Available online at www.sciencedirect.

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Bioresource Technology 99 (2008) 67096724

Review

Heavy metal adsorbents prepared from the modication

of cellulose: A review
David William OConnell a,c, Colin Birkinshaw b,c, Thomas Francis ODwyer a,c,*
a

Chemical and Environmental Sciences Department, University of Limerick, Ireland

b
Materials Science and Technology Department, University of Limerick, Ireland
c
Materials and Surface Science Institute, University of Limerick, Ireland

Received 26 October 2007; received in revised form 24 January 2008; accepted 27 January 2008
Available online 10 March 2008

Abstract
A number of industries currently produce varying concentrations of heavy metal laden waste streams with signicant consequences
for any receiving environmental compartment. In recent years, increasing emphasis has been placed on environmental impact minimisation and resulting from this the range and capability of natural and prepared materials capable of heavy metal removal has seen steady
development. In particular considerable work has been carried out on the use of both natural materials and their modications. These
natural materials, in many instances are relatively cheap, abundant in supply and have signicant potential for modication and ultimately enhancement of their adsorption capabilities. This review paper reviews the current state of research on the use of the naturally
occurring material cellulose, its modied forms and their ecacy as adsorbents for the removal of heavy metals from waste streams.
Adsorbents based on direct modication of cellulose are evaluated initially and subsequently modications resulting from the grafting
of selected monomers to the cellulose backbone with subsequent functionalisation are assessed. The heavy metal adsorption capacities
for these modied cellulose materials were found to be signicant and levels of uptake were comparable, in many instances, to both other
naturally occurring adsorbent materials and commercial ion exchange type resins. Many of the modied cellulose adsorbents proved
regenerable and re-usable over a number of adsorption/desorption cycles allowing recovery of the adsorbed heavy metal in a more concentrated form.
2008 Elsevier Ltd. All rights reserved.
Keywords: Cellulose; Modication; Adsorption; Heavy metals; Wastewater

1. Introduction
Heavy metals is a general collective term applying to
the group of metals and metalloids with an atomic density
greater than 6 g cm3. Although it is only a loosely dened
term it is widely recognised and usually applied to the elements such as Cd (cadmium), Cr (chromium), Cu (copper),
Hg (mercury), Ni (nickel), Pb (lead) and Zn (zinc) which
are commonly associated with pollution and toxicity problems. Unlike most organic pollutants, heavy metals occur
*
Corresponding author. Address: Chemical and Environmental Sciences Department, University of Limerick, Castletroy, Limerick, Ireland.
Tel.: +353 61 202691.
E-mail address: tom.odwyer@ul.ie (T.F. ODwyer).

0960-8524/$ - see front matter 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.biortech.2008.01.036

naturally in rock-forming and ore minerals and so a range

of normal background concentrations is associated with
each of these elements in soils, sediments, waters and living
organisms. On an annual basis, signicant quantities of
various heavy metals are produced from the mining of their
respective ores. In the year 2004, approximately 14,500 
103 tons of copper was produced (US Geological Survey,
2004).
Industrial uses of metals and other domestic processes
(e.g. burning of fossil fuels, incineration of wastes, automobile exhausts, smelting processes and the use of sewage
sludge as landll material and fertiliser) have introduced
substantial amounts of potentially toxic heavy metals into
the atmosphere and into the aquatic and terrestrial environments. Discharged toxic metals typically include Cd,

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D.W. OConnell et al. / Bioresource Technology 99 (2008) 67096724

Cu, Ni, Cr, Co, Zn and Pb (Babich et al., 1985). Table 1

outlines the industrial sources and potential for pollution
for a range of metals discharged.
While many of the heavy metals are needed by plants at
the micronutrient level, higher concentrations are known to
produce a range of toxic eects. At high exposure levels,
Lead causes encephalopathy, cognitive impairment, behavioural disturbances, kidney damage, anaemia and toxicity
to the reproductive system (Pagliuca and Mufti, 1990).
Chromium is widely recognised to exert toxic eects in its
hexavalent form (Rowbotham et al., 2000). Human exposure to Cr(VI) compounds is associated with a higher incidence of respiratory cancers (IARC, 1990). Cadmium is
associated with nephrotoxic eects particularly at high
exposure levels; long-term exposure may cause bone damage as well (Friberg, 1985). High concentrations of mercury
can lead to neurobehavioural disorders and developmental
disabilities including dyslexia, attention decit hyperactivity disorder, intellectual retardation (Weiss and Landrigan,
2000). Excessive copper concentrations can lead to weakness, lethargy and anorexia, as well as damage to the gastrointestinal tract (Theophanides and Anastassopoulou,
2002). The toxic eects of nickel and other heavy metals
are discussed in some detail by Nordberg et al. (2007).
Various methods exist for the removal of heavy metal
ions from wastewater which include chemical precipita-

tion/coagulation, membrane technology, electrolytic reduction, ion exchange and adsorption (Kurniawan et al., 2006;
Wang et al., 2003). The advantages and disadvantages
associated with each method are listed in Table 2.
The most widely used method of removing heavy metals
from solution is to increase the pH of the euent, thus converting the soluble metal into an insoluble form (i.e. its
hydroxide). Ion exchange is the second most widely used
method for heavy metal removal from aqueous streams
(Shukla et al., 2002). During removal, recovery, or processing of metals, ion exchange acts as a concentrator of metals. The chemistry of the inuent stream becomes very
important to the success of the ion exchange application.
Coagulationocculation can also be employed to treat
wastewater laden with heavy metals wherein the coagulation process destabilises colloidal particles by adding a
chemical agent (coagulant) and results in sedimentation
(Wang et al., 2004). Coagulation is followed by occulation
of the unstable particles in order to increase their size and
form into bulky occules which can be settled out. Flotation is employed to separate solids or dispersed liquids
from a liquid phase using bubble attachment (Wang
et al., 2004). Adsorptive bubble separation employs foaming to separate the metal impurities. Ion otation, precipitate otation and sorptive otation are the main otation
process mechanisms for removal of metal ions from solu-

Table 1
Signicant anthropogenic sources of metals in the environment
Industry

Metals

Pollution arising

Reference

Metalliferous mining

Cd, Cu, Ni, Cr, Co, Zn

Acid mine drainage, tailings, slag heaps

Babich et al. (1985)

Aswathanarayana (2003)

Agricultural materials
Fertilisers

Cd, Cr, Mo, Pb, U, V, Zn

Manures sewage
sludge

Zn, Cu, Ni, Pb, Cd, Cr, As,

Hg

Run-o, surface and groundwater contamination, plant

bioaccumulation
Landspreading threat to ground and surface water

Nicholson et al. (2003)

Otero et al. (2005)
Nicholson et al. (2003)
Cheung and Wong (1983)
Walter et al. (2006)

Manufacture, disposal and recycling of metals. Tailings

and slag heaps

Alloway and Ayres (1993)

Rule et al. (2006)
Cheng (2003)

Landll leachate, contamination of ground and surface

water
Aqueous and solid metallic waste from manufacturing
and recycling process

Kjeldson et al. (2002)

Fernandez et al. (2005)
Veglio et al. (2003)

Liquid euents from plating processes.

Castelblanque and Salimbeni

(2004)
Zhao et al. (1999)
Alvarez-Ayuso et al. (2003)

Waste battery uid, contamination of soil and

groundwater.
Aqueous waste from manufacture, old paint
deterioration and soil pollution.

