DOI: 10.5772/intechopen.

76380

Provisional chapter
Chapter 3

Heavy Metals
Removal of Heavy Metals Using
Using Bentonite
BentoniteClay
Clayand
and
Coagulants
Inorganic Coagulants

Oupa
Oupa I.I. Ntwampe and Kapil
Ntwampe and Kapil Moothi
Moothi

Additional information isis available

Additional information available at
at the
the end
end of
of the
the chapter
chapter

http://dx.doi.org/10.5772/intechopen.76380

Abstract
Heavy metals have always been defined as elements with a density higher than 5 g/cm3.
They are regarded as serious wastewater contaminants with detrimental effect to human
and environment. Their removal from wastewater poses a serious challenge as they
require cost-effective reagent and treatment technique. About 200 mL solution of acid
mine drainage (AMD) collected from the Western decant in Krugersdorp, South Africa
was poured into five 500 mL glass beakers. Three different sets of experiments (employing
mixing, shaking and no mixing) were conducted using a jar test and a shaker with 1.5 g
bentonite clay, 20–60 mL of 0.043 M FeCl3 and Al2(SO4)3 and a flocculent of bentonite clay
and FeCl3 dosage, respectively. The experiments were conducted without pH adjustment.
The samples settled for 1 hour after which the pH, conductivity and turbidity were
measured. The results show that a combination of bentonite clay and FeCl3 exhibits a
better turbidity removal efficiency compared to the samples with bentonite clay, FeCl3 and
AlCl3 respectively. The variation of the turbidity removal in the samples with mixing
shaking and without mixing is insignificant, showing that destabilization-hydrolysis
depends upon the strength of the reagent and the physicochemical properties of the
solution. The results also show that hydrolysis occurs at low pH, indicating that it plays
an insignificant role in destabilization. The SEM micrographs show that turbidity removal
is a physical phenomenon.

Keywords: heavy metals, wastewater, pH, turbidity, destabilization

1. Introduction

Heavy metals have always been defined as elements with a density higher than 5 g/cm3 [1, 2].
On the contrary, most of the heavy metals have density equal or less than 3 g/cm3, hence the
name has been changed to toxic metals. Heavy metals are geologically occurring substances

© 2016 The Author(s). Licensee InTech. This chapter is distributed under the terms of the Creative Commons
© 2018 The Author(s). Licensee IntechOpen. This chapter is distributed under the terms of the Creative
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distribution, and eproduction in any medium, provided the original work is properly cited.
distribution, and reproduction in any medium, provided the original work is properly cited.
34 Heavy Metals

which react physicochemically to form economic mineral resources such as coal, gold and
copper, among others. They have a semi- or non-degradability property and can accumulate
in the food chain, causing danger to human [3, 4]. Apart from their toxicity, they play a pivotal
role in domestic and industrial activities. Drinking contaminated water containing heavy
metals even in very small quantity may be detrimental to human and aquatic life [4]. A wide
range of research projects has been exploited relating to new trends of removing heavy metals
from industrial wastewater [5]. Some of the metals are both toxic and radioactive, e.g. ura-
nium, which is normally embedded in mineral deposits of other metals such as gold, radium,
selenium and thorium. There are some of the heavy metals, i.e. arsenic, cadmium, chromium,
lead and mercury, which are classified as priority metals due to high toxicity to public health
[6]. Despite their toxic nature, their use is unavoidable as they are necessary in daily activities
of economic value, including metal-containing compounds [7–10]. Apart from normal natural
causes, heavy metals are also introduced to the environment through natural phenomena such
as weathering and volcanic eruptions [7, 11–14]. They are mostly transition elements where
some are metalloids, e.g. arsenic, exhibiting toxicity at low level to soil, vegetation, rivers [6, 10,
11]. Environmental degradation is caused by the emissions from power utilities, mining and
chemical industries is a serious global concern. The latter is responsible for the high concentra-
tion of lead and chromium in several water bodies, predominantly due to lack or ineffective
purification systems [15]. On the other hand, some of the heavy metals, i.e. lead and chro-
mium, are toxic and carcinogenic in their oxidation state, e.g. Pb2+ and Cr3+, respectively [16].
Coal and gold mining discharges wastes or wastewater (Figure 1) are highly polluted with
heavy metals. Alternately, they are the source of pyrite (FeS2), a geologically, chemically or
microbially formed mineral derived from the reaction between iron and sulfur under thermal
conditions [17].

