Journal of Environmental Management: Tholiso Ngulube, Jabulani Ray Gumbo, Vhahangwele Masindi, Arjun Maity

Journal of Environmental Management 191 (2017) 35e57
Contents lists available at ScienceDirect
Journal of Environmental Management

journal homepage: www.elsevier.com/locate/jenvman
Review
An update on synthetic dyes adsorption onto clay based minerals: A

state-of-art review
Tholiso Ngulube a, *, Jabulani Ray Gumbo b, Vhahangwele Masindi c, d, Arjun Maity e
a
Department of Ecology and Resources Management, University of Venda, Private Bag X5050, Thohoyandou, 0950, Limpopo, South Africa
b
Department of Hydrology and Water Resources, School of Environmental Sciences, University of Venda, Private Bag X5050, Thohoyandou, 0950, Limpopo,
South Africa
c
Council of Scientific and Industrial Research (CSIR), Building Science and Technology (BST), Built Environment, P.O Box 395, Pretoria, 0001, South Africa
d
Department of Environmental Sciences, School of Agriculture and Environmental Sciences, University of South Africa (UNISA), P. O. Box 392, Florida, 1710,
South Africa
e
Smart Polymers Group, Polymers and Composites, Council for Scientific and Industrial Research (CSIR), Pretoria, South Africa
a r t i c l e i n f o a b s t r a c t
Article history: Dyes are growing to be a problematic class of pollutants to the environment. The disposal of dyes in
Received 20 September 2016 water resources has bad aesthetic and health effects, hence the need to remove them from the envi-
Received in revised form ronment. The need for treatment methods that are effective and low in price is rising hence a lot of
8 December 2016
research interest is being diverted towards adsorbents that are cheap, preferable naturally occurring
Accepted 12 December 2016
Available online 10 January 2017
materials like clays. In most reported dye adsorption studies, limited information on the relationship
between characterization results with adsorbent performance on dye removal has been given. This re-
view article seeks to report on the link between the adsorption characteristics of the clays and their
Keywords:
Clays
adsorption capacities and to gather information on the modifications done on clays to improve their
Dyes adsorption capacities. A critical analysis of the different mechanisms involved during the decolouration
Wastewater process and their application for dye removal has been discussed in detail in this up-to-date review. From
Adsorption capacity and mechanisms a wide range of consulted literature review, it is evident that some clays have appreciable adsorption
capacities on top of being widely available. It was also noted that several parameters like contact time,
dosage, concentration, temperature and pH affect the removal of dyes. Furthermore, the application of
clay minerals for decolourising water represents economic viable and locally available materials that can
be used substantially for pollution control and management. Conclusions were also drawn and sug-
gestions for future research perspectives are proposed.
© 2016 Elsevier Ltd. All rights reserved.
Contents
1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36
2. Dyes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36
2.1. Physico-chemical properties of dyes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37
3. Dye effluent treatment methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37
4. The adsorption process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38
5. Clays . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38
5.1. Clays and adsorption: physicochemical characteristics favouring adsorption . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39
5.2. The relationship between clay surface area, size/mesh and adsorption capacity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40
5.3. The role of clay morphology in the adsorption process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41
5.4. The role of electrical charges in the adsorption process: point of zero charge (pHpzc), point of zero net proton charge (PZNPC), zeta potential and
charge density . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43
5.5. Clay charge density and swelling properties: effect on the adsorption process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 44
* Corresponding author.
E-mail address: tholisongulube@gmail.com (T. Ngulube).
http://dx.doi.org/10.1016/j.jenvman.2016.12.031
0301-4797/© 2016 Elsevier Ltd. All rights reserved.
36 T. Ngulube et al. / Journal of Environmental Management 191 (2017) 35e57
6. Disadvantages of clays leading to modification to enhance their adsorption capacities . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 44

6.1. Cationic and anionic surfactant modification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45
6.2. Magnetic modification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45
6.3. Mechanochemical modification of palygorskite . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 46
6.4. Structural and chemical changes after clay modification: effect on adsorption . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 46
6.5. Clay composite materials: clay nanocomposites, clay/polymer nanocomposite and clay/polymer nanocomposite hydrogels . . . . . . . . . . . . . . . . 47
7. The effect of variables and their interaction on dye adsorption . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 48
7.1. Effect of solution pH . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 48
7.2. Effect of adsorbent dose . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49
7.3. Effect of initial dye concentration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50
7.4. Effect of contact time . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50
7.5. Effect of temperature . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51
7.6. Effect of ionic strength . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51
8. Process optimization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 52
9. Adsorption isotherms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 52
9.1. The Langmuir isotherm . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 52
9.2. The Freundlich isotherm . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 52
10. Desorption studies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 53
11. Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 54
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 54
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 54
1. Introduction Chemical coagulation processes produce huge amounts of

sludge thereby causing a lot of pollution as a result of the different
Different classes of dyes are used in numerous industries chemical reactions that would have taken place during the waste-
including rubber, textiles, cosmetics, plastics, leather, food and water treatment processes (Balik and Aydin, 2016). Merzouk et al.
paper making. The variability of these dyes is seen in wastewaters (2011) reported that the most effective and important treatment
discharged from these industries. “Generally dyes are stable to method is chemical degradation using oxidative agents like chlo-
light, heat and oxidizing agents and are usually non-biodegradable” rine, however the disadvantage of this method is the production of
(Kono, 2015). Because these dyes give colour to the receiving water highly toxic products like organochlorine compounds. Amongst
bodies hence degrading their aesthetic values, it is of paramount other oxidation processes, there are more advanced processes not
importance that their presence in a water body be managed (Kant, limited to some of the following: fenton reactive and ultrasonic
2012). oxidation, UV and ozoneeUV combined oxidation and photo-
The presence of colour in an aquatic ecosystem reduces the catalysis. These oxidation processes are said to be not economically
penetration of sunlight to benthic organisms thus limiting the feasible (Daneshvar et al., 2006). The great variability of the
process of photosynthesis. Dyes also affect the aesthetic value of an wastewater composition often leads to inefficiencies or inadequate
aquatic ecosystem due to colouration of water resources (Yagub treatment of the dye effluents (Drouiche et al., 2011). Having
et al., 2014). The key concern in the treatment of wastewater is pointed out the above, adsorptions seems to be among the most
the release of dyes and their metabolites into the environment, as favoured wastewater treatment technique because of its environ-
some may be mutagens and carcinogens. Some of these dyes are mental and economic sustainability.
xenobiotic in nature and aerobically recalcitrant to biodegradation
(Gupta et al., 2013) and thus pose a threat when wastewater is 2. Dyes
disposed off to the adjacent environment without being treated. In
that regard, there is a need to find treatment technologies that can Dyes can be defined as organic compounds that have colour and
decolourise the water and at the same time reduce the toxic effects are used to give colour to different substrates like cosmetics, paper,
of the dyes to within the recommended water quality guidelines. drugs, leather, fur, greases hair, waxes, plastics and textile mate-
Being among the most demanding environmental tasks of the rials. “Dyes are basically chemical compounds that can connect
modern day, the increasing amount of toxic industrial waste has led themselves to surfaces or fabrics to impart colour” (Yagub et al.,
to the development of various methods for its eradication and 2014). Dyes can be classified according to where they are derived.
removal from wastewaters (Chollom, 2014). Usually industrial ef- They can be from natural or synthetic sources. Natural dyes are
fluents are treated by several methods including chemical degra- extracted from sources including plants, animals and minerals.
dation, advanced oxidation processes, adsorption, precipitation, Natural dyes were used mostly during early textile industry and
biodegradation and chemical coagulation (Pajootan et al., 2012). these include Jackfruit, Onion, eucalyptus, Turmeric, Weld and
These methods have been extensively applied, however they have henna (Dawood and Sen, 2014). However, because of population
some shortcomings (Kobya et al., 2007; Mohan et al., 2007). For increase and industrial activities, people are moving away from
instance, a lot of time is needed for the biological methods and natural dyes because they are failing to meet the industrial demand
more often than not, the biological methods are less effective when hence their application nowadays is mostly found in the food in-
it comes to highly structured polymer dyes. Buthelezi et al. (2012) dustry. Synthetic dyes have replaced natural dyes almost
reported that dyes are non-biodegradable by nature, as such, bio- completely particularly in the fabrics and textile industry. Several
logical methods will be inapplicable and their applicability is types of dyes are used in numerous industries and these include
limited to few dyes because many dyes in the market are toxic to basic, acid, reactive, direct, vat and disperse dyes (Chen et al., 2016).
the organisms used hence the biological methods cannot be All these dyes are soluble in water except for disperse and vat dyes.
applied to treat those dyed wastewaters. Dyes also contain traces of metals like chromium, copper, lead, zinc,
T. Ngulube et al. / Journal of Environmental Management 191 (2017) 35e57 37
and cobalt apart from vat and disperse dyes. Dye effluents from
industries are known for their organic content, high colour and are
harmful as well (Gupta et al., 2013).
2.1. Physico-chemical properties of dyes
Normally dyes are soluble in water or water dispersible organic

Fig. 2. Example of a chromophores.
compounds that are capable of being absorbed into the substrate
destroying the crystal structure of the substance (Hunger, 2003).
Molecules of dyes are chemically bonded to the surface and after include colour removal by Sphingomonas, white rot fungi, pseudo-
application to a material they become a part of it. For dyes to be monas strains, and microbial cultures, under aerobic and anaerobic
marketable in the commercial industry, they should have high or mixed conditions as well as adsorption using living and dead
colour intensity and the colour must not fade away with time. The biomass (Adensola et al., 2016; Babarinde and Onyiaocha, 2016;
intensity of the colour depends on how strongly it absorbs radiation Tahir et al., 2016). Most of these dye compounds are however
in the visible region (Zollinger, 1987). The structures in dyes that very stable and resistant to biological degradation. The isolation of
give colour (unsaturated groups that can undergo p-p and n-p new strains or the adaptation of existing ones to the decomposition
transitions) are called chromophores (see Figs. 1 and 2): of dyes will probably increase the efficacy of bioremediation of dyes
There is also another group of structures that cause colour in the near future. The biodegradation of dye effluents by the use of
intensification and these structures are called auxochromes. Unlike microorganisms is an acceptable and easy method by operation
chromophores, auxochromes cannot undergo p-p transitions, but (Buthelezi et al., 2012).
instead can undergo n electrons transition. The following are ex- Chemical wastewater treatment methods include precipitation,
amples of chromophores: eOH, eOR, eNH2, eNHR, eNR2 and eX. flocculation, coagulation, flotation and filtration, electrokinetic
coagulation, oxidation methods, electroflotation, irradiation or
3. Dye effluent treatment methods electrochemical processes (Pajootan et al., 2012). The effectiveness
of chemical methods depends on the interaction between the
Several technologies to treat dye wastewater have been devel- contaminants in the wastewater and the nature of chemical used
oped and these include coagulation, adsorption, membrane sepa- (Iqbal et al., 2014). The chemicals treat the wastewater by way of
ration process, precipitation, electrochemical, chemical oxidation either assisting in the separation process or helping to ruin and
and biological processes (Yagub et al., 2014). The several methods neutralise some of the detrimental effects caused by the pollutants
mentioned however can be divided into three major types which (Mohan et al., 2007). These techniques are good at decolorizing
are: biological, chemical and physical and their major strengths and water but at the same time are expensive and disadvantageous
weaknesses are shown in Table 1. because they create a lot of sludge after use and therefore lead to a
The biodegradation of synthetic dyes by microorganisms is a sludge disposal problem (Kobya et al., 2007). Moreover, secondary
common and simple method of wastewater treatment by operation pollution problem can arise because of too much chemical use.
but the processes involved in the biological degradation can be Oxidation processes generate powerful oxidizing agents like as
complex. A number of microorganisms have been used for the hydroxyl radicals and these have been used successfully for
decolouration of dyes. These methods of biological treatment
Fig. 1. The chemical structures of some synthetic dyes (Hunger, 2003).

