ADVANCES IN USE OF CLAY IN INDUSTRIAL WASTE WATER TREATMENT

By

Ganiyu Soliu Oladejo

ABSTRACT
This review enumerates the advances in the use of clays as low cost materials in remediation of waste
water for the past few years. The past, present and future of natural clays, activated clays, modified clays
and clay based composites in removal of both organic and inorganic pollutants from waste water is
presented. The uses of clays as substrate to immobilize photo catalyst in photo degradation of refractory
pollutants is an emerging area of nano technology employed in environmental remediation technologies.
The kinetics and thermodynamics of the adsorption processes as well as future and challenges of the use
of these materials in depollution of waste water is also presented in this communication.
1.0 INTRODUCTION
Water soluble organic and inorganic pollutants are major components of industrial waste water. The
removal of these contaminants is of paramount important because these compounds and their degradation
products are not only toxic and carcinogenic but their pilling up in environment has hazardous effects on
both aquatic and terrestrial life. Not only because of their toxicity but they also alter the colour of the
water body, thus disturb the transparency of the water to light and reduces oxygen in it [1]. Global
industrialization has caused enormous consumption of huge amount of hazardous chemicals in different
industrials setup and the effluents from these plants poses increased environmental dangers if directly
released to water body without effective treatment. Biological treatment, chemical oxidation, coagulation
of pollutants, aeration, chlorination, media filters and reversed osmosis are some of the techniques that
have been used for pollutants removal from waste water but most of these technique are either not
economically viable or complex in operation for commercial application [2]. Adsorption of the pollutants
on suitable adsorbents

has been the most widely used technique because of its economic viability and

simplicity in operation [3].

In recent years, adsorption has been widely studied because of its simplicity and availability of wide
varieties of adsorbents which has made it suitable for both small scale and industrial usage. Zeolites, peat,

wood, agricultural waste, red mud, fly ash, activated silica and clay minerals [4] are some of the
adsorbents that have been studied and considered as an alternative low-cost replacement for relatively
expensive activated carbon. Among these low-cost adsorbents, clay minerals have received major
attention because of their large deposits across the globe, high adsorption capacities, large surface area,
easy accessibility, high surface reactivity and environmental friendly [5].
Smectite and kaolinite group clay are the most widely adopted clay based adsorbents in waste water
treatment. Although, there are increase in use of modified sepiolite and palygorskite in removal of organic
pollutants due to their large surface area [6]. The Smectite clays are expandable 2:1 layered silicate with
an octahedral sheet sandwiched between two tetrahedral sheets. There is isomorphous substitution of
lower charge cations for high charge cations in either octahedral or tetrahedral sheet or both. This results
in charge deficit in the layers of the clay which are balanced by counter ions in the interlayer site of the
silicates. There are two major categories of Smectite clay: di-octahedral in which two out of three
octahedral sites are occupied by cations (Montmorillonite, beidellite, nontronite) and tri-octahedral
which has all the three octahedral sites occupied by cations (hectorite, saponite and sauconite).
The kaolinite clays on the other hand are 1:1 layered silicates in which one octahedral sheet is joined to
one tetrahedral sheet. They are non-expandable and have no crystal defects (substitution). Kaolinite,
dickite, nacrite and halloysite are di-octahedral while antigorite, chamosite and chrystotile are trioctahedral clay minerals. Sepiolite and palygorskite are other clay minerals that have received more
attention in removal of organic pollutants from waste water in the last decade. They occur in fibrous or
tubular brick-like structure and have great capacity to adsorb pollutants because of their high surface area
[7].
As a way of improving the adsorption capacity of Smectite and attapugite clays, pillars of inorganic metal
oxides like Al, Zr, and Fe have been incorporated in the interlayers of these clays. This increases the
surface area of the clays by creating micro-pores within the interlayers of the clays [8]. The major
challenge with the use of clays is that they have low affinity for organic pollutants as well as inorganic
anions due to the hydrophilic nature and negatively charge layers which electrostatically repel anionic
pollutants. In recent years, research has been tailored towards the modification of clay minerals to render
them hydrophobic by intercalation of suitable organic cations to replace the inorganic once in their
interlayer. By doing so, this will increase the clay affinity for both polar and non-anionic pollutants
because of their organophilic nature. Alky-ammonium and phosphonium (aliphatic or aromatic, short or
long chain) were the most widely used organic cations in the modification of clays but of recent silane
and other organic functional groups have been successfully intercalated in clay minerals [9].
Another widely used technique in remediation of pollutants in waste water is photo catalysis using titania
as catalyst. Again, clay minerals have been widely employed in this field both as substrate to immobilize

