption [101]. Adsorp- The separation factor (RL) is an important specification for
tion isotherms are derived from conducting batch studies at the Langmuir adsorption isotherm model and is explained by
constant temperature values. This constant figure estimated
through the isotherm equation gives an equilibrium adsorption 1
RL ¼ (3)
capacity plus an affinity for the adsorbents. 1 þ bco
Isotherms describing adsorption of organic compounds are
spread over four major groups based on the behavior of slope at The value of RL showcases the process feasibility. It holds
the starting part of the curve, and further into sub-categories. favorable at 0 < RL < 1 and unfavorable at RL > 1. RL = 0 con-
The main categories are: (i) S curves, indicating vertical incli- veys that the adsorption reaction has attained equilibrium
nation of molecules getting adsorbed, (ii) L curves, the normal whereas RL < 0 conveys that the adsorption in this case is irre-
or Langmuir isotherms, mostly suggesting the molecules ad- versible [105].
sorbed on the surface, or, occasionally, of vertically arranged
adsorbed ions with specifically severe intermolecular attraction,
(iii) H curves (high affinity), usually brought by solutes ad- 8.2 Freundlich Isotherm
sorbed in the form of ionic micelles, and through high-affinity
ions exchanging with low-affinity ions, and (iv) C curves (con- For scenarios where the assumptions of Langmuir isotherm
stant partition) and linear curves, coming from solutes which stand invalid, different models have been suggested. Similar to
pass through into the solid much easily than the solvent. The the Langmuir isotherm, they comprise the first and zero order
sub-groups of these categories are considered based on the con- regions over some stretch of partial pressure or concentration.
figuration of the sections of the curves that are away from the Freundlich isotherm is one of the common methods here
origin. Therefore, if the solute molecules getting adsorbed are [106]. The Freundlich isotherm model holds good in the case
set in a way that the novel surface has very less attraction for of heterogeneous surfaces as this model elucidates the mono-
further solute particles and the curve thus has a long plateau; layer and the multilayer adsorption, and it even signifies the
and if adjusted such that the new surface has a greater attrac- point that the adsorbent carries surface with different affinities
tion for the further solute, the curve sees a steady rise without for adsorption on heterogeneous surfaces.
any plateau [102].
1
In case of a monolayer process (model 1): lnðqe Þ ¼ lnðKf Þ þ Ce (4)
n
nS
Qe ¼ m n (1) where Kf and n are Freundlich constants representing the
1 þ C1=2 =Ce
approximate indicators of the capacity and intensity of the pro-
cess respectively [107]. There are several kinds of energy
There are three parameters inculcated into this model, where
adsorption sites, but with similar entropy distributed with
n stands for the number of adsorbate molecules for every adsorb-
respect to an exponential law which depends on the heat of
ent site, Sm denotes the density of receptor sites and C1/2 repre-
adsorption. The density of the site records an exponential
sents the concentration at half-saturation. Accordingly, the ad-
decrease. This isotherm is presented with the help of the non-
sorption capacity at saturation can be determined by Q = nSm.
linear Eq. (7) or linear models.
In case of a double-layer process (model 2)
ðCe =C1 Þn þ 2ðCe =C2 Þ2n Qe ¼ kF Ce1=n (5)