Table 1
The pros and cons of wastewater treatment methods (Robinson et al., 2001).
Treatment Method Pros Cons
Ion-exchange Adsorbent can be regenerated and therefore used for several times Only effective for certain types of dyes.
Membrane processes Reuse of water salts and heat Handling and disposal of concentrate stream, flux decline
Electrochemical processes Breakdown compounds and are non-hazardous Economically less feasible because high electricity costs
Photochemical No sludge production Formation of by products
Ozonation processes Applied in gaseous state: no modification of volume Ozonation processes have a very short half-life
Coagulation/flocculation Insoluble dyes can be removed and it is economically feasible The amount of sludge produced is high.
degrading pollutants but they are also very expensive and between the two types of adsorption is that, in physical adsorption
commercially unattractive because of high consumption of chem- the adsorbate sticks to the surface through weak intermolecular
icals and electrical energy demand (Bilal et al., 2014; Jamal et al., interactions like such as Van der Waals forces, hydrophobicity,
2015; Qureshi et al., 2015). hydrogen bonding, polarity, static interactions, dipoleedipole in-
Physical methods are also extensive and these include adsorp- teractions and P- P interactions (Dawood and Sen, 2014). On the
tion techniques, reverse osmosis, electrodialysis, membrane- other hand, in chemisorption, molecules stick to the surface by
filtration processes and nanofiltration (Khan et al., 2015; Shon forming a chemical bond through electron exchange (Artioli, 2008).
et al., 2013). The main drawback of the membrane processes is Some of the differences between physiosorption and chemisorp-
the short period of use before the membrane starts fouling and the tion are shown in Table 2.
various costs coming as a result of constant replacement of the In adsorption processes, the contaminated water is passed
membranes eventually leading to membrane processes being through a sorbent bed. The adsorbent material will retain the
economically unviable (Shamraiz et al., 2016). According to docu- contaminants by either chemical, physical or ion exchange mech-
mented studies, adsorption is one of the most widespread waste- anisms. After a certain period of time of operation, the adsorbent
water treatment approach that has been proven effective and gets saturated and will require regeneration/replacement
efficient in depollution science since it can remove contaminants depending on regeneration feasibility (Chapman and Siebold,
and decolour the water resources (Gomes et al., 2015; Mu and 1912).
Wang, 2016; Tahir et al., 2016; Srinivasan, 2011). If a treatment Worch (2012) pointed out that the extent of adsorption is
plant is given a proper adsorption process design, it produces a high directly proportional to the specific area of the adsorbent. The
quality treated effluent. Adsorption processes offer an attractive specific area is that part of the entire area available for adsorption. It
alternative treatment method for contaminated waters, particu- is related to the grain size of the adsorbent. The choice of particle
larly in cases where the adsorbent is inexpensive, locally available, size is made by considering the following factors:
abundant and requires less additional pre-treatment step before it
is used (Crini, 2006). ❖ the ease of mass transfer from the fluid to the surface,
Although, the adsorption process has been deemed to offer an ❖ creation of as much interfacial surface area as possible and
attractive alternative treatment technology for polluted waters, it reduction of antiparticle diffusion path length, all of which favor
also has its drawbacks. Adsorption is known to produce highly smaller particles
concentrated sludge that lead to a problem of sludge disposal. It has ❖ maintenance of a low pressure drop, which favors larger parti-
also been reported to be less effective for some dyes, especially the cles (Worch, 2012).
highly concentrated dyes. Moreover it can be very expensive when
using high cost adsorbents like activated carbon which are also For an adsorbent to be selected as favorable, a number of factors
costly to regenerate. A number of investigations have shown that are looked at. These include ease of operation, cost of the medium,
several factors affect the adsorption process but worth to note is adsorption capacity, potential for reuse and likelihood of regener-
that adsorption is vastly dependent on the pH media, basically ation (Worch, 2012). Various naturally occurring materials that are
meaning that to attain maximum adsorption capacities, the pH has both readily available and abundant have been explored as adsor-
to be adjusted in most cases. Besides that, the physical and chem- bents for the removal of dyes from wastewater (Ghosh and Reddy,
ical characteristics of the adsorbent can have an intense influence 2014; Ali et al., 2012; Tehrani-Bagha et al., 2011; Rafatullah et al.,
on the capacity and rate of the adsorption process. e.g low surface 2010). A great interest has grown towards naturally occurring ad-
area for some adsorbents leads to low adsorption capacity sorbents, preferably developing sorbents that have a high adsorp-
(Benefield et al., 1982). tion capacity and has low cost for removing pollutants from
contaminated waters. Although a wide variability of sorbents have
been used for wastewater treatment, naturally available clays have
4. The adsorption process
been the adsorbents of choice in most developing countries (Ali
(2007) defines adsorption as “a process that occurs et al., 2012; Hajjaji et al., 2016; Mu and Wang, 2016; Santos and
Oremusova
Boaventura, 2016).
when a gas or liquid solute accumulates on the surface of a solid or
a liquid (adsorbent), forming a molecular or atomic film (the
adsorbate)”. Generally, the adsorbent has a fixed total uptake, 5. Clays
where a particular solute is replaced by another for example, in ion
exchange processes. When an adsorbent is contacted with liquid “Clays are hydrous aluminosilicates broadly defined as those
containing an absorbable solute, adsorption occurs until equilib- minerals that make up the colloid fraction of soils, sediments, rocks
rium is achieved or when the surface of an adsorbent is saturated and water and may be composed of mixtures of fine grained clay
with an adsorbate (Kalibantonga, 2004). minerals and clay-sized crystals of other minerals such as quartz,
The adsorption process can be divided into two main types, carbonate and metal oxides” (Pinnavaia, 1983). Clay materials
namely, physical and chemical both sometimes referred to as possess structures that are organized in layers and they are cate-
physiosorption and chemisorption respectively. The difference gorized by those different layered structures (Ajbary et al., 2013; Li
Table 2
Comparison between physiosorption and chemisorption (Jaafar, 2006).
Physiosorption Chemisorption
Weak intermolecular forces like van der Waals forces Strong covalent bonding involving electron exchange
Low enthalpy: DH < 20 kJ/mol High enthalpy: DH ~ 400 kJ/mol
Multilayer adsorption Monomolecular adsorption
Low temperature, constantly lower than the adsorbate critical temperature High temperatures
Low activation energy High activation energy
Reversible Non-reversible.
Nonselective surface attachment Selective surface attachment
et al., 2013; Savic et al., 2014). Clay materials fall under various characteristics arise from their large pore sizes and surface area
types like pyrophyllite - talc, smectites - montmorillonite, mica - (Yan et al., 2015). Generally, clays have exchangeable ions on their
illite, kaolinite, serpentine, vermiculite and sepiolite (Shichi and surface (Eren, 2010). This characteristic leads to clays playing a
Takaqi, 2000). Fig. 3 shows the structure of a typical clay. crucial role in the environment by being natural pollutant scav-
engers by way of cations and anions take up through adsorption
5.1. Clays and adsorption: physicochemical characteristics and ion exchange. Ions that are usually found on surfaces of the clay
favouring adsorption include Hþ, Kþ, Naþ, Ca2þ, Mg2þ, NHþ 2 3
4 and Cl , SO4 , PO4 , NO3 .
Cation exchange with occurs readily without affecting the clay
The chemistry which occurs on the surfaces of clay gives them mineral's structure (Huang et al., 2011).
high flexibility in adsorption processes. The surface chemistry in- Clay minerals display a strong attraction to cationic and anionic
volves the structure, ion exchange capacity, specific surface area, dyes (Crini, 2006; Hajjaji et al., 2016; Santos et al., 2016; Sarma
mechano-chemical stability, water holding capacity and reactivity et al., 2016; Yan et al., 2015; Yu et al., 2015). Nevertheless, the
of the surface which influences physical and chemical properties of adsorption capability for basic dyes is comparable greater than that
clay minerals (Eren, 2010). Usually, these clay materials are used as of acid dyes as shown in Table 2. From Table 2, it can be seen that
natural as they are without being chemically modified. Nonethe- the adsorption capacities recorded on basic dye like Methylene Blue
less, chemical modification can improve the clay‘s adsorption ca- and Malachite Green were approximately three times higher than
pacity leading to its widespread use in novel technologies (Liang that recorded for acid dyes like Congo Red and Methyl Orange. The
et al., 2013). main reason behind the differences in adsorption capacities is the
According to Elmoubarki et al. (2015), clay adsorption capacities charges on the dyes and surface characteristics of clay materials. As
are usually dependent on the net negative charge found on the clay stated earlier by Elmoubarki et al. (2015), clay minerals have a net
minerals. The negative charge contributes to the clay's ability to negative charge hence they will strongly attract positively charged
adsorb positively charged ions. Furthermore, clays' adsorption basic dyes.
Fig. 3. Structure of a typical clay material (Masindi et al., 2014).

Nonetheless, adsorption capacities can differ even though the mud mixes (Hajjaji et al., 2016); Brilliant green dye by red clay
dyes have the same charge. Yu et al. (2015) explored the effect of (Rehman et al., 2013); methylene blue and methyl orange by
molecular structure on the adsorption of basic dyes, where the bentonite (Fosso-Kankeu et al., 2014); Congo red by a mixture of
adsorption behaviour of methylene blue (MB) and crystal violet Kaolin and Bentonite clay (Vimonses et al., 2009) and Reactive red
(CV) onto natural vermiculite were studied. CV and MB have an 120 by raw clay (Errais et al., 2012). Table 3 shows various
ionic charge of þ1, so CV was used as a comparative dye, but it has a adsorption capacities obtained by different clays for the treatment
triangular molecular structure that is considerably different from of various dyes.
the molecular structure of MB which is linear. The isotherm
modelling results indicated that MB's equilibrium adsorption ca- 5.2. The relationship between clay surface area, size/mesh and
pacity at 25 C decreased from 0.076 to 0.053 mmol/g with increase adsorption capacity
in initial dye concentration from 0.3 to 0.5 mmol/L. A similar
phenomenon was observed by Almeida et al. (2009). Results of this The major reason for the high adsorption capacity of clay ma-
study demonstrate that even though dyes have the same charge, terials is their high surface areas. If a particular clay has a higher
their molecular structure can also play a vital role in the adsorption surface area, it means that it will also have a higher adsorption
processes. The decrease of MB's adsorption at high initial concen- capacity compared to clays with lower surface areas (Cadena et al.,
trations could be due to its molecular structure. The linear structure 1990). However, this notion may not always be the case for some
of MB might have had a steric effect on the adsorbate e adsorbate clays but a number of studies have proved that the surface area of a
medium more than that of CV causing an equilibrium adsorption clay is directly proportional to the adsorption capacity of the clay
density decrease (Yu et al., 2015). (Sarma et al., 2016; Santos and Boaventura, 2016; Elmoubarki et al.,
It is also important to note that, is not always the case that clays 2015; Auta and Hameed, 2013).
have a higher adsorption capacity towards basic dyes than acid Elass et al. (2011) investigated the removal of methyl violet from
dyes. This generalisation is made solely depending on the net aqueous solution using Moroccan clays. Their study showed that
negative charges of clays but there are instances where clays soils the fine mineral fraction had a surface area of 137 m2/g. As it is
exhibited a much higher adsorption capacity towards acid dyes expected of high surface area clays, the Morrocan clays had an
compared to basic dyes. Santos and Boaventura (2016) reported on adsorption capacity of 625 mg/g. The adsorption capacities of other
the removal of a basic and acid dye on sepiolite clay and their re- clay based adsorbents for dyes obtained by some other in-
sults showed the amount of dye adsorbed was higher for the acid vestigators are presented in Table 3. Comparing of these values
dye than that of the basic day. They investigated the removal of with the one obtained by Elass et al. (2011) shows that the
Basic Red 46 (BR) and Direct Blue 85 (DB) and the obtained stevensite-rich clay from Morocco has a comparable higher surface
maximum adsorption capacities at 25 C and pH 9, were 110 and area and high adsorption capacity too. The authors however made
232 mg/g, respectively. Ideally, it would be expected that the results an overall conclusion that the mechanisms of adsorption could be
show a vice versa trend because of the nature of clays. The authors explained by electrostatic attraction between the surfaces of the
explained these results in terms of other variables that can affect clay which are negatively charged and the dye molecules which are
dye adsorption like temperature and pH. They reported that, in the positively charged and not highly dependent on the high surface
case of basic red adsorption, the increase in temperature and pH area of the clay. However, as the clays have a notable higher surface
favoured the adsorption extent (from 25 to 35 C). Regarding the area, the fact that the higher surface area contributed to the high
direct blue dye, the adsorption was not influenced by temperature adsorption capacity cannot be ruled out.
(15e35 C), but a significant effect of pH was observed, with a sharp On a different study by Yan et al. (2015), the notion that if a
decrease in the uptake capacity for strong alkaline conditions. The particular clay has a higher surface area, means that it will also have
main reason why sepiolite clay showed a tendency to adsorb acidic a higher adsorption capacity does not hold true. Their study
dyes than basic dyes was explained in terms of sepiolite's point of focused on using cetyltrimethyl ammonium bromide (CTMAB)
zero net proton charge (PZNPC) (Santos and Boaventura, 2016). To modified organobentonite to remove acid dyes from aqueous so-
estimate the ranges where the clay surface charge is positive or lution. The BET results showed that the specific surface area of the
negative, usually the pH of zero charge is determined using elec- modified clay which was measured to be 4.42 m2/g is comparable
trolytes of different concentrations. When a common intersection lower than that of other adsorbents (Table 3) and even lower than
point is obtained for the curves resulting from different electrolyte that of raw bentonite (10.2 m2/g). According to Yan et al. (2015), the
concentrations, the intersection point is not dependent on the ionic reduction in surface area indicates the entrance of organic mole-
concentration and it can be designated as a zero point of charge. cules into bentonite interlayers leading to the blockage of layer
The results for sepiolite however showed three distinct intersection channels and thus reducing the surface area. A similar phenome-
points which are referred to as the PZNPC rather than one inter- non was reported by Heinz et al. (2007). Even though CTMAB-Bent
section for PZC. This observation is due to the dual nature of surface recorded a very low surface area it showed very interestingly high
charge in minerals, where two different surface charges are pre- adsorption capacities for different dyes. From the Langmuir
sent: a permanent negative charge (resulting from the structural isotherm results, the maximum adsorption capacities of CTMAB-
isomorphous substitutions) and a pH-dependent charge (primarily Bent for Acid Blue 25, Acid Blue 93 Acid Turquoise Blue A, Acid
related to the dissociation of hydroxyl groups). The high PZNPC Turquoise Blue A and Acid Golden Yellow G are 360.8 mg/g,
values allow to predict a higher propensity of sepiolite to adsorb 226.0 mg/g, 487.2 mg/g and 304.7 mg/g, respectively. For a clay
the anionic dye in pH conditions up to 10. The different pH effects with a surface area of below 5 m2/g, the reported adsorption ca-
observed for BR (cationic) and DB (anionic) have been also reported pacities are obviously very high and therefore it can be established
for other cationic (Han et al., 2014) and anionic species (Han et al., that other characteristics of the soil other than its surface area
2014; Tabak et al., 2009; Tümsek and Avci, 2013). played a vital role in the adsorption of the four dyes.
Many studies have been done using several type of clays in the The surface area of an adsorbent including its pore size are
removal of dyes like cationic, anionic and azo dyes and clays largely important in the description of adsorbent quality because
exhibited different adsorption capacities varying from as low as they directly affect their analyte retention abilities and for that
7 mg/g to as high as about 200 mg/g. Some of the dye removed by reason it becomes imperative to choose adsorbents with high
various types of clays include: Acid Orange 7 dye by clay and red surface area before conducting studies. In a bid to increase the
Table 3
Adsorption capacities of different clays.
Type of clay Dye removed Adsorption capacity (mg/g) Reference
Sepiolite clay Direct Blue 106 Santos and Boaventura, 2016

