Accepted Manuscript

Accepted Manuscript
Review
Applicability of agricultural waste and byproducts for adsorptive removal of
heavy metals from wastewater
T.A.H. Nguyen, H.H. Ngo, W.S. Guo, J. Zhang, S. Liang, Q.Y. Yue, Q. Li, T.V.
Nguyen
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DOI:
Reference:
S0960-8524(13)01375-8
http://dx.doi.org/10.1016/j.biortech.2013.08.124
BITE 12323
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Bioresource Technology
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14 July 2013
19 August 2013
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Please cite this article as: Nguyen, T.A.H., Ngo, H.H., Guo, W.S., Zhang, J., Liang, S., Yue, Q.Y., Li, Q., Nguyen,
T.V., Applicability of agricultural waste and byproducts for adsorptive removal of heavy metals from wastewater,
Bioresource Technology (2013), doi: http://dx.doi.org/10.1016/j.biortech.2013.08.124
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Applicability of agricultural waste and byproducts for adsorptive

removal of heavy metals from wastewater
T. A. H. Nguyen a, H. H. Ngo a*, W. S. Guo a, J. Zhang b, S. Liang b, Q. Y. Yue b, Q. Lib, T. V. Nguyen a
a
Centre for Technology in Water and Wastewater, School of Civil and Environmental Engineering,
University of Technology, Sydney, Broadway, NSW 2007, Australia
b
Shandong Key Laboratory of Water Pollution Control and Resource Reuse, School of Environmental
Science & Engineering, Shandong University, Jinan 250100, PR China
* Corresponding author: School of Civil and Environmental Engineering, University of Technology,
Sydney (UTS), P.O. Box 123, Broadway, NSW 2007, Australia. Tel.: +61 2 9514 2745; Fax: +61 2 9514
2633. E-mail address: ngohuuhao121@gmail.com
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ABSTRACT
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(AWBs) for sequestering heavy metals in terms of their adsorption capacities, binding
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mechanisms, operating factors and pretreatment methods. The literature survey
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indicates that AWBs have shown equal or even greater adsorption capacities compared
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to conventional adsorbents. Thanks to modern molecular biotechnologies, the roles of
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functional groups in biosorption process are better understood. Of process factors, pH
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appears to be the most influential. In most cases, chemical pretreatments bring about an
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obvious improvement in metal uptake capacity. However, there are still several gaps,
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which require further investigation, such as (i) searching for novel, multi-function
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AWBs, (ii) developing cost-effective modification methods and (iii) assessing AWBs
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under multi-metal and real wastewater systems. Once these challenges are settled, the
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replacement of traditional adsorbents by AWBs in decontaminating heavy metals from
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wastewater can be expected in the future.
This critical review discusses the potential use of agricultural waste based biosorbents
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Keywords: Agricultural waste based biosorbents; Biosorption capacity; Heavy metals;