EU Directorate general of the

Environment (2004)
Davis and Burns (1999)
Barnes and Davis (1996)
Monken (2000)

Metallurgical industries
Specialist alloys and
Pb, Mo, Ni, Cu, Cd, As, Te,
steels
U, Zn
Waste disposal
Landll leachate
Electronics

Zn, Cu, Cd, Pb, Ni, Cr, Hg

Pb, Cd, Hg, Pt, Au, Cr, As,
Ni, Mn

Metal nishing industry

Electroplating
Cr, Ni, Zn, Cu

Miscellaneous sources
Batteries

Pb, Sb, Zn, Cd,Ni, Hg

Paints and pigments

Pb, Cr, As, Ti, Ba, Zn

D.W. OConnell et al. / Bioresource Technology 99 (2008) 67096724

6711

Table 2
Treatment technologies for the removal of heavy metals from wastewaters and associated advantages and disadvantages
Technology

Advantages

Disadvantages

Reference

Chemical
precipitation

Process simplicity
Not metal selective
Inexpensive capital cost

Large amount of sludge containing metals

Sludge disposal cost
High maintenance costs

Aderhold et al. (1996)

Ion exchange

Metal selective
Limited pH tolerance
High regeneration

High initial capital cost

High maintenance cost

Aderhold et al. (1996)

Coagulation
occulation

Bacterial inactivation capability

Good sludge settling and dewatering
characteristics

Chemical consumption
Increased sludge volume generation

Aderhold et al. (1996)

Flotation

Metal selective
Low retention times
Removal of small particles

High initial capital cost

High maintenance and operation costs

Rubio et al. (2002)

Membrane
ltration

Low solid waste generation

Low chemical consumption
Small space requirement
Possible to be metal selective

High initial capital cost

High maintenance and operation costs
Membrane fouling
Limited ow-rates

Madaeni and
Mansourpanah (2003)
Qin et al. (2002)

Electrochemical
treatment

No chemical required can be engineered to

tolerate suspended solids
Moderately metal selective Treat euent
> 2000 mg dm3

High initial capital cost Production of H2

(with some processes)
Filtration process for ocs

Kongsricharoern and
Polprasert (1995)
Kongsricharoern and
Polprasert (1996)

Adsorption

Wide variety of target pollutants

High capacity
Fast kinetics
Possibly selective depending on adsorbent

Performance depends on type of

adsorbent
Chemical derivatisation to improve its
sorption capacity

Crini (2005)

tion. Membrane ltration has received considerable attention for the treatment of inorganic euent, since it is capable of removing not only suspended solid and organic
compounds, but also inorganic contaminants such as heavy
metals.
Amongst all the treatment processes mentioned, adsorption using sorbents is one of the most popular and eective
processes for the removal of heavy metals from wastewater.
The adsorption process oers exibility in design and operation and in many cases produces treated euent suitable
for re-use, free of colour and odour. In addition, because
adsorption is sometimes reversible, the regeneration of
the adsorbent with resultant economy of operation may
be possible (Kelleher, 2001).
Activated carbon adsorbents are used widely in the
removal of organic contaminants and to a lesser extent
heavy metal contaminants in product purication and pollution control. Carbon is converted to activated carbon by
heating in the absence of air. The activation process results
in the creation of a network of ne pores in the carbon particles. The vast areas (3004000 m2 g1) of the walls within
these pores account for the most of the total surface area of
the carbon (OCooney, 1998). In spite of its prolic use,
activated carbon remains an expensive material and the
higher the quality of activated carbon, the higher its cost.
Also, in practice activated carbon is employed more frequently for adsorption of organic compounds rather than
heavy metal ions.

Characterisation of the adsorption process is often carried out using a number of isotherm models. These include
the most common Langmuir (1918) (Eq. (1)) and Freundlich (1926) (Eq. (2)) isotherms and other related models
as described by Peric et al. (2004) and Altin et al. (1998)
K L  Ce
1
qe
1 AL  C e
1

qe K F  C ne

In the case of the Langmuir model, equivalence of adsorption sites and monolayer of adsorbate coverage is predicted. The amount of solute adsorbed, qe, in mg g1, Ce
is equilibrium concentration in solution in mg L1, KL
and AL are Langmuir constants. A plot of Ce/qe versus
Ce from the linear form of Eq. (1) can be used to determine
the values of KL (intercept) and AL/KL (slope). Saturation
coverage on the adsorbent is obtained as KL/AL.
The Freundlich isotherm model is an entirely empirical
isotherm and assumes a logarithmic relationship between
the level of adsorption and equilibrium sorbate concentration. The Freundlich constants KF and n are related to
adsorption capacity and energy of adsorption, respectively
(Ortiz et al., 2001).
2. Cellulose
Cellulose constitutes the most abundant and renewable
polymer resource available worldwide. It is estimated that

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D.W. OConnell et al. / Bioresource Technology 99 (2008) 67096724

by photosynthesis, 10111012 tons of cellulose are synthesised annually in a relatively pure form, for example, in
the seed hairs of the cotton plant, but more often are combined with lignin and other polysaccharides (so-called
hemicelluloses) in the cell wall of woody plants (Klemm
et al., 2002). Cellulose has been used in the form of wood
and cotton for thousands of years as an energy source, a
building material and for clothing.
The molecular structure of cellulose as a carbohydrate
polymer comprises of repeating b-D-glucopyranose units
which are covalently linked through acetal functions
between the OH group of the C4 and C1 carbon atoms
(b-1,4-glucan). Cellulose is a large, linear-chain polymer
with a large number of hydroxyl groups (three per anhydroglucose (AGU) unit) and present in the preferred 4C1
conformation. To accommodate the preferred bond angles,
every second AGU unit is rotated 180 in the plane. The
length of the polymeric cellulose chain depends on the
number of constituent AGU units (degree of polymerisation, DP) and varies with the origin and treatment of the
cellulose raw material (Klemm et al., 2002).
Cellulose has a ribbon shape which allows it to twist and
bend in the direction out of the plane, so that the molecule
is moderately exible. There is a relatively strong interaction between neighbouring cellulose molecules in dry bres
due to the presence of the hydroxyl (OH) groups, which
stick out from the chain and form intermolecular hydrogen
bonds. Regenerated bres from cellulose contain 250500
repeating units per chain (Klemm et al., 2002). This molecular structure gives cellulose its characteristic properties of
hydrophilicity, chirality and degradability. Chemical reactivity is largely a function of the high donor reactivity of
the OH groups (Klemm et al., 2005).
In particular, two main approaches have been tried in
the conversion of cellulose into compounds capable of
adsorbing heavy metal ions from aqueous solutions. The
rst of these methods involves a direct modication of
the cellulose backbone with the introduction of chelating
or metal binding functionalities producing a range of heavy
metal adsorbents. Alternative approaches have focused on
grafting of selected monomers to the cellulose backbone
either directly introducing metal binding capability or with
subsequent functionalisation of these grafted polymer
chains with known chelating moieties.
3. Adsorbents produced by direct modication of cellulose
Unmodied cellulose has a low heavy metal adsorption
capacity as well as variable physical stability. Therefore,
chemical modication of cellulose can be carried out to
achieve adequate structural durability and ecient adsorption capacity for heavy metal ions (Kamel et al., 2006).
Chemical modication can be used to vary certain properties of cellulose such as its hydrophilic or hydrophobic
character, elasticity, water sorbency, adsorptive or ion
exchange capability, resistance to microbiological attack
and thermal resistance (McDowall et al., 1984). The b-D-