Palygorskite Methylene blue 132.72 Mu and Wang, 2016
Red mud Acid Orange 7 32.36 Hajjaji et al., 2016
Acid Activated Kaolinite Congo Red 12.36 Hai et al., 2015
Bis-imidazolium modified bentonite Telon dyes 108 Makhoukhi et al., 2015
Montmorillonite Methylene blue 74 Zhou et al., 2014
Acid modified clay beads Methylene blue 223.19 Auta and Hameed, 2012
Safi decanted clays Malachite green 88.70 Elmoubarki et al., 2015
Modified natural bentonite Di azo dye 7.14 Toor and Jin, 2012
Modified montmorillonite Methyl Orange 24 Chen et al., 2011
surface areas of clays, researchers tend to chemically modify their To examine the effect of the particle size on basic green 4
adsorbents to increase their surface areas (Hai et al., 2015). Auta adsorption by granular organoeinorgano pillared clays (GOICs) in
and Hameed (2012) reported on the effects of modifying surface column reactor, Cheknane et al. (2016), varied particle size ranges
areas of Raw Ball Clay (RBC) by H2SO4. The RBC and Modified Ball of GOICs from 300e400 mm to100e1200 mm. Results show that a
Clay (MBC) BET surface area, pore width and total pore volume decrease in particle size improves the performance of the adsorp-
were found to be 10 m2/g, 19.62 nm, 0.0519 cm3/g and 92 m2/g, tion column from 221 to 428 mg/g. According to their previous
9.54 nm, 0.2183 cm3/g, respectively. The surface area and pore work, the adsorption capacities of dye depended strongly on
volume of MBC, were expectedly higher than those of RBC. A granulation and particle size of the granule pillared clay (Cheknane
possible explanation to this is the leaching and loss of some ions et al., 2010; 2012). On the other hand, the comparison between the
during the acid treatment and calcinations processes. Watanabe adsorption capacities of BG4 (mg/g) determined from respective
et al. (2011) reported similar results after ultrasonically treating batch and continuous reactors, showed the same decrease of
SP (0.0)-cal which led to an increase in both surface area and sphere adsorption capacity with the size of particles.
pore volume. Auta and Hameed (2012) reported an 82% increase in The authors explained the observed behavior using the
surface area which then led to a 188.60% in adsorption capacity following mechanism:
with MBC. Results of all these studies show that indeed some Firstly, the limitation of active mass of pillared clay to the
chemical treatments to raw clay can increase surface areas and external surface of granular organoeinorgano pillared clay was
ultimately leading to increased adsorption capacities of modified influenced by the silicone used for granulating the powder orga-
clays. noeinorgano pillared clay (Cheknane et al., 2010; 2012). Secondly,
The vital part played by surface area on adsorption processes has the interparticle porosity of the adsorption beds are reduced for the
been shown by various studies on the adsorption of dyes by small particle size ranges. The column packed with larger particle
different clays including kaolinite, montmorillonite and smectites. sized GOICs had lower adsorption efficiencies lower than the one
Table 3 shows numerous clays used for dye adsorption, their sur- packed with smaller diameter GOICs.
face areas and their adsorption capacities. From Table 4 we can Jaafar (2006) also stipulates that small particle sizes of the clay
derive a clear relationship between surface areas and adsorption adsorbent enhance the adsorption capacity of the adsorbent. A
capacities. study using diatomite for the removal of SB showed that the
The size of clay particles plays an indispensable role in all decreasing of particle size of diatomite from 300 to 60 mm increased
interphase interactions in clays including ion-exchange and the adsorption rate of SB. This is because increasing the external
adsorption processes (Mandzhieva et al., 2014). Therefore, the surface area of the diatomite particle exposes more active sites to
evaluation of the effect of the particle size on the adsorption SB molecules. There is a slight effect of particle size of diatomite on
properties of soils is a vital mission in adsorption processes. Small €
adsorption of textile dyes (Ozcan €
and Ozcan, 2004).
particle sizes causes equilibrium to be achieved more easily and
near maximum adsorption capability can be attained because they
reduce internal diffusion and mass transfer limitation to the 5.3. The role of clay morphology in the adsorption process
penetration of the adsorbate inside the adsorbent.
It is well known that the adsorption capacity of clays depend on
Table 4
Surface area of different clays used in the adsorption of dye.
Clay type Dye adsorbed Surface area (m2/g) Adsorption capacity (mg/g) Reference
Red mud Acid Orange 7 74 32.36 Hajjaji et al., 2016