the catalyst as well as in clay-titania nano-composites for photo degradation of pollutants. The presence of
clay in the composites or as immobilizer not only enhances the efficiency of the photo catalyst by
maintaining it surface area but also improve post separation recovery of the photo catalyst [10]. This has
found applications not only in waste water treatment but in decomposition of gaseous pollutants and
adsorption of cigarette smoke [11].
2.0 CLAY AS ADSORBENT IN WASTE WATER TREATMENT: PAST AND PRESENT.
2.1 Unmodified Natural Clay Adsorbents
2.1.1

Removal of organic pollutants

Clay minerals have been successfully used for the remediation of organic pollutants from waste water
most especially cationic pollutants. Their high surface area coupled with negatively charged layers and
high hydrophilicity made them an efficient adsorbent for removal of cationic surfactants and some nonionic pollutants. But as stated earlier, their potential as adsorbent for anionic and non-polar organic
pollutants as well as anionic inorganic contaminants is limited because of the hydrophilic and anionic
nature. Nevertheless, Lin et al [12] studied the adsorption of three surfactants (hexadecylpyridinium
chloride, sodium dodecyl sulfate and triton X-102) from water onto raw Montmorillonite and kaolinite
(SAz-1, SWy-2 & KGa-1b) in a fixed bed. A solution containing known amount of surfactant
concentration was allow to percolate through the bed from the top at a controlled rate and temperature.
The adsorption capacities of the clays were found out to strongly depend on the pH of the surfactants
solutions. For each surfactant, SAz-1 has the highest adsorption capacity, followed by SWy-2 while KGa1b has the lowest affinity for the surfactants. It was established that the adsorption capacity of each clays
is proportional to their expandability. Similarly, the mechanism of acridine orange (AO) removal from
water by low charge swelling clays (SWy-2 and SHca-1) has been reported [13]. Complete removal of
AO from water by both clays was observed at initial concentration of 12 mmolL-1, resulting in adsorption
capacity of 1.2 mmolg-1 for each clays. Desorption of exchangeable cations from the clays with
concurrent adsorption of AO molecules was proposed as the predominant mechanism for removal of AO
from solution. The XRD and TGA show the intercalation of AO molecules with different conformations
at low and high AO adsorption level. Nkansah et al [14] investigated the use of lightweight expandable
clay aggregate (LECA) as adsorbent for removal of phenantherene, fluoranthene and pyrene (PAHs) from
water. It was found that the amount of PAHs up taken increases with increase in contact time and physical
sorption induced by aromatic nature of the pollutants was suggested as main mechanism of the adsorption
process though; it was influenced by hydrophobicity of the PAHs. Further, the PAHs removal was also
enhanced with increase in adsorbent dosage up to 4.0 g at which maximum PAHs removal of 94% was
obtained. El-Geundi et al [15] found the removal capacity of Egyptian clay (Minia) for insecticide
(methomyl) from aqueous solutions in percent to be 27.6 and 32.9 mg/g for initial concentration of 43.71

and 19.99 mg/l respectively. The experimental data fitted well with Langmuir isotherm and the adsorption
process was exothermic in nature. In the same vein, physisorption on the edges of broken clay particles
was the major mechanism of adsorption of Reactive Red 120 on Fouchana (Tunisia) clay. The adsorption
capacity of the clay increases with temperature and the process is exothermic. The clay was identified to
contain: Smectite, illite/Smectite, illite and kaolinite [16]. Li et al [17] proposed that simultaneous
stoichiometric desorption of exchangeable cations and adsorption of diphenhydramine (DPH) from water
play the major role in DPH removal by expandable clay minerals SAz-1. The increase in d001 spacing of
the clay confirmed the intercalation of DPH and the swelling clays are excellent environmental sink for
DPH as shown by the results of this study. The kinetic of adsorption of methylene blue MB from
solutions by Moroccan clay followed pseudo second order rate model [18]. The adsorption process was
well described by both Langmuir and Freundlich models. Maximum adsorption capacity of 135 mg/g was
obtained suggesting that the clay is a potential adsorbent for MB. In a similar report, spent bleaching earth
(SBE) was used to remove basic textile dye (Asucryl red GRL) from aqueous solution [19]. The
adsorption experiment was best described by Langmuir model and pseudo second order fitted the kinetic
rate of the adsorption process. 73 mg/g was found to be maximum adsorption capacity suggesting the clay
as good adsorbent for the dye. The up taken of di-ethyl ketone by four clay minerals from solution
followed the sequence: vermiculite > sepiolite = kaolinite = bentonite [20]. Sips isotherm best described
the adsorption of di-ethyl ketone on bentonite and kaolinite while sepiolite and vermiculite fitted well by
Dubinin-Raduskevich model. Kinetic data were best described by pseudo first order and the results show
that the clays studied are very appropriate for removal of di-ethyl ketone from waste water
2.1.2

