Advances in Colloid and Interface Science 166 (2011) 36–59

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Advances in Colloid and Interface Science

j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / c i s

Industrial wastes as low-cost potential adsorbents for the treatment of wastewater

laden with heavy metals
M. Ahmaruzzaman
Department of Chemistry, National Institute of Technology Silchar, Assam, 788010, India

a r t i c l e i n f o a b s t r a c t

Available online 30 April 2011 Industrial wastes, such as, fly ash, blast furnace slag and sludge, black liquor lignin, red mud, and waste slurry,
etc. are currently being investigated as potential adsorbents for the removal of the heavy metals from
Keywords: wastewater. It was found that modified industrial wastes showed higher adsorption capacity. The application
Industrial wastes of low-cost adsorbents obtained from the industrial wastes as a replacement for costly conventional methods
Fly ash of removing heavy metal ions from wastewater has been reviewed. The adsorption mechanism, influencing
Sludge
factors, favorable conditions, and competitive ions etc. on the adsorption of heavy metals have also been
Red mud
Metals
discussed in this article. From the review, it is evident that certain industrial waste materials have demonstrated
Adsorption high removal capacities for the heavy metals laden with wastewater. However, it is to be mentioned that
Adsorbent adsorption capacities of the adsorbents vary depending on the characteristics of the adsorbents, the extent of
Wastewater treatment chemical modification and the concentration of adsorbates. There are also few issues and drawbacks on the
utilization of industrial wastes as low-cost adsorbents that have been addressed. In order to find out the practical
utilization of industrial waste as low-cost adsorbents on the commercial scale, more research should be
conducted in this direction.
© 2011 Elsevier B.V. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37
2. Current technologies available for treatment methods of heavy metals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37
3. Industrial wastes as an adsorbent for removal of heavy metals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38
3.1. Adsorption of heavy metals on fly ash . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38
3.2. Adsorption of heavy metals on blast furnace slag, sludge and dust . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 42
3.3. Adsorption of heavy metals on red mud . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43
3.4. Adsorption of heavy metals on lignin, a black liquor waste of paper industry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 44
3.5. Adsorption of heavy metals on waste hydroxide, a fertilizer industry waste . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45
3.6. Adsorption of heavy metals on miscellaneous industrial adsorbents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 46
4. Competitive adsorption . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47
5. Leaching of fly ash, red mud, blast furnace slag, and other wastes in water system . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 48
6. Efficiency and cost comparison . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50
7. Combination of methodologies/techniques . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50
8. Adsorption isotherms and mechanism . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51
9. Kinetic modeling of adsorption in a batch system . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 53
10. Factors affecting adsorption of heavy metals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 53
10.1. Effect of contact time and initial concentration of heavy metals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 53
10.2. Effect of pH . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 53
10.3. Effect of particle size . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 54
10.4. Effect of ionic strength . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 54
11. Column studies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 55
12. Comparison of adsorption performance . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 55

E-mail address: md_a2002@rediffmail.com.

0001-8686/$ – see front matter © 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.cis.2011.04.005
 M. Ahmaruzzaman / Advances in Colloid and Interface Science 166 (2011) 36–59 37

13. Discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 56
14. Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 57
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 57

1. Introduction reduce hazardous metals present in the effluents. Activated carbon –

Contamination of water by toxic heavy metals through the dis-
charge of industrial wastewater is a worldwide environmental problem.
Rapid industrialization has seriously contributed to the release of toxic
heavy metals to water streams. Mining, electroplating, metal processing,
textile, battery manufacturing, tanneries, petroleum refining, paint
manufacture, pesticides, pigment manufacture, printing and photo-
graphic industries [1,2] are the main sources of heavy metal ion con-
tamination. Metals such as lead, cadmium, copper, arsenic, nickel,
chromium, zinc and mercury have been recognized as hazardous heavy
metals. Unlike organic wastes, heavy metals are non-biodegradable and
they can be accumulated in living tissues, causing various diseases and
disorders; therefore they must be removed before discharge.
Heavy metal toxicity can result in damage or reduced mental and
central nervous function, lower energy levels and damage to blood
composition, lungs, kidneys, liver and other vital organs. Presence of
metals in water streams and marine water causes a significant health
threat to the aquatic community — most common being the damage of
the gill of the fish [3,4]. Consequently, in many countries, more strict
legislation has been introduced to control water pollution. Various
regulatory bodies have set the maximum prescribed limits for the
discharge of toxic heavy metals in the aquatic systems. However, the
metal ions are being added to the water stream at a much higher
concentration than the prescribed limits by industrial activities, thus
leading to the health hazards and environmental degradation. Table 1
shows the permissible limits and health effects of various toxic heavy
metals [5–8]. Removal of metal ions from wastewater in an effective
manner has become an important issue today. Precipitation followed
by coagulation has been extensively employed for the removal of heavy
metals from water. However, this process usually produces large
volumes of sludge consisting small amounts of heavy metals. Membrane
filtration is a proven way to remove metal ions but its high cost limits
the use in practice [3]. Adsorption is one of the most effective pro-
cesses of advanced wastewater treatment, which industries employ to
produced by carbonizing organic materials – is the most widely used
adsorbent. Activated carbon has shown good metal ion adsorption
capacities [9–13]. However, the high cost of the activation process limits
the utilization in wastewater treatment. Over the last few years, a large
number of investigations have been conducted to test the low cost
adsorbents for the removal of heavy metals. Waste biomass, industrial
waste, and mineral waste have been investigated by many workers and
biomass has shown better adsorption properties [14].
An overview of some industrial wastes as low-cost adsorbents is
presented in this paper and their removal performance is compared.
The main goal of this review is to provide a summary of informa-
tion concerning the use of industrial waste materials as adsorbents for
the removal of heavy metals from wastewater. The review also
presents some critical issues and drawbacks on the utilization of
industrial wastes as low-cost adsorbents. This review also (i) presents
a critical analysis of these industrial waste materials; (ii) describes
their characteristics and (iii) discusses various factors and mecha-
nisms involved. A comparison of the adsorption capacity of various
industrial wastes on the removal of heavy metals is also presented in
this article.
2. Current technologies available for treatment methods of
heavy metals
Heavy metals are not biodegradable and tend to accumulate in
living organisms, causing various diseases and disorders. There are
various treatment processes available for metal-contaminated waste
streams, such as, chemical precipitation, coagulation, solvent extrac-
tion, ultra filtration, biological systems, electrolytic processes, reverse
osmosis, oxidation with ozone/hydrogen peroxide, membrane filtra-
tion, ion exchange, photo catalytic degradation, and adsorption. The
technologies can be divided into three categories: biological, chemical
and physical. Currently, the major methods of industrial wastewater
treatment involve physical and/or chemical processes. Because of the

Table 1
Permissible limits and health effects of various toxic heavy metals [5–8].

Metals Permissible limits for industrial Permissible limits for Health hazards
effluent discharge (mg/L) potable water (mg/L)

Indian standard WHO

Inland Public Marine Inland Indian WHO USEPA EU

surface sewers coastal surface standard Standard
water areas water IS 10,500

Nickel 3.0 3.0 5.0 – 0.02 0.02 0.1 0.02 Causes chronic bronchitis, reduced lung function, cancer of lungs.
Zinc 5.0 15.0 15.0 5.0–15.0 5.0 3.0 5.0 – Causes short-term illness called “metal fume fever” and restlessness
Copper 3.0 3.0 3.0 0.05–1.5 1.5 2.0 1.3 2.0 Long term exposure causes stomachache, irritation of nose,
mouth, eyes, headache
Cadmium 2.0 1.0 2.0 0.1 0.01 0.003 0.005 0.005 Carcinogenic, cause lung fibrosis, dyspnoea
Lead 0.10 1.0 2.0 0.1 0.05 0.01 0.015 0.01 Suspected carcinogen, anemia, muscle and joint pains,
kidney problem and high blood pressure
Total 2.0 2.0 2.0 – 0.05 0.05 0.1 0.05 Suspected human carcinogen, producing lung tumors
chromium
Arsenic 0.2 0.2 0.2 – 0.01 0.01 0.01 0.01 Carcinogenic, producing liver tumors, and gastrointestinal effects
Mercury 0.01 0.01 0.01 – 0.001 0.001 0.002 0.001 Excess dose may cause headache, abdominal pain, and diarrhea,
paralysis, and gum inflammation, loosening of teeth, loss of appetite, etc.
Iron 3.0 3.0 3.0 0.1–1.0 0.3 0.2 0.3 0.2 Excess amounts cause rapid pulse rates, congestion of
blood vessels, hypertension
Manganese 2.0 2.0 2.0 0.05–0.5 0.1 0.5 0.05 0.05 Excess amounts toxic, and causes growth retardation, fever,
sexual impotence, muscles fatigue, eye blindness.
Vanadium 0.2 0.2 0.2 – – 1.4 – – Very toxic, and may cause paralysis
38 M. Ahmaruzzaman / Advances in Colloid and Interface Science 166 (2011) 36–59

high cost and disposal problems, many of these conventional methods Table 2
for treating wastewater have not been widely applied at large scale. Current treatment technologies for heavy metals removal involving physical and/or
chemical processes [19].
At the present time, there is no single process capable of ade-
quate treatment, mainly due to the complex nature of the effluents. In Physical and/or Advantages Disadvantages
practice, a combination of different processes is often used to achieve chemical methods

the desired water quality in the most economical way. Biological Oxidation Rapid process for toxic High energy costs
treatment is often the most economical alternative when compared pollutants removal and formation of
by-products
with other physical and chemical processes. Biodegradation methods
Ion exchange Good removal of a Absorbent requires
are commonly applied to the treatment of industrial effluents, because wide range of heavy metals regeneration or
many microorganisms such as bacteria, yeasts, algae and fungi are able disposal
to accumulate and degrade different pollutants [15–17]. However, Membrane filtration Good removal of Concentrated sludge
their application is often restricted because of technical constraints. technologies heavy metals production,
expensive
Biological treatment requires a large land area and is constrained by
Adsorption flexibility and simplicity of Adsorbents requires
sensitivity toward diurnal variation as well as toxicity of some che- design, ease of operation and regeneration
micals, and less flexibility in design and operation [18]. Chemical insensitivity to toxic pollutants
methods include coagulation or flocculation combined with flotation Coagulation/flocculation Economically feasible High sludge
production and
and filtration, precipitation–flocculation, electroflotation, electroki-
formation of large
netic coagulation, conventional oxidation methods by oxidizing agents particles
(ozone), irradiation or electrochemical processes. These chemical Electrochemical Rapid process and effective High energy costs
techniques are often expensive, and although the toxic pollutants treatment for certain metal ions and formation of
are removed, accumulation of concentrated sludge creates a disposal by-products
Ozonation Applied in gaseous state: Short half life
problem. Different physical methods are also widely used, such as
alteration of volume
membrane-filtration processes (nanofiltration, reverse osmosis, elec- Photochemical No sludge production Formation of
trodialysis, etc.) and adsorption techniques. The major disadvantage of by-products
the membrane process is that of a limited lifetime, before membrane Irradiation Effective at lab scale Required a lot
of dissolved 02
fouling occurs and the cost of periodic replacement must be included
Electrokinetic Economically feasible High sludge
in any analysis of their economic viability. In accordance with the very coagulation production
abundant literature data, liquid-phase adsorption is one of the most Fentons reagents Effective and capable of Sludge generation
popular methods for the removal of toxic pollutants from wastewater, treating variety of wastes
since proper design of the adsorption process will produce a high- and no energy input necessary
to activate hydrogen peroxide
quality treated effluent. This process provides an attractive alternative
Biological treatment Feasible in removing some Technology yet to
for the treatment of contaminated water, especially if the adsorbent is metals be established and
inexpensive and does not require an additional pre-treatment step commercialized
before its application. Adsorption has been found to be superior
compared to the other techniques for water re-use in terms of initial
cost, flexibility and simplicity of design, ease of operation and insen- mentioned previously in terms of their removal performance,
sitivity to toxic pollutants. Adsorption also does not result in the adsorption capacity, and cost effectiveness.
formation of harmful substances. Table 2 showed the advantages and
disadvantages of various processes used for the removal of heavy 3.1. Adsorption of heavy metals on fly ash
metals from wastewaters [19].
Fly ash as coal combustion residue has a great potential in en-
3. Industrial wastes as an adsorbent for removal of heavy metals vironmental applications and an interesting alternative to replace
activated carbon or zeolites as an adsorbent for the treatment of
Heavy metals are nowadays the most important pollutants and wastewater. However, adsorption performance of fly ash strongly
becoming a severe public health problem. Heavy metal and metalloid depends on fly ash origin and chemical treatment. Economic barriers
removal from aqueous solutions has been commonly carried out by have to be overcome in terms of high value and high volume uti-
several processes such as, chemical precipitation, solvent extraction, lization. The chemical compositions of fly ash are high percentage
ion-exchange, reverse osmosis or adsorption etc. Among these pro- of silica (60–65%), alumina (25–30%), magnetite, Fe2O3 (6–15%) and
cesses, the adsorption process may be a simple and effective technique other important physicochemical characteristics of the fly ash, like bulk
for the removal of heavy metals from wastewater. density, particle size, porosity, water holding capacity, and surface
Industrial waste is also one of the potentially low-cost adsorbent area — makes it suitable for use as adsorbent. Moreover, the alkaline
for the removal of heavy metals from wastewaters. It requires little nature of fly ash makes it a good neutralizing agent. Generally, in order
processing to increase its adsorptive capacity. Generally industrial to maximize metal adsorption by hydrous oxides, it is necessary to
wastes are generated as by-products. Since these materials are locally adjust the pH of wastewater using lime and sodium hydroxide [20]. Raw
available in large quantities, they are inexpensive. Various types of fly ash generally has low adsorption capacity. Modification by physical
industrial wastes such as fly ash, blast furnace sludge, waste slurry, and chemical treatment would enhance the adsorption capacity [21],
lignin, iron (III) hydroxide, and red mud, have been explored for their thereby increasing the value for application.
technical feasibility to remove toxic heavy metals from contaminated Fly ash has been widely used as a low-cost adsorbent for the re-
water. Other industrial wastes, coffee husks, Areca waste, tea factory moval of heavy metals. Table 3 summarizes the results of the impor-
waste, sugar beet pulp, waste pomace of olive oil factory waste, tant metals investigated on fly ash. Among these metals, Ni, Cr, Pb, As,
battery industry waste, waste biogas residual slurry, sea nodule Cu, Cd and Hg are the most investigated. The use of fly ash for the
residue, and grape stalk wastes have been utilized as low-cost removal of heavy metals was reported as early as in 1975. Gangoli
adsorbents for the removal of toxic heavy metals from wastewater. et al. [22] reported the utilization of fly ash for the removal of heavy
Although, many research works have been carried out recently to find metals from industrial wastewaters.
the potential of using various alternative adsorbents, so far no efforts Removal of chromium ions including Cr(VI) and Cr(III) using fly
have been made to obtain a comparative overview of all adsorbents ash has been investigated by several researchers. Grover and
 M. Ahmaruzzaman / Advances in Colloid and Interface Science 166 (2011) 36–59 39

Table 3 Table 3 (continued)