Sepiolite clay Direct Blue 108 332 Santos and Boaventura, 2016
Safi raw clays Malachite green 34.07 156.43 Elmoubarki et al., 2015
Halloysite Direct orange 34 20 7.75 Chaari et al., 2015
Montmorillonite K10 Crystal violet 173 370.37 Sarma et al., 2016
Acid-activated kaolinite Azo dyes 358.6 12.36 Hai et al., 2015
Raw clay beads Methylene blue 58.02 19.32 Auta and Hameed 2013
Modified clay beads Methylene blue 223.19 101 Auta and Hameed 2013
Raw bentonite Acid dyes 10.2 e Yan et al., 2015
CTMAB-Bentonite Acid Turquoise Blue A 4.42 487.2 Yan et al., 2015
Raw bentonite Diazo dye 25.7 e Toor and Jin (2012)
Acid bentonite Diazo dye 84.6 69.44 Toor and Jin (2012)
Swelling clays Methylene blue 65 e Li et al., 2011
their chemical composition and structure (Mu and Wang, 2016). soil sample of smectite rich soils from Limpopo, South Africa. At
The structure of clay includes crystalline unit growth mechanics, lower magnifications, the smectite rich clay soils showed irregular
crystallites interlocking and interpenetration, crystal habits porous structure that is a good characteristic of a good adsorbent
including helical growth, twinning, and tapotaxis (Bohor and material (Mudzielwana et al., 2016).
Randall, 1970). The Scanning Electron Microscope (SEM) is Mu and Wang, 2016 postulates that the effect of different clay
uniquely suited for studying the structure of clays because it origins (which lead to different morphological structures) on
magnifies the three dimensional view of clay surfaces with great adsorption properties of clays is rarely studied. Hence the re-
depth of focus. It brings out the configuration, texture and fabric of searchers selected three representative samples of palygorskite
clay samples. Fig. 4(a)e(F) shows how SEM can solve the problem of (PAL) from Gansu, Anhui and Jiangsu provinces of China to study
determining the morphology of clay powders. Figures (a) and (b) the effect of different origins on MB adsorption (Zhang et al., 2016).
show Suzhou kaolin with a typical sheet structure and a Longyan The results revealed that the Mg-poor sample of Jiangsu charac-
kaolin containing tubular Halloysite particles respectively (Zhang terised by short rods and a dioctahedral structure exhibited the
et al., 2016). Figures (c) and (d) show natural and Al/Fe oxide- highest adsorption capacity for MB, whereas the Mg-rich sample
modified diatomaceous earth (DE) respectively and differences from Anhui characterised by long rods and an intermediate struc-
pores sizes and DE appearance before and after modification can be ture of trioctahedral and dioctahedral phyllosilicates exhibited
seen. The modified DE pores appear to be packed by the deposition lesser adsorption capacity for MB. From this study we can clearly
of Al/Fe oxide as compared to the clear, net-like pores in the natural see how the structures of the selected PAL samples affected their
DE. The proximate closure of the pores of the modified DE is evi- adsorption capacity, showing that it is not only the chemical
dence that natural DE was modified (Izuagie et al., 2016). Figure (e) composition that affects adsorption capacity but morphology. Clays
shows a highly magnified view of a bentonite clay sample and the rich in Mg recorded a low adsorption capacity but clays with lower
platy-like features characteristic of clay minerals are seen. Pro- Mg concentrations had a higher adsorptive removal towards MB.
truding rodlike structures are clearly visible in the montmorillonite Furthermore, it is worth noting that although the maximum
rich bentonite clay (Masindi et al., 2015). Figure (f) shows a natural adsorption of natural palygorskite toward dyes far exceeded the
Fig. 4. Clay particles SEM images: (a) - Suzhou kaolin (Zhang et al., 2016); (b) - Longyan kaolin (Zhang et al., 2016); (c) - raw diatomaceous earth (Izuagie et al., 2016); (d) - Al/Fe
oxide-modified diatomaceous earth (Izuagie et al., 2016); (e) - bentonite clay (Masindi et al., 2015); (g) - Mukondeni smectite rich clay (Mudzielwana et al., 2016).
cation exchange capacity of palygorskite, it is difficult to completely adsorption is favoured at pH 7. Electrostatic forces operate because
release the adsorption capacity of palygorskite toward dyes due to the RC surface will be negatively charged at pH > pHZPC, and BG
the existence of the bulk crystal bundles or aggregates originated molecules are positively charged. At high pH there is charge
from the interparticle Van der Waals’ and hydrogen bonding neutralization on RC surfaces leading to enhanced adsorption of BG
interactions. (Ghaedi et al., 2011). At pH > 7 there was no significant adsorption.
Another common structural feature characteristic of clay soils is Nandi et al. (2009) and Shirsath et al. (2013) also studied the
their fibrous and porous nature. It is interesting to note the differ- adsorption of BG by kaolin clay at pH 7 and they described the same
ence in adsorption capacities with respect to different dyes on results. However, high BG adsorption capacity (108.4 mg/g) at
fibrous clays. Sarma et al., 2016 used raw and acid-treated mont- pH 4 exposed that BG dye adsorption was not the only due to
morillonite to adsorb CV. With a more similar structure to mont- electrostatic attraction.
morillonite is bentonite which was studied by Chinoune et al., 2016 Besides the point of zero charge there is also the pH at which
for the removal of Procion blue HP (PB) and Remazol brilliant blue R there is a zero net adsorption of Hþ/OH, designated as points of
(RB), both anionic reactive dyes. The SEM images of montmoril- zero net proton charge (PZNPC) (Avena and De Pauli, 1998). A study
lonite showed that the clay had a fluffy appearance of different using sepiolite clay on the adsorption of cationic and anionic azo
shapes and sizes with some bigger particles appearing broken dyes by Santos and Boaventura (2016) determined the PZNPC at
down into small and medium sized particles with no particular three different ionic strengths by the pH-drift method (Lazarevic
shape. On the other hand, bentonite appeared either as thin, ul- et al., 2007). The results showed three distinct intersection points
trafine, leaf-like crystals forming dense aggregates or in a more for different ionic concentrations: 10.4; 10.0 and 9.8, respectively
open honeycomb texture. The Langmuir monolayer adsorption for NaCl 0.001 M, 0.01 M and 0.1 M. The authors concluded that this
capacities of PB and RB on bentonite in aqueous solution were observation was due to the dual nature of surface charge in min-
estimated to be 40.22 and 66.90 mg/g, respectively while the erals. Where two different surface charges are present: a perma-
Langmuir monolayer adsorption capacity of raw montmorillonite nent negative charge (resulting from the structural isomorphous
was found to be 370.37 mg/g. It is very interesting to note how substitutions) and a pH-dependent charge (primarily related to the
much the adsorption capacities of more or less similar fibrous clays dissociation of hydroxyl groups). The authors further on reported
are so different with montmorillonite having an adsorption ca- that the intersection points obtained, corresponding to zero net
pacity almost 7 times greater than that of bentonite. The fibrous adsorption of Hþ/OH should be named as PZNPC, instead of PZC,
surface topography of the clays are expected to increase the degree since they represent the conditions where the pH-dependent
of unsaturation of the surface with dangled bonds and free va- charge is null (Avena and De Pauli, 1998) and not the conditions
lences, thus amassing the total surface area of the clay. The lower under which the total charge is null. The high PZNPC values allowed
adsorption capacity of the bentonite clay compared to that of for the prediction of a higher tendency of sepiolite to adsorb the
montmorillonite could be due to the dense aggregates in the clays anionic dye in pH conditions up to 10. The different pH effects
that did not create enough pores to allow for adsorption compared observed by Santos and Boaventura (2016) for cationic and anionic
to the broken down particles that appeared on the species (Han et al., 2014; Tumsek et al., 2013; Tabak et al., 2009) and
montmorillonite. are explained by the electrostatic attraction. With the increase in
pH, the dependent charge tends to be more negative and hence
5.4. The role of electrical charges in the adsorption process: point of amenable to adsorb cationic species and less to adsorb anionic
zero charge (pHpzc), point of zero net proton charge (PZNPC), zeta ones. The PZNPC of sepiolite occurs at pH 10 and then a significant
potential and charge density increase in BR dye adsorption was observed from an equilibrium pH
8.5e8.7 to 9.2e9.5; in turn, a sharp decrease in the DB uptake was
Point of zero charge (pHpzc) is among the significant factors observed from final pH 9.3 to 9.8.
which can help indicate the type of surface active centres on the Greenwood and Kendall (1999) defines zeta potential as “the
adsorbent and the adsorption ability of the surface (Yagub et al., electric potential in the interfacial double layer (DL) at the location
2014). The point of zero charge (pzc) is the pH at which the net of the slipping plane versus a point in the bulk fluid away from the
surface charge is zero and is typically used to define the electro- interface”. Zeta potential is an important parameter because its
kinetic characteristics of a surface. The value of pH is used to value helps to determine colloidal dispersion stability. It indicates
describe pzc only for systems in which Hþ/OH are the potential the degree of repulsion between particles with similar charges in a
determining ions. Studies on point of zero charge (pHpzc) of a dispersion. So, colloids with high negative or positive zeta potential
number of clay adsorbents have been conducted in order to un- values are said to be electrically stabilized whereas those with low
derstand the adsorption mechanism in relation to pzc (Ghaedi zeta potential values have a tendency to flocculate (Hanaor et al.,
et al., 2011; Shirsath et al., 2013; Tümsek and Avci, 2013). Cationic 2012). The zeta potential of clays also plays a very important role
dye adsorption is high at pH > pHpzc because of the presence of in dye adsorption and this can be seen when the effect of pH on dye
functional groups like OH while, anionic dye adsorption is high at adsorption is investigated (Fayazi et al., 2015).
pH < pHpzc when the surface is positively charged. Zeta potentials of modified sepiolite (MS) and natural sepiolite
Chemical characterization of red clay by Rehman et al. (2013) (NS) at various pHs were determined and it was established that NS
showed that it had a point of zero charge at pH 6.8. It is well and MS isoelectric points were around 6.8 and 7.9, respectively.
known that dye adsorption is dependent on pH of the solution Comparable values, between pH 3.2 and 7.4 have also been reported
because the surface charge of the adsorbent and the degree of by other researchers (Lazarevi c et al., 2007; Sabah et al., 2007) for
ionization of the adsorbate and degree of dissociation of functional the isoelectric point of natural Sepiolite, and 7.7 to 8.5 for that of
groups differ with various pHs (Nandi et al., 2009; Ghaedi et al., iron-coated Sep (Liu et al., 2014; Lazarevi c et al., 2010). The sepiolite
2011). The adsorption of Brilliant Green dye by red clay was used in the various studies had different mineralogical composition
higher at circumneutral pH. However, the highest adsorption effi- and clay mineral preparation methods for electro kinetic mea-
ciency (97%) and capacity (121 mg/g) was recorded at pH 7. The surements differ hence we see a wide range of values for Sepiolite.
information on pHpzc of red clay best explains the impact that (Fayazi et al., 2015). The surface charges of adsorbent materials are
solution pH has on the adsorption of BG. As stated earlier, the pzc of usually influenced by pH because of the effect it has on the degree
red clay was established to be 6.8 and the results show BG of ionization of the adsorbate. When pH is less than 7.9, the MS
nanocomposite surface is positively charged because of surface density in the adsorption of dyes by numerous layered silicates was
functional groups protonation and when pH is greater than 7.9 the also examined by other authors (Miyamoto et al., 2000; Bujda k
surface is negatively charged due to the dehydroxylation of the MS et al., 2010).
surface groups. In acidic conditions, the Hþ compete with positively Bentonite possesses an excess negative charge on its lattice and
charged dye molecules for available adsorption sites, hence the is characterized by a three-layer structure having two silicate layers
decrease in removal efficiency. As pH increases, there is also a rise covering an aluminate layer (Adeyemo et al., 2015). This comes as a
in removal efficiency due electrostatic attraction between the result of the partial replacement of tetravalent Si with trivalent Al
negatively charged surface of the MS nanocomposites and cationic that leads to the replacement of trivalent Al with divalent Ca. Since
Safranin molecules. Given the above, we can then say pH has a very opposite charges attract, the negatively charged surface lattice of
important role to play in adsorption processes. the bentonite clay may have an affinity for cationic dye. Therefore,
it can be expected that bentonite clay exhibits a greater capacity to
5.5. Clay charge density and swelling properties: effect on the take up cationic dyes. On the other hand, kaolinite has a hetero-
adsorption process geneous surface charge. The basal surface of kaolinites is believed
to carry a constant structural charge, which is attributed to the
The reactivity of clay minerals is commonly due to a charge they isomorphous substitution of Si4þ by Al3þ. The presence of a charge
carry. The presence of this charge is the basis of their exchange on the edges is a result of protonation/deprotonation of surface
capacity and consequently swelling. The relationship between clay hydroxyl groups and therefore depends on the solution pH (Zhou
charge and swelling lies in the fact that as clay charge density in- and Gunter, 1992). Kaolinite is reported to be the least reactive
creases, the attraction energies on the clay predominate and clay (Suraj et al., 1998). However, it's high dependency on pH in-
therefore the clay does not swell, whereas the vice versa is true creases or constrains the adsorption of dyes according to the pH of
with decrease in charge density (Miyamoto et al., 2000). There are the solution (Mitchell, 1993). Adsorption may also take place on the
three main groups of clay minerals which are kaolinite, illite and flat exposed planes of the silica and the alumina sheets (Spark et al.,
smectites (Liu and Zhang, 2007). Nevertheless, the most commonly 1995).
used clays in dye adsorption processes are smectites and kaolinites. Extensive studies have been done utilization swelling clays to
Structurally, illite clays are similar to muscovite, but are typically eliminate cationic dyes from aqueous media. Many of these studies
deficient in alkalis, with less Al substitution for Si and because of sought to evaluate the applicability and feasibility of using basic
possible charge imbalance, Ca and Mg can also sometimes substi- dyes adsorption for cation exchange capacity (CEC) and specific
tute for K. The K, Ca, or Mg interlayer cations prevent the entrance surface area (SSA) determination. Li et al. (2011) did a study to
of H2O into the structure hence making this type of clay to be non- explain the mechanism of MB adsorption on low-charge mont-
expanding clays (Moore and Reynolds, 1997). Just like illite clays, morillonite as a swelling clay. The stoichiometric desorption of
kaolinite also does not absorb water and does not expand when it exchangeable cations from the clays associated with MB adsorption
comes in contact with water. However, smectites or montmoril- together with the close match between the CEC of the clays and
lonites show a different behavior when contacted with water. adsorption capacity established cation exchange as the central
Smectites are weakly linked by cations like Naþ, Ca2þ which result mechanism for MB elimination. XRD and TGeDTG analyses indi-
in the high swelling/shrinking potential of this type of clay. The cated interlayer adsorption, hence, intercalation of MB molecules.
interlayer in smectites is not only hydrated, but it is also expansible FTIR analyses indicated that hydrogen bonding might not be a
and because of this, they are often referred to as “swelling clays” major interaction in the adsorption of MB. The results confirmed
(Grim, 1962). that the charge density, rather than the SSA was the limiting factor
The charge densities of clay minerals are important not only for for MB adsorption. The authors concluded that for the treatment of
structural studies but in the application of clays in the adsorption wastewater having cationic dyes, swelling clays with a high CEC
processes. Whether or not a clay becomes totally dissociated or not, values would be efficient adsorbents.
depends on the available interlayer cations and the layer charge Another study by Lv et al. (2011) also confirmed that with low
(Liu and Zhang, 2007). For example, vermiculites have a high charge swelling clays, CEC is the single most important mechanism
charge and for that reason, they will not completely dissociate. for dye removal from water. Lv and coworkers investigated the
Essentially, without a charge, kaolinites are never separated to start adsorption of acridine orange (AO), a cationic dye, on low charge
with, because they do not have interlayer cations that hydrate. montmorillonite to better understand the mechanism behind AO
