Biosorption For Metal Ions Removal From Aqueous Solutions: A Review of Recent Studies

International Journal of Latest Research in Science and Technology ISSN (Online):2278-5299
Volume 3, Issue 1: Page No.24-42 ,January-February 2014

https://www.mnkpublication.com/journal/ijlrst/index.php
BIOSORPTION FOR METAL IONS REMOVAL

FROM AQUEOUS SOLUTIONS: A REVIEW OF
RECENT STUDIES
Nour T. Abdel-Ghani1 and Ghadir A. El-Chaghaby2*
1
Chemistry Department, Faculty of Science, Cairo University, Egypt.
2
* RCFF, Agricultural Research Center, Giza, Egypt.
Abstract- The presence of metal ions in aqueous solutions represents a major environmental problem. These inorganic species are persistent and
non-biodegradable pollutants that should be eliminated from water. In the recent years biosorption have emerged as an economical and
environmental friendly method for the decontamination of polluted water. The present work represents a review of the recently published
literature discussing the use of non-modified biosorbents for the removal of metal ions from aqueous solution. In this review the main classes of
biomass materials used as biosorbents are discussed along with the principle factors affecting the biosorption process such as: solution pH,
biomass dose, metal ion concentration and contact time. The potential health and environmental hazards of metal ions in addition to the kinetic
and isothermal models usually assessed to fit the biosorption experimental data were also reviewed.
Keywords - Biosorption; biosorption capacity; isotherm; kinetics; metal ions; mechanism
I. INTRODUCTION
commonly found in contaminated water [6]. Manganese is
The presence of inorganic pollutants such as metal ions in the
released into the environment by industries such as those
ecosystem causes a major environmental problem. Toxic
involved in the production of fertilizer, petrochemicals,
metal compounds coming to the earth's surface not only
electroplating, tanneries, metal processing, and mining [7].
contaminate earth's water (seas, lakes, ponds and reservoirs),
Mercury can be found in wastewater discharged from chlor-
but can also contaminate underground water in trace amounts
alkali, paper and pulp, oil refinery, paint, fossil fuel burning,
by leaking from the soil after rain and snow [1]. The numerous
metallurgical processes, pharmaceutical and battery
metals which are significantly toxic to human beings and
manufacturing [8]. Effluents from production of batteries,
ecological environments, include chromium (Cr), copper (Cu),
gasoline additives, pigments, alloys and sheets etc. contain
lead (Pb),cadmium (Cd), mercury (Hg), zinc (Zn), manganese
often high concentrations of lead ions [9]. Mining and
(Mn) and nickel (Ni), etc [2].
metallurgy of nickel, stainless steel, aircraft industries, nickel
Metal ions are released into the environment from many
electroplating, battery and manufacturing, pigments and
sources. Arsenic is introduced in water through natural and
ceramic industries wastewaters contain high amounts of nickel
anthropogenic sources: release from mineral ores, probably
ions [10]. Zinc can be found in wastewater from metallurgical
due to long term geochemical changes and from various
processes, galvanizing plants, stabilizers, thermoplastics,
industrial effluents like metallurgical industries, ceramic
pigment formation, alloys and battery manufacturing in
industries, dye and pesticides manufacturing industries and
addition to the discharges of municipal wastewater treatment
wood preservatives [3]. The major sources of antimony
plants [8].
released into the environment through wastewater streams are
Metal ions are reported as priority pollutants, due to their
such industries as lead-storage batteries, soldering, bearing
mobility in natural water ecosystems and due to their toxicity
and power transmission equipment, sheet and pipe metals,
[11]. The problem associated with metal ions pollution is that
ammunition, flame retardants, ceramics, casting, pewter,
they are not biodegradable and are highly persistent in the
enamels, and paints [4]. Wastewaters such as those generated
environment. Thus they can be accumulated in living tissues,
during dyes and pigments production, film and photography,
causing various diseases and disorders [12]. Heavy metals
galvanometry, metal cleaning, plating and electroplating,
toxicity can result in damage or reduced mental and central
leather and mining may contain undesirable amounts of
nervous function, lower energy levels and damage to blood
chromium (VI) anions [5]. Cobalt, which is widely used in
composition, lungs, kidneys, liver and other vital organs [13].
alloys (especially magnetic steels and stainless steels),
The potential health hazards of some metal ions as given by
electronics, porcelain and radioisotope therapy, is now
the EPA [14] are summarized in Table1.
Publication History 24
Manuscript Received : 25 February 2014
Manuscript Accepted : 28 February 2014
Revision Received : 1 March 2014
Manuscript Published : 2 March 2014
International Journal of Latest Research in Science and Technology.
In many countries, more strict legislations have been

Infants and children: Delays in physical
introduced to control water pollution. Various regulatory
or mental development; children could
bodies have set the maximum prescribed limits for the
show slight deficits in attention span
discharge of toxic heavy metals in the aquatic systems [13].
Lead and learning abilities
The permissible limits for industrial effluents discharge set by
the world health organization WHO [13] are 5-15(Zn), 0.05-
1.5(Cu), 0.1(Cd), 0.1(Pb), 0.1-1 (Fe) and 0.05-0.5 (Mn). Adults: Kidney problems; high blood
It is thus a necessity to remove metal ions from wastewater pressure
before it can be discharged. In this respect, many Mercury
physicochemical methods have been developed for the Kidney damage
(inorganic)
removal of metal ions from aqueous solutions including
precipitation, evaporation, electro deposition, ion exchange,
Hair or fingernail loss; numbness in
membrane separation, coagulation etc., [15]. However these Selenium
fingers or toes; circulatory problems
methods have disadvantages such as secondary pollution, high
cost, high energy input, large quantities of chemical reagents Biosorption is a physical-chemical process, simply defined
or poor treatment efficiency at low metal concentration [16].It as the removal of substances from solution by biological
can be said that the conventional methods for metal ions material. This is a property of both living and dead organisms
removal from wastewater are limited by technical and (and their components), and has been heralded as a promising
economical barriers, especially when concentration of metals biotechnology because of its simplicity, analogous operation
in the wastewater is low (<100 ppm) [17]. Therefore the to conventional ion-exchange technology, apparent efficiency
search and development of an efficient and low-cost metal and availability of biomass and waste bio-products
removal processes is of utmost importance. [19].Various waste biomaterials, micro-organisms, bacteria,
In this endeavor, biosorption has emerged as an alternative fungi, yeast and algae have been reported for the removal of
and sustainable strategy for cleaning up water [18]. metal ions from aqueous solutions [20].
