DESALINATION

ELSEVIER Desalination 175 (2005) 305-316

www.elsevier.com/locate/desal

Rice husk as a potentially low-cost biosorbent for heavy metal

and dye removal: an overview
T.G. Chuah a*, A. Jumasiah a, I. Azni a, S. Katayon b, S.Y. Thomas Choong a
°Department of Chemical and Environmental Engineering, bDepartmentof Civil Engineering, Faculty of Engineering,
Universiti Putra Malaysia, 43400 UPM Serdang, Selangor DE, Malaysia
Tel. +60 (3) 8946-6288; Fax +60 (3) 8656-7120; email."chuah@eng.upm.edu.my
Received 31 August 2004; accepted 18 October 2004

Abstract
Rice husk as a low-value agricultural by-product can be made into sorbent materials which are used in heavy metal
and dye removal. It has been investigated as a replacement for currently expensive methods of heavy metal removal
from solutions. CkLrrently,the study of rice husk as a low-cost sorbent for removing heavy metals has regained
attention. The heavy metals being studied are: As(V) [1], Au [2,3], Cr(IV) [4], Cu and Pb [5,6], Fe, Mn, Zn, Cu [7]
and Cd(II) [8-10]. Rice husk is also being used to treat textile dyes such as like malachite green [11,12] and acid
yellow 36 [13]. The treatment and preparation office husk activated carbon are of importance and became a subject
of study [14-16]. In this review an extensive list ofprevions and current literature on rice husk activated carbons in
removing heavy metals and dyes, their preparation or treatment and isotherms studies were complied to provide a
summary of available information on rice husk and its potential as a low-cost sorbent.

Keywords: Rice husk; Heavy metals; Adsorption; Dye; Isotherms; Sorbents

I. Introduction
Heavy metal contamination exists in aqueous
waste streams from many industries such as metal
plating, mining, tanneries, painting, car radiator
manufacturing, as well as agricultural sources
where fertilizer and fungicidal spray are intens-
ively used. Cu, Zn, Cr, Cd, etc., are harmful
wastes produced by industry that pose a risk of
*Corresponding author.
contaminating groundwater and other water
resources. Heavy metals are not biodegradable
and tend to accumulate in living organisms, caus-
ing various diseases and disorders. For example,
chromium causes serious ailments in both animal
and plant bodies [4]. Table 1 shows the Environ-
mental Quality Act 1974, Environmental Quality
(Sewage and Industrial Effluents) Regulations,
1979, in Malaysia with selected parameter limits
of effluent o f heavy metals.

0011-9164/05/$- See front matter © 2005 Elsevier B.V. All fights reserved
doi: 10.1016/j.desal.2004.10.014
306 T.G. Chuah et al. / Desalination 175 (2005) 305-316

Table 1 chemicals and, therefore, are difficult to be de-

EnvironmentalQualityAct 1974, EnvironmentalQuality colourised once released into the aquatic environ-
(Sewage and Industrial Effluents) Regulations, 1979, ment [ 19,20].
Malaysia: Selected parameter limits of effluent of Treatment processes for metal-contaminated
Standards A and B (Department of Environment, DOE,
waste streams include chemical precipitation,
Malaysia)
membrane filtration, ion exchange, carbon
Parameters, mg/l Standard adsorption and coprecipitation/adsorption [21]
Theses processes usually require expensive facili-
Aa B ties and have high maintenance costs. More
Mercury 0.005 0.05 economical alternative technologies or sorbents
for the treatment of metal-contaminated waste
Cadium 0.01 0.02
streams are needed.
Arsenic 0.05 0.10
Various techniques have been employed for
Lead 0.10 0.50
the removal of dyes from wastewaters [22-30].
Chromium,Irivalent 0.20 1.0
Conventional physical and chemical methods are
Copper 0.20 1.0
either costly, e.g., activated carbon, or produce
Nickel 0.20 1.0 concentrated sludge, e.g., Fenton's reagent, or
Zinc 1.0 1.0 may not capable of treating large volumes of
Iron 1.0 5.0 effluent without the risk of clogging, e.g., mem-
brane filtration [31]. Pearee et al. [32] made
IThis standard applies to the industrial and development a comprehensive review of a method using
projects which are located within catchment areas (areas
bacterial cells to remove the dye from textile
upstream of surface or above sub-surface water supply
intakes, for the purpose of human consumptionincluding wastewater.
drinking). Natural materials that are available in large
quantities, or certain waste products from indus-
trial or agricultural operations, may have poten-
tial as inexpensive sorbents. Due to their low
Dyes are widely used in industries such as cost, after these materials have been expended,
textiles, rubber, paper, plastics, cosmetics, etc., to they can be disposed of without expensive
colour their products. The dyes are invariably left regeneration. The abundance and availability of
as the major waste in these industries. Many of agricultural by-products make them good sources
the organic dyes are hazardous and may affect of raw materials for activated carbons. Many car-
aquatic life and even the food chain. For example, bonaceous materials such as bark, coal, lignite,
malachite green, a common silk and cotton dye- coconut shells, wood, dead biomass, seaweed,
ing agent, has been found to be highly cytotoxic pecan shell and peat are used in the production of
in mammalian cells and also acts as a liver commercial activated carbons [21,33]. However,
tumour-enhancing agent [17]. The removal of the review presented here concerns the use office
dyes is an essential task for environmental protec- husk for the removal of heavy metals and of
tion. In developed countries such as the UK and water-soluble dyes present in wastewater.
many EU countries, environmental policies have Rice husk, an agricultural waste, contains
required that zero synthetic chemicals should be about 20% silica, and has been reported as a good
released into the marine environment [ 18]. Due to sorbent of many metals and basic dyes [34-36].
their chemical structures, dyes are resistant to According to the statistics compiled by the
fading on exposure to light, water and many Malaysian Ministry of Agriculture, there are
 T. G. Chuah et al. / Desalination 175 (2005) 305-316 307