glucopyranose units which make up the cellulose chain

contain one primary hydroxyl group and two secondary
hydroxyl groups. Functional groups may be attached to
these hydroxyl groups through a variety of chemistries.
The principle and main routes of direct cellulose modication in the preparation of adsorbent materials are esterication, etherication, halogenation and oxidation.
3.1. Esterication
Low et al. (2004), used heat to convert citric acid to citric acid anhydride which can further react with the cellulosic hydroxyl groups in wood pulp to form an ester
linkage. This reaction introduced carboxyl functional
groups to the cellulosic wood pulp material. The esterication process increases the carboxylic content of the wood
bre surface leading to a corresponding increase in the
sorption of divalent metal ions. This modied wood pulp
had Cu(II) and Pb(II) binding capacities of 24 mg g1
and 83 mg g1, respectively. Through a similar esterication reaction, Marchetti et al. (2000), chemically modied
wood pulp using succinic anhydride, in the presence of a
number of catalysts, leading to the introduction of carboxyl groups. The cadmium(II) binding capacity of the
modied sawdust was directly related to the acid value estimated by titration and could reach uptakes of up to
169 mg g1.
3.2. Halogenation
Halogenation represents another cellulose modication
technique. Tashiro and Shimura (1982) synthesised chlorodeoxycellulose by reacting cellulose powder with thionyl
chloride in dimethylformamide solvent. The chlorodeoxycellulose was functionalised with ethylenediamine, thiourea, thiosemicarbazide, thioacetamide, hydroxylamine
and hydrazine. However, the synthesis was dicult due
to the relatively low reactivity of cellulose with thionyl
chloride. Aoki et al. (1999a) synthesised 6-deoxy-6-mercaptocellulose and its S-substituted derivatives from 6bromo-6-deoxycellulose. The reactivity of cellulose and
bromine compared to cellulose and chlorine was higher.
Carboxyl, amino, isothiouronium, mercapto and additional hydroxyl groups were introduced to cellulose and
their adsorption behaviour for metal ions was examined.
The derivatives containing carboxyl groups due to the reaction with 2-mercaptobutanedioic acid had an adsorption
capacity for Cu(II), Ni(II) and Pb(II) of 36 mg g1,
9 mg g1 and 104 mg g1 respectively. The derivatives with
amino and carboxyl groups due to the reaction with cysteine had an adsorption capacity for Cu(II), Ni(II) and
Pb(II) of 22 mg g1, 8 mg g1 and 28 mg g1 respectively.
3.3. Oxidation
Reactive cellulose derivatives can also be prepared by
oxidation and the subsequent functionalisation of the oxi-

D.W. OConnell et al. / Bioresource Technology 99 (2008) 67096724

dised cellulose. Maekawa and Koshijima (1984), prepared

dialdehyde cellulose by periodate oxidation of cellulose.
This dialdehyde cellulose was further oxidised using mildly
acidied sodium chlorite. The 2,3-dicarboxy cellulose oxidised to nearly 100% oxidation level was completely soluble in water, but the 2,3-dicarboxy cellulose of 70%
oxidation was largely insoluble. The latter was assessed
for its heavy metal adsorption capability and uptake levels
of 184 mg g1 and 236 mg g1 were achieved for Ni(II) and
Cu(II), respectively. Subsequently, Maekawa and Koshijima (1990), synthesised cellulose-hydroxamic acid derivatives from dialdehyde cellulose obtained by the previous
periodate oxidation method and their heavy metal adsorption capacities were investigated. These materials were
capable of adsorbing 246 mg g1 Cu(II) from aqueous
solution.
3.4. Etherication
Most cellulose ethers are prepared by reacting alkali cellulose with organic halides and Navarro et al. (1996) modied porous cellulose carriers through this type of
etherication reaction. This was achieved by initially reacting the cellulose carrier with sodium methylate to form
alkali cellulose, which was subsequently reacted with the
organic halide, epichlorohydrin, yielding reactive epoxy
groups for further functionalisation with polyethyleneimine as a chelating agent. The prepared adsorbent
(Cell-PEI) had metal uptake anities for Co(II), Cu(II)
and Zn(II), respectively, of 2.5 mg g1, 38 mg g1 and
12 mg g1.
In another study, Saliba et al. (2005) chemically modied sawdust with amidoxime groups by reacting acrylonitrile with the sawdust through an etherication reaction
in order to add cyano groups to the cellulose structure.
These cyano groups were then amidoximated by reaction
with hydroxylamine. This amidoximated sawdust had a
high adsorption capacity for Cu(II) of 246 mg g1 and
for Ni(II) of 188 mg g1. Table 3 summarises methods
for direct modication of cellulose leading to heavy metal
adsorbent materials.
The methods outlined in this section produced sorbent
materials by directly modifying cellulose. As an alternative,
valuable properties decient in native cellulose can be
imparted to cellulose by grafting a second polymer as a
long branch on the cellulose molecule. The following section will review these grafting possibilities.
4. Adsorbents based on monomer grafting to cellulose
Graft copolymerisation is a process in which side chain
grafts are covalently attached to a main chain of a polymer
backbone to form branched copolymer. The extent of polymerisation graft is referred to as the degree of grafting
(grafting yield) and is gravimetrically determined as the
percentage of mass increase following copolymer preparation. Both the backbone and side chain grafts can be either

6713

homopolymer or copolymer. The active sites initiating

polymerisation reactions may be free radical or ionic chemical groups (Nasef and El-Sayed, 2004). Various methodologies including high energy radiation, photochemical and
chemical initiation techniques have been used to activate
or initiate the backbone cellulose polymer (Bhattacharya
and Misra, 2004). Initiation methods which generate free
radicals have received the greatest amount of attention
due to their practicality. Free radicals are formed on the
cellulose molecules either by decomposition of a chemical
initiator, ultraviolet (UV) light or high energy radiation.
During the copolymerisation, the radical formation for
the initiation reaction can occur either on the cellulose
backbone or on the monomer to be grafted. The radical
formation on the monomer results in homopolymerisation
of the monomer. Therefore, initiators capable of creating
radicals at various sites on the cellulose backbone are
clearly preferred (Gurdag et al., 1997). Table 4 outlines
the general nature of and the advantages and disadvantages associated with each grafting initiation process. Specic examples of where these techniques have been used are
outlined in Table 5.
4.1. Photografting
Photografting is a useful means for the introduction of
various vinyl monomers onto cellulose materials (Kubota
and Shigehisa, 1995). The energy from the incident ultraviolet light is absorbed by sensitizer, monomer, and/or polymer, or by an electron band structure of the excited
cellulose molecule (Harris et al., 1978). When a chromophore on a molecule absorbs light, it goes to an excited
state producing dissociation into reactive free radicals
and initiating the grafting process. If the adsorption of light
does not lead to the formation of free radical sites through
bond rupture, the process can be promoted by addition of
photosensitizers e.g. benzoin ethyl ether, dyes such as acrylated azo dye and aromatic ketones. Photochemical grafting can be achieved with or without a sensitizer. The
mechanism without sensitizer involves the generation of
free radicals on the cellulose backbone which react with
the monomer free radical to form the graft copolymer. In
the mechanism with the sensitizer, the sensitizer forms free
radicals, which can undergo diusion so that they abstract
hydrogen atoms from the base polymer, producing radical
sites required for grafting to take place (Bhattacharya and
Misra, 2004). In the presence of vinyl monomers these free
radicals initiate growth of polymer chains from the surface
of the activated cellulose and also homopolymerisation of
the vinyl monomers. Photografting has many advantages
including readily available UV light sources, the reactions
are selective and photoenergy requirements are low relative to other higher energy sources such as c-ray and electron beam, resulting in less deterioration of polymeric
materials.
Kubota and Suzuki (1995) introduced amidoxime
groups to cellulose using a photografting technique.