Qe ¼ nSm (2)
1 þ ðCe =C1 Þn þ ðCe =C2 Þ2n where Ce is the equilibrium concentration (mg L–1), kF stands
for the Freundlich isotherm constant based on the adsorption
In this type of adsorption, the dual concentrations at half-
capacity; n for the adsorption intensity, and Qe is the quantity
saturation are figured and matched to the development of the
of adsorbate in the adsorbent at equilibrium (mg g–1) [108].
two initial layers, respectively; they are mentioned as C1 and
The value of n is a crucial aspect, acting as a sign of the curva-
C2. Accordingly, the adsorption capacity at saturation can be
ture of the isotherm. If the value of n is found to be 1, then the
calculated by: Q = 2nSm [103].
process is said to be linear, and if n is greater than 1, then it is a
favorable physical process. Similarly, if n has a value below 1,
the adsorption is termed as a chemical process and is unfavora-
8.1 Langmuir isotherm ble [109]. An adsorption process is termed co-operative based
on the 1/n values, wherein a value of 1/n greater than 1 sug-
The Langmuir isotherm is developed on these assumptions: (1)
gests a high co-operative process and its counterpart stands for
the adsorption process occurs as a monolayer process (chemi-
a less co-operative process. Additionally, a decreasing value of
cal adsorption), (2) homogeneous adsorption site which could
1/n leads to a heterogeneous process whereas the process
be adsorption pellets, and (3) an unchanged adsorption heat
becomes more efficient at low adsorbate concentrations [110].
with the coverage. Thus, as per the Langmuir isotherm, adsorp-
tion occurs on the collision of a free adsorbate molecule with
an unoccupied adsorption site and also when every adsorbed
molecule has a similar desorption percentage [104].
8.3 Sips Isotherm (Langmuir-Freundlich) 8.6 Temkin Isotherm
Equation
Initially, the Temkin empirical isotherm model was imple-
The Sips isotherm is the combined outcome of the Freundlich mented for the explanation of the adsorption of hydrogen on
and Langmuir isotherms. Its behavior is quite identical to the platinum electrodes kept in an acidic solution which acts as a
Freundlich isotherm. But it differs in the aspect of having a chemisorption system. This system takes into account the
finite saturation limit with a high concentration extent. This interaction between the adsorbent and the adsorbate while
isotherm is generally valid in cases where both models are neglecting the high and low concentration values [116]. It also
inapplicable [111]. assumes that the adsorption heat varies along with tempera-
ture, and that of all the molecules remaining in the layer, it
ðKS Ce ÞnS drops linearly and not logarithmically as a result of the expand-
qe ¼ qm (6)
1 þ ðKS Ce ÞnS ing surface coverage owing to the sorbent–sorbate interactions
[117].
Here, KS is an affinity constant and nS indicates surface The Temkin model also considers that the adsorption proc-
heterogeneity. If nS is equal to 1, Sips isotherms tend toward ess occurs in multi-layers. Drastically high and low concentra-
the Langmuir isotherm and suggest homogeneous adsorption. tion of the adsorbate in the liquid phase is neglected. Yang
Also, the deviation of the value of nS from 1 indicates surface [171] deduced the statistical mechanical equation in the case of
heterogeneity. At high concentration levels, Sips reach a con- the Temkin isotherm and replaced it back into the Clapeyron-
stant value whereas Freundlich isotherm is applied in case of Clausius equation, and assured that the differential heat related
low concentrations [112]. to adsorption had a linearly decreasing trend with the increas-
ing coverage.
8.4 BET (Brunauer-Emmett-Teller) Isotherm RT