408,000 t of rice husk produced in Malaysia 2. Properties of rice husk

annually [5]. These rice husks, as the commodity
The abundance of rice husk has been well
waste, can be made into activated carbons which
documented by Grist [46]. From the statistical
are used as adsorbents in water purification or the
data of the Food and Agriculture Organisation,
treatment of industrial wastewater. It would add
1995, there is an estimated annual rice production
value to these agricultural commodities, help
of 500 million tonnes in developing countries;
reduce the cost of waste disposal, and provide a
approximately 100 million tonnes of rice husk is
potentially cheap alternative to existing commer-
available annually for utilization in these coun-
cial carbons.
tries alone. However, the amount of rice husk
The removal of heavy metals by agricultural
waste or by-products has been extensively
reviewed by Bailey et al. [21]. However, they Table 2
only reported little information on rice husk being Typical compositionoffice husk [52-54]
a low cost sorbent. Robinson et al. [31 ] has inves-
tigated and reported on several available treat- Composition Percent
ment technologies on dye removal. Removal of Cellulose 32.24
dye by agricultural by-products and other low- Hemicellulose 21.34
cost sorbents has also been investigated intens- Lignin 21.44
ively by Banat [37], Garg et al. [38], Guo et al. Extraetives 1.82
[11,12], Low and Lee [39], Malik [14], McKay et Water 8.11
al. [40], Nawar and Doma [41 ], Nigam et al. [42], Mineral ash 15.05
and Robinson et al. [43-45]. Chemicalcompositionin mineral ash:
An overview of some of the literature on rice SiO~ 96.34
husk as a sorbent of both heavy metals and dyes K20 2.31
is presented as follows. Reported adsorption MgO 0.45
capacities are noted when possible to give some Fe20a 0.2
idea ofsorbent effectiveness and carbon prepara- Al203 0.41
tion. Sorption depends heavily on individual CaO 0.41
experimental conditions such as pH, metal con- K~o 0.08
centration, temperature, contact time, competing
ions and particle size. It is advised that the Table 3
reported sorption capacities should be taken as an Reported physicochemical characteristics of dee husk
example of values that can be achieved under a [13]
specific set of conditions and not as maximum
sorption capacities. The authors strongly recom- Characteristics Values 1
mend that the reader should refer to the original Bulk density (g/ml) 0.73
articles for information on experimental condi- Solid density (g/ml) 1.5
tions. The report will also review those effects on Moisture content (%) 6.62
the adsorption using rice husk and mechanisms. Ash content (%) 45.97
It also covers the methodology on modification of Particle size (mesh) 200-16
rice husk in order to enhance sorption capacities Surface area (m2/g) 272.5
for metal ion and dyes. Surface acidity (meq/gm) 0.1
Surface basicity (meq/gm) 0.45
308 T.G. Chuah et al. / Desalination 175 (2005) 305-316