Biosorption uses inexpensive biomaterials to sequester The present work was carried out to provide a review of the
environmental pollutants from aqueous solutions by a wide recent researches discussing the potential use of cost effective,
range of physicochemical mechanisms, including ion natural and non-modified biosorbents for the removal of metal
exchange, chelation, complexation, physical adsorption, and ions from aqueous solutions.
surface microprecipitation. The biomaterials used in this
process are termed biosorbents [18]. 2. Origin of biosorbents
2.1.Biosorbents from agricultural wastes
TABLE 1. LIST OF SOME METAL IONS AND THEIR HEALTH
HAZARDS [14] Agricultural wastes represent a potential source for
producing biosorbents as they have no prominent utilization
Potential Health Effects from Long- [21]. Biosorbent production may be added value to the agro-
Contaminant Term Exposure Above the maximum wastes and eventually reduced the agro-wastes management
contamination level problems over the world [21].
Agro-materials usually are composed of lignin and cellulose
Increase in blood cholesterol; decrease as major constituents and may also include other polar
Antimony
in blood sugar functional groups of lignin, which includes alcohols,
aldehydes, ketones, carboxylic, phenolic and ether groups
Skin damage or problems with [21]. These groups have the ability to some extent to bind
Arsenic circulatory systems, and may have heavy metals by donation of an electron pair from these
increased risk of getting cancer groups to form complexes with the metal ions in solution [11].
During the past few years, several research articles were
Barium Increase in blood pressure published reporting the successful use of different kinds of
Beryllium Intestinal lesions agricultural wastes in the removal of metal ions from aqueous
Cadmium Kidney damage solution.
Munagapati et al. [22] reported the use of Acacia
Chromium (total) Allergic dermatitis leucocephala bark powder as an effective, low cost, and
environmental friendly biosorbent for the removal of Cu(II),
Short term exposure: Gastrointestinal Cd(II) and Pb(II) ions from aqueous solution with sorption
distress capacities of 147.1, 167.7 and 185.2 mg/g; respectively.
Copper Moringa oleifera bark (MOB), an agricultural solid waste by-
Long term exposure: Liver or kidney product has been developed into an effective and efficient
damage biosorbent for the removal of Ni (II) from aqueous solutions
with maximum biosorption capacity of 30.38mg/g [23]. Cork
ISSN:2278-5299 25
waste biomass has been proved to be an efficient biomaterial to adsorb Cd(II) ions from aqueous solution and treated urban
useful for Cd(II) and Pb(II) removal from aqueous effluents in presence of Pb(II), Cu(II) and Ni(II) ions. The
solutions[24]. The maximum uptake of Cu (II) and Cr (III) feasibility of adsorption of uranium(VI) from aqueous solution
ions by peanut shells was found to be 25.39 mg/g and was studied and the peel exhibited a high U(VI) sorption
27.86 mg/g; respectively [17]. capacity 270.71 mg/g [33]. A feasibility study was performed
Rice straw was shown to have a high Cd(II) removal on Indian almond leaf biomass (Terminalia catappa L.) to
potential to from large-scale effluent contaminated by heavy remove palladium (Pd(II)) and platinum (Pt(IV)) ions from
metals with a biosorption capacity of 13.9 mg/ g [16]. aqueous solution by biosorption. The maximum biosorption
Alomá et al. [10] suggested that sugarcane bagasse waste capacity of T. catappa L. biomass for Pd(II) and Pt(IV) ions
can be used beneficially for nickel removal from aqueous were 41.86 and 22.50, respectively [34]. Torab-Mostaedi et al.
solution with a maximum sorption capacity of 2 mg/g. [30] reported adsorption capacities of 42.09 and 46.13 mg/g
Sunflower hulls were used for the biosorption of heavy metal for the biosorption of cadmium and nickel, respectively from
ions Cu (II) from aqueous solutions [25] and showed a aqueous solution onto grapefruit peel using batch technique.
maximum sorptive capacity amounting to 57.14 mg/g. The The latest published research articles reporting the use of
garden grass (GG) was firstly used by Hossain et al. [21] to agricultural biosorbents for metal ions removal from aqueous
remove copper (II) from water as bioadsorbent and the solutions include the use of: buckwheat hulls for the removal
maximum adsorption and desorption capacities were 58.34 of Hg(II) ions [35]; Morus alba L. pomace for Cd(II) removal
and 319.03 mg/g, respectively. (Qmax=21.69 mg/g) [36]; mango leave dust for Cr(VI) removal
Martins et al. [26] reported that Castor leaf powder can be (Qmax=250.23 mg/g) [37]; water hyacinth for Cu(II) and Zn(II)
applied immediately to remove Cd(II) and Pb(II) from removal (Qmax= 0.49 and 2.66 mg/g, respectively) [38]; spent
contaminated water with adsorption capacities of 0.340 and coffee ground for Cu(II) removal (Qmax= 0.214mmol/g) [39];
0.327 mmol/ g, respectively. Unmodified spent oil palm shell, Lathyrus sativus husk for Cr(III) and Cr(VI) removal (Qmax=
a waste from palm oil industry, was effectively applied as a 24.6 and 44.5 mg/g, respectively) [40]; Mosambi (Citrus
potential filter bed media for constructed wetland application limetta) peel dust for Cr(VI) removal (Qmax= 250 mg/g) [41];
and its monolayer adsorption capacities for Cu(II) and Pb(II) pinion shell for Cu(II) removal (Qmax= 4.29 mg/g) [42].
