In G. Crini, E. Lichtfouse (eds.

), Green Adsorbents for Pollutant

Removal, Environmental Chemistry for a Sustainable World 18.
Springer, pp. 23-71
https://doi.org/10.1007/978-3-319-92111-2_2

Adsorption-Oriented Processes Using

Conventional and Non-conventional
Adsorbents for Wastewater Treatment

Grégorio Crini, Eric Lichtfouse, Lee D. Wilson, and Nadia Morin-Crini

Contents
2.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
2.2 Wastewater Treatment by Adsorption . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27
2.2.1 Definition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27
2.2.2 Adsorption, Sorption, Biosorption, Absorption or Bioaccumulation: What is
the Most Appropriate Term? . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28
2.2.3 Contacting Systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30
2.2.4 Desorption of Contaminants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31
2.2.5 Control Adsorbent Performance . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32
2.3 Types of Materials for Contaminant Removal . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 33
2.3.1 Adsorbents Classification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 33
2.3.2 Analytical Techniques for the Characterization of an Adsorbent . . . . . . . . . . . . . . . . . 35
2.3.3 Commercial Activated Carbons . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36
2.3.4 Other Commercial Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38
2.3.5 Non-conventional Green Adsorbents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38
2.3.6 Which is the Best Non-conventional Adsorbent? . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41
2.4 Modeling and Mechanisms of Adsorption . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50
2.4.1 Batch Experiments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50
2.4.2 Modeling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 52
2.4.3 Mechanisms of Adsorption . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 57
2.5 Concluding Remarks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 60
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 61

G. Crini (*) · N. Morin-Crini

Laboratoire Chrono-environnement, UMR 6249, UFR Sciences et Techniques, Université
Bourgogne Franche-Comté, Besançon, France
e-mail: [email protected]
E. Lichtfouse
CEREGE, Aix Marseille Univ, CNRS, IRD, INRA, Coll France, Aix-en-Provence, France
L. D. Wilson
Department of Chemistry, University of Saskatchewan, Saskatoon, SK, Canada
Abstract The removal of contaminants from wastewaters is a matter of great
interest in the field of water pollution. Amongst the numerous techniques of con-
taminant removal, adsorption using solid materials (named adsorbents) is a simple,
useful and effective process. The adsorbent may be of mineral, organic or biological
origin. Activated carbon is the preferred material at industrial scale and is exten-
sively used not only for removing pollutants from wastewater streams but also for
adsorbing contaminants from drinking water sources (e.g. rivers, lakes or reservoirs).
However, its widespread use is restricted due to high cost. In the last three decades,
numerous approaches have been studied for the development of cheaper and more
effective adsorbents capable to eliminate pollutants at trace levels. This chapter gives
a general overview of liquid-solid adsorption processes using conventional and
non-conventional materials for pollutant removal. It outlines some of the principles
of adsorption and proposes a classification for the different types of materials.
Finally, the chapter discusses different mechanisms involved in the adsorption
phenomena.

Abbreviations

AAS Atomic absorption spectroscopy

AC Activated carbons
BOD Biochemical oxygen demand
CAA Commercial activated alumina
CAC Commercial activated carbons
COD Chemical oxygen demand
DSC Differential scanning calorimetry
ESR Electron spin resonance spectroscopy
FT-IR Fourier transform infrared spectroscopy
GAC Granular activated carbon
ICP Inductively coupled plasma
ISE Ion selective electrode
LC-MS Liquid chromatography mass spectrometry
NMR Nuclear magnetic resonance
OM Organic matter
PAC Powder activated carbon
PAH Polycyclic aromatic hydrocarbons
PCB Polychlorobiphenyls
PET Polyethylene terephthalate
PZC Point of zero charge
SEM Surface electron microscopy
SMEs Small and medium-size enterprises
SS Suspended solids
TGA Thermogravimetric analysis
TOC Total organic carbon
VOC Volatile organic compounds
XAS X-ray absorption spectroscopy
XPS X-ray photoelectron spectroscopy

2.1 Introduction

Man’s use of chemical substances, in particular metals, began to affect the environ-
ment during the “Industrial Revolution”. Although some metal ions are disseminated
into the environment naturally by both geological and biological activity, human
activity today produces a greater input. The toxicity of many of these pollutants/
contaminants is well known. Today, we are in the “Pollutant Removal Age” and, it
is, therefore, not surprising that there has been considerable effort to develop
technologies to reduce contaminant emissions (Morin-Crini and Crini 2017). A
significant proportion of these emissions are in the form of industrial wastewaters.
Indeed, the industrial sector consumes significant volumes of water, and conse-
quently generates considerable amounts of wastewater discharge containing both
mineral and organic contamination. This sector is today considered to be one of the
most polluting in spite of the considerable effort made to clean up the processes over
the last 30 years (Berefield et al. 1982; Liu and Liptak 2000; Landy et al. 2012a;
Khalaf 2016; Morin-Crini and Crini 2017).
Wastewater treatment is becoming ever more critical due to diminishing water
resources, increasing wastewater disposal costs, and stricter discharge regulations
that have lowered permissible contaminant levels in waste streams. The diversity of
water pollutants calls for a wide range of treatment methods that are not only
effective, but also technologically and economically feasible. The most common
methods for the removal of contaminants from industrial effluents include biodeg-
radation, precipitation, chemical oxidation, solvent extraction, evaporation, electro-
chemical approaches, cementation, membrane filtration, phytoremediation,
ion-exchange, and carbon adsorption (Berefield et al. 1982; Volesky 1990; Liu
and Liptak 2000; Harvey et al. 2002; Crini and Badot 2007; Cox et al. 2007; Sharma
2015; Morin-Crini and Crini 2017).
Over the last few decades, adsorption has gained importance as a separation,
purification and/or detoxification process on an industrial scale (Table 2.1). Adsorp-
tion is used to purify, decolorize, detoxify, deodorize, separate, and concentrate to
allow removal and to recover the harmful products from liquid solutions and gas
mixtures (Dąbrowski 2001; Crini and Badot 2010; Kyzas and Kostoglou 2014).
Consequently, adsorption is of interest to many economic sectors and concerns areas
such as chemistry, food and pharmaceutical industries, and the treatment of drinking
water and industrial wastewater. Indeed, adsorption is – along with biodegradation –
one of the two major treatments applied to the decontamination of water. Adsorption
processes are considered the best choice compared to other methods due to their
convenience, easy operation and simplicity of design, high efficiency, and also for
Table 2.1 Fundamental practical applications of adsorption-oriented processes
Separation and purification of gas and liquid mixtures
Drying gases and liquids
Solvent recovery
Purification of air
Separation and purification of chemicals, pharmaceutical and biological substances
Removal of impurities from liquid and gas media
Decolorizing applications
Water purification (pesticides removal, arsenic elimination. . .)
Wastewater decontamination

their wider applicability in water pollution control (McKay 1996; Babel and
Kurniawan 2003; Swami and Buddhi 2006; Crini 2006; Qu 2008; Vijayaraghavan
and Yun 2008; Gadd 2009). From an industrial point of view, adsorption is both
technologically simple and economically feasible while also being a process that
produce high quality water, with pollutant concentrations under the legal limits for
discharge waters.
In general terms, activated carbons (AC) must be thought of as being most
effective adsorbents and, as such, their performance in removing contaminants
such as metals, radionuclides, rare earth elements, phenolic and aromatic derivatives
(including dyes and pesticides), pharmaceuticals and drugs have been examined
widely (Dąbrowski et al. 2005). In addition, in the field of wastewater treatment,
adsorption onto commercial AC (CAC) has proved efficient in removing colloidal
substances and soluble organic substances that are non-biodegradable or chemically
stable like recalcitrant synthetic molecules. Attention has also focused on adsorption
onto commercial activated alumina (CAA), ion-exchange using organic polymeric
resins and zeolites as other non-consumptive materials (Wang and Peng 2010).
However, despite the excellence of their performance, these systems are expensive
to use and, as such, cannot be thought of as a truly viable option in many parts of the
world.
Because of this, attention has turned to the adsorptive properties of other
non-conventional solid materials proposed as low-cost, efficient and green adsor-
bents for pollutant removal (Pollard et al. 1992; Ramakrishna and Viraraghavan
1997; Houghton and Quarmby 1999; Blackburn 2004; Gavrilescu 2004; Crini 2005,
2006; Li et al. 2008; Oliveira and Franca 2008; Ngah and Hanafiah 2008; Gupta and
Suhas 2009; Rafatullah et al. 2010; Crini and Badot 2010). The past three decades
have shown an explosion in the development of new materials including new
carbons produced from wastes or natural by-products, natural or synthetic adsor-
bents or sorbents, and biological materials or biosorbents. Table 2.2 show the top ten
most cited reviews in the ISI Web of Science database for 2000–2017 with “Adsor-
bents”, “Wastewater and “Review” in the topic. The number of reviews appearing
with these three terms in the topic in 2017, 2016, 2015, 2014, 2013 and 2012 is
66, 59, 54, 46 and 39, respectively (ISI Web of Science database).
Table 2.2 The top ten most cited reviews in the ISI Web of Science database for 2000–2017 with
“Adsorbents”, “Wastewater” AND “Review” in the topic (out of a total of 383 reviews appearing,
December 04, 2017)
1. Crini G (2006) Non-conventional low-cost adsorbents for dye removal. Bioresource Technol-
ogy 97:1061–1085. Times cited: 1989.
2. Babel S, Kurniawan TA (2003) Low-cost adsorbents for heavy metals uptake from contami-
nated water: A review. Journal of Hazardous Materials 97:219–243. Times cited: 1589.
3. Mohan D, Pittman CU (2007) Arsenic removal from waste/wastewater using adsorbents – A
critical review. Journal of Hazardous Materials 142:1–53. Times cited: 1561.
4. Gupta VK, Suhas (2009) Application of low-cost adsorbents for dye removal – A review.
Journal of Environmental Management 90:2313–2342. Times cited: 1285.
5. Crini (2005) Recent developments in polysaccharide-based materials used as adsorbents in
wastewater treatment. Progress in Polymer Science 30:38–70. Times cited: 982.
6. Kannan N, Sundaram MM (2001) Kinetics and mechanism of removal of methylene blue by
adsorption on various carbons. Dyes and Pigments 51:25–40. Times cited: 903.
7. Crini G, Badot PM (2008) Application of chitosan, a natural aminopolysaccharide, for dye
removal from aqueous solutions by adsorption processes using batch studies: A review of recent
literature. Progress in Polymer Science 33:399–447. Times cited: 894.
8. Rafatullah M, Sulaiman O, Hashim R, Ahmad A (2010) Adsorption of methylene blue on
low-cost adsorbents: A review. Journal of Hazardous Materials 177:70–80. Times cited: 855.
9. Ngah WSW, Hanafiah MAKM (2008) Removal of heavy metal ions from wastewater by
chemically modified plant wastes as adsorbents: A review. Bioresource Technology 99:3945–
3948. Times cited: 639.
10. Wang SB, Peng YL (2010) Natural zeolites as effective adsorbents in water and wastewater
treatment. Chemical Engineering Journal J 156:11–24. Times cited: 601.