Apart from the economic value associated with heavy metals (mineral resources), they play a
pivotal role in the formation of clay. On the other hand, clay minerals form a larger fraction of
coal and also used as catalysts during coal combustion (oxidation). Extensive alteration of
rocks to the formation of clay minerals produces relatively pure clay deposits that serve a
variety of economic applications such as manufacturing of cooking pots, bricks, porcelain,
drainage pipe, floor and wall tiles, tobacco pipes, oil drilling, cat litter, heat resistant tiles,
construction of lime mortars, building materials and equipment, among others [18, 19]. Some
are fluxing agent and carry some problematic compounds which are responsible for slagging

Figure 1. Geochemical surface feature along the river concentrated with metals (www.earth.illinois.edu).
 Removal of Heavy Metals Using Bentonite Clay and Inorganic Coagulants 35
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and clogging of the boilers of the power utilities. Some are emitted to the atmosphere during
industrial operation, thus causing a serious environmental catastrophe. Disposal of the
chemicals and barren ore deposits which are polluted with heavy metals is the main attribute
to the environmental degradation, which is predominant in the dumping sites.

2. Impact of waste materials on the environment

The purpose of this review does not cover the use of the heavy metals in industrial processes,
i.e. cyanide and mercury, among others. The impact of heavy metals is mostly apparent in
tailing dumps. Tailings contribute towards environmental degradation, and the impact does
not take into account the amounts of toxic materials they contain. They host heavy metals,
predominantly gangue minerals such as silicates, oxides, hydroxides, carbonates and sulfides.
Some of the heavy metals in the tailings exist as iron-sulfide minerals, e.g. pyrite, pyrrhotite,
chalcopyrite, arsenopyrite (FeAsS), sphalerite (ZnS) and galena (PbS), whereas others contain
sulfur-containing minerals (Pb, Zn, Cd, Se, As) and compounds that are critically harmful.
Apart from that, sulfide-bearing tailings can be oxidized during weathering before the forma-
tion of the AMD and release metals/metalloids (As, Cd, Co, Cr, Cu, Fe, Hg, Mn, Ni, Pb and Zn)
[9]. The toxic metals are distributed throughout the environment by severely leaching out into
the surroundings, causing serious health problem due to non-degradable property [20]. The
leaching of the heavy metals into the soil may endanger natural population of bacteria, leading
to disintegration of bacterial species responsible for nutrient cycling, thus affecting the ecosys-
tem negatively [21]. Under such conditions, they have to devise means of survival under such
adverse conditions, i.e. develop and establish detoxifying mechanisms (biotransformation,
biosorption and bioaccumulation) [22].

Uranium, the most radioactive element, has a molecular weight of 238.03 mol/g and detrimen-
tal to humans through chemical toxicity, radiation and other uranium by-products. It is highly
harmful and can lead to kidney, respiratory and neurological dysfunctionalities [23]. It exists in
six radioactive isotopes (232–238) as classified from mother element which causes instability of
the highly reactive nuclei. Its radioactivity becomes apparent when the nucleus emits minute
particles during elemental transformation (radioactive decay), when α and β particles and γ-
rays are emitted. Figure 2 illustrates the spillage of radioactive uranium. There are countries
where millions of tons of tailing cover wide areas, considering South Africa (SA) which
produced over 43,500 tons of gold and 73,000 tons of uranium within 1953–1995. The basin
covers an area of 1600 km2 leading to 400 km2 tailings dams which contained 6 billion tons of
pyrite tailings and 430,000 tons (600,000 t) low-grade uranium. That resulted in the contami-
nation of about 6000 km2 of soils gold mining operations [24].

The most detrimental effects of uranium to human and environment include (1) aquatic
physiological defects and fatalities, (2) disruption of water bodies, i.e. aquatic physiological-
biochemical process, (3) deterrence of aquatic activities due to the presence of Fe, Zn, Cu, Mn
and Pb, (4) disturbance of biodiversity of aquatic life, (5) depression of the dissolved oxygen
in the water bodies, (6) modification of the nutrient availability which may cause loss of
36 Heavy Metals

Figure 2. Spillages and remaining of dumps of uranium in West Rand (SA) [24].

Fraction Name Chemical formula

Gauge Quartz SiO2

Mineral K-feldspar KAlSi3O8
Na-feldspar NaKAlSi3O8
Ca-feldspar CaKAl2Si2O8
Serisite KAl (AlSi)(F,OH)
Chlorite (Mg,Fe)3(Si,Al)4O10(OH)2(OH)6)
Calcite CaCO3
Dolomite Ca,Mg(CO3)2
Sulfide-oxide Pyrite/pyrrhotite FeS2/FeS
Arsenopyrite FeAsS
Galena PbS
Sphalerite ZnS
Chalcopyrite CuFeS2
Magnetite Fe3O4

Table 1. Mineralogy of a tailing dump in South Africa [29].

vegetation, (7) change of the direction of the roots growth and (8) cause of ailments due
building up in aerian organs of plants and human.