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D.W. OConnell et al. / Bioresource Technology 99 (2008) 67096724

Table 3
Cellulose modication methods with various chemical reagents and associated functional groups
Modication
reaction

Modifying chemicals (Chelating

group)

Esterication
Wood pulp

Succinic anhydride (Carboxyl)

Structure

Adsorption
capacity
(mg g 1)

pH

Isotherm
model

Reference

O
Cell

CH

Cd(II) 169

Marchetti et al.
(2000)

CH
O
CH
C

HO

Wood pulp

Citric acid (Carboxyl)

Cell

CH 2O

OH

Etherication
Cellulose
Carrier
(aquacel)

OH

Cu(II) 24
Pb(II) 83

Low et al. (2004)

Hg(II) 288

Navarro et al.
(1996)

HO

(1) Sodium methylate

(2) Epichlorohydrin
(3) Polyethyleneimine (Amino)

Cell

CH2O CH2

CH

OH
(NH CH2 CH2)n

CH2

NH2

Wood
sawdust

Acrylonitrile
Hydroxylamine (Amidoxime)

Cell

CH2

CH2

CH2

Cu(II) 246
Ni(II) 188

C
N

Halogenation
Cellulose
6-Bromo-6-deoxycellulose + 2powder
Mercaptobutanedioic acid
(Carboxyl)

Cysteine (Amino + Carboxyl)

Cell

CH2

CH

CH2

Cu(II) 36
Pb(II) 105
Ni(II) 0.93
NH 2

CH

CH 2

CH2

COOH

a-Thioglycerol (Hydroxyl)

Oxidation
*Cellulose
powder

Cell

3-Mercaptopropionic acid
(Carboxyl)

Cell

CH2

2-aminoethanethiol (Amino)

Cell

CH2

CH2

CH2

CH2

CH2

CH

CH2

OH

OH

CH2

CH2

COOH

NH2

Sodium metaperiodate (Carboxyl)

Saliba et al.
(2005)

5.0

Aoki et al.
(1999a)

OH

COOH COOH

Cell

6.0
6.0

Cu(II) 22
Pb(II) 28
Ni(II) 8

5.0

Cu(II) 2
Pb(II) 6
Ni(II) 10

5.0

Cu(II) 24
Pb(II) 20
Ni(II) 1

5.0

Cu(II) 6
Pb(II) 81
Ni(II) 5

5.0

Ni(II) 184
Cu(II) 236

Maekawa and
Koshijima (1984)

Cu(II) 246

Maekawa and
Koshijima (1990)

CH OH

*Cellulose
powder

Sodium metaperiodate Hydroxamic

acid (Amino)

H
C

H
OH

OH

C
HON

NOH

L, Langmuir; F, Freundlich; *, adsorption was carried out under competitive conditions.

Initially, acrylonitrile was grafted to the cellulose surface,

subsequently the cyano groups were amidoximated by
reaction with hydroxylamine. The ability of these cellulose
amidoximated samples to adsorb Cu(II) were examined
and the maximum adsorption capacity achieved was
51 mg g1.

Kubota and Suzuki (1995) also grafted acrylonitrile

(AN) to cellulose using the photografting technique. The
resultant AN-grafted celluloses were subjected to reactions
with triethylenetetraamine (Trien). The sample containing
triethylenetetraamine groups showed an ability to adsorb
Cu(II) to the extent of 30 mg g1.

D.W. OConnell et al. / Bioresource Technology 99 (2008) 67096724

6715

Table 4
Grafting techniques and associated advantages and disadvantages
Grafting
technique

Nature

Advantages

Disadvantages

Reference

Photochemical
initiation

UV light creates
free radicals with
or without
sensitizer

Mild reaction conditions, Low cost

of operation

Initial cost of equipment,

reaction time

Bhattacharya and Misra (2004)

Hilal et al. (2003)
Li et al. (2007b)
Rajam and Ho (2006)

High energy
initiation

Irradiation
causes homolytic
ssion and free
radicals form

No catalyst or additives required

for initiation, Ease of variation of
parameters, Materials modied in
prefabricated form

Material deterioration,
High cost

Khan et al. (2003)

Bhattacharya (2000)
Benke et al. (2007)

Chemical
initiation

Free radicals
created on
surface by
chemical agent

Relatively cheap, Little

homopolymer in certain cases,
Ease of use and application

Catalysts and additives need for

initiation, Grafting limited by
concentration and purity of initiator,
Dependant on temperature

Bhattacharya (2000)
Sharma et al. (2002)
Russell (2002)
Liu and Sun (2008)

4.2. High energy radiation grafting

High energy radiation (c-rays or X-rays) can be used to
graft various functional polymers to cellulose. Radioactive
isotopes such as Cobalt-60 (Co-60) and Cesium-137 (Cs137) are the main sources of c-irradiation (Nasef and ElSayed, 2004).
Bao-Xiu et al. (2006) recently prepared an adsorbent
resin by graft copolymerisation of acrylic acid and acrylamide onto cellulose under microwave irradiation (electromagnetic radiation). This material was examined for its
adsorption capacity for Cu(II) from wastewater. At optimal adsorption conditions, a maximum adsorption capacity for Cu(II) of 49.6 mg g1 was achieved.
Orlando et al. (2002) utilised microwave radiation to
produce chelating agents from sugarcane bagasse by reaction of urea with reactive sites present in bagasse. This
adsorbent showed a maximum chelating capacity of
76 mg g1 for Cu(II) and 280 mg g1 for Hg(II).
Abdel-Aal et al. (2006) used c-irradiation for the graft
copolymerisation of acrylic acid onto wood pulp. The
parameters aecting the abilities of the grafted wood pulp
for removing Fe(III), Cr(III), Pb(II) and Cd(II) from aqueous solutions were investigated. The maximum uptake
capacity was 7 mg g1 Fe(III), 7 mg g1 Cr(III), 4 mg g1
Cd(II) and 6 mg g1 Pb(II).
4.3. Chemical initiation grafting
The chemical initiation method has been extensively
used and generally gives higher graft yields (Shukla and
Athalye, 1994). Among the various redox-type initiators,
ceric ion (Ce(IV)) has gained great importance because of
its high grafting eciency (Hon, 1982). With many of the
aforementioned methods, the extent of ungrafted homopolymer has been high in comparison with that from ceric
(IV) ion-initiated grafting (Gupta and Khandehar, 2002),
in which homopolymerisation of vinyl monomers has been
minimal. Previously, researchers have used this ceric ion
initiation method to graft functional polymers to cellulose