However, they can undergo interparticle swelling as opposed to removal using swelling clays. The proportional desorption of
intraparticle swelling. Unlike the other two types of clays, smectites exchangeable cations from the clays followed by AO adsorption
will undergo complete dissociation by osmotic swelling when established cation exchange as the most leading mechanism for AO
saturated with cations possessing a hydration energy greater than removal. Moreover, FTIR analyses confirmed the presence of
or equal to Naþ (Moore and Reynolds, 1997). cationic dye AOHþ on the surface and in the interlayer of the
Numerous clay adsorption properties can be associated with the swelling clays. XRD and TG-DTG results also showed interlayer
layer charge density (Mermut, 1994). Bujda k and Komadel (1997) adsorption, thus, intercalation of AO molecules with different
studied the interaction between modified clays with different conformations at low and higher AO adsorption levels. The authors
layer charges and the cationic dye (methylene blue) in aqueous then concluded that the amount of AO adsorbed far exceeded the
suspension. The authors concluded that the strong aggregation and CEC of the low charge swelling clays and that was seen as an
redistribution of the molecules in the clays with higher layer charge advantage of using swelling clays to remove cationic dyes from
was due to the proximity of the negative sites in the clay surfaces water. They further reported that the uptake of AO was attributed
and the different coverage of the clay surfaces. This suggests that to cation exchange when the amount of AO adsorbed was less than
MB is initially adsorbed only on a minor fraction of the clay, fol- the CEC.
lowed by a redistribution with passing time. The higher layer
charges on the particles of the studied montmorillonites resulted in 6. Disadvantages of clays leading to modification to enhance
a larger aggregation of the dye. The higher charge holds together their adsorption capacities
the layers of the clay more tightly, preventing the movement of the
dye molecules to the interlamellar region. The effect of layer charge Although clays have shown to be good adsorbents for dyes, they
have several limitations which have led to several forms of modi- anionecationic modified MMT were compared. Their findings
fications to enhance their adsorption capacities. Clay modification showed that CTMAB/10SSTAeMMT has a higher adsorption ca-
is the introduction of an alien material to clay matrices with the aim pacity than CTMABeMMT and 10SSTAeMMT because of the for-
of improving its adsorption capacity for a given pollutant. There are mation of a highly effective partition medium by anionecationic
different ways of clay modification which include pillaring, mech- surfactant micelle.
anochemical modification, ion exchange, organo-modification and Li et al. (2010) reported on the adsorption of a polymer loaded
sonochemical treatment. A variety of studies have reported on the bentonite (EPIDMA) and raw bentonite for Acid Scarlet (AS GR) and
modifications of clay including chemical treatments such as Acid Dark Blue 2G (ADB 2G) dyes from aqueous solution. After the
Mg(OH)2 coating of bentonite (Chinoune et al., 2016), clay ion- adsorption experiments, the adsorption capacities of raw
exchange using bis-imidazolium salts (Makhoukhi et al., 2015), bentonite, cationic surfactant cetyltrimethylammonium bromide
quaternary ammonium cationic surfactants addition onto (CTMAB) modified bentonite (CTMAB/bentonite) and cationic pol-
bentonite external surfaces (Yan et al., 2015), modifying bentonite ymerpolydiallydimethylammonium (PDMDAAC) modified
by a cationic surfactant (Hexadecyltrimenthylammonium chloride) bentonite (PDMDAAC/bentonite) were compared. For AS GR, the
(Anirudhan and Ramachandran, 2015) and treating the clays with observed adsorption capacities were 4.12, 30.28 and 42.72 mg/g for
€
acid (Espantaleon et al., 2003; Ozcan €
and Ozcan, 2004). raw bentonite, CTMAB/bentonite and PDMDAAC/bentonite
respectively whereas for ADB 2G the adsorption capacities were
6.1. Cationic and anionic surfactant modification 3.67, 24.85 and 33.34, respectively for the three different adsor-
bents. All the above mentioned adsorption capacities were lower
Generally, clays are applied in the elimination of basic dyes than that of EPI-DMA/bentonite for AS GR and ADB 2G which
because they have a natural negative charge but chemical modifi- recorded maximum adsorption capacities of 45.54 and 35.93 mg/g
cations to the surfaces of the clay can change the surface charge of respectively. This comparison study confirmed that EPI- DMA/
clays from negative to positive (Errais et al., 2012). These alterations bentonite is the best adsorbent for AS GR and ADB 2G among the
enhance the sorption of anionic dyes. Baskaralingam et al. (2006) selected adsorbents.
stipulates that bentonite adsorbs acidic pollutants weakly
because of repellant forces between the negatively charged sur- 6.2. Magnetic modification
faces and the anions. A number of authors have reported on the
modification of bentonite with cationic surfactants for the removal Due to their high dispersion, waste clay particles can prove
of acidic dyes. They showed that the main mechanism of the acidic difficult to remove from solution after adsorption. To overcome this
dye adsorption can be can be explained in terms of the anionic limitation, magnetizing clays can be an option using a simple
exchange between the excessive anions and the cations from the procedure referred to as magnetic separation which removes the
surfactant (Ceyhan and Baybas, 2001; Jovic-Jovicic et al., 2008; clay particles from water (Xu et al., 2012; Gao et al., 2015; Wang
Ozcan et al., 2004). Ma et al. (2013) compared the performances of et al., 2014). Magnetic materials such as ferrite (MFe2O4, where
raw bentonite and surfactant-modified bentonite. Their findings M ¼ Co, Mn, Cu, Zn, etc), Fe3O4, Fe2O3 and so on have been used as
showed that CTAB-modified bentonite has a comparable high adsorbents for the removal of toxic pollutants because they can be
adsorption capacity towards acid dyes, whereas the raw bentonite easily separated from the reaction medium by using an external
showed a lower adsorption capacity. The adsorbed amount of Cong magnetic field within a short time. Unfortunately, their low
Red was found to be 210.10 mg/g for CTABMBn and 37.10 mg/g for adsorption capacity and narrow pH range restrict their large-scale
raw bentonite. practical application (Li et al., 2016). Therefore, to improve
Clays are also known to have low organic carbon content and adsorption performances, great efforts have been made to func-
because of their hydrophilic surfaces, they are usually less effective tionalize magnetic materials (Fan et al., 2012; Ge et al., 2012; Peng
in adsorbing nonionic organic contaminants in water (Boyd et al., et al., 2012).
1998). However, simple ion-exchange reactions with surfactants The introduction of magnetic particles in the nano scale in-
causes the clay to be altered from being organophilic to being dustries is attracting the attention of numerous researchers
organophobic and hence enhancing nonionic organic contaminants (Hashem, 2013). Nano particles are exceptionally fine sized and this
adsorption. Studies have shown that cationic surfactants interca- property makes them favorable adsorbents. When the size of a
lation does not only change the hydrophilic surface characteristics particle is reduced, the surface of the particles becomes more
of the clay, but it also significantly increases the clay interlayer basal accessible to atoms resulting in an increased surface area ultimately
spacing. Many studies have investigated the modification of changing the surface morphologies and surface energies of the
montmorillonite (MMT) by alkyl quaternary ammonium cationic nanoparticles. The aforementioned factors modify the elementary
surfactants like dodecyltrimethylammonium, benzyldimethylter- properties and the chemical reactivity of nanomaterials
adecylammonium and cetyltrimethylammonium. Few studies have (Hashemian, 2010). Hashem (2013) studied the effect of covering
reported on anionic surfactant modification mainly because anionic bentonite nanocomposite with magnetite on the removal of
surfactants have a negative charge thus making it difficult to enter methylene blue. According to the author, the introduction of Fe3O4
into the interlayer spacing of the clays (Zhang et al., 2011). magnetic nanoparticles into the surface of bentonite generates a
Chen et al. (2011a) disclosed that surfactants that are anionic porous surface with high surface area which is suitable for the
enter the interlayer space as pairs of ions with protons (H3Oþ ions) adsorption of cationic dyes such as methylene blue. The findings of
or as counter ions (Naþ and Ca2þ). Zhu and Chen (2000) studied the the batch adsorption experiments revealed that, increasing the
adsorption characteristics of MMT modified by an anionecationic initial pH of MB solutions as well as the contact time also increased
surfactant and they established that a combination of cationic and the adsorption capacity. However, a different trend was observed
anionic surfactants form mixed micelles, producing organic com- with adsorbent dosage as the adsorption capacity decreased with
pounds synergies solubilization. On another study Chen et al. increasing mass of the adsorbent. The maximum adsorption ca-
(2011), modified MMT by anionecationic, anionic and cationic pacity was 1600 mg/g.
surfactants by adding anionic surfactants cetyl trimethyl ammo- Another reason why magnetic materials are preferred in the
nium bromide (CTMAB) and anionic surfactants sodium stearate adsorption process is because they have been proved to have more
(SSTA) to MMT. The mechanisms of adsorption of methyl orange on advanced mesoporosity and microporosity compared to natural
clays (Giakisikli and Anthemidis, 2013). Ambasht and Sillanpa the untreated montmorillonite was 370.37 mg/g while that of
(2010) also stipulated that magnetic composites have high sur- 0.25 M and 0.50 M acid treated montmorillonite was 384.62 and
face areas compared to natural clay and this makes them to produce 400.0 mg/g respectively at 303 K. Treatment with acid removes
fast adsorption kinetics i.e. comparatively little contact time is impurities in the clay at the same time substituting exchangeable
needed for the adsorption process to reach equilibrium. Determi- cations with Hþ. Acid treatment can also lead to cation leaching
nation of sorption properties of magnetic nanocomposite sorbents some from the tetrahedral and octahedral sites opening up platelet
showed that the adsorption efficiency of nanocomposites is edges. This may result in an increase in the surface area and the
considerably greater than the separate phases of the composite. pore dimensions (Diaz and Santos, 2010; Auta and Hameed, 2013)
Moreover, studies have shown that all the residual composite subsequently leading to an enhanced adsorption capacity.
magnetic sorbents can be successfully removed from aqueous so- Anirudhan and Ramachandran (2015) used Hexadecyl-
lution by magnetic separation (Makarchuk et al., 2016). A study to trimenthylammonium chloride as a cationic surfactant to modify
assess the adsorption of MB by nanocomposite sorbents, saponite bentonite clay. Characterization of the clay before and after modi-
and magnetic liquid revealed that among the three tested adsor- fication showed significant changes in the chemical composition
bents, the magnetic composite sorbents (MCS) were the most and surface properties of adsorbent. The changes included a
effective adsorbents. With respect to all dyes, the adsorption ca- decrease in Fe2O3 and Al2O3 content, implying that the surfactant
pacity of MCS increased as the magnetite content increased from 2 adsorption was through the exchange of inorganic cations, the BET
to 7 wt%. However, modifying saponite by magnetite by 10 wt% led surface area of the organoclay was reduced from 36.5 to 27.9 m2/g.
to the decrease of MCS 10 sorption properties. These results Unlike surface area, the PZC and CEC of the bentonite increased
corroborated with the characteristic of nanocomposites porous after modification from 4.5e7.8 and 0.52e0.71(meq/g) respectively.
structure. The prepared organo bentonite clay was later evaluated for its
adsorption behaviour for the basic dye removal CV, MB and Rho-
6.3. Mechanochemical modification of palygorskite diamine B (RB). The findings showed that the modified clay
demonstrated better adsorption capacity for the removal of all the
Mu and Wang (2016) compiled a comprehensive review on the selected dyes. pH was found to play an imperative role in the
modification of palygorskite with different physical or chemical adsorption process, moreover the removal of dyes was found to be
methods and palygorskite-based composite used as adsorbents for dependent on initial dye concentration. The adsorption capacities
the adsorption of dyes from aqueous solution. Traditionally for the dyes were established to be 399.74 mol/g for MB,
grinding and extrusion methods were widely used on palygorskite 365.11 mol/g for CV and 324.36 mol/g for RB. The adsorption effi-
to modify it to increase its adsorption capacity before use because ciency of the organobentonite was higher than the unmodified
of their simple operation process, low cost, and easy industrial bentonite as expected. The results also showed that organoclay was
application. However, the enhancement in the adsorption capacity 1.6, 1.7 and 1.75 times more effective than natural bentonite for MB,
of palygorsite toward dyes is limited by these traditional methods. CV and RB adsorption respectively because after modification, the
Therefore, other treatments also have been adopted to activate porosity of the clay increased. The authors attributed the mecha-
palygorsite for the adsorption of dyes, such as acid- or alkali- nism of the adsorption process to the adsorption/partition model
activation, thermal treatment, hydrothermal or solvothermal (Zhu and Chen, 2000). This study basically showed us that surfac-
treatment. To have a full understanding on the various mechanisms tant modification of clay can enhance their adsorption capacities.
involved in the dye removals and specifications in the modification In a study done by Chinoune et al. (2016), an effective brucite-
processes, readers are advised to consult the review article by Mu coated bentonite was synthesised and assessed for anionic dye
and Wang (2016). However Table 5 summarises some of the removal from water. The obtained results from this study showed
methods of palygorsite modifications that have been used and how that, coating bentonite clay with Mg(OH)2 considerably improved
these various modifications impacted the adsorption capability of the removal of reactive dyes. At a pH of 5, which was greater than
the palygorsite. Because palygorsite is an example of a clay, the the acidity constant, reactive dyes mainly existed as anions and
same modifications can be applied to some clays. were probable going to be repelled by the montmorillonite surfaces
because they are negatively charged. The BeMg(OH)2 contains
6.4. Structural and chemical changes after clay modification: effect more polar acid SieOe groups and basic Mg(OH) sites that have a
on adsorption tendency to react with organic compounds because they are polar
in addition to several other functional groups. The ability of
To follow the structural and chemical changes made after modified bentonite to take up dyes showed that van der Waals and
various modifications, the adsorbents are usually characterised pp interactions take place amongst OH ions available on the clay.
before and after modifications. Most modifications are aimed at pH had a major influence on the adsorption of ions on the com-
increasing the surface area of the clay soils or adding the functional posite surface, mainly on the extent of adsorbate ionization. The
groups that are responsible for dye uptake and all this will be maximum dye removal was achieved at pH 2. This could be as a
basically aimed at enhancing the adsorbent material's adsorption result of electrostatic interaction between cationic dye molecules
capacity. Sarma et al., 2016 reported on the treatment of mont- and the negatively charged BeMg(OH)2 surfaces. Nonetheless, the
morillonite (Mt) with 0.25 and 0.50 M sulfuric acid and how this adsorption still took place in basic conditions, showing the occur-
treatment affected the adsorption capacity of the clay. Character- rence of intermolecular interaction.
ization by BET showed that pore volume and surface area were On the work done on bentonite, Ozcan et al. (2004) proposed
greater than before acid treatment. The pore volume showed an that natural bentonite surfaces makes it less effective for taking up
increase from 0.1 cm3/g to 0.8 cm3/g after treatment and the surface hydrophobic organic compounds owing to the electrical charges
area increased from 173.0 to 221.38 m2/g and further to 228.95 m2/ and hydrophilic surface. The authors recommended that raw
g on treatment with 0.25 M acid and 0.50 M acid respectively bentonite can be treated by organic cations to yield a Dodecyl-
recording a 28 and 32.3% increase for the different acid molar trimethylammonium bromide-modified bentonite (DTMA-
concentrations respectively. This increase in surface area may have bentonite) thus considerably improving its ability of adsorbing
led to the increase in adsorption capacities as reported by the au- hydrophobic pollutants from aqueous solution. A comparison of the
thors. The Langmuir data disclosed that the adsorption capacity of findings with Na-bentonite revealed that Na-bentonite and DTMA-
Table 5
Various palygorsite modifications for the adsorption of dyes.