qe ¼ lnðACe Þ (9)
b
The BET (Brunauer-Emmett-Teller) model is a variation of the
Langmuir isotherm, suggesting the occurrence of adsorption where A and b are constants [118].
due to coagulation by the attraction of the adsorbate over the
adsorbent surface in an uneven distribution and multilayer for-
mation of the adsorbed particle [113]. This is a general multi- 8.7 Dubinin-Radushkevich (D-R model)
layer model which assumes that a Langmuir model works for
each layer and that transmigration does not occur among the The Dubinin-Radushkevich (D-R) equation is generally men-
layers. Matching energy of adsorption for all the layers except tioned to explain the physical adsorption of organic vapors
the first one is also an assumption considered. over microporous adsorbents. The adsorption process was
studied by the D-R isotherm model to assure that the process
KBET qmax Ceql was chemisorption or physical adsorption [119]. The D-R
qeql ¼
1 C =C
(7)
Cinit Ceql 1 þ KBET eql init model is made as per Polanyi’s theory and the assumption in
consideration that the spread of pores in the adsorbent is
where Cinit is metal ion concentration at saturation (in mmol L–1) according to the Gaussian energy distribution [120].
and KBET is a parameter based on the intensity of binding of all
the layers; There are two limiting scenarios identified here, when D R system : lnðQe Þ ¼ lnðQm Þ b2e (10)
Ceql << Cinit and KBET >> 1, this model tends towards Langmuir
isotherm (KL = KBET/Cinit) [114].
1
e ¼ RT ln 1 þ (11)
Ce
8.5 Redlich-Peterson Isotherm where b (mol2J–2) represents the adsorption energy constant,
e (kJ mol–1) is the potential Polanyi energy obtained from
Redlich-Peterson model comprises three modifiable features
Eq. (10), Polanyi sorption potential denoted by e is the amount
combined to form an empirical isotherm. This finds wide-
of work needed to shift a molecule from its position in the
spread use because of its adjustment between Langmuir and
sorption space to infinity, independent of temperature [121].
Freundlich systems. The model equation, in this case, is given
R (8.314 J (mol K)–1) is the molar gas constant; T (K) is adsorp-
as
tion temperature; Qe (mg g–1) and Qm (mg g–1) are the equilib-
KRP Ce rium and maximum adsorption capacities respectively, and
qe ¼ b
(8) Ce (mg L–1) is the equilibrium constant [122]. Various adsorp-
a R Ce þ 1
tion isotherm models were applied and the best fits obtained
where KRP and b are the constants. With b getting equal to 1, are summarized in Tab. 2.
the model takes the form of Langmuir Isotherm and mean-
while it deduces to Freundlich isotherm, in scenarios where the
value of the term aRCbe goes above 1. The ratio of KRP/aR
stands for the adsorption capacity [115].
Table 2. Adsorbents and the adsorption isotherm models from the literature. 9 Kinetic Models
Adsorbent Adsorbate Models best fit Models tested Ref.
The two major aspects to under-
Date seeds Methyl violet dye Langmuir Langmuir and Freundlich [123] stand the processes of adsorption
and desorption are equilibria and
Fly ash Tannery effluent Freundlich Freundlich [124]
kinetics. With respect to these pro-
Synthetized cobalt Phenol Langmuir Freundlich model and the [125] cesses, thermodynamics only helps
oxide Langmuir model us with data about the ultimate
state of a system whereas kinetics is
Papaya bark fiber Methylene Blue Langmuir Langmuir and Freundlich [126]
adsorption isotherms concerned with variations in chem-
ical properties with time and in all
Palm kernel shell Methane Freundlich Langmuir, Freundlich, and [127] the rate of changes [131]. The
Temkin kinetic theories indicate the ad-
Carbon nanotubes Metal ions Redlich-Peterson Redlich-Peterson, Sips, [128] sorption rate and are studied in
Langmuir, Freundlich terms of the reaction-based models
(pseudo first-order, pseudo second-
Kaolin and kaolin/ Pollutants from Redlich-Peterson Langmuir, Freundlich, Halsey, [129]
order) and diffusion-related mod-
TiO2 nano- industrial waste- (R-P), Jovanovic, Redlich-Peterson
adsorbents water (R-P), Flory-Huggins
els. Various kinetic models were
tested and the best fits obtained are
Cashew nut shell Brilliant green dye Langmuir isotherm Langmuir isotherm [130] summarized in Tab. 3.
activated carbon
9.1 Pseudo First-Order