Removal efficiency
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1. Introduction
Heavy metals in the aquatic medium may originate from wastewater of many
industries, such as batteries, tanneries, electrical, electroplating, fertilizers, pesticides,
mining, refining ores, etc. (Banerjee et al., 2012; Manzoor et al., 2013; ). Due to their
hazardous effects, persistency and accumulation tendency, heavy metals can pose a risk
to the human and environmental health (Kumar et al., 2012; Marin et al, 2010). The
exposure to heavy metals can cause damage to many parts of human bodies, even at
very low concentrations. Therefore, the removal of heavy metals from aqueous
solutions is of extreme importance. The United States Environmental Protection Agency
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(USEPA) has set up the maximum contamination levels (MCLs) of heavy metals for
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surface or groundwater to be used in the drinking supply. Table 1 describes the typical
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poisoning symptoms and MCLs of the most common heavy metals (Barakat, 2011).
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Table 1
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Numerous technologies have been developed for heavy metal decontamination.
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Traditional treatment processes include precipitation, ion exchange, membrane
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filtration, electroplating, adsorption (Banerjee et al., 2012; Chowdhury and Saha, 2011).
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These methods represent significant demerits, such as high chemical and energy
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requirements, hazardous sludge formation, low efficiency when heavy metals
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concentration below 100 mg/L, high cost at large scale (Marin-Rangel et al., 2012;
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Mishra et al., 2012). Likewise, high price and limited reusability are key problems,
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hindering the widespread application of activated carbon, a commonly used adsorbent in
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heavy metal treatment (Turan and Mesci, 2011). In that context, biosorption has
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emerged as a promising method, with such advantages as (1) high efficiency even with
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low metal concentrations, (2) low cost, (3) no additional nutrients requirements, (4) easy
operation, (5) potential metal recovery, and (6) without detrimental effects on the
environment (Jimnez-Cedillo et al., 2013; Manzoor et al., 2013; Mishra et al., 2010). A
wide variety of agricultural waste and byproducts has been explored for the elimination
of heavy metals. This article aims at evaluating the feasibility of using AWBs for heavy
metal decontamination based on (1) heavy metals adsorption capacities of AWBs; (2)
the effects of operating parameters for process optimization; (3) biosorption
mechanisms and (4) modification methods for producing better bio-sorbents. We have
included mostly recent studies on heavy metal elimination using AWBs in this review.
Table 2
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2. The application of AWBs for heavy metal removal
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2.1. Background
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AWBs may be different parts of plant, such as bark, stem, leaves, root, flower, fruit
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biomass, husk, hull, skin, shell, bran and stone. AWBs mainly compose of cellulose,
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hemi-cellulose and lignin which have a high content of hydroxyl groups. Consequently,
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they have good abilities to attach heavy metals (Okoro and Okoro, 2011). Besides,
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AWBs contain a variety of other functional groups, such as acetamido, carboxyl,
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phenolic, structural polysaccharides, amido, amino, sulphydryl carboxyl groups,
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alcohols and ester. These functional groups substitute hydrogen ions for metal ions in
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solution or donation of an electron pair to form complexes with the metal ions in
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solutions. Due to abundant binding groups, AWBs could be an enormous potential
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source of adsorbent materials for decontaminating heavy metals from wastewater
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(Jimnez-Cedillo et al., 2013; Marin-Rangel et al., 2012; Zafar et al., 2007 ).
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2.2. Advantages of using AWBs as biosorbents
There are more and more studies using AWBs to replace current conventional
systems in decontaminating heavy metals because of their significant merits. The main
advantage of AWBs over other conventional adsorbents is their strong affinity and high
selectivity toward heavy metals due to the abundant availability of binding groups on
the AWBs surface (Banerjee et al., 2012). In addition, AWBs are usually of low cost
because of being generated from easy acquiring, abundant, agricultural origin materials
(Marin-Rangel et al., 2012). Furthermore, AWBs can be easily processed, applied and
recovered without adverse impacts on the environment (Wan Ngah and Hanafiah,
2008). These characteristics of AWBs may probably play critical roles in industrial
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applications, and thus making AWBs become superior to conventional adsorbents. Last
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but not least, the recycle of agricultural wastes and byproducts for the purpose of heavy
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metal treatment is believed to reduce wastes in an eco-friendly way. Hence, it agrees
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well with concepts of effective, innovative and sustainable waste management (Okoro
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and Okoro, 2011).
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2.3. Selection of AWBs
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Searching for good AWBs among various agricultural wastes and by-products is
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not an easy work for biosorption researchers. In an attempt to make this task easier,
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researchers have done much work in building selection criteria. According to Park et al.
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(2010), availability and cheapness are key factors in choosing AWBs for practical
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application. Based on these criteria, they proposed agro-industrial wastes and
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biomaterials as the potential sources of AWBs. On the other hand, Chojnacka (2010)
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argues that adsorption capacity should be considered as the decisive factor in the
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selection process of AWBs. This result is consistent with that revealed by Wang and
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Chen (2010). They suggested that only some bio-sorbents with sufficiently high binding
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capacity and selectivity for heavy metals are suitable for use in a full-scale biosorption
process. Most researchers agree that good AWBs need to meet several requirements,
including abundant availability, high cost-effectiveness, easy desorption, high
regeneration capability, negligible release of unexpected compounds into aqueous
solutions.
2.4. Comparison of adsorption capacity of AWBs with conventional adsorbents
Some studies have made comparisons between biosorbents based on the removal
percentages. However, this could lead to misleading conclusions as removal efficiency
does not always reflect exactly the adsorption capability of biosorbents. For example,
Aman et al. (2008) reported that one gram of potato peel charcoal could remove 99.8%
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of the copper from the solution of 150 mg/L (100 ml) at pH 6.0 with a shaking time of
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20 min. However, this biosorbent hold a relatively low maximum adsorption capacity
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(0.3877 mg/g). Similar observation was reported in a research conducted by Saka et al.
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(2012). It was found that Palmyra palm fruit seed showed higher Pb(II) removal
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percentage (100%) than onion skins (93%). Nevertheless, the adsorption capacity for
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Pb(II) of Palmyra palm fruit seed (24.6 mg/g) was found far lower than that of onion
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skins (200 mg/g). For that reason, in searching for a good biosorbent, comparison
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should be made based on the maximum adsorption capacity (qmax) rather than on
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percentage removal (%) of heavy metals.
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Table 3
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As shown in Table 3, the adsorption capacities of AWBs vary significantly. The
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influential factors include types of crop residues, elements of heavy metals,
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pretreatments of AWBs and especially operating conditions. AWBs tended to prefer
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some heavy metals to others. Kelly-Vargas et al. (2012) reported that lemon peel and
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orange peel demonstrated the adsorption capacities for Cu and Pb 48% and 15% higher
than banana peel, respectively. In contrast, the Cd uptake by banana was higher than
that of lemon peel and orange peel 82% and 57%, respectively. A study, conducted by
Mosa et al. (2011) released that the removal efficiency of heavy metals decreased in the
order cotton stalks > maize stalks> rice straw. They attributed the highest removal
percentage by cotton stalks to its highest concentration of cellulose, hemicellulose, and
lignin as compared to other crop-residues. Osman et al. (2010) reported that rice hull
showed the highest efficiency in sequestering zinc, cadmium and iron among
biosorbents investigated. For example, the removal efficiencies by rice hull, sawdust,
sugarcane bagasse and wheat straw were 98.15, 96.90, 93.00 and 91.19%, respectively.
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They suggested that the higher adsorption capacity of rice hull than other sorbents for
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removal of heavy metals was probably due to the presence of silanol (SiOH) groups in
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structure of rice hull and higher surface area of rice hull.
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As can be seen in Table 3, most AWBs even without any chemical pretreatments
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showed better adsorption capacities for heavy metals as compared with conventional
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adsorbents. For instance, the Cu uptake capabilities of cortex banana, orange, lemon
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waste, garden grass, palm oil fruit shell, etc. in the raw form (ranging from 27.68 to
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70.40 mg/g) were similar to or even higher than that of ion exchange resins (26.73
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mg/g). Some other kinds of original AWBs, such as tamarind seed, watermelon shell or
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rose petal waste exhibited the adsorption capacity for Cu(II) ions 210%, 315% and
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364% higher than that of above ion exchange resins. This can be attributed to the
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abundant availability of binding sites on the AWBs, which enhances the retention of
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heavy metals onto AWBs surface (Jimnez-Cedillo et al., 2013; Marin-Rangel et al.,
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2012). Particularly, cashew nut shell modified with H2SO4 exhibited an extremely high
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adsorption capacity (406.6 mg/g) for Cu(II) ions. The remarkable enhancement in
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adsorption capacity for Cu(II) using H2SO4 is probably due to elimination of competing
cations and the increase in surface area as well as the porosity on the biosorbent surface
(Boota et al., 2009; Lasheen et al., 2012; Osman et al., 2010). Some AWBs showed
very high affinity toward heavy metals in the natural form. For example, the adsorption
capacity for Cr(VI) ions of the raw coir pith was relatively high (165 mg/g). However,
coir pith grafted with acrylic acid even exhibited much better Cr(VI) uptake capability
(196 mg/g) (Suksabye and Thiravetyan, 2012). Obviously, chemical pretreatments can
vastly enhance adsorption capacities of ABWs. These effects will be further discussed
in Section 5 later. Similar observations can be reported for the remaining heavy metals
in Table 3, such as As, Cd, Cr, Pb, Zn.
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The experimental conditions in the literature were very diverse. Therefore, it would
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be challenging to identify the best AWBs for this purpose (Sahmoune et al., 2011). Saka
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et al. (2012) claimed that AWBs with loading capacities 90 mg/g should be considered
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as good biosorbents. Based on this criteria, this present review introduces the promising
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AWBs including prawn shell activated carbon (Arulkumar et al., 2012); watermelon
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shell/ rind (Banerjee et al., 2012; Liu et al., 2012); rose petals waste (Bhatti et al., 2011;
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Manzoor et al., 2013); orange peel (Feng et al., 2011; Liang et al., 2009); durian shell
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waste (Kurniawan et al., 2011); Cedrus deodara sawdust (Mishra et al., 2012); onion
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skins (Saka et al., 2011); cashew nut shell (Senthil Kumar et al., 2012); coir pith
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(Suksabye and Thiravetyan, 2012).
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3. Mechanisms of metal uptake on AWBs