ions were 1.756 and 3.390 mg/g, respectively [27]. Antimony
2.2.Biosorbents from algae biomass
(III) was removed using green bean husk (GBH) as the
adsorbent. The equilibrium adsorption capacity of GBH was The term “algae” refers to a large and diverse assemblage
found to be 20.14 mg/g [4]. The potential use of Ficus carcia of organisms that contain chlorophyll and carry out oxygenic
leaves (fig leaves) for the removal of cadmium (II) and photosynthesis [43].
lead(II) ions from aqueous solutions has been investigated and Among biosorbent materials, algae have proved to be both
the maximum monolayer biosorption capacity was found to be economic and eco-friendly, as they are abundantly available,
30.31 mg of Cd(II)/g of and 34.36 mg of Pb(II)/g [28]. The have regeneration and metal recovery potentiality, lesser
biosorption of copper(II), zinc(II), cadmium(II) and lead(II) volume of chemical and/or biological sludge to be disposed
from aqueous solutions by dead Avena fatua biomass and the off, high efficiency in dilute effluents and high surface area to
effect of these metals on the growth of this wild oat were volume ratio [44]. They provide a cost effective solution for
investigated. The maximum values for the adsorption of industrial wastewater management [44]. Generally speaking
copper, zinc, cadmium and lead by A. fatua were determined about the biosorption mechanism it can be said that the
to be 0.27, 0.25, 0.73 and 0.84 mmol g−1, respectively [29]. presence of biosorbents’ cell wall as well as its chemistry are
Recently fruit wastes have been reported to have relatively of greater importance. In this respect, the biosorption in algae
good uptake capabilities for metal ions removal. Fruit peels has mainly been attributed to the cell wall properties where
that are typically generated in large quantities by the fruit juice both electrostatic attraction and complexation can play a role
industry have received little scientific attention, in spite of [43]. Algal biomasses contain high content of carboxyl groups
their high quantity of pectin, which contains carboxylate from mannuronic and guluronic acids on the cell wall
groups [30]. The biosorption of lead, copper and cadmium polysaccharides [45].
using different cortex fruit wastes including banana (Musa According to Romera et al. [46] algae are divided into
paradisiaca), lemon (Citrus limonum) and orange (Citrus several evolutionary pathways completely independent: a “red
sinensis) peel has been evaluated [19]. The authors of that pathway” with red algae (Rhodophyta), a “brown pathway”
study found that banana peel was capable of adsorbing around with brown algae (inter alia, Chromophyta) and a “green
65 mg of Pb and Cd per gram but only 36 mg of Cu per gram. pathway” that includes green algae (Chlorophyta). The cell
For lemon and orange peels, the best retention rate was for Pb walls of brown algae generally contain three components:
(77.6 and 76.8 mg/g) then Cu (70.4 and 67.2 mg/g) and finally cellulose, alginic acid and sulphated polysaccharides. As a
Cd (12 and 28.8 mg/g). The maximum biosorption capacity consequence, carboxyl and sulphate are the predominant
for lead (II) ions adsorption onto Punica granatum L. (P. active groups in this kind of algae [46]. Red algae also contain
granatum L.) peels was found to be 193.9 mg/g [31]. cellulose, but their interest in connection with biosorption lies
Bayo [32] demonstrated the effectiveness of native in the presence of sulphated polysaccharides made of
grapefruit biomass (NGB), a by-product of the food industry galactanes (agar and carragenates) [46]. Green algae are
ISSN:2278-5299 26
mainly cellulose, and a high percentage of the cell wall maximum uptake of Cu(II) by dried green alga Oscillatoria sp.
proteins bonded to polysaccharides to form glycoproteins. was 36.2 mg/g[56]. The maximum adsorption capacities for
These compounds contain several functional groups (amino, Co(II), Cr(II), Cd(II), and Pb(II) onto nonliving biomass
carboxyl, sulphate and hydroxyl) which could play an (Neochloris pseudoalveolaris, Np) were found to be 20.1,
important role in the biosorption process [46]. 9.73, 51.4 and 96.2 mg/g, respectively[57].
Several authors were interested in studying the More recent, Sargassum filipendula (a marine alga) was
application of algal biomass for metal ions removal from found to be an efficient biosorbent for copper and nickel with
contaminated water. Rathinam et al. [47] evaluated the maximum capacities of 1.324 and 1.070 mmol/g, respectively
biosorptive removal of cadmium by red macro alga Hypnea [58]. The biosorption of cadmium(II) and lead(II) ions from
valentiae and observed a maximum removal of about 17 mg of aqueous solution was evaluated using the algae nonliving
cadmium per g of micro algae. Gupta et al. [48] reported a biomass (Rivularia bulata) and the maximum adsorption
maximum capacity of 40.9 mg/g for the biosorption of nickel capacities for Cd(II) and Pb(II) were found to be 26.36 and
ions from aqueous solutions onto the biomass of Oedogonium 34.30 mg/g [59]. The maximum adsorption capacity of Cu(II)
hatei. using a dried and untreated macro algae species (Ulva lactuca)
Four red macroalgal species of Corallina mediterranea, was calculated as 38 mg/g [60]. The maximum uptake
Galaxaura oblongata, Jania rubens and Pterocladia capacities of Cu (II) and Ni (II) ions using marine brown algae
capillacea were examined by Ibrahim [45] to remove Co(II), Sargassum angustifolium were 0.94 and 0.78 mmol/g dry alga,
Cd(II), Cr(III) and Pb(II) ions from aqueous solution with the respectively [61].