Summary of adsorption of metals on fly ash.
Metals Adsorbent Adsorption Capacity Temperature References
Metals Adsorbent Adsorption Capacity Temperature References (mg/g) (°C)
(mg/g) (°C)
Fly ash(II) 0.06–1.16 20 [47]
Zn2+ Fly ash 6.5–13.3 30–60 [44] Bagasse fly ash 1.12–1.70 30–50 [58]
Fe impregnated fly 7.5–15.5 30–60 [44] Fly ash 3.9 [49]
ash Fly ash zeolite 4A 8.96 [60]
Al impregnated fly 7.0–15.4 30–60 [44] Afsin–Elbistan fly 0.98 [28]
ash ash
Fly ash 0.25–2.8 20 [46] Seyitomer fly ash 1.16 [28]
Fly ash(I) 0.25–1.19 20 [47] Bagasse fly ash 6.48 [214]
Fly ash(II) 0.07–1.30 20 [47] Fly ash 0.03 [33]
Bagasse fly ash 2.34–2.54 30–50 [56] Cr3+ Fly ash 52.6–106.4 20–40 [53]
Bagasse fly ash 13.21 30 [57] Bagasse fly ash 4.35 [59]
Fly ash 4.64 23 [69] Fly ash zeolite 4A 41.61 [60]
Fly ash 0.27 25 [70] Cr6+ Fly ash + 2.92 – [25]
Fly ash 0.068–0.75 0–55 [71] wollastonite
Fly ash 3.4 – [49] Fly ash + China 0.31 – [25]
Fly ash zeolite 4A 30.80 [60] clay
Rice husk ash 5.88 [167] Fly ash 1.38 30–60 [45]
Bagasse fly ash 7.03 [214] Fe impregnated fly 1.82 30–60 [45]
Fly ash 11.11 [156] ash
Rice husk ash 14.30 [96] Al impregnated fly 1.67 30–60 [45]
Fly ash 7.84 [156] ash
Cd2+ Fly ash 1.6–8.0 – [42] Fly ash(I) 0.55 20 [48]
Fly ash zeolite 95.6 20 [42] Fly ash(II) 0.82 20 [48]
Fly ash 0.67–0.83 20 [46] Bagasse fly ash 4.25–4.35 30–50 [59]
Fly ash(I) 0.08–0.29 20 [48] Fly ash 23.86 – [26]
Fly ash(II) 0.0077–0.22 20 [48] Rice Husk Ash 25.64 – [26]
Fly ash 198.2 25 [41] Co2+ Fly ash zeolite 4A 13.72 [60]
Fly ash-washed 195.2 25 [41] Hg2+ Fly ash 2.82 30 [36]
Fly ash-acid 180.4 25 [41] Fly ash 11.0 30–60 [45]
Bagasse fly ash 1.24–2.0 30–50 [58] Fe impregnated fly 12.5 30–60 [45]
Fly ash 0.05 25 [70] ash
Coal Fly ash 18.98 25 [32] Al impregnated fly 13.4 30–60 [45]
Rice husk ash 3.04 [167] ash
Coal Fly ash pellets 18.92 [32] Sulfo-calcic 5.0 30 [49]
Afsin–Elbistan fly 0.29 [28] Silico-aluminous 3.2 30 [49]
ash ashes
Seyitomer fly ash 0.21 [28] Fly ash-C 0.63–0.73 5–21 [37]
Bagasse fly ash 6.19 [214] Treated rice husk 9.32 15 [39]
Fly ash zeolite X 97.78 [67] ash
Pb2+ Fly ash zeolite 70.6 20 [101] As3+ Fly ash coal-char 3.7–89.2 25 [74]
Fly ash 444.7 25 [63] As5+ Fly ash 7.7–27.8 20 [72]
Fly ash-washed 483.4 25 [63] Fly ash coal-char 0.02–34.5 25 [74]
Fly ash-acid 437.0 25 [63] Cs+ Fly ash zeolite 443.9 25 [80]
Fly ash 753 32 [63]
Bagasse fly ash 285–566 30–50 [77]
Fly ash 18.8 [72] Narayanaswamy [23] studied the effects of hexavalent chro-
Fly ash zeolite X 420.61 [67] mium concentrations, fly ash dosage, contact time, and pH on the
Treated rice husk 12.61 30 [39]
removal of Cr(VI) and found that removal was effective at lower pH.
ash
Cu2+ Fly ash 1.39 30 [30] Dasmahapatra et al. [24] investigated the adsorption of Cr(VI) on fly
Fly ash 1.18 30 [30] ash and reported that the percent removal of Cr(VI) by fly ash is
+ wollastonite affected by its concentration in aqueous solution, temperature, par-
Fly ash 1.7–8.1 – [42] ticle size, and pH. A homogeneous mixture of fly ash and wollastonite
Fly ash(I) 0.34–1.35 20 [47]
Fly ash(II) 0.09–1.25 20 [47]
(1:1) was also utilized for the removal of Cr(VI) from aqueous solu-
Fly ash 207.3 25 [49] tions by adsorption [25]. Bhattacharya et al. [26] studied the removal
Fly ash-washed 205.8 25 [49] of Cr(VI) from aqueous solution using fly ash. The influence of pH,
Fly ash-acid 198.5 25 [49] adsorbent type, initial Cr(VI) concentration and contact time on the
Fly ash 0.63–0.81 25 [31]
selectivity and sensitivity of the removal process was investigated.
Bagasse fly ash 2.26–2.36 30–50 [56]
Fly ash 0.76 32 [62] They also compared the adsorption capacity of fly ash with other low-
Fly ash 7.5 – [49] cost adsorbents, such as, clarified sludge, saw dust, neem bark and
Coal Fly ash pellets 20.92 25 [32] rice husk ash, and found that clarified sludge was the most effective
Fly ash zeolite 4A 50.45 [60] among the studied adsorbents for the removal of Cr(VI) from aqueous
Fly ash 7.0 [165]
CFA 178.5–249.1 30–60 [34]
solution. The results suggest that adsorption of Cr(VI) on the selected
CFA-600 126.4–214.1 30–60 [34] adsorbents involves a complex mechanism and that in the adsorption
CFA–NAOH 76.7–137.1 30–60 [34] process there are two distinct stages — the initial stages of boundary
Fly ash zeolite X 90.86 [67] layer diffusion was due to external mass transfer effects and in the
Fly ash 7.0 [156]
later stages it was due to intraparticle diffusion which contributes to
Ni2+ Fly ash 9.0–14.0 30–60 [44]
Fe impregnated fly 9.8–14.93 30–60 [44] the rate determining step [26].
ash In another study, Sharma et al. [27] investigated the potential of fly
Al impregnated fly 10–15.75 30–60 [44] ash for the removal of chromium from aqueous solutions and
ash wastewaters. Intraparticle diffusion was found to control the removal
Fly ash(I) 0.40–0.98 20 [47]
of Cr(VI) and the value of coefficient of intraparticle diffusion was
(continued on next page)
40 M. Ahmaruzzaman / Advances in Colloid and Interface Science 166 (2011) 36–59
found to be 2.25 × 10 − 11 cm 2/s at 298 K. The value of the co-efficient
of mass transfer, βl, 2.15 × 10 − 2 cm/s at 298 K, suggested the transfer
of Cr(VI) onto the adsorbent surface to be rapid enough. The process
of removal is highly dependent on pH of the solutions with maxi-
mum removal (89.12%) at pH 2.5. Comparison of the adsorbent used
with other non-conventional adsorbents shows that fly ash is a good
adsorbent and can be recommended for the treatment of metal rich
wastewater in general and that of Cr(VI) in particular.
The removal of Cr(VI) and Cd(II) from an aqueous solution on
Turkish fly ash was compared by Bayat [28]. The effect of contact time,
solution pH, and ash quality on the removal was investigated. Fly
ash was found to have a higher adsorption capacity for Cd(II) as com-
pared to that of Cr(VI). The lime (crystalline CaO) content in the fly
ash seemed to be a significant factor in influencing the adsorption of Cr
(VI) and Cd(II). Recently, fly ash obtained from the combustion of
poultry litter was utilized as an adsorbent for the removal of Cr(III) from
aqueous solution [29].
Fly ash was also utilized for the removal of copper from aqueous
solution. The removal efficiency was found to be dependent on con-
centration, pH and temperature [30]. The kinetics of adsorption indi-
cated the process to be diffusion controlled. Fly ashes with different
quantities of carbon and minerals were also used for the removal of
Cu(II) from aqueous solution [31]. The carbon fraction in fly ash was
important in the removal of Cu(II). The specific adsorption capacities
of carbon ranged from 2.2 to 2.8 mg Cu/g carbon, while those for
mineral were only about 0.63–0.81 mg Cu/g mineral. Fly ash can also
be shaped into pellets and used for the removal of copper and
cadmium ions from aqueous solutions [32]. The adsorption of copper
and cadmium fitted well with the Langmuir isotherm. The calculated
adsorption capacities for copper and cadmium were found to be 20.92
and 18.98 mg/g, respectively. They reported that fly ash shaped into
pellets could be considered as a potential adsorbent for the removal of
copper and cadmium from wastewaters.
Raw bagasse and fly ash have also been used as low-cost adsorbents
for the removal of chromium and nickel from an aqueous solution [33].
The extent of adsorption at equilibrium was found to be dependent on
the physical and chemical characteristics of the adsorbent, adsorbate
and experimental system. Raw and modified coal fly ash effectively
adsorb Cu(II) from wastewater [34]. These adsorptions were endother-
mic in nature; the values of activation energy (between 1.3 and
9.6 kJ mol − 1) were consistent with an ion-exchange adsorption
mechanism. The adsorptions of Cu(II) onto coal fly ash (CFA), CFA-
600, and CFA–NaOH followed pseudo-second-order kinetics. CFA was
found to be a cheap and effective adsorbent for the removal of Cu(II)
ions from water. The nature of CFA did not improve its ability to adsorb
Cu(II). The removal characteristics of Pb(II) and Cu(II) ions from
aqueous solution by fly ash were investigated [35]. The level of uptake of
Pb(II) and Cu(II) ions by the fly ash generally increased, but not in a
progressive manner, at higher pH values. The main mechanisms
involved in the removal of heavy metals from solution were adsorption
at the surface of the fly ash and precipitation.
Fly ash was also found to be effective for the removal of mercury
from aqueous solution. Sen and De [36] showed that the adsorption
capacity of coal fly ash for mercury was comparable to that of activated
powdered charcoal. The pH of the solution was found to be the most
important parameter affecting the adsorption. The effectiveness of fly
ash in adsorbing mercury from wastewater has been studied [37].
Batch kinetic and isotherm studies have been carried out to determine
the effect of contact time, pH and temperature on the adsorption.
Rice husk ash was found to be a good adsorbent for the removal of
Hg (II) from aqueous solution [38]. Batch studies indicated that
percent adsorption decreased with increased initial concentration of
Hg(II) and particle size of the adsorbent. Maximum Hg(II) removal
was observed near a pH of 6.0. Column experiments indicated that the
adsorbed amount of Hg(II) decreased with increased flow rate and
decreased bed height. An attempt was made for the removal of lead
and mercury from aqueous water by using rice husk ash as an
adsorbent and found to be a suitable adsorbent for the adsorption of
lead and mercury ions [39]. The Bangham equation was used to
express the mechanism for adsorption of lead and mercury ions by
rice husk ash. Its adsorption capability and adsorption rate are con-
siderably higher and faster for lead ions than for mercury ions. The
finer the rice husk ash particles used, the higher the pH of the solution
and the lower the concentration of the supporting electrolyte, potas-
sium nitrate solution, the more lead and mercury ions adsorbed on
rice husk ash.
Papachristou et al. [40] determined the selective adsorption of
various metal ions (Na, K, Mg, Ca, Cu, Cd, Mn, Hg, Cr, Pb, and Fe) by
two different fly ashes. Lead ions were found to be selectively
adsorbed at a mean value of 19 meq of Pb(II) per 100 g of fly ash. This
selective adsorption could be due to the formation of crystalline
ettringite mineral after the hydration of the fly ash. Coal fly ashes have
also been used for the removal of toxic heavy metals, i.e. Cu(II), Pb(II)
and Cd(II) from water [41]. The breakthrough volumes of the heavy
metal solutions have been measured by dynamic column experiments
so as to determine the saturation capacities of the adsorbents. The
adsorption sequence is Cu N Pb N Cd in accordance with the order of
insolubility of the corresponding metal hydroxides. Similar results
on the adsorption of Cd and Cu by fly ash were also reported by Ayala
et al. [42]. Adsorption capacity increased with decreased initial con-
centration of the metals. The presence of high ionic strength or ap-
preciable quantities of calcium and chloride ions does not have a
significant effect on the adsorption of these metals by fly ash.
The utilization of zeolites synthesized from fly ash (FA) and related
co-disposal filtrates as low-cost adsorbent material was investigated
[43]. When raw FA and co-disposal filtrates were subjected to alkaline
hydrothermal zeolite synthesis, the zeolites, faujasite, sodalite and
zeolite A were formed. The synthesized zeolites were explored to
establish its ability to remove lead and mercury ions from aqueous
solution in batch experiments, to which various dosages of the syn-
thesized zeolites were added. The lead concentrations were reduced
from 3.23 to 0.38 and 0.17 μg/kg, respectively, at an average pH of 4.5,
after the addition of raw FA zeolite and co-disposal filtrate zeolite to
the AMD wastewater. On the other hand, Somerset et al. [43] showed
that the mercury concentration was reduced from 0.47 to 0.17 μg/kg
at pH = 4.5 when increasing amounts of co-disposal filtrate zeolite
were added to the wastewater. The experimental results had shown
that the zeolites synthesized from the co-disposal filtrates were ef-
fective in reducing the lead and mercury concentrations in the AMD
wastewater by 95% and 30%, respectively [43].
Banerjee et al. [44,45] studied the adsorption of various toxic metal
ions, Ni(II) and Zn(II), Cr(II) and Hg(II), on fly ash and Al- and Fe-
impregnated fly ash. The impregnated fly ash showed much higher
adsorption capacity for all the ions as compared to that of untreated
fly ash. The adsorption was found to be exothermic for Ni(II) and
endothermic in case of Zn(II). The adsorption capacity of FA, Al-FA,
and Fe-FA for Cr(VI) was found to be 1.379, 1.820, and 1.667 mg/g and
that of Hg(II) was 11.00, 12.50, and 13.40 mg/g. Bayat investigated
the removal of Zn(II) and Cd(II) [46], Ni(II) and Cu(II) [47], and Cr(VI)
[48] using lignite-based fly ash and activated carbon and found that
the fly ash was effective as activated carbon. The parameters studied
include contact time, pH, temperature, initial concentration of the
adsorbate, and fly ash dosage. The percent adsorption of Zn(II) and Cd
(II) increased with an increase in concentration of Zn(II) and Cd(II),
dosage of fly ash and temperature and the maximum adsorption
occurred in the pH range of 7.0–7.5. Thermodynamic parameters sug-
gested the endothermic nature of the adsorption process. The effec-
tiveness of the fly ash as an adsorbent improved with increased amount
of calcium (CaO). Fly ashes were found to have a higher adsorption
capacity for Cd(II) as compared to that of Cr(VI).
Ricou et al. [49,50] studied the removal of Cu, Ni, Zn, Cd and Pb by
fly ash and fly ash/lime mixture. The removal extent was achieved in
 M. Ahmaruzzaman / Advances in Colloid and Interface Science 166 (2011) 36–59
the order of Pb(II) N Cu(II) N Ni(II) N Zn(II) N Cd(II). Formation of calci-
um silicate hydrates (CSH) was supposed to be responsible for in-
creasing removal as also for decreasing desorption. Two fluidized-bed
sourced fly ashes with different chemical composition, silico-aluminous
fly ashes and sulfo-calcic fly ashes, were tested to remove Pb(II), Cu(II),
Cr(III), Ni(II), Zn(II), Cr(VI) [51] and Hg(II) [52] from aqueous solutions.
The percentage of adsorbed ions was found to be greater when they
were in contact with silico-aluminous fly ashes than sulfo-calcic fly
ashes, except in the case of the ion Ni(II). However, sulfo-calcic fly ash
removed mercury more efficiently and more steadily. The results
showed that mercury is bound to ash surface due to several chemical
reactions between mercury and various oxides (silicon, aluminum and
calcium silicate) of the surface of fly ash.
Cetin and Pehlivan [53] compared fly ash and activated carbon
for their ability to remove nickel [Ni(II)] and zinc [Zn(II)] from an
aqueous solution. Batch kinetic studies showed that an equilibrium
time of 1 h was required for the adsorption of Ni(II) and Zn(II) on both
adsorbents. The maximum metal removal was found to be dependent
on solution pH. With an increase in the concentrations of these metals,
the adsorption of Ni(II) and Zn(II) decreased on both of the ad-
sorbents. The effectiveness of fly ash as an adsorbent improved with
increasing calcium (CaO) content. Adsorption data in the range of pH
values (3.0–8.0) using Ni(II) concentration of 25 ± 2 mg/L and Zn(II)
concentration of 30 ± 2 mg/L in solution were correlated using the
linear forms of the Langmuir and Freundlich equations.
The changes in toxicity and heavy metals in a municipal waste-
water treatment plant effluent on treatment with fly ash were
measured [54]. The effluent after the treatment with fly ash showed
a significant reduction in the toxicity, Cu, Pb and PO4 3− and NO3−
contents. Fly ash removed Cu and Pb from the effluent and the re-
moval of these toxic heavy metals resulted in the reduction of toxicity.
Gupta research group [55–59] conducted a series of investigations on
the adsorption of heavy metals by using fly ash as adsorbents. They
have used bagasse fly ash from sugar industries for the removal of lead
[55], copper and zinc [56,57], cadmium and nickel [58] and chromium
[59] from aqueous solutions. Copper and zinc are adsorbed by the
developed adsorbent up to 90–95% in batch and column experiments.
The adsorption was found to be endothermic in nature and follows
both the Langmuir and Freundlich models. The batch test showed 90%
removal for Cd and Ni, in about 60 and 80 min, respectively. The
removal of Zn is 100% at low concentrations, whereas it is 60–65% at
higher concentrations. The uptake decreases with increase in tem-
perature indicating the process to be exothermic in nature. Lead and
chromium are also adsorbed by the developed adsorbent up to 96–
98%. The removal of these two metal ions up to 95–96% was achieved
by column experiments at a flow rate of 0.5 mL/min.
Removal of mixed heavy metal ions in wastewater by zeolite 4A
and residual products from recycled coal fly ash was investigated by
Hui et al. [60]. The adsorption capacities of fly ash zeolite 4A were
reported to be 30.80, 50.45, 8.96, 41.60, and 13.72 (mg/g) for Zn(II),
Cu(II), Ni(II), Cr(III), and Co(II) ions respectively. The feasibility of fly
ash for the removal of Cu(II) and Pb(II) from wastewater was studied
by Lin et al. [61]. Results showed that the cation exchange capacity
and specific surface area of fly ash increased with increasing the
carbon content. The adsorption of metal ions onto the surfaces of fly
ashes was found to be proportional to the carbon contents. This is
because the amounts of adsorption or ion exchange sites on carbon
soot are higher than those on mineral surface. This is consistent with
the cation exchange capacity and specific surface area. Consequently,
carbon residual in the fly ashes played an important role than mineral
matter in the removal of metals by the fly ashes. Rao et al. [62] also
utilized fly ash along with other low-cost adsorbents for the removal
of copper and lead.
Yadava et al. [63] investigated the removal of cadmium from
aqueous solution by fly ash. The removal of cadmium from aqueous
solutions by adsorption on fly ash increased with time and that
41
equilibrium is attained within 2 h. The adsorption of cadmium on fly
ash could be explained by the Langmuir equation. Prabhu et al. [64]
showed that fly ash was a good adsorbent for the removal of zinc
from aqueous solutions; maximum removal was obtained in the pH
range of 3 to 4. They found that adsorption fitted the Freundlich
isotherm. Studies by Gashi et al. [65] indicated that fly ash showed
good adsorptive properties of removal of lead, zinc, cadmium and
copper from effluents of battery industry and fertilizer industry.
Removal efficiencies were greater than 70%. Adsorption studies
carried out to estimate heavy metal removal using fly ash on waste-
water at Varnasi, India showed that removal was in the following
order: Pb N Zn N Cu N Cr N Cd N Co N Ni N Mn [66].
Coal fly ash (CFA) was modified to zeolite X and used as an
effective sorbent for removing of Cu(II), Cd(II), and Pb(II) from their
aqueous solution [67]. It required a longer time to reach equilibrium
for higher initial metal concentration and lower sorbent dose but all
reached equilibrium within 120 min. External mass transfer step
seemed to take part as a rate limiting step for the sorption of Pb(II) at
low initial concentration and high adsorbent dose, on the contrary,
the process was controlled more significantly by intraparticle dif-
fusion step at high initial concentration and low sorbent dose. How-
ever, Cu(II) was found to be generally controlled by intraparticle
diffusion step within all concentration ranges studied. The adsorption
of Cd(II), on the other hand was controlled both by external mass
transfer and intraparticle diffusion steps at all ranges of initial con-
centration. The order of maximum adsorption capacity in a unit of
mol/kg was: Pb(II) N Cu(II) N Cd (II). The adsorption energy falls in the
range of physico-sorption. Equilibrium sorption capacity and removal
percentage were governed by both initial concentration and sorbent
dose. A general mathematical model was developed for describing the
adsorption under the variations in initial metal concentration and
zeolite doses. Solid state conversion of fly ash to an amorphous alu-
minosilicate adsorbent (geopolymer) has been investigated for the
removal of Cu(II) from aqueous solution [68]. It has been found that
higher reaction temperature and sodium:fly ash ratio will make the
adsorbent achieve higher removal efficiency. The adsorption capacity
of the synthesized adsorbent (92 mg/g) shows a much higher value
than fly ash (0.1 mg/g) and natural zeolite (3.5 mg/g).
A process for the treatment of industrial wastewater containing
heavy metals, using fly ash adsorption and cement fixation of the
metal-laden adsorbent, was investigated by Huang research group
[69,70]. Results showed that the fly ash could be an effective metal
adsorbent, at least for Zn(II) and Cd(II) in dilute industrial
wastewaters. Fly ash adsorption capacities for Zn(II) and Cd(II)
were 0.27 and 0.05 mg/g, respectively. A 10% metal laden fly ash was
tested for leaching and it exhibited metal concentrations lower than
the drinking water standards. They [71] further examined the
adsorption characteristics of Zn(II) onto fly ash. In general, the
amount of Zn adsorbed increased as the solid concentration and pH
increased, and sharply reached a 99% removal at a specific pH value,
then it remained constant over a wide pH region. The fly ash
adsorption capacities of Zn ranged from 1.04 × 10 − 6 to
1.15 × 10 − 5 mol/g in the pH range of 6.0–7.5. Experimental results
indicated that the adsorption was favorable at lower ionic strength,
higher pH, and higher temperature and that the adsorption is a
physical process enhanced by the electrostatic effect. Fly ash was also
found to be effective for the removal of arsenic from aqueous solution.
Fly ash obtained from coal power stations was examined for As (V)
removal from water [72]. Kinetic and equilibrium experiments were
performed to evaluate the As(V) removal efficiency by lignite-based
fly ash. Removal at pH 4 was significantly higher than that at pH 7 or
10. Maple wood ash without any chemical treatment was also utilized
to remediate As(III) and As(V) from contaminated aqueous streams in
low concentrations [73]. Static tests removed ≤80% arsenic while the
arsenic concentration was reduced from 500 to b5 ppb in dynamic
column experiments.
42 M. Ahmaruzzaman / Advances in Colloid and Interface Science 166 (2011) 36–59
The As(V) and As(III) removal efficiency of a char-carbon (CC),
derived from fly ash is compared with those of a commercially activated
carbon [74]. The results indicate that CC and AC adsorbents remove
almost equal amounts of As(V) at optimum conditions; however, on
a percent basis CC removes more As(III) than does AC. The investigation
revealed that the adsorption of As(V) onto CC is influenced by pH, initial
metal concentration and temperature. Zeta potential measurements
were obtained to explain the metal removal behavior of the adsorbents
used in this investigation.
A special iron-abundant fly ash was used to develop a novel adsor-
bent for arsenic (V) removal from wastewater through simple chemical
processes [75]. The inherent iron in the fly ash was rearranged and
loaded on the surface of the fly ash by dissolution and precipitation
processes. The results showed that porous amorphous FeOOH was
loaded on the surface of the adsorbent (HIOFAA) successfully. The ad-
sorption capacity for arsenic removal was found to be 19.46 mg/g.
A cancrinite-type zeolite was synthesized from Class C fly ash by
molten-salt method and the product obtained (ZFA) was used as the
adsorbent for the arsenate removal from water [76]. The adsorption
equilibriums of arsenate are investigated on various adsorbents. ZFA
showed a higher adsorption capacity (5.1 mg/g) than activated carbon
(4.0 mg/g), silica gel (0.46 mg/g), zeolite NaY (1.4 mg/g), and zeolite
5A (4.1 mg/g). The relatively higher adsorption capacity of ZFA than
zeolite NaY and 5A was attributed to the low Si/Al ratio and the
mesoporous secondary pore structure of ZFA. However, it was found
that the adsorption capacity of zeolites was generally lower than
activated alumina (16.6 mg/g), which is ascribed to the small pores in
zeolite frameworks. The adsorption capacity of ZFA was significantly
improved after alumina loading via a wet-impregnation method. The
modified ZFA (ZFAAl50) with the optimum alumina loading showed
an adsorption capacity of 34.5 mg/g, which was 2.1 times higher than
activated alumina. The Toxicity Characteristic Leaching Procedure
(TCLP) leachability tests indicated that the spent ZFA and alumina-
modified ZFA complied with the EPA regulations for safe disposal.
The removal of arsenic from drinking water by filtration through
modified fly-ash bed is also reported [77]. The preparation and char-
acteristics of the bed material and the effects of different parameters
like pH and the presence of other constituents are described. Various
arsenic compounds in synthetic mixtures as well as drinking water
samples containing arsenic have been investigated. The effectiveness
of the modified fly-ash bed for the control of arsenic has been dem-
onstrated by taking different quantities of arsenic(III) and arsenic(V)
salts. The results of filtering through a fly-ash bed were found to
be satisfactory which makes it a low cost treatment method for
the removal of arsenic, improving the quality of drinking water. The
utilization of the bed material after use is also discussed.
Surface-modified zeolite materials have been developed from
commercial zeolites and fly ash-based zeolites by treating them with
surface modifiers like hexadecyltrimethylammonium bromide and
tetramethylammonium bromide [78]. The adsorbent has been eval-
uated for the removal of arsenic and chromate anions. High selectivity,
faster kinetics and high adsorption capacity ensure cost effectiveness
of these materials compared to other conventional materials for
dearsenification.
It has been reported that coal fly ash is a good adsorbent for both
radionuclides of 137Cs and 90Sr [79]. Radiocesium adsorption is max-
imal around the neutral region whereas radiostrontium adsorption
increases with pH, especially above pH 8. The retention of Cesium
sharply drops with ionic strength, whereas the adsorption of stron-
tium increases sharply and steadily at low and moderate concentra-
tions of the inert electrolyte, respectively. The suggested mechanism
of radionuclide retention by fly ash is specific adsorption of Cs(I) and
irreversible ion-exchange uptake of Sr(II).
In addition, fly ash has been converted to zeolites by hydrothermal
treatment and used as an adsorbent for the removal of metal ions,
radiocesium [80], lead and cadmium [81]. The maximum uptake
capacity was found to be 3.34 mmol Cs/g, which was 2–3 times
higher than those of synthetic zeolite P and natural mordenites.
The adsorption capacity for lead and cadmium was found to be
70.58 mg lead/g-zeolite and 95.6 mg cadmium/g-zeolite, respectively,
when the initial concentration for both the ions was 100 mg/L. Recently,
Wang and Wu [82] had written a nice review on the environmental
benign utilization of fly ash as low-cost adsorbents for the removal of
various pollutants from wastewaters. It is recognized that fly ash is a
promising adsorbent for removal of various pollutants. Chemical treat-
ment of fly ash will make conversion of fly ash into a more efficient
adsorbent for water cleaning. Investigations also revealed that the
unburned carbon component in fly ash plays an important role in ad-
sorption capacity. The technical feasibility of utilization of fly ash as a
low-cost adsorbent for various adsorption processes for removal of
pollutants in water systems has been reviewed.
3.2. Adsorption of heavy metals on blast furnace slag, sludge and dust
The sludge is a dried waste from the electroplating industry, which
is produced by precipitation of metal ions in wastewater with calcium
hydroxide. It contains insoluble metal hydroxides and other salts.
Another low-cost adsorbent showing capability to adsorb heavy
metals is blast furnace slag, an industrial by-product generated in the
steel plants. Steel plants generate a large volume of granular blast
furnace slag which is also being used as filler or in the production of
slag cement. Blast furnace flue dust is a waste material from steel
industries and may be used to remove heavy metal ions from aqueous
solutions. The adsorption of Cu(II), Zn(II), and Ni(III) using blast