This chapter presents adsorption processes as a decontamination method for the

removal of contaminants from synthetic solutions and industrial effluents. It outlines
some of the principles of contamination adsorption onto solid materials. The chapter
also proposes a classification for the different types of materials used and discusses
different mechanisms involved in the adsorption phenomena.

2.2 Wastewater Treatment by Adsorption

2.2.1 Definition

Adsorption is a process of separation during which the substances of a fluid, liquid or

gas, bind to the exterior and interior surfaces of a solid material called the adsorbent.
The separation is based on the selective adsorption (i.e. thermodynamic and/or
kinetic selectivity) of the contaminants by an adsorbent owing to specific interac-
tions between the surface of the adsorbent material and the adsorbed contaminants:
simple mass transfer from the liquid phase towards the solid phase (Dubinin 1966).
This surface phenomenon is a manifestation of complicated interactions among the
Fig. 2.1 Schema depicting
the relationships between
the three components of an
adsorption system (Crini
2005)

three components involved, i.e. the adsorbent, the adsorbate and the wastewater
(e.g. effluent, synthetic solution or water).
Figure 2.1 shows a schematic adsorption model for the three components and
their interactions. Generally, in this ternary system, the affinity between the adsor-
bent and the adsorbate is the main interaction force controlling adsorption (Furuya
et al. 1997; Crini 2005; Crini and Badot 2010). However, the affinities between the
adsorbate and the solution, the adsorbent and the solution, and the contaminant
molecules can also play a major role in adsorption. In aqueous solution, hydrophobic
compounds have low solubility and tend to be pushed to the adsorbent surface. It is
reasonable to expect that adsorption capacity will be dependent upon the interaction
forces between the three adsorption components.

2.2.2 Adsorption, Sorption, Biosorption, Absorption or

Bioaccumulation: What is the Most Appropriate Term?

“Adsorption”, “sorption”, “biosorption”, “bio-adsorption”, “absorption” or

“bioaccumulation”: What is the most appropriate term? Although this is not difficult
to answer, there is a lot of confusion in the abundant literature (Dąbrowski et al.
2005; Crini 2005, 2010; Gadd 2009).
The change in the concentration of a molecule in the surface layer of a solid
material in comparison with the bulk phase with respect to unit surface area is termed
adsorption. Sorption is a general term used for both absorption and adsorption (Crini
2010). These terms are often confused. Absorption is the incorporation of a sub-
stance in one state into another of a different state (e.g. liquids being absorbed by a
solid or gases), i.e. into a three-dimensional matrix (Gadd 2009). Adsorption is the
physical adherence or bonding of molecules (or ions) onto the surface of another
substance, i.e. onto a two-dimensional surface. In this case, the material accumulated
at the interface is the adsorbate and the solid surface is the adsorbent.
Adsorption, strictly speaking, defines binding in terms of a physical rather than
chemical surface phenomenon. In processes using carbons, adsorption is generally
the preferred term (Dąbrowski 2001; Dąbrowski et al. 2005). If adsorption occurs
and results in the formation of a stable molecular phase at the interface, this can be
described as a surface complex. Two general kinds of surface complex exist: inner-
and outer-sphere surface complexes. An interesting discussion on this subject can be
found in the review by Gadd (2009). Adsorption is the most common treatment used
in conventional clean-up technologies but unless it is clear which process, absorption
or adsorption, is operative, sorption is a more general term, and can be used to
describe any system where a sorbate (e.g. a molecular ion, a molecule, a polymer)
interacts with a sorbent (i.e. a solid surface) resulting in an accumulation at the
sorbate-sorbent interface.
Biosorption or bio-adsorption may be simply defined as the removal of sub-
stances from solution by biological materials (Gadd 1990; Garnham 1997; Volesky
2001; Veglio’ and Beolchini 1997; Davis et al. 2003; Vijayaraghavan and
Balasubramanian 2015). This is a physicochemical process and includes several
mechanisms. The precise binding mechanism(s) may range from physical
(i.e. electrostatic interactions, van der Waals forces, hydrogen bond) to chemical
binding (i.e. ionic and covalent). Some of the reported mechanisms include absorp-
tion, (surface) adsorption, ion-exchange, binding or surface complexation, (surface)
precipitation or micro-precipitation, and mineral nucleation. Biosorption is a prop-
erty of both living and dead organisms, and their components. While most
biosorption research concerns metals and related substances (Gadd 1990), the term
is now applied to particulates and all manner of organic substances as well. Practi-
cally all biological material has an affinity for metal species (Wase and Forster 1997;
Aksu 2005; Gadd 2009). However, the term “biosorption” refers to passive or
physicochemical attachment of a sorbate to a biosorbent, essentially the binding of
a chemical species to biopolymers. The definition, thus, specifically excludes met-
abolic or active uptake by living, metabolizing cells. In the literature, the term
“biosorbent” includes the usage of dead biomass such as fibers, peat, rice hulls,
forest by-products, chitosan, and agro-food wastes as well as living plants, fungi,
algae (unicellular microalgae, cyanobacteria, multicellular macroalgae), and bacte-
ria. Biosorbents represent cheap filter materials often with high affinity, capacity and
selectivity, and they are abundant and already available in most places (Aksu 2005;
Sudha and Giri Dev 2007; Vijayaraghavan and Yun 2008; Gadd 2009; Crini and
Badot 2010; Michalak et al. 2013; Kyzas et al. 2013a; Lim and Aris 2014; Ong et al.
2014; Gupta et al. 2015). Some types of materials are broad range with no specific
priority for metal ion bonding, while others can be specific for certain types of
metal ions.
“Bioaccumulation” is also another term which induces confusion. Using
biosorbents such as algae for metal ions removal, another mechanism can occur.
Indeed, precipitation or crystallization of metals may occur within and around cell
walls as well as the production by biomass of metal binding polysaccharides: These
processes which could be considered as biosorption are better termed
“bioaccumulation” (Gadd 1990; Garnham 1997). These two terms ‘biosorption’
and ‘bioaccumulation’ have been adopted for the description of the two mechanis-
tically different types of metal sequestering by microorganisms. The first has been
proposed for the sequestration by non-metabolically mediated process (inactive
microorganisms) and the second for the sequestration of metal ions by metabolically
mediated processes (living microorganisms). Biosorption tends to be very rapid and
reversible while bioaccumulation tends to be slower and irreversible. An interesting
discussion on the features of biosorption and bioaccumulation can be found in the
review by Vijayaraghavan and Yun (2008). So, there are mechanistic differences
between these two terms. However, the two mechanisms can co-exist in a
biosorption system, and can also function independently.

2.2.3 Contacting Systems

When studying adsorption from solutions on materials it is convenient to differen-

tiate between adsorption from dilute solution and adsorption from binary and multi-
component mixtures covering the entire range of mole fractions. To judge by the
number of papers published annually on adsorption from dilute (single) solution, this
subject is more important than adsorption from binary mixtures. It is also important
to consider the modes of contacting the solid adsorbent and the wastewater when
applying the adsorption system to both industrial large scale treatments and labora-
tory scale (McKay 1996; Bajpai and Rajpoot 1999; Ali 2014). There are several
types of contacting systems available to obtain experimental data and for industrial
applications, including batch methods, fixed-bed type processes, pulsed beds, mov-
ing mat filters and fluidized beds. However, the two most frequently used systems
applied in solid/liquid adsorption processes are the batch-type contact and fixed-bed
type processes (Fig. 2.2).
Adsorption processes for decontamination of wastewaters can be carried out
either discontinuously in batch reactors or continuously in fixed-bed reactors or
columns (Volesky and Holan 1995; Volesky 2001; Crini 2003; Ali 2014). Fixed-bed
reactors or dynamic continuous-flow systems are commonly used in the industrial
world while batch methods are preferred on the laboratory scale because, apart from
their simplicity and ease of operation, they are limited to the treatment of small
volumes of solution. Fixed-bed systems have an important advantage because
adsorption depends on the concentration of the solute in the solution being treated
(Ali 2014). The adsorbent is continuously in contact with fresh solution; hence the
concentration in the solution in contact with a given layer of adsorbent in a column is
relatively constant. Conversely, the concentration of adsorbate in contact with a
given quantity of adsorbent, as in a batch system, is continuously changing due to the
adsorbate being adsorbed (McKay 1996). Other advantages of employing fixed-bed
columns for industrial adsorption processes are higher residence times and better
heat and mass transfer characteristics than batch reactors.
Batch methods are also widely used because this technology is cheap and simple
to operate and, consequently often favored for small and medium size process
applications using simple and readily available mixing tank equipment. Simplicity,
well-established experimental methods, and easily interpretable results are some of
the main reasons frequently evoked for the extensive use of these methods. Another
interesting advantage is the fact that, in batch systems, the parameters of the solution/
effluent such as contact time, pH, strength ionic, temperature, etc. can be controlled
and/or adjusted.
Fig. 2.2 Schematic representations of two mains schemes used for adsorption of pollutants from
wastewaters: batch process and continuous process

2.2.4 Desorption of Contaminants

It is important to point out that adsorption using batch systems is a non-destructive

technique involving only a phase change of contaminants, and hence imposes further
problems in the form of sludge disposal. For fixed-bed reactors, Fig. 2.3 shows two
main strategies (regeneration step or replacement) that could be used to deal with
spent adsorbent after its usage. One of the important characteristics of a solid
material is whether it can be regenerated if necessary. The regeneration of the
adsorbent may be crucially important for keeping the process costs down and
Fig. 2.3 Schematic representations of two mains strategies (regeneration step or replacement) that
could be used to deal with spent adsorbent after its usage

opening the possibility of recovering the contaminant extracted from the solution.
For this purpose, it is desirable to desorb the adsorbed contaminants and to regen-
erate the material for another cycle of application. Desorption studies also reveal the
mechanism of adsorption. However, except for commercial activated carbons and
organic resins, this aspect has not been adequately studied and there is little literature
focusing on this topic.

2.2.5 Control Adsorbent Performance

In an adsorption-oriented process, separation is defined as a system that transforms a

mixture of substances into two or more products that differ from each other in
composition. The process is difficult to achieve because it is the opposite of mixing,
a process favored by the second law of thermodynamics. For many separation
processes, the separation is caused by a mass separating agent, the solid material
or adsorbent (King 1980; McKay 1996; Yang 2003). Consequently, the performance
of any adsorptive separation or purification process is directly determined by its
quality. So, the first important step to an efficient adsorption process is the search for
a solid material with high capacity, selectivity, and rate of adsorption.
In principle, as adsorption is a surface phenomenon, any porous solid having a
large surface area may be an adsorbent (McKay 1996). Other requirements to be
taken into account in choosing a material are based on the following criteria: low
cost and readily available, suitable mechanical properties, high physical strength (not
disintegrating) in solution, a long life, able to be regenerated if required, etc. The data
from the literature show that the control of adsorption performances of a solid
material in liquid-phase adsorption depends on the following factors: (i) the origin
and nature of the solid such as its physical structure (e.g. particle size, specific
surface area, porosity), chemical nature and functional groups (e.g. surface charge,
pH at the point of zero charge), and mechanical properties; (ii) the activation
conditions of the raw solid (e.g. physical treatment, chemical modification); (iii)
the influence of process variables used in the contacting system such as contact time,
initial pollutant concentration, solid dosage and stirring rate; (iv) the chemistry of the
pollutant(s) (for instance, for a dye molecule, its pKa, polarity, size and functional
groups); and finally, (v) the solution conditions, referring to its pH, ionic strength,
temperature, presence of multi-pollutant or impurities, and its variability (Crini
2005, 2006; Park et al. 2010; Crini and Badot 2010).