Removal of Inorganic Pollutants

Clay minerals in general have excellent adsorption capacities for heavy metal ions (cations) because of
the negatively charged layers although, the removal of some anions from aqueous solutions have been
reported. The simultaneous desorption of exchangeable cations and adsorption of the metal ions is the
predominate mechanism of the adsorption process. The pH of the solution plays important role here
because it controls the protonation and de-protonation of water molecules sorbed at the edges of the
particles of the clay material. At lower pH there is protonation of sorbed water creating more positively
charged sites while at high pH there is de-protonation which provides more negatively charged sorption
sites on the surface of the aggregates. Hamdi et al [21] investigated the removal of phosphate ions from
solution using kaolinitic and smectitic clay minerals and synthetic zeolites. Phosphate ions were
efficiently removed at pH 4-6 and rate kinetic was well described by second order model for all
adsorbents. Experimental data were best fitted by both Langmuir and Freundlich models with zeolite have
the highest adsorption capacity of 52 mg/g. Comparative studies of adsorption of Zn II onto alkaline Cabentonite ACB and raw bentonite RB show that surface precipitation, cation exchange and fixation were

mechanisms of sorption of Zn II on ACB while cation exchange was the major mechanism of sorption
onto RB [22]. Maximum removal capacity of 149 mg/g was obtained for ACB which was doubled the
removal capacity of RB (73 mg/g). In different studies, Sharma and Vieira et al [23, 24] confirmed that
the sorption of Cd II ions and Ni II ions on china kaolinite and Bofe bentonite clay was spontaneous and
exothermic in nature. The adsorption data in both cases were best fitted by Langmuir isotherm and second
order rate kinetic was suggested for the adsorption of Ni II onto bentonite. Similarly, the adsorption of
Pb II; Cu II and Zn II onto Turkish kaolinite and bentonite was mainly by ion exchange mechanism [25,
26]. Further, the thermodynamic data in both studies show that the sorption process was spontaneous and
exothermic in nature while both Langmuir and Freundlich models were appropriate to describe the
sorption processes. Jiang et al [27] proposed kaolinite clay from Longyan (China) for efficient removal of
Pb II, Cd II, Ni II and Cu II ions from waste water. The experimental data were fitted with Freundlich
model and alkaline pH favours the adsorption of the metal ions. In similar studies, Sdiri et al [28]
suggested the suitability of montmorillonitic and calcareous clays of Aleg formation (Tunisia) for the
removal of several heavy metals (Pb, Cd, Ni and Cu). Higher removal efficiency (maximum adsorption
capacity varied between 6.78 to 131.58 mg/g) was obtained and the amount of calcium carbonate in the
clays has greater influence on the sorption of the metal ions.
2.2 Activated Clay Adsorbents
The adsorption capacity of clays can be greatly modified either by calcination or acid/basic treatment.
Calcination removes both structural and sorbed water depending on the calcination temperature. This
result in increases specific surface area of the clay, thus enhance adsorption process. Acidic/basic
treatment on the other hand leaches away some of the octahedral cations (Al, Fe & Mg) thus, creating
more sorption sites in the layer. Vimonses et al [29] studied the enhancement of removal efficiency of
anionic dye from solution by optimum combination of Na-bentonite, kaolin, zeolite and Ca(OH)2
followed by calcination at 100-3000C. High removal capacity (> 575 mg/g) was obtained at low adsorbent
dosage for optimum mixture. Further, thermal treatment was used to easily recover the spent adsorbent.
After few cycles of removal and regeneration, the recovered adsorbent showed an enhanced removal
capacity towards the dye. The removal capacity of thermally activated palygorskite towards methylene
blue increases with increase in temperature up to 7000C but reduces with further temperature increase
[30]. The heat-treatment (< 7000C) removes both structural and zeolitic water in the channels and tunnels
of the clay, thus increase the surface area. The tunnels collapsed at high temperature due to
dehydroxylation and reduce the surface area clay. More so, desorption of cations and adsorption of
methylene blue was the mechanism of the adsorption process. Paul et al [31] studied organosilane grafted
acid-activated beidellite clay for the removal of alachlor and imazaquin from aqueous solution. 3chloropropyltriethoxysilane (CPTES) or octyltriethoxysilane (OTES) was grafted to acid treated clay by