furnace slag was studied by Dimitrova [83]. It was found that the
adsorption of metal ions takes place in the form of hydro-oxo com-
plexes and that the high adsorption capacity is related to the for-
mation of soluble compounds on the internal surface of the adsorbent.
Srivastava et al. [84] investigated the activated blast furnace slag for
the removal of lead and chromium. The maximum uptake of metals
was found to be 40 and 7.5 mg/g for lead and chromium, respectively.
The adsorption on activated slag followed both Feundlich and Lang-
miur isotherms. It was also reported that the performance of activated
slag is comparable to that of commercially available activated carbon.
The Lopez research group investigated the potential of blast
furnace sludge for the removal of heavy metals from aqueous solution.
The effectiveness of blast furnace sludge to purify Cu(II) containing
solutions was studied by determining the adsorption of Cu(II) ions
from aqueous solution on flue dust [85] and corresponds to a typical
endothermic physical adsorption process. The results suggest that
blast furnace sludge is a good adsorbent for the removal of Cu(II) from
aqueous solutions. They [86,87] also studied the adsorption of Pb(II),
Zn(II), Cd(II), Cu(II) and Cr(III) on the sludge. Blast furnace sludge was
found to be an effective adsorbent for Pb, Zn, Cd, Cu and Cr-ions within
the range of ion concentrations employed. High temperature favors
the adsorption of lead ions from aqueous solutions on samples with
lower carbon content. However, the adsorption capacity of samples
with higher carbon contents decreased with increased temperature.
The increase of adsorption capacity with increasing Fe2O3/C ratio in the
sludge indicates that under these experimental conditions, the process
of lead ion adsorption occurs more strongly on the hematite phase
than on the carbon phase. This research group [88] also investigated
the potential of blast furnace sludge for the removal of Pb(II) from
industrial effluents. The blast furnace sludge was found to have a high
adsorption capability, up to 80 mg Pb per g dried sludge at saturation.
The order of magnitude of the adsorption enthalpy, calculated from the
apparent equilibrium constant, indicates that the adsorption of Pb(II)
on the sludge is of a physical nature. XPS and EDAX analysis suggest
that the physical adsorption process partially occurs through ionic
exchange between Pb(II) and other ions such as Ca(II).
Blast furnace flue dust may also be used for the removal of divalent
Cu(II) and Pb (II) ions from aqueous solutions [89]. The carbon,
 M. Ahmaruzzaman / Advances in Colloid and Interface Science 166 (2011) 36–59
metallic iron and aluminosilicate phase present in the flue dust
sample are responsible for the removal of metal ions. The adsorption
kinetic was rapid over an initial time period followed by the slower
rate at final stage. The removal of Pb(II) by adsorption on granulated
blast-furnace slag was investigated as a function of pH, the metal ion
concentration, the particle size and the amount of sorbent [90]. The
percentage of lead removal at equilibrium increases with increasing
slag amount but the adsorption capacity decreases. The results ob-
tained could be useful for the application of granulated slag for the Pb-
ions removal from industrial waste water. The utilization of granular
blast furnace slag packed columns to treat Pb(II)-containing solutions
has been investigated [91]. The results obtained indicated that the slag
usage rate decreased with increasing flow velocity, particle size, initial
lead concentration and decreasing bed height. It was found that Pb(II)
was removed selectively in the presence of other heavy metal ions.
High concentrations of sodium and especially calcium in the solutions
impeded the uptake of Pb(II). Column pH was an important parameter
in Pb(II) removal under dynamic conditions and reflected the in-
fluence of the investigated factors. During all runs Pb(II) breakthrough
coincided with an abrupt drop in effluent pH. The apparent mech-
anisms of Pb(II) removal in the blast furnace slag packed column
are sorption (ion exchange and adsorption) on the slag surface and
precipitation.
A comparative study of the adsorbents prepared from several
industrial wastes viz. carbon slurry and steel plant wastes viz. blast
furnace (B.F.) slag, dust, and sludge for the removal of Pb(II) has been
carried out [92]. The adsorption of Pb(II) on different adsorbents has
been found in the order: B.F. sludge N B.F. dustN B.F. slagN carbonaceous
adsorbent. The least adsorption of Pb(II) on carbonaceous adsorbent
even having high porosity and consequently greater surface area as
compared to other three adsorbents, indicates that surface area and
porosity are not important factors for Pb(II) removal from aqueous
solutions. Since all three waste products from the steel industry showed
higher potential for the removal of lead from water, therefore, it is
suggested that these metallurgical wastes can be fruitfully employed as
low-cost adsorbents for effluent treatment containing toxic metal ions.
The adsorbent derived from sewage sludge through chemical
pyrolysis has been used for the removal of Cd(II) and Ni(II) from
aqueous solution [93]. The capacity of adsorption calculated from the
Langmuir isotherm was 16 and 9 mg/g for Cd(II) and Ni(II), respec-
tively. The mechanism of adsorption seems to be ion exchange. As the
sewage sludge is discarded as a waste from wastewater treatment
processing plant, the adsorbent derived from sewage sludge is ex-
pected to be an economical product for metal ion remediation from
water and wastewater.
Storm water and landfill leachate can both contain significant
amounts of toxic metals such as Zn, Cu, Pb, Cr and Ni. Pine bark and
blast furnace slag are both residual waste products that have shown a
large potential for metal removal from contaminated water [94]. The
results showed that pine bark was generally more efficient than blast
furnace slag when the metal concentrations were relatively small,
whereas blast furnace slag adsorbed most metals to a larger extent at
increased metal loads. In addition, adsorption to blast furnace slag was
found to be faster than metal binding to pine bark.
In another study, the removal of chromium (VI) from aqueous and
industrial effluent was carried out using distillery sludge [95]. The
Langmuir adsorption capacity was found to be 5.7 mg/g. Desorption
studies indicated the removal of 82% of hexavalent chromium. The
efficiency of adsorbent towards the removal of chromium was also
tested using chromium-plating wastewater.
Clarified sludge (a steel industry waste material) was also used for
the removal of Zn(II) from aqueous solution [96]. The adsorption
capacity (qmax) calculated from Langmuir isotherm and the values of
Gibbs free energy obtained showed that clarified sludge has the
largest capacity and affinity for the removal of Zn(II) compared to
other adsorbents, such as, rice husk ash, activated alumina and neem
43
bark, respectively. Bhatnagar et al. [97] investigated the potential of
metal sludge, a waste product of electroplating industry, for the re-
moval of vanadium from water. The adsorption capacity of metal
sludge for vanadium was found to be 24.8 mg/g at 25 °C. After ad-
sorption studies, the metal-laden sludge adsorbent was immobilized
into the cement for its ultimate disposal. Physical properties such
as initial and final setting time, and compressive strength of cement
stabilized wastes were tested to see the effect of metal-laden sludge in
cement. The study clearly revealed that metal sludge can be fruitfully
employed in treating industrial effluents containing vanadium and
further safely disposed of by immobilizing it into cement. The pro-
posed technology provides a two-fold advantage of wastewater treat-
ment and solid waste management.
Waste sludge from laboratory units at four different steady-state
conditions (5–20 days sludge ages) was employed for studying heavy
metal shock load by the jar test system [98]. Metal uptake (Hg, Cd, Ni)
and oxygen depletion rates were simultaneously followed. The po-
tential adsorption constants (kam) measured reveal a metal affinity
sequence of Hg N Cd N Ni, in partial contrast to the metal toxicity (MT)
one, Hg N Ni N Cd. This suggests different sludge adsorption sites. Hg
is preferentially adsorbed on the cell, while Cd is adsorbed on extra-
cellular polymer slimes and Ni on capsular polymers and the cellular
wall. Therefore sludge age influences Cd and Ni toxicity, while no
effect is observed for Hg.
Blast furnace slag was converted into an effective and economical
scavenger and utilized for the remediation of aqueous chromium [99].
Erdem et al. [99] applied ferrochromium slag for the removal of Cr(VI)
from aqueous solution. The Cr(VI) concentration in water that con-
tacted with the ferrochromium slag (W/FS = 10) was 0.61 mg/L after
50 batches. Ten grams per liter ferrochromium slag dosage and
3.5 mL/L H2SO4 (5 M) were sufficient to reduce all Cr(VI) in the model
solution containing 10 mg/L Cr(VI) during contact time of 60 min at
25 °C.
For years, the microwave technique, offering the advantage of
uniform and rapid heating, has been widely applied for the treatment of
some environmental materials. Moreover, the stabilization and immo-
bilization of metal ions in soil and metal sludge through the microwave
treatment are also reported [100–102]. This demonstrates that
microwave treatment is quite efficient in inhibiting the leaching of
metal ions from soil or sludge. Hence, the treated soil or sludge becomes
a stable matrix for application. For reducing the problems of metal
ions in aqueous solution, sewage sludge has been used efficiently as
low-cost adsorbents [103]. Microwave stabilized heavy metal sludge
was used as an adsorbent to remove the copper ions from aqueous
solution [104]. Results show that the pHzpc of stabilized-sludge was at
9.2–9.5. Moreover, the adsorption of copper ions onto the stabilized-
sludge surface was mainly on account of the heterogeneous surface of
the stabilized-sludge. In the dynamic study, the experimental data was
fitted to the intraparticle diffusion model, pseudo-first order model and
pseudo-second order model. From the Langmuir equation, the adsorp-
tion capacity increased from 18 to 28 mg/g as the temperature increased
from 15 to 55 °C, since this adsorption process was an endothermic
reaction.
3.3. Adsorption of heavy metals on red mud
Another abundant industrial by-product is a red mud. Waste red
mud is a bauxite processing residue discarded in alumina production.
Red mud is a waste material formed during the production of alumina
when bauxite ore is subjected to caustic leaching. A typical Bayer
process plant generates a 1–2 tonnes of red mud per ton of alumina
produced [105]. Red mud is principally composed of fine particles of
silica, aluminum, iron, calcium and titanium oxides and hydroxides,
which are responsible for its high surface reactivity. Because of these
characteristics red muds have been the subject of many investigations,
including some on the removal of toxic heavy metals from wastewater
44 M. Ahmaruzzaman / Advances in Colloid and Interface Science 166 (2011) 36–59
and acid mine drainage. Red mud has been explored as an alternate
adsorbent for arsenic [105,106]. An alkaline aqueous medium (pH 9.5)
favored As(III) removal, whereas the acidic pH range (1.1–3.2) was
effective for As(V) removal [106]. Heat and acid treatments on red
mud increased its adsorptive capacity [107]. Arsenic adsorption on
acid and heat treated red mud is also pH-dependent, with an optimum
range of 5.8–7.5 for As(III) and 1.8–3.5 for As(V) [95]. Adsorption
followed a first-order rate expression and fit the Langmuir isotherm
well. The As(III) adsorption was exothermic, whereas As(V) adsorp-
tion was endothermic [94,95]. As(V) removal by using liquid phase of
red mud (LPRM) was also reported [108]. Authors suggested that it is
advantageous to use a waste material of red mud liquid phase in the
treatment of arsenical wastewater, possibly in conjunction with red
mud solids as an adsorbent.
Seawater-neutralized red muds (Bauxol) [109], Bauxsol activated
by acid treatment, and by combined acid and heat treatment, and
Bauxsol with added ferric sulfate or aluminum sulfate [110], activated
Bauxsol (AB), and chemically modified and activated Bauxsol (AB)-
coated sand [111] were also utilized for the removal of arsenic. The
acid, and heat treatment, increased the removal efficiency of arsenic
[110,111]. Addition of ferric sulfate or aluminum sulfate suppressed
the removal of arsenic. The activated Bauxsol (AB) produced using
combined acid and heat treatment removed approximately 100% of
the arsenate (at pH 4.5) with or without the presence of competing
anions (i.e., phosphate, bicarbonate, and sulfate).
Red mud was found to remove effectively nickel ions from dilute
aqueous solutions [112]. Red mud, being an industrial solid by-
product/waste from alumina production during bauxite processing,
was found to act simultaneously as an alkalinity regulator, causing
precipitation of nickel as the insoluble hydroxide, as an adsorbent of
the formed nickel hydroxide and as a flocculant of the resultant fine
particulate matter. Sedimentation was subsequently considered as a
possible solid/liquid separation technique. Adsorption by activated
red mud (ARM) is investigated as a possible alternative to the con-
ventional methods of Cr(VI) removal from aqueous synthetic solu-
tions and industrial effluents [113]. Adsorption characteristics suggest
the heterogeneous nature of the adsorbent surface sites with respect
to the energy of adsorption. The influence of the addition of anions on
the adsorption of Cr(VI) depends on the relative affinity of the anions
for the surface and the relative concentrations of the anions.
Santona et al. [114] investigated the heavy metal adsorption of
non-treated (RMnt) and acid-treated red muds (RMa), in order to
evaluate how efficient they are in reducing metal solubility and bio-
availability in polluted soils. Red mud samples were artificially pol-
luted with solutions containing increasing concentrations of Pb, Cd
and Zn. Cancrinite and hematite were the main phases of the red
muds, and also the components which adsorbed most heavy metals.
The results showed that the RMnt adsorption capacity for the three
heavy metals was Zn ≥ Pb N Cd. Acid treatment with HCl decreased the
adsorption capacity of red mud for heavy metals by 30%. To study the
heavy metal–RM interaction mechanisms, all samples after artificial
contamination were treated with solutions with gradually increasing
extraction capacity. H2O and Ca(NO3)2 treatments only extracted very
low concentrations of Pb, Cd and Zn, while EDTA treatment extracted
the most adsorbed heavy metals from the sorbent particles. In par-
ticular the water-soluble and exchangeable metal fractions were
higher in the RMa than they were in the RMnt, while the concen-
trations of Pb, Cd and Zn extracted with EDTA were lower.
The adsorption of Cu(II), Cd(II), and Pb(II), on red mud has been
interpreted with respect to pH and metal concentration by means of
the modified Langmuir single-site and double-site models [115].
Although red mud is a heterogeneous adsorbent, the binding of the
sole metal cation (M 2+) onto one or two types of surface sites at pH
6.0 and less than 50% surface coverage in the form of ~ SOM + mono-
dentate surface complex, which results in the release of protons from
the surface, effectively explains the observed metal adsorption. The
adsorption intensity and surface binding constant of Cu(II) were
highest among the studied metals, in accordance with the Irwing–
Williams order of complex formation. They [116] have also used the
mixture of bauxite waste red mud and coal fly ash for the removal of
copper(II), lead(II) and cadmium(II) from aqueous solution. These
heavy-metal-loaded solid wastes may then be solidified by adding
cement to a durable concrete mass assuring their safe disposal. The
distribution ratios of metals between the solid adsorbent and aqueous
solution have been found as a function of adsorbent type, equilibrium
aqueous concentration of metal and temperature. Guclu and Apak
[117] investigated the adsorption of Cu(II), Cd(II), and Pb(II), from
metal–EDTA mixture solutions on a composite adsorbent having a
heterogeneous surface, i.e., bauxite waste red mud, and modeled with
the aid of a modified surface complexation approach in respect to pH
and complexant dependency of heavy metal adsorption. EDTA was
selected as the modeling ligand in view of its wide usage as an
anthropogenic chelating agent and abundance in natural waters. The
adsorption experiments were conducted for metal salts (nitrates),
metal–EDTA complexes alone, or in mixtures containing (metal–
metal–EDTA). For all studied cases, the solid adsorbent phase con-
centrations of the adsorbed metal and metal–EDTA complexes were
found by using the derived model equations with excellent compat-
ibility of experimental and theoretically generated adsorption iso-
therms. The model was useful for metal and metal–EDTA mixture
solutions either at their natural pH of equilibration with the sor-
bent, or after pH elevation with NaOH titration up to a certain pH.
Thus adsorption of every single species (M 2+ or MY 2−) or of possible
mixtures (M 2+ or MY 2−) at natural pH or after NaOH titration could
be calculated by the use of simple quadratic model equations, once
the initial concentrations of the corresponding species, i.e., [M 2+]0 or
[MY 2−]0, were known. The findings of this study can be further de-
veloped so as to serve environmental risk assessment concerning the
expansion of a heavy metal contaminant plume with groundwater
movement in soil consisting of hydrated-oxide type minerals. Lopez
et al. [118] assessed the feasibility of using red mud (RM), a residue
from bauxite refining, for waste-water treatment. Moistened mixtures
of RM and 8% (w/w) CaSO4 form aggregates which are stable in
aqueous media. The adsorption capacities were reported to be 19.72,
12.59, 10.95 and 10.57 mg/g for Cu(II), Zn(II), Ni(II) and Cd(II),
respectively. Red mud has been converted into an inexpensive and
efficient adsorbent and used for the removal of lead and chromium
from aqueous solutions [119]. The effect of presence of other metal
ions/surfactants on the removal of Pb(II) and Cr(VI) has also been
studied. The maximum adsorption capacity for Pb(II) and Cr(VI) by
red mud were reported as 64.79 mg/g (batch capacity), 88.20 mg/g
(column capacity), and 35.66 mg/g (batch capacity), 75.00 mg/g
(column capacity) respectively. Wang et al. [120] presents an excellent
review on the utilization of red mud in water treatment for the removal
of toxic heavy metal and metalloid ions from their aqueous solu-
tion. They have also discussed the environmental compatibility of red
mud. Red mud presents a promising application in water treatment
for the removal of toxic heavy metal and metalloids from wastewaters.
3.4. Adsorption of heavy metals on lignin, a black liquor waste of paper
industry
Black liquor is a waste product originated from paper industry.
Lignin, extracted from black liquor, could be used as adsorbents for
the removal of heavy metals from wastewater. Lignin is a natural
amorphous cross-linked resin that has an aromatic three-dimensional
polymer structure containing a number of functional groups such as
phenolic, hydroxyl, carboxyl, benzyl alcohol, methoxyl, and aldehyde
groups [121], making it potentially useful as an adsorbent material for
removal of heavy metals from wastewater. The elemental analysis
shows that the lignin had the following percentage composition (%)
[122]: C, 60.8; H, 5.8; N, 1.3; S, 2.1; ash, 5.5; K, 0.24; Ca, 0.06; Na, 1.4;
 M. Ahmaruzzaman / Advances in Colloid and Interface Science 166 (2011) 36–59
Mg, 0.01; Fe, 0.007; and Al, 0.03. Suhas et al. [123] have reviewed the
literature on the utilization of lignin for the removal of harmful
substances from wastewater and focused on the utilization of lignin
as an adsorbent, its conversion into chars and activated carbons.
Srivastava et al. [124] obtained remarkably high uptake of Pb(II) and
Zn(II), up to 1587 and 73 mg/g for Pb(II) and Zn(II), respectively, by
using lignin extracted from black liquor. The uptake of lead is found to
be greater than the uptake of zinc, and the sorption capacity increased
with increased pH. Several polyhydric phenols and other substituted
analogs may be involved in the uptake of metal ions. Demirbas [125]
reported a maximum adsorption capacity of 8.2–9.0 mg/g for Pb(II)
and 6.7–7.5 mg/g for Cd(II) on lignin from beech and poplar wood
modified by alkaline glycerol delignification. Mohan et al. [126]
extracted lignin from black liquor waste, and utilized for the removal
of copper and cadmium from aqueous solutions. The maximum lignin
adsorption capacities at 25 °C were 87.05 mg/g and 137.14 mg/g for
Cu(II) and Cd(II), respectively. They reported that adsorption occurs
through a particle diffusion mechanism at temperatures of 10 and
25° C while at 40° C it occurs through a film diffusion mechanism.
To assess the possibility of using lignin to remove Cr(III) from waters,
the adsorption of Cr(III) on lignin isolated from black liquor, was
investigated [127]. The equilibrium data can be well fitted using
Langmuir two-surface model with a maximum adsorption capacity of
17.97 mg/g. The authors suggested that Cr(III) adsorption on lignin was
mainly through the ion-exchange mechanism and formed inner-sphere
complexes with lignin. Crist et al. [128] utilized kraft lignin, a by-product
of paper production, for the removal of toxic metals from industrial
process water. They reported that uptake of divalent toxic metals is
accompanied by a release of protons or existing metals from the lignin.
Equilibrium constants for displacement of protons decreased with
pH, and equilibrium constants for metal-metal exchange showed that
binding strengths followed the order: Pb N Cu N Zn N Cd N CaN Sr.
In another study, Guo et al. [122] investigated the adsorption of
heavy metal ions Pb(II), Cu(II), Cd(II), Zn(II), and Ni(II) on lignin
isolated from black liquor. Lignin has affinity with metal ions in the
following order: Pb(II) N Cu(II) N Cd(II) N Zn(II) N Ni(II). They reported
that lignin surfaces contain two main types of acid sites attributed to
carboxylic- and phenolic-type surface groups and the phenolic sites
have a higher affinity for metal ions than the carboxylic sites. Metal
ion adsorption onto deprotonated carboxyl and phenolic sites was the
dominant mechanism that could reasonably explain the observed
adsorption behavior [122].
Lignin was also utilized for the removal of Cr(III) from waters
[129]. The Cr(III) adsorption was strongly dependent on pH and
adsorbent dosage, but independent of ionic strength and other metal
ions. The adsorption kinetic data can be described well with pseudo-
second-order model and the equilibrium data can be well fitted using
Langmuir two-surface model with a maximum adsorption capacity
of 17.97 mg/g. Cr(III) adsorption on lignin was mainly through the
ion-exchange mechanism and formed inner-sphere complexes with
lignin. The independence of ionic strength suggests that Cr(III) pri-
marily forms inner-sphere complexes with lignin. The low cost, the
high adsorption capacity and the successful application in removing
Cr(III) from wastewater demonstrate that lignin has a great potential
to be an economical and efficient adsorbent for the removal of Cr(III)
from industrial effluents. Carboxymethylated lignin isolated from
sugar cane bagasse has been investigated for the removal of Cd(II) and
Pb(II) from wastewater [130]. A factorial design showed that the most
important variables are temperature and ionic strength for the Pb(II)
adsorption in single and binary systems respectively. For both metals,
maximum binding capacity decreased with increased ionic strength.
From the above data and the review by Suhas et al. [123] there are
significant differences in the metal adsorption capacities of different
types of lignin. Moreover, the related mechanisms of metal adsorption
by lignin are still subject to debate. Some studies have found that ion-
exchange mechanisms may be responsible for the adsorption of metal
45
ions on lignin [131,132]. Several processes including ion exchange,
surface adsorption, and complexation, have been suggested to ex-
plain the mechanisms involved. Detailed studies are therefore re-
quired to achieve a quantitative and mechanistic understanding of
the adsorption of metal ions by lignin.
3.5. Adsorption of heavy metals on waste hydroxide, a fertilizer industry
waste
Iron (III)/Cr(III) hydroxide is one of the waste materials obtained
from fertilizer industries. It can be used for the removal of heavy
metals from wastewater. Navasivayam and Ranganathan [133–135]
investigated the potential of Fe(III)/Cr(III) hydroxide for the removal
of Cr(VI), Cd(II), Pb(II), and Ni(II) ions from wastewater. The max-
imum adsorption capacity of Cr(VI) was found to be 0.47 mg/g. The
intraparticle diffusion of Cd(II) through pores of adsorbent was shown
to be main rate limiting step. They [135] also studied the effect of
ligands, such as, ethylenediamine tetraacetic acid, citrate and acetate,
on the adsorption of metal ions such as Pb(II), Ni(II) and Cd(II). All
three ligands decreased the adsorption of Pb(II) in a pH range of 3.5–
8.5. The presence of citrate and EDTA considerably decreased the
adsorption of Ni(II), however, acetate showed a slight increase in
adsorption capacity. The adsorption of cadmium decreased signifi-
cantly in the presence of acetate and citrate.
Fe(III) hydroxide was also used for the removal of metal ions
including Cr(VI), Ni(II), Cu(II), Cd(II) and Zn(II) from electroplating
waste water [136]. The adsorption of heavy metals on hydrous oxides
depends upon the oxidation potential, pH and complex forming
ability. These factors also play an important role in the transport of
heavy metals in the aquatic environment [137]. Hydrous oxides of Fe
(III) and Mn(II) have been found to be very effective in controlling the
concentration of heavy metals in sea water [138]. The adsorption of
metal ions on hydrous oxides of Fe(III) and Mn(II) has also been
studied [139]. Huang et al. [140] investigated the potential of waste
iron oxide material for the removal of Cu(II) from aqueous solutions.
The highest Cu(II) adsorption capacity of waste iron oxide adsorbent
was determined as 0.21 mmol/g for 0.8 mmol dm − 3 initial Cu(II)
concentration at pH 6.0 and 300 K. Chromium(VI) [Cr(VI)] is adsorbed
as HCrO −4 on iron(III) hydroxide at a pH below 8.5 [141]. The Cr(VI)
adsorption is suppressed by the presence of other anions such as SO42−
and SCN −, and enhanced by the presence of metal ions such as Cd(II)
and Pb(II). The suppression is due to the competitive adsorption of
other anions, depending upon the stability of their iron complexes.
The enhancement is probably due to the increase in adsorption sites
as a result of co-precipitation of metal ion with iron(III) hydroxide.
The effects of chromate, cyanide, pyrophosphate and tripolypho-
sphate on the adsorption of metals (Cd, Cu, Cr, Zn, Ni and Pb) onto iron
oxyhydroxide have been investigated [142]. In absence of complexing
agents, adsorption of the strongest adsorbing metals (Pb, Cu, Cr)
slightly inhibited that of the remaining metals when all were present
at concentrations of 10 − 4 M and 10 − 3 M and total iron was available
as the adsorbent. The presence of up to 10 − 3 M CrO4 had no significant
effect on removal of the cationic metals from solution. The presence of
cyanide (CN) strongly inhibited the adsorption of Ni and Cu, but did
not affect other metals. These effects can be explained based on
changes in metal speciation when the CN was added. Cyanide was
found to form strong soluble complexes with Ni. Also, reduction of Cu
(II) to Cu(I) by CN, and subsequent formation of Cu +–CN complexes,
was thermodynamically favorable. The remaining metals in the system
did not form strong complexes under the experimental conditions and
were therefore unaffected. At low concentration, pyro- and tripoly-
phosphate enhanced adsorption of all the metals, but at high concen-
tration they led to a qualitative change in the metal sorption behavior.
Whereas in absence of the phosphate ligands, metal sorption is
strongly pH dependent, at high polyphosphate concentration, this
dependence almost disappears. Simultaneously, some of the Fe
46 M. Ahmaruzzaman / Advances in Colloid and Interface Science 166 (2011) 36–59