2.3 Types of Materials for Contaminant Removal

2.3.1 Adsorbents Classification

Solid materials used as adsorbents can take a broad range of chemical forms and
different geometrical surface structures. This is reflected in the range of their
applications in industry, or helpfulness in laboratory practice. Adsorbents can be
usually classified in five categories: (1) natural materials such as sawdust, wood,
fuller’s earth or bauxite; (2) natural materials treated to develop their structures and
properties such as activated carbons, activated alumina or silica gel; (3) manufactured
materials such as polymeric resins, zeolites or aluminosilicates; (4) agricultural solid
wastes and industrial by-products such as date pits, fly ash or red mud; and
(5) biosorbents such as chitosan, fungi or bacterial biomass. Another classification
was introduced by Dąbrowski (2001) as shown in Table 2.3. Another simplified
classification, introduced by Crini (Crini 2005, 2006; Crini and Badot 2007), can be
used as follows: conventional and non-conventional adsorbents. The list of conven-
tional adsorbents includes commercial activated carbons (CAC), commercial
ion-exchange resins (polymeric organic resins) and inorganic materials such as
commercial activated aluminas (CAA), silica gel, zeolites and molecular sieves

Table 2.3 Basic types of industrial adsorbents

Carbon adsorbents Mineral adsorbents Other adsorbents
Activated carbons Silica gels Synthetic polymers
Activated carbon fibres Activated alumina Composite adsorbents (mineral-carbons)
Molecular carbon sieves Metal oxides Mixed adsorbents
Fullerenes Metal hydroxides
Carbonaceous materials Zeolites
Clay minerals
Pillared clays
Inorganic nanomaterials
Fig. 2.4 Conventional and non-conventional adsorbents for the removal of pollutants from waste-
waters according to Crini (Crini 2005, 2006; Crini and Badot 2007)

(which are formally not zeolites) (Fig. 2.4). Only four types of generic adsorbents
have dominated the commercial use of adsorption: CAC >> zeolites >> silica
gel > CAA (Yang 2003). The list of non-conventional adsorbents includes activated
carbons (AC) obtained from agricultural solid waste and industrial by-products,
natural materials such as clays, industrial by-products such as red mud, biosorbents
such as chitosan, and miscellaneous adsorbents such as alginates (Fig. 2.4).
Table 2.4 Analytical techniques used in adsorption research in order to obtain information on
adsorbent characterization, adsorbate characterization and adsorption mechanism
Objective/analytical technique(s)
Characterization of the adsorbent
Elemental composition and distribution: element analysis, energy dispersive X-ray spectros-
copy (EDS)
Surface area, porosity (pore size, pore size distribution): nitrogen adsorption (BET
measurements)
Crystallographic structure: X-ray diffraction (XRD)
(Surface, inner) morphology: surface electron microscopy (SEM), transmission electron
microscopy (TEM), often coupled with EDS
Chemical structure: solid state nuclear magnetic resonance (NMR) spectroscopy, X-ray pho-
toelectron spectroscopy (XPS), X-ray absorption spectroscopy (XAS)
Ion-exchange capacity: titration
Surface chemistry, surface acid-base characterization: titration, calorimetry, XPS
Surface properties (hydrophilicity, hydrophobicity): contact angle measurements
Determination of the active sites: titration, NMR, Fourier transform infrared spectroscopy
(FT-IR), electron spin resonance spectroscopy (ESR)
Swelling capacity: (hypo)osmotic test, pure mechanical swelling
Stability of the material: thermogravimetric analysis (TGA), differential scanning calorimetry
(DSC)
Characterization of the adsorbate in the aqueous solution
Determination of the contaminant concentration: atomic absorption spectroscopy (AAS),
inductively coupled plasma (ICP), UV-Vis spectrophotometry, fluorescence spectroscopy, pho-
tometry (kits tests), ion selective electrode (ISE)
Separation and identification of the contaminant components existing in the solution: liquid
chromatography mass spectrometry (LC-MS)
Adsorption mechanism
Chemical characterization of contaminant bound on the material: EDS, NMR, FT-IR
Chemical composition of contaminant bound on the material: XRD
Determination of the oxidation state of contaminant (metal bound): XPS, XAS

2.3.2 Analytical Techniques for the Characterization of an

Adsorbent

Table 2.4 shows examples of analytical techniques used for the characterization of
an adsorbent, and more generally available in adsorption research (Crini and Badot
2010; Park et al. 2010; Michalak et al. 2013; Fomina and Gadd 2014; Ramrakhiani
et al. 2016). Such techniques often provide distinctive but complementary informa-
tion not only on the characterization of the adsorbent used but also on adsorption of a
target contaminant onto the material and its performance. For example, the charac-
terization of the morphological structure and chemistry of a biomass-based adsor-
bent used for metal removal is essential for understanding the metal binding
mechanism on the biomass surface (Park et al. 2010). This can be elucidated using
different techniques such as potentiometric titrations, Fourier transform infrared
spectroscopy (FT-IR), energy dispersive X-ray spectroscopy (EDS), X-ray diffrac-
tion (XRD), X-ray photoelectron spectroscopy (XPS), and also surface electron
microscopy (SEM), transmission electron microscopy (TEM). SEM interpretation
provides topography of the surface feature and elemental information/metal distri-
bution with a virtually unlimited depth of field. TEM also provides information on
the topographical, morphological, compositional and crystalline structures. In gen-
eral, combination of SEM-EDS and TEM-EDS are performed in order to obtain
information regarding the location of the metal. X-ray absorption spectroscopy
(XAS) determines the oxidation state of a metal bound to the biosorbent and its
coordination environment (Ramrakhiani et al. 2016).
It is well-known that the addition of electrolytes can increase the aggregation of
the dye molecules due to reducing the electrical double layer effects to favour self-
assembly. For instance, the addition of NaCl in relatively high concentrations can
induce the size of the particles in the solution, reducing the space available for dye
adsorption (due to occupancy of ions at active sites in competition with dye species),
leading to higher aggregation, in accordance with DVLO theory (Blokzijl and
Engberts 1993). Liquid chromatography mass spectrometry analysis are useful
tools to separate and identify the dye components existing in the solution (Won
et al. 2008). Because of their high molar absorptivity, dye molecules and their
aggregates are also easily detected by spectrophotometric and photophysical tech-
niques, even at relatively low concentrations. This approach provides information to
analyze the type of adsorption mechanisms.

2.3.3 Commercial Activated Carbons

Many wastewaters contain significant levels of organic and mineral contaminants

which are toxic or otherwise undesirable because they create, in particular, odor, bad
taste and color (McKay 1996; Kannan and Sundaram 2001; Swami and Buddhi
2006; Crini 2006; Qu 2008). Amongst the numerous techniques of contaminant
removal, liquid-solid adsorption using AC is the procedure of choice and gives the
best results as it can be used to remove different types of contaminants (Dubinin
1966; Manes 1998; Dąbrowski 2001; Dąbrowski et al. 2005; Crini and Badot 2008).
Indeed, carbons are one of the oldest and most widely used adsorbents in industry.
Due to their great capacity to adsorb contaminants, commercial activated carbons
(CAC) are the most effective adsorbents, and if the adsorption system is properly
designed they give a good-quality output. This capacity is mainly due to their
structural characteristics and their porous texture which gives them a large surface
area, and their chemical nature which can be easily modified by chemical treatment
in order to vary their properties. The processes that use these usual adsorbents are
often carried out in a batch mode, by adding activated carbon to a vessel containing
the contaminated solution, or by feeding the solution continuously through a packed
bed of carbon.
 In general, CAC are used as very good adsorbents of organic matter (OM) to
reduce the organic load in secondary and/or tertiary treatment, for instance to process
heavily polluted effluent (color, COD, TOC) from the textile industry. They are
generally very broad spectrum adsorbents that efficiently eliminate man-made pol-
lutants such as pesticides, aromatic and phenolic derivatives (PAH, PCB, etc.),
pharmaceutics, volatile organic compounds (VOC), hydrocarbons and surfactants,
minerals including metals but also the molecules that discolor water (dyes), or that
cause a taste or smell. They also retain toxic organic compounds refractory to
treatments upstream, or they finish off the elimination of OM before discharge in
the tertiary treatment of industrial effluent. Also, macroporous CAC can be used as
supports for bacteria: the bacteria then degrade part of the adsorbed OM (biological
elimination) and thus participate in the in situ regeneration of the sorbent. This type
of treatment is, in general, coupled to an ozonation stage, further improving the
performance of the process. CAC biological filters are, for instance, used for the
detoxification of effluent loaded with ions (removal of iron, manganese, nitrate) or
for the reduction of BOD, COD and TOC (Radovic et al. 2000). An additional major
advantage of treatment with CAC is the fact that no by-products are produced, unlike
during treatment by chemical oxidation. To obtain cost-effective technology (espe-
cially in the field of water recycling) CAC powder is used in conjunction with an
ultrafiltration membrane or with other techniques, such as oxidation. Active carbon
competes favorably with nanofiltration and has completely replaced oxidation with
ozone.
Although CAC have been used for a long time, development is still being pursued
particularly as there is increasing demand for very clean water. Research, both
fundamental and applied, is currently very active concerning (i) the possible use of
new precursors for the CAC such as agricultural and industrial wastes, water bottles
made of PET, scrap tyres; (ii) the development of novel classes of materials such as
activated carbon cloth, nanotubes; (iii) understanding the mechanisms of activation,
sorption and regeneration (e.g. microwave techniques, techniques not requiring heat)
(Mui et al. 2004; Aktas and Ceçen 2007; Dias et al. 2007; Li et al. 2010).
AC technology also presents several disadvantages. CAC is quite expensive
(e.g. the higher the quality, the greater the cost), and non-selective. Different
qualities of carbon also exist which vary not only as a function of the raw material
used but also of the carbonization conditions and of the way in which activation is
performed (physical or chemical). And yet, even though the high absorbing power of
active carbons no longer needs to be proved, not only is there the problem of disposal
of spent CAC, there is also the drawback of their rapid saturation, and thus their
regeneration. This regeneration step of saturated carbon is also expensive, not
straightforward, and results in loss of the adsorbent. For these reasons, their wide-
spread use is restricted, in particular small and medium-size enterprises (SMEs)
cannot employ such treatment due to high cost.
2.3.4 Other Commercial Materials

Various studies have been carried out to replace AC by other commercial adsorbent
materials (Allen 1996; Allen and Koumanova 2005; Aksu 2005; Crini 2006; San
Miguel et al. 2006; Sudha and Giri Dev 2007; Crini and Badot 2007; Tang et al.
2007; Vijayaraghavan and Yun 2008; Qu 2008; Wan Ngah et al. 2008; Sud et al.
2008). Those adopted on an industrial scale are zeolites, commercial activated
alumina, silica gels, ion-exchange resins, and sand (Yang 2003; Crini and Badot
2007; Crini 2010). The resins reduce the discharge of polluted water into the
environment and are successfully applied, for instance, in the elimination of mineral
and organic contaminants including numerous types of dye molecules from rinsing
water or polluting metals from pickling baths. The advantages of ion-exchange
include no loss of adsorbent on regeneration, reclamation of solvent after use and
the removal of soluble contaminants at trace levels. However, like commercial
activated carbons, these materials are not cheap (except sand) – a factor that cannot
be ignored.