ultrasonically disperse 2g of activated clay in 60 ml of toluene and then mixed with silane in different
silane/clay ratio. The modified clay demonstrated high adsorption capacity for the herbicides and the
removal capacity increases with mass of silane grafted. The CPTES-grafted clay is efficient for both
alachlor and imazaquin while OTES-grafted clay is only effective for alachlor. Similarly, adsorption was
the mechanism of removal of chlorobenzene from solution by chemical and thermally activated bentonite
[32]. Thermal activation strongly improved the adsorption capacity than chemical activation (HCl and
H2O2). Further, experimental data shows that the adsorption process was spontaneous, exothermic and
well fitted by Freundlich isotherm. Li et al [33] investigated tannin-immobilized activated clay for
adsorption of Cr (VI) ions from aqueous solution. Adsorption and oxidation-reduction was the
mechanism of removal of Cr VI and maximum removal capacity of 24.09 mg/g was obtained. Further,
pseudo second order kinetic and Freundlich model best describe the adsorption process. The study
suggested that tannin-activated clay was a potential low-cost adsorbent for removing Cr VI from solution.
2.3 Modified Clay Adsorbents
As stated earlier, the negative charge layers of the clay minerals make them suitable for sorption of
cations and some non-ionic contaminants. However, their hydrophilic nature and negative charge layers
limited their affinity for many organic pollutants as well as anionic impurities (As III, As V, Cr VI, e.t.c.).
Therefore, recent studies have been focus on efficient ways of modification of clay minerals with suitable
organic/inorganic molecules or both to render them organophilic and effective in remediation of nonpolar or slightly polar organic pollutants. The exchangeable cations in the interlayer of the clay minerals
(expandable clays) and/or negatively charge layers make them suitable for surface modification by
organic cation surfactants (long or short chain). The modified clay becomes hydrophobic and easily
retains organic pollutants. More so, inorganic pillaring of the clay interlayer were the earlier modification
performed on swelling clays. Polyoxocation of Al, Fe or Zr are exchange with interlayer cations in the
clay and then calcined to for a rigid pillar which create more micropores within the clay and thus
increases the surface area. Alkyl ammonium and phosphonium salts with aliphatic or aromatic-short or
long chain were the most widely organic surfactants used in functionalizing clay minerals. However, they
are not thermally stable in the interlayer of the clay due to the weak interaction between the organic
cations and the layers of the clay, thus difficult to recover and regenerate. For this reasons,
silane/organosilane have been developed as good surfactants which can be easily grafted within the
interlayers of the clays and form strong interaction with the layers [8]
2.3.1

Removal of Organic Pollutants

Pillared clays were one of earlier modified clay that showed improved adsorption capacity for dyes
removal. Gil et al [34] synthesized two pillared clays by intercalation of solutions of aluminum and
zirconium and used them to adsorbed orange II and methylene blue from solution. Both clays have