Table 3. Summary of Kinetic models and the best fit as obtained from the literature.
Kinetics
Adsorbent Operating Models best fit Models tested Ref.
parameters
The pseudo first-order model
assumes that the rate of adsorption
Activated carbon in pH, time, and con- Linear pseudo Pseudo first-order kinetic [132] varies proportionally to the
the form of carbo- centration second-order (PFOK) model and pseudo amount of active adsorption spots
naceous hydrochar kinetic model second-order kinetic (PSOK) on the adsorbent [28]. The equa-
model tions being considered to develop
Turkish lignite Contact time, dye Pseudo second- Pseudo first-order and pseudo [133] pseudo first-order kinetics for an
concentration, order kinetic model second-order model, adsorption system are:
temperature, pH, intraparticle diffusion
adsorbent dosage lnðQe Qt Þ ¼ lnðQe Þ k1 t
CTMAB-Bent Adsorbent dosage, Pseudo second- First-order, pseudo second- [134] (12)
solution pH, order order, intra-particle diffusion
contact time and and Elovich
dye concentration Q t ¼ Qe 1 e k 1 t (13)
Simarouba glauca Adsorbent dosage, Pseudo second- Pseudo second-order kinetics, [135]
seed shell carbon contact time, pH order kinetics intra-particle diffusion where Qt is the quantity adsorbed
at time t, Qe for the equilibrium
Sugarcane bagasse Contact time, Pseudo second- Pseudo first-order (PFO), [136] amount, t for time (min), and k1 is
adsorbent dose, dye order pseudo second-order (PSO), the rate constant [140].
concentration, and intra-particle diffusion
temperature, pH, (IPD) models
and NaCl dose
9.2 Modified Pseudo
Tea waste/Fe3O4 Adsorbent dosage, Pseudo second- Pseudo first-order, pseudo [137] First-Order Model
magnetic compo- dye concentration, order second-order, Elovich, intra-
site contact time, pH particle diffusion model With this model consisting of no
A-zeolite/bacterial Dye concentration, Pseudo second- Linear and non-linear forms [138] theoretical derivation, the pseudo
cellulose composite adsorbent type, order of pseudo first-order, pseudo first-order expression is changed
membrane contact time, tem- second-order, and intra- with respect to its rate constant by
perature, and pH, particle diffusion models. substituting k1 by K1, where
Bio-nanocomposite Temperature, and Pseudo second- Pseudo first-order , pseudo [139] k1 = K1(qe/qt) provides the rate
based on whey pro- pH, adsorbent dose, order and intra- second-order, and intra- equation
tein nanofibrils and dye concentrtaion particle diffusion particle diffusion
nano-clay
dqt q above-described models are insufficient to figure out the diffu-
¼ K1 e ðqe qt Þ (14) sion mechanism, and hence the intra-particle diffusion model
dt qt
was introduced. The early rate of intra-particle diffusion
Integrating and implementing the boundary conditions, for (Eq. (18)) can also be written as
qt = 0 at t = 0 and qt = qt at t = t, the Eq. (13) becomes
qt ¼ kp t 1=2 (19)
qt
þ lnðqe qt Þ ¼ lnðqe Þ k1 t (15)
qe where kp is the intra-particle rate constant (g mg–1min–1/2)
which varies according to equilibrium concentration in solid
This is the final equation for the modified pseudo first-order phase qe and intra-particle diffusivity D, is given in the form of
reaction, where K1 denotes the rate constant of the modified an equation like Eq. (20)
pseudo first-order (min – 1) [141]. rffiffiffiffi
6qe D
kp ¼ (20)
r P
9.3 Pseudo Second-Order Kinetics
where, r stands for particle radius and D for intra-particle dif-
The two mechanisms of sorption are film diffusion and particle fusivity [147].
diffusion controlled. Prior to adsorption, various diffusion pro-
cesses affecting the adsorption process occur. The sorbate then
diffuses through the volume to the layer covering the adsorbent 10 Thermodynamic Considerations
and finally towards the micro pores and macrospores on the
adsorbent [142]. Kinetic results can be studied with the intra- Thermodynamic parameters obtained through equilibrium cal-
particle diffusion model which explains the diffusion mecha- culations denote the internal energy of a system and the poten-
nism [143, 144]. tial of the processes taking place instantaneously. The thermo-
dynamic parameters can be explained by
t 1 t
¼ þ form (16) Co Ce V
Qt k2 Q2e Qe Kd ¼ (21)
Ce m
k2 Q2e t where Kd denotes the equilibrium distribution coefficient, Co