Lead (Pb) and chromium (Cr) are toxic metals especially to plants and animals and cannot be
easily treated due to non-biodegradability and subjection to bioaccumulation in living cells
[25, 26]. They can form multiple-oxidation states, where Cr forms Cr2+, Cr3+ and Cr6+, the
highly toxic and reactive and highly soluble in solutions of varying pH values [27]; however,
their toxicity is less compared to Cr6+. Pb is a bluish-white, soft metal, which is highly flexible
and ductile and resistant to corrosion [28]. The types of mineral matter (Table 1) are complex
compounds, which are main constituents of both clay and coal.
Oxidation of the pyrite acidifies the water percolating through the dumps, which then enters
the groundwater regime beneath the dumps [30]. This acidic water is believed to be entering
 Removal of Heavy Metals Using Bentonite Clay and Inorganic Coagulants 37
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Figure 3. Gold mine tailing dumps in Johannesburg, South Africa (UGS stock photo by George Steinmetz).

streams along the Witwatersrand in SA [30, 31]. Apart from direct metals contamination,
tailings are also sources of environmental degradation. Gauteng Province (SA) is highly con-
centrated with tailings, which contaminate the environment through metals leachate during
heavy rainfall [30]. Figure 3 illustrates tailing dump.
A general characteristic of tailings is the pyrite content of up to 6% pyrite, highly saline, low
nutritional value and low organic matter content [32–34]. High sulfide content causes high
acidity and high metal concentrations in groundwater around the proximity of the tailings
[32]. Rafiei et al. [35] reported a pH value of 7.35 in gold mine tailings in Iran, whereas Mitileni
et al. [36] reported pH values of 3.25–6.28 in South Africa. Harish et al. [37] reported pH value
of 3.48–8.12 in India. pH is essential to aquatic life as different species behave differently,
whereby high soil acidity from mine pollution may destroy microbes responsible for breaking
down organic matter into nutrients. In addition, acidity can dissolve aluminum to form free
organic materials, which is toxic to plant roots, and also reduce the concentrations of essential
nutrient. The characteristic features of gold mine tailings are the elevated concentrations of
toxic heavy metals, i.e. As, Cd, Ni, P, Cu, Zn, Co and Hg [38].

3. The effect of chemical treatment to the ecosystem

Industrial and population expansions are the main attributes to increasing concentration of
heavy metals, and inevitably, their escalating quantity is uncontrollable as their genesis is
natural and anthropogenic [39]. Gold mining has been identified as an operation which results
in the accumulation of thousands of voluminous tailings dumps scattered all over the coun-
tries, potentially degrading the ecosystem [40]. Nuclear power generation is another source of
toxic waste generation as it uses uranium as fuel. The problem with nuclear is its difficulty in
handling waste materials. This review study suggests that one of the solutions around the
management of toxic minerals is proper mineral processing using mineral liberation-
classification, but mineral slipping is inevitable. Although mineral liberation-classification
does not produce all the minerals in their pure form, some are in complex compounds which
require further separation. There is an enormous amount of waste generated during various
processes, especially in gold mining where approximately 99% of the waste disposal consists
mainly of ore [41]. The use of bacteria is another technique but the main problem is the rate of
38 Heavy Metals

production and the timing for their growth as they rely mainly on pH and temperature. The
pH-dependent bacteria, e.g. acidophilic, chemolithotrophic iron- and sulfur-oxidizing bacteria,
assist in solubilizing the sulfides contained in the gold ore deposits by liberating gold from the
deposit [42]. Although biomining poses less danger to the environment than many physico-
chemical extraction processes [42], it is perceived to be unsustainable. Bacteria such as
Acidithiobacillus obtain energy by oxidizing Fe2+ to Fe3+ ions or elemental sulfur (S0). Eqs. (1)–
(3) illustrate oxidation-reduction of iron and sulfur from pyrite, a mineral exposed during both
gold and coal mining. The bacteria (acidithiobacvillus) obtain energy by oxidizing ferrous iron
(Fe2+) to ferric iron (Fe3+) or reduction of elemental sulphur (S0) to form sulphuric acid [45, 46],
thus resulting in the production of AMD.