It is essential to investigate the adsorption mechanisms to obtain understandings
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about the process, which are useful for improvement of the system in the future (Park et
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al., 2010). Several factors are found to affect the heavy metal adsorption by AWBs,
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including types of AWBs, properties of metal solution chemistry and environmental
conditions. As a result, the actual mechanism of the metal biosorption is not fully
understood, though many mechanisms have been proposed for the retention of heavy
metals onto AWBs (Figure 1).
Figure 1
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It is likely that various mechanisms can operate simultaneously to varying degrees.
Netzahuatl-Muoz et al. (2012) examined mechanisms involved the removal of Cr(III)
and Cr(VI) by Cupressus lusitanica bark. Ion exchange and electrostatic interaction
were considered as the principal mechanisms for Cr(III) biosorption while Cr(VI)
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biosorption was supposed to occur in four reaction steps: (1) formation of Cr(VI)
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complexes, (2) reduction of Cr(VI) to Cr(III), (3) formation of carboxyl groups and (4)
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interaction of Cr(III) with carboxyl groups to form Cr(III) - carboxylate complexes.
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Feng and Guo (2012) reported that ion exchange might be the dominant mechanism in
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the removal of Cu(II), Zn(II) and Pb(II) using orange peel. The results of an X -ray
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fluorescence for modified orange peel (SCOP) showed that the adsorption process
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followed an ion exchange mechanism between Ca(II) from SCOP and metals in
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solution. Njoku et al. (2011) also claimed that Pb(II) and Cu(II) biosorption on Cocoa
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pod husk followed an ion exchange mechanism. Similar results were obtained by Taha
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et al. (2011) in case of removal of Pb(II) Cd(II) and Zn(II) using potato peel. A decrease
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in the solution pH values, after shaking heavy metal solution with potato peel, suggested
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that ion exchange might be one of the mechanisms. They attributed the high adsorption
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capacity of potato peels to active functional groups such as carboxylic, phenolic and
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hydroxyl groups. These findings agree with previous studies performed by Panda et al.
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(2008). In contrast, Sen et al. (2011) reported that Hg(II) adsorption on Rambai leaves
was a two step process, a rapid adsorption of metal ion to the external surface followed
by intra-particle diffusion into the interior of adsorbent.
Due to the complicated nature of biosorption mechanisms, the combination of
modern methods e.g. FTIR (Fourier Transform Infra Red), SEM (Scanning Electron
Microscopy), EDX (Energy Dispersive X-Ray), TEM (Transmission Electron
Microscopy), etc. and traditional methods e.g. titration are essential. By employing
FTIR, SEM, EDX methods, Witek-Krowiak et al. (2013) discovered that the dominant
mechanisms for the biosorption of Cr(III) and Cu(II) onto soybean meal waste included
(1) ion exchange, (2) chelation by carboxyl and hydroxyl groups, and (3) precipitation.
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Equally, via the desorption results, the Dubinin - Radushkevich isotherm, and energy
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parameter (E), Ofomaja et al. (2010) proposed that ion - exchange was dominant
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mechanism in the removal of Cu(II) and Pb(II) using KOH treated pine cone powder.
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Vzquez et al. (2012) highlighted the role of functional groups in the biosorption of
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Cu(II), Zn(II), Pb(II) and Cd(II) into Chestnut (Castanea sativa) shell. They reported
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that there was a decline in adsorption capacity of Cd(II), Cu(II), and Zn(II) up to 32.8,
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58.5 and 65.3% respectively due to the chemical blocking of carboxyl groups of
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pre-treated Chestnut (Castanea sativa) shell. This results show the important role of
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carboxyl groups in the biosorption process. Similarly, the blockage of hydroxyl groups
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reduced the adsorption percentages for Cd(II), Cu(II), and Zn(II) by 30.9, 27.5 and
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46.1%, respectively. These decreases confirm the role of OH groups in Cd(II), Cu(II),
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and Zn(II) adsorption by the alkali pre-treated chestnut shell. Conversely, carboxyl and
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hydroxyl groups blocking of chestnut shell had no significant effect on Pb(II)
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adsorption. Kumar et al. (2012) also found that a variety of functional groups, such as
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carboxyl and hydroxyl groups, involved in the binding mechanisms of Cd(II) by cashew
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nut shell. Based on FTIR spectra, Lasheen et al. (2012) indicated the involvement of
carboxylic groups in Pb(II) ions adsorption process using chemically modified orange
peel. With the help of FTIR, Gutha et al. (2011) reported that hydroxyl, amine,
carboxyl, and carbonyl functional groups were responsible for Ni(II) biosorption onto
Caesalpinia bonducella seed powder, while Feng et al. (2011) revealed that carboxyl
and hydroxyl groups involved in the biosorption of the metal ions by grafted
polymerization-modified orange peel.
It is obvious that hydroxyl, carboxyl, phosphate, hydroxyl, amino and thio groups
on AWBs cell walls play major roles in binding heavy metals. These functional groups
make AWBs be capable of binding heavy metals by changing their hydrogen ions for
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metal ions or giving an electron pair to form complexes with the metal ions (Kumar et
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al., 2011; Wang and Chen, 2010). However, the existence of these functional groups on
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the surface of AWBs does not guarantee an effective removal of heavy metals as the
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biosorption process may be influenced by several other factors, such as (1) the number
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of active sites, (2) accessibility of the sites, (3) chemical state of the sites and (4) affinity
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between the sites and the target metal ions (Park et al., 2010).
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4. Parameters affecting heavy metal biosorption

The biosorption process of heavy metals from wastewater might be influenced by
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several physical and chemical factors, such as pH, temperature, initial heavy metal
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concentration, biosorbent dose, biosorbent size, ionic strength, co-ions, etc. These
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factors determine the overall biosorption through affecting the uptake rate, selectivity
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and amount of heavy metals removed. Extensive research has been undertaken to
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investigate effects of these operating parameters. This section is dedicated to briefly
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discuss the effects of these process factors.
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4.1. Influence of pH
Among process factors, pH seems to play a significant role in controlling the
biosorption of heavy metals. pH values can affect the surface charge of AWBs, the
degree of ionization and speciation of heavy metals, the competition of the metal ions
with coexisting ions in solution (Park et al., 2010). This pH dependency could be
explained by the involvement of functional groups in metal uptake and metal chemistry
(Kumar et al., 2012). As a rule, as solution pH increases, the biosorptive removal of
cationic metals increases, whereas that of anionic metals decreases. At lower pH, the
overall surface charge of AWBs will be positive. The H+ ions compete effectively with
the metal cations causing a decrease in biosorption capacity. When pH values increase,
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the AWBs surface becomes increasingly negatively charged which favors the metal ions
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uptake due to electrostatic interaction. At very high pH, the biosorption stops and the
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hydroxide precipitation starts (El-Sayed et al., 2011; Njoku et al., 2011; Taha et al.,
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2011).
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Similar tendencies were found in biosorption processes using diverse AWBs. Giri
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et al. (2012) studied the effect of pH on the removal of Cr (VI) using Eichhornia
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crassipes root activated carbon. They reported that the Cr(VI) adsorption efficiency
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increased from 41.22% to 85.52% for 10 mg/L, 45.34% to 89.23% for 50 mg/L and
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50.23% to 92.24% for 100 mg/L with the increase of pH from 1.5 to 4.5. Taha et al.
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(2011) investigated the role of pH in the adsorption Pb(II), Cd(II) and Zn(II) ions using
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potato peels. They reported that the removal efficiency increased with increasing pH
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values from 2 to 6; after pH 6, there was a decrease in metal ion removal. Similar trend
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was reported by Reddy et al. (2011) in case of removal Ni(II) with Moringa oleifera
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bark. They found that, under highly acidic conditions, the removal percentage of Ni(II)
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was very small. The adsorption increased with the increase in pH from 3.0 to 6.0 and
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then decreased in the range of pH between 7.0 and 8.0. These results agree with those
reported by Feng et al. (2011). They revealed that the percent biosorption for Pb(II),
Cd(II) and Ni(II) by grafted copolymerization-modified orange peel was minimal at pH
2.0 and increased with increasing pH from 2.0 to 5.5.
For optimization of biosorption processes, a large part of biosorption studies are
devoted to investigating the optimum pH values. Table 4 summarizes the findings on
optimum pH values in various heavy metals - AWBs systems. It can be seen that the
optimum pH values are dependent on types of ABWs. Aman et al. (2008) reported that
the optimum pH for Cu(II) - potato peel adsorption system was 6.0. The pH dependence
of metal uptake might be associated with the surface functional groups on AWBs cell
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walls. Different types of ABWs contain various functional groups on their cell walls
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thereby reaching the maximum adsorption capacity at different pH values. In order to
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avoid the precipitation of metal hydroxides, several studies have been conducted to
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identify pH values, at which metal hydroxide precipitation starts. Aman et al. (2008)
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reported that precipitation of Cu(OH)2 took place at pH greater than 6.0 in case of
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removal of Cu(II) by potato peels.
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Table 4
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4.2. Influence of temperature