2.3.5 Non-conventional Green Adsorbents

Although these commercial materials are preferred conventional adsorbents for

contaminant removal, their widespread industrial use is restricted due to high cost.
In addition, Streat et al. (1995) previously reported that the use of commercial
carbons based on relatively expensive starting materials is unjustified for most
pollution control applications and environmental purposes. As such, alternative
non-conventional adsorbents, mainly products and by-products of biological
(named biosorbents including biomasses), industrial and agricultural origin and
from forest industries (green adsorbents), were proposed, studied and employed as
inexpensive and efficient adsorbents (Volesky 1990, 2004, 2007; McKay 1996;
Varma et al. 2004; Crini 2005, 2006; Gerente et al. 2007; Li et al. 2008; O’Connell
et al. 2008; Oliveira and Franca 2008; Gadd 2009; Crini and Badot 2010; Elwakeel
2010; Sanghi and Verma 2013). These include algae, bacteria, fungi, and yeasts,
bark, sawdust, peat, natural products (e.g. cotton, flax, hemp), polysaccharides such
as starch, cellulose, chitosan, and alginates, industrial byproducts (e.g. red mud,
sludge. . .), plants, and innovative nanomaterials.
All these non-conventional materials are interesting due to the fact that they are
abundant in nature, available in large quantities, inexpensive, and may have potential
as complexing materials due to their physicochemical characteristics and particular
structure. However, it is important to point out that the adsorption processes using
these materials are basically at the laboratory stage in spite of unquestionable
progress (Gadd 2009; Crini and Badot 2010). Table 2.5 shows a selection of
different reviews on non-conventional adsorbents used for pollutant removal.
Table 2.5 Selected comprehensively reviews on non-conventional adsorbents used in adsorption-
oriented processes (selected references)
Adsorbent Contaminant(s) Reference(s)
Agricultural Metals, dyes, PAH Oliveira and Franca (2008), Crini and
byproducts Badot (2010), Sharma et al. (2011),
Nguyen et al. (2013), Rangabhashiyam
et al. (2014), Lim and Aris (2014),
Kharat (2015), Zhou et al. (2015),
Emenike et al. (2016), and Sulyman et al.
(2017)
Agri-food Metals, dyes Demirbas (2008), Oliveira and Franca
wastes (2008), and Kumar et al. (2011)
Fruit and vege- Metals, dyes Swami and Buddhi (2006) and Patel
table wastes (2012)
Sawdust Metals, dyes, phenols Shukla et al. (2002), Swami and Buddhi
(2006), Larous and Meniai (2012),
Kharat (2015), and Sahmoune and
Yeddou (2016)
Bark Metals, dyes, PAH, chlorinated Ahmaruzzaman (2008), Demirbas
phenols (2008), Kharat (2015), and Sen et al.
(2015)
Rice husk Metals, dyes Chuah et al. (2005), Ahmaruzzaman
(2011), Nguyen et al. (2013), Dhir
(2014), and Sulyman et al. (2017)
Wheat Metals Ngah and Hanafiah (2008) and Farooq
et al. (2010)
Sugar-beet pulp Metals Ngah and Hanafiah (2008),
Ahmaruzzaman (2011), and Dhir (2014)
Coconut Metals, phenols Swami and Buddhi (2006), Bhatnagar
et al. (2010), Patel (2012), and
Bazrafshan et al. (2016)
Opuntia ficus- Nharingo and Moyo (2016)
indica
Coffee Anastopoulos et al. (2017a) and
Sulyman et al. (2017)
Tea factory Metals Ahmaruzzaman (2011) and Sulyman
waste et al. (2017)
Peat Metals, dyes, phosphorus Brown et al. (2000), Vohla et al. (2011),
and Raval et al. (2016)
Lignocellulosic Metals Miretzky and Cirelli (2010), Abdolali
wastes et al. (2014), and De Quadros Melo et al.
(2016)
Cellulose Metals, dyes, organics O’Connell et al. (2008), Hubbe et al.
(2011), Vandenbossche et al. (2015),
and Grishkewich et al. (2017)
Microbial Metals, dyes Solis et al. (2012), Mudhoo et al. (2012),
biosorbents Ahluwalia and Goyal (2007), and
Srivastava et al. (2015)
Bacterial Metals, dyes Vijayaraghavan and Yun (2008) and
biosorbents Mudhoo et al. (2012)
(continued)
Table 2.5 (continued)
Adsorbent Contaminant(s) Reference(s)
Fungi Metals, dyes Kaushik and Malik (2009), Wang and
Chen (2009), and Dhankhar and Hooda
(2011)
Extracellular Metals, phosphorus More et al. (2014) and Li et al. (2015)
polymeric
substances
Algae, marine Metals, dyes Brinza et al. (2007), Wang and Chen
algae (2009), Mudhoo et al. (2012), He and
Chen (2014), and Zeraatkar et al. (2016)
Plants Metals, dyes Ahluwalia and Goyal (2007), Srivastava
et al. (2015), and Saba et al. (2016)
Pectins Metals, dyes Miretzky and Cirelli (2010),
Vandenbossche et al. (2015), and Zhao
and Zhou (2016)
Starch Metals, dyes Crini (2005), Crini and Badot (2010),
Panic et al. (2013), Wang et al. (2013),
and Vandenbossche et al. (2015)
Chitin Dyes Yong et al. (2015), Barbusinski et al.
(2016), and Anastopoulos et al. (2017b)
Chitosan Metals, dyes, phenols No and Meyers (2000), Elwakeel (2010),
Li et al. (2008), Crini and Badot (2008),
Kyzas et al. (2013b), Liu and Bai (2014),
Vakili et al. (2014), Yong et al. (2015),
Barbusinski et al. (2016), and Azarova
et al. (2016)
Alginate Metals, dyes Vandenbossche et al. (2015) and
Grishkewich et al. (2017)
Cyclodextrins Metals, dyes, organics Mocanu et al. (2001), Crini and
Morcellet (2002), Crini (2005, 2014),
Crini and Badot (2010), Landy et al.
(2012a, b), and Panic et al. (2013)
Hydrogels Metals, dyes, organics Panic et al. (2013), Khan and Lo (2016),
Mittal et al. (2016), Muya et al. (2016),
and Grishkewich et al. (2017)
Clays Metals, dyes Bhattacharyya and Gupta (2008) and
Ngulube et al. (2017)
Industrial Metals, dyes Crini (2005, 2006) and El-Sayed and
byproducts El-Sayed (2014)
Fly ash Metals, dyes Swami and Buddhi (2006),
Ahmaruzzaman (2010, 2011), and Raval
et al. (2016)
Red mud Phosphorus, phosphate, fluroride, Wang et al. (2008) and Ahmaruzzaman
nitrate, metals, metalloids, dyes, (2011)
bacteria, virus
(continued)
Table 2.5 (continued)
Adsorbent Contaminant(s) Reference(s)
Municipal Metals, dyes Bhatnagar and Sillanpää (2010)
wastes
Sludge-based Metals, dyes Raval et al. (2016) and Devi and Saroha
adsorbents (2017)
Nanomaterials Metals, dyes Crini and Badot (2010), Ali (2012),
Kumar et al. (2014), Zhao and Zhou
(2016), and Sadegh et al. (2017)