maximum biosorption capacities ranging from 28.5 mg/g to From the former reviewed studies it can be noticed that
105.2 mg/g. the biosorption capability of the alga biosorbents depend
Lee and Chang conducted a study to evaluate the somewhat on the type of the algal biomass used in the
biosorption capacity from aqueous solutions of the green algae biosorption process. Several authors have reported that
species, Spirogyra and Cladophora, for lead (Pb(II)) and “brown algae” have higher metal ions biosorption capacity
copper (Cu(II)) [49]. The capacity of Spirogyra to adsorb compared to red and green algae species. This was attributed
Pb(II) and Cu(II) was 87.2 mg/g and 38.2 mg/g, respectively according to Romera et al. [46] to the presence of alginates in
and the capacity of Cladophora to adsorb Pb(II) and Cu(II) the cell wall of brown algae which could be responsible for
was 45.4 mg/g and13.7 mg/g, respectively. Arsenic (III) such behaviour by anchoring the metal to the biomass.
biosorption from aqueous solution by dead green algae
(Maugeotia genuflexa) biomass was successfully achieved 2.3.Biosorbents from bacterial biomass
with a maximum biosorption capacity of 57.48 mg/g [3].
A comparative evaluation of bioaccumulation and As previously discussed, the cell wall structure plays an
biosorption of Cu (II) and Pb (II) ions by algal cells of important role in the biosorption process. A variety of
Chlamydomonas reinhardtii was conducted by Flouty and functional groups located on the bacterial cell wall are known
Estephane [50] and the amount of Pb (II) and Cu (II) to be included in metal biosorption. These include carboxyl,
biosorbed by the algal biomass were 0.286 and 0.109 mg/g, amine, hydroxyl, phosphate, and sulfhydryl groups. The
respectively.The biosorption of trivalent chromium by mechanism of metal biosorption by bacterial biomass occurs
protonated brown algae, Pelvetia canaliculata, was studied in through complexation, coordination, physical adsorption,
batch system and the maximum chromium uptake was found chelation, ion exchange, inorganic precipitation and/or a
to be 0.6 mmol/g [51]. combination of these processes [62]. The metabolism-
The biosorption of Pb(II), Cd(II), and Co(II) from aqueous independent process of metal binding to the cell walls of
solution on green algae waste biomass from Ulva lactuca sp. bacterial biomass and external surfaces is the main mechanism
was investigated and the maximum biosorption capacities present in the case of non-living biomass; and involves an
were reported as 0.27, 0.26 and 0.19 mmol/ g for Pb(II), adsorption process, such as ionic and physicochemical
Cd(II) and Co(II), respectively [52].The biosorption of Cd(II) adsorption [62].
and Pb(II) from aqueous solution onto the biomass of the blue Chatterjee et al. [63] found that the maximum adsorption
green alga Anabaena sphaerica was investigated by Abdel- capacities (mg/g) for the different metals by dead biomass of
Aty et al. [53] and the maximum biosorption capacities for thermophilic bacteria Geobacillus thermodenitrificans were
Cd(II) and Pb(II) were found to be 111.1 and 121.95 mg/g, 79.9 mg/g for Fe+3 > 70.7 mg/g for Cr+3 > 69.76 mg/g for Co+2
respectively. > 50.0 mg/g for Cu+2 > 48.26 mg/g for Zn+2 > 42.9 mg/g for
González et al. [54] reported the usefulness of Sargassum Cd+2 > 37.86 mg/g for Ag+ > 32.26 mg/g for Pb+2.The
muticum brown alga for the biosorption of hexavalent maximum adsorption capacities by Pseudomonas aeruginosa
chromium from the aqueous solutions with maximum ASU 6a (Gram-negative) and Bacillus cereus AUMC B52
biosorption capacity equal to 196.1 mg/g. The maximum (Gram-positive) used as inexpensive biosorbents for Zn(II)
biosorption capacities for Co (II), Cr (III), Cd (II) and Pb (II) were found to be 83.3 and 66.6 mg/g, respectively [62]. Also,
ions from water using dead algae biomass (Scenedesmus the biosorption of Pb(II) ions from aqueous solutions using the
quadricauda Chodat) were found to be 32.8, 20.3, 63.9 and bacteria Rhodococcus opacus was investigated and the
123.0 mg/g, respectively [55]. In the same trend, the maximum biosorption capacity obtained was 95.2 mg/g [64].
ISSN:2278-5299 27
Abu Hassan et al. [7] showed that Bacillus sp. was a more 2.4.Biosorbents from fungal biomass
effective biosorbent than activated sewage sludge for the “Fungi” represent another group of microorganisms that
removal of Mn2+ from aqueous solution with a maximum have been efficiently used in the preparation of biosorbents for
sorption capacity equal to 43.5 mg Mn2+/g biomass. The
metal ions removal from contaminated waters. Fungi are easy
potential use of B. cereus and B. pumilus as metal sorbents for
to grow; produce high yields of biomass and at the same time
the removal of Pb+2 was studied and the adsorption capacities
can be manipulated genetically and morphologically [75].
of B. cereus and B. pumilus were found to be 22.1 mg/g and
28.06 mg/g, respectively [65]. The ability of Trametes The cell wall composition is the characteristic feature of
versicolor biomass for biosorption of Cu(II) ions from the fungal species as it shows excellent metal-binding
aqueous solution was studied and its maximum biosorption properties [76]. The major constituents of fungal cell wall are
capacity was found to be 140.9 mg/g [66]. The maximum carbohydrates chitin (3-39%), chitosan (5-33%), polyuronide
adsorption of Co(II) and Mn(II) using the bacterial strain and polyphosphates (2-12%), lipids (2-7%) and proteins (0.5-
Rhodococcus opacus as biosorbent was found to be 13.4 mg/g 2.5%) and there are marked variations in the wall composition
and 6.91 mg/g for cobalt and manganese respectively [67]. between different fungal taxonomic groups [76].