Biosorption researchers have performed a large number of studies on the effects of
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temperature on metal uptake. The change in solution temperature affects not only
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diffusion rate of metal ions but also the solubility of metal ions (Park et al., 2010).
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Depending on surface functional groups of a given AWB, temperature has a given
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impact on the adsorption capacity. However, it is a common conclusion of many studies
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that the influence of temperature is to a limited extent and only in a certain temperature
range (Sahmoune et al., 2011). The biosorption process can be affected by temperature
in different ways depending on the exothermic or endothermic nature of the process.
Many researchers reported that biosorption processes are exothermic which means
that adsorption capacity is inversely proportional to the temperature (Sahmoune et al.,
2011). Kumar et al. (2012) found that the biosorption of Cd(II) by cashew nut shell
decreased from 80.13% to 74.32% with the rise in temperature from 30 to 60oC. They
attributed this to the decrease in surface activity of AWBs. Similar trend was noticed by
El-Sayed et al. (2011) in case of Zn(II), Cd(II) and Mn(II) biosorption onto maize
stalks. The biosorption percentage decreased from 52% to 28% for Zn(II) ions, from
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34% to 16% for Cd(II) ions and from 39% to 13% for Mn(II) ions as the temperature
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increased from 25 to 550C. The authors explained this trend by the damage of active
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adsorption sites of AWBs or increasing number of metal ions escaped from the AWBs
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surface to the solution. The same behavior can be detected in a research performed by
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Boota et al. (2009) sequestering Cu(II) and Zn(II) ions by Citrus reticulate.
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In contrast, in their 2010 review paper, Park et al. (2010) argued that biosorption of
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heavy metals was endothermic in nature. They suggested that higher temperature
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improved the elimination of heavy metals owing to an increase in its surface activity
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and kinetic energy. Giri et al. (2012) reported the similar trend in case of adsorption
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Cr(VI) by the activated carbon originated from Eichhornia crassipes roots. They
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explored that the percentage removal of Cr(VI) increased from 79.24% to 92.24% as the
21
temperature increased from 25 to 550C. In the same way, Garca-Rosales and
22
Coln-Cruz (2010) observed that the adsorption of Pb(II) and Cd(II) by the stalk sponge
23
of Zea mays increased 1.1- 1.8 times with increasing temperature from 200C to 400C.
24
Banerjee et al. (2012) reported similar observation in case of adsorption of Cu(II) by
25
watermelon shell. They attributed this trend to either increase in number of available
active sites or decrease in the boundary layer thickness surrounding the AWBs.
Nevertheless, Park et al. (2010) claimed that high temperature might result in the
physical damage of AWBs. For this reason, the room temperature is commonly used in
most biosorption experiments.
4.3. Effect of initial concentration
Heavy metal ions can transport from the solution to the surface of AWBs owing to
a driving force made by the initial metal concentration (Sahmoune et al., 2011; Taha et
al., 2011). Researchers have carried out several studies to clarify the effect of initial
concentration on metal uptake by AWBs.
10
It is a common finding that the maximum adsorption capacity of a specific AWB
11
increases as the initial metal concentration increases. Kumar et al. (2012) reported that
12
there was a rise in Cd(II) adsorption capacity, from 2.671 to 11.095 mg/g, as a result of
13
increasing Cd(II) concentration from 10 to 50 mg/L. Also, Reddy et al. (2010) revealed
14
that the Pb(II) uptake by Moringa oleifera leaves increased from 12 to 23mg/g as the
15
initial concentration of Pb(II) increased from 10 to 40mg/L. Wang and Chen (2010)
16
explained this by a higher collision between metal ions and AWBs.
17
Conversely, the increase of initial metal concentration usually leads to a decrease
18
of the removal efficiency. Kannan and Veemaraj (2010); Kumar et al. (2012) attributed
19
this behaviour to the saturation of adsorption sites on AWBs surface, whilst Kumar et
20
al. (2011) explained this by the lower rate of transporting metal ions from solution to
21
AWBs surface. Kumar et al. (2012) reported that an increase in Cd(II) concentration,
22
from 10 to 50mg/L, resulted in a decrease in Cd(II) removal percentage from 80.13% to
23
66.57%. Ashraf et al. (2011) reported a similar trend for the case of removing Pb(II),
24
Cu(II), Zn(II) and Ni(II) by the banana peel (Musa sapientum). At the highest metal
25
concentration (150 mg/L), the removal efficiencies of Cu(II), Pb(II), Zn(II) and
Ni(II) were 92.52%, 79.55%, 63.23% and 68.10% while at the lowest metal
concentration (25 mg/L), the removal percentages of these metals were 94.80%,
86.81%, 84.63% and 82.36%, respectively. Kannan and Veemaraj (2010) reported that
the percentage removal of Cd(II) by jack fruit seed (JFS) decreased from 66.28% to
22.43% with an increase in initial Cd(II) concentration from 10 to 100 ppm.
Conversely, Giri et al. (2012) reported that as the initial Cr(VI) concentration increased
from 10 mg/L to 100 mg/L, the removal of Cr(VI) by Eichhornia crassipes root
activated carbon increased from 77.22% to 92.24%. They suggested that the initial
metals concentration provided a driving force to overcome mass transfer resistance of
10
Cr(VI) ions between the aqueous and solid phase. Hence, further work is required to
11
elucidate this disagreement in the literature.
12
4.4. Effect of biosorbent dosage
13
Several researchers report that the removal percentages of metal ions increase with
14
increasing AWBs dosages. Kumar et al. (2012) found that the Cd(II) removal increased
15
rapidly as cashew nut shell dosage increased. The maximum percentage removal of
16
Cd(II) ion was 75.35% at the cashew nut shell concentration of 3 g/L. They attributed
17
this behaviour to the higher number of available adsorption sites. Similar observations
18
were obtained by Gala and Sanak-Rydlewska (2011). On the other hand, maximum
19
adsorption capacities of AWBs are found to decrease with increasing biosorbent doses.
20
Boota et al. (2009) revealed that there was a remarkable decrease in the adsorption
21
capacities of Cu(II) and Zn(II) as Citrus reticulata dose increased. They ascribed this
22
effect to overlapping of adsorption sites leading to a decrease in the total surface area.
23
4.5. Effect of ionic strength
24
Real industrial wastewater contains not only heavy metals but also other metal
25
ions, such as Na+, K+, Ca2+, Mg2+. Therefore, NaCl, NaNO3, KCl, MgCl2, CaCl2 are
usually added into heavy metal solutions to investigate effects of ionic strength on the
biosorption of heavy metal ions. El-Sayed et al. (2011) reported that a rise in ionic
strength led to a decrease in the metal uptake capacity. They ascribed this to the
decrease in the activity of metal ions and the increase in concentration of competing
cations. Njoku et al. (2011) observed that the effect of Ca2+ on the biosorption of the
metal ions was more significant than that of Na+. They explained this by the fact that the
divalent Ca2+ ion had a greater affinity to the active sites and thereby might compete
more strongly for binding sites than the monovalent Na+ ions. Conversely, Reddy et al.
(2010) explored that the presence of common metal ions like Na+, K+, Ca2+ and Mg2+
10
had no significant effects on the biosorption of Pb(II) by Moringa oleifera leaves.
11
4.6. Effect of co-ions
12
The real wastewaters generally contain multi heavy metals rather than single metal.
13
The presence of one heavy metal may hinder the adsorption of other heavy metals. Thus,
14
the investigation of effects of co-ions is useful for enhancing the application of
15
biosorbents at industrial scales. Diverse effects of co-exiting ions on the biosorption of
16
heavy metals are reported by different researchers. Goyal and Srivastava (2009) found
17
that the removal percentages of heavy metals by Zea mays in single metal solutions (Pb
18
87.34%, Cd 79.36%, Ni 71.98% and Cr 76.43%) were higher than those in a
19
multi-metal solution (Pb 81.21%, Cd 73.72%, Ni 64.03% and Cr 68.91%). They
20
attributed this effect to the competition between cations. In the contrary,
21
Garca-Mendieta et al. (2012) reported that the removal percentages of Mn and Fe from
22
a binary system were similar to the values found in single systems. This behavior
23
indicated that Fe and Mn did not compete for the adsorption sites on the green tomato
24
husk. Chiban et al. (2012) studied the removal of arsenate using W.frtescens and
25
C.rhizome plants. They found that the presence of Mg2+, Cd2+, Cu2+ and Zn2+ ions in the
metal solution had no significant effects, whereas HPO42- interfered strongly. They
found that the effect of competing anions on arsenate adsorption reduced in the order
HPO42-> SO42-> Cl-> NO3-. The authors concluded that the interfering effects on the
arsenate biosorption became stronger with the increasing valence of competing anions.
Ofomaja et al. (2010) revealed that there was mutual interference effect in the
adsorptive Cu-Pb system, using pine corn powder treated with KOH. However, the
competing effect was stronger for the Cu-Pb system compared to the Pb-Cu system. The
biosorption studies in binary and ternary systems are essential to promote the real
application of biosorbents at large scales. However, little information on this content is
10
published.
11
4.7. Selectivity
12
A given AWB tends to prefer some heavy metals to the others. Vimala and Das
13
(2009) found that oyster mushroom (Pleurotus platypus) showed the highest adsorption
14
capacity for Cd, whereas button mushroom (Agaricus bisporus) exhibited maximum
15
metal uptake for Pb(II). Milky mushroom (Calocybe indica) showed the lowest metal
16
uptake for both metals. Mosa et al. (2011) reported that cotton stalks showed high
17
affinity to Pb(II), but extremely low affinity to Mn(II). Taha et al. (2011) found that the
18
adsorption capacity by potato peels reduced in the order Pb(II) > Cd(II) > Zn(II), whilst
19
the hydrated ionic radii increased in the order Pb(II) < Cd(II) < Zn(II). They concluded
20
that the removal percentages of metal ions increased with their decreasing hydrated
21
ionic radii. Jimnez-Cedillo et al. (2013) explored that iron-modified non-pyrolyzed
22
parsley biomass (PCFe) eliminated 16 times more As(V) than As(III), whereas
23
iron-modified pyrolyzed parsley biomass (PCTTFe) removed 2.5 times more As(III)
24
than As(V). Based on these results, they concluded that PCFe was selective for As(V),
25
while the removal of As(V) was favored by PCTTFe.
4.8. Effect of particle size
The particle size of AWBs can influence their adsorption capacities due to the
change in total surface area which is necessary for metal adsorption. Banerjee et al.
(2012) reported that the smaller particles of watermelon shell showed higher removal
efficiency of Cu(II). These results are consistent with findings reported by other
authors. Kelly-Vargas et al. (2012) explored that removal percentage of metal ions by
banana cortex (Musa paradisiaca) with 1 mm of particle size was higher than that of 2
mm of particle size up to 12%. In the same way, Kannan and Veemaraj (2010) observed
that the removal of Cd(II) increased from 10.07% to 53.16% with decreasing particle
10
size of Jackfruit seed carbon, from 250 m to 90 m. They attributed this to the increase
11
in the available surface area. Boota et al. (2009) reported similar findings for
12
sequestering Cu(II) and Zn(II) using Citrus reticulata. In contrast, Taha et al. (2011)
13
explored that a decrease in particle size of potato peels did not profoundly change the
14
adsorption capacities of Pb(II) Cd(II) and Zn(II).
15
16
17
5. Effects of pretreatment on heavy metal biosorption