2.3.6 Which is the Best Non-conventional Adsorbent?

Since the range of non-conventional adsorbents proposed in the literature is

extremely extensive, attempting to provide a comprehensive list of potential effec-
tive materials would be unrealistic. For instance, agricultural wastes and byproducts
from forest industries include tea waste, coffee, hazelnut shells, peanut hull, sawdust,
barks, palm kernel husk, coconut husk, peanut skins, cellulosic and lignocellulosic
wastes, hemp-based products, cotton and modified cotton, corncobs, rice hulls, apple
wastes, wool fibers, olive cake, almond shells, cactus leaves, banana and orange
peels, sugar beet pulp, palm fruit bunch, maize leaf, and other different by-products.
Adsorption onto these biosorbents has been the focus of much attention and abun-
dant data on their performance can be found in the literature (Sharma 2015; Crini
2015; Vandenbossche et al. 2015; Khalaf 2016; Morin-Crini and Crini 2017).
In Table 2.6 we reported the features, advantages and limitations of some selected
non-conventional and conventional adsorbents (Crini 2005, 2015; Allen and
Koumanova 2005; Crini and Badot 2007, 2008, 2010; Bhattacharyya and Gupta
2008; Wang and Peng 2010). Which is the best adsorbent? There is no direct answer
to this question because each adsorbent has advantages and drawbacks (Crini 2006;
Gadd 2009).
The comparison of adsorption performance depends on several parameters and a
direct comparison of data obtained using different materials is not possible since
experimental conditions are not systematically the same. Most of the information is
related to a single contaminant removal individually in batch experiments and little
or no data on removal of contaminants in complex form in real wastewater. Other
factors such as operation difficulty, practicability, regeneration potential and envi-
ronmental impact, need to be taken into consideration when selecting one adsorbent
over another. Due to the scarcity of consistent cost information, cost comparisons are
also difficult to estimate.
Generally, the adsorption capacity exhibited by each material relates primarily to
its textural and chemical properties. It is also important to point out that a particular
non-conventional adsorbent is only applicable to a particular class of contaminants.
Thus, using only one type of material is difficult for the treatment of the complex
mixtures of pollutant wastewaters. For instance, bentonite is an ineffective adsorbent
for nonionic organic compounds in water. Chitosan without chemical modification is
Table 2.6 Principal commercial, conventional and emerging materials for contaminant removal by
adsorption and/or ion-exchange processes
Adsorbent Features/advantages/mechanisms Limitations/comments
Activated carbons The most effective adsorbents in Initial cost of the carbon
industry (charcoal is the oldest
material known in wastewater)
Powder activated car- Porous adsorbents with large sur- The higher the quality, the
bon (PAC) face area greater the cost
Versatile material Performance is dependent on the
type of carbon used
Two main forms: powdered Non-selective process
(PAC) forms to be used in batch
experiments followed by filtration
and granular (GAC) forms for use
in column (more adaptable to
continuous contacting)
Granular activated PAC: used in batch experiments Problems with hydrophilic
carbon (GAC) due to low capital cost and lesser substances
contact time requirements
Other forms Widely applied in the treatment of Ineffective against As(III), dis-
(drinking) water and wastewater perse and vat dyes
Great capacity to adsorb a wide Require complexing agents to
range of pollutants including improve their removal
metals and metalloids (As(V)), performance
dyes, phenols and chlorophenols,
pesticides, and pharmaceutics and
drugs
Extensively used for organic con- Many problems connected with
taminant removal (COD, BOD regeneration (large capital
and TOC removal) investments, expensive steps,
loss of adsorbent)
High capacity and high rate of GAC regeneration is easier than
adsorption PAC
Fast kinetics Identification of adsorption
Produce a high-quality treated mechanisms (in particular for
effluent modified activated carbons)
Interesting technology in combi-
nation with other techniques
(precipitation, sand filtration,
ion-exchange) or in conjunction
with microorganisms
Physisorption mechanisms
Activated carbons Inexpensive and renewable addi- The performance depends on the
from solid wastes tional sources of carbon raw material, the history of its
preparation and treatment
conditions
A potential alternative to existing Reactivation results in a loss of
CAC the carbon
(continued)
Table 2.6 (continued)
Adsorbent Features/advantages/mechanisms Limitations/comments
Agricultural wastes Interesting properties in terms of Laboratory stage
surface chemistry, surface charge
and pore structure like CAC
Wood wastes Efficient for a large range of Identification of adsorption
City wastes pollutants mechanisms
Industrial
by-products
Sand A very common adsorbent, Construction cost depending on
mainly in granular form, used in kinds of filters and technologies
pre- or post-treatment (rapid or slow processes)
Well-known filtration technique Requires a pre-treatment
(pH adjustment, coagulation,
flocculation) and also a post-
treatment (disinfection)
Large choice of filtration medium Filters become clogged with
with a wide variety in size and flocs after a period in use
specific gravity
Rapid and efficient for SS Frequent cleaning required
removal (every 24–72 h)
No limitations regarding initial Cost of energy (regeneration)
turbidity levels (if coagulant or and cost for treatment of gener-
flocculant is correctly applied) ated sludge
Widely applied for treating large Not effective for viruses, fluo-
quantities of drinking water ride, arsenic and salts
Somewhat effective for odor,
taste, bacteria and OM
Rapid cleaning time
Interesting as pretreatment in
combination with CAC treatment
Physisorption and diffusion
mechanisms
Activated alumina Relatively well-known and com- Cost of the adsorbent
mercially available
Bauxite Highly porous materials with a pH-dependent
high surface area and an interest-
ing distribution of both macro and
micropores
Used mainly as desiccants Requires a pre-treatment to pre-
vent clogging of the material bed
when the water contains SS or to
remove certain ions
Efficient filter for fluoride, sele- Fluoride removal: regeneration is
nium and arsenic removal often required to make it cost-
effective
Also interesting for the treatment Arsenic removal: needs replace-
of copper, zinc, mercury, uranium ment after four or five
and phosphates regeneration
Classified by the USEPA as Can accumulate bacteria
among one of the best available
(continued)
Table 2.6 (continued)
Adsorbent Features/advantages/mechanisms Limitations/comments
technologies for arsenic removal
in drinking water
The presence of impurities Use of strong acid and base
(iron. . .) do not affect the solutions for regeneration step
performance
Zeolites Easily available and relatively More than 40 natural species:
cheap (the price depends on the adsorption properties depend on
quality of zeolite) the different materials
Aluminosilicates 40 natural and over 100 synthetic Not suitable for reactive dyes
materials; clinoptilolite: The most
abundant and frequently studied
mineral
Clinoptilolite Highly porous aluminosilicates Low permeability
with different cavity structures
and unique surface chemistries
(a three dimensional framework
having a negatively charged lat-
tice) and valuable physicochemi-
cal properties (cation exchange,
molecular sieving, catalysis and
adsorption)
Chabazite Suitable adsorbents for dyes, Complex adsorption mechanism
metals, phenols and
chlorophenols: high ion-exchange
capacity and high selectivity
Modified materials A high capacity to be easily Requires chemical modification
regenerated (while keeping their
initial properties)
Main applications: softening and
deionization of water, waste
treatment, purification of
products
Ion-exchange mechanism
Silica A very common adsorbent, Cost of the adsorbent
mainly in granular form
Silica gel A highly porous solid with Hydrophilic material
mechanical stability
Silica beads High surface area Low values for the pH of point of
zero charge
Glasses Numerous industrial environmen- High affinity for water (silica gel
tal applications is a drying agent)
Silica modified Efficient for removal of organics Low resistance toward alkaline
(toluene, xylene, dyes) solutions
Hybrid materials Very high adsorption capacities Requires chemical modification
(acid dyes)
Physisorption and chemisorption
(ion-exchange) mechanisms
(continued)
Table 2.6 (continued)
Adsorbent Features/advantages/mechanisms Limitations/comments
Siliceous materials Abundant, available and low-cost Important role of the pH of the
inorganic materials solution
Alunite Porous texture with high surface Requires physical and chemical
area modification
Perlite Regeneration (alunite) is not Variable differences in composi-
necessary tion (perlite)
Dolomite Promising adsorbent for dyes Results depend on the types of
Diatomite Perlite: an amorphous siliceous perlite used (expanded and
mineral, inexpensive and easily unexpanded) and on its origin
available in many countries
Dolomite: a common double
carbonate mineral consisting of
alternative layers of calcite and
magnesite
Chemisorption mechanism
Clays Natural well-known minerals Not efficient for pollutants hav-
(several classes of clays) ing a strong acid character
Montmorillonite Low-cost and abundance on most Requires chemical modification
continents or activation (bentonite)
Bentonite Layered structures with large sur- Results are pH-dependent
face area and high porosity, and
high
Fuller’s earth chemical and mechanical stability Identification of adsorption
Sepiolite Strong candidates for mechanism (for modified
ion-exchange (high cation materials)
exchange capacity)
Kaolinite Considered as host materials
with a strong capacities to adsorb
positively charged species; they
can also adsorb anionic and neu-
tral species
Modified materials Efficient for basic dyes, phenols
and metal ions
High adsorption capacities with
rapid kinetics
Montmorillonite: clay with the
largest surface area and the
highest cation exchange capacity
Fuller’ earth: a natural clay with
an open porous structure
Bentonite: a fine powder clay
with a high surface area and an
efficient sorbent for acid, basic
and disperse dyes (very interest-
ing material when coupled with
ultrafiltration)
Organobentonites: powerful
adsorbents
Formation of dye-clay complex
or organoclay
(continued)
Table 2.6 (continued)
Adsorbent Features/advantages/mechanisms Limitations/comments
Commercial polymeric Established treatment process Derived from petroleum-based
organic resins and raw materials
synthetic organic
resins
Porous cross-linked A large choice of commercially Commercial resins are quite
polymers available materials: regular expensive
spherical beads with high surface
area, a wide range of pore struc-
ture, high mechanical strength
and high chemical resistance, and
with chelating properties, compa-
rable with those of AC
Macroporous Industrial use for adsorption and Sensitive to particle, suspended
copolymers ion-exchange processes solids, COD and oils
Hypercross-linked Effective materials – produce a Performance is dependent on the
polymers high-quality treated effluent type of resin used
Organic resins High adsorption capacities toward Incapable of treating large
target pollutant including pheno- volumes
lic derivatives, metals, ionic con-
taminants (fluorides. . .) and dyes
Chelating polymers Very interesting technology in pH-dependence
combination with CAC treatment
Hydrogels Economically valid for precious Poor contact with aqueous
metal recovery pollution
Synthetic- or natural- Can remove unwanted molecules Requires a modification for
based polymers to lower concentrations than CAC enhanced the water wettability
does
No loss of material on Non-selective process (conven-
regeneration tional resins)
Organic resins: mechanism due to Not effective for all dyes (dis-
ion-exchange and/or diffusion perse dyes)
into the porous network
Hydrogels (super-swelling poly-
mers): mechanisms involve both
electrostatic interactions and dif-
fusion into the three-dimensional
polymeric structures
Industrial by-products Low-cost materials and local Adsorption properties strongly
availability depend on the different materials
(fly ash, red mud)
Fly ash Effective for metal and dye Contain hazardous substances
removal with interesting adsorp- (coal fly ash may contain harmful
tion capacities metal oxides)
Red mud Fly ash: a waste material pro- Low surface area
duced in great amounts in com-
bustion processes
Metal hydroxide Metal hydroxide sludge: a Require physical and chemical
sludge low-cost waste material from the modification (red mud)
(continued)
Table 2.6 (continued)
Adsorbent Features/advantages/mechanisms Limitations/comments
electroplating industry containing
insoluble metal hydroxides and
salts (calcium, sodium)
Blast furnace slag and Red mud: efficient for metalloids Results are pH-dependent (metal
sludge etc. and anions removal hydroxide sludge)
Ion-exchange mechanism and/or Influence of salts (metal hydrox-
diffusion ide sludge)
Agricultural solid Cheap and readily available Adsorption properties depend on
wastes and byproducts resources the different materials
from forest industries
Sawdust Effective for many types of pol- Adsorption mechanism must be
Bark lutants and pollution (metals, clarified (bark)
dyes, oils, salts)
Date pits Bark: a polyphenol-rich material Results are pH-dependent
containing a high tannin content
Pith Sawdust: an abundant by-product Require chemical pre-treatment
available in large quantities at to improve the adsorption capac-
zero or negligible price containing ity and enhance the efficiency
various organic compounds with (sawdust)
polyphenolic groups
Possible regeneration (sawdust)
Physisorption and chemisorption
(ion-exchange, hydrogen bond-
ing) mechanisms
Biomass Interesting competitive, cheap Slow process and limiting pH
and effective technology tolerance (algae)
Dead or living Publicly acceptable Performance depends on the
biomass biomass species (algal species),
differences in the cell wall com-
position of the species, cell size
and morphology, and on some
external factors (pH, salts, com-
petitive adsorption, metal speci-
ation, temperature)
Fungi Simplicity, versatility, flexibility Results depend on the functional
for a wide range of applications groups present in the biomass
Algae Availability of different bio- Not appropriate for column sys-
masses in large quantities and at tems (an immobilization step is
low cost necessary for use in column
reactors)
White-rot fungi Effective and selective adsorbents Technologies are still being
containing a variety of functional developed
(continued)
Table 2.6 (continued)
Adsorbent Features/advantages/mechanisms Limitations/comments
groups: more selective than tradi-
tional ion-exchange resins and
CAC
Yeasts Important adsorption capacities
reported for metal ions and dyes
Agricultural wastes Suitable for a wide range of
metal concentrations from
100 ppm to 100 ppb or even less
(algae)
Food processing Fungi can reduce pollutant con-
centrations to ppb levels
Aquatic plants Regeneration is not necessary
Physisorption and chemisorption
mechanisms
Peat Plentiful, inexpensive and widely Low mechanical strength
available biosorbent
Raw material A porous and complex soil mate- A high affinity for water
rial with a polar character
Modified materials A low-grade carbonaceous fuel Poor chemical stability
containing lignin, cellulose and
humic acids
Excellent adsorption and A tendency to shrink and/or
ion-exchange properties (contains swell
various functional groups); good
adsorption capacities for a variety
of organic and inorganic pollut-
ants; particularly effective adsor-
bent for basic dyes and metal ions
Chemisorption mechanisms Requires a pre-treatment or a
chemical activation step
Influence of some factors (pH,
agitation speed, initial dye
concentration)
Chitosan Abundant, renewable, biodegrad- Nonporous material
able and environmentally friendly
resource
Chitin and derivatives Chitin, the second most abundant Low surface area
natural polysaccharide next to
cellulose, is fairly abundant
(found in the exoskeleton of
shellfish and crustaceans); con-
sidered as a byproduct of food
processing
Chitosan-based Low-cost biopolymer and The performance depends on the
derivatives extremely cost-effective origin of the polysaccharide, the
(continued)
Table 2.6 (continued)
Adsorbent Features/advantages/mechanisms Limitations/comments
degree of N-acetylation and the
treatment of the polymer
Hydrophilic biopolymer with Variability in the polymer char-
high reactivity and cationic prop- acteristics and in the materials
erties in acidic medium used
Excellent diffusion properties Not effective for cationic dyes
(except after derivatization)
Versatile materials (powders, Requires chemical modification
gels, beads, fibres. . .) with excel- to improve both its performance
lent chelation and complexation and stability
behavior
Outstanding metal-binding Results depend on the functional
capacities (useful for the recovery groups grafted
of valuable metals) and extremely
high affinities for many classes of
dyes
High efficiency and selectivity in Results are strongly
detoxifying both very dilute or pH-dependent
concentrated effluents; a high-
quality treated effluent is obtained
Easy regeneration if required Hydrogels: not appropriate for
Physisorption (van der Waals column systems (except for
attraction, hydrogen bonding, cross-linked beads)
coulombic attraction) and chem-
isorption (chelation, complexa-
tion) mechanisms
Miscellaneous Renewable resources (starches, Cost (calixarenes, cucurbiturils,
adsorbents cotton waste, cellulose), econom- cyclodextrins)
ically attractive and feasible
Cellulose A remarkably high swelling Low mechanical strength
capacity in water
Starch Relatively low-cost materials with Low surface area
good adsorption capabilities for a
variety of pollutants (can reduce
pollutant concentrations to ppb
levels)
Cyclodextrin Good removal of a wide range of Variability in the materials used
contaminants
Alginates Capable of forming host-guest A high affinity for water
complexes (cyclodextrins,
calixarenes, cucurbituril)
Cotton waste Starch: the most abundant carbo- Poor chemical stability
hydrate (next to cellulose) with
numerous biological and chemi-
cal properties – abundant bio-
polymer and widely available in
many countries
(continued)
Table 2.6 (continued)
Adsorbent Features/advantages/mechanisms Limitations/comments
Calixarenes Cyclodextrins: natural macrocy- A tendency to shrink and/or
clic oligomers having a hydro- swell
phobic cavity and a amphiphilic
character; exhibit high adsorption
capacities towards organic species
Cucurbiturils Cucurbituril: macrocyclic ligand Not appropriate for column sys-
with interesting complexing tems (hydrodynamic limitations,
properties; a high capacity to column fouling, technical
adsorb (textile) dyes and lantha- constraints)
nide cations
Chemisorption mechanism (com- Requires pre-treatment and/or
plexation, inclusion complex for- chemical modification
mation, ion-exchange) Cucurbituril: dissolution
problem