Modification method Dye removed Effect of modification on adsorption Reason for change in adsorption capacity References
capacity
Extrusion Methylene blue Adsorption capacity was observed to Partial disaggregation of crystal bundles of Zhang et al., 2015a,b
increase to 158 mg/g, 78 mg/g and 98 mg/g. PAL.
Grinding Methylene blue Percentage dye removal increased by 25% Specific surface area increased from 153 to Liu et al., 2012
229 m2/g.
High-pressure Methylene blue Percentage dye removal increased by 21% Disaggregation of PAL crystal bundles. Zhang et al., 2015a
homogenization
Ion beam Methylene blue Better adsorption capacity in comparison to A larger interspace, better separation, Cai et al., 2010
bombardment the raw PAL. higher pore-size (with micro/nanoscale) Zhang et al., 2013
and porosity, and doubling of the BET
surface area of the PAL nanonetworks.
Acid activation Quinalizarin Percentage dye removal increased by 50% Increase the surface area. Frini-Srasra and
Srasra, 2009
Alkali-activation Methylene blue Exhibited a far better adsorption capacity No clear explanation because the rod-like Wang et al., 2015
compared to that of raw PAL inferred from morphology almost disappeared and BET
the colour of 200 mg/L MB. specific surface area of PAL was highly
reduced after the treatment with 5.0 M of
NaOH solution.
Thermal activation Methylene blue Adsorption capacity increased with Cation exchange was a main mechanism in Chen et al., 2011b
calcination temperature and reached the the adsorption process.
maximum at 700 C (about 78.1 mg/g), and
then decreased with further increasing
temperature.
Hydrothermal or Methylene blue Adsorption properties of PAL for MB were Disaggregation of crystal bundles, PAL Zhang et al., 2015b
solvothermal evidently improved from 119 mg/g to nanorods became more uniform and an
treatment 171 mg/g after modification increase in pore size of adsorbent.
Surfactant Orange II Adsorption capacities were observed to be Electrostatic attraction as well as van der Sarkar et al., 2011
modification 92 and 88 mg/g. Waals interaction.
Silane coupling agent Reactive Red 3BS, 34.24 mg/g, 38.60 mg/g, and 60.13 mg/g Activity of the amino groups. Xue et al., 2010
modification Reactive Blue KE-R and respectively. Xue et al., 2011
Reactive Percentage increase from 1.16 to 99.32%;
Black GR 3.30e99.67% and 2.88e96.42% respectively.
Polymer modification Reactive yellow 3RS Langmuir model was 71.38 mg/g which was Cationicity Peng et al., 2013
much higher than that of the raw PAL
(6.3 mg/g).
bentonite synthesized from natural materials are able to remove like exchangeable cations, the space between the clay inter layers,
acid blue 193 from aqueous solution. Nevertheless, DTMA and whether or not there are water molecules between those
bentonite displayed a greater removal capacity than raw bentonite. layers. On the other hand, polymers are considered multipurpose
DTMA-bentonite had an adsorption capacity of 740.5 mg/g which is materials because they can be easily manipulated, they are simple
approximately 11 times greater than that of Na-bentonite (67.1 mg/ to produce and are highly flexible. However, there are cases where
€
g). Acid blue 193 was also adsorbed effectively by Ozcan et al. polymers need to be altered for them to achieve certain perfor-
(2005) by treating bentonite using benzyltrimethylammonium mance requirements. One way of modifying polymer properties is
(BTMA) chloride surfactant. Furthermore, Ozcan et al. (2007) mixing them with solid fillers such as fibers, platelets, particles,
applied the DTMA-bentonite for the elimination of reactive blue other polymers, clays or clay minerals, resulting in polymeric
19 from water. The results showed that the modified bentonite had composites or blends (Mahdavinia et al., 2012c). These polymeric
an adsorption capacity of 206.58 mg/g for DTMA-bentonite at pH of blends can then be used for adsorption processes and studies have
about 1.5. This suggested that electrostatic interactions occurred shown that they exhibit exceptionally good adsorption capacities
between bentonite's adsorption site and the anionic dye. (Table 3).
There are different types of polymers used for adsorption pro-
cesses and hydrogels are amongst those polymer materials per-
6.5. Clay composite materials: clay nanocomposites, clay/polymer forming successfully in the removal of contaminants from aqueous
nanocomposite and clay/polymer nanocomposite hydrogels solution. They are a group of polymers capable of absorbing a lot of
water without dissolving because of the physical or chemical
One promising approach to resolve the disadvantages of the low crosslinking of the hydrophilic polymer chains (Schacht, 2004).
adsorption capacities of natural clay minerals is to mix it with other Hydrogels have functional groups that can ionize easily and
advanced adsorbents like polymers and/or activated carbon which therefore repel each other, capturing more water molecules.
have proven to be exceptionally efficient in the removal of organic Additionally, these ionized functional groups let hydrogels absorb
compounds. In recent years, composite materials have received and trap different types of contaminants with the opposite ionic
extensive interest for their potential applications in wastewater charges. As such, hydrogels, as potential adsorbents have attracted
treatment because they can combine the properties and advantages much attention in recent years for dye adsorption. Furthermore
of each component and may also exhibit some attractive perfor- hydrogels have a relatively low production cost and high adsorp-
mances (Mahdavinia et al., 2012a; Hosseinzadeh et al., 2015). A tion capacity for some dyes (Wang et al., 2010).
composite could be defined as a mixture of two or more materials Kamal et al. (2014) prepared copolymer hydrogels made up of
possessing different physical and chemical properties with a very Poly vinyl alcohol (PVA) and Poly acrylic acid (PAA) through g-
distinct interface. irradiation. This polymer was prepared having N,N0 methylene bis
Dye adsorption onto clay minerals is affected by different factors
acrylamide (MBAM) as a crosslinking agent. The adsorption ex- dye, therefore reducing the adsorption capacity and anionic dyes
periments revealed that the adsorption of CV dye onto PVA/PAA percentage removal (Han et al., 2014; Tümsek and Avci, 2013).
and PVA/PAA/clay composite hydrogels depended on a number of To corroborate the general trends shown by the effect of pH on
variables like solution pH, concentration dye concentration, PVA/ dye adsorption, we looked at a few studies that investigated pH
PAA/clay composition, temperature of the solution and ionic influence on the removal of dyes from solution. To study the effect
strength amongst other variables. It can be concluded that the PVA/ of pH on adsorption, Anirudhan and Ramachandran (2015) per-
PAA/clay composite hydrogel is a more efficient adsorbent than formed batch experiments using organoclay on dyes with initial
PVA/PAA hydrogel for CV dye, since its removal efficiency reached concentrations of 200 and 400 mmol/L solutions of Methylene Blue
92% for the composite hydrogel containing 4% clay and of compo- (MB), Reactive Blue (RB) and Crystal Violet (CV). The findings
sition 50/50 (wt%). showed that increasing pH also increases the adsorption capacity. A
Clays like bentonite, laponite, sepiolite enhance the adsorption possible explanation to this observation is that, increase in pH,
capacity and mechanical properties of hydrogels and in most cases decreases the positive charges on the surface thereby increasing
nanocomposite hydrogels are loaded with such types of clays the negatively charged sites. Negatively charged surfaces on the
(Shirsath et al., 2011). A study that corroborate this findings was clay will favour the uptake of cationic dye molecules due to elec-
carried out by Li et al. (2012) where nanocomposites hydrogels trostatic attraction. Earlier we mentioned that cationic dye
were prepared by loading laponite clay into a poly(acryl amide) adsorption improves with a rise in pH. Results on the specific
hydrogel via in situ polymerization to assess the adsorption prop- adsorption capacities of the of the clay for dyes were 99 and
erties of the composite onto CV. The experimental results of the 97 mmol/g for MB, 95 and 184 mmol/g at initial concentrations of
removal of cationic dye showed that, as the clay content in the 200 and 400 mmol/L for CV and 90 and 174 mmol/g for RB, respec-
hydrogel increased, the adsorption capacity of the hydrogel tively at pH 9. The dyes were taken up in the order: MB > CV > RB.
increased hence confirming the aforementioned statement about The authors reported that order of affinity could be explained on
clays enhancing the adsorption capacity and mechanical properties the basis that dyes have different molecular size, structure and
of hydrogels. Li and coworkers also prepared another hydrogel functional groups hence electrostatic and other physical forces they
nanocomposite (poly(acrylic acid)-bentonite-FeCo (PAA-BeFeCo)) experience will be different (Allen et al., 1989). Essentially most
through ultrasound assisted in situ emulsion polymerization. The cationic dyes yield molecular cations (Cþ) as well as reduced ions
incorporation of FeeCo and exfoliated bentonite clay platelets also (CHþ) (Kavitha and Namasivayam, 2007). There is a decrease in dye
increased the stability and strength of hydrogel thereby aiding the adsorption in acidic conditions due to the electrostatic repulsion
dye adsorption process. The adsorption results showed that a pH of because the protonated adsorbent surface repel the cationic dye
11 produced the maximum dye adsorption because at that high pH, molecules. The adsorbent surface becomes positive after modifi-
there is dissociation of COO ions which attracts cationic organic cation giving a pHpzc of 7.8 and the maximum removal occurred at
compounds. pH 9. Beyond the pHpzc, the clay surface was negative and
Adsorption studies using a variety of composites including adsorption occurred by electrostatic attraction between the nega-
nanocomposites, polymer composites, clay nanocomposites tive surface of adsorbent and cationic dye species. These results
hydrogels has acquired relevance due the potential it offers, as show that indeed the surface characteristics of the adsorbent in-
shown on Table 6. fluence its adsorption capacity.
As it has already been indicated earlier, anionic dye adsorption
7. The effect of variables and their interaction on dye strongly depends on pH, and low pH ranges are ideal for their
adsorption removal when metal oxides are used as sorbents (Afkhami and
Moosavi, 2010; Saha et al., 2011). Hai et al. (2015) also obtained
Dye adsorption studies using clays are usually carried out in a similar results in their study. These researchers used acid-activated
batch approach to evaluate the influence of experimental param- kaolinite with TiO2 to remove azo dyes CR, Direct Fast Scarlet 4BS
eters including contact time, pH, adsorbent dose, initial dye con- (4BS), and weak acid dark blue 5R (5R)) from aqueous solution and
centration and temperature. Batch experiments investigate one like many dye removal studies, they also investigated the effect of
factor a time in order to acquire optimum conditions of dye pH to see how it will influence the percentage dye removal. Their
adsorption. findings showed that all the three dyes were maximally removed in
acidic conditions than basic conditions. To explain their findings,
7.1. Effect of solution pH the authors stated that pH determines TiO2 nanoparticles surface
charges and the ionic nature of dyes. Anirudhan and Ramachandran
By definition, pH is a measure of hydrogen ions concentration. (2015) also gave the same explanation for dye adsorption earlier on.
The variability of the pH of the aqueous solution in which the CR, 4BS, and 5R are anionic dyes and are negatively charged, it was
adsorption process takes place, plays a vital role in the whole quite expected that their removal be greater in acidic conditions
adsorption process (Elmoubarki et al., 2015). Generally, pH in- and the results came out as expected. However, the same expla-
fluences the dye adsorption because of change in surface charac- nation cannot be given in the case of metal oxide adsorbents. The
teristics of the adsorbent and that of the dye chemistry. Solution pH increased adsorption of the dyes on the metal oxide modified ad-
also determines the extent of protonation of the OH exchange sorbents under acidic conditions was mainly attributed to the
sites and the extent of protonation of the adsorbate thus deter- electrostatic attraction between the negatively charged dye ions
mining the specific charge of an exchange site and therefore ulti- and the positively charged TieOHþ 2 . On the contrary, under basic
mately the adsorption tendency of the substrate also (Tomar et al., conditions, OH groups on the surface of TiO2 dissociates forming
2014). Therefore the adsorption capacity of the adsorbent will also TiO and therefore TiO2 nanoparticles surfaces become negatively
depend on solution pH. In general, at low pH values (acidic con- charged causing electrostatic repulsion between the dye anions and
ditions) there is an increase in the amount of anionic dye removal. the negatively charged TiO2 nanoparticles, resulting in a decrease in
This is due to the electrostatic attraction occurring between the dye adsorption.
anionic dye and the positively charged surface of the adsorbent. At It is worth noting that it is not always the fact that adsorption
high pH values (basic conditions), there is electrostatic repulsion processes always depend on pH, sometimes the adsorption may
between the negatively charged adsorbent surface and the anionic totally be independent of pH though this is not always the case for
Table 6
Comparison of adsorption properties of different clay composite materials.
Clay polymer nanocomposites Dye Enhancement action of polymer system References
Poly (acrylamide-co acrylic acid)/Kaolinite P(AAm- Bromophenol Blue An increase in temperature resulted in increase in El-Zahhar et al. (2014)
AAc/Kao) Clay composite the amount of BPB dye adsorbed per unit mass of
sorbents
Chitosan/Modified Ball (MBC-CH) Clay composite Methylene Blue Adsorption of MB on MBCeCH was found to Auta and Hameed (2014)
increase as the initial concentration, solution pH
and temperature of the solution were increased.
Poly(ethylene glycol-co-acrylic acid)/Bentonite Clay Congo Red and Methyl The nanocomposites showed high adsorption Bhattacharyya and Kumar-
nanocomposite semi-IPN type hydrogel Violet capacity and removal-% of CR and MV at a solution Ray (2015)
pH of 7
Poly(Acrylamide)/k-Carrageenin/Sodium Alginate Crystal Violet Dye adsorption capacity of hydrogels was Reza-Mahdavinia et al.
Sodium Montmorillonite (MMT) Clay hydrogel influenced by both clay content and biopolymers (2013)
nanocomposite weight ratio. At acidic media, the dye adsorption
capacity of nanocomposites was enhanced as the
carrageenan and clay content were increased.
Poly(acrylicacid)/Bentonite/FeCo particles (PAAc- Crystal Violet Exfoliated bentonite clay and FeeCo particles Shirsath et al. (2011)
BFeCo) hybrid hydrogel nanocomposite increased the strength and stability of hydrogel and
assisted the adsorption of CV
CarAlg/MMt nanocomposite hydrogels crystal violet The adsorption capacity of nanocomposites was Mahdavinia et al. (2013)
enhanced as the clay content was increased.
kappa-carrageenan-g-poly(acrylamide)/sepiolite crystal violet The speed of adsorption of cationic CV dye onto Mahdavinia and Asgari
nanocomposite hydrogels obtained hydrogels was improved by introducing (2013)
sepiolite nanoclay.
Novel kappa-carrageenan/poly (vinyl alcohol)/ Crystal violet Compared with clay-free hydrogel, the Hosseinzadeh et al. (2015)
montmorillonite nanocomposite hydrogels nanocomposites indicated a relatively improved
adsorption capacity at the same batch system.
Magnetic carboxymethyl chitosan- Crystal violet By introducing magnetic laponite RD, the Mahdavinia and Karami
gpoly(acrylamide)/laponite RD nanocomposites nanocomposites showed an enhanced adsorption (2015)
capacity for CV dye.
carrageenan-based nanocomposite Crystal violet The rate of dye adsorption is enhanced by Mahdavinia et al. (2012a)
superabsorbents increasing the clay content up to 14 wt% of clay.
Novel carrageenan-based hydrogel nanocomposites The effect of carrageenan and clay contents on the Mahdavinia et al. (2012b)
containing laponite RD speed of dye adsorption revealed that while the rate
of dye adsorption is enhanced by increasing the clay
content, it was depressed as the carrageenan
content increased in nanocomposites composition.
most studies. Santos et al. (2016) evaluated the effect of pH on Basic investigated the effectiveness of several sorbent dosages on the
Red 46 uptake by bentonite clay. Contrary to the usual findings on removal both anionic and cationic dyes (Anirudhan and
the effect of pH on dye removal, their results show that the amount Ramachandran, 2015; Chaari et al., 2015; Yan et al., 2015). Gener-
of adsorbed dye was not considerably affected by pH. They reported ally, the percentage removal of dye is directly proportional to the
that, for initial pH values between 2 and 6, the BR adsorbed amount adsorbent dosage (as the adsorbent dosage increases, the per-
was approximately 220 mg/g and pH did not have a considerable centage removal of the dye also increases). A possible explanation
impact on that adsorption capacity. Chemical adsorbent charac- for such a trend is that, with increase in adsorbent dosage,
terization before the dye adsorption experiments showed that 0.1, adsorption sites that can take up dye ions become more available.
0.01 and 0.001 mol/L, NaCl concentrations recorded the PZNPC of When the adsorbent dosage is low the adsorption rate is quick