available is far in excess of any local uses and,
thus, has posed disposal problems [ 15]. Rice husk
accounts for about 20% of the whole rice and
contains about 20% silica. Rice husk possesses a
granular structure, is insoluble in water, has
chemical stability and high mechanical strength.
A previous study reported that rice husk has a
low calorific value of 3585 kcal kg-1 and high ash
content [47]. Due to its high ash content, a proper
method of disposal and utilization of rice husk
has yet to be developed [48]. However, studies
have also shown that rice husk is suitable for
the production of activated carbon [16,49-51].
Tables 2 and 3 show the typical composition and
chemical compositions office husk and reported
values on their physicochemical characteristics.
3. Current technologies available for treatment
methods of heavy metals and dyes
Heavy metals are not biodegradable and tend
to accumulate in living organisms, causing vari-
ous diseases and disorders. Treatment processes
for metal-contaminated waste streams include
chemical precipitation, membrane filtration, ion
exchange, and carbon adsorption. Currently, the
maj or methods of industrial wastewater treatment
involve physical and/or chemical processes.
Some examples are summarised in Table 4.
4. Rice husk as a sorbent for heavy metal and
dye removal
Rice husk used as a sorbent in removing heavy
metals has been intensively studied and reported.
Among the metal ions studied are: As(V), Au,
Cd, Co, Cr (III), Cr(VI), Cu, Hg, Ni, Pb and Zn.
The maximum ofsorption capacity for each metal
ion from previous works are summarized in
Table 5.
McKay [19,59] and his co-workers [40] first
reported their works on colour removal using rice
husk and other low-cost sorbents. Many subse-
quent works studied basic dyes. McKay [59]

Table 4
Current treatment technologies for heavy metals and dyes removal involving physical and/or chemical processes

Physical and/or chemical methods Advantages Disadvantages

Oxidation Rapid process for dye removal High energy costs and formation
of by-products
Ion exchange Good removal of a wide range of heavy Absorbent requires regeneration
metals and dyes or disposal
Membrane filtration technologies Good removes of heavy metals and dye Concentrated sludge production,
expensive
Coagulation/flocculation Economicallyfeasible High sludge production and
formation of large particles
Electrochemicaltreatment Rapid process and effective for certain High energy costs and formation
metal ions of by-products
Ozonation Applied in gaseous state: alteration of Short half life
volume
Photochemical No sludge production Formation of by-products
Irradiation Effective at lab scale Required a lot of dissolved 0 2
Electrokineticcoagulation Economicallyfeasible High sludge production
Fentons reagents Effective decolourisationof both soluble Sludge generation
and insoluble dyes
Biological treatment Feasible in removing some metals Technology yet to be established
and dyes and commercialized
 T.G. Chuah et al. / Desalination 175 (2005) 305-316 309

Table 5
Reported maximum heavy metals adsorption capacities (mg/g) for rich husk

Heavy metal Researchers [ref.] Capacities

As(V) Roy et al., 1993 [55] 615.11
Lee et al., 1999 [1] 18.98
Au Nakbanpote et al., 2000 [2] 21.12
Nakbanpote et al., 2002 [3] 39.84 (20°C)
50.50 (30°C)
64.1o (4o0c)
Cd(I1) Roy et al., 1993 [55] 21.36
Munafand Zein, 1997 [56] 0.16
Tarley et al., 2004 [10] 7 (modified with NaOH solution)
4 (unmodified)
Co (II) Marshall et al., 1993 [35] 0.32
Cr (III) Marshall et al., 1993 [35] 1.90
Cr (VI) Roy et al., 1993 [55] 164.31
Munafand Zein, 1997 [56] 4.02
Guo et al., 2002 [4] 14.2-31.5
Cu(II) Marshall et al., 1993 [35] 1.21
Munafand Zein, 1997 [56] 0.2
Wong et al., 2003 [5] 29 (27°C)
22 (50°C)
18 (70°C)
Wong et al., 2003 [6] 31.85 (single metal solution)
15.58 (bi-metal solution)
Hg Tiwari et al., 1995 [57] 66.66 (dp= 37-50 #m)
55.55 (alp= 63-130 #m)
40.0 (dp= 130--600 #m)
Ni (II) Marshall et al., 1993 [35] 0.23
Pb Roy et al., 1993 [55] 11.40
Wong et al., 2003 [5] 108 (27°C)
105 (50°C)
96 (70°C)
Wong et al., 2003 [6] 129.48 (single metal solution)
48.31 (bi-metal solution)
Tarley et al., 2004 [10] 21.55 (modified with NaOH solution)
45 (unmodified)
Zn Marshall et al., 1993 [35] 0.75
Mishra et al., 1997 [58] 26.94 (20°C)
28.25 (30°C)
29.69 (40°C)
30.80 (50°C)
Mtmafand Zein, 1997 [56] 0.173
310 T. G. Chuah et al. / Desalination 175 (2005) 305-316