excellent and the same capacity for orange II whereas Zr-PILC performed better than Al-PILC for
adsorption of methylene blue. The mechanism of adsorption was by diffusion into micro pores. Basly et
al [35] studied removal of neutral/anionic biocide (pentachlorophenol) and a cationic dye (Safranine)
from aqueous solution using alginate encapsulated pillared clays. Al-pillared clay and surfactant modified
pillared clay were synthesized by technique reported by khalaf et al and Bouras et al [36, 37]. 2-6 g of
either clay dispersed in water was mixed with 100 ml of alginate and the mixture was forced through
pipette orifice to form micro-beads which were used for adsorption of the contaminants. The adsorption
kinetic followed pseudo second order model and the modification of the biopolymer by pillared clay
enhanced its adsorption capacity. Moreover, the adsorption of dyes, volatile organic pollutants (VOCs)
and petroleum products was investigated on mesoporous organic-inorganic hybrid aerogel silica-PEG in
bentonite [38]. 10 g of homoionic clay dispersed in water was added to silica sol [39] under continuous
ultra-sonication either in step-wise or direct intercalation. The porous clay-hybrid materials demonstrated
high adsorption capacities for organic dyes (MB, MG), VOCs (phenol and toluene) and petroleum
products (kerosene, engine oil and diesel). Interestingly this hybrid was easily recovered by thermal
regeneration. Complete simultaneous sorption of naphthalene and several derivatives of phenol in
sequential batch and column filter were made on crystal violent and tetraphenylphosphonium modified
montmorillonite [40]. The amount of pollutants adsorbed were of similar magnitude to those estimated for
high quality activated carbon but contrary to adsorption on activated carbon that take tens of minutes to
state, the adsorption on organoclays proceeds almost immediately. Hameed et al [41] achieved 188% and
820% increase in adsorption capacity and surface area by modified ball clay with chemical treatment,
calcination and Na-alginate for adsorption of methylene blue. The adsorption process was spontaneous
and physisorption was the major mechanism of the removal of MB. The results showed that modified ball
clay can be used efficiently for removal of MB from solution. Baudu et al [42] studied the impact of wet
granulation on the up taken and removal capacity of granular inorgano-organo pillared clays using BY28
as model pollutant. Al-pillared montmorillonite produced by the method reported earlier by the same
authors [36] was modified with cetyltrimethylammonium bromide CTAB and mixed with silicone-acrylic
polymer in a laboratory high-shear mixer. Granular modified clay produced low removal efficiency
compared to the inorgano-organo pillared clay. Due to ineffectiveness of granular modified clay, the
authors in a separate report [43] used alginate-encapsulated Al-pillared clay micro beads fixed bed
column for removal of pentachlorophenol from aqueous solution. High removal capacities were obtained
for encapsulated CTAB-modified Al-pillared clay compared to unmodified encapsulated Al-pillared once.
Further, the results compare favorably well with those reported for other low-cost adsorbents in literature.
Similarly, in an earlier report by these authors [44], the sorption of Cu2+ and 4-nitro phenol on Na-Mont
and alginate-Na-Mont microcapsule were studied and compared. The beads adsorbed significantly both

pollutants and the sorption of Cu2+increases with amount of alginate in the composite while sorption of
nitro phenol increases with proportion of montmorillonite in the mixture. Drying of the beads affects only
the Cu2+ sorption but no influence on sorption of nitro phenol.
Meanwhile, most surface water contains natural organic matters (humic acids HA) aside from
contaminants from industrial plants. Bollinger et al [45] investigated the influence of these humic acids on
sorption of pentachlorophenol PCP onto CTAB modified Fe and Al-pillared montmorillonite. Initially,
the modified pillared clays demonstrated high removal capacities for PCP in the absence of HA (530
mg/g and 300 mg/g for CTAB-Fe and Al-pillared clay respectively). In the presence of HA, the sorption
capacities of both modified pillared clays were strongly reduced (133 and 53 mg/g) due to competition
between PCP and HA. Nevertheless, because of their high thermal stability and affinity for organic
compounds, CTAB-Fe and Al- pillared clays were strongly suggested for removal of organic pollutants
from surface and waste water. In the same vein, comparative sorption of methyl orange on glycol bis-Ncetylnicotinate di-bromide (gemini surfactant) and CTAB modified bentonite showed that glycol
modified bentonite has higher decoloration rate and removal efficiency (99.02% and 90.62%) for methyl
orange than CTAB modified bentonite (80.12% and 75.49%) [46]. This was attributed to high expansion
in interlayer of the clay modified by Gemini surfactant (2.65 nm) than CTAB modified one (2.14 nm).
However, gemini surfactant-bentonite was less effective at pH > 6 due to hydrolysis of ester groups in it.
Remediation of several anionic contaminants from wastewater was conducted using hydroxyl-CaBentonite- bentonite activated with HCl and Ca(OH)2 [47]. Higher adsorption capacities (50.07, 29.1,
239.5 & 293.5 mg/g for F-, PO43-, orange II and SDBS) better than those reported for low-cost adsorbent
were obtained. Anion/OH- exchange reaction was the suggested adsorption mechanism for the sorption of
anions onto the activated bentonite. In a similar report, Kaghazchi et al [48] modified HCl-activated Cabentonite with HDTMA and used it for removal of phenol from wastewater. The surface area of activated
HDTMA-bentonite was 40% larger than non-activated HDTMA-bentonite and the adsorption capacity of
this modified clay was 10 times greater than that of natural bentonite. Further, the mechanism of sorption
process was by physisorption and it exothermic in nature. Phenol and benzene derivatives BTEX were
sorbed from solution onto HDTMA modified Na2CO3-activated Smectite [49]. Phenol and ethyl benzene
have high maximum adsorption (8.28 & 6.67 mg/g) onto organoclay while the removal efficiency of
others were still within acceptable limit (> 55%). More so, removal capacity of montmorillonite for telon
dye was improved by intercalating p, m and o bis( triphenyl phosphonium methylene)-benzene-dichloride
[50]. Adsorption tests showed a significant increase in adsorption capacities (11-26 to 110-160 mg/g) due
to improvement in organophilic character of the clay. Meanwhile, suspended solids were effectively
removed by organosepiolite/raw sepiolite particles from winery effluents [51]. The dispersed organic
materials in the effluents adsorbed onto organosepiolite, yielding larger particles and settled.