Abd-Alla et al. [68] found the maximum adsorption The biosorptive capacity of dead fungal biomass has been
capacities Rhizobium spp. a gram-negative soil bacteria for studied extensively by several authors during the last few
Cd2+ and Co2+ biosorption to be 135.3 and 167.5 mg/g, years. Velmurugan et al. [77] reported a maximum biosorption
respectively. Puyen et al. [69] reported that Micrococcus capacity of Penicillium sp. MRF-1 for Pb(II) to be 72.5 mg/g.
luteus DE2008 exhibited a specific removal capacity of Xiao et al. [78] studied the biosorption of cadmium by
408 mg/g for copper and 1965 mg/g for lead. Cadmium endophytic fungus (EF) Microsphaeropsis sp. LSE10 and their
removal from aqueous solutions using a Streptomyces results showed that the maximum biosorption capacity
lunalinharesii strain was successfully achieved with maximum was247.5 mg/g. in the same way, the filamentous industrial
uptake of 24.8 mg g−1 [70]. The maximum Cu and Pb fungus, Rhizopus cohnii (R. cohnii), was used as an efficient
biosorption capacities on B. thioparans U3 were found to be biosorbent for removing cadmium from wastewater and the
42.3 and 210.1 mg g−1, respectively [71]. biosorption experimental results showed that the maximum
The sorption of four heavy metals, cadmium (Cd), uptake of cadmium was 40.5 mg/g [79].
chromium (Cr), mercury (Hg), and lead (Pb), on living and
nonliving Bacillus subtilis B38 was investigated using batch Bairagi et al. [80] demonstrated a viable option for the
experiments. The nonliving biomass generally showed greater removal of lead from contaminated water with Aspergillus
or similar adsorptive capacities as compared with the living versicolor biomass (AVB). The maximum adsorption capacity
biomass, the bacterium had a stronger affinity to the cationic of AVB has been found to be 45 mg Pb (II) per gram of the
heavy metals than to the anionic one, and the equilibrium dry weight of the biomass. Similarly, Pang et al., [81] showed
sorption amounts were 210.6, 332.3, and 420.9 mg/g for that Penicillium citrinum can effectively remove uranium from
Cd(II), Hg(II), and Pb(II), respectively [72]. aqueous solutions with maximum capacity of 127.3mg/g. The
The biosorption properties of dead sulfate reducing sorption of Cr(VI), Ni(II) and Zn(II) ions from synthetic
bacteria (SRB) for the removal of Cu(II) and Fe(III) from solutions and electroplating effluent by immobilized
aqueous solutions were studied. The maximum specific metal Trichoderma viride biomass was studied and the fungal
biosorption was 93.25 mg·g-1 at pH 4.5 for Cu(II) and 88.29 biomass recorded maximum biosorption capacities of 4.23,
mg·g-1 at pH 3.5 for Fe(III) [73].The ability of Streptomyces 7.41 and 6.27 mg/g for Cr(VI), Ni(II) and Zn(II); respectively
lunalinharesii to sorb copper and zinc from aqueous solutions [82]. Javaid et al. [76] explored the adsorption potential of
was investigated through batch experiments and maximum Pleurotus ostreatus (a macro-fungus) to remove copper,
capacities for Cu(II)and Zn(II) biosorption were found to be nickel, zinc and chromium from water all together and
11.53 and 13.64 mg/g, respectively [74]. achieved maximum biosorption capacities of 8.06, 20.40, 3.22
It is interesting to note that some authors reported that the and 10.75 mg g−1 for Cu(II), Ni(II), Zn(II) and Cr(VI);
difference in biosorption capacities of the various bacterial respectively.
biomasses depends on the nature of the bacteria. Gram-
positive or Gram-negative bacteria have significant In the year 2012, the Clitopilus scyphoides (Pleurotus
differences in their cell wall structure. mutilus) fungal biomass residue displayed promising
Joo et al. [61] found that P. aeruginosa ASU 6a (Gram- adsorption characteristics for cadmium recovery from
negative) have a higher metal biosorption capacity compared contaminated water with maximum biosorption capacity equal
to B. cereus AUMC B52 (Gram- positive). The authors to 200mg/g [83]. Whereas a fungus, XJ-1, isolated from
explained their finding by the fact that Gram-positive bacteria chicken manure compost that was phylogenetically related to
normally showing lower levels of surface complexation due to Penicillium chrysogenum showed a maximum adsorption of
the heavily cross-linked peptido-glycan layer, while in Gram- 100.41 (mg/g dry biomass) for Cd2+ ions [84]. Duygu Ozsoy
negative bacteria, most of their lipo- polysaccharide (LPS), and van Leeuwen [85] found that it is possible to use dried
phospholipids, and proteins are exposed on the cell surface Rhizopus oligosporus biomass to remove Ni (II) ions from
and are responsible for efficient metal binding capacity. their aqueous solutions with a capacity value of 116 mg/g.