Table 6 sium hydroxide and sodium hydroxide [7,10-12],

Reporteddye adsorptioncapacities (mg/g)for rich husk quatemized method [1,36,39] and tartaric acid
[5,61.
Type of dye Researchers
[ref.] Capacities Studies have shown that treated rice husk
Safranine McKay, 1986 760 possessed a better adsorption capacity on metal
Sandolanrhodine [59] 0 ions. Suemitsu et al. [34] and Marshall et al. [35]
Congored 0 reported that better adsorption capacity on metal
Foron brill red 30 ions was achieved with treated rice husk.
Methyleneblue 280 Marshall et al. [35] also reported that different
Sandolanblue MeKay et al., 12 treatment methods would yield different adsorp-
Solar blue 1987a [40] 38 tion capacities. Tarley et al. [10] also reported
Foron blue 6 that modified rice husks have a higher sorption
Sandocryl orange Nawarand Dorna, 27 capacity on Pb(II) and Cr(II) compared with the
Lanasyn black 1989 [41] 9 unmodified rice husks (Table 5).
Acid yellow36 Malik, 2003 [13] 86.9 2
"Adsorptioncapacity is measuredin mg/l. 5. Sorption isotherms
The adsorption data from previous studies are
[59] reported that untreated rice husk does not either fitted to a Langmuir or Freundlich model.
work for Congo red, Sandolan blue, Sandolan The Langmuir isotherm presents here in a general
rhodine, Solar blue and Foron blue, and has a low linearized form:
adsorption capacity for Foron brill red. However,
his findings show that the complicated chemical 1 1 1
nature of dyestuffs and adsorbents is involved in
N, C.N'b N*
the adsorption phenomenon rather than on the
simple dependence on the type of ions being where Ce is the equilibrium concentration of the
adsorbed. His findings also show that no treat-
solute (mg/1), Ne is the amount of solute adsorbed
ment is not a good adsorbent for several basic
per unit weight of adsorbent (mg/g), N" is the
dyes. Few works have been reported on removal
maximum capacity of adsorbent of the system
reactive dyes using rice husk. However, Low and
(mg/g) and b is an adsorption equilibrium con-
Lee [39] have reported their studies on quater-
stant related to the energy of the sorption (1/mg).
nized rice husk as a sorbent for reactive dyes. A
The Freundlich isotherm presented here is in the
summary of reported dye adsorption capacities
following form:
using rich husk is listed in Table 6.
The rice husk is in the either untreated, treated
or modified form using different agents. Adsorp- ae
- KC
- --e
ll~

tion studies using untreated or high-temperature

carbonized rice husks were carded out by McKay
[40,59], Roy et al. [55], Tiwari et al. [57], Mishra
et al. [58], Malik [ 13], Nakbanpote et al. [2,3] and
Tarley and Arruda [9]. Chemical treatment was
commonly used in the treatment of rice husk,
including sulphuric acid [40], sodium carbonate
[41 ], hexane [35], hydrochloride acid [56], potas-
where ae and Ce are the amounts (mol/g) adsorbed
at equilibrium and equilibrium bulk concentration
(mol/dm3), respectively; 1/n and K are the Freund-
lich constants which correspond to adsorption
intensity and adsorption capacity, respectively.
Tables 7 and 8 show the reported Langmuir
and Freundlich isotherms parameters from
 T.G. Chuah et al. / Desalination 175 (2005) 305-316 311

Table 7
Reported Langmuir isotherms from previous batch studies using rice husk as adsorbent

Metal ion/dyes Temperature Maximum sorption capacity Constant Researchers [ref.]

(°C) at equilibrium, (rag/g) (l/rag)

Au 20 39.84 0.059 Nakbanpote et al., 2002

30 50.50 0.050 [3]
40 64.10 0.031
Co 20 0.32 1.62 Marshall et al., 1993 [35]
Cr(III) 20 1.90 0.48 Marshall et al., 1993 [35]
Cu 20 1.21 0.90 Marshall et al., 1993 [35]
27 29 0.10 Wong et al., 2003 [5]
50 22 0.05
70 18 0.03
Hg(II) 29-31 66.66 (de -- 37-50 #m) 0.0037 Tiwari et al., 1995 [57]
55.55 (de = 63-130 #m) 0.003
40.00 (de = 130-600 #m) 0.0025
15 9.3200 0.0115 Feng et al., 2004 [64]
30 6.7200 0.0158
Ni(II) 20 0.23 1.62 Marshall et al., 1993 [35]
Pb 27 108 0.09 Wong et al., 2003 [5]
50 105 0.02
70 96 0.01
15 12.3460 0.3250 Feng et al., 2004 [64]
30 12.6100 0.1630
Zn(II) 20 0.75 1.94 Marshall et al., 1993 [35]
Acid yellow 36 dye 30 86.9 0.002 Malik, 2003 [13]
Acid blue dye 25 50.0 0.1 Mohamed, 2004 [67]

Table 8
Reported Freundlich isotherms from previous batch studies using rice husk as adsorbent

Metal ion/dyes Temperature (°C) Adsorption Adsorption capacity, Researchers [re£]

intensity, 1/n K (tool/g)

Cr (VI) 0.6387 56.6 Sumathi et al., 2004 [65]