Untreated AWBs have been used for eliminating heavy metals from wastewater in
18
many studies conducted by Ashraf et al. (2011), Banerjee et al. (2012), El-Sayed et al.
19
(2011), Gala and Sanak-Rydlewska (2011), Gutha et al. (2011), Kelly-Vargas et al.
20
(2012), Kumar et al. (2012), Liu et al. (2012), Netzahuatl-Muoz et al. (2012), Njoku et
21
al. (2011), Reddy et al. (2011), Sen et al. (2011), etc. However, the application of
22
untreated AWBs has significant drawbacks such as low adsorption capacity, high
23
release of soluble organic compounds into the solution. The increase in chemical
24
oxygen demand (COD), biological oxygen demand (BOD) and total organic carbon
25
(TOC) may lead to the depletion of dissolved oxygen (DO) concentration in aquatic
solutions and consequently this affects aquatic lives. For these reasons, it is highly
recommended that AWBs need to be pretreated before being used in biosorption
processes (Feng et al., 2011). There is an increasing trend of modifying AWBs to
improve the removal efficiency of heavy metals, remove soluble organic compounds
and eliminate coloration of the solutions (Wan Ngah and Hanafiah, 2008).
Figure 2
7
8
9
The modification methods include physical modifications, chemical modifications

and other methods (Figure 2). Physical modifications are usually considered being
10
simple and inexpensive. However, they are not widely used because of their low
11
effectiveness. Conversely, chemical modifications are preferred, due to their simplicity
12
and efficiency (Park et al., 2010). Modifying agents can be classified as bases, mineral
13
and organic acids, organic compounds, oxidizing agents, etc. However, the most
14
commonly used chemicals are acids and bases. Other modification methods include
15
enhancement of binding groups, elimination of inhibiting groups or graft
16
polymerization.
17
Regarding the effects of chemical pretreatments, the literature reveals that,
18
chemically modified AWBs showed better adsorption capacities than unmodified forms
19
(Wang and Chen, 2010). It can be attributed to the higher number of binding sites,
20
better ion-exchange ability, and formation of new functional groups that favor metal
21
uptake. Chemical pretreatments can improve the adsorption capacity of AWBs to
22
various extents. Table 5 summarizes the findings on the effects of AWBs modification
23
methods on metal removal efficiencies.
24
Table 5
Bases are found to be effective modifying agents. Feng and Guo (2012) reported
that the adsorption capacity of Cu(II), Pb(II) and Zn(II) increased 59.73%, 84.84% and
164.38%, respectively as a result of modifying orange peel with sodium hydroxide
(NaOH) and calcium chloride (CaCl2). Mosa et al. (2011) revealed that, among
different modifying chemicals, NaOH resulted in the highest percentage removal. They
explained that the pretreatment with NaOH led to the transformation of methyl esters as
inhibiting groups to carboxylate ligands. Consequently, the metal binding capability
was substantially improved.
The efficacy of different inorganic acids in modification of AWBs has been
10
confirmed by many researchers. Lasheen et al. (2012) explored that Cd(II) uptake
11
capacity increased 61.38% as a result of pretreating orange peel with 0.1M HNO3. They
12
suggested that HNO3 helped to remove excess cations such as K(I), and Ca(II) on the
13
surface of orange peel and thereby reducing the competition between these ions with
14
Cd(II) ions. Similar observation was noticed by Osman et al. (2010) in case of
15
modifying AWBs with 0.1M HNO3. They found that the removal efficiencies of metal
16
ions by modified AWBs (Zn 88.41% - Cd 84.30% - Fe 94.81%) were substantially
17
higher than those of raw forms (Zn 77.34% - Cd 69.78 - Fe 86.36%). They attributed
18
this enhancement to the increasing surface area. These results are in good agreement
19
with those reported by Boota et al. (2009). They found that, among different modifying
20
chemicals, H2SO4 resulted in the highest metal uptake capacities. They suggested that
21
pretreatment with H2SO4 led to a negative charge surface of biomass, increased surface
22
area and porosity of biomass. Similarly, Elangovan et al. (2008) reported that acid
23
pretreatment substantially improved Cr(VI) uptake capacity of mangrove leaves and
24
water lily. In contrary, Manzoor et al. (2013) revealed that, the pretreatment of Rosa
25
bourbonia phyto-biomass with organic acids (i.g. acetic acid, benzoic acid, citric acid)
led to a decrease in its sequestering ability of Pb(II) and Cu(II). They attributed this to
the damage or occupation of active binding sites by these organic acids.
In some instances, organic compounds as modifying agents are found to increase in
the metal uptake capacity of AWBs. Garca-Mendieta et al. (2012) found that the
adsorption capacities of Fe(II) and Mn(II) were slightly improved as the result of
pretreating green tomato husk with 0.2% formaldehyde. Bhatti et al. (2011) reported
that pretreatments of red rose biomass with methanol and polyethyleneimine +
glutraldehyde brought about highest adsorption capacities for Pb(II) and Co(II),
respectively.
10
Vast improvements in the adsorption capacity of AWBs can be obtained by
11
modifying their functional groups. Suksabye and Thiravetyan (2012) reported that the
12
Cr(VI) adsorption capacity of acrylic acid grafted coir pith (196 mg/g) was markedly
13
higher than that of the natural coir pith (165 mg/g). Based on the FTIR results, they
14
ascribed this to the increase in the carbonyl groups (C=O) on the surface of coir pith,
15
resulted from grafting with acrylic acid. Feng et al. (2011) found that grafted
16
copolymerization of orange peel increased the metal uptake of Pb(II), Cd(II) and Ni(II)
17
up to 4.2 - 4.6 - 16.5 times, respectively. They suggested that modified orange peel had
18
higher ion exchange and chelating capacity than raw orange peel. Goyal and Srivastava
19
(2009) reported that the metal uptake capacity was proportional to the number of
20
functional groups on the AWBs. They revealed that adding carboxyl groups into
21
nitrogen ligand of Zea mays cob powder led to a considerable enhancement (5-15%) in
22
adsorption efficiency of Pb(II), Cd(II), Ni(II) and Cr(III). These results agree with a
23
previous study by Panda et al. (2008). They explored that the adsorption capacity of
24
Cd(II) and Ni(II) by functionalized husk of Lathyrus sativus was 50% higher than that
25
of the pristine one.
Cationization of biosorbents by impregnation of biomaterials with metal solutions
was supposed to improve clearly their adsorption abilities towards heavy metals in the
form of anions, e.g. As(V), Cr(VI). Majumdar et al. (2013) reported that the maximum
removal percentage of Cr(V) using untreated rice husk silica-carbon (RHSC-U) was
74.7%, whereas for the iron impregrated rice husk silica-carbon, it reached up to 85.9%.
Similarly, the impregnation of silica-carbon with 1% Fe solution resulted in an increase
by 19% in the As(V) pick up percentage. Among different metals (i.e. Zn, Fe, and Ag)
which were used for this purpose, Ag led to the highest enhancement (20%), followed
by Fe (19%) and Zn (14%). This demonstrates the need of further exploration of
10
11
specific metals for impregnation.