in various forms. Hence, these reactive sites are introduced

for either direct chelation of metal ions or subsequent reaction with a chelating agent for the same purpose.
Raji and Anirudhan (1998) grafted sawdust with acrylamide using the redox initiator potassium permanganate.
The polyacrylamide grafted sawdust was further functionalised with ethylenediamine to convert the material into an
anion exchanger polymerised product. The maximum
adsorption capacity of this material for Cr(VI) was
45 mg g1. The presence of diverse ions did not aect the
adsorption performance.
Shibi and Anirudhan (2002) grafted acrylamide onto
banana stalk using the ferrous ammonium nitrate/H2O2
redox initiator system. The material was then aminated
by reacting it with ethylenediamine and then reuxed with
succinic anhydride to functionalise it with carboxylate
groups. The maximum adsorption capacity of the adsorbent material for Hg(II) was 138 mg g1 at 30 C which
increased to 210 mg g1 at 60 C.
Bicak et al. (1999) grafted polyacrylamide onto cotton
cellulose using ceric ammonium sulphate as initiator and
studied the removal of Hg(II) from aqueous solution and
achieved a Hg(II) uptake level of 12.5 mg g1.
In another study, Hashem (2006) grafted sunower
stalks with acrylonitrile using KMnO4/citric acid redox initiator system. Amidoximation of the grafted stalks with
hydroxylamine hydroxide in alkaline medium was carried
out. The maximum uptake capacity of this adsorbent for
Cu(II) was 39 mg g1.
Liu et al. (2001, 2002) grafted regenerated cellulose
beads with arylonitrile using ceric ammonium nitrate
(CAN) as initiator. A saponication reaction using sodium
hydroxide was subsequently carried out on this material.
The saponication converts the same grafted poly(acrylonitrile) with its cyano groups as the main group to both
amide (CONH2) and carboxylate (COONa) groups.
Adsorption of trivalent chromium on the amide functionalised compound reached 73.5 mg g1 whereas Cu(II) uptake
on the carboxylate functionalised compound was
70.5 mg g1.

6716

D.W. OConnell et al. / Bioresource Technology 99 (2008) 67096724

Table 5
Chemically modied and grafted celluloses and associated adsorption capacities
Grafted
Cellulose
Adsorbent

Grafting Agent
(Chelating group)

Chemical Initiation
Sawdust
Acrylic Acid
(Carboxyl)

Structure

Cell

CH2

CH
mon

Cellulose
powder

Acrylic Acid
(Carboxyl)

Sawdust

Acrylamide (Amino)

OH

Cell

CH2

Adsorption
Capacity
(mg g1)

pH

Isotherm
Model

Cu(II) 104
Ni(II) 97
Cd(II) 168
Pb(II) 55.9
Cu(II) 17.2
Cd(II) 30.3
Cr(VI) 45

4.9
5.9
5.7
4.5
4.5
4.5
3.0

Hg(II) 712

6.0

Hg(II) 138

5.0

Shibi and
Anirudhan
(2002)

Cu(II) 39

3.05.0

Hashem (2006)

Cr(III) 73.5
Cu(II) 70.5

5.0
5.0

L,F

Liu et al. (2001,

2002)

Cu(II) 68.5
Ni(II) 48.5
Pb(II) 75.8

4.05.5
4.06.0
4.06.0

OConnell et al.
(2006a,b,c)

Cu(II) 60
Co(II) 20
Zn(II) 27

6.0
6.0
6.0

Navarro et al.
(1999)

Cu(II) 51

5.0

Kubota and
Suzuki (1995)

Cu(II) 30

5.0

Kubota and
Suzuki (1995)

Cu(II) 49.6

5.0

Bao-Xiu et al.
(2006)

Cu(II) 76
Hg(II) 280

5.0
5.0

Orlando et al.
(2002)

Fe(III) 7
Cr(III) 7
Cd(II) 4
Pb(II) 6

4.0
4.0
4.0
4.0

Gaey et al.
(2000)
Guclu et al.
(2003)
F

CH
mon

Cotton cellulose

Acrylamide (Amino)

Sunower stalks

(1) Acrylamide
(2) Ethylenediamine
(3) Succinic anhydride
(Carboxyl)
(1) Acrylonitrile
(2) Hydroxylamine
(Amidoxime)

Cell

CH 2 CH

CONH

(CH2)2

NHCO(CH2)2

COOH

NH2
Cell

CH2

Raji and
Anirudhan
(1998)
Bicak et al.
(1999)

NH2

Banana stalk

Reference

CH2

mon

NOH

Cellulose bead

(1) Acrylonitrile
(2) Sodium hydroxide
(Carboxyl)

Cell

CH2

CH

CH2

CH

mon

mon

COOH

CN

Cellulose

(1) Glycidyl
methacrylate
(Imidazole)

Cell
C

CH2

CH

CH2

OH

Porous cellulose

(1) Glycidyl
methacrylate
(2) Polyethyleneimine
(Amine)

Cell
C

CH2

Photochemical Initiation
Wood pulp
(1) Acrylonitrile
(2) Hydroxylamine
(Amidoxime)
Wood pulp
(1) Acrylonitrile
(2) Tetraethyleneamine
(Amino)
High Energy Radiation Initiation
Cellulose pulp
(1) Acrylic Acid
(2) Acrylamide
Carboxyl (Amino)

CH

NH CH2

CH2

Cell

CH2

mon

CH
C

CH2
O

mon

OH

Sugarcane
bagasse
cellulose
Wood pulp

Urea (Amino)
NH

CH
C

O mon

NH2

O
Cell

Acrylic Acid
(Carboxyl)

CH2

OH

NH2

Abdel-Aal et al.
(2006)

D.W. OConnell et al. / Bioresource Technology 99 (2008) 67096724

In another study, Aoki et al. (1999b) grafted bead cellulose with acrylonitrile, again utilizing ceric ammonium
nitrate as the initiator. The cyano groups on the poly(acrylonitrile) chains coming o the cellulose backbone polymer
were amidoximated by reacting with hydroxylamine in
methanol. Amidoxime groups can chelate a range of heavy
metal ions. In this study, alkali treatment of amidoxime
functionalised cellulose accelerated the sorption of metal
ions.
Guclu et al. (2003) grafted cellulose powder with acrylic
acid (AA), N,N0 -methylene bisacrylamide (NMBA), 2acrylamido-2-methylpropane sulphonic acid (AASO3H)
and a mixture of acrylic acid (AA) and 2-acrylamido-2methylpropane sulphonic acid (AASO3H). Ceric ammonium nitrate was used as the initiator in all cases. All four
grafted cellulose materials were compared in the adsorption of Pb(II), Cu(II) and Cd(II) under competitive conditions. Uptake on each prepared material were 0.27, 0.24
and 0.02 mmol g1 for cellulose grafted with p(AA),
p(AA-NMBA) and p(AASO3H), respectively. Cellulose-gpAA proved to be the most ecient adsorbent under these
conditions with its carboxyl groups responsible for chelating the divalent metal ions.
Gaey et al. (2000) reported a method to graft polyacrylic
chains onto sawdust using KMnO4 as initiator to attain an
inexpensive adsorbent. The material had a high adsorption
capacity for Cu(II) 104 mg g1, Ni(II) 97 mg g1 and
Cd(II) 168 mg g1.
The monomer glycidyl methacrylate was also chosen by
Bicak and Senkel (1998) as a reactive monomer for grafting
due to the subsequent availability of its reactive epoxy
groups for further functionalisation. These epoxy groups
are highly reactive to amines, alcohols, phenols, carboxylic
acids, carboxylic anhydrides, lewis acids and their complexes (Kondo et al., 1989).
OConnell et al. (2006a,b,c) grafted glycidyl methacrylate to a cellulose backbone and further functionalised
the grafted product with the imidazole ligand. Adsorption levels on this material for Cu(II), Ni(II) and Pb(II)
reached 68.5 mg g1, 48.5 mg g1 and 75.8 mg g1, respectively.
Navarro et al. (1999) modied a porous cellulose material (aquacel) for heavy metal adsorption through graft
polymerisation of glycidyl methacrylate using ceric ammonium nitrate as the initiator. This was followed by the functionalisation of the reactive epoxy groups present in
poly(glycidyl methacrylate) with polyethyleneimine to
introduce nitrogenous ligands. This material showed an
adsorption capacity of 60 mg g1 Cu(II), 20 mg g1 Co(II)
and 27 mg g1 Zn(II) from aqueous wastewater.
5. Regeneration of modied cellulose adsorbents
Natural polymers or biopolymers are biodegradable.
This may be a serious disadvantage for long-term application in sorption processes as sorbent recycling is necessary
for cost ecient use of these biopolymers for environmen-