Hg (II) 15 0.4932 0.4179 Feng et al., 2004 [64]
30 0.4691 0.5363
Pb 15 0.2475 4.7097 Feng et al., 2004 [64]
30 0.3094 3.4986
Zn (II) 20 0.909 2.238 Mishra et al,, 1997 [58]
Acid yellow 36 30 0.435 2.1 Malik, 2003 [13]
312 T.G. Chuah et al. / Desalination 175 (2005) 305-316
previous studies. Most of the reported heavy
metal systems suggest the applicability Langmuir,
which assumes there is monolayer coverage and
constant sorption energy on the sorbent surface.
Mishra et al. [58], however, reported that the data
of Zn ion adsorption are well fitted to the Freund-
lich isotherm rather than the Langmuir isotherm.
This may be due to the adsorbent's heterogeneity
of the surface, and is further confirmed with the
fractional value of 1/n of 0.909 (0< 1/n<l) [60].
Malik [13] reported that both Langmuir and
Freundlich models could be used to represent the
trends of adsorption on Acid yellow 36 dye. His
finding indicates that Acid yellow 36 is favour-
ably adsorbed by the activated carbon prepared
from rice husk.
It should be noted that some studies have
shown data well fitted in the Freundlich isotherm;
however, the values of 1/n and K were not in their
works [ 11,12,41 ]. Guo et al. [ 11,12], however,
emphasized that the Freundlich model in no way
is meant to imply that the model assumptions are
valid for their works. Moreover, the model used
is only to provide a simple representation of the
trends they observed.
6. Effect of contact time and effect of initial
concentration
Tiwari et al. [57] found that the initial concen-
tration of Hg(II) has little effect on the contact
time to reach equilibrium. However, adsorption
capacity is increased with the increment of initial
concentration. A similar situation was observed
for Zn(II) adsorption by rice husk [58]. Initial
concentration of Zn(II) has little effect on the
contact time to reach equilibrium. The adsorption
capacity is also increased with the increment of
initial concentration of Zn(II).It should be noted
that Marshall et al. [35] and Munaf and Zein [56]
did not report on the effect of contact time and
effect initial concentration of Zn(II) by rice husk.
Lee et al. [ 1] have reported that the amount of
uptake of As (V) by rice husk follows the trend of
a greater amount of uptake with decreasing initial
concentration. However, sorption of As(V) was
very rapid, taking 20 min to achieve equilibrium
irrespective of the initial concentration. It also
attains equilibrium faster than the adsorption such
as fly ash and chrome waste, which attained equi-
librium after 72 min and 2 h, respectively [61,62].
Guo et al. [4] reported their findings in ad-
sorption of Cr(VI); equilibrium was achieved in
about 2 h and it was found that the equilibrium
time was much faster than any other adsorbents
such as cow dung carbon, coconut shell carbon
and peach stones. The same equilibrium time was
achieved and observed by them on the adsorption
of malachite green using the same adsorbent dose
of 0.8 g/1 of rice husk [11]. Both experimental
results indicate the rapid uptake of the treated rice
husk on heavy metals and dyes.
Nawar and Doma [41] studied the effect of
contact time on basic dye (Sandocryl orange
B-3RLE) and acid dye (Sandoz lanasyn black
BRL ABK). The contact time required to reach
equilibrium for the basic dye is short using rice
husk - - 15 min. This agreed with the findings
reported by Tinh et al. [63] on saturation of mate-
dais with a cellulose-type structure that was
achieved after only 15 min for low concentrations
of a basic dye. However, for acid dyes, lower
uptake is observed at equilibrium.
7. Effect of pH
It is known that the sorption of heavy metal
ions by solid substracts depends on the pH of the
solution. Mishra et al. [58] suggested that the
contents of amino acids, the active functional
groups and metal oxides in rice husk, may have
an effect on the uptake process. Adsorption of
Zn(II) increases with the increase of pH values.
Rice husk could exhibit a hydration shell at lower
pH positively charged by the hydronium ion, H+,