2 S0 þ 3 O2 þ 2 H2 O ! 4 Hþ þ 2 SO4 2 (1)

FeS2 ðAuÞ þ 2 Fe3þ ! 3 Fe2þ þ 2 S0 þ ðAuÞ (2)

FeS2 ðAuÞ þ 14 Fe3þ þ 8 H2 O ! 15 Fe2þ þ 2 SO4 2 þ 16 Hþ þ Au (3)

Another distinct characteristic of the bacteria in gold purification includes their ability to
excrete ligands that stabilize gold by forming gold-rich complexes and/or colloids [43–45]. This
review invokes the functions and integrity of the use of bacteria in gold purification, but
residual heavy metals remain a challenge, moreover that they form part of waste which is a
danger to the ecosystem.
Mercury, one of the toxic metals used in gold purification, is accomplished by mixing it with
mineral ore deposits extracted from the ground or stream beds to form an amalgam. The
burning of the latter vaporizes elemental mercury into a toxic plume, resulting the separation
of the gold from the ore deposit. The technique is globally regarded as the second largest
source of atmospheric mercury pollution after coal combustion [46]. Apart from mercury,
cyanide is another toxic metal which is employed in gold purification process (Eq. (4)), a two-
stage process which includes extraction and recovery. Eq. (4) shows dissolution of gold:

4 AuðsÞ þ 8 NaCNðaqÞ þ O2 ðgÞ þ 2 H2 OðlÞ ! 4 NaAuðCNÞ2 ðaqÞ þ 4 NaOHðaqÞ (4)

Cyanide, one of the toxic metals, is employed in the extraction process of gold. The process also
uses another toxic metal, i.e. zinc to cement cyanide solution [46]. Environmental degradation
occurs during the spillages of cyanide solution, whereas activated carbon can also be used
when the gold content is high. The ground and crushed ore deposits are enclosed in large
tanks with agitators to dissolve gold which then adhere to particles of activated carbon. The
activated carbon and the gold are separated from the solution, which is discarded together
with the leached ore [46]. The residual trace heavy metals from the process act as potential
hazards to the ecosystem. It has been noted that sludge from gold and cold operations contains
mercury amalgam, cyanide, uranium and mineral matter, among others. Since gold recovery
from ore deposit is not 100%, small quantities remained in the tailings, where they will
subsequently decompose to form other complexes or react with other toxic substances to form
new toxic compounds.
 Removal of Heavy Metals Using Bentonite Clay and Inorganic Coagulants 39
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Lime has been used in previous studies to regulate the pH of the AMD solution [47]. The
challenge with such a technique is excess sludge generated, which requires further treatment
of heavy metals polluted sludge. Instead, the sludge is pumped to large dumps (slimes dumps).

4. The effect of metal salts during the removal of turbid materials

Mine wastewater and AMD are the main carriers of the heavy metals produced from mining
operations. According to a trend of various studies to investigate a cost-effective mine waste-
water treatment, the use of inorganic coagulants seems to be regarded as a primitive technique.
The study conducted in this review study focuses on conventional treatment process using
inorganic coagulants. Their advantage is based on their hydrolysis potential to form flocs
which are adsorbents. In case of Fe, there are at least four species that co-exist in aqueous
solution in the pH range of 1–5, namely Fe3+, Fe(OH)2+, Fe(OH)2+ and a very small fraction of
dimer Fe2(OH)24+ [48]. On the other hand, Al species prefer a slightly higher pH than Fe in a
range of 3–8. Apart from positive contributions, naturally formed iron is a source of AMD
formation. It reacts with sulfur through a geological phenomenon to form FeS2, which has
negative environmental impact. Pyrite is not toxic as a mineral until it is oxidized by oxygen in
an aquatic medium to form sulfuric acid, an environmental degradation agent, Eq. (5).

2 FeS2 þ 7 O2 þ 2 H2 O ! 2 Fe2þ þ 4 SO4 2 þ 4 Hþ (5)

Fe2+ ions may be oxidized to form Fe3+ ions (Eq. (5)), which oxidize excess pyrite:

FeS2 þ 14 Fe3þ þ 8 H2 O ! 15 Fe2þ þ 2 SO4 2 þ 16 Hþ (6)

Eq. (6) yields unstable Fe2+ ions species which are further oxidized by excess Fe3+ ions that are
subjected to hydrolysis when added to wastewater.

The catastrophe associated with the AMD (Figure 4) is not only about the surface or ground
water pollution and degradation of the quality of the soil, but endanger it poses to aquatic
sediments and fauna, allowing heavy metals to seep into the environment.

Figure 4. Diagram of AMD pumped from the underground workings [48].