Qt ¼ linear form (17)
k2 Qe tþ1 (mmol L–1) for the initial concentration, Ce (mmol L–1) is the
equilibrium concentration in solution after being adsorbed and
V (L) is the volume of solution. The distribution coefficient
(Kd) denotes the ability of clay minerals to hold a solute and
9.4 Kinetic Model of Intraparticle Diffusion the extent of its mobility in a solution phase. Kd holds a signifi-
cant role in comparing the adsorption capacity of different
The two mechanisms of sorption are film diffusion or particle
clays for specific ions under identical experimental conditions.
diffusion controlled. Prior to adsorption, various diffusion pro-
Moreover, Kd values are implemented in the graph of ln (Kd)
cesses affecting the adsorption process occurs. The sorbate then
versus 1/T so as to estimate the Gibbs energy change (DG0) of
diffuses through the volume to the layer covering the adsorbent
adsorption at various temperature values [148].
and finally towards the micro pores and macrospores on the
The distribution coefficient (Kd) can be denoted with respect
adsorbent [142]. Kinetic results can be studied with the intra-
to the change in enthalpy (DH0), which is also the adsorption
particle diffusion model which explains the diffusion mecha-
heat and the standard entropy change (DS0) (J (mol K)–1) of
nism [143].
adsorption which varies according to temperature.
qt ¼ k3 t 1=2 þ C (18) DS0 DH 0
lnðKc Þ ¼ (22)
R RT
k3 (mg g–1min–1/2) stands for the equivalent adsorption rate
constants, and qe (mg g–1) and qt (mg g–1) stand for the Pb(II) where Kc denotes the distribution coefficient for the adsorp-
and Ni(II) ions getting adsorbed at equilibrium and at time t, tion, DH0 is the enthalpy change, DS0 for the entropy change,
respectively [145]. DG0 denotes Gibb’s free energy change, R stands for the gas
The intercept in the form of the constant C determines if the constant and T is the absolute temperature [149].
controlling step classifies as intra-particle diffusion. If C is not The thermodynamic study greatly influences the absorption
equal to zero, the process is complicated, and if C equals zero, process conditions like DG (standard Gibbs free energy), DH
the process kinetics is determined just by intra-particle diffu- (enthalpy change) and DS (entropy change) irrespective of an
sion. The constant is always associated with a non-zero value endothermic or exothermic reaction taking place and works as
in the theory, suggesting that this process is just not influenced an adsorption process itself. The variation in Gibbs free energy
by intra-particle diffusion but also comprises a complex mech- (DG) is given by Eq. (23)
anism pathway, which includes the chemisorption of chitosan
and predominantly the physisorption process of GO [146]. The DG0 ¼ DH 0 TDS0 (23)
R is equal to 8.314 J (mol K)–1 and T is the absolute tempera- 11 Regeneration and Reuse
ture (K). The graphical derivation of thermodynamic features
was performed by Haghighizadehet et al. [172]. The absolute An adsorbent to be effective should have a high adsorption effi-
magnitude of standard free energy change (DG0) for physisorp- ciency plus regeneration capacity. The study related to regener-
tion falls in the range of 0 and –20 kJ mol–1, while for chemi- ation is important to find out about the recovery of pollutants
sorption it ranges from –80 to –400 kJ mol–1 [150]. and adsorbent compatibility [173]. Hence, the regeneration of
If the standard enthalpy DH0 has a value lesser than zero, it support that has been used in the batch or the dynamic adsorp-
suggests that the adsorption process is of exothermic nature, tion is a required aspect to minimize the expenses. And there-
Rahdar et al. [152]. The negative value of Gibbs free energy fore, the regeneration and desorption experiments help to
(DG0) indicates the spontaneity of the process and the positive determine the ideal desorption of an eluent [154]. Tab. 4 repre-
enthalpy (DH0) figures of RhB adsorption onto MgO-FCM- sents a summary of the regeneration studies done on certain
NPs suggest an endothermic nature. adsorption studies.
Thermodynamic parameters supply the required data to Regeneration is a special technology which has the ability to
develop an adsorption mechanism. Mostly, thermodynamic restore the adsorption ability of used adsorbents by desorption
parameters, namely heat of enthalpy (DH), Gibbs free energy of the impurities already adsorbed. This is generally a cost-
(DG), and entropy (DS) are important features that determine effective and better alternative than changing the adsorbents