in the solution. This restricted the uptake of
Zn(II) ions. Adsorption capacity increases with
increasing pH values. At moderate to high pH
 T.G. Chuah et al. /Desalination 175 (2005) 305-316
values, zinc ions exist as Zn 2+, Zn(OH) ÷ and
Zn(OH)2 , which are favourable species for
adsorption of trace zinc ions. A similar observa-
tion was found in the adsorption ofCr(IV), Cu(II)
and Cd(II) by rice husk [56]. This is further
supported by the work of Wong et al. [5].
The effect of pH on Hg(II) adsorbed by rice
husk was studied by Tiwari et al. [57]. They
found that a maximum adsorption efficiency at
pH 6 seems to be related to the dominant species
of Hg(OH)2. Chloride species, such as HgC12,
dominate at pH <6. Disappearance of hydroxyl-
mercury group species at pH <6 caused a de-
crease in adsorption. Dissolution of metal oxides
office husk may also increase the pH value of the
solution. This is further supported by the findings
observed by Feng et al. [64]. By using solutions
with an initial pH of 5.60-5.80, they obtained the
highest absorption capacity values on Hg.
Guo et al. [4] observed the maximum adsorp-
tion of Cr(VI) was found in the range below 5,
and the adsorbed amount was found to be negli-
gible in the pH value over 8. These findings are
further supported by the work of Sumathi et al.
[65]. They found that the solution pH had a
marked influence on Cr(VI) adsorption. Gene-
rally, adsorption of Cr(VI) was higher at lower
pH and decreased with increasing pH. This could
be due to the redox reaction between the sorbent
surface groups and sorbate. Higher H + ion con-
centration could strengthen the redox reaction and
enable the carbon to adsorb more Cr(VI). Vasan-
thy and Lakshmanaperumalsamy [66] also sug-
gested that the high adsorption of Cr(VI) at low
pH was due to the fact at low pH a large number
of hydrogen ions can neutralize the oppositely
charged surface and thus enhance the electrostatic
attraction between the adsorbent and adsorbate
overcoming electrostatic repulsion between them.
The effect of different pH values on dye
adsorption capacity of rice husk was studied by
Nawar and Doma [41 ]. They observed that there
is a general trend for the adsorption capacity to be
constant at pH values between 3and 9 for a basic
313
dye (Sandocryl orange) and an acid dye (Sandoz
lanasyn black).
The adsorption of malachite green [11] was
increased with pH when the same rice husk was
used. This may be due to the increase of negative
charges on the carbon surface; hence, the electro-
static force, like van de Waals, between the car-
bon surface and dye ion, were increased.
8. Effect of particle size
The adsorption capacity of rice husk 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 surface area. In other
words, smaller particle size increases the adsorp-
tion capacity. Munaf and Zein [56] reported that
when the size of rice husk particles increases,
metal ions decrease. Similar trends have been
reported by Wong et al. [5]. Adsorption being a
surface phenomenon, the smaller adsorption sizes
will offer comparatively larger surface areas and
higher adsorption will occur at equilibrium.
Tiwafi et al. [57] found that the adsorption
capacity of Hg(II) on rice husk decreased with
increasing particle size. Higher sorption for
smaller particle size seems due to larger surface
area per unit mass of rice husk. His findings also
indicated that, in the initial stage of adsorption,
Hg(II) adsorption was dominated by diffusional
transport.
9. Effect of agitation rate
Wong et al. [5] show that the uptakes of Pb
and Cu increased with increasing agitation rates.
An increasing agitation rate may reduce the film
boundary layer surrounding the sorbent particles,
thus increasing the external film diffusion rate
and the uptake rate. However, Lee et al. [1]
showed that varying the agitation rate does not
314 7'.(7. Chuah et al. / Desalination 175 (2005) 305-316
have any effect on the uptake rate of As(V) on
rice husks. This is due to the As(V) by quatenized
rice husk, is a very rapid process. It can be con-