40 Heavy Metals

Long-term exposure to drinking water polluted with AMD may lead to increased rates of
ailment such as cancer, decreased cognitive function and appearance of skin lesions. Heavy
metals in drinking water may impair the development of the neurons of the fetus, resulting in
mental retardation. In addition, AMD is attributed to loss of stream bed, drying of the rivers,
limited water supply for growing industrialization and population and limiting the quantity of
water for irrigation. Acidified water (AMD) seepage from the mine tailing dumps concentrated
with heavy metals causes serious environmental degradation especially stream flow around
the vicinity [49, 50]. The condition reduces the pH and adds high metal loads to the water
resulting in extreme iron hydroxide precipitation in the stream which endangers aquatic life.
Possible evaporation of groundwater from the capillary zone above the water table may
contaminate the surface soil layer with heavy metals. Dissolution of the metals on the Earth’s
crust and surface soil may add to the metals load in the stream. The oxidation of iron intro-
duced into the stream by seepage may behave as redox buffer, controlling the pH of the stream
water. Increasing the pH of AMD above 3, either through contact with fresh water or neutral-
izing minerals, precipitates Fe3+ ions to form iron hydroxide species. Other types of iron
precipitates are possible, including iron oxides and oxyhydroxides [48]. All such species cause
discoloring of the water and smother aquatic plant and animal life, disrupting stream ecosys-
tems.
Literature [47] states that optimal removal of turbid materials occurs in an alkaline medium;
however, the findings of this review portray a different view. Despite the findings of this
review, the results of the studies on the AMD samples using inorganic coagulants, metal
hydroxide and bentonite clay [51, 52] revealed that the removal of turbid materials/heavy
metals is dependent upon the physicochemical properties of both the colloidal suspension
and the reagents and that which also includes structural morphology of the flocs (SEM micro-
graphs).The hypothesis relating to pH adjustment is not only depend upon the metal hydrox-
ide but also the OH ions released from the cleavage of bipolar water molecules. This is based
on the high ionic strength of the AMD and the charges in the solution to enhance dehy-
droxylation of hydrated metal ions, releasing the OH ions which react with metal ions to
form metal hydroxide precipitates.

5. Factors that affect the removal of heavy metals

A lot of studies have been conducted on the investigation of ideal techniques employable in the
removal of heavy metals, but most are costly and complicated in operation. Factors, such as
dosage, destabilization-hydrolysis, time, concentration of the heavy metals, type of colloidal
suspension, the reagent(s), temperature, retention time, sorption capacity and structural mor-
phology of a substrate, among others, are most influential during treatment. Although pH is
considered as a determinant of the removal of turbid materials as alluded later, studies
conducted by Ntwampe et al. [53, 54] on paint wastewater and AMD using traditional inor-
ganic coagulants, metal hydroxide or bentonite clay revealed that pH of the colloidal suspen-
sion plays an insignificant role in the removal of turbid material/heavy metals. The studies
revealed that the optimal removal of turbid materials is a physicochemical phenomenon,
 Removal of Heavy Metals Using Bentonite Clay and Inorganic Coagulants 41
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which is determined by the rate of destabilization-hydrolysis. Although the reaction consists of

two reactions, this review considers them as a single stage because of their co-existence, i.e.
destabilization occurs on the colloidal suspension whereas hydrolysis on the metal ions [55].

5.1. Destabilization-hydrolysis reaction

In this reaction, the reagent disturbs the equilibrium state of a colloid due to equal counter
forces of van der Waals attractive and electrostatic repulsive force [56, 57]. The reaction which
is a physico-chemical phenomenon, determines the effectiveness of the succeeding reactions.
The colloid is separated into two ionic regions, namely diffuse and Stern layers to form
electrical double layer (EDL) [58]. The efficiency of a reagent during treatment is determined
by the ability to compress EDL, resulting in the reduction of the radius which enhances
particle-particle collision to form agglomerates, flocs.

5.2. Type of a colloid

Colloids are classified according to hydrophilicity (water-loving) or hydrophobicity (water-

hating), where treatment with the former is difficult as turbid materials dissolve completely in
the solvent, making flocculation difficult. On the other hand, hydrophobic colloid consists of
suspended solids, some of which settle spontaneously due to gravitational force [58].

5.3. Type of a reagent

An effective coagulant is characterized by destabilizing potential attributed to high valence

and electronegativity. This is apparent after addition to a colloidal suspension when the metal
ions of a salt disperse throughout the colloidal particle to destabilize the system, resulting in
flocs formation. Nucleation occurs and small flocs form larger flocs, which remove turbid
materials [58].