6717

tal applications (Guibal, 2004). Cellulose exhibits good

chemical stability and mechanical strength. Its bres exhibit regions in which the molecules are densely and orderly
packed, and where extensive intermolecular hydrogen
bonding is observed. These regions are referred to as crystalline domains and they impart strength, swelling resistance and stability to the bre (Sionkowska et al., 2002).
Li et al. (2007a) prepared an citric acid modied orange
peel cellulose adsorbent for the removal of Cd(II) from
aqueous solutions. Maximum Cd(II) uptake reached
101.2 mg g1. Desorption studies were performed using
varying concentrations of hydrochloric acid. Maximum
recovery of Cd(II), at 94%, was achieved with a
0.15 mol L1 HCl desorbing solution.
Bicak et al. (1999) prepared a graft copolymer of acrylamide onto cellulose to selectively recover mercury. These
researchers used hot acetic acid to recover the bound
Hg(II). Some 6872% of the sorbed mercury can be desorbed within 30 min of treatment. Complete desorption
occurs on a second treatment. Re-use of the regenerated
sorbent yielded 100% Hg(II) uptake.
Zhou et al. (2004) prepared cellulose/chitin beads capable of adsorbing Pb(II), Cd(II) and Cu(II) from aqueous
solution. Uptake capacities of 68.4 mg g1 Pb(II),
38.2 mg g1 Cd(II) and 19.1 mg g1 Cu(II) were achieved.
Ninety-eight percent recovery of the adsorbed metals was
achieved within 15 min using 1 mol L1 HCl and the beads
can be re-used a number of times in further adsorption/
desorption work.
Gaey et al. (2000) chemically modied sawdusts using
polyacrylic chains. The modied sawdusts possessed 15
40 times higher adsorption capacity for Cu(II), Ni(II)
and Cd(II) than the unmodied sawdusts. Uptake on modied sawdusts was a function of the extent of incorporation
of polyacrylic acid side chains, the higher the extent of
incorporation, the higher the resultant heavy metal uptake.
At 2.8% weight gain following sawdust modication
uptake levels for Cu(II), Cd(II) and Ni(II) were
46.9 mg g1, 76.1 mg g1 and 39.8 mg g1, respectively.
At 31.2% weight gain following modication, the higher
uptake levels of 104 mg g1, 168 mg g1 and 97.3 mg g1
for Cu(II), Cd(II) and Ni(II), respectively, were achieved.
Regeneration of the modied sawdusts and recovery of
the metals was achieved using 0.001 mol L1 HCl. It was
possible to recover up to 98% Cu(II) and Ni(II) and 99%
Cd(II). Guclu et al., 2003 prepared similar polyacrylic acid
graft copolymers of cellulose (cellulose-g-pAA) and looked
at the competitive adsorption/desorption of Cu(II), Cd(II)
and Ni(II) as a function of the percentage pAA graft.
Unlike the outcomes of Gaey et al., 2000, metal ion
removal capacity did not change with the percentage of
pAA graft. Regeneration of the cellulose-g-pAA was
carried out using 1 mol L1 HCl and no change in the
adsorption capacity of the adsorbent materials was
observed.
Bao-Xiu et al. (2006) prepared a graft copolymerisation
of acrylic acid and acrylamide onto cellulose under micro-

6718

D.W. OConnell et al. / Bioresource Technology 99 (2008) 67096724

wave irradiation which was capable of removing

49.6 mg g1 of Cu(II) from aqueous solution. Regeneration
of the adsorbent material was achieved using an 8% (v/v)
ammonia solution and this regeneration could be achieved
on seven successive occasions without any signicant loss
in Cu(II) uptake capacity.
Orlando et al. (2002) used microwave radiation to produce neutral chelating agents (BCA) from sugarcane
bagasse by reaction of urea with the reactive sites present
in bagasse such as hydroxyl and carboxylic groups. The
prepared material had a Cu(II) and Hg(II) adsorption
capacity of 76.2 mg g1 and 280.8 mg g1, respectively.
The stability of the prepared material was signicantly
interfered with at low and high pH as evidenced by the loss
of the chelating amide groups and, in eect, regeneration of
the adsorbent material was not possible.
Liu et al. (2002) used a spheroidal cellulose adsorbent
containing carboxyl anionic groups to remove Cr(III) from
aqueous solution. Approximately 80 mg g1 of Cr(III) can
be adsorbed and desorption of the metal can be achieved
using either HCl or NaOH, but at high pH Cr(OH)3 may
precipitate on the adsorbent so in practice a 1.2 mol L1
HCl solution proved the optimum choice achieving 86%
metal recovery. A single regeneration of the adsorbent
material leads to a 10% loss in adsorption capacity but
no further loss in capacity was observed in further cycles.
Ethylenediaminetetraacetic acid (EDTA) was used in a
study by Saliba et al. (2005) for the desorption of Cu(II),
Cr(III), Cd(II) and Ni(II) from amidoximated wood sawdust. Nearly total desorption was achieved, with approximately 90% or more of the metal ions being desorbed
from the metal loaded amidoximated wood sawdust samples. In the case of the Cu(II) ion, the adsorption capacity
was retained even after ve adsorption/desorption cycles.
The regeneration of amidoximated wood sawdust in the
case of all four metals was ecient after several cycles.
In a recent study Shibi and Anirudhan (2006) grafted
acrylamide onto banana stalk and functionalised this to
give carboxyl functional groups. This material was successfully used as an alternative adsorbent for Pb(II) and Cd(II)

from aqueous solutions. Desorption of the metals and

regeneration of the adsorbent was carried out using dilute
hydrochloric acid (0.2 mol L1 HCl) solution. Initially the
recovery of Pb(II) and Cd(II) was 98.1% and 96.3%,
respectively. The recovery decreased after the third cycle
to 98% for Pb(II) and 94% for Cd(II), respectively. The
metals which were not recovered were presumed to be
bound through strong interaction and as a result the
adsorption capacity decreased in successive cycles.
Liu et al. (2002) desorbed Cu(II) from cellulose beads
containing metal binding carboxyl anionic groups using
0.52 mol L1 HCl or NaOH. The recovery percentage
reached 100% when a 2.0 mol L1 HCl was used. In addition, after 30 replications of adsorption and desorption,
only 7.2% of the adsorption capacity was lost.
The potential recovery of each of the metals Cu(II),
Ni(II) and Pb(II) from the cellulose-g-GMA-imidazole
was assessed as a function of aqueous acidic pH (OConnell
et al., 2006a,b,c). This was achieved by treating the metal
saturated cellulose-g-GMA-imidazole adsorbent with solutions of varying acidic pH. In the case of the Cu(II) and
Ni(II) loaded adsorbent the pH of treatment solutions were
adjusted by hydrochloric acid (HCl) and by nitric acid
(HNO3) in the case of Pb(II) loaded adsorbent. In the case
of Cu(II) loaded cellulose-g-GMA-imidazole almost 95%
of the metal was recovered at pH 1. This metal recovery
level dropped sharply to 30% following treatment at pH
2. Thereafter the level of recovery reduced further but levelled o at around 10% over the pH range of pH 3 to pH 6.
A generally similar metal desorption prole was observed
for recovery of Ni(II) from the loaded cellulose-g-GMAimidazole. In the case of lead, Pb(II) recovery levels at
pH 1 were considerably lower at 62% than those observed
for Cu(II) and Ni(II). While good recovery of the adsorbed
metals was achieved at low pHs, there was a strongly negative eect on the ability of the modied cellulose adsorbent to re-adsorb the metals in further cycles. Table 6
summarises the research work to date on metal adsorption/desorption/regeneration on selected modied cellulose
adsorbents.