cluded that due to the nature of sorbents and
sorbates, the effect of agitation is varied.
10. Effect of competitive ions
Different reasons have been given regarding
the sorption affinity of biosorbent such as rice
husk. The amount of sorbed ions depends on the
equilibrium between sorption competition from
all the cations, ionic size, stability of bonds
between metal ions and biosorbent [68]. Wong et
al. [5] investigated the effect of competitive ions
between Pb and Cu. The finding shows that the
affinity of a modified rice husk (MRH) for metal
ions is Pb>Cu in mixed metal solutions. The
stability and enthalpy of formation are greater for
Pb-MRH than for Cu-MRH.
11. Effect of activation conditions
The effect of activation conditions on rice
husk was studied intensively by Guo et al. [15]. A
characterization of porous rice husk carbon pre-
pared with different precalcination times was
made. Precalcination time has a great effect on
the porosity of the porous carbons prepared by
KOH but not significant for the carbon prepared
by NaOH. Lower precalcination time can produce
carbons exhibiting microporosity and meso-
porosity. Microporous carbon can be produced
with higher precalcination times. It was found
that there is no increase of pore volume in the
presence of alkali chlorides, which restrict the
activating agents from entering into the interior of
the carbon structure. It can be concluded that the
activation mechanism of rice husk carbon is
complicated.
12. Conclusions
Rice husk as an agricultural by-product has
been made into a potentially low-cost biosorbent
material used in heavy metal and dye removal.
Previous studies have focused on untreated rice
husk. However, a study of treated rice husk on
removing heavy metals has been of interest by
many researchers. This paper summarizes the
studies that have been carded out by many other
workers on the adsorption of heavy metals and
dyes. It was found that rice husk possesses
different characteristics due to the method of
treatment. Treatment methods on rice husk have
a strong infiuenee on adsorption efficiency. Opti-
mization of biosorption parameters using rice
husks can be achieved by manipulating the ope-
rating parameters and sorbent characteristics.
References
[1] C.K. Lee, K.S. Low, S.C. Liew and C.S. Choo,
Environ. Technol., 20 (1999) 971-978.
[2] W. Nakbanpote, P. Thiravavetyan and C. Kalam-
baheti, Mineral Eng., 13 (2000) 391-400.
[3] W. Nakbanpote, P. Thiravavetyan and C. Kalam-
bahefi, Mineral Eng., 15 (2002) 549-552.
[4] Y. Guo, J. Qi, S. Yang, K. Yu, Z. Wang and H. Xu,
Mat. Chem. Physics, 78 (2002) 132-137.
[5] K.K. Wong, C.K. Lee, K.S. Low and M.J. Haron,
Chemosphere,50 (2003) 23-28.
[6] K.K.Wong, C.K. Lee, K.S. Low and M.J. Haron,
Process Bioehern.,39 (2003) 437--445.
[7] A.A.M. Daifulla,B.S. Girgis and H.M.H. Gad, Mat.
Lett., 57(2003) 1723-1731.
[8] M. Ajmal, R.A.K. Ran, S. Anwar, J. Ahamad and
R. Abroad, Bioresource Technol., 86 (2003) 147-
149.
[9] C.ILT.Tarley and M.A.Z. Arruda, Chemosphere,54
(2004) 987-995.
[10] C.R.T. Tarley, S.L.C. Ferreira and M.A.Z. Arruda,
Microchem.J., 77 (2004) 163-175.
 T.G. Chuah et al. / Desalination 175 (2005) 305-316
[11] Y. Guo, S. Yang, W. Fu, J. Qi, R. Li, Z. Wang and
H. Xu, Dyes Pigments, 56 (2003) 219-229.
[12] Y. Guo, H. Zhang, N. Tao, Y. Liu, J. Qi, Z. Wang
and H. Xu, Mat. Chem. Physics, 82 (2003) 107-115.
[13] P.K. Malik, Dyes Pigments, 56 (2003) 239-249.
[14] N. Yalcin and V. Sevinc, Carbon, 38 (2000) 1943-
1945.
[15] Y. Guo, K. Yu, Z. Wang and H. Xu, Carbon, 41
(2000) 1645-1687.
[16] Y. Guo, J. Qi, S. Yang, K. Yu, J. Zhao, Z. Wang and
H. Xu, Mat. Chem. Physics, 74 (2002) 320-323.
[17] K.V.K. Ran, Toxicol. Lea., 81 (1995) 107-113.
[18] C. O'Neill, F.R. Hawkes, N.D. Lourenco, H.M.
Pinbeiro andW. Deice, J. Chem Technol. Bio-
teehnol., 74 (1999) 1009-1018.
[19] G. McKay, Am. Dyest. Rep., 68 (1979) 29-36.
[20] V.J.P. Poots and G. McKay, Water Res., 10 (1976)
1061-1066.
[21 ] S.E. Bailey, T.J. Olin, R.M. Bricka and D.D. Adrian,
Water Res., 33 (1999) 2469-2479.
[22] K.K.H. Choy, G. MeKay and J.F. Porter, Resour.