2.3.2 Removal of Inorganic Pollutants

30% improvement was obtained by modifying Cameroonian magnetite rich clay with Eriochrome Black
T [52]. The adsorption process was best described by pseudo second order rate model and Tempkin
isotherm. In a similar report, Owolabi et al [53] modified bentonite with sulphate and phosphate anions to
improve it adsorption capacity towards Cu2+ and Zn2+. Phosphate modified clay has highest removal
capacities for both cations and the process was endothermic and spontaneous. The modification reduces
the surface area of the clay and the interaction between the phosphate and sulphate ions with clay
particles were chemisorption and physisorption respectively. Further, the sorption of both Cu2+and Zn2+
were majorly by chemisorption.

Guerra eta al [54] used modified kaolinite ({N-3-trimethoxysilyl-

propyl}diethylenetriamine) for removal of U VI from aqueous solution. The sorption process was well
fitted by Sip isotherm model and pseudo second order reaction with maximum adsorption capacities of
8.37 X10-3 and 13. 87 X 10-3 mg/g for natural and modified kaolinite respectively.
2.4 Clay Based Composites
In recent years, clay based composites have received much attention, including studies on development
of composites as adsorbents for pollutants, clay matrix to immobilize or support catalyst/photo catalyst as
well as enhancing post treatment separation of the adsorbents.
2.4.1 Clay Based Composites as Adsorbents
Zhou et al [55] used cellulose acetate-organo-montmorillonite for removal of anionic dye from water.
The adsorption of acid scarlet G was found to be kinetically controlled, spontaneous, endothermic and
better than sorption on each of the components of the composite. In related studies, Xing et al [56]
improved the sorption of brilliant blue X-BR by cationic starch intercalated composite matrix. The
composite exhibited excellent adsorption of X-BR (122 mg/g) and the process was best fitted by
Langmuir and pseudo second order models. Similarly, polycation-clay nanocomposites were used for
removal of trinitrophenol PA and trichlorophenol TCP [57]. Almost complete removal PA was obtained
by using PVPcoS-MMT while up to 60% TCP was removed. Adsorption isotherm suggested electrostatic
interactions for the sorption of PA while enhanced TCP removal was achieved with dry composites due to
its hydrophobic properties. In similar studies, Shirsath et al [58] removed crystal violent from water using
poly (acrylic acid)-bentonite-FeCo hydrogel nanocomposite. High alkaline pH gave high adsorption of
dye and concurrent dissociation of COO- ions in the acid and sorption of cationic dye was the mechanism
of the process. Further, ionization of Fe-Co in the hybrid at low pH resulted in low adsorption of the dye
due to competition.
Meanwhile, inorganic pollutants have also been removed by clay based composites. Just of recent,
Owolabi et al [59] evaluated the dynamics and performance of polymer-clay (polyvinyl alcohol-kaolinite)
based composites for the removal of Pb ions in a fixed bed. The adsorption capacity of the Pb ion was