also ineffective for the removal of cationic dyes. Red mud, alumina, zeolite, calcite
and clay have been proposed for fluoride removal but, with fluoride concentration
decreasing, these materials lose the fluoride removal capacity. Inherent limitations of
raw clays as adsorbents of metals are their low loading capacity, relatively small
metal ion binding constants, and low selectivity to the type of metal.
Despite the number of papers published on conventional and non-conventional
adsorbents for pollutant removal from contaminated solutions, there is, as yet little
literature reporting a full study of comparisons between materials. The data have not
been compared systematically with commercial activated carbons or synthetic
ion-exchange resins which show high removal efficiencies and rapid kinetics.
Finally, despite continuing dramatic increases in published research, there has
been little or no exploitation in an industrial context.

2.4 Modeling and Mechanisms of Adsorption

2.4.1 Batch Experiments

Batch experiments provide fundamental information on the behavior of the adsor-

bents used and are thus necessarily carried out in all adsorption studies. Indeed, these
methods are widely used to describe the adsorption capacity, the adsorption kinetics
and the thermochemistry of the process. The experimental protocol used is simply
and easily reproducible. The solution to be treated and the adsorbent are intimately
mixed in an agitated contacting reactor/tank for a set time to enable the system to
approach equilibrium, following which the thin slurry is filtered to separate the solid
adsorbent and adsorbate from the solution. Batch studies use the fact that the
adsorption phenomenon at the solid/liquid interface leads to a change in the con-
centration of the solution. Adsorption isotherms are then constructed by measuring
the concentration of adsorbate in the medium before and after adsorption at a fixed
temperature. In this respect, in general, adsorption data including equilibrium and
kinetic studies are performed using standard procedures which consist in mixing a
fixed volume of contaminant solution, at a known concentration in a tightly closed
flask, with a known amount of material (the adsorbent is usually applied in the form
of a finely ground powder) in controlled conditions of contact time, agitation rate,
temperature, and pH. The solution is stirred on a thermostatic mechanical shaker
operating at a constant agitation speed. The solution is then, for example, centrifuged
to remove any adsorbent particles, and the supernatant is analyzed for the final
contaminant concentration: at predetermined times, the residual concentration is
determined by using chemical analysis.
Contaminant concentrations in solution can be estimated quantitatively thanks to
a linear regression equation obtained by plotting a calibration curve over a range of
concentrations. The amount of contaminant adsorbed (i.e. adsorption capacity,
contaminant uptake or abatement) is calculated by subtracting the final solution
concentration from the initial value. The results are in general reproducible. Blanks
containing no contaminant or adsorbent can be conducted in similar conditions as
controls to evaluate possible contaminant change (for example color change in the
case of dye molecules) and/or precipitation processes for both components. The
amount of contaminant adsorbed at time t by the material (qt) was obtained from the
differences between the concentrations of contaminant added to that in the superna-
tant. qt was calculated from the mass balance equation given by Eq. (2.1) where Co
and Ct are the initial and final adsorbate concentrations in liquid phase (mg L
1),
respectively, V is the volume of adsorbate solution (L) and m the mass of adsorbent
used (g). When t is equal to the equilibrium time (i.e., Ct ¼ Ce, qt ¼ qe), then the
amount of contaminant adsorbed at equilibrium, qe, can be calculated by using
Eq. (2.2) where Ce is the liquid phase contaminant concentration at equilibrium
(mg L
1). The amount of adsorbate adsorbed can be also expressed as percentage of
removal (uptake) or abatement (R in %) by using Eq. (2.3). The term “abatement”,
used by the industrial sector, illustrates the ability of the material to reduce the
pollutant load or the concentration of contaminant(s) in effluent to be treated.

V ðC o
C t Þ
qt ¼ ð2:1Þ
m
V ðC o
C e Þ
qe ¼ ð2:2Þ
m
100ðC o
C t Þ
R¼ ð2:3Þ
Co
2.4.2 Modeling

Adsorption properties and equilibrium data, commonly known as adsorption isotherms,

describe how pollutants interact with adsorbent materials and so are critical in optimizing
the use of adsorbents. In order to optimize the design of an adsorption system to remove
contaminant from solutions, it is important to establish the most appropriate correlation
for the equilibrium curve. An accurate mathematical description of equilibrium adsorp-
tion capacity is indispensable for reliable prediction of adsorption parameters and
quantitative comparison behavior for different materials (or for varied experimental
conditions) within any given system (Crini and Badot 2007, 2008).
Adsorption equilibrium is established when the amount of contaminant being
adsorbed onto the adsorbent is equal to the amount being desorbed (Giles et al.
1958). It is possible to depict the equilibrium adsorption isotherms by plotting the
concentration of the contaminant in the solid phase versus that in the liquid phase.
The distribution of contaminant molecule (or ion) between the liquid phase and the
material is a measure of the position of equilibrium in the adsorption process and can
generally be expressed by one or more of a series of isotherm models. The shape of
an isotherm may be considered with a view to predicting if an adsorption process is
“favorable” or “unfavorable”. The isotherm shape can also provide qualitative
information on the nature or the molecule-surface interaction.
There are several isotherm equations available for analyzing experimental data and for
describing the equilibrium of adsorption, including the Freundlich, Langmuir, BET,
Langmuir-Freundlich, Generalized, Höll-Kirch, Sips, Koble-Corrigan, Radke-Prausnitz,
Dubinin-Radushkevich-Kaganer, Redlich-Peterson, Tóth, Temkin, Elovich, Kiselev,
Hill-de Boer, Fowler-Guggenheim, Frumkin, Harkins-Jura, Halsey, Nitta, Myers, Hen-
derson, Jossens, Weber-van Vliet, Fritz-Schlunder, and Baudu models (Freundlich 1906;
Langmuir 1916, 1918; Radushkevich 1949; Sips 1948; Redlich and Peterson 1959;
Dubinin 1960; Toth 1971; Tien 1994; Ho 2003; Allen et al. 2004; Song and Won
2005; Hamdaoui and Naffrechoux 2007a, b; Crini and Badot 2010). The different
equation parameters and the underlying thermodynamic assumptions of these models
often provide insight into both the adsorption mechanism and the surface properties and
affinity of the adsorbent. The two most frequently used equations applied in solid/liquid
systems to describe adsorption isotherms are the Langmuir and the Freundlich models
and the most popular isotherm theory is the Langmuir type, although these models were
initially developed for the modelling of the adsorption of gas solutes onto metallic
surfaces (Langmuir 1916, 1918; Polanyi 1920; Dubinin 1966, 1972), and are based on
the hypothesis of physical adsorption.
The Langmuir isotherm model is widely used in the literature due to the fact that it
incorporates an easily interpretable constant which corresponds to the highest possible
adsorbate uptake (i.e. the complete saturation isotherm-curve plateau). The Langmuir
equation is represented by Eq. (2.4) where x is the amount of pollutant adsorbed (mg), m
is the amount of adsorbent used (g), Ce (mg/L) and qe (mg/g) are the liquid phase
concentration and solid phase concentration of adsorbate at equilibrium, respectively, and
KL (L/g) and aL (L/mg) are the Langmuir isotherm constants. The Langmuir isotherm
constants, KL and aL are evaluated through linearisation of Eq. (2.4). By plotting Ce/qe
against Ce, it is possible to obtain the value of KL from the intercept which is 1/KL and the
value of aL from the slope which is aL/KL. Using these constants, it is also possible to
obtain an interesting parameter widely used in the literature to promote a solid material as
adsorbent, i.e., the theoretical monolayer capacity of an adsorbent (qmax in mg/g). Its
value, numerically equal to KL/aL, permits to evaluate the maximum adsorption capacity
of a material for the adsorption of a target pollutant (Crini 2003, 2005, 2006, 2015). At
this stage, it is important to note that the uptake of a contaminant by two material
adsorbents must be compared not only at the same equilibrium concentration but also
in the same experimental conditions (particularly pH). Another essential feature of the
Langmuir isotherm can be expressed in terms of a dimensionless constant called sepa-
ration factor (RL, also called equilibrium parameter) which is defined by the Eq. (2.5)
where Co is the initial concentration (mg/L) and aL is the Langmuir constant related to the
energy of adsorption (L/mg). The value of RL indicates the shape of the isotherms to be
either unfavorable (RL > 1), linear (RL ¼ 1), favorable (0 < RL < 1) or irreversible
(RL ¼ 0).