Table 4 Table 4 (continued)

Summary of adsorption of metals on other industrial by-products/wastes. Metals Adsorbent Adsorption Capacity References
(mg/g)
Metals Adsorbent Adsorption Capacity References
(mg/g) Tea industry waste 8.64 [192]
Zn2+ Blast furnace slag 103.3 [83] Fly ash 1.38 [168]
Lignin 73 [124] Apple waste 10.8 [169]
Acid washed-tea industry waste 12 [143] Phosphated apple waste 36.2 [169]
Tea industry waste 11 [144] Sugar beet pulp 38.0 [179]
Clarified sludge 15.53 [96] Orgabosolv lignin 1.10 [83]
Acid-washed-tea industry waste 31 [143]
Sugar beet pulp 35.6 [184]
Tea industry waste 11.29 [192]
Lignin 11.24 [122]
Solid residue of olive mill products 5.40 [145] Olive stone waste 7.73 [149]
Red mud 12.59 [118] Crop milling waste 39.99 [148]
Blast furnace slag 17.65 [146] Cellulose pulp waste 5.82 [197]
Powered waste sludge 168 [147] Lignin 25.40 [129]
Coffee Husk 5.57 [173] Carboxymethylated lignin 107.53 [130]
Ni2+ Red mud 160 [112] Areca waste (AW) 1.12 [177]
Sugar beet pulp 46.1 [183]
Tea industry waste 5 [144]
Native sugar beet pulp 38.0 [179]
Tea factory waste/waste tea 18.42 [259]
Grape stalk wastes 1.06 [187] Treated sewage sludge 16.7 [93]
Lignin 5.98 [129] Coffeee Husk 6.85 [173]
Exhausted coffee wastes 7.25 [198] Pb2+ Waste slurry 1030 [159]
Grape stalk wastes 38.31 [198] Lignin 1865 [124]
Sugar beet pulp 11.85 [179] Blast furnace slag 40.0 [84]
Crop milling waste 20.15 [148] Lignin 1587 [124]
Lignin 8.2–9.0 [125]
Olive stone waste 2.13 [149]
Treated sewage sludge 9.09 [93] Acid washed-tea industry waste 79 [143]
Cu2+ Blast furnace slag 133.3 [83] Tea industry waste 2 [144]
Waste slurry 20.97 [172] Tea industry waste 65 [175]
Sour orange residue 21.7 [151] Olive stone waste 9.26 [149]
Olive mill residue 13.5 [150] Crop milling waste 49.97 [148]
Red mud 106.44 [153] Lignin 89.51 [129]
Carboxymethylated lignin 37.99 [130]
Rud mud/blast-furnace sludge 10.57 [154]
Sugar beet pulp 43.5 [183]
Slag 11.23 [155]
Lignin 6.7–7.7 [125] Sludge 39.3 [178]
Seafood processing waste sludge 15.73 [172] Waste biogas residual slurry 28.0 [186]
Tea industry waste 11.29 [192] Fe3+ Tea industry waste 24 [144]
Iron oxide 98.0 [157] As3+ Zr(IV)-loaded orange waste 130 [170]
Fe(III)/Cr(III) 39.0 [158] As5+ Leather industry waste 26 [180]
Acid washed-tea industry waste 27 [143] Zr(IV)-loaded orange waste 88.0 [170]
V5+ Waste metal sludge 24.8 [97]
Tea industry waste 48 [175]
Olive stone waste 2.03 [149]
Sugar beet pulp 30.9 [184]
Grape stalk wastes 1.01 [187]
Cellulose pulp waste 4.98 [197] adsorbent dissolves as Fe–P complexes. The changes in metal behavior
Lignin 22.87 [129] with increasing ligand concentration reflect the totality of interactions
Areca waste (AW) 1.12 [177]
in the system, which includes complexation, adsorption of free metal
Grape stalk wastes 42.92 [198]
Exhausted coffee wastes 11.60 [198] and complexes, iron dissolution and changes in the surface charge
Sugar beet pulp 21.16 [179] associated with the various sorption reactions. The effects of metal,
Crop milling waste 27.97 [148] chromate and CN concentrations do not appear to be major impe-
Olive stone waste 2.02 [149] diments to the utilization of adsorption as a treatment process. The
Coffeee Husk 7.50 [173]
Dried sugar pulp 18.2 [194]
effects of P-containing ligands are more complicated: they may either
Cr6+ Waste slurry 640 [159] increase or decrease metal adsorption depending on the particular
Iron(III) hydroxide 0.47 [160] water under study.
Blast furnace slag 7.5 [161]
Activated red mud 1.6 [162]
Paper mill sludge 7.4 [163]
Red mud 75 [119] 3.6. Adsorption of heavy metals on miscellaneous industrial adsorbents
Clarified sludge 26.31 [164]
Tea industry waste 455 [165] The literature also showed that other industrial wastes, such as,
Leather industry waste 133 [180] waste slurry, coffee husks, Areca waste, tea factory waste, sugar beet
Distillery sludge 5.70 [167]
Olive oil factory wastes 12.15 [181]
pulp, waste pomace of olive oil factory waste, battery industry waste,
Tea factory waste 54.65 [174] waste biogas residual slurry, sea nodule residue, sour orange residue,
Sugar beet pulp 17.2 [166] and grape stalk wastes have been utilized as low-cost adsorbents for
Sugar cane Bagasse 13.4 [166] the removal of toxic heavy metals from wastewater. Table 4 showed
Coffee Husk 6.96 [173]
the results of important metals reported on various industrial based
Cr3+ Lignin 17.97 [122]
Hg2+ Waste slurry 560 [159] adsorbents [143–170].
Cd2+ Waste slurry 15.73 [172] The potential of sour orange residue for the removal of copper
Lignin 6.7–7.5 [125] ions from aquatic systems was investigated by Khormaei et al. [170].
Fly ash 207.3 [152] Effects of particle size on adsorption efficiencies were small, but rate
Red mud 66.67 [153]
Rud mud/blast-furnace sludge 16.07 [154]
of adsorption decreased with increasing the particles size. Additional
Blast furnace slag 38 [156] chemical treatment of the adsorbent by NaOH, increased the adsorp-
Seafood processing waste sludge 20.97 [172] tion capacity. The interactions between Cu(II) ions and functional
groups on the surface of the orange residue are confirmed by FTIR
 M. Ahmaruzzaman / Advances in Colloid and Interface Science 166 (2011) 36–59 47