ISSN:2278-5299 28
Huang et al. [86] investigated the bio-sorption characteristics biosorbents structure should be discussed. As earlier
of Cd2+, Cu2+, and Pb2+ by the fruiting body of jelly fungus mentioned the main functional groups usually found on a
Auricularia polytricha and the biomass provided maximum biosorbent surface include carboxyl, sulfhydryl, hydroxyl, and
biosorption capacities for of 63.3, 73.7, and 221 mg/g for Cd amino groups. Deprotonation of these functional groups
2+, Cu2+, and Pb2+, respectively. occurs on increasing pH and these behave as negatively
charged moieties which start attracting the positively charged
Recently in 2013, Rani et al. [87] achieved maximum metal ions [92]. On the other hand as the pH is lowered, the
biosorption capacity of 26.1 mg/g for Ni (II) ions from overall surface charges will become positive, which will
aqueous solutions using Aspergillus fischeri fungi as a inhibit the approach of positively charged metal cations [48].
biosorbent. Meanwhile, Subbaiah and Yun [88] reported The effect of pH on the biosorption process may also be
maximum capacity of 212.5 mg/g for Ni (II) biosorption from explained in terms of pH of the point of zero charge, (pHpzc)
aqueous solution by the fungal mat of Trametes versicolor at which the biosorbent surface is neutral. When the biomass
(rainbow) biomass. Aspergillus fumigatus was isolated from a is kept in a solution having pH less than pHpzc of biomass, the
gold mine tailings and its ability to remove metal ions from protonation of certain functional groups occur and the biomass
aqueous solutions was assessed. The maximum sorption behaves as a positively charged polymatrix [92]. An increase
capacity of the fungal biomass for As(III), As(V), Fe, Mn, Pb, in pH above this point makes the functional groups on the
and Zn were 11.2, 8.57, 94.33, 53.47, 43.66, and 70.4mg/g, biomass type deprotonate and act as negative species [92].
respectively [89]. Farooq et al. [92] represented the effect of pHpzc
It has been confirmed by many authors that the effective considering that (–BH) represents the biomass type bearing
biosorption of heavy metals by fungal biomass can be caused zero charge by the following equation:
by different mechanisms including ion exchange,
complexation, chelatation, adsorption and microprecipitation
[78]. Many works indicate that heavy metals ion exchange According to Ahmaruzzaman [13] at pH below the
with K+,Na+,Ca2+ and Mg2+ from the biosorption sites of pHzpc, the predominant metal species (M2+ and M(OH)+) are
biomass as a key mechanism in metal biosorption processes positively charged and therefore, the uptake of metals in the
[78,90]. pH range below pHzpc is H+¯M2+ (or M(OH)+) exchange
process. With an increase in pH above pHpzc, although the
3. Factors affecting metal ions biosorption surface of the adsorbent is negatively charged, the adsorption
3.1. Effect of pH still increases as long as the metal species are still positively
charged or neutral. When both the surface charge of the
In the biosorption phenomenon, the pH value affects two
adsorbent and metal species charge become negative, the
aspects: metal ion solubility and biosorbent total charge, since
adsorption will decrease significantly [13].
protons can be adsorbed or released [46]. The acidity of the
Another aspect that must be considered is the metal
medium affects the competition ability of hydrogen ions with
speciation in solution, which is also pH dependent [91].
metal ions to active sites on the biosorption surface [48].
Figs.1 give representative examples for metal speciation
According to Romera et al. [46] the pH value of the diagrams (adopted from references [93] and [94]).
medium affects the system’s equilibrium state, can be Reviewing the metal ions predominant species as function
represented by the following equations: of the solution pH, the following information could be
B¯H ↔ B- + H+ obtained:
Ka= [B-][H+]/[B¯H]  At pH < 3, Sb(III) exists as [SbO]+ and [Sb(OH)2]+
pKa- pH = log ([B¯H]/ [B-]) species, whereas HSbO2 and Sb(OH)3 species
For pH values lower than pKa, equilibrium (1) shifts to the predominate at the pH range of 3–10, while [SbO2]−
left, consuming protons and increasing pH until its value species is predominant at pH > 10[4].
equals pKa. When the pH of the medium is higher than pKa,
the opposite will happen [48].  Cu(II) exists as Cu2+ at pH 3 and above this pH other
It has been generally reported that in highly acidic Cu(II) species like Cu(OH)+ exist at pH 4-5 and
medium (pH≈2) the removal of metal ions is almost negligible Cu(OH)2 is found at pH>6 [15].
and it increases by increasing the solution pH up to a certain  For chromium ions, at pH values lower than 3 the
limit. predominant species is Cr3+, at pH close to 4
According to Feng et al.[91] the minimum biosorption at approximately the same proportion of Cr3+ and
low pH is due to the fact that high concentration and high Cr(OH)2+ exists, around pH=7 the chromium is
mobility of H+ ions, the hydrogen ions are preferentially mainly found precipitated as Cr(OH)3 and finally at a
adsorbed rather than the metal ions. At higher pH values, the basic pH the predominant species is Cr(OH)4− [94].
lower number of H+ and greater number of ligands with
negatives charges results in greater metal ions biosorption  Free cadmium (II) and lead (II) ions are the
[91]. predominant species formed in the pH between 3.5
Regarding the role of pH in relation to the biosorbent and 5. At pH values higher than 8 for cadmium, or
surface, the different functional groups present on the higher than 5 for lead, several hydroxyl low-soluble
ISSN:2278-5299 29
species can be formed, i.e. Cd(OH)2, Cd(OH)3− or 2.0 to 4.5 and then reached a plateau in the pH range of 4.5 to
Pb(OH)2 [95]. 6.5.
 In the pH range 2-3 Nickel is predominantly present
as Ni2+ whereas at higher pH range (4.5-6) partial
hydrolysis of the metal ions occur resulting in the
formation of Ni(OH)+ and Ni(OH)2 [96].
 Se(IV) species in aqueous solution include seleniuos
acid (H2 SeO3), biselenite (HSeO3-) and
selenite(SeO32-). Between pH 3.5 and 9.0 biselenite
ion is the predominant ion in water. Above pH 9.0
selenite species dominate and as pH decreases below
pH 3.5, selenious acid dominates [97].