x K L Ce
qe ¼ ¼ ð2:4Þ
m 1 þ aL C e
1
RL ¼ ð2:5Þ
1 þ aL C 0
The Freundlich isotherm is expressed by Eq. (2.6) where Ce (mg L
1) and qe
(mg g
1) are the liquid phase concentration and solid phase concentration of
adsorbate at equilibrium, respectively, KF is the Freundlich constant (L
1 mg) and
1/nF is the heterogeneity factor. The Freundlich constants are empirical constants
which depend on several environmental factors. The value of 1/nF ranges between
0 and 1, and indicates the degree of non-linearity between solution concentration and
adsorption as follows: if the value of 1/nF is equal to unity, the adsorption is linear; if
the value is below unity, this implies that the adsorption process is chemical; if the
value is above unity, adsorption is a favorable physical process; the more heteroge-
neous the surface, the closer 1/nF value is to 0.

qe ¼ K F C e 1=nF ð2:6Þ

In single-component isotherm studies, the optimization procedure also requires

an error function to be defined in order to quantitatively compare the applicability of
different models in fitting data. To determine isotherm constants for two-parameter
isotherms such as the Langmuir and the Freundlich models, a linear method is
available which is based on converting the equation into a linear form by
transforming the isotherm variables (Choy et al. 1999; Ho et al. 2000, 2002, 2005;
Allen et al. 2003, 2004). Indeed, the typical assessment of the quality of the isotherm
fit to the experimental data is based on the magnitude of the correlation coefficient
for the regression, i.e. the isotherm giving an R2 value closest to unity is deemed to
provide the best fit. Linearization using such data transformations implicitly alters
the error structure however, and may also violate the error equality of variance
(homoscadasticity) and normality hypotheses for standard least squares. This may
help to explain earlier observations according to which isotherm parameters derived
from the linearized forms of the equations are biased in that the Freundlich param-
eters produce isotherms which tend to fit the data better at low concentrations
whereas those derived for the Langmuir isotherm tend to fit the data better at higher
concentrations (Allen et al. 2003; Crini and Badot 2010).
In the literature, linear regression is the most commonly used method to estimate
adsorption, and linear coefficients of determination are preferred (Ho et al. 2000,
2005; Allen et al. 2004; Crini and Badot 2010; El-Khaiary 2008; El-Khaiary and
Malash 2011). However, the use of this method is limited to solving linear forms of
equation which measure the difference between experimental data and theoretical
data in linear plots only, but not the errors in isotherm curves. The linearization of a
non-linear isotherm expression can produce different outcomes (Allen et al. 2003,
2004; Crini and Badot 2008, 2010). The values of individual isotherm constants can
change with the error methodology selected.
As an alternative to the linear transformation, nonlinear optimization has also
been applied to determine isotherm parameter values. It most commonly uses
algorithms based on the Levenberg-Marquardt or Gauss-Newton methods. The
optimization procedure requires an error function to be defined in order to enable
the optimization process to determine and evaluate the fit of the isotherm to the
experimental equilibrium data (Allen et al. 2003, 2004). Different error functions
were proposed such as the sum of the squares of the errors (Eq. 2.7), the hybrid
fractional error function (Eq. 2.8), the Marquardt’s percent standard deviation
(Eq. 2.9), the average relative error (Eq. 2.10) and the sum of the absolute errors
(Eq. 2.11). In each case, the isotherm parameters can be determined by minimizing
the respective error function across the concentration range studied when using the
solver add-in with Microsoft’s spreadsheet, Excel.

X
p
 2
qe, calc
qe, meas i
ð2:7Þ
i¼1
" 2 #
100 Xp
qe, meas
qe, calc
ð2:8Þ
p
n i¼1 qe, meas
0vu
ffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi

i ffi
 2 1

u 1 X qe, meas
qe, calc
p
100@t A ð2:9Þ
p
n i¼1 qe, meas
p   i
100 X  qe, calc
qe, meas 
ð2:10Þ
p i¼1  qe, meas 
i
Xp 
q
q  ð2:11Þ
e, calc e, meas i
i¼1
 Several kinetic models can be also used to find the best fitted model for the
experimental data obtained (Lagergren 1898; Boyd et al. 1947; Reichenberg 1953;
Weber and Morris 1963; Weber et al. 1963; Hall et al. 1966; Blanchard et al. 1984;
Treybal 1987; Al-Duri 1996; Ho and McKay 1998, 2003; McKay et al. 1999; Ho
2004, 2006; Azizian 2004; Liu and Liu 2008; Plazinski et al. 2009; Largitte and
Pasquier 2016). It is well-accepted that there are several steps in a solid-liquid
adsorption process: initially the adsorbate molecules/ions migrate from the bulk of
the solution to the material surface (bulk diffusion); the molecules diffuse through
the boundary layer to the surface of the material (film diffusion); then, the adsorbate
diffuses from the surface to the interior of the particle (pore diffusion, intraparticle
diffusion); and finally the molecules reacts with the active sites on the surface of the
material (physical adsorption, chemical reaction).
The use of kinetic models such as diffusional models and adsorption models
permit elucidation of the adsorption mechanism. The diffusional models assume that
the diffusion is the rate limiting step. They are divided in two groups (Crini and
Badot 2010). The first is the external mass transfer model which assume that the
transfer is controlled by boundary layer diffusion (e.g. Boyd’s film-diffusion equa-
tion, Spahn and Schlunder model). The adsorbate molecules must pass through the
hydrodynamic layer to the surface of the material. Transportation through the
boundary layer is due to molecular diffusion, and the distance the adsorbate must
travel, or the thickness of the boundary layer, depends on the velocity of the bulk
solution. The size of the boundary layer affects the rate of transportation (the thinner
the boundary layer, the higher the rate of the transportation). The second gathers the
internal diffusion models suggesting a mass transfer through the pores (e.g. Crank
model, Weber and Morris model, Bangham model). The internal transport occurs
after the adsorbate has passed through the boundary layer and must be transported
through the pores to adsorption sites. This intraparticle transportation may occur by
molecular diffusion through the solution in the pores (pore diffusion) or by diffusion
along the material surface (surface diffusion) after adsorption takes places. The final
step, adsorption, is the attachment of the adsorbate onto the material surface at
available sites. This step is very rapid, and therefore one of the preceding diffusion
steps will control the rate of mass transfer.
In the adsorption models, the adsorption is considered to be the slowest process.
This is the case when the adsorbate uptake on the material is of chemical nature.
These models include the pseudo-first order model (Lagergren model), the pseudo-
second order model (Ho and McKay equations), the pseudo-n order model (for n
different from zero), the Langmuir model, and the Elovich equation. The two most
popular kinetic equations are pseudo-second-order kinetic and intraparticle diffusion
equations proposed by Ho and McKay, and Weber and Morris, respectively.
The pseudo-second order model can be represented in the linear form described
by Eq. (2.12) where qt (mg/g) and qe (mg/g) are the amount of pollutant adsorbed at
time t and equilibrium, respectively, and k2 is the equilibrium rate constant of
pseudo-second order adsorption (g/mg min). The parameters k2 and qe can be
directly obtained from the intercept and slope of the plot of t/qt against t. This
model is commonly used to describe kinetics of contaminant adsorption on solid
adsorbents, although as pointed out by McKay’s group (Ho and McKay 1998;
McKay et al. 1999), the application of a single kinetic model to the adsorption on
materials may be questionable because of the heterogeneity of the adsorbent surfaces
and diversity of adsorption phenomena (i.e. transport, diffusion, reactions). Such
approach has no physical significance and it is more reasonable to interpret the
kinetic data in term of mass transfer.

t 1 1
¼ þ t ð2:12Þ
qt k2 q2e qe

In a batch system under rapid stirring, there is a possibility that the transport of the
adsorbate from the solution into the bulk of the adsorbent is the rate controlling step.
This possibility was tested in terms of a graphical relationship between the amount of
pollutant adsorbed and the square root of time. According to the intraparticle
diffusion model proposed by Weber and Morris, the initial rate of intraparticle
diffusion is given by the Eq. (2.13) where qt is the amount of pollutant on the surface
of the sorbent at time t (mg/g), ki is the intraparticle diffusion rate constant (mg/g min1/2),
t is the time (min) and C is the intercept (mg/g). According to Eq. (2.13), a plot of
qt versus t1/2 should be a straight line when adsorption mechanism follows the
intraparticle diffusion process. In general, the plots present a multi-linearity,
which indicates that two or more steps occur in the process.

qt ¼ ki t 1=2 þ C ð2:13Þ

Finally, the adsorption characteristics of a material can be expressed in thermo-

dynamic parameters such as ΔG, ΔH and ΔS (entropy change). These parameters
can be calculated by using the thermodynamic equilibrium coefficient obtained at
different temperatures and concentrations. The models of Arrhenius, Gibbs, van’t
Hoff and Clausius-Clapeyron can be used (Crini and Badot 2008). The values of
ΔG, ΔH and ΔS provide valuable information about the thermodynamics of the
adsorption process. ΔG addresses the possibility and feasibility of a certain reaction.
Its negative value shows the process is feasible and spontaneous. ΔH shows the
route of energy in the process and its positive value indicates an endothermic system.
Some authors conclude that the nature of the contaminant adsorption is predomi-
nantly physical, involving weak interactions. ΔS can be used to describe the
randomness at the solid/solution interface during the adsorption process.
There is no doubt that mathematical modeling is an invaluable tool for the
analysis and design of adsorption systems and also for the theoretical evaluation
and interpretation of thermodynamic parameters (Allen et al. 2004). However, two
important points must be pointed out. The first is that, although these adsorption and
kinetic models remain a useful and convenient tool for the comparing results from
different sources due to their highly idealistic simplicity, a given plot is an empir-
ically relationship (Liu and Liu 2008; Liu and Wang 2008; Lin and Wang 2008; Wu
et al. 2009; Rudzinski and Plazinski 2009; Douven et al. 2015). An isotherm may fit
experimental data accurately under one set of conditions but fail entirely under
another. No single model has been found to be generally applicable. This is readily
understandable in the light of the hypotheses associated with their respective devi-
ations. In addition, the two-parameter isotherm model such as the Langmuir and the
Freundlich models are based on the hypothesis of physical adsorption. In the case of
dye adsorption onto a biosorbent, which is more chemical than physical, it would be
more appropriate to consider pollutant adsorption with models based on chemical
reactions. However, these models are complicated in nature. Simple kinetic models
used in the literature are also questionable because, generally speaking, these models
cannot represent the real course of adsorption and thus cannot offer useful informa-
tion to gain insight in mechanism. It is more reasonable to interpret the kinetic data in
term of mass transfer (homogeneous diffusion model, double exponential model,
etc.) but these models are also complex and effective graphical analysis software are
required to solve mathematical models. The book published by Tien (1994) can be
consulted on this topic. The second point is related the abundant literature data.
Despite the number of papers published, there is as yet little literature containing a
full study comparing various models and this topic clearly needs further detailed
research (Wase and Forster 1997; McKay 1999; Cooney 1999; Yang 2003;
Hamdaoui and Naffrechoux 2007a, b; Crini and Badot 2007, 2010).