the adsorbent as 9.6, 9.9 and 10.1 respectively. Considering those because of the readily available active sites and when the adsorbent
PZNPC results, at low pH values, there is a positive pH-dependent dosage is high, the dye ions cannot readily access the adsorption
charge meaning that it is only the negative permanent constant sites easily until the attainment of equilibrium (Sarma et al., 2016).
charge that is in charge for BR adsorption. As pH was increased an Acid Blue 25 (AB25), Acid Blue 93 (AB93), Acid Golden Yellow G
increase of adsorption capacity from 220 mg/g at pH 6e319 mg/g at (AGYG) and Acid Turquoise Blue A (ATBA were used as model dyes
pH 10 was observed and in that basic solution, equilibrium pH in a study by Yan et al. (2015). Raw bentonite and CTMAB-Bentonite
values ranging from 8.7 to 9.3 and those values were closely similar were used to test the effect of adsorbent dosage for this particular
to PZNPC values. The negative pH-dependent charge and the per- study. As expected, the results followed the general trend with
manent charge, plays a pivotal role in the improved adsorption adsorbent dosage. Their findings revealed that the amount of dye
capacity. Similar tendencies were also reported for the cationic dye uptake increased with the increasing amount of the modified
adsorption by montmorillonite and palygorskite (Al-Futaisi et al., adsorbent. An 80% removal was achieved for AB93 and AB25 with a
2007; Roulia and Vassiliadis, 2008). These findings clearly in- 0.02 g dosage. For the other 2 dyes, there was a rapid adsorption,
dicates that BR dye (a cationic dye) can be taken up extensively with the equilibrium state being achieved at 0.05 g. All four dyes
even under unfavourable (acidic) conditions and furthermore recorded more than 88% removal with the modified clay, while for
bentonite clay did not show the weakness of being strongly raw bentonite the percentage removals were all lower than 30%.
dependent on pH to perform well. The findings showed that the adsorption ability of CTMAB-Bent was
strongly enhanced by surfactant modification, by changing the
hydrophilic surface to hydrophobic. A similar trend of results was
7.2. Effect of adsorbent dose also reported by Chaari et al., 2015 on the interactions of C.I. direct
orange 34 (DO34) with Tunisian raw clay. To assess the adsorption
To determine a minimum adsorbent dosage that is economically capability of the clay, the dosage was varied in the range 0.3e1.5 g/
viable in wastewater treatment processes, many studies have
L. The percent removal improved from 87 to 85% with dose increase L) on the adsorption of BG showed that adsorption efficiency and
from 0.3 to 1 g/L. The authors reported that this might have been sorption capacity displayed opposite trends with increasing initial
ascribed to an improved surface area of the adsorbent and the BG concentration. RC sorption capacity rose from 48 to 119.5 mg/g,
availability of additional adsorption sites. Nonetheless, above 1 g/L while the adsorption efficiency declined from 96% to 47% with an
dose, there was a reduction in dye adsorption, which might have increase in BG concentration from 20 mg/L to 100 mg/L, respec-
been caused by the reduction of the available surface area due to tively. Numerous scholars similarly established comparable results
the formation of agglomerates by the clay minerals thereby using BG (Auta and Hameed, 2012, 2013; Nandi et al., 2009). Kismir
blocking some of the binding sites. and Aroguz (2011) revealed that the adsorption efficiency of BG by
Rehman et al. (2013) are also among many researchers that Saklikent mud improved with increasing initial BG concentration
investigated the adsorbent dose effect on dye removal and they also but their highest initial dye concentration used was 20 mg/L and it
acknowledge that it is important to select a proper initial adsorbent recorded a 96% removal. Auta and Hameed (2012; 2013) maintain
dosage because it controls adsorption by way of available adsorp- that surfaces of the adsorbent have a fixed number of binding sites
tion sites and surface area (Javaid et al., 2011; Safa and Bhatti, 2011). per unit mass of the sorbent. At lower initial dye concentration, the
These authors studied the removal of Brilliant Green dye by red clay number of available sites is higher when compared to those at
(RC) and they varied the adsorbent dosage between 0.3 and 1.5 g/L. higher initial concentrations. As a result, majority of the dye ions
Their results showed an inverse relationship between removal ef- are taken up by RC leading to greater percentage removal. Dye
ficiency and adsorbent dosage. Dye adsorption rose from 67% to particles have to compete for the fixed number of adsorption sites
94%, while the adsorption capacity declined from 117.3 to 31.4 mg/g at higher initial concentration hence some of dye particles cannot
at a dose of 0.3e1.5 g/L. Mane and Babu (2011) and Safa and Bhatti be taken up. The findings from the experiments confirmed that
(2011) also described a similar performance of adsorption against residual dye increased with the increase in initial dye concentration
adsorbent amount. Increasing the amount of RC increases the which resulted in lower adsorption efficacy (Nandi et al., 2009).
available adsorption sites up to a particular level against a fixed dye
molecules number (Ghaedi et al., 2011). 7.4. Effect of contact time
7.3. Effect of initial dye concentration Researchers have done contact time studies to show a rela-
tionship between the amounts of dye adsorbed onto a fixed
To evaluate the amount of dye adsorbed and consequentially the adsorbent mass with agitation/contact time (Chinoune et al., 2016;
percentage of dye removed from a solution, investigating effect of Elmoubarki et al., 2015; Fayazi et al., 2015; Santos and Boaventura,
the initial dye concentration becomes imperative. Previous studies 2016). Contact time aids in finding the optimum time at which
have shown a general trend wherein increasing the initial dye equilibrium is reached which can later on be applied in wastewater
concentration leads to a decrease in the percentage of dye removal treatment plants based on wastewater process design. Contrary to
(Anirudhan and Ramachandran, 2015; Yu et al., 2015). Various other adsorption parameters, the effect of contact time does not
authors have attributed this to the saturation of adsorption sites on have a definite general trend. However, most cases show that
the sorbent surface by the adsorbate species. The percentage of dye adsorption happens rapidly at the very first few minutes of contact
adsorption rises with increasing contact time at all initial dye and then proceeds gradually until equilibrium is reached after
concentrations (Dawood and Sen, 2014). What happens is that a which the percentage removal of the dye will not change.
driving force to overcome the resistance to the mass transfer of dye The same can be said for Safranin dye removal by magnetic
is provided by the initial dye concentration between the aqueous mesoporous clay (MMC) reported by Fayazi et al. (2015). The effect
and the solid phase (Rafatullah et al., 2010). of agitation time on the adsorbed amount of Safranin was studied
This phenomenon of saturation of sorption sites on the sorbent from 0 to 90 min and the results revealed that dye removal took a
surface by the adsorbate species was also observed by two-stage process, with a fast initial Safranin adsorption followed
Ogunmodede et al. (2015). They studied the removal of acid dye by slow adsorption. It was clear that much of the dye molecules
from using a combination of bentonite and kaolin clay and among were adsorbed during the initial 10 min where the adsorption
other variables, also investigated the effect of initial dye concen- amount (qt) was about 10.7 mg/g and nearly levelling off after
tration on dye uptake. The adsorption efficiency of kaolin-bentonite 10 min such that Safranin removal remained almost constant as
improved as the initial dye concentration increased. The authors contact time was increased. The authors suggested that the rapid
suggested that increasing the dye concentration leads to a rise in initial uptake rate was due to the rapid diffusion of the dye from
mass gradient between the adsorbent and solution, hence acting as aqueous solution to the MMC composite external surface. Gradually
a driver to transfer the dye ions from bulk solution to the particle occupation of the adsorption sites by Safranin dye occurs when dye
surface. An increase in the proportional dye adsorption was molecules are transported from the bulk phase to the inner-sphere
attributed to the equilibrium shift during the clay adsorption pro- pores of MMC. At a later stage, the slow diffusion process decreased
cess (Ogunmodede et al., 2015). A different study by Makhoukhi the adsorption rate and after 30 min of shaking, a steady equilib-
et al., 2015 also revealed that the amount of dye adsorbed rium state could be considered.
increased with increasing dye concentration up to a saturation A more or less similar trend of results was also obtained by
level. Makhoukhi et al. (2015) reported on Telon dyes adsorption by Ogunmodede et al. (2015) who studied how contact time would
bis-imidazolium modified bentonite from aqueous solutions and affect the amount of CR taken up by kaolin-bentonite. Their find-
their findings showed that all organo-Bt adsorbents showed ings indicated that when contact time is increased, the amount of
improved capacities for dyes retention. dye taken up was not considerably increased. CR adsorption was
Rehman et al. (2013) also did a study on the uptake of BG by red very quick from the start of the experiments until around 50 min
clay (RC) and reported that the adsorption process was directly where a slight increase was observed until 80 min recording the
proportional to the initial dye concentration because it drove the maximum CR adsorption. It can be seen that above 80 min there
mass transfer rate under a higher concentration gradient between was almost no change in the CR adsorption. Chaari et al. (2015) had
the RC surface and the dye solution. The same explanation has been a comparable observation concerning contact time effect on dye
reported by other studies including Aroguz et al. (2008) and Auta adsorption. The results of percent uptake of DO34 by HC was
and Hameed (2012). Initial dye concentration effect (20e100 mg/ investigated at time intervals ranging from 5 to 90 min and the
findings showed DO34 uptake increased with time until 60 min. of dye wastewater. Accordingly they did data collection at five
Just like the other authors, the initial rapid adsorption was attrib- temperatures ranging from 10 to 50 C. The quantities of MB, MG
uted to large number of adsorbent sites that were available for and MO adsorbed on the clays as function of the temperature of
DO34 molecules and beyond 60 min, the adsorption capacity solution indicated that increasing solution temperature led to an
remained constant due to the saturation of adsorption sites. The increase of adsorbed MG. However, the adsorbed quantity of MO
overall conclusion on contact time studies is that adsorption occurs decreases significantly with an increase in temperature and lastly,
rapidly within the first few minutes of contact and then proceeds the adsorption of MB was less influenced by temperature as the
gradually until equilibrium is reached after which the dye per- adsorbed amounts slightly decreases with the increase in solution
centage removal remains constant. temperature from 10 to 50 C. Thermodynamic parameters results
which include the change in free energy (DG), enthalpy (DH) and
entropy (DS) were used to define the thermodynamic behaviour of
7.5. Effect of temperature the adsorption of MB, MG and MO onto the clays. From the calcu-
lated constants it was concluded that, the adsorption was
In order to determine if the adsorption process is going to occur exothermic in the case of MB and MO. To further determine the
in any adsorption process, energy and entropy values must be taken type of adsorption, the magnitude of enthalpies was calculated and
into consideration (Chen et al., 2011). The practical applicability of the process recorded a decrease in entropy. The negative DS value
the process is indicated by thermodynamic parameter values. suggested a decline in the randomness at the solid/solution inter-
These parameters of thermodynamics on adsorption are usually face during the adsorption. The Gibbs energy (DG) increased when
obtained from the experimental data acquired at different tem- the temperature was increased from 10 to 50 C indicating a
peratures (Chen et al., 2011). Evaluating thermodynamic parame- decrease in feasibility of adsorption at higher temperatures. In the
ters involves calculating the Gibbs free energy variation (DG), case of MG, the adsorption was endothermic and accompanied by a
enthalpy variation (DH) and entropy (DS) according equations (1) decrease in DG values with the increase in temperature. The MG
and (2) (Yousef et al., 2011): result indicated an increase in feasibility of adsorption at higher
The standard free energy change DG is calculated using the temperatures. The DS values were found to be positive which
following equation: suggested an increase in the randomness at the solid/solution
interface during the adsorption. From all this results, it could be
DG ¼ RT ln Ka (1)
concluded that adsorption of methyl orange was more influenced
by the change in solution temperature.
where DG is the free energy of sorption (kJ/mol), T is the temper-
Another study to examine the influence of temperature on dye
ature in Kelvin (K), R is the universal gas constant (8.314 J/mol/K)
uptake was carried out by Toor and Jin, 2012 using modified
and Ka is the sorption equilibrium constant.
bentonite to remove diazo dye. They evaluated the effect of tem-
The sorption equilibrium constant Ka can be expressed in terms
perature on Congo Red (CR) adsorption on bentonite at 25, 30, 40,
of enthalpy change (DH) and entropy change (DS) as a function of
50 and 60 C. The temperature impact graph showed that as tem-
temperature and is shown below: (Alver and Metin, 2012; Ma et al.,
perature was increased from 25 to 60 C there was a minor decrease
2012).
in the removal of CR. These findings revealed that the adsorption
DH DS process was exothermic and lower temperatures favoured the
ln Ka ¼ þ (2) adsorption process hence the negative Ho values. The change in
RT RT
enthalpy was found to be between 20 and 0 kJ mol1, indicating a
where DH is the heat of sorption (kJ/mol) and DS is the standard physical reaction. From 400 to 80 kJ mol1 chemisorption be-
entropy change (kJ/mol/K). comes predominant (Lian et al., 2009). Similar results were also
The positive values of DH imply that the adsorption process is reported by Vimonses et al. (2009) and Chatterjee et al. (2009).
endothermic and it is an indication that the nature of the dye They argue that the decline in dye removal with rising tempera-
adsorption is predominantly physical, involving weak interaction tures is because of poor interaction between CR and bentonite
forces. The positive values of DS suggest an improved chance of the because hydrogen bonds and Van der Waals are weak. Calculating
solid to solution interface with some sorption system structural the Gibbs energy gave negative values which is indicative of a
changes and an attraction to the adsorbate. Moreover, a positive DS spontaneous and feasible adsorption process. This further suggests
value relates to a rise in the adsorbed species degree of freedom that the adsorption of CR adsorption by modified clay does not
(Ma et al., 2012). considerable change internal structure of the clay. These findings
Temperature usually has a notable effect on reaction rate. If were similar to those described by Ozcan et al. (2004) for the up-
temperature increases, the rate of chemical reaction also increases take of Acid Red 57 by acid activated bentonite. “The decrease in
(Mekatel et al., 2015). Hence the temperature of the aqueous so- entropy implies the positive affinity of the adsorbents towards the
lution has a vital role on the whole adsorption process. The increase CR adsorption” (Chatterjee et al., 2009).
or decrease of the adsorption capacity with temperature can help
tell what type of adsorption took place. If the adsorption capacity 7.6. Effect of ionic strength
increases with temperature then the adsorption is endothermic
and if the adsorption capacity decreases with increasing tempera- Ionic strength is an important parameter to be investigated in
ture then the adsorption is an exothermic process (Zhao et al., 2013; adsorption experiments because it is well known that industrial
Zulfikar, 2013; Khorramabadi et al., 2012). A number of in- wastewaters always have pollutants such as inorganic salts. The
vestigations have shown that temperature plays an important role availability of such salts in solution leads to high ionic strength
in the adsorption process (Anirudhan and Ramachandran, 2015; affecting the whole adsorption process at large (Anirudhan and
Chinoune et al., 2016; Rehman et al., 2013). Ramachandran, 2007). Usually, the variation of the concentration
Elmoubarki et al., 2015 used Morrocan clays to adsorb MB, MG of salts like NaCl, KCl and CaCl2 have a notable effect on the
and MO from aqueous solution. These authors evaluated the tem- adsorption of acidic dyes. Most of the times, NaCl is used to stim-
perature effect in a bid to test the capability of the clays to remove ulate the dying process. A study by Ma et al. (2013) to assess the
dyes from a variety of effluents, considering specific circumstances removal of Congo Red, an acid dye using raw bentonite and
surfactant-modified bentonite indicated that the adsorption of 9. Adsorption isotherms