analysis and the spectra showed that carboxyl and hydroxyl groups Na and Cl ions does not have a significant effect on the adsorption of
are involved in Cu binding to the sour orange residue. these metals by SBP.
Waste slurry, generated by the combustion of liquid fuel in a Sea nodule residue (SNR), a solid waste generated during the pro-
fertilizer production plant was pretreated with peroxide and then cessing of polymetallic sea nodules for copper, nickel, and cobalt re-
air activated at 450 °C and utilized for the removal of Cu(II), Cr(VI), covery, has been demonstrated to be an effective adsorbent for removing
Hg(II), and Pb(II) from aqueous solution [171]. Lee and Davis [172] an inorganic pollutant such as zinc from wastewaters/industrial ef-
studied the adsorption of Cu(II) and Cd(II) using waste slurry from fluents by adsorption [185]. Waste biogas residual slurry (BRS) was
seafood processing factories. The adsorption capacity of the waste investigated for the adsorption of Pb(II) from aqueous solution [186]
slurry was found to be 20.97 and 15.73 mg/g for Cu(II) and Cd(II), and the adsorption capacity was found at 28 mg/g. The usefulness of
respectively. Coffee husks, a coffee processing residue, were used for grape stalk wastes generated in the wine production process has been
the removal of heavy metal ions from aqueous solutions [173]. The investigated for the removal of copper and nickel ions from aqueous
uptake of hexavalent chromium Cr(VI) from aqueous solutions onto solutions [187]. Maximum uptake obtained was 1.59 × 10− 4 mol of
tea factory waste (TFW) has been assessed [174]. The maximum copper and 1.81 × 10− 4 mol of nickel per gram of dry sorbent. Sorption
adsorption capacity was found to be 54.65 mg/g of Cr(VI) ions on of copper and nickel on grape stalks released an equivalent amount of
TFW. Adsorption of copper and lead ions onto tea waste from aqueous alkaline and alkaline earth metals (K+, Mg2+, Ca2+) and protons, in-
solutions was also studied [175] and highest metal uptake of 48 and dicating that ionic exchange is predominantly responsible for metal
65 mg/g were observed for Cu and Pb, respectively. Pb showed higher ion uptake. Fourier transform infrared (FTIR) spectrometry analysis
affinity and adsorption rate compared to Cu under all the experi- indicated that lignin C―O bond might be involved in metal uptake. In
mental conditions. Increase in the total adsorption capacity was another study, Vegliò et al. [188] utilized olive mill residues (OMR) as
observed when both Cu and Pb ions are present in the solution. A copper adsorbing material. Regenerated residues by acid solutions gave
study is made on the use of a steel-making by-product (rolling mill a copper removal of about 40%, in the same experimental conditions of
scale) as a material for removing Cu(II) ions from aqueous solutions the first adsorption test: regeneration with EDTA at different concen-
[176]. The removal of Cu(II) ions from an aqueous solution involves trations suggested that it presents a damage of adsorption active sites.
two processes: (i) adsorptions of Cu(II) ions on the surface of mill On the other hand, the utilization of HCl and CaCl2 found to completely
scale due to the presence of iron oxides and (ii) cementation of Cu(II) regenerate the adsorbent material.
onto metallic iron present in the mill scale.
Areca waste (AW) has been investigated for the removal of
cadmium and copper from aqueous solution [177]. The highest value 4. Competitive adsorption
of Langmuir maximum uptake was found for cadmium (1.12 mg/g)
and copper (2.84 mg/g). Ion-exchange and surface adsorption might Industrial effluents rarely contain a single component; hence,
be involved in the adsorption process of cadmium and copper. De- design of adsorption systems must be based on multi-component
sorption studies revealed that cadmium and copper can be easily systems. Therefore, competitive adsorption is very important in water
removed from AW by altering the pH values of the solution using and wastewater treatment because most metal ions to be adsorbed
HNO3. The adsorption of cadmium, Cu(II), lead and zinc from aqueous exist in solution with other adsorbable metal ions. Industrial effluents
solution by paper mill waste (PMW) and composted PMW was also contain apart from various pollutants, different salts at different
investigated by Lister and Line [178]. Sugar beet pulp generated by levels of concentration. Table 5 showed the adsorption capacities for
sugar-refining factories has been shown to be an effective adsorbent metal ions in multi-component systems on various adsorbents. More-
for the removal of heavy metals from aqueous solutions [179]. The over, the utilization of fixed bed is more preferable than a batch reactor
structural components related to the metallic adsorption being deter- in industrial applications, as it is able to treat wastewater with large
mined, batch adsorption studies were performed for several metal quantity. Different reasons have been given regarding the adsorption
ions, namely, Pb(II), Cu(II), Zn(II), Cd(II), and Ni(II). Ion exchange affinity of industrial waste materials on heavy metals. The amount of
with Cd(II) ions neutralizing the carboxyl groups of the polysaccha- adsorbed ions depends on the equilibrium between adsorption com-
ride was found to be the predominant mechanism, added with com- petition from all the cations, ionic size, stability of bonds between
plexation for Pb(II), Cu(II), and Zn(II) metals. metal ions and adsorbent [189]. Wong et al. [190] investigated the
The feasibility of using a solid waste from the leather industry as effect of competitive ions between Pb and Cu and shows that the
an adsorbent for removal of Cr(VI) and As(V) from aqueous media affinity of a modified rice husk (MRH) for metal ions is Pb N Cu in mixed
was studied [180]. The high amounts of Cr(VI) — 133 mg/g and As
(V) — 26 mg/g adsorbed demonstrates the good potential for using
this leather industry waste as a low-cost alternative to the tradi- Table 5
tionally used adsorbent materials. The waste pomace of olive oil Adsorption capacities for various metal ions in multi-component systems on various
adsorbents.
factory (WPOOF) was tested for its ability to remove chromium(VI)
from aqueous solution [181]. The adsorption potential of battery Metal System Adsorbent Adsorption Reference
industry waste as an adsorbent has been investigated for the removal capacity (mg/g)
of cobalt from aqueous solutions [182] and showed that the prepared Cu Cu(Cu–Cd) Black liquor lignin 38.71 [126]
adsorbent adsorbs cobalt to a sufficient extent (35 mg/g). Further, the Cu Cu(Cu–Zn) Black liquor lignin 43.81 [126]
metal-laden adsorbent was immobilized into cement for ultimate Cu Cu(Cd–Cu–Zn) Black liquor lignin 9.95 [126]
Cd Cd(Cd–Cu) Black liquor lignin 25.71 [126]
disposal and no significant leaching was observed from the stabilized Cd Cd(Cd–Zn) Black liquor lignin 36.93 [126]
products. The adsorption of Cd(II) and Pb(II) on sugar beet pulp (SBP) Cd Cd(Cd–Cu–Zn) Black liquor lignin 16.12 [126]
has been reported [183] and overall uptake for the (SBP) is found to Cu Cu(Cu–Cd) Tea industry waste 6.65 [192]
be 46.1 mg/g for Cd(II) at a pH of 5.3 and 43.5 mg/g for Pb(II) at a pH Cd Cd(Cu–Cd) Tea industry waste 2.59 [192]
Cu Cu(Cu–HA) Fly ash 28.0 [193]
of 5.0, which seems to be removed exclusively by ion exchange,
Pb Pb(Pb–HA) Fly ash 37.0 [193]
physical adsorption and chelation. The abilities of native sugar beet Cd Cd(Cu–Cd) Anaerobic sludge 8.94 [197]
pulp (SBP) to remove copper Cu(II) and zinc Zn(II) ions from aqueous Cu Cd(Cu-Cd) Cellulose pulp waste 4.55 [197]
solutions were compared [184]. The maximum overall uptake for the Cd Cd(Cu–Cd) Cellulose pulp waste 1.82 [197]
SBP is 30.9 mg/g for copper at a pH of 5.5 and 35.6 mg/g for zinc at a Pb Pb(Pb–Cd) Carboxymehtylated lignin 123.07 [130]
Cd Cd(Pb–Cd) Carboxymehtylated lignin 9.33 [130]
pH of 6.0. The presence of low ionic strength or low concentration of
48 M. Ahmaruzzaman / Advances in Colloid and Interface Science 166 (2011) 36–59
metal solutions. The stability and enthalpy of formation are greater for
Pb-MRH than for Cu-MRH.
Aksu and Gonen [191] reported the simultaneous adsorption of
phenol and chromium(VI) ions on the Mowital®B30H resin immo-
bilized activated sludge from binary mixture and compared with
single phenol or chromium(VI) situation in a packed bed column. It
has been demonstrated that dried activated sludge offers interesting
possibilities as a metal ion and an organic adsorbent, showing rapid
binding. The data obtained in the single and dual systems indicated
that the adsorption capacity of Mowital®B30H resin immobilized
activated sludge for chromium(VI) is generally higher than that of
phenol. The uptake capacity of dried activated sludge for chromium
(VI) and phenol increased with increased influent concentration of
each component from bi-solute aqueous solutions. However, the
presence of a second component decreased both the capacities. This
may be attributed due to the fact that both the components are com-
peting for same adsorption sites on the activated sludge. The mono-
and two-component sorption phenomena were expressed by
Yoon and Nelson model to predict the breakthrough curves for each
component. The relation between Yoon and Nelson model rate con-
stant of each component and the concentrations of each component
in the binary sorption system was determined using the method
of response surface analysis. Such relationships can be used to find
rate constants in a mixture containing unstudied concentrations of
phenol and chromium (VI). The adsorption ability of Turkish tea
waste (fibrous) obtained from various tea-processing factories was
investigated for the removal of Cu(II) and Cd(II) from single (non-
competitive) and binary (competitive) aqueous systems [192]. The
maximum adsorption capacities of Cu(II) and Cd(II) per gram tea
waste were calculated as 8.64 ± 0.51 and 11.29 ± 0.48 mg for single
and 6.65 ± 0.31 and 2.59 ± 0.28 mg for binary systems, respectively.
Heavy metals and humic acid (HA) are two important pollutants in
surface and waste water systems. Wang et al. [193] utilized fly ash as a
low-cost adsorbent for the simultaneous removal of heavy metals
and humic acid. The investigations were conducted for individual
pollutant adsorption along with co-adsorption of both pollutants
and found that, for a single pollutant system, fly ash can achieve
adsorption of lead ion at 18 mg/g, copper ion at 7 mg/g and humic acid
at 36 mg/g, respectively. For co-adsorption, complexation of heavy
metals and humic acid plays an important role. The presence of humic
acid in water will provide additional binding sites for heavy metals,
thus promoting metal adsorption on fly ash. For Pb–HA and Cu–HA
systems, Pb(II) and Cu(II) adsorption can increase to 37 and 28 mg/g,
respectively, at pH 5 and 30 °C. However, the heavy metal ions present
in the system will compete with the adsorption of humic acid on fly
ash, thus resulting in a decrease in humic acid adsorption. Simulta-
neous adsorption of Gemazol Turquoise Blue-G reactive dye anions
and copper(II) cations to dried sugar beet pulp, from binary mixtures
was studied and compared with single dye and metal ion situation in a
batch system [194]. The presence of increasing concentrations of
copper(II) ions increased the equilibrium uptake of dye anions while
the increasing concentrations of dye diminished the copper(II) ion
uptake for both pH values studied. This situation showed the syn-
ergistic effect of copper(II) cations on dye adsorption and the antag-
onistic effect of dye anions on copper(II) adsorption. Adsorption
isotherms were developed for single-dye, single copper(II) and dual-
dye-copper(II) ion systems at these two pH values and expressed by
the mono-component Langmuir model and multi-component syner-
gistic and antagonistic Langmuir models and model parameters were
estimated by the non-linear regression. The competitive adsorptive
removal of Cd(II) and Zn(II) ions from binary systems using rice
husk ash (RHA), as an adsorbent was reported by Srivastava et al.
[195]. The initial pH (pH0) significantly affects the capacity of RHA for
adsorbing the metallic ions in the aqueous solution. The pH0 ≈ 6.0 is
found to be the optimum for the removal of Cd(II) and Zn(II) ions by
RHA. The single ion equilibrium adsorption from the binary solution is
better represented by the non-competitive Redlich–Peterson (R–P)
and the Freundlich models than by Langmuir model in the initial
metal concentration range of 10–100 mg/l. The adsorption of Zn(II)
ion is more than that of Cd(II) ion, and this trend is in agreement
with the single-component adsorption data. The equilibrium metal
removal decreased with increased concentrations of other metal ions
and the combined effect of Cd(II) and Zn(II) ions on RHA is found to
be antagonistic. The extended-Freundlich model satisfactorily repre-
sents the adsorption equilibrium data of Cd(II) and Zn(II) ions onto
RHA. Heavy metal adsorption onto solid wastes from olive oil pro-
duction plants, olive pomace, has also been investigated [196]. Acid–
base properties of the active sites of olive pomace were determined
by potentiometric titrations and represented by a continuous model
accounting for two main kinds of active sites. Competition among pro-
tons and heavy metals in solution was considered by performing ad-
sorption tests at different equilibrium pH with single (Cu and Cd) and
binary metal systems (Cu–Cd).
The adsorption of copper and cadmium ions using waste materials
such as compost, cellulose pulp waste and anaerobic sludge as adsor-
bents is reported [197]. A competitive uptake was observed when
both metals are present; copper being preferentially adsorbed by all
materials with the exception of anaerobic sludge. Anaerobic sludge
has a greater preference for cadmium, even in the presence of copper,
with a removal efficiency of 98%. Two industrial vegetable wastes,
grape stalk, coming from a wine producer, and exhausted coffee,
coming from a soluble coffee manufacturer, have been investigated
for the removal of Cu(II) and Ni(II) from aqueous solutions in pre-
sence and in absence of the strongly complexing agent EDTA [198].
Effects of pH and metal–EDTA molar ratio, kinetics as a function of
sorbent concentration, and sorption equilibrium for both metals onto
both sorbents were evaluated in batch experiments. EDTA was found
to dramatically reduce metal adsorption, reaching total uptake
inhibition for both metals onto both adsorbents at equimolar metal:
ligand concentrations. Grape stalk showed the best performance for
Cu(II) and Ni(II) removal in presence and in absence of EDTA, despite
exhausted coffee appearing as less sensitive to the presence of
complexing agent. The performance of Cu(II) and Ni(II) sorption onto
grape stalk in a continuous flow process was evaluated. In solutions
containing EDTA, an initial metal concentration in the outlet flow
corresponding to the complexed metal fraction was observed from
the beginning of the process. A high metal recovery yield (N97%) was
achieved by feeding the metal-loaded column with 0.05 M HCl. From
the above studies, it has been found that very few studies have been
reported for the removal of heavy metals from real wastewaters.
However, some investigations have been carried out to see the effect of
metal adsorption in presence of other organic substances. Therefore,
competitive metal adsorption either in presence of other metals or
organic impurities is very important and needs to be addressed in
detail in the future.
5. Leaching of fly ash, red mud, blast furnace slag, and other wastes in
water system
Utilization of fly ash in water involves the potential leaching
of some elements into water. This creates a problem of secondary
environmental pollution. It was found that the surface layer of fly ash
particles probably microns in thickness contains a significant amount
of readily leachable material which is deposited during cooling after
combustion. Therefore, the charge on the surface of fly ash particle
and formation of the diffuse double layer plays a significant role in
leaching. The elements present were divided into two groups on the
basis of their concentration dependence on particle size. Results of
the analysis by particle size indicates that the elements Mn, Ba, V, Co,
Cr, Ni, Ln, Ga, Nd, As, Sb, Sn, Br, Zn, Se, Pb, Hg and S are usually volatile
to a significant extent in the combustion process. The volatility for
these elements is inversely proportional to the particle size. Elements,
 M. Ahmaruzzaman / Advances in Colloid and Interface Science 166 (2011) 36–59
such as, Mg, Na, K, Mo, Ce, Rb, Cs and Nb appear to have a smaller
fraction volatilized during coal combustion [199]. Here the volatility
is directly proportional to particle size. The elements Si, As, Fe, Ca,
Sr, La, Sm, Eu, Tb, Py, Yb, Y, Se, Zr, Ta, Na, Th, Ag and Zn are either not
volatilized or may show minor trends which are related to the
geochemistry of the mineral matter. The volatility of trace elements
increased from a larger particle size to a smaller particle size which
establishes an inverse relationship of volatility and particle size [200].
Studies have shown that only about 1–3% fly ash material is soluble
in water with lignite fly ashes having a higher proportion of water
soluble constituents [201]. The leaching of major elements from
coal fly ash has been extensively reviewed [202]. Analysis of water
extracts [203,204] showed that the principal cations in water extracts
are calcium and sodium whereas anions are dominated by OH −, CO3
with aqueous extracts of the ash nearly saturated with Ca(OH)2. The
alkalinity and acidity controlled the extractability of elements like As,
B, Be, Cd, Cr, Cu, F, Mo, Se, V and Zn. Aqueous extracts of an acidic fly
ash contained concentrations of Cd, Co, Cu, Mn, Ni, Zn, As, B, Be, Cd, F,
Mo, Se and V [205,206]. Leachate waters can have markedly different
compositions, depending on the surface of fly ash, flue gas process
conditions design of combustion systems and whether lime or lime
stone injection processes were implemented for desulfurization. Total
dissolved solid concentrations may vary from hundreds to tens of
thousands of milligrams/liter. Even a small sample can show marked
differences in leachate water chemistry, depending on reaction time
and water/solid ratio in batch equilibrations or with column length
and flow rate in a dynamic leaching test. The mineral and glass
phases that constitute fly ash material are formed over a wide range of
temperatures in the furnace environment. All these phases are unstable.
They dissolve and then precipitate as stable and less soluble secondary
phases. The primary phases even though highly soluble especially in
water are dissolved very slowly as they are trapped in the glass and
crystalline alumina silicates. Secondary hydrous alumino silicate
products are shown to be very insoluble [207] and build up on rinds
on the surfaces of primary phases. The dissolution of primary phases is
slowed down as the mass transport of ions and water between phases
becomes diffusion controlled.
Many important aspects of the leaching behavior of fly ash have been
covered by a number of researchers [199,208–210]. Experimental
results indicate that leachability of heavy metals from the coal fly ash is
relatively low and leaching extent is dependent on the conditions of
water system. Trace metal concentration in the leachate depends on fly
ash weight/solution, pH, concentration of the elements, temperature,
pressure and time. In water, rapid leaching of most of the trace metals
(except Cu) takes place from the surface of ash particles in the lower pH
range; all the trace elements lie within acceptable limits [210].
A complex mixture of organic compounds is also associated with
fly ash particles. The organic compounds identified in fly ash extracts
include known mutagens and carcinogens. There are leaching pro-
cedures for the dissolution of the organic compounds of FA in 30%–
40% hydrogen peroxide, concentrated nitric acid under microwave
conditions, or benzene. However, this chemical treatment also leaches
components associated with both organic and inorganic compounds
in fly ash. For example, some unstable minerals from the chloride,
sulfate, sulfide, oxide, and carbonate classes may be leached, destroyed,
or altered during this procedure. Formations of artificial minerals and
phases such as oxyhydroxides, calcium oxalate, nitrates, and others are
also possible. Hence, such minerals are not available or actual in the fly
ash residue for any future mineralogical study. On the other hand,
portions of organics may remain in the residue, because of the less-
soluble behavior or when the solvent cannot contact with organics
encapsulated in other inorganic matrixes (especially glass). There are
traces of polycyclic aromatic hydrocarbons present in the coal fly ash,
typically up to 25 mg/kg. Due to the low solubility, the leachate from
coal fly ash contains very low concentrations of polycyclic aromatic
hydrocarbons (PAHs).
49
Red mud may impose a risk for living organisms, due to its caustic
nature. Neutralization of red mud allowed its reuse to achieve better
performance. Red mud can be used for the treatment of wastewater,
after its neutralization. However, leaching of red mud will be a big
problem and the environmental compatibility has to be evaluated for
its ultimate disposal.
Some investigations have been carried out to understand the
leaching behavior of red mud. Leachability of chromium and iron from
the reacted wastes was determined by Singh and Singh [211] using
the TCLP. This test showed a very low level of leachability of chro-
mium as Cr(III) and iron from the reacted wastes. To minimize their
leachability further, Cr(VI)-reacted solid wastes were stabilized with
Portland cement. Leachability tests of stabilized wastes by the TCLP
indicated a considerable decrease in leachability of chromium and
iron compared with that of reacted wastes alone. McConchie et al.
[212] also conducted TCLP tests of Bauxsol TM and found that the
metal leaching capacity was far below the standard limits. Brunori
et al. [213] reported a leaching test on unwashed and seawater-
washed red muds (BauxsolTM). The BauxsolTM showed a general
high metal trapping capacity and the release of the trapped metals
was also generally low even at low pH values. The leaching tests at
pH 5 showed that less than 6% of trapped metal was leached (As, Cd
and Cu), while 10–30% was leached in the case of Mn and Zn. Ho et al.
[214] investigated a long-term effect of leaching of red mud. The
major salts released were sodium sulfate, a product of red mud
alkalinity neutralization by gypsum, and excess gypsum released at its
solubility concentration. The leaching of Al, Fe, and Cd from the red
mud and gypsum was negligible, while the retention of superphos-
phate was over 99%. Fluoride from the waste gypsum was leached
rapidly and reduced to background concentration (less than 1 mg/l).
The physical, chemical and genotoxic properties of ARM and its waste
mud remaining after waste water treatment were also studied by
Orešcanin et al. [215]. The sequential leaching of waste mud under
different conditions was investigated. Heavy metal content and other
parameters, as well as the genotoxicity of water extract of new
coagulant produced for industrial waste water treatment, were inves-
tigated to confirm its non-toxicity before its commercial production
and usage. Kutle et al. [216] reported an assessment of environmental
effects of leaching from red mud with waste base in a waste disposal
site. They reported that a possible threat to the environment from red
mud under normal environmental conditions could be caused only by
leaching of alkalis and V. Wang et al. [120] reported that leaching and
eco-toxicological tests indicate that red mud does not present high
toxicity to the environment before or after reuse. Leaching tests also
indicate that red mud presents a much lesser leachability and thus no
serious secondary contamination will occur. All of the above inves-
tigations suggest that red mud exhibits low leaching of its compo-
nents. After reuse for some wastewater treatment, red mud can be
employed for brick production or disposed in nonhazardous landfills
without causing significant environmental toxicity.
The BF slag is basically inorganic in nature. It contains mainly
inorganic constituents such as silica (30–35%), calcium oxide (28–
35%), magnesium oxide (1–6%), and Al2O3/Fe2O3 18–258%. Two types
of blast furnace slag such as air-cooled slag and granulated slag are
being generated from the steel plants. The crystalline phases of slag
were identified as gehlenite, diopside pyroxene and barium alumi-
num silicate. It is necessary to assess the environmental impact of slag
and sludge, especially for the hazardous elements (heavy metals)
being present and the possible risk of their leacheability into soil and
groundwater, according to leaching test. The recovery of silica gel
from blast furnace slag has been attempted by leaching with H2SO4,
separation of gypsum, precipitation of silica gel at a pH of 3.2, followed
by the washing of the raw precipitate [217].
Matei et al. [218] tested blast oxygen furnace slag (BOF) and
electric arc furnace (EAF) slags to see their leaching of heavy metals
(Ni, Pb, Zn, Cd, Cr, Cu, Ca and Fe) from aqueous solution. The obtained
50 M. Ahmaruzzaman / Advances in Colloid and Interface Science 166 (2011) 36–59
results showed the presence of calcium, silicium and iron oxides, in
the large amounts, as a result of used fluxes. Applying this laboratory
test on steel wastes (basic oxygen furnace slags and electric arc
furnace slags) it is observed that not one of these heavy metal ions is
presented in high quantities in the leachate over the permissible
values. There are high quantities of some elements from leachate,
such as iron and calcium, due to their presence in initial composition
of the slags; the concentration values of these ions do not exceed the
maximum admitted values for potable water. The leaching of copper
ions from the industrial sludge was investigated using sulfuric acid
and reported that the concentration exceeds 15 mg/L, which is the
leaching standard of the toxicity characteristic leaching procedure
(TCLP) for hazardous waste in Taiwan [219]. A study on the metal
leaching from blast furnace steel slag has been studied and showed
that although blast furnace slags do leach heavy metals, this occurs to
a very low degree [220]. The leaching from the slag was found to be in
the same range as the corresponding leaching from natural gravel.
Similarly, the Landcare Research Institute from New Zealand and
natural Steel Slag Association in the United States performed research
on metal leaching from eight steel slag materials and found that
leaching from steel slag is not detrimental to the environment or
human health [221–223].
Lignin has an aromatic, three-dimensional polymer structure with
apparent infinite molecular weight and contains several functional
groups such as methoxyl, hydroxylaliphatic and phenolic, carboxyl,
etc. The lignin obtained from many of these precursors contains
significant amounts, up to 15%, of ash. This appears to be mainly silica,
with lower amounts of sodium and calcium, and trace quantities of
other metals but can be readily removed by sulfuric acid washing.
Thus, there is a lesser chance of metal leaching from the aqueous
lignin solution. However, leaching of lignin from their aqueous
solution should be performed and evaluated before it can be used as
an adsorbent.
Similarly, other industrial wastes, such as, waste slurry, coffee
husks, Areca waste, tea factory waste, sugar beet pulp, waste pomace
of olive oil factory waste, battery industry waste, waste biogas
residual slurry, sea nodule residue, and grape stalk wastes should be
tested for their metal leaching behavior in aqueous solution before
being used as an adsorbent for the removal of heavy metals. Therefore,
it is recommended that the following measures/steps should be
taken before any industrial waste material is used as adsorbent for
the treatment of wastewater: (1) leaching test of the industrial wastes
as adsorbent should be preformed for the investigated water system;
(2) forced extraction of mobile/labile substances present in the in-
dustrial waste; (3) destruction or ultimate disposal of persistent
heavy metals from industrial waste (adsorbent)-loaded heavy metals.
6. Efficiency and cost comparison
The two most important factors for the adsorption process to be
economically feasible are efficiency (adsorption capacity) and cost of
the adsorbent used. However, adsorption capacity is relative as
compared with some standard adsorbent, as it depends on various
factors, including initial concentration of the adsorbate under inves-
tigation. The cost of the precursor or the final material (adsorbents)
depends on various factors which include its availability, whether it
is natural, industrial/agricultural/domestic wastes or by-products or
synthesized products, the processing required, the treatment condi-
tions and both recycle and lifetime issues. For example, fly ash is
available free of cost at the power plant and hence only transportation
cost, laying and rolling cost are there in case of fly ash [20]. Waste
baggase fly ash is available for US $ 0.002 kg − 1, and considering the
cost of transport, chemicals, electrical energy, etc., used in the process,
the finished product would cost approximately US $0.009 kg − 1[224].
However, the cost of adsorbent is rarely reported in the literature.
Table 6 presents cost estimates of some industrial based adsorbents
Table 6
Cost of low-cost adsorbents and commercial activated carbons as reported in literature.
Adsorbent Price (US $ kg− 1) Reference
Blast furnace waste 0.038 [84]
Carbonaceous adsorbent (Blast furnace waste) 0.052 [84]
Carbonaceous adsorbent (waste metal sludge) 0.1–0.2 [97]
Waste metal sludge 0.004–0.005 [97]
Bagasse fly ash 0.009 [224]
Carbonaceous adsorbent (fertilizer industry waste) 0.1 [225]
Blast furnace slag 0.04 [226]
Commercial activated carbon 20 [226]
Commercial granular activated carbon 3.30 [227]
along with commercial activated carbons [225–227]. According to
these coal fly ash, bagasse fly ash, blast furnace waste, waste metal
sludge, carbonaceous adsorbent (fertilizer and waste metal sludge
industry waste) are the materials costing ≤0.1 US $ per kg making
them useful materials in terms of cost as compared to commercial
activated carbons which normally cost more than 3.0 US $ per kg.
Mainly a combination of these two factors, i.e., adsorption capacity and
cost of the adsorbent can be helpful in predicting the actual applicability
of these industrially available waste materials.
It is difficult to estimate a reliable treatment cost for metal-
contaminated wastewater because of the involvement of many cost
components, such as, pumping equipment and treatment facility. In
addition, changes in the quality and quantity of the various wastewaters
due to the fluctuating market demand also contribute to the variations
of its treatment cost. Therefore, full information on the treatment cost
of wastewater involving adsorption is rarely reported in the literature.
Therefore, total cost–benefit analysis of adsorption process for the
removal of heavy metals should be studied in detail and recommended
for future. Basically, the treatment cost of contaminated wastewater
varies, depending on its strength and quantity, the process employed,
the amount and composition of impurities, as well as the extent of
purification. The overall treatment cost includes the construction costs
as well as the operational and maintenance costs (O&M). The con-
struction costs normally depend on the effluent quality required and
the capacity of the installation, while the O&M costs cover manpower,
energy, chemicals and maintenance. The manpower cost varies from
one country to another. To obtain an accurate assessment of the
operational cost for the treatment of wastewater, a pilot-scale study
needs to be carried out. Most of the data presented in this review are
derived from research conducted on a laboratory scale and therefore,
further experiments on a pilot scale are needed to quantify the overall
treatment cost associated with the proposed treatment. A direct com-
parison of the overall treatment cost of each technique presented above
may be difficult due to their different operating conditions. In addition,
the overall treatment cost for various wastewaters varies depending on
the process employed and the local conditions. This may be attributed
to the fact that most of the industries are located either in the com-
mercial area of a town or in industrial estates, where wastewater
is discharged into sewers after neutralization with acids/alkalis. Wide
variations in the flow and the characteristics of the effluent wastewater
also present difficulties in estimating the treatment cost accurately. Such
inconsistency in data presentation makes a cost comparison among
the available treatment technologies for wastewater laden with heavy
metals difficult to materialize.
7. Combination of methodologies/techniques
Some researchers have used the adsorption methods in conjunction
with other process. Adsorption/catalytic oxidation, adsorption coupled
with redox process and adsorption/catalytic reduction process can be
suggested as processes for the removal of heavy metals from wastewater.
Adsorption/catalytic oxidation process can be categorized into two parts:
in situ and ex situ adsorption with catalytic oxidation, according to
 M. Ahmaruzzaman / Advances in Colloid and Interface Science 166 (2011) 36–59 51