As a rule, the adsorption capacity of metal ions by AWBs can be remarkably
12
enhanced with proper chemical pretreatments. Nevertheless, this may contain some
13
drawbacks. The chemical pretreatments may increase the cost of treatment, thereby
14
reducing advantages of AWBs over conventional adsorbents (Park et al., 2010).
15
Furthermore, chemical pretreatments may result in biomass loss, thus hindering their
16
use for long term. In this regards, Lasheen et al. (2012) claimed that there was no
17
significant weight loss during protonation of orange peel with 0.1M HNO3. In contrast,
18
Garca-Mendieta et al. (2012) revealed that the weight loss, which was caused by
19
modifying green tomato husk with 0.2% formaldehyde, was 26.7%. Finally, the use of
20
diverse chemicals for the purpose of AWBs pretreatments may lead to discharging of
21
unexpected compounds into water bodies, e.g. colored organic compounds (Kumar et
22
al., 2011). In contrast, Jimnez-Cedillo et al. (2013) reported that only marginal
23
amounts of iron were released into aqueous solution during the adsorption process of
24
As(III) and As(V) using non-pyrolyzed and pyrolyzed Petroselinum crispum (parsley)
25
biomass modified with FeCl3. However, for similar studies, when biosorbents are
impregnated with metals to enhance their removal efficiencies towards anions, the
detachment of loading metal should be examined thoroughly. This is because it can not
only deteriorate the quality of aqueous solutions but also affect reusability of
biosorbents. For that reason, it is very necessary to find out efficient methods to
mitigate the adverse effects of pretreatments while enhancing the adsorption capacity of
AWBs.
7
8
9
6. Conclusions and future research directions

AWBs can successfully eliminate heavy metals from wastewater. Therefore,
10
AWBs should be further explored for novel, cost-effective and more selective
11
biosorbents.
12
Despite existing limitations, chemical pretreatments of AWBs may result in
13
remarkable enhancement in their metal uptake capacities. Thus, more attention should
14
be paid to improving the pretreatment methods.
15
A majority of biosorption studies have employed AWBs in single metal systems.
16
Hence, further work is required in multi metal systems and real wastewater to make
17
industrial usage of AWBs more feasible. Particularly, there is a need to develop
18
versatile biosorbents for the simultaneous decontamination of several pollutants.
19
20
21
Acknowledgements
This research was supported by Research Theme of Sustainable Water - Wastewater
22
Treatment and Reuse technologies, Centre for Technology in Water and Wastewater
23
(CTWW), School of Civil and Environmental Engineering, University of Technology,
24
Sydney (UTS) and Australian Scholarships for Development in Vietnam (ASDiV). The
25
research collaboration between UTS and Shandong University is also grateful.
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FIRGURE CAPTIONS
1
2
Figure 1
Mechanisms of heavy metal capture onto AWBs.
Figure 2
Modification methods for producing better AWBs.
1
2
3
4
Figure 1
Figure 2
1
2
TABLES
3
4
5
Table 1 The maximum contaminant levels (MCL) for the most common heavy metals
(adapted from Barakat, 2011).
Heavy metal
Arsenic (As)
Cadmium (Cd)
Chromium (Cr)
Copper (Cu)
Nickel (Ni)
Zinc (Zn)
Lead (Pb)
Mercury (Hg)
Toxicities
Skin manifestations, visceral cancers, vascular disease
Kidney damage, renal disorder, human carcinogen
Headache, diarrhea, nausea, vomiting, carcinogenic
Liver damage, Wilson disease, insomnia
Dermatitis, nausea, chronic asthma, coughing, human carcinogen
Depression, lethargy, neurological signs and increased thirst
Damage the fetal brain, diseases of the kidneys, circulatory system, and nervous system
Rheumatoid arthritis, and diseases of the kidneys, circulatory system, and nervous system
MCL b (mg/L)
0.05
0.01
0.05
0.25
0.20
0.80
0.006
0.00003
34
1
2
3
Table 2 Comparison of different technologies for removing heavy metals from

wastewater
No
1
Methods
Chemical precipitation
Chemical coagulation
Ion-exchange
Electrochemical methods
Adsorption using activated carbon
Biosorption
Membrane filtration
Electro dialysis
Photo catalysis
Disadvantages
Large amounts of sludge
Extra operational cost for sludge disposal
High cost
Large consumption of chemicals
High cost
Less number of metal ions removed
High capital and running cost
Initial solution pH and current density
Cost of activated carbon
No regeneration
Performance depends upon adsorbent
Early saturation, limited potential for
biological process improvement, no potential
for biologically altering the metal valence state
High operational cost due to membrane
fouling
High operational cost due to membrane
fouling and energy consumption
Long duration time, limited applications
Advantages
Simple operation, inexpensive, can
remove most of metals
Sludge settling
Dewatering
High regeneration of materials
Metal selective
Metal selective
No consumption of chemicals
Pure metals can be achieved
Most of metals can be removed
High efficiency (>99%)
Low cost, high efficiency, minimization of
sludge, regeneration of biosorbents, no
additional nutrient requirement, metal
recovery
Small space requirement, low
pressure, high separation selectivity
High separation selectivity
Removal of metals and organic
pollutant simultaneously, less
harmful by-products
4
5
6
35
1
2
3
Table 3 Comparison of AWBs with conventional adsorbents using the maximum

adsorption capacity (qmax - mg/g).
Metal ion
As(V)
Adsorbent
Type of adsorbent
qmax (mg/g)
Reference
Parsley
Hematite
Kaolinite
Lemon residues
Pine leaves
Sponge
Coconut coir pith
MB (Iron modified non-pyrolyzed)

CA
CA
MB (FeCl3)
NB
CA (Iron oxide coated)
MB (Hydrochloric acid,
epichlorohydrin, dimethylamine )
MB (Iron modified pyrolyzed)
0.19
0.20
0.23
0.47
3.27
4.50
13.75
Jimnez-Cedillo et al., 2013