the feasibility and spontaneity. For estimating these parameters, altogether. This process varies with experimental temperature,
KL (Langmuir constant), Kd (solute coefficient distribution), pH, time, and the cycles necessary for processing [160]. Addi-
and Ce (equilibrium fluoride concentration) which depend on tionally, if the adsorbent is not amenable to regeneration, it has
temperature are given by Eqs. (24)–(31). to be discarded after every use, which is one of the main draw-
Distribution coefficient backs of this technique [161]. Post the adsorption process, the
DS DH used dye adsorbents are removed as waste, but a decline in
lnðKd Þ ¼ (24) waste generation, regeneration, and reuse of the deployed
R RT
adsorbent are noteworthy. Out of these, the regeneration proc-
DG ¼ DH TDS (25) ess should be economical and with less energy consumption
[162]. With respect to the environmental, economic and practi-
qe cal aspects of view, regenerability is a key point in estimating
Kd ¼ (26)
Ce the efficiency of an adsorbent. The advantages and disadvan-
tages of the regeneration process have been shown in Fig. 7.
Langmuir Constant The definition of regeneration describes it as the continuous
DS DH recycling or recovery of the used adsorbents with methods that
lnðKL Þ ¼ (27) are viable both technically and economically [163].
R RT
The process of desorption is one of the economical and effec-
DG ¼ RT lnðKL Þ (28) tive regeneration process, reserving the process of adsorption.
Research on desorption gives a clear image of the kind of ad-
Equilibrium constant sorption which can turn out to be either physical or chemical
DH
lnðCe Þ ¼ lnðKo Þ þ (29) Table 4. Summary of recent adsorption studies with regeneration of adsorbent.
RT
Study Regents of regeneration Regeneration efficiency [%] Ref.
DS is calculated using the Gibbs-
Helmholtz equation Sb-SnO2/C membrane to treat phe- NaOH 80.6 [155]
DH DG nolic wastewater
DS ¼ (30)
T Removal of organic micropollutants Ozone ~70 [156]
from wastewater effluent: selective
DG ¼ nRT (31) adsorption by a fixed-bed granular
zeolite filter
where n is the Freundlich constant Removal of ciprofloxacin from waste- NaCl ~60 [157]
[152]. water by intercalated Ti3C2Tx MXene
The entropy change DS can be
procured from these expressions: Coupling ammonia nitrogen adsorp- NaClO–NaCl ~94 [158]
tion and regeneration unit with a
d lnðPÞ high-load anoxic/aerobic process to
Qst ¼ RT 2 q (32)
dT achieve rapid and efficient pollutants
removal for wastewater treatment
Qst
lnðPÞ ¼ þL (33) Adsorptive treatment of coking Fenton’s reagent 89.7 [159]
RT wastewater using raw coal fly ash:
adsorption kinetic, thermodynamics
where L is the integration constant
and regeneration by Fenton process
and DH = –Qst [153].
adsorption. It also emphasizes the performance of the adsorb- 13 Conclusion
ent for further use, causing a reduction in related expenses.
Desorption is classified into 1) thermal desorption, where From the study, we see that separation of contaminants should
desorption is conducted with heat. Keeping its speed and effi- be done through unique adsorbents. Properties such as their
ciency aside, this process involves heavy expenses, pre-treat- pore dimension, alkalinity, negative charge, exceptional perme-
ment which liberates toxic contaminants, associated unsafe ability, and surface area along with their cost-effective and sus-
process conditions, challenges due to regulations and public tainability should be considered. This review discusses the type
perceptions, etc. 2) Solvent desorption, which is environmen- of contaminants and the different molecules that can be used
tally feasible, cheap, fast, and has high potential [55, 164]. as adsorbents. Despite the successful use of different materials,
Adsorbent regeneration is a process that can be brought about there are still various limitations, making commercial and
by numerous methods like temperature swing regeneration practical use difficult. Therefore, there is a need for further
(TSR), pressure swing regeneration (PSR), reactive regenera- development for enhanced adsorption capacity to adsorb var-
tion, or altering the envelope around the adsorbent with a fluid ious types of environmental pollutants. From the cost perspec-
which can extract the adsorbate. Within these mentioned tive, the ability of adsorbents to be recycled is also an impor-
methods, TSR and PSR are widely used for adsorbent regenera- tant criterion in industrial applications.
tion, although, TSR is mostly used for purification purposes Apart from the adsorbent type, there are various physical