Table 6
Cellulose based adsorbents, potential desorbing solutions and metal recovery percentages
Cellulose adsorbent

Desorbing solution

Metal recovery percentages

Reference

Cellulose-g-acrylamide[Hg(II)]
Cellulose/Orange peel/Citric acid [Cd(II)]
Cellulose/Chitin beads [Pb(II), Cd(II), Cu(II)]
Carboxylated polyacrylamide grafted
Sawdust [Cd(II), Cu(II), Ni(II)]
Cellulose-g-polyacrylic acid
Cellulose-g-acrylic acid/acrylamide [Cu(II)]
Bagasse/Urea [Cu(II), Hg(II)]
Spheroidal cellulose/carboxyl [Cr(III)]
Amidoximated wood sawdust
[Cu(II), Cr(III), Cd(II), Ni(II)]
Cellulose-g-GMA-imidazole
[Cu(II), Ni(II), Pb(II)]
Carboxylated polyacrylamide grafted banana
stalk [Pb(II) and Cd(II)]

Hot acetic acid

0.15 M HCl
1 M HCl
Dilute HCl

6872% on 1st cycle and 100% after 2nd cycle

94%
98% over a number of cycles
98%

Bicak et al. (1999)

Li et al. (2007a)
Zhou et al. (2004)
Gaey et al. (2000)

1 M HCl
NH3 8 %(v/v)
N/A
1.2 M HCl
EDTA

100% over a number of cycles

90% over 7 adsorption/desorption cycles
Unstable at low and high pHs
86%
>90% of after 4 cycles

Guclu et al. (2003)

Bao-Xiu et al. (2006)
Orlando et al. (2002)
Liu et al. (2002)
Saliba et al. (2005)

0.1 M HCl
0.1 M HNO3
0.2 M HCl

95% Cu(II) &Ni(II)(HCl)

62% Pb(II)(HNO3)
98% Pb(II) and 94% Cd(II) after three cycles

OConnell (2006)
Shibi and Anirudhan (2006)

D.W. OConnell et al. / Bioresource Technology 99 (2008) 67096724

6. Discussion
Tables 3 and 5 clearly indicate the signicant adsorption
capabilities of the modied cellulose materials. In the case

6719

of each cationic species signicant variation in adsorption

levels are observed depending on the cellulose modication
method and the nature of the chelating or metal binding
ligand. The mechanism of each adsorption process is not

Table 7
Selected heavy metal adsorption capacities for selected low cost adsorbents
Metal

Uptake (mg g1)

Isotherm model

pH

Reference

Ni(II)
Cu(II)
Pb(II)
Zn(II)
Cd(II)
Cr(III)
Ni(II)
Cu(II)
Pb(II)
Zn(II)
Ni(II)
Cd(II)
Cr(III)

0.9
25.4
124
2.7
3.7
2.4
4.5
5.1
6.0
3.6
68
70
118

4.05.0
4.87.0
4.0

Ouki and Kavanagh (1999)

Peric et al. (2004)
Berber-Mendoza et al. (2006)

4.05.0
4.05.0
4.05.0
4.05.0
4.57.0

Ouki and Kavannagh (1997)

Ni(II)
Cu(II)
Ni(II)
Cu(II)
Pb(II)
Pb(II)
Cd(II)

3.6
3.0
1.7
10.8
9.3
22.0
2.8

Abollino et al. (2003)

M
M

5.5
5.5
5.0
5.0
5.0
5.5

Pb(II)
Cu(II)
Cr(III)
Zn(II)
Ni(II)
Cu(II)
Cu(II)
Pb(II)
Cu(II)
Pb(II)
Ni(II)
Cu(II)

64.2
16.1
9.6
4.3
55.9
133.4
88.5
95.2
16.2
32.2
10.9
19.7

L
L
L
L,F
F
F
L
L
L
L
L
L

Cu(II)
Pb(II)
Cd(II)
Ni(II)
Cu(II)
Pb(II)
Zn(II)

26.5
85.9
27.8
57.0
116.9
229.9
109.2

Sugar beet pulp

Ni(II)
Cu(II)
Ni(II)
Ni(II)
Cu(II)
Pb(II)
Pb(II)

10.1
65.6
80.0
10.6
10.1
49.9
73.8

Lignin
Lignin (sugar cane bagasse)
Tree bark

Pb(II)
Cu(II)

133.6
21.6

Adsorbent
Zeolites
Clinoptilolite

Chabazite

Scolecite

Clays
Montmorillonite
Kaolinite

Organophilic bentonite
Industrial by-products
Blast furnace sludge

Blast furnace slag

Iron slag
Steel slag
Red mud
Biomass
P. chrysosporium

P. versicolor (white rot fungus)

Trametes versicolor

Agricultural waste
Hazelnut shell
Peanut hulls
Orange peel (citrus reticulate)
Grape stalk waste

L, Langmuir; F, Freundlich.

F
F
F

L
L

Dal Bosco et al. (2005)

Yavuz et al. (2003)

Orumwense (1996)
Andini et al. (2006)

Lopez-Delgado et al. (1998)

4.2
4.2
3.58.5
3.58.5
5.28.5
5.28.5
5.6

Dimitrova (1996)

L
L
L
L,F
L,F
L,F
L,F

6.0
6.0
6.0
5.0
4.06.0
4.06.0
4.06.0

Say et al. (2001)

L
L
L,F
L
L
L
L

3.07.0
5.0
6.0
5.56.0
5.56.0
5.5
5.5

Demirbas et al. (2002)

Periasamy and Namasivayam (1996)
Ajmal et al. (2000)
Villaescusa et al. (2004)

6.0
5.5

Peternele et al. (1999)

Gaballah and Kilbertus (1998)

Feng et al. (2004)

Lopez et al. (1998)

Dilek et al. (2002)

Bayramoglu et al. (2003)

Martinez et al. (2006)

Reddad et al. (2003)