Shafique et al., 2012
Marin-Rangel et al., 2012
Nguyen et al., 2010
Anirudhan and Unnithan, 2007
18.17
Jimnez-Cedillo et al., 2013
Commercial activated
carbon
Granular activated carbon
Castor seed hull
carbon F.400
Coffee grounds
Maize stalks
Rice husk
CA
0.70
Kannan and Veemaraj, 2010
CA
NB
CA
1.39
6.98
8.21
Sen et al., 2010

Sen et al., 2010
Azouaou et al., 2010
NB
NB
MB (NaOH)
15.65
18.05
20.24
Cashew nut shell

Pineapple peel fibre
Wheat straw
Husk of Lathyrus sativus
Cortex banana waste
Orange peel
Orange peel
Cashew nut shell
NB
MB (Succinic anhydride)
MB (Urea)
MB (Introducing thio groups)
NB
MB (Mercapto-acetic acid)
MB (grafted copolymerization)
MB (H2SO4)
22.11
34.18
39.22
52.80
67.20
136.05
293.3
436.7

El-Sayed et al., 2011
Kumar and Bandyopadhyay,
2006
Kumar et al., 2012
Hu et al., 2011
Farooq et al., 2011
Panda et al., 2008
Kelly-Vargas et al., 2012
Liang et al., 2009
Feng et al., 2011
Senthil Kumar et al., 2012
Water lily flower

Mangrove leaves
Eichhornia crassipes root
activated carbon
Red rose distillation waste
Activated carbon
(Filtrasorb-400)
Cotton fiber
Cross-link chitosan
Cupressus lusitanica bark
Prawn shell activated carbon
Durian shell waste
carbon
Coir pith
Coir pith
NB
NB
NB
8.44
8.87
36.34
Elangovan et al., 2008

Elangovan et al., 2008
Giri et al., 2012
MB (Sodium alginate)
CA
57.68
57.70
Shafqat et al., 2008

Arulkumar et al., 2012
MB (ZrO2 composite)
CA
NB
NB
CA
69.15
78.00
87.5
100.60
117.00
153.96
Muxel et al., 2011

Suksabye and Thiravetyan, 2012
Netzahuatl-Muoz et al., 2012
Arulkumar et al., 2012
Kurniawan et al., 2011
NB
MB (Grafted with acrylic acid)
165.00
196.00

Bentonite
Kaolinite
CA
CA
4.00
4.42
Zeolite
Chitosan immobilized on
bentonite
Pine cone powder
Ion exchange resins
Cortex banana waste
Garden grass
Palm oil fruit shell
Cortex orange waste
Cortex lemon waste
Orange peel
Orange peel
Tamarin seed
Watermelon shell
Rose petals waste
Cashew nut shell
CA
CA
5.20
12.60
Aman et al., 2008

Shahmohammadi-Kalalagh et
al., 2011
Aman et al., 2008
Futalan et al., 2012
MB (KOH)
CA
NB
NB
NB
NB
NB
MB (Mercapto-acetic acid)
MB (NaOH and CaCl2)
NB
NB
NB
MB (H2SO4)
26.32
26.73
27.68
36.00
58.34
60.00
67.20
70.40
70.67
70.73
82.97
111.10
124.21
406.6
Ofomaja et al., 2010

Banerjee et al., 2012
Hu et al., 2011
Hossain et al., 2012a
Hossain et al., 2012b
Liang et al., 2009
Feng and Guo, 2012
Chowdhury and Saha, 2011
Manzoor et al., 2013
CA
6.10
Parsley
Cd(II)
Cr(VI)
Cu(II)
Ni(II)
36
bentonite
Moringa oleifera bark
Powder activated carbon
Rice bran
Cassava peel
Orange peel
Litchi chinensis seeds
Orange peel
Caesalpinia bonducella seed
Cashew nut shell
NB
CA
MB (H3PO4)
NB
NB
NB
MB (NaOH, H2SO4)
MB (H2SO4)
30. 38
31.08
46.51
57.00
62.30
66.62
162.60
188.67
456.30
Reddy et al., 2011

Gutha et al., 2011
Zafar et al., 2007
Gonen and Serin, 2012
Flores-Garnica et al., 2013
Feng et al., 2011
Gutha et al., 2011
carbon
Kaolinite
CA
5.90
Dubey and Shiwani, 2012
CA
7.75
bentonite
Portulaca plant biomass
Cocoa pod husk
Pine cone powder
Cortex orange waste
Watermelon rind
Red rose waste
Rose petals waste
Onion skins
Orange peel
Orange peel
CA
15.00
al., 2011
NB
NB
MB (KOH)
NB
NB
MB (Methanol)
NB
MB (Boiled+Formaldehyde)
MB (NaOH and CaCl2)
17.24
20.10
32.26
70.29
76.80
98.06
99.72
119.92
200.00
209.8
476.1

Njoku et al., 2011
Hu et al., 2011
Liu et al., 2012
Bhatti et al., 2011
Saka et al., 2011
Feng and Guo, 2012
Feng et al., 2011
Bentonite clay
Kaolinite
CA (calcined)
CA
4.95
4.95
Araujo et al., 2013

al., 2011
Marin et al., 2010
Feng and Guo, 2012
Horsfall et al., 2006
Mishra et al., 2012
Pb(II)
Zn(II)
1
2
Maize stalks
NB
30.30
Orange waste
NB
43.16
Orange peel
MB (NaOH and CaCl2)
56.18
Cassava tuber bark waste
MB (Thioglycollic acid)
83.30
Cedrus deodara sawdust
NB
97.39
Cashew nut shell
MB (H2SO4)
455.7
Note: CA: Conventional adsorbent; NB: Natural or unmodified biosorbent; MB:Modified biosorbent.
37
Table 4 Optimum pH values in various heavy metals - AWBs adsorption systems.

Metal ion
As(V)
Adsorbent
Optimum pH
Reference
Pine leaves
4.0
Coffee grounds
Maize stalks
Wheat straw
Cashew nut shell
Castor seed hull
Cashew nut shell
Potato peels
Oyster mushroom, button mushroom
and milky mushroom
7.0
6.0
6.0
7.5
5.0
5.0
6.0
5.0
6.0

Farooq et al., 2011
Hu et al., 2011
Kumar et al., 2012
Panda et al., 2008
Sen et al., 2010
Taha et al., 2011
6.0
Vimala and Das, 2009
Eichhornia crassipes root activated

carbon
Durian shell waste
Cotton fiber
Coir pith
4.5
Giri et al., 2012
2.5
4.0
2.0

Muxel et al., 2011
Potato peels
Watermelon shell
Garden grass
Palm oil fruit shell
Orange peel
Watermelon rind
Cocoa pod husk
Pine cone powder
Cashew nut shell
Soybean meal waste
6.0
8.0
6.0
6.5
5.4
5.0-7.0
5.0
6.0
5.0
5.0
5.0
Aman et al., 2008

Hossain et al., 2012a
Hossain et al., 2012b
Hu et al., 2011
Liang et al., 2009
Liu et al., 2012
Njoku et al., 2011
Witek-Krowiak et al., 2013
Litchi chinensis seeds

Orange peel
Caesalpinia bonducella seed
Cassava peel
Moringa oleifera bark
Cashew nut shell
Rice bran
7.5
5.0
5.0
4.5
6.0
5.0
6.0
Flores-Garnica et al., 2013

Gonen and Serin, 2012
Gutha et al., 2011
Reddy et al., 2011
Zafar et al., 2007
Portulaca plant biomass

Watermelon rind
Cocoa pod husk
Pine cone powder
Onion skins
Potato peels
Oyster mushroom, button mushroom
and milky mushroom
6.0
5.6
6.8
6.0
5.0
6.0
6.0

Hu et al., 2011
Liu et al., 2012
Njoku et al., 2011
Saka et al., 2011
Taha et al., 2011
5.0
Vimala and Das, 2009
6.0
5.0
6.8
6.0
5.0
5.0
5.0
6.0
Boota et al., 2009

Liu et al., 2012
Marin et al., 2010
Mishra et al., 2010
Mishra et al., 2012
Taha et al., 2011
Cd(II)
Cr(VI)
Cu(II)
Ni(II)
Pb(II)
Zn(II)
Citrus reticulata (Kinnow) waste
Maize stalks
Watermelon rind
Orange waste
Eucalyptus leaf biomass
Cedrus deodara sawdust
Cashew nut shell
Potato peels
38
Table 5 Effects of modifications of AWBs on heavy metal removal from wastewater.