5.4. Structural morphology

The crystal morphology shown by the scanning electron microscopy (SEM) micrographs is
illustrative of the ability of a reagent to adsorb the absorbate. Most of the SEM micrographs
which correspond to optimal adsorption consist of dense flocs joined together with limited or
without voids [51]. Such a SEM micrograph is indicative of no slipping through of the turbid
materials (heavy metals); on the contrary, the SEM micrograph with flocs and voids has less
adsorption potential [51].

5.5. pH of the solution

Some studies [59–61] state that the rate of adsorption of turbid materials/heavy metals is more
favorable in an acidic colloidal suspension, i.e. low pH. This observation is in agreement with
aforementioned studies revealing that the treatment of the AMD using inorganic coagulant(s)
without pH adjustment yields optimal adsorption. An acidic solution is highly concentrated
with hydronium ions (H+), which are prone to strengthen the electrostatic forces of attraction
42 Heavy Metals

between negatively charged heavy metal oxyanions and protonated sorbent, and the reaction
occurs according to Eq. (7).

Fe0 þ 2 Hþ þ Fe2þ þ H2 (7)

Fe2+ can be further oxidized to form Fe3+.

2 Fe2þ ðaqÞ þ 2 Hþ ðaqÞ þ 0:5 O2ðaqÞ ! 2 Fe3þ ðaqÞ þ O (8)

6. Treatment of the AMD to remove heavy metals

The removal of heavy metals from industrial effluent discharge has been a serious challenge
for decades due to the complex compounds formed during chemical reactions. The wastewater
consists of metals as pure and trace elements, where the latter always disperse throughout the
solution and sorbed onto other compounds or form other compounds during nucleation. The
problem associated with trace elements or compounds consisting of trace elements is a plausi-
bility to slip through the adsorbents. The residual heavy metals are caused by the existence of
the trace elements in the system [62], a problem caused by low adsorption potential of an
adsorbent in a medium with low concentration of absorbate. Technologies such as membrane
separation, electrochemical, precipitation, ion exchange and adsorption were investigated to
treat wastewater/AMD [63]. The results showed that they are expensive and incur high waste
disposal costs, apart from high costs, some studies [64] revealed that some of the new technol-
ogies have a tendency of regenerating pollutants back to the environment by producing toxic
chemicals such as sodium borohydride (NaBH4). Chemical reaction between iron salt and
sodium borohydride to release flammable hydrogen gas [65] is shown in Eq. (9).


4Fe3þ þ 3BHþ þ
4 þ 9H2 O ! 4F ↓ þ 3H2 BO3 þ 12H þ H2 ↑
0
(9)

Some studies were conducted [51, 54] to reduce turbid materials from AMD using a combina-
tion of bentonite clay and inorganic coagulants. Among their studies, a combination of ben-
tonite clay and Na2CO3 [53] was employed to remove the heavy metals from the AMD sample.
Inorganic coagulants, mainly the metal ions (Mn+), have exhibited a significant influence in
wastewater and AMD treatment [51–53], including the pivotal role played by the bentonite
clay. There are more studies which have been conducted in the treatment of AMD sample
using a variety of metal salts without or with a combination of bentonite clay [51–53]. The
results show that the turbid materials removal efficiency of inorganic coagulants is optimal
when dosed alone or in combination. The observations show that they are all subjected to
hydrolysis to form species which are adsorption substrates. On the other hand, bentonite clay
also exhibits ionic exchange, sorption and intercalation as the main reactions leading to the
removal of turbid materials/heavy metals [52, 53]. The mineralogy of the AMD (Table 2), i.e.
pH and conductivity of the AMD sample, treated with a combination of bentonite clay and
Na2CO3 with mixing is shown in Figure 5.
 Removal of Heavy Metals Using Bentonite Clay and Inorganic Coagulants 43
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Element Conc. (ppm)

Al 1.171
Ca 182.1
Co 39.7
Cu 0.14
Fe 28.3
K 4.5

Mg 67.3
Mn 35.3
Na 44.5
Ni 27.6
Pb 35.2
As 45.2
Se 0.71
Zn 31.7

Table 2. ICP-OES analyses of untreated AMD sample with clay (5 dilution).

Figure 5. Residual turbidity of AMD with FeCl3, Na2CO3 and a combination of bentonite clay and Na2CO3 with and
without mixing and shaking.

According to Table 1, the concentration of the metals, i.e. Ca, Mg and Na, in the AMD is high,
182, 67 and 46 ppm, respectively, and that of non-toxic heavy metals, Fe and Mn, is 28 and
35 ppm, respectively. The concentration toxic metal content, Co, Ni, Pb, As and Zn is also high,
the main toxic metals to the ecosystem.