Congo Red, onto the negatively charged bentonite and positively
charged CTABMBn was enhanced by adding the salts in the order: The adsorbate concentration in a solution is in dynamic equi-
NaCl < KCl < CaCl2. Ionic strength increase in solution may result in librium with the interface of the adsorbent. Analysing equilibrium
the compression of the diffuse double layer on the adsorbent thus data aids in the development of mathematical models which might
easing the electrostatic attraction and the adsorption process be useful in the quantitative description of results. The equations
consequently (Li et al., 2010; Peng et al., 2006). together with the basic assumptions of these equilibrium models
Kamal et al. (2014) investigated the adsorption properties of can predict the adsorption ions at the same time giving important
PVA/PAA/clay composite hydrogel towards crystal violet. Among data on the adsorption mechanisms. The Langmuir and Freundlich
many of the parameters evaluated, the effect of NaCl concentration isotherms are the most common adsorption isotherm models
on the adsorption capacity of the PVA/PAA and PVA/PAA/clay applied in dye adsorption studies.
composite hydrogels for CV dye was also studied. The findings
show that the adsorption capacities of the adsorbent decreased 9.1. The Langmuir isotherm
with increasing NaCl concentration. The findings corroborate what
was also reported by Bayramoglu et al. (2009). Generally what The Langmuir isotherm model is based on the assumption that
happens is that, as the ionic strength is increased with addition of adsorption cannot proceed beyond the monolayer. It furthermore
NaCl, excessive Naþ ions may screen the negatively charged says that the adsorption of a particular molecule on a given
adsorbent surfaces, leading to the reduction of electrostatic adsorption does not depend on the occupation of the next
attractive force, and as a result, the cationic dye adsorption de- adsorption site (Li et al., 2011).
creases. The authors concluded that NaCl addition deteriorates the Expressed mathematically by Equation (3) as,
performance of such prepared hydrogels for dye adsorption.
Fil et al. (2014) studied the effect of electrolyte concentrations Ce 1
on the removal of astrazon red violet (ARV) using montmorillonite. ¼ (3)
Qe Qmb
Unlike the above mentioned researchers who used different Cl
salts, Fil et al. (2014) used different molar concentrations of NaCl where Ce is the dye concentration at equilibrium (mg/L), Qe is the
solutions. The adsorption of ARV onto the montmorillonite surface adsorbed amount of dye at equilibrium (mg/g), b represents the
was negatively affected by NaCl in aqueous solutions. Increasing the Langmuir isotherm constant and Qm is the maximum adsorption
NaCl concentration from 0 mol/L - 0.1 mol/L, decreased the capacity for a total monolayer coverage.
adsorption capacity from 194.12 mg/g to 179.05 mg/g. A possible
explanation to this trend is that as ionic strength is increased 9.2. The Freundlich isotherm
electrostatic attraction between the adsorbate molecule and the
adsorbent surface is reduced consequently reducing the removal Contrary to the Langmuir isotherm, the Freundlich isotherm
efficiency. Ultimately, increasing solution ionic strength, also de- describes the adsorption characteristics for heterogeneous adsor-
creases the final pH of the suspension. As a result, positive ions bent surfaces (Singh et al., 2015).
increase at the montmorillonite surface, screening electrostatic Expressed mathematically by Equation (4) as,
interactions between charges and decreasing adsorption (Dogan
et al., 2009; Weng et al., 2009). log Qe ¼ =n log Ce þ log KF
1 (4)
Srivastava and Sillanp€ € (2016) studied the regeneration of a
aa
basic and an acidic dye on a clay nanocomposite. Desorption study KF and 1/n are the Freundlich constants, describing the
showed that among all tested regenerants (0.5 mol/L HCl, NaOH, adsorption capacity and intensity respectively. The constants n and
CH3COOH, C2H5OH, 1:1 mixture of C2H5OH: HCl, acetone and KF are determined from the slope and the intercept respectively.
ethylene glycol), acetone proved to be the highly efficient eluent by Researchers have used these two common adsorption isotherms
successfully desorbing the highest amount of dye from dye loaded to describe the mechanisms of dye adsorption onto various types of
adsorbent. Related results were also reported by other studies adsorbent surfaces. Chaari et al. (2015) applied the Langmuir and
(Chowdhury et al., 2009; Dave et al., 2012). Accordingly, for further Freundlich isotherm models to study the mechanisms of adsorption
adsorptionedesorption cycles, acetone was selected as a regener- of Direct Orange 34 (DO34) onto natural clay. The isotherms factors
ation medium for the adsorbent. The regenerated sorbent was were evaluated at pH 3. By way of comparing correlation co-
efficient for the removal of both dyes (>55%) for to two adsorp- efficients values (R2) for the two isotherms, the Freundlich
tionedesorption cycles. Nevertheless, the third cycle showed isotherm gave the best fitting model for the adsorption of DO34
decreased adsorption to 44% and 48% respectively for CR and MB onto halloysitic clay with a high correlation coefficient value of
and as a result, further cycles were not investigated. 0.99. This is indicative of adsorption of DO34 taking place on het-
erogeneous surfaces (Chaari et al., 2015). These results are also the
same with those obtained by Yan et al. (2015). They also applied the
8. Process optimization Langmuir and the Freundlich models to their data on acid dyes
adsorption by CTMAB modified bentonite from aqueous solution.
One of the major objectives of dye adsorption studies is finding Their findings showed that the Freundlich model gave the best fit
the optimum process parameters to maximize the removal of dyes. having an R2 vale of 0.93 compared to the Langmuir model which
To this aim, numerical optimization is employed to determine gave an R2 value of 0.86. These results also corroborated with other
appropriate amounts or values needed for the different parameters studies on the adsorption of acid dyes by clays and organoclays
to attain the maximum removal efficiency which is mostly (Hao et al., 2014; Hameed et al., 2007; Tümsek and Avci, 2013).
measured as percentage removal (%). Table 7 summarizes the re- It is interesting to note that some data will however conform to
sults of optimization conditions attained by different researchers the Langmuir isotherms more they will conform to the Freundlich
on dye adsorption using various types of clays. Such results show indicating adsorption on homogenous surfaces. In another study by
the reliability of the applied model for the appraisal of real condi- Abidi et al. (2015), equilibrium modelling was studied using Fou-
tions (Hassani et al., 2015). chana clay for the adsorption of Reactive Red 120 dye in the
Table 7
Optimum conditions of dye adsorption using various clays.
Clay Dye Experimental conditions Optimised conditions References
Red clay Brilliant Green pH (2e10), particle size (58e150 mm), pH ¼ 7, contact time ¼ 240 min, Rehman et al. (2013)
dye adsorbent dose (0.3e1.5 g), contact time dose ¼ 0.4 g, initial dye
(5e1500 min), initial dye concentration concentration ¼ 20 mg/L, particle
(20e100 mg/L), and temperature size ¼ 58 mm and temperature ¼ 45 C.
(25e65 C)
Surfactant modified Basic dyes 0.1 g of organoclay with 50 mL of various pH ¼ 9.0 temperature ¼ 30 C. Anirudhan and
bentonite clay dye solutions (200e1000 mol/L) and time contact time ¼ 240 min. Ramachandran (2015)
(organoclay) up to 4 h.
Natural clay Direct orange 34 pH (2e8), contact time (5e90 min), and HC pH ¼ 6.61 Chaari et al. (2015)
dose (0.3e1.5 g) and dye initial contact time ¼ 60 min and dose ¼ 1 g,
concentration (20e150 mg/L).
Dirty bentonite Reactive dyes Dose (1e5 g) Dose ¼ 3 g, contact time ¼ 180 min, pH ¼ 2 Chinoune et al. (2016)
Temperature (278e313 K), initial dye and temperature ¼ 298 K
concentration (20e120 mg/L) and pH
(2e12).
Alginateeclay Methylene blue Dose (2e10 mg/mL) Dose ¼ 8 g, contact time ¼ 100 min, Uyar et al., 2016
quasi-cryogel Temperature (20e60 C) and initial dye temperature ¼ 40 C and initial dye
beads concentration (0.2e1.6 mg/mL) concentration ¼ 0.8 mg/mL.
Modified natural Diazo dye pH (3e11), contact time (2e30 h), and HC Dose ¼ 14 g, contact time ¼ 24 h, Toor and Jin, 2012
bentonite dose (2e26 g) and initial dye concentration temperature ¼ 40 C and initial dye
(100e1000 mg/L). concentration ¼ 1 L and pH > 10
Stevensite-rich Dose of 1 g/L, pH (3e10), Contact time ¼ 2 h, temperature ¼ 55 C Elass et al., 2011
Moroccan clay Temperature (25, 45, and 55OC) and initial and initial dye concentration ¼ 1 L and
dye (200e1000 mg/L) pH ¼ 10
Magnetic Safranin dye Contact time (0e90 min), dose (0.03 Contact time ¼ 30 min, temperature ¼ low Fayazi et al., 2015
mesoporous clay e0.07 g), pH (6e10), temperatures
and initial dye concentration (40e80 mg/L)
Kaolin and Contact time (1e80 min), pH (5e13), and Contact time ¼ 50 min, initial dye Ogunmodede et al.,
Bentonite clay initial dye concentration (75e300 mg/L) concentration ¼ 100 mg/L and pH ¼ 10 2015
mixture
presence of CHT-Catalase. The results were obtained from using the during the desorption process.
Langmuir and Freundlich isotherm models. In all cases, the Lang- Mahdavinia et al. (2016) used ethanol (96% V/V), 0.5 M of KCl
muir isotherm gave the best fit compared to the Freundlich solution, 50/50 V/V of ethanol/water mixture and 0.5 M of KCl in
isotherm. Data fitting best to the Langmuir isotherm indicates that 50/50 V/V of ethanol/water mixture to desorb dyes from spent
in the presence of CHT Catalase, the dye alone forms a monolayer nanocomposites. The use of the above mentioned solutions was
on the surfaces of Fouchana clay (Abidi et al., 2015). Chinoune et al. ineffective for desorption purposes and therefore there was a need
(2016) reported on the removal of reactive dyes by dirty bentonite to try other different solutions. For more practical applications of
from aqueous solution. In this case, the Langmuir isotherms R2 the desorption study the authors attempted to desorb the dye via a
values were found considerably higher than those of the Freundlich mixture of ethanol/water and KCl. The spent adsorbents were
isotherms too. Since the Langmuir isotherms fitted the experi- desorbed by 0.5 M of KCl in ethanol/water leading to a desorption
mental data best it showed the presence homogenous distribution efficiency of more than 94%. Because of the successful desorption
of active sites on the magnesium hydroxide coated bentonite, (Be results, Mahdavinnia and coworkers decided to carry out 5
Mg(OH)2) surface. This conclusion is based on the fact that the desorptione adsorption processes using the same regeneration
Langmuir model assumes that adsorption takes place on homoge- agent. Throughout all the regeneration cycles, the nanocomposite
nous surfaces. Another adsorption isotherm modelling study was mCarraLap3 showed a constant dye adsorption capacity and the
also done Fayazi et al., 2015 and the Langmuir and Freundlich change in desorption efficiency and adsorption capacity for all
constants calculated and reported. The adsorption of Safranin was other composites was almost negligible. In actual fact, the findings
well fitted to the Langmuir isotherm model with the higher R2 showed that the nanocomposites could be used for multiple cycles
(0.98). It indicated the adsorption took place at specific homoge- without a decrease in adsorption capacity for CV dye.
neous sites within the adsorbent forming monolayer coverage of To evaluate the regeneration of sepiolite clay and study the
Safranin on the surface of the absorbent. mechanisms involved in BR sorption, Santos and Boaventura (2016)
carried out desorption experiments using NaOH and HCl as
regeneration agents. Desorption studies conducted for BR-loaded
10. Desorption studies sepiolite showed that the maximum BR desorbed percentage was
9.4% and it was obtained for strong acidic conditions (pH 2). For
Even though some clays have high adsorption capacities with higher pH values, desorption was very low and limited to 2e3%,
respect to the removal of dyes, the ability of the adsorbents to be which reflects the establishment of strong chemical bonds between
regenerated is a crucial factor to assess their reusability. Regener- the basic dye and the sepiolite in the adsorption. The results
ation of a spent adsorbent is usually carried out in order to reuse it, showed no feasible regeneration by using acid or alkaline solutions.
avoid the cost of a new acquisition and minimizing the amount of The reduced color leachability from the dye-loaded sepiolite is, on
waste. Many researchers have investigated desorption of adsorbed the other side, a good feature considering the disposal in landfill or
dye using various types of eluents. Some adsorbents can be effi- reuse for other purposes, such as incorporation in construction
ciently adsorbed and reused again for many times but unfortu- materials or in polymeric composites (Zhou et al., 2014).
nately some adsorbents do not perform efficiently after desorption
and some materials may be lost or their structures destroyed
11. Conclusions Alver, E., Metin, A.U., 2012. Anionic dye removal from aqueous solutions using
modified zeolite: adsorption kinetics and isotherm studies. Chem. Eng. J.
200e202, 59e67.
This review paper was mainly looking at the adsorption of Ambasht, R., Sillanpa, M., 2010. Water purification using magnetic assistance: a
different dyes onto various clay based adsorbents. Various mate- review. J. Hazard Mater 180, 38e49.
rials are currently available to remove dyes from water, but clays are Anirudhan, T.S., Ramachandran, M., 2007. Surfactant-modified bentonite as adsor-
bent for the removal of humic acid from wastewaters. Appl. Clay Sci. 35,
generally considered attractive because of their effectiveness, 276e281.
convenience, ease of operation, simplicity of design and for eco- Anirudhan, T.S., Ramachandran, M., 2015. Adsorptive removal of basic dyes from
nomic and environmental reasons. Performance comparison of aqueous solutions by surfactant modified halloysite clay (organoclay): kinetic
and competitive adsorption isotherm. Process Saf. Environ. Prot. 95, 215e225.
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Journal of Environmental Management 191 (2017) 35e57

Contents lists available at ScienceDirect

Journal of Environmental Management

An update on synthetic dyes adsorption onto clay based minerals: A

6. Disadvantages of clays leading to modification to enhance their adsorption capacities . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 44

1. Introduction Chemical coagulation processes produce huge amounts of

2.1. Physico-chemical properties of dyes

Normally dyes are soluble in water or water dispersible organic

Fig. 1. The chemical structures of some synthetic dyes (Hunger, 2003).

Treatment Method Pros Cons

Fig. 3. Structure of a typical clay material (Masindi et al., 2014).

Type of clay Dye removed Adsorption capacity (mg/g) Reference

Sepiolite clay Direct Blue 106 Santos and Boaventura, 2016

Red mud Acid Orange 7 74 32.36 Hajjaji et al., 2016

Clay polymer nanocomposites Dye Enhancement action of polymer system References

surfactant-modiﬁed bentonite indicated that the adsorption of 9. Adsorption isotherms

Clay Dye Experimental conditions Optimised conditions References

5681e5689. pp. 405e445.

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