Biosorbents
Modifying agents
Metal ions
References
Cd(II)
Cu(II)
Changes in adsorption
capacity (%)
822.82
59.73
Wheat straw
Orange peel
Orange peel
Urea
NaOH 0.8M and
CaCl2 0.8M
NaOH 0.8M and
CaCl2 0.8M
NaOH 0.8M and
CaCl2 0.8M
The grafted polymerization
Pb(II)
84.84
Feng and Guo, 2012
Zn(II)
164.38
Feng and Guo, 2012
Pb(II)
420
Feng et al., 2011
Orange peel
Cd(II)
460
Feng et al., 2011
Orange peel
Green tomato husk

Formaldehyde 0.2%
Ni(II)
Fe(III)
1650
5.09
Green tomato husk
Formaldehyde 0.2%
Mn(II)
10.89
Zea mays cob powder
Acetylation
Cr(III)
2-8
Pineapple peel fibber
Succinic anhydride
Cu(II)
336.26
Feng et al., 2011

Garca-Mendieta et al. ,
2012
Garca-Mendieta et al. ,
2012
Goyal and Srivastava,
2009
Hu et al., 2011
Succinic anhydride
Cd(II)
374.05
Hu et al., 2011

Parsley
Succinic anhydride
Pyrolysis + FeCl3
Pb(II)
As(V)
242.7
9463.16
Parsley
Pyrolysis + FeCl3
As(III)
416.67
Rice husk
Epichlorohydrin, NaOH,
NaHCO3
Thermal treatment (1800C);
H3PO4
HNO3 0.1M
Mercapto acetic acid
Mercapto acetic acid
Acetic acid, benzoic acid, citric
acid 0.1N
Acetic acid, benzoic acid, citric
acid 0.1N
Introducing thio groups
Cd(II)
29.60, 135.90, 88.58
Zn(II)
93.96
Hu et al., 2011
Jimnez-Cedillo et al.,
2013
Jimnez-Cedillo et al.,
2013
Kumar and
Bandyopadhyay, 2006
Kumar et al., 2011
Cd(II)
Cu(II)
Cd(II)
Pb(II)
61.38
38.73
185.82
39.64, 43.89, 23.01
Lasheen et al., 2012

Liang et al., 2009
Liang et al., 2009
Cu(II)
14.10, 15.19, 20.24
Cd(II)
50
Panda et al., 2008
Sodium alginate
Cr(III)
23.36
Sodium alginate
Cr(VI)
18.31
Orange peel
Orange peel
Corncobs
Orange peel
Orange peel
Orange peel
Rosa bournobia phyto
biomass
Rosa bournobia phyto
biomass
Rosa gruss an teplitz (red
rose) distillation waste
Rosa gruss an teplitz (red
rose) distillation waste
Farooq et al., 2011

Feng and Guo, 2012
2
3
4
5
6
39
Highlights
Ability of AWBs for heavy metal detoxification was evaluated.

Influential factors on heavy metal biosorption were presented.
Insights of binding mechanism were revealed and essential tools were introduced.
Merits and demerits of pretreatment methods for better biosorbents were highlighted.
Recommendation to use AWBs as green and cost-effective biosorbents was made.

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Applicability of agricultural waste and byproducts for adsorptive

mechanisms, operating factors and pretreatment methods. The literature survey

to conventional adsorbents. Thanks to modern molecular biotechnologies, the roles of

functional groups in biosorption process are better understood. Of process factors, pH

replacement of traditional adsorbents by AWBs in decontaminating heavy metals from

wastewater can be expected in the future.

Keywords: Agricultural waste based biosorbents; Biosorption capacity; Heavy metals;

industries, such as batteries, tanneries, electrical, electroplating, fertilizers, pesticides,

solutions is of extreme importance. The United States Environmental Protection Agency

Numerous technologies have been developed for heavy metal decontamination.

Traditional treatment processes include precipitation, ion exchange, membrane

requirements, hazardous sludge formation, low efficiency when heavy metals

hindering the widespread application of activated carbon, a commonly used adsorbent in

the effects of operating parameters for process optimization; (3) biosorption

2. The application of AWBs for heavy metal removal

AWBs contain a variety of other functional groups, such as acetamido, carboxyl,

phenolic, structural polysaccharides, amido, amino, sulphydryl carboxyl groups,

solutions. Due to abundant binding groups, AWBs could be an enormous potential

source of adsorbent materials for decontaminating heavy metals from wastewater

(Jimnez-Cedillo et al., 2013; Marin-Rangel et al., 2012; Zafar et al., 2007 ).

2.2. Advantages of using AWBs as biosorbents

metal treatment is believed to reduce wastes in an eco-friendly way. Hence, it agrees

and Okoro, 2011).

2.3. Selection of AWBs

application. Based on these criteria, they proposed agro-industrial wastes and

including abundant availability, high cost-effectiveness, easy desorption, high

regeneration capability, negligible release of unexpected compounds into aqueous

2.4. Comparison of adsorption capacity of AWBs with conventional adsorbents

percentages. However, this could lead to misleading conclusions as removal efficiency

percentage removal (%) of heavy metals.

As shown in Table 3, the adsorption capacities of AWBs vary significantly. The

influential factors include types of crop residues, elements of heavy metals,

pretreatments of AWBs and especially operating conditions. AWBs tended to prefer

percentage by cotton stalks to its highest concentration of cellulose, hemicellulose, and

structure of rice hull and higher surface area of rice hull.

in Table 3, such as As, Cd, Cr, Pb, Zn.

(Suksabye and Thiravetyan, 2012).

3. Mechanisms of metal uptake on AWBs

including types of AWBs, properties of metal solution chemistry and environmental

metals onto AWBs (Figure 1).

It is likely that various mechanisms can operate simultaneously to varying degrees.

Netzahuatl-Muoz et al. (2012) examined mechanisms involved the removal of Cr(III)

interaction of Cr(III) with carboxyl groups to form Cr(III) - carboxylate complexes.

by intra-particle diffusion into the interior of adsorbent.

Due to the complicated nature of biosorption mechanisms, the combination of

Microscopy), EDX (Energy Dispersive X-Ray), TEM (Transmission Electron

hydroxyl groups blocking of chestnut shell had no significant effect on Pb(II)

polymerization-modified orange peel.

4. Parameters affecting heavy metal biosorption

investigate effects of these operating parameters. This section is dedicated to briefly

discuss the effects of these process factors.

Among process factors, pH seems to play a significant role in controlling the

(Kumar et al., 2012). As a rule, as solution pH increases, the biosorptive removal of

Cd(II) and Ni(II) by grafted copolymerization-modified orange peel was minimal at pH

2.0 and increased with increasing pH from 2.0 to 5.5.

For optimization of biosorption processes, a large part of biosorption studies are

devoted to investigating the optimum pH values. Table 4 summarizes the findings on

thereby reaching the maximum adsorption capacity at different pH values. In order to

removal of Cu(II) by potato peels.

4.2. Influence of temperature

Depending on surface functional groups of a given AWB, temperature has a given