whether adsorption process and oxidation process occur in the
same reactor. The photocatalytic degradation of heavy metals by adsor-
bents supported with TiO2 belongs to the former. Adsorption/catalytic
reduction process has been observed to be efficiently utilized in the
purification of wastewater as well as water. Recently, various types of
adsorbents with the catalytic reduction function, for example, modified
hydrotalcite-type (HT) adsorbent, were developed and utilized in the
removal of heavy metals from wastewater. Several redox composite
adsorbents have been developed and applied in water purification, by
the combination of oxidation and reduction effect in the adsorption
process. Arsenic is primarily present in inorganic forms and exists in two
predominant species, namely, arsenate (As(V)) and arsenite (As(III)) in
wastewater. As(III) is found to be much more toxic [228], more soluble,
and more difficult to dispose than that of As(V). To achieve higher
removal of arsenic, a pre-treatment for As(III) oxidation is, involved
followed by adsorption of the As(V) formed onto metal oxy-hydroxides.
The pre-treatment method not only increased the running cost but also
the complexity of the operation. Traditional oxidants such as chlorine,
ozone, and hydrogen peroxide are not suitable for a specific oxidation
of As(III), due to some side reactions with natural organic matter present
in wastewater. Therefore, the development of adsorbents from waste
materials which could simultaneously oxidize arsenite and adsorb the
formed arsenate is becoming the focus of research in recent years
[229,230]. More research should be conducted for the removal of heavy
metals from wastewater by using adsorption in combination with other
methods.
8. Adsorption isotherms and mechanism
Assessment of a solid–liquid adsorption system is generally depen-
dent on two types of investigations: (i) equilibrium batch adsorption,
and (ii) dynamic continuous-flow adsorption studies. Equilibrium
isotherm models are generally divided into empirical equations and
mechanistic models. The mechanistic models are based on the mech-
anism of metal ion adsorption and able to explain and predict the
observed experimental behavior. Several empirical models are re-
ported for single solute adsorption systems [231–244] and shown in
Table 7. The Langmuir and Freundlich models are found to be the most
widely used isotherm models reported in the literature. The
BET model assumes that the Langmuir isotherm applies to each
layer and describes multi-layer adsorption at the adsorbent surface.
These models can provide information on the adsorption capacity of
metals from their aqueous solution. The models, such as, Langmuir
and Freundlich also do not incorporate the effects of any external
variable environmental factors. However, they are capable of
describing many adsorption isotherms in most of the cases. The
mechanistic conclusions from the good fit of the observed experi-
mental data with the empirical models should be avoided. However,
adsorption isotherms may exhibit an irregular pattern due to the
complex nature of both adsorbents and its varied multiple active sites,
as well as the complex solution chemistry of some metallic
compounds. Foo and Hameed [245] recently, presents a state of art
review of adsorption isotherms modeling, its fundamental

Table 7
Single-component adsorption models reported in the literature.