Fig. 2a: Effect of pH on Cd(II) biosorption capacity using

biosorbent R. cohnii at different Cd(II) concentrations at
contact time 12 h, dosage of 1 g/L and at 298 K (adopted from
reference [79]).
Luo et al. [79] attributed that to the biosorption capacities of

biosorbents which depend on the available binding sites
provided by the functional groups existing on the surface of
the biosorbents. Such sites were not available due to
competition between Cd2+ and H+ ions at pH 2.0. With the
acidity decreasing in the solution, the deprotonation of acid
functional groups, such as carboxyl, phosphonate and
phosphodiester, was strengthened and the attraction increased
between negative charge on biomass and positive metal
Fig.1a: Aqueous speciation of Cu, Cd, Pb and Zn as a function cations.
of pH in the single-element system (from reference [93]).
Reddy et al. [23] provided another explanation for the effect
of solution pH on the biosorption of Ni(II) by Moringa
oleifera bark (MOB). The authors observed that under highly
acidic conditions (pH≈2.0) the amount of Ni(II) removal was
very small, while the sorption had been increased with the
increase in pH from 3.0 to 6.0 and then decreased in the range
7.0 and 8.0 (Fig.2b). They explained their results by
considering the point of zero charge of MOB which they have
determined to be 4.2±0.67 (PZC). Thus, at pH below (PZC),
the surface of MOB would be positively charged due to
protonation. This protonation effect was more pronounced at
lower pH values due to the presence of higher concentration of
Fig.1b: Speciation diagram for Cr (III) at 25°C and 10 mg/L H+ ions in the solution which resulted in more unfavorable
ion content (from reference[94]) Ni(II) biosorption. At the optimum pH value (pH 6.0) the
surface of the MOB is negatively charged and favorable to the
Some examples of how the preceding information biosorption of Ni(II). Decreased biosorption at higher pH
have been adopted by the authors working in the biosorption (pH>6) was due to the formation of soluble hydroxylated
field to interpret their results are summarized as follows: complexes of the metal ions and their competition with the
Luo et al. [79] studied the effect of initial solution active sites, and as a consequence, the retention had been
pH on Cd (II) biosorption by the biomass of Rhizopus cohnii decreased again.
(R. cohnii) and stated that barely any biosorption was
observed for a pH less than 2.0 (Fig.2a). The cadmium uptake
of biosorbent R. cohnii increased with the pH increasing from
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As a rule, increasing the initial metal concentration

results in an increase in the biosorption capacity because it
provides a driving force to overcome mass transfer resistance
between the biosorbent and biosorption medium [44].
The removal efficiency of the ions by the biosorbent

initially increases with increasing the initial ion concentration.
At lower ions concentration in the solution, the ions would
interact with the binding sites and thus facilitated almost 100%
adsorption whereas at higher concentrations, more ions are left
Fig. 2b: Effect of pH on the sorption of Ni(II) by MOB. Error un-adsorbed in the solution due to the saturation of the binding
bars represent ±S.D (adopted from reference [23]) sites [105].
It is interesting to point out that the authors working with
Cr(VI) biosorption indicated that the maximum chromium Rathinam et al. [47] studied the effect of different initial
biosorption takes place at highly acidic pH values (pH=2) for cadmium concentrations of 25, 50, 150, 250, 500 mg L−1 on its
various types of studied biomasses e.g. sawdust [5], pistachio removal using H. valentiae biomass. The percentage (%)
hull waste biomass [99, Sargassum muticum brown alga [54], removal of cadmium has been found to be higher at lower
sugarcane baggasse biomass [100], Rosa damascena concentration of cadmium solution (25 mg L−1); a maximum
phytomass [101], etc. cadmium removal of 86.8% has been obtained for H. valentiae
biomass. However, the effective biosorption of cadmium (qe)
The explanation of this behavior was given by considering by seaweed in terms of mg of cadmium per gram of seaweed
the effect of initial solution pH in relation to the metal ion increased from 4.34 to 24.60 mg g−1 as the initial cadmium
(chromium) species present in solution. According to concentration was varied from 25 to 500 mg L− (Fig.3a).
González et al. [54] concerning Cr(VI) biosorption in the pH These authors concluded that the increase of cadmium
range 2.0-6.0, HCrO4− and CrO42− ions are in equilibrium [98]. biosorption capacity of biosorbent with an increase in
At lower pH (pH < 2) values, Cr3O102− and Cr4O103− species cadmium concentration is probably due to higher interaction
are formed. The distribution of Cr(VI) and Cr(III) is strongly between metal ions and the biosorbent.
dependent on the pH of the solution, of the initial metal
concentration and the dosage of the biosorbent. All the species In studying the biosorption of copper onto cashew nut shell
of chromium in the solution were in their trivalent form at pH (CNS) Senthilkumar et al. [106] found that the percentage
< 2 [102]. copper(II) ion adsorption decreased from 86.03% to 76.17%
with the increase of the initial copper(II) ions concentration
González et al. [54] further reported that the decrease in the from 10 to 50 mg/L (Fig. 3b). At low concentration values, a
biosorption with increase of pH may be due to the decrease in larger surface area of the CNS being available for the
electrostatic force of attraction between the sorbent and adsorption of copper (II) ions and the ions are adsorbed at
sorbate ions. At lower pH ranges, due to the high electrostatic specific sites. Whereas with increasing copper (II) ion
force of attraction, the percentage of Cr(VI) removal is high. concentrations the available sites of the adsorption became
At very low pH value, the surface of sorbent would also be less, the specific sites are saturated with and exchange sites are
surrounded by the hydronium ions which enhance the filled, thus as a result adsorption percentage was less.