6720

D.W. OConnell et al. / Bioresource Technology 99 (2008) 67096724

fully understood but a number of fundamental interactions

are possible including ion exchange, complexation, co-ordination/chelation, electrostatic interactions, acidbase interactions, hydrogen bonding, hydrophobic interactions,
physisorption and possibly precipitation (Lee et al.,
2001). It is possible that more than one of these factors
can be present to eect the adsorption interaction, depending on the chemical and physical composition of the modied cellulose, the nature of the metal and solution
conditions such as pH, metal concentration and solubility
product issues.
The modied cellulose adsorbent materials reviewed in
this paper contain a range functional or ligand groups
based around elements in groups V (nitrogen, phosphorus)
and VI (oxygen, sulphur) of the periodic table. A typical
metal binding ligand may be dened as any ion or molecule
possessing a pair of nonbonding electrons. Bicak et al.
(1999) grafted cotton cellulose with polyacrylamide and
used it eectively as a selective sorbent for removal of
Hg(II) ions from aqueous solutions. These polyacrylamide
chains have monodentae ligands in the form of the amide
nitrogen. Carboxyl groups have two lone pair of electrons
on the oxygen. Two carboxyl groups are required to form a
chelate with a divalent metal. In this regard, Liu et al.
(2002) synthesised a spheroidal cellulose adsorbent through
a grafting reaction using acrylonitrile and subsequent
saponication using sodium hydroxide giving the cellulose
carboxyl groups on its surface. This modied cellulose
adsorbent was used for the removal of Cu(II) ions from
aqueous solutions by forming a bidentate arrangement
between the Cu(II) and the carboxyl groups on the adsorbent. In another study, Low et al. (2004) modied wood
pulp using citric acid for the sorption of Cu(II) and Pb(II)
ions from aqueous solutions. The citric acid modication
on the wood involved an esterication reaction process of
the carboxyl groups of the citric acid and the hydroxyl
groups of the wood surface. The esterication process
increases the carboxylic acid content of the wood surface
and leads to an increase in the sorption of the Cu(II) and
Pb(II) cations.
Amino groups have a lone pair of electrons on the nitrogen and may form a covalent bond with a metal. The amidoxime group, for example, is a bidentate ligand and has
both an acidic group which loses a proton and a basic lone
pair of electrons on the nitrogen which can co-ordinate
with the metal ion (Liu et al., 2002; Lutfor et al., 2000).
Lutfor et al. (2000) prepared a chelating ion exchange resin
containing amidoxime functional groups by grafting polyacrylonitrile (PAN) onto sago starch. This adsorbent was
most eective in the adsorption of Cu(II) ion from aqueous
solution.
Imidazole has also been used by OConnell et al.
(2006a,b,c) as a binding agent on a glycidyl methacrylate
grafted cellulose adsorbent. The imidazole is a ve-membered ring molecule containing two nitrogen atoms. The
imidazole group has the ability to impart rigidity to the
ligand system, due to its aromatic ring system. An impor-

tant aspect of unsaturated nitrogen donors such as imidazole is the possibility of p-backbonding between it and the
metal ion (Hancock and Martell, 1989).
In particular, in a signicant number of studies outlined
in this review paper, the inuence of solution pH is critical
and optimum pH or pH ranges are provided in Tables 3
and 5. Variation in pH can aect the surface charge of
the adsorbent and the degree of ionisation and speciation
of the metal adsorbate. At very low solution pH, the binding sites on the modied cellulose materials are likely to be
protonated resulting in poor metal binding levels. An optimum pH range usually between pH 4.0 and pH 6.0 leaves
the binding sites unprotonated and metal binding is maximised. At pHs above this optimum range, most metals
tend to precipitate out of solution in the hydroxide form.
Table 7 outlines the heavy metal adsorption capabilities
of a host of naturally occurring adsorbent materials. Comparison of the capacities of the modied cellulose adsorbents with these natural materials shows clearly that, in
many instances, the cellulose based adsorbents are equally
eective as heavy metal adsorbents. In comparison to the
adsorption of copper on commercial resins (Table 8), copper uptake on cellulose powder modied by sodium
metaperiodate and hydroxamic acid is superior (Table 5)
(Maekawa and Koshijima, 1990). This is also the case for
wood sawdust modied with acrylonitrile and subsequently
hydroxylamine (Saliba et al., 2005). Further studies by
Gaey et al. (2000), Liu et al. (2001, 2002), OConnell et al.
(2006a), Navarro et al. (1999) and Orlando et al. (2002),
as outlined in Table 5, also show strong and equivalent
comparisons of Cu(II) uptake with the commercial resins.
The use of various models for isotherm modelling of the
uptake of the various metals indicated that many of the
adsorption processes can best be described in terms of the
Langmuir approach (Langmuir, 1918). This general model
describes a situation where at low metal adsorbate concentrations in solution, strong uptake of the metal on the modied cellulose adsorbent is observed but beyond a certain
adsorbate concentration a plateau is reached in metal
uptake. The latter corresponds to maximum binding of
the metal to the adsorbent or a type of saturation coverage.
The model itself is based on a number of assumptions
Table 8
Cu(II) adsorption levels on commercial adsorbent/ion exchange materials
Adsorbent/ion
exchanger

Chelating
group

Commercial adsorbents
Dowex 50WX4 Sulphonic acid
Amberlite
Carboxylic
IRC-86
acid
Duolite GT-73 Thiol
Amberlite
Iminodiacetic
IRC-718
acid
Amberlite 200
Sulphonic acid
Lewatit TP207 Iminodiacetic
acid

Cu(II)
Uptake
(mg g1)

Reference

71.4
130

Cochrane et al. (2006)

Marshall and Wartelle
(2006)
Vaughan et al. (2001)

61.6
127
89
85

Brown et al. (2000)

D.W. OConnell et al. / Bioresource Technology 99 (2008) 67096724

including equivalence of binding sites in terms of spatial

issues and energy of interaction which may not be particularly relevant in the context of this review, but notwithstanding this, the model provides a good empirical
representation of many of the adsorption processes forming
this review. Some of the other adsorption processes in this
review are best described by the Freundlich model which
does allow for variation in energy of the binding sites (Freundlich, 1926).
One of the fundamental requirements with any adsorbent is its ability to be regenerated and re-used over a number of adsorption/desorption cycles. The data presented in
Table 6 clearly indicates that, in many instances, it is possible to regenerate the modied cellulose adsorbents with a
number of chemical agents ranging from hydrochloric acid
to ethylenediaminetetraacetic acid. Re-use of the adsorbents in further adsorption/desorption cycles is possible
with minimum loss of heavy metal adsorption capacity
being observed.
7. Conclusions
In recent years, increasing costs and environmental considerations associated with the use of commercial adsorbents, has led to a signicant body of research work
aimed at developing new low cost adsorbents derived from
renewable resources. In this context, the advantages of
using cellulose as the basis for new adsorbent design lie primarily in its high abundance, low cost and the relative ease
with which it can be modied chemically. Approaches to its
modication, as reviewed in this paper, have been based
around a direct chemical modication approach or by the
grafting of suitable polymeric chains to the cellulose backbone followed by functionalisation. The latter has been
achieved by the addition of amine, amide, amidoxime, carboxyl, hydroxyl and imidazole type binding ligands to the
adsorbent backbone. Both broad methodologies produced
adsorbents with a range of heavy metal binding capacities,
comparable to other researched naturally occurring materials and in some cases comparable to the more commercial
type ion exchange resins. Generally, optimum pH conditions for the heavy metal binding on the modied celluloses
tended to occur in the range pHs 4.06.0. In the context of
wastewaters, this pH range is quite narrow whereas most of
the commercial resins reviewed are eective ion exchangers
over a wide range of pH conditions. Regeneration and reuse of a number of the modied cellulose adsorbents is
demonstrated in a number of papers reviewed in this work.
Many of the adsorption interactions between the modied
cellulose adsorbents and heavy metals have been characterised by the Langmuir approach or in a lesser number of
cases by the Freundlich model of adsorption.
On the evidence presented in this review paper, there
exists signicant potential for future research on the use
of modied cellulose materials as heavy metal adsorbents.
Specic focus should be placed on modication of the cellulose backbone, cross-linking as a means of enhancing sta-

6721

bility, the use of alternative ligands, the nature of the

metalligand interaction, broadening the optimum pH
range for eective adsorption and enhancing the regenerability of the modied cellulose materials.
Acknowledgement
The authors would like to acknowledge the support of
the Materials & Surface Science Institute at the University
of Limerick.
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