Isotherm types Equations Nomenclature References

Langmuir Q0 bCe qe is equilibrium metal sorption capacity; Ce is equilibrium solute concentration in solution; [231]
qe =
1 + bCe qmax and b are Langmuir constants related to maximum sorption capacity (monolayer capacity)
and bonding energy of adsorption (or “affinity”), respectively
Freundlich qe = KFCe1/n KF is a adsorption equilibrium constant, representative of the sorption capacity; and n is a [232]
constant indicative of adsorption intensity
Sips Isotherm Ks CeβS Where, βs is the Sips constant [233]
qe =
1 + as CeβS
BET model qs CBET Ce Where CBET, Cs, qs and qe are the BET adsorption isotherm (L/mg), adsorbate monolayer [234]
qe =
(multilayer sorption) ðCs −Ce Þ½1 + ðCBET −1ÞðCe = Cs Þ saturation concentration (mg/L), theoretical isotherm saturation capacity (mg/g) and
equilibrium adsorption capacity (mg/g), respectively
Redlich–Peterson kR Ce KR, aR, and β are the Redlich–Peterson parameters. The exponent β lies between 0 and 1. [235]
qe =
1 + aR Ceβ For β = 1 the model converts to the Langmuir form

Radke–Prausnitz aRP rR CeβR Its model exponent is represented by aRP, where aR and rR are referred to the model constants [236]
qe =
aRP + rR CeβR −1
(Frenkel–Halsey–Hill)

 Where d, α and r are the sign of the interlayer spacing (m), isotherm constant (Jmr/mole) [237]
Ce α qs r
FHH ln =− and inverse power of distance from the surface (about 3), respectively
Cs RT qde

Tempkin RT Where AT (L/g) and bT are the Tempkin constants which can be determined from a plot of [238]
qe = ln AT Ce
bT qe versus lnCe
Toth bT Ce Where, bT and nT are two constants. Obviously, if nT = 1, Toth isotherm reduces to the [239]
Qe = Q max h iη T
1 + ðbT Ce Þ
1 = ηT Langmuir-type isotherm equation

Flory–Huggins θ Where, θ is the degree of surface coverage, where KFH and nFH are the indication of its [240]
= KFH ð1−θÞnFH
C0 equilibrium constant and model exponent

Koble–Corrigan ACen The isotherm constants, A, B and n are evaluated from the linear plot using a trial and [241]
qe =
1 + BCen error optimization

1 = 3
(MacMillan–Teller) MET k Where k is an isotherm constant [242]
qe = qs
lnðCs = Ce Þ
Dubinin–Radushkevich qe = (qs)exp(− kdε2) where, kd is denoted as the
 isotherm
 constant. Meanwhile, the parameter ε can be [243]
1
correlated as: ε = RT ln 1 + ,where R, T and Ce represent the gas constant
Ce
(8.314 J/mol K), absolute temperature (K) and adsorbate equilibrium concentration (mg/L),
respectively
Khan q s bK C e bK and aK are devoted to the model constant and model exponent. [244]
qe = α
ð1 + bK Ce Þ K
52 M. Ahmaruzzaman / Advances in Colloid and Interface Science 166 (2011) 36–59

characteristics and mathematical derivations. The key advance of the
error functions, its utilization principles together with the comparisons
of linearized and non-linearized isotherm models has been highlighted
and discussed. They also concluded that, the expanding of the nonlinear
isotherms represents a potentially viable and powerful tool, leading to
the superior improvement in the area of adsorption science. They also
highlighted that the next real challenge in the adsorption field is the
identification and clarification of both isotherm models in various ad-
sorption systems. Further explorations on developing in this area
are recommended. Real wastewaters commonly contain a mixture of
metal ions. Therefore, multi-component metal adsorption models have
to be developed to describe the binary or ternary, and multi-component
adsorption systems. To describe two- or multi-metal ion adsorption
systems, various models, such as, extended Langmuir, modified Langmuir,
non-modified Redlich–Peterson, Sheindorf–Rebuhn–Sheintuch (SRS)
and extended Freundlich models have been developed and reported in
the literature [246–250]. Table 8 showed some of multi-component
adsorption models reported in the literature. However, these empirical
models hardly reflect any adsorption mechanism. These empirical
models hardly reflect any mechanisms of metal uptake and do not have
a meaningful physical interpretation for the adsorption process.
The mechanisms by which the metal ions are adsorbed onto
various industrial wastes are very complicated and appear attributable
to electrostatic attraction, ion-exchange, adsorption–precipitation,
hydrogen bonding, and chemical interaction between the metal ions
and the surface functional groups of the various industrial adsor-
bents. It is commonly believed that the chemical interaction between
the metal ions and the surface functional groups of various industrial
wastes is the major adsorption mechanism. It is known that heavy
metal adsorption is effective in an alkaline region. However, when
the medium pH is controlled by the adsorbent (as in the cases of
various alkali and alkali earth silicates), the mechanism of heavy
metals removal is difficult to determine. According to Dushina and
Aleskovaski [251], the ion exchange is a first step of metal ion de-
tention on the surface of various calcium silicate materials, including
slag. Depending on the nature of the material and the conditions of
the experiment, the process may continue with further interac-
tions between the metal ions and the solid matrix. The formation of
sparingly soluble compounds of the type of metal silicates (surface
precipitation) is possible. Yamashita et al. [252] have reported that
the mechanism of adsorbing and fixing heavy metals of the converter
furnace slag can be attributed to one or more of following effects:
adsorption, co-precipitation, hydroxide precipitation as hydroxide,
sulfide and ion exchange. Lopez et al. [87] evaluated the applicability
of blast furnace sludge for the removal of Pb(II) from their aqueous
solution and showed that adsorption is of a physical nature and
physical adsorption process partially occurs through ionic exchange
between Pb (II) and other ions such as Ca (II). The mechanisms
involved in metal retention by slag are thought to be ion exchange
with calcium on particle surfaces and precipitation on Al(OH)3 and
SiO2 [90].
Guo et al. [122] investigated the adsorption of the heavy metal
ions Pb(II), Cu(II), Cd(II), Zn(II), and Ni(II) on a lignin isolated from
black liquor and reported that surface complexation mechanism
was involved in the adsorption process. They also found that lignin
surfaces contain two main types of acid sites attributed to carboxylic-
and phenolic-type surface groups and the phenolic sites have a higher
affinity for metal ions than the carboxylic sites. Metal ion adsorption
onto deprotonated carboxyl and phenolic sites was the dominant
mechanism that could reasonably explain the observed adsorption
behavior. Crist et al. [128,131,132] observed that metal ion sorption
was accompanied by stoichiometric release of protons and existing
metals, and concluded that ion exchange mechanisms were re-
sponsible for the removal of metals by lignin. In order to see if a
similar process was occurring in the study, release of the cations Na(I),
Mg(II), and Ca(II) was recorded while the metal ion was adsorbed, by
taking Cu as an example. Compared to the amount of Na(I) released,
the release of Mg(II) and Ca(II) was negligible. When the pH value
was increased from 2.5 to 4.5, the molar ratios of Na(I) released to Cu
(II) adsorbed were found between 1.28 and 1.39, but when the pH
value reached 4.8, the ratio decreased to 0.66. The amount of Cu(II)
adsorbed was more than the equivalent cations released, indicating

Table 8
Multi-component adsorption models reported in the literature.

Isotherm types Equations Nomenclature References

Non-modified Langmuir qm;i KL;i Ce;i Where, Ce,i and qe,i are the unadsorbed concentration of each component in the mixture at [246]
qe;i = N equilibrium and the adsorbed quantity of each component per gm of adsorbent at equilibrium
1 + ∑ KL;j Ce;j respectively, KL,i and qm,i are derived from the corresponding individual Langmuir
j=1
isotherm equations.
 
Modified Langmuir qm;i KL;i Ce;i = ηL;i Where, ηL,i is the Langmuir correction coefficient of the i component where estimated [246]
qe;i = N   from competitive adsorption data
1 + ∑ KL;j Ce;j = ηL;j
j=1

Extended Langmuir q max KEL;i Ce;i qmax and K EL,i are the model parameters (the subscripts 1 and 2 represent the [247]
qe;i = corresponding adsorbates) obtained experiemtnally single-solute Langmuir isotherm.
N
1 + ∑ KEL;j Ce;j
j=1

Sheindorf–Rebuhn–Sheintuch !ð1 = ni Þ−1 The competition coefficients aij in the SRS model describe the inhibition to the adsorption [248]
N
(SRS) qe;i = KF;i Ce;i ∑ aij Ce; j of component i by component j, and can be determined from the thermodynamic data,
j=1
or more likely, from the experimental data of multi-component systems.
Non-modified KR;i Ce;i Where, KR,i, Ce,i and βj are the Redlich–Peterson parameters derived from the corresponding [249]
qe;i =
Redlich–Peterson N individual Redlich–Peterson isotherm equations
1+ ∑ aR;j Ce;β;jj
j=1
 
Modified Redlich–Peterson KR;i Ce;i = ηR;i Where, ηR,i is the Langmuir correction coefficient of the i component where estimated from [249]
qe;i = N  β; j competitive adsorption data.
1 + ∑ aR; J Ce;i =ηR; j
j=1

Extended Freundlich ð1=n1 Þ + x1 Where, KF,1, KF,2 and n1 and n2 are derived from the corresponding individual Freundlich
KF;1 Ce;1 [250]
qe;1 = x1 z1 isotherm equations and the six other parameters (x1,y1,z1 and x2,y2,z2 are the multi-component
Ce;1 + y1 Ce;2
Freundlcih adsorption constants of the first and the second components, respectively,
ð1=n2 Þ + x2 for binary system) are the competition coefficients for two species.
KF;2 Ce;2
qe;2 = x2 z2
Ce;2 + y2 Ce;1
 M. Ahmaruzzaman / Advances in Colloid and Interface Science 166 (2011) 36–59 53

Table 9
Single-component kinetic models used in the literature.

Isotherm types Equations Nomenclature References

Lagergren's first order k1 Where qe and q are the amounts of phenol adsorbed at equilibrium and at time t in [255]
logðqe −qt Þ = log qe − t
rate equation 2:303 milligrams per gram, respectively, k1 is the rate constant of Lagergren first-order adsorption
Pseudo-second-order t 1 1 Where k2 is the rate constant of second-order adsorption [257]
= + t
kinetic model qt k2 q2e qe



Elovich Equation 1 1 Where, a and b are the constants for this model obtained from the slope and intercept [258]
qt = ln ðabÞ + ln t
b b of the linear plot of qt versus ln t.