interaction of Cr(VI) with binding sites of the biosorbents by
greater attractive forces. A sharp decrease in biosorption Chong et al. [27] observed that the adsorbed amount of
above pH 4 may be due to occupation of the biosorption sites Cu(II) and Pb(II) ions per unit weight of oil palm shell
by anionic species like HCrO4−, Cr2O72−, CrO42−, which retards increased with the increase of initial concentration over the
the approach of such ions further toward the sorbent surface range of 5–400 mg/L (Fig.3c). This is because of the reduction
[103]. in the total fraction of adsorbate ions adsorbed at higher initial
concentration which created a driving force to overcome mass
3.2. Effect of initial metal ion concentration transfer resistance that enabled the adsorbate ions to move
sufficiently close to the oil palm shell to be adsorbed onto its
The initial concentration of metal ions in the solution plays a binding sites. The authors also reported that nevertheless
key role as a driving force to overcome the mass transfer insufficient binding sites to accommodate excessive adsorbate
resistance between the aqueous and solid phases [104]. ions at high initial concentration caused a reduction in fraction
It is generally agreed that the biosorption capacity increases of adsorbate ions adsorbed [27].
as the initial metal ion concentration in the solution increases,
whereas the metal removal percentage (also called removal
efficiency) decreases by increasing the metal ion initial
concentration.
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of different initial ions concentrations on the biosorption of

Fe+3 ,Cr+3 ,Co+2,Cu+2 ,Zn+2 ,Cd+2 ,Ag+ and Pb+2 by the dead
biomass of G. thermodenitrificans and found that the increase
in initial metal concentration resulted in increase in the
capacity of metal adsorption from 25 to 175mg/L with a
maximum adsorption at 175mg/L for all the metals. The actual
amount of copper adsorbed per unit mass of Garden Grass
increased from 14.06 to 137.12 mg/g with the increase in
copper concentration from 10 to 100 mg/l in the test water
[21]. The increasing of initial concentration of palladium and
platinum led to the maximum capacity of Indian almond leaf
biomass adsorption [34].With the increase in initial Ni(II)
concentration from 10 to 750 mg L-1, the Ni(II) biosorption
Fig. 3a: Effect of initial concentration of cadmium on capacity by Litchi chinensis seeds rose from 5.44 to 66.34 mg
cadmium biosorption by seaweed (adopted from reference g-1 [18]
[47])
3.3. Effect of biomass dosage
Biomass provides binding sites for the sorption of metal

ions, and hence its concentration strongly affects the sorption
of metal ions from the solution [108]. The amount of
biosorbent used for the treatment studies is an important
parameter, which determines the potential of biosorbent to
remove metal ions at a given initial concentration [47].
For a fixed metal initial concentration, increasing the
Fig. 3b: Effect of initial copper (II) ions concentration for the adsorbent dose provides greater surface area and availability
adsorption of copper(II) ions onto CNS (the initial copper(II) of more active sites, thus leading to the enhancement of metal
ions concentration =10 to 50 mg/L, pH=5.0, CNS dose=3 g/L ion uptake [108]. At low biomass dosage, the amount of ions
and time=30 min) (adopted from reference [106]). adsorbed per unit adsorbent weight is high. The adsorption
capacity is reduced when the biomass dosage increases as a
result of lower adsorbate to binding site ratio where the ions
are distributed onto larger amount of biomass binding sites.
However, at higher dosage, the ions adsorbed are higher due
to the availability of more empty binding sites as compared to
lower dosage which has less binding sites to adsorb the same
amount of metal ions in the adsorbate solution [27].
The effect of biomass dosage on metal ions biosorption was
investigated by many authors. Rathinam, et al. [47]
demonstrated that an increase in the amount of seaweed
decreases cadmium biosorption capacity of the seaweed H.
valentiae biomass. On increasing the quantity of seaweed from
4 to 8 g L-1, biosorption capacity decreases from 27.08 to 6.21
mg g-1 for H. valentiae biomass. These authors indicated that
the decrease in biosorption capacity may be due to splitting
effect of concentration gradient between sorbate and sorbent
Fig. 3c: Effect of initial concentration on adsorption of Cu(II) with increasing seaweed concentration causing a decrease in
and Pb(II) ions by oil palm shell. (adopted from reference amount of cadmium adsorbed onto unit weight of H. valentiae
[27]). biomass.
Simillarly, Chowdhury and Mulligan [107] found that the In their study Abdel-Atty et al. [53] evaluated the effect of
amount of As(III) adsorbed increased from 106 to 155µg/g different biomass dosage of the water algae Anabaena
with the increase of initial concentration from 500 to sphaerica on the biosorption of Cd(II) and Pb(II) ions. The
4000µg/L but the removal efficiency decreased from 85 to data revealed that the biosorption of Cd(II) and Pb(II) ions
16%. Pang et al. [81] also stated that the adsorption capacity was increased with subsequent increasing the biosorbent dose
of the dead fungal biomass of Penicillium citrinum increased and almost became constant at higher biomass dosage (Fig.4).
with an increase in the initial uranium (VI) concentrations This behavior could be explained by the formation of
from 30 to 80µg/ml. Chatterjee et al. [63] studied the effect
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aggregates of the biomass at higher doses, which decreases the concentration gradient between the surface of the sorbent and
effective surface area for biosorption. the internal groups due to the change in the concentration of
the solution when the dosage of adsorbent increases.
In real applications, the most favorable biosorbent
dose should be defined as the lowest quantity that gives a
reasonable level of removal efficiency, and additionally,
adjusts to environmental regulations to discharge metal ions in
the environment [74].
3.4. Effect of contact time

In batch biosorption experiments, the determination
of the optimum contact time required to achieve the highest
removal of metal ions is one of the key factors usually
Fig. 4a: Effect of the dose of Anabaena sphaerica biomass on assessed. Equilibrium time is one of the important parameters
the biosorption of Cd and Pb (adopted from reference [53]) for selecting a wastewater treatment