The turbid materials of the AMD (Figure 5) are identified as turbidity, which includes
the suspended and soluble solids, inorganic material, heavy metals and any trace substances.
44 Heavy Metals

The treatment with shaking and without mixing does not form part of this review study and
therefore will not be elucidated extensively. Owing to a high turbidity of the AMD sample,
residual turbidity below 10 NTU is highly acceptable, 10–15 NTU acceptable, above 15–20
NTU moderately acceptable and above 20 NTU is poor. However, the experimental results of
the samples with FeCl3 and Na2CO3 mixing are in the range of 8.4–14.0 and 8.2–16.5 NTU,
respectively. Notwithstanding the fact that they are both efficient, dosage in a pure form is
unaffordable compared to the dosage recommended in the study by Ntwampe et al. [51],
which includes the investigation of the efficiency of bentonite clay in AMD treatment. Table 3
shows the weight percentage of the mineral matter of the bentonite clay.
The weight % mineral content (Table 3), where CO2 and FeO representing siderite (FeCO3)
form a larger weight % (33.2 and 45.3 wt. %) of the total complex compounds contained in both
coal/gold mineral composition, and the rest are trace elemental compounds. The particle size
of the bentonite clay is 180 μm mesh size with intensive mineral liberation (Table 3). The
mineralogy of the tailing dump (Table 1) shows complex compounds of which some are
original and others reacted to form new complex compounds; however, the chemical com-
pounds are also representative of the clay minerals. Pulverizing the mineral compound
(Table 1) results in minerals liberation to form simple compounds (Table 3). The elements/
metals with high weight percentage include Fe, K and O, an indication of oxidation-reduction
of ferric and ferrous ions during chemical reactions. A simple chemical composition of simple
compounds (Table 3) indicates a high rate of chemical reactions by the colloid or the reagent(s).
The residual turbidity in the samples with bentonite clay mixing is in a range of 9.8–12.0 NTU,
without mixing in a range of 10.5–19.2 NTU and shaking in a range of 10.4–13.3 NTU. As
indicated, the method of chemical dispersion, i.e. mechanical agitation, is insignificant in this
review, and the focus is on the efficiency of the combination of bentonite clay and Na2CO3
during AMD treatment. The mineral matter composition and structural configuration of the

Element Wt.% Wt.% Atomic% Compd% Formula No. of ions

CK 9.07 0.46 16.55 33.22 CO2 2.15

Mg K 0.91 0.08 0.82 1.50 MgO 0.11
Al K 1.56 0.08 1.26 2.94 Al2O3 0.16
Si K 5.06 0.13 3.95 10.82 SiO2 0.51
SK 1.48 0.10 1.01 3.69 SO3 0.13
Ca K 1.14 0.08 0.62 1.60 CaO 0.08
Ti K 0.53 0.09 0.24 0.89 TiO2 0.03
Fe K 35.25 0.49 13.84 45.34 FeO 1.79
O 45.02 0.58 61.70 8.00
Total 100.00

Where Wt is weight and Compd is compound.

Table 3. Weight % of the mineral content in the bentonite clay.

 Removal of Heavy Metals Using Bentonite Clay and Inorganic Coagulants 45
http://dx.doi.org/10.5772/intechopen.76380

bentonite clay play a pivotal role during treatment process. The former identifies the metals
and content present in the colloidal suspension, the information which are indicative of inev-
itable electrochemical reactions. On the other hand, the latter is distinguished by the planar
layers, which include octahedral and tetrahedral formation to form T-O-T. According to min-
eralogy of the bentonite clay (Table 1), dehydroxylation and processes are plausible. On the
other hand, the structural configuration (T-O-T) is effective in sorption by intercalation of the
turbid materials (heavy metals) onto the sheets and porous surface of the bentonite clay. In
addition, the mineralogy (Table 1) is indicative of a series of physicochemical reactions in the
system, especially on the serisite and chlorites, and oxidation of Fe on the iron-bearing com-
pounds (chlorite, pyrite, pyrrhotite, arsenopyrite, chalcopyrite and magnetite). The formation
of CO2 from the decomposition of dolomite is inevitable, including oxidation of metals and
other physico-chemical reactions. These form the main chemical reactions occurring in the
bentonite clay in the system to form new simple compounds suitable for further reactions or
sorption. Na2CO3 component in the flocculent also plays a pivotal role which includes increas-
ing of the pH when it solubilizes to NaCO3 and CO32. A slight pH rise decreased the
solubility of the metals in the colloidal suspension, thus ameliorating the rate of agglomera-
tion. Table 4 illustrates the ICP-OES results of treated AMD samples.
The results of the treated AMD with a bentonite clay mixing (Table 4) show a considerable
heavy metals removal of As, Co, Ni, Pb and Zn from 45.5, 39.7, 27.6, 35.2 and 31.7 to 4.1, 3.2,
6.6, 5.4 and 4.8 ppm, respectively. Figure 6 shows SEM micrograph of the sludge of the AMD
samples with FeCl3 (Figure 6A) and bentonite clay (Figure 6B) mixing, respectively.