found out to increase with bed height and initial metal ion concentration. Further the presence of other
cations (Na+ and Ca2+) have strongly reduced the sorption of Pb ions onto the composite due to
competition between ions in the electrolyte and the Pb ions. In similar studies, selenium was removed
from drinking water by adsorption onto chitosan-clay composites and oxides [60]. The adsorption studies
revealed high adsorption capacity of selenium for the composite (18.4 mg/g) compared to Al-oxide and
Fe-oxide (17.2 & 8.2 mg/g). Further, the adsorption onto the composite was not pH dependent and not
influence by the presence of sulphur while it was otherwise for the oxides. More so, enhanced removal of
nitrate was obtained by novel composite made by nanoscale zero valent iron supported on pillared clay
[61]. Results showed complete removal of nitrate was obtained by NZVI/PILC which is not possible with
commercial iron or NZVI. Kinetic studies suggested that adsorption of nitrate by PILC enhances mass
transfer of nitrate ions from solution to iron surface thus expedite reduction rate.

2.4.2

Clay as Support or Substrate for Catalyst/Photo Catalyst

Yu et al [62] immobilized nano-scaled titania by interacting hydrothermally prepared DEA-TiO2 in

CTAB on surface of MMT. After calcined at 5000C, results of comparative photo catalytic degradation of
methyl orange by modified composite was 10% higher than efficiency of Degussa P25. In similar studies,
Karamanis et al [63] supported TiO2 on sepiolite and evaluated its degradation efficiency using naphthol as a model pollutant. In all the studied cases, the prepared nanocomposite exhibited high
activities than using bare TiO2. In the same vein, Frost et al [64] immobilized anatase on laponite by
reacting TiOSO4 with laponite and used it for degradation of pesticides. The porous photo catalyst
demonstrated high degradation rate than P25 based on amount of photo active phase per unit mass of the
clay mineral. More importantly this catalyst has high settling properties than P25, thus enhancing post
treatment separation from slurry system. Meanwhile, Fe supported on ball clay has been reported as
effective heterogeneous catalyst for decoloration of Reactive Blue 4 [65]. Up to 99% decoloration was
obtained within 140 min. reaction time under optimum condition. In a related report, nanosized -Fe2O3
(hematite) was supported on Algerian clay and used for degradation of Cr VI ion [66]. Uniformly spread
hematite was observed with high specific surface area (140 m2/g) and remarkable degradation of Cr VI
was obtained in less than 3h.
3.0 FUTURE AND CHALLENGES
No doubt clay minerals and its functionalized products have found wide applications in environmental
remediation technology. However, it has not been widely employed in storage of nuclear waste. The
engineering properties of clay minerals and its adsorption capacity can be explored in the storage of
radionuclides and other waste from nuclear plant. The selectivity and specificity of clay minerals towards
pollutant is one of the main challenges in water treatment because most wastewater contains numerous

organic and inorganic pollutants. Therefore, it is of paramount important to developed multifunctionalized

clay adsorbents capable of adsorb both ionic and non-ionic organic and inorganic pollutants. Adsorbents
with multiple adsorption sites must be investigated.
Further, the charged layers of clay minerals render it less effective for organic pollutants and low thermal
stability of organic molecules in organo-modified clays made its regeneration very difficult. Biological
degradation, photo-assisted oxidation, chemical oxidation, supercritical extraction and thermal desorption
were some of techniques for regenerating spent adsorbents from wastewater but not all these techniques
are suitable, most especially for organo-modified clay adsorbents due to either technical or economic
feasibility. Therefore, commercial method of adsorbent regeneration must be investigated.
4.0 CONCLUSION
Clay minerals are excellent adsorbents for cationic pollutants but have less affinity for anionic and nonionic pollutants most especially organic pollutants due to it hydrophilic nature. It can be easily modified
by both metallic polycations and organic cations due to its layer charge and exchangeable interlayer
cations. Organically modified clays are hydrophobic and have excellent removal of organic pollutants but
cannot be regenerated by thermal desorption. Organo-silane modified clays are the only multifunctionalized clay adsorbent developed so far and can be easily recuperated by thermal desorption.
Polymer-clay composites are emerging materials in environmental remediation technology. Clay minerals
are good substrate to immobilize catalyst and photo catalyst. Clay minerals are promising materials in
nuclear waste storage. Finally, multi-functionalized clay adsorbents must be developed.

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