2.4.3 Mechanisms of Adsorption

In the context of adsorption, the major challenge is to select the most promising types
of adsorbent, mainly in terms of low-cost, high capacity (often expressed by the qmax
value), high adsorption rate, high selectivity, and rapid kinetics. The next real
challenge is to clearly identify the adsorption mechanism(s), in particular the inter-
actions occurring at the adsorbent/adsorbate interface (Veglio’ and Beolchini 1997;
Crini 2005). This is an important topic because the adsorption mechanisms involved
in contaminant uptake can orientate the design of the desorption strategy (for
example, the recovery of certain contaminants such as “precious” metal ions is
also an important parameter for the economics of the process).
Despite the large number of papers devoted to the adsorption of contaminants
onto conventional or non-conventional adsorbents, most focus on the evaluation of
adsorption performances and only a few aim at gaining a better understanding of
adsorption mechanisms (Veglio’ and Beolchini 1997; Crini 2005). These mecha-
nisms are not fully understood because a large number of interactions are possible.
Some of the reported interactions include (Crini 2005):
– physisorption (physical adsorption)
– surface adsorption
– van der Waals interactions
– hydrogen bonding
– electrostatic interactions (attraction interactions)
– ion-exchange
– complexation (coordination)
– chelation
– acid-base interactions
– proton displacement
– precipitation (surface precipitation, microprecipitation)
– hydrophobic interactions (π-π interactions, Yoshida’s interactions)
– oxidation/reduction
– inclusion complex formation
– diffusion into the network of the material
– covalent binding
An interesting question remains: Must all these interactions be taken into account
to explain the adsorption mechanism? The answer to this question is not so easy. In
an oriented-adsorption process using a given adsorbent, it is possible that more than
one of these interactions can occur simultaneously depending on the composition of
the material, the contaminant structure and its properties, and the solution conditions
(pH, ionic strength, temperature).
Crini reported the simplified classification of contaminant adsorption mecha-
nisms described in Fig. 2.5 (Crini 2005, 2006, 2010; Crini and Badot 2007). Four
main mechanisms have been proposed, namely physisorption, chemisorption,
ion-exchange and precipitation. Some authors consider ion-exchange process as a
chemisorption mechanism. Davis et al. (2003) reported that the term ion-exchange
does not explicitly identify the binding mechanism, rather it is used as an umbrella
term to describe the experimental observations. The use of the “microprecipitation”
term is also a source of debate. This term is used to indicate precipitation taking place

Fig. 2.5 Classification of pollutant adsorption mechanisms according to Crini (Crini 2005, 2006;
Crini and Badot 2007)
locally at the surface of a biosorbent due to particular conditions. A discussion on
these terms can be found in the recent review by Robalds et al. (2016). Other
classifications of contaminant adsorption mechanisms can be found in the following
references: Veglio’ and Beolchini (1997), Srivastava and Goyal (2010), Naja and
Volesky (2011), Asgher (2012), Michalak et al. (2013) and Robalds et al. (2016).
Literature based on commercial activated carbons clearly shows a greater number
of studies on the adsorption of organic compounds as compared with the inorganic
ones, and it is well known that carbon adsorbents are very versatile due to their high
surface area, well-developed pore structure, and surface properties (Radovic et al.
1997, 2000; Ania et al. 2002). The main mechanism is physisorption. However,
although extensive experimental and modeling studies on activated carbons have
been reported, the subject remains highly controversial as described by Radovic
et al. (2000). Much confusion exists in the literature, especially on the role of
surface-oxygen functions in the adsorption of aromatic compounds (Moreno-Castilla
et al. 1995; Dubinin 1966; Radovic et al. 2000; Pereira et al. 2003).
For biosorbents, the adsorption mechanism are yet not fully understood although
some are now well-accepted. In the case of biosorption of metals by biomass, the
mechanisms can be viewed as being extracellular or occurring discretely at the cell
wall. Intracellular adsorption would normally imply bioaccumulation by a viable
organism. Gadd (1990), Veglio’ and Beolchini (1997), Volesky (2001), and Aksu
(2005) previously discussed various mechanisms involved in biosorption using
microorganisms (fungi, yeasts or bacteria, etc.). Gadd (1990) commented that “a
large variety of physical, chemical and biological mechanisms may be involved,
including adsorption, precipitation, complexation and transport”. In general, two
different metal-binding mechanisms have been postulated to be active in biosorption
pollutant uptake: (1) chemisorption by ion-exchange, complexation (including coor-
dination) and/or chelation (biosorption process), and (2) physical adsorption and/or
(micro)precipitation (in this case, the process is termed bioaccumulation). Other
interactions have been proposed, including metabolism-dependent transport, adsorp-
tion of simple ionic species, hydrogen bonding interactions, biological mechanisms,
reactions involving hydrolysis products of metal ions or oxidation/reduction.
Accumulation of metals and radionuclides by algae can be described as being
composed of two phases: a rapid phase of metabolism-independent binding to the
cell surface (biosorption) followed by a slower phase due to simultaneous effects of
growth and surface adsorption, active or intracellular uptake by passive diffusion
(Garnham 1997). Biosorption- and bioaccumulation-based mechanisms have been
adopted for the description of the mechanistically different types of metal seques-
tering by microorganisms. However, the nature of the binding processes in
biosorption is yet complex and unknown, due to the complexity of most
biopolymers.
Numerous authors accept that the decolourisation process using
non-conventional materials generally results from two main mechanisms – adsorp-
tion and ion exchange (Allen and Koumanova 2005; Crini 2006), and is influenced
by many factors including the type of adsorbents/biosorbents and dyes, and the
process variables. For instance, ion-exchange and hydrogen bonding interactions are
the main mechanisms for the removal of metals by sawdust (Shukla et al. 2002). The
cell walls of sawdust mainly consist of cellulose and lignin, with many hydroxyl
groups such as those on tannins or other phenolic compounds. All these components
are active ion-exchange compounds.
Polysaccharide-based materials are mainly used as a chelating or complexing
ion-exchange media. These biopolymers (i.e. starch, cellulose, chitin and alginates)
and their derivatives (e.g. chitosan, cyclodextrin) contain a variety of functional
groups, which can chelate ionic species of a specific size and charge. Such materials
are thus often much more selective than traditional ion-exchange resins and can
reduce heavy metal ion concentrations to ppb levels (Kentish and Stevens 2001;
Crini and Badot 2008). Crini (2015), reviewing dye removal by starch-based
materials reported that the adsorption mechanisms were not fully understood
because numerous interactions were possible, including ion-exchange, acid-base
interactions, precipitation, hydrogen bonding, hydrophobic interactions and
physisorption.
For cyclodextrin-based adsorbents, inclusion complex formation and diffusion
into the polymer network are the preferred concepts in biosorption because they
account for many of the observations made during contaminant uptake studies (Crini
2014). In a comprehensive review, Morin-Crini et al. (2017) recently reported that,
in spite of the abundance of literature and conclusive results obtained at the labora-
tory scale, interpreting the mechanism of pollutant elimination remains an interesting
source of debate and sometimes of contradiction.
Plant fibers used as biosorbents consist mainly of cellulose, hemicelluloses, lignin
and some pectin and extractives (fats, waxes, etc.). Metal ions mainly adsorb to
carboxylic (primarily present in hemicelluloses, pectin and lignin), phenolic (lignin
and extractives) and to some extent hydroxyl (cellulose, hemicelluloses, lignin,
extractives and pectin) and carbonyl groups (lignin). Strong bonding of metal ions
by the hydroxyl, phenolic and carboxylic groups often involves complexation and
ion-exchange (Crini and Badot 2010).

2.5 Concluding Remarks

Preserving the environment, and in particular the problem of water contamination,

has become a major preoccupation for everyone – the public, industry, scientists and
researchers as well as decision-makers on a national, European, or international
level. The public demand for pollutant-free waste discharge to receiving waters has
made decontamination of industrial wastewaters a top priority. This is a difficult and
challenging task. It is also difficult to define a universal method that could be used
for the elimination of all contaminants from wastewaters. Among the numerous and
various treatment processes currently cited for wastewater treatment, only a few are
commonly used by the industrial sector. However, it is now accepted that adsorption
is the procedure of choice and gives the best results as it can be used to remove many
different types of contaminants.
 In this chapter, a general overview on adsorption processes for contaminant
removal has been presented, including a classification for the different types of
conventional and non-conventional adsorbents used for this purpose and the inter-
actions proposed to explain adsorption mechanisms. Commercial activated carbon is
extensively used not only for adsorbing contaminants from drinking water sources
but also for removing pollutants from wastewater streams. Other conventional
materials include organic resins, activated alumina, zeolites, and sand.
Non-conventional adsorbents can be also obtained and employed as low-cost and
efficient solid adsorbents. These materials have not yet been significantly commer-
cialized even though they possess numerous advantages over currently available
carbon and organic resins for pollutant removal. Perhaps one reason why
non-conventional adsorbents have not been widely used in industry is the lack of
knowledge about the engineering of such materials. We think that, for novel
adsorbents to be accepted by industry, it will be necessary to adopt a
multidisciplinary approach in which chemists, engineers, material scientists, biolo-
gists, microbiologists, and computer scientists work together. The opportunity now
exists to consider other solid materials such as biomass, cellulose and chitosan for
emerging applications. They will undoubtedly be at the centre of some extremely
profitable commercial activities in the future although their development requires
further investigation in the direction of mechanisms (modeling), of regeneration of
the adsorbent material (if necessary), and of testing materials with real industrial
effluents.

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