Element Conc. (ppm)

Al 1.023
Ca 142.1
Co 3.2
Cu 0.14
Fe 19.2
K 4.14
Mg 55.7
Mn 23.1
Na 27.4
Ni 6.6
Pb 5.5
As 4.1
Se 0.71
Zn 4.8

Table 4. ICP-OES analyses of treated AMD sample with clay (5 dilution).
46 Heavy Metals

Figure 6. SEM of samples the sludge of AMD sample with FeCl3 and bentonite clay respectively (25,000) [53].

The SEM micrographs show the dry sludge of the AMD (Figure 6) with FeCl3 (Figure 6A) and
bentonite clay (Figure 6B) dosage. The former shows flocs which are bound together to form
clusters of separate dense and small non-spherical porous structures with some voids in-between
surface. The structural morphology is indicative of subjection of shear stress during treatment.
On the other hand, the micrograph (Figure 6B) exhibits more condensed clusters of flocs with
uniform crystal morphology, showing fewer voids compared to those obtained in Figure 6A.

7. Conclusion

Heavy metals have exhibited both economic and detrimental implications, a condition which
uplifts the economy and degrades the environment, respectively. The removal of heavy metals
from the medium (solvent) is not cost-effective as they sometimes appear as trace elements
which are not easily removable. On the other hand, the trace elements found in tailings accumu-
late with time and form new complex and toxic compounds to the environment. Treatment of
tailings is a very expensive exercise, which has never been deliberated, thus causing degradation
especially after rainfall where the toxic compounds dissolve and disperse throughout the envi-
ronment. A majority of modern technologies which have been explored are not cost-effective and
sustainable, a conclusion emanating from employing sophisticated and foreign equipment. In
addition, developing and underdeveloped countries cannot cope with such expenditures.
The only solution to the existing challenge relating to environmental degradation by the
mine’s wastewater is around a choice of a cost-effective treatment technique, which includes a
simple operation and uses the most abundant reagent(s) that are affordable in any way.
Natural inorganic coagulants have been used to treat industrial wastewater, but the problem
is the damage to plant and equipment when dosed in pure form, i.e. corrosion, scaling or
addition to sludge. The present review investigates the efficiencies of a combination of benton-
ite clay and inorganic coagulants (flocculent) in the treatment of the AMD sample in reduced
mass fraction. Bentonite clay was chosen due to chemical composition and crystal morphology,
which are indicative of effective physicochemical adsorption. On the other hand, inorganic
 Removal of Heavy Metals Using Bentonite Clay and Inorganic Coagulants 47
http://dx.doi.org/10.5772/intechopen.76380

coagulants also employ a physicochemical reaction to remove turbid materials as exhibited by

SEM micrographs, but the bentonite clay is prone to perform better as it applies ion exchange,
adsorption and intercalation. The advantage of the mixture of bentonite clay with inorganic
coagulants in reduced molarity by half, i.e. 50% molarity (m=m %), serves both to reduce their
detrimental effect and alleviate over or underdosage, which may cause restabilization and
deflocculation, respectively. A flocculent, prepared by a combination of bentonite clay and
Na2CO3, employed in the present review exhibited an optimal heavy metals removal potential.

Although some of the inorganic coagulants exhibited optimal turbid materials removal, vary-
ing atmospheric conditions affect the operating conditions during treatment, thus requiring
continuous adjustments. Although it is also plausible that such a phenomenon can still occur
with the flocculent used in this study, bentonite clay always behaves as a principal substrate
due to multiple adsorption characteristics. The other advantage with this technique is that it
does not require pH adjustment as the reagents exhibited a high destabilization-hydrolysis
potential, a reaction which is shown by the removal of the turbid materials. The removal of the
turbid materials from the AMD indicates that bentonite clay and Na2CO3 (flocculent) are
complementary.

Author details

Oupa I. Ntwampe* and Kapil Moothi

*Address all correspondence to: ontwampe@gmail.com

Department of Chemical Engineering, School of Chemical Engineering and Built Environment,
University of Johannesburg, Doornfontein, Johannesburg, South Africa

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