[165]. and chemical parameters that play an important role in the
process. So, theoretical knowledge is necessary to understand
the interaction mechanism between the contaminants and
12 Challenges adsorbent. The theoretical background and physical meaning
for the most relevant adsorption kinetic models was reviewed
When novel sorbents are being implemented for wastewater and discussed. The empirical pseudo second order and pseudo
treatment, a major issue that accompanies is an ineffective or first order models are adaptations to heterogenous systems;
slow rate of desorption/regeneration. At present, the bound- however, they can be obtained from fundamental theories such
aries on adsorption keep an extensive use of technological as Langmuir kinetics. For selecting the optimum model ,
innovations away making it difficult to tackle the dearth of assessment and comparing the error functions such as R2,
regeneration techniques to facilitate the recycling of the adsor- RMSE (root mean square error), c2 (chi-square) and so on are
bent. As a result, the pollutants end up being disposed into the essential. Calculating R2 value is a common practice for evalu-
environment without the process of regeneration. The com- ating fitting results. However, the differences in R2 values are
pounds acting as regenerative agents are hazardous to the poly- very small in some cases; hence calculating R2 alone is insuffi-
mer backbone of the biosorbents, and hence finding a better cient for model comparison. The model parameters are
alternative poses a challenge to the researchers. Also, the gaps strongly dependent on the operating conditions. It is recom-
found demand further research to develop a cost-effective mended to use the complete isotherm to correlate with the ex-
modification technique. The waste-derived adsorbents have to perimental data. The adsorption mechanisms and surface
be modified by means of either physical or chemical processes properties are not directly related to the isotherm models.
owing to their inherent shortcomings. There has been consid- The process of adsorption brings along features like simplic-
erable development in terms of the introduction of new adsor- ity, high efficiency and extensive availability making it an
bents, but they are yet inapplicable as they need a compara- emerging treatment process for dye removal. This also pushes a
tively acidic environment and create sludge at the end even need for adsorbents that perform with more efficiency in the
though they have been tested and improved over time.
Figure 7. Regeneration associated advantages and disadvantages depicted schematically.
domain of water treatment which would enhance pollution CP coordination polymers
control at large scale for commercial applications. CY Cationic yellow
This review paves a foundation for the researchers in chemi- GAC granular activated carbon
cal engineering by giving an idea about each module involved GN graphene
in the process of adsorption related to exclusion of contami- GO graphene oxide
nants from wastewater along with the explanation of the mech- HCP Hyper cross-linked polymers
anism or kinetics. On the basis of the diverse contaminants MB Methylene blue
and adsorbents discussed here, new researchers can choose the PAC powdered activated carbon
right combination of adsorbent and contaminant for the treat- SG Sesbania gum
ment process. TSR Temperature swing regeneration
Conflicts of Interest Authors Contributions

The authors declare no conflict of interest.
Dr. Divyashree Somashekara has contributed to the write up
and Dr. Lavanya Mulky has conceptualized the manuscript
Divyashree Somashekara is an content.
Assistant Professor Selection
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ChemBioEng Reviews - 2023 - Somashekara - Sequestration of Contaminants From Wastewater A Review of Adsorption Processes

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Sequestration of Contaminants from Wastewater: A Review

1 Introduction stances has been in the limelight as the chemical industries

Pharmaceutical industries are working on

4.3 Particle Size

The adsorption ability steps up with a decreasing adsorbent

5.2 Carbon-based Adsorbents

The materials out of carbon are either finely

ðCe =C1 Þn þ 2ðCe =C2 Þ2n Qe ¼ kF Ce1=n (5)

8.4 BET (Brunauer-Emmett-Teller) Isotherm RT

9.1 Pseudo First-Order

k2 Q2e t where Kd denotes the equilibrium distribution coefficient, Co

Figure 7. Regeneration associated advantages and disadvantages depicted schematically.

Conflicts of Interest Authors Contributions

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