Conserv. Recy., 27 (1999) 57-71.
[23] M.P. Gupta and P.K. Bhattaeharrya, J. Chem.
Teehnol. Bioteehnol,m 35B (1985) 23.
[24] S.D. Khattri and M.K. Singh, Water Air Soil Poll.,
120 (2000) 283-294.
[25] L. Kun-She, L. Chnoong-Kheng and T. Bee-Foong,
App. Biochem. Bioteetmol., 87 (2000) 233-245.
[26] R.M. Liversidge, G.J. Lloyd, D.A.J. Wase and
C.F. Forster, Proc. Biochem., 32 (1997) 473-477.
[27] G. McKay, M.S. Otterburn and A.G. Sweeney,
Water Air Soil Poll., 24 (1985) 147-161.
[28] A.K. Mittal and S.K. Gupta, Water Sci. Technol.,
34 (1996) 81-87.
[29] F. Perineau, J. Molinier and A. Gaset, J. ChertL
Technol. Biotechnol., 32 (1982) 749-758.
[30] V.N. Singh, G. Mishra and K.K. Panday, Ind. J.
Teehnol., 22 (1984) 70-71.
[31] T. Robinson, G. McMuUan, R. Marchant and P.
Nigam, Bioresource Teehnol., 77 (2001) 247-255.
[32] C.I. Pearce, J.R. Lloyd and J.T. Guthrie, Dyes
Pigments, 58 (2003) 179-196.
[33] R.R. Bansode, J.N. Losso. W.E. Marshall, R.M. Rao
and R.J. Portier, Bioresource Technol., 89 (2003)
115-119.
315
[34] R. Suemitsu, R. Uenishi, I. Akashi and M. Nakano,
J. Appl. Polym. Sci, 1 (1986) 75-83.
[35] W.E. Marshall, E.T. Champagne and W.J. Evans,
J. Environ. Sei. Health, A28 (1993) 1977-1992.
[36] C.K. Lee, K.S. Low and S.J. Mah, Adv. Environ.
Res., 2 (1998) 351-359.
[37] F. Banat, S. A1-Asheh and L. AI Makhadmeh, Proc.
Biochem., 39 (2003) 193-202.
[38] V.K. Garg, R. Gupta, A.B. Yadav and R. Kumar,
Bioresouree Technol., 89 (2003) 121-124.
[39] K.S. Low and C.K. Lee, Bioresource Technol., 61
(1997) 121-125.
[40] G. McKay, G. Ramprasad and P. Mowli, Water Res.,
21 (1987) 375-377.
[41] S.S. Nawar and H.S. Doma, Sci. Total Environ., 79
(1989) 271-279.
[42] P. Nigam, G. Armour, I.M. Banat, D. Singh and
R. Marchant, Bioresource Technol., 72 (2000) 219-
226.
[43] T. Robinson, B. Chandran and P. Nigam,
Bioresource Technol., 85 (2002) 119-124.
[44] T. Robinson, B. Chandran and P. Nigarn, Environ.
Internat., 28 (2002) 29-33.
[45] T. Robinson, B. Chandran and P. Nigam, Water Res.,
36 (2002) 2824-2830.
[46] D.H. Grist, Rice, 5th ed, Longman, London, 1975.
[47] H. Olmez, Utilization of agriculture and industrial
wastes in production of the cement, Samsun:
Ondokuz Mayis University, Publ. No. 47, 1988.
[48] K.G. Mansaraly and A.E. Gbaly, Energy Sources, 20
(1998) 653-663.
[49] U. Sanigok, Inorganic Industrial Chemistry, Istanbul
University Press, Istanbul., 1987.
[50] T.H. Usmani, T.W. Ahmad, S.Z. Ahmed and A.H.K.
Yousufzai, Pakistan J. Sci. Indus., 36 (1993) 236--
239.
[51 ] T.H. Usmani, T.W. Ahrnad, S.Z. Ahmed and A.H.K.
Yousufzai, Pakistan J. So. Indus., 36 (1993) 240-
243.
[52] I.A. Rahman and J. Ismail, J. Mater. Chem., 3 (1993)
931-934.
[53] I.A. Rahman, J. Ismail and H. Osman, J. Mater.
Chem., 7 (1997) 1505-1509.
[54] S.A. Darnel, Rice hull ash as a piazzolanic material,
Masters Thesis, Asian Institute of Technology, 1976.
316 T.G. Chuah et al. /Desalination 175 (2005) 305-316
[55] D. Roy, P.N. C_rreenlawand B.S. Shane, J. Environ.
Sci. Health, A28 (1993) 37-50.
[56] E. Munafand R. Zein, Environ. Teehnol., 18 (1997)
359-362.
[57] D.P. Tiwari, D.K. Singh and D.N. Saksena, J. Env.
Eng., 121(1995) 479-481.
[58] S.P. Mishra, D. Tiwari and R.S. Dubey, Appl.
Radiat. Isot., 48 (1997) 877-882.
[59] G. McKay, Water Air Soil Poll., 29 (1986) 273-283.
[60] P. Benes, Tmee Chemistry of Aqueous Solutions,
Elsevier, Amsterdam, 1980.
[61] E. Diamadopoulos, S. Ioanidis and G.P. Sakellarou-
polos, Water Res., 27 (1993) 1773-1777.
[62] M. Sadiq, T.H. Zaida and A.A. Mian, Water Air Soil
Poll., 26 (1983) 369-377.
[63] V.Q. Tinh, R. Leblane, J.M. Janssens and M. Ruel,
Can. Mining Metall. Bull., 64 (1971) 99.
[64] Q. Feng, Q. Lin, F. Gong, S. Sugita and M. Shoya,
J. Coll. Interf. Sei., 278 (2004) 1-8.
[65] K.M.S. Sumathi, S. Mahirnairaja and R. Naidu,
Bioresource Technol., in press.
[66] M. Vasanthy and P. Lakshmanaperumalsamy, Eco-
toxieol. Environ. Monit., 3 (1995)47-50.
[67] M.M. Mohamed, J. Coll. Interf. Sci., 272 (2004)
28-34.
[68] K.S. Low, C.K. Lee and A.C. Lee, Bioresource
Technol., 51 (1995) 227-231.