that there may some other mechanisms at work in addition to ion hydrodynamic parameters, are very important for the design of
exchange. adsorption process. However, adsorption kinetics studies are insuffi-
Moreover, the related mechanisms of metal sorption by lignin are cient according to the literature published so far. The kinetics of
still subject to debate. However, ion-exchange mechanisms may be adsorption is very important from the point of view that it controls the
responsible for the adsorption of metal ions on lignin as mentioned process efficiency.
previously [131,132]. Srivastava et al. [124] and Mohan et al. [126]
suggested that no single mechanism could explain the process of
10. Factors affecting adsorption of heavy metals
metal removal by lignin. Ion exchange may also dominate where
heavier and higher valence metal ions replace H +, Na + and other ions
10.1. Effect of contact time and initial concentration of heavy metals
on lignin surface functions. Traces of metals present in the as-obtained
lignin can enter into reactions with metal ions lower in the elec-
The initial concentrations of metals have a strong effect on the
trochemical series, causing heavy metals to deposit on the surface
adsorption capacity of various industrial waste materials. Generally,
[126]. Several processes including ion exchange, surface adsorption,
adsorption capacity increased with increased initial concentrations of
and complexation, have been suggested to explain the mechanisms
the heavy metals. The initial concentration provides an important
involved. Detailed studies are therefore required to achieve a quan-
driving force to overcome all mass transfer resistance of heavy metals
titative and mechanistic understanding of the sorption of metal ions
between the aqueous and solid phases. The removal of heavy metals
by lignin.
to reach the equilibrium also varied with contact time. Bhattacharya
The Al, Fe oxides and hydroxides of the red muds, principally the
et al. [96] reported the effect of contact time and initial concentration
hematite, were the other active components in heavy metal adsorp-
of heavy metals on the adsorption of Zn(II) on various adsorbents and
tion. Since the pH of solutions at equilibrium in the experiments was
showed that increase in contact time from 0.5 to 2.0 h enhanced
lower of the point of zero charge of the red muds, as reported by
significantly the percent removal of Zn(II). The initial rapid adsorption
several authors (pzc = 8–8.5) [113,253,254]; the adsorption of heavy
gives away a very slow approach to equilibrium. The nature of adsor-
metals on Al, Fe oxides and hydroxides occurred on positively charged
bent and its available adsorption sites affected the time needed to
surfaces through the formation of specific inner-sphere bonds.
reach the equilibrium. They [96] reported that times needed to reach
the equilibrium are 1 h, and 3 h for clarified sludge and rice husk
9. Kinetic modeling of adsorption in a batch system
ash, respectively. For the other two adsorbents, activated alumina
and neem bark, a contact time of 4 h is needed for equilibrium to be
Numerous kinetic models have been suggested to describe the
established. The results are similar to those reported by Zheng et al.
reaction order of adsorption systems based on concentration of the
[177] for the adsorption of heavy metals by areca — a food waste (AW)
solution [255,257,258] and reported in Table 9. Kinetic models based on
in which equilibrium was attained within 2 h. The Nickel(II) adsorp-
the capacity of the adsorbent have also been presented, such as the
tion capacities of waste tea were presented as a function of contact
Lagergren's first-order equation [255] and Ho's second-order expression
time in Fig. 1 [259]. The initial concentration (C0, mg/L) was changed
[256]. The first-order equation of Lagergren [255] and the pseudo
in the range of 50–300 mg/L. When the initial nickel(II) ion con-
second-order equation are the most widely used kinetic models to
centration increased from 50 to 300 mg/L, the residual Ni(II) concen-
describe the adsorption of a solute from a liquid solution. The pseudo
tration (Cres, mg/L) of solution increased from 5.8 to 159 mg/L. The
second-order equation fitted the adsorption data very well in a large
removal of Ni(II) ions increased rapidly with time up to 20 min and
quantity of literature reported [256–257]. Ho [255] reviewed the ap-
thereafter increased slowly. While initial metal concentration was
plication of second-order kinetic models to adsorption systems,
100 mg/L, the uptake of Ni(II) ions was 8.12 mg/g at 30 min and
including an earlier adsorption rate equation based on the solid capac-
8.24 mg/g at 120 min. The amount of nickel(II) ions adsorbed per unit
ity for a system of liquids and solids, the Elovich equation for adsorp-
mass of the adsorbent increased with the initial concentration of
tion of gases onto a solid, and applying a second-order rate equation
metal ions. When the initial nickel(II) ion concentration increased
for gas/solid and solution/solid adsorption systems, a second-order rate
from 50 to 300 mg/L, the initial adsorption capacity of waste tea
expression for ion exchange reactions, and a pseudo-second-order
increased from 4.413 to 14.04 mg/g. The effect of initial chromium ion
expression. The pseudo-second-order rate expression was used to de-
concentrations on the adsorption of Cr(VI) ions from aqueous solution
scribe chemisorption involving valency forces through the sharing or
on tea factory waste was also investigated [174].
exchange of electrons between the adsorbent and adsorbate as covalent
forces, and ion exchange. In recent years, the pseudo-second-order
rate expression has been widely applied to the adsorption of pollutants 10.2. Effect of pH
from aqueous solutions [255]. The advantage of using this model is
that there is no need to know the equilibrium capacity from the experi- The solution pH has a pronounced influence on the adsorption of
ments, as it can be calculated from the model [255]. In addition, the metal ions on various industrial wastes. In a certain pH range, most
initial adsorption rate can also be obtained from the model. Kinetics metal adsorption increases with increasing pH up to a certain value
studies and dynamic continuous-flow investigations, offering informa- and then decreases with further increase in pH. This is readily ex-
tion on the rate of the adsorption uptake of metals, together with the plained by the adsorption mechanism.
54 M. Ahmaruzzaman / Advances in Colloid and Interface Science 166 (2011) 36–59
Fig. 1. The uptake and residual amount of Ni(II) by waste tea as a function of initial metal
concentration.(adsorbent dose= 10 g L− 1, agitating rate = 360 rpm, pH 4.0) [237].
Therefore, there is a favorable pH range for the adsorption of
every metal on a certain industrial waste material. The effect of pH
may also be accounted in terms of pHzpc of the adsorbent, at which
the adsorbent is neutral. The surface charge of the adsorbent is posi-
tive when the media pH is below the pHzpc value, while it is nega-
tive at a pH over the pHzpc. On the other hand at pH below the pHzpc,
the predominant metal species (M 2+ and M(OH) +) are positively
charged and therefore, the uptake of metals in the pH range below
pHzpc is H +―M 2+ (or M(OH)+) exchange process. With an increase
in pH above pHzpc, although the surface of the adsorbent is negatively
charged, the adsorption still increases as long as the metal species are
still positively charged or neutral. When both the surface charge of the
adsorbent and metal species charge become negative, the adsorption
will decrease significantly. According to the mechanism and the
discussion of pH effect, the adsorption will lead to a decrease in pH as
equivalent H + will be released along with the adsorption. This is the
case for most metal adsorption, but there is always exception. Some
metals existing as negative species in solution, such as hexavalent
chromium, may release hydroxide (OH −) instead of proton (H +)
when they are adsorbed by waste materials, and therefore result in an
increase in pH. Fig. 2 shows the effect of pH on Ni(II) uptake and
residual concentration by waste tea [259].
10.3. Effect of particle size
Intra-particle diffusion study shows that particle size of the waste
materials used greatly influences the adsorption rate. Decrease in
particle size would lead to increase in surface area and then increase
in the adsorption opportunity at the outer surface of the waste mate-
rials. Besides adsorption at the outer surface of the waste material
there is also a possibility of intra-particle diffusion from the outer
surface into the pores of the material. The diffusional resistance to
mass transfer is higher for large particles. Due to various factors, such
as diffusional path length or mass transfer resistance, contact time,
and blockage of some diffusional path, most of the internal surface
of the particle may not be utilized for adsorption; consequently the
adsorption efficiency may become low.
The adsorption capacity of waste materials very much depends on
the surface activities — in other words, specific surface area available
for solute surface interaction, which is accessible to the solute. It is
expected that adsorption capacity will be increased with a larger sur-
Fig. 2. Effect of pH on Ni(II) uptake and residual concentration by waste tea (adsorbent
dosage = 10 g/L, agitating rate = 360 rpm, C0 = 100 mg L− 1) [259].
face area. In other words, smaller particle size increases the adsorp-
tion capacity. Amarasinghe and Williams [175] studied the effect of
particle size of tea waste on the adsorption capacity of heavy metals.
The results showed that for tea waste particles of mean size 1250, 925
and 575 μm, the percentage removal of Cu ion were 41, 53 and 57,
respectively. Batch adsorption experiments were also carried out to
investigate the effect of particle size of bagasse fly ash on the removal
of Pb and Cr (VI) from their aqueous solution [59]. Studies were carried
out using three different particle sizes, 100–150, 200–250, and 300–
350 μm at pH 6.0 for lead and 5.0 for chromium, with an adsorbent
dose of 10 g/L, shaking time 80 min for lead and 60 min for chromium
at 30 °C. The adsorption of lead and chromium was found to be 99.9,
95.0, and 88.0%, respectively using the above mentioned sizes.
10.4. Effect of ionic strength
Ionic strength is a general property of the solution affecting the
affinity between the solute and the aqueous phase. This is one of the
important factors which influence the aqueous phase equilibrium.
Generally, adsorption decreases with increasing ionic strength of the
aqueous solution. This effect may be ascribed to changes in the metal
activity, or in the properties of the electrical double layer. According to
surface chemistry theory, when two phases, e.g. waste particles and
metal species in aqueous solution, are in contact, they are bound to be
surrounded by an electrical double layer owing to electrostatic
interaction. If the adsorption mechanism is significantly the electrostatic
attraction, adsorption decreases with increase in ionic strength. Some
inorganic anions, such as chloride, may form complexes with some
metal ions and therefore, affect the adsorption process. The effect of
different competitive ions like nitrate (NO3−), sulfate (SO42−), and
phosphate (PO43−) on the adsorption of Cr(VI) was studied at various
concentrations [101]. It was observed that the percentage of adsorp-
tion of Cr(VI) decreased with increasing concentrations of externally
added ions. The affinity sequence for adsorption of such anions on
activated red mud is PO43− N SO42− N NO3−. Increasing dosages of these
ions from 5 to 20 mg/L had little effect. Similar observations were made
for fluoride removal using treated alum sludge [260]. Weng and Huang
[71] also studied the effect of ionic strength on the removal of Zn(II)
from aqueous solution by using fly ash and reported that Zn(II) removal
is higher at a lower ionic strength under the same pH value.
Fiol et al. [149] shows the effect of NaCl and NaClO4 on the removal
of metal by olive stone waste. The presence of both salts indicated a
dramatic decrease on the uptake of metal (N70%) with the exception
 M. Ahmaruzzaman / Advances in Colloid and Interface Science 166 (2011) 36–59
of copper. The presence of NaCl was found to exert a slightly greater
influence than NaClO4 on the removal of metal. The decrease of metal
removal in the presence of NaCl was also observed when grape stalk
wastes [187] and cork [261] were used to remove copper and nickel
from aqueous solutions. Some authors explain that the percentage
reduction of metal removal is due to the increase of NaCl and thus
by the presence of competing Na + ions for metal binding [262].
Other authors reported that there was a decrease of adsorption with
increasing ionic strength, where the adsorption process involved
electrostatic attraction between adsorbent and adsorbate [263]. Thus,
in the case of metal adsorption by olive stones, both phenomena could
be considered to provoke the decrease of metal uptake. In addition, all
the studied metals form complexes with chloride ions; therefore, the
formation of chloro-complexes would explain the slight difference on
metal adsorption when this medium was employed instead of NaClO4.
11. Column studies
Column-type continuous flow operations appear to have a distinct
advantage over batch type operations because the rate of adsorption
depends on the concentration of solute in the solution being treated.
For column operation the adsorbents are continuously in contact
with a fresh solution. Consequently the concentration in the solution
in contact with a given layer of adsorbent in a column is relatively
constant. For batch treatment, the concentration of solute in contact
with a specific quantity of adsorbent steadily decreases as adsorption
proceeds, thereby decreasing the effectiveness of the adsorbent for
removing the solute. The breakthrough capacity, which is the amount
adsorbed before the appearance of adsorbates in the effluent, and the
total capacity, which is the amount adsorbed until the effluent
concentration of the adsorbate is equal to the influent solution
concentration, are computed from the breakthrough curves. Gupta
and Ali [59] reported that the removal of lead and chromium ions up
to 95–96% was achieved using baggase fly ash by column experiments
at a flow rate of 0.5 mL/min. The flow rate was varied to achieve the
maximum removal of the adsorbates and it was found that the
maximum uptake of lead and chromium was achieved at a flow rate of
1.0 mL/min. The column adsorption capacity at complete exhaustion
was found to be 35.0 and 25.0 mg/g for lead and chromium,
respectively, which is greater than in the batch experiments (30.0
and 20 mg/g of lead and chromium, respectively). The high column
capacity may be due to the fact that a continuously large concentra-
tion gradient occurred at the interface zones as it passes through the
column, while the concentration gradient decreased with time in the
batch experiments.
Regeneration and recovery of the column is a very important aspect
in wastewater treatment processes and, therefore, desorption of lead
and chromium was tried with a number of eluents (methanol, ethanol,
sodium hydroxide, sulfuric acid, hydrochloric acid, nitric acid, etc.) and
it was found that the desorption of these two metal ions occurred by 5%
HNO3 [59]. The column was allowed to pass 5% HNO3 at a flow rate of
2.5 mL/min for about 3 h and then again allowed to pass deionized
water at a flow rate of 2.50 mL/min for about 3 h. It was observed that
the column loses about 2% capacity after the first run and about 3–10%
after more than five runs. Therefore, the column can be used for at least
10 runs without any problem. It is very important to mention that
bagasse fly ash is an easily available, inexpensive material, and its cost
is very low in comparison to the cost of regeneration. Moreover, the
used bagasse fly ash can be used as raw material for building materials.
Therefore, there is no need to regenerate bagasse fly ash in columns.
The use of granular blast furnace slag (GBFS)-packed columns to
treat lead-containing solutions has been reported by Dimitrova [91]. The
results obtained indicated that the slag usage rate decreased with
increased flow velocity, particle size, and initial lead concentration and
decreased with bed height. Lead removed selectively in the presence of
other heavy metal ions. High concentrations of sodium and especially
55
calcium in the solutions impeded the uptake of lead. The apparent
mechanisms of lead removal in GBFS column are sorption (ion exchange
and adsorption) on the slag surface and precipitation. Adsorption of
copper and lead ions onto tea waste from aqueous solutions was studied
in column mode to enable comparison with alternative commonly
available absorbents [175]. Fixed bed column experiments were
performed to study practical applicability and breakthrough curves
were obtained. Breakthrough curves for Cu and Pb adsorption onto tea
waste from single metal ion solutions of concentration 100 mg/L are
shown in Fig. 3. The removal efficiency of waste tea from nickel con-
taining aqueous solutions in fixed-bed column was investigated [259].
The total adsorbed quantities, equilibrium uptakes and total percent
removal of Ni(II) related to the effluent volumes were determined by
evaluating the breakthrough curves obtained at different flow rates,
different inlet Ni(II) concentrations, different pH value, different bed
height and different particle size for waste tea.
12. Comparison of adsorption performance
Suitable industrial waste materials should possess several require-
ments for the adsorption of metals, such as, (i) efficient for the removal
of a wide variety of heavy metals (ii) maximum removal of specific
metals (iii) high adsorption capacity (iv) low-processing cost (v) easily
regenerated/disposed off after adsorption and (vi) tolerant of a wide
range of concentration of heavy metals and other wastewater
parameters.
Certain industrial wastes, such as, fly ash, blast furnace slag and red
mud have been tested by various workers and proposed for the
removal of heavy metals. Each industrial waste material has its own
specific physical and chemical characteristics such as porosity, surface
area and physical strength. The waste materials have also their in-
herent advantages and disadvantages in the wastewater treatment.
Adsorption capacities of the adsorbent were also found to vary, de-
pending on their experimental conditions. It is evident from the
present review that industrial waste material as adsorbents may have
potential as readily available, inexpensive and effective adsorbents.
They also possess several other advantages that make them excellent
materials for environmental purposes, such as high capacity and rate
of adsorption (Tables 3, 4, and 5).
Table 3 presents a summary of the adsorption capacities of fly ash for
the removal of heavy metals. However, the adsorption capacities for
metal ions in multi-component systems are reported in Table 4. Table 5
shows the adsorption capacities for heavy metals on other industrial
adsorbents. From the recent literature reviewed, adsorbents that stand
out for high adsorption capacities for the removal of Zn(II) metals are
Fig. 3. Breakthrough curves for adsorption of Cu and Pb onto tea waste: 15 g of tea, flow
rate — 20 mL/min [175].
56 M. Ahmaruzzaman / Advances in Colloid and Interface Science 166 (2011) 36–59
bagasse fly ash (13.21 mg/g), rice husk ash (14.30 mg/g), coal fly ash
(11.11 mg/g), fly ash zeolite 4A (30.80 mg/g), blast furnace slag
(103.3 mg/g), lignin (73.3 mg/g), powered waste sludge (168 mg/g),
sugar beet pulp (35.6 mg/g), and clarified sludge (15.53 mg/g).
Adsorbents showing high adsorption capacities for the removal of Cd
(II) metals are bagasse fly ash (6.19 mg/g), fly ash (198.2 mg/g), fly ash
zeolite (95.6 mg/g), fly ash zeolite X (97.78 mg/g), waste slurry
(15.73 mg/g), red mud (66.67 mg/g), lignin (25.40 mg/g), carboxy-
mehtylated lignin (107.53 mg/g), sugar beet pulp (38.6 mg/g), and
phosphate apple waste (36.2 mg/g). The literature also indicated
some of the adsorbents that showed high adsorption capacities for
the removal of Pb(II) metals which are bagasse fly ash (285.56 mg/g),
fly ash (444.7 mg/g), fly ash zeolite (70.6 mg/g), fly ash zeolite X
(420.61 mg/g), blast furnace slag (40 mg/g), waste slurry (1030 mg/g),
lignin (1865 mg/g), sugar beet pulp (43.5 mg/g),tea industry waste
(65 mg/g), crop milling waste (49.97 mg/g/m), carboxymehtylated
lignin (37.99 mg/g), sludge (39.3 mg/g), and waste biogas residual
slurry (28.0 mg/g). Adsorbents, such as, coal fly ash (178.5–249.1 mg/g),
fly ash zeolite (50.45 mg/g), fly ash zeolite X (90.86 mg/g), blast furnace
slag (133.3 mg/g), waste slurry (20.97 mg/g), red mud (106.44 mg/g),
sugar beet pulp (30.9 mg/g), iron oxide waste (98.0 mg/g), and grape
stalk wastes (42.92 mg/g) showed high adsorption capacities for
the removal of Cu(II) metals. Adsorbents that indicated high adsorp-
tion capacities for the removal of Ni(II) metals are bagasse fly ash
(6.48 mg/g), Al-impregnated fly ash (10–15.7 mg/g), Fe-impregnated
fly ash (9.8–14.93 mg/g), fly ash zeolite 4A (8.96 mg/g), red mud
(160 mg/g), tea factory waste (18.42 mg/g), grape stalk wastes
(38.31 mg/g), sugar beet pulp (11.85 mg/g), crop milling waste
(20.15 mg/g/m), and treated sewage sludge (9.09 mg/g). Lastly,
adsorbents that stand out for high adsorption capacities for the re-
moval of Cr(VI) metals are bagasse fly ash (4.25–4.35 mg/g), fly ash
(23.86 mg/g), rice husk ash (25.64 mg/g), waste slurry (640 mg/g),
clarified sludge (26.31 mg/g), tea industry waste (455 mg/g), leather
industry waste (133 mg/g), sugar beet pulp (17.2 mg/g), and sugar cane
bagasse (13.4 mg/g).
13. Discussion
The adsorption of heavy metal ions from aqueous solutions using
industrial wastes as an adsorbent has been extensively studied. How-
ever, there are several issues and drawbacks concerned that should be
addressed. These can be summarized as shown below:
(i) In most of the article, no attempts were made to relate the
characterization results with the performance of the adsor-
bents for the removal of heavy metals.
(ii) Metal ion adsorption is well known to be pH dependent.
However, in most of the cases, the pH effect was invariably
investigated in terms of the initial pH of the solution. Not in a
single case data has been reported for the changes of the
solution pH during the course of the adsorption.
(iii) The equilibrium data reported, without exception, were empiri-
cally correlated with conventional isotherm (Freundlich, Langmuir
and a few others). In a few cases, the authors have proposed the
mechanism of the adsorption. However, the proposed mechanisms
were hardly used in interpreting the equilibrium data obtained.
(iv) The kinetic data were fitted with the Lagergren equation (or its
variant). How this equation and the parameter values obtained
can be used in the design calculations of fixed-bed operation
was ignored in most of the studies.
(v) The competitive metal adsorption on various adsorbents
was reported in a few cases. However, there is scarce data
available for the adsorption of heavy metals in presence of
organic and other contaminants. Therefore, the potential of
industrial wastes as low-cost adsorbents under multi-component
pollutants/contaminants need to be addressed. This would make
a significant impact on the commercial application of industrial
waste as low-cost adsorbents for the treatment of industrial
wastewater.
(vi) No literature is available to apply the well-developed surface
ionization/complexation model or the double layer retention
model to investigate the effect of ionic strength or pH on the
extent of adsorption.
(vii) Further, detailed systematic studies are needed to find out
which component in the precursor is primarily responsible for
the development of surface area or micro/meso porosity or is
helpful in the development of functional groups.
(viii) Combination of methodologies/system should also be encour-
aged since one perfect method/system is practically difficult.
Besides these, strategies to minimize metal and related chemical
effluent at all levels and designing more environmentally friendly
chemicals are also needed. More comprehensive or specific
models for equilibrium or kinetic studies that can simulate more
complex adsorption systems, such as hybrid adsorption system,
should be developed.
(ix) The cost of the various industrial wastes (along with the cost of
processing) is seldom reported in any of the publications.
However, the expense of individual adsorbents varies, depend-
ing on the processing conditions and local availability. In spite of
the scarcity of consistent cost information, the widespread uses
of low-cost adsorbents in industries for wastewater treatment
applications today are strongly recommended due to their
local availability, technical feasibility, engineering applicability,
and cost effectiveness. If low-cost adsorbents such as fly ash, red
mud, waste slurry, and lignin perform well in removing heavy
metals at a low cost, they can be adopted and widely used in
industries not only to minimize cost inefficiency, but also
improve profitability. Therefore, a cost–benefit analysis of using
low-cost adsorbents for heavy metal removal needs to be
conducted to judge the economic feasibility of its practical use
in wastewater treatment applications today.
(x) It is also evident from the literature that most of the adsorption
studies were carried out in a batch operation. Very few studies
were reported on the adsorption of heavy metals on column
operation. Thus, it is required to carry the adsorption experi-
ments in column mode in the laboratory and then the studies
should be conducted on pilot plant scale utilizing industrial
waste as low-cost adsorbents to see their feasibility on the
utilization in the commercial scale.
(xi) Selection and identification of an appropriate industrial waste as
low-cost adsorbent is one of the key issues to achieve the max-
imum removal of specific metals depending on the adsorbent–
adsorbate interaction.
(xii) Leaching of industrial wastes in water is very important in
order to see the dissolution of the various substances present in
the wastes. This interference will lead to the erroneous results
in the adsorption experiments. However, very few authors
studied the leaching of industrial wastes when it is as such used
as an adsorbent. Therefore, more research should be performed
in this direction in order to see the practical utility of as such
industrial waste.
(xiii) The conditions for the production of suitable adsorbents from
industrial wastes by treating with various reagents for higher
uptake of heavy metals need to be optimized.
(xiv) Adsorption mechanisms of heavy metals from wastewater need
to be studied in detail. It is required to propose a correct binding
mechanism of heavy metals with industrial waste. This can be
done by blocking the functional group responsible for the ad-
sorption of heavy metals. However, in very few cases the binding
mechanism is reported. Therefore, more emphasis should be
given on this direction to impart knowledge/highlight the new
dimension regarding adsorption phenomenon.
 M. Ahmaruzzaman / Advances in Colloid and Interface Science 166 (2011) 36–59
(xv) Regeneration/recovery of heavy metals from metal-loaded
adsorbent should be performed in detail. Disposal of the
metal-laden industrial waste is again a big problem. Therefore,
more research should be conducted on the various methods
utilized for the environmental friendly safe disposal of metal-
laden adsorbents. It will enhance the economic feasibility of
the process as well as reduce the environmental pollution.
(xvi) To promote the adsorption rate, some special type of composite
adsorbents with the redox, catalytic, and adsorptive functions
which can carry out the processes of oxidation/reduction and
adsorption of pollutants simultaneously, may be developed.
14. Conclusion
The role of industrial wastes in the removal of heavy metals from
wastewater has been investigated. Among the industrial waste
products, fly ash, waste slurry, red mud, lignin, sugar beet pulp, blast
furnace slag, tea industry waste, and sugar cane bagasse have been
proven to be a promising material for the removal of heavy metals
from waste waters. The adsorption phenomenon could be generally
modeled by Langmuir and Freundlich isotherms. However, other
models, such as, Redlich–Peterson, Dubinin KR, Tempkin, Toth, BET,
Radke–Prausnitz, Flory–Huggins, and Sips models are also used. The
various parameters such as adsorption capacity, adsorption intensity
and energy of adsorption can be determined by linear regression.
The adsorption could be influenced by a number of factors, such as,
adsorbent dose and size, contact time, agitation speed, temperature,
pH and ionic strength of the aqueous solution. Generally, percent
adsorption increased with increased adsorbent dose, contact time,
and agitation speed. However, favorable conditions may be different
for different materials and adsorptions. For each type of material, there
is a neutral pH beyond which the material will be either positively
or negatively charged. For every heavy metal, there is a favorable
pH range in which maximum adsorption was observed. If it is possible
to develop such adsorbents from industrial wastes possessing all the
above-mentioned characteristics, then these adsorbents may offer sig-
nificant advantages over currently available expensive commercially
activated carbons, and in addition contribute to an overall waste mini-
mization strategy. Further studies are required to apply the design and
simulation model to larger scale pilot plant and not on small scale
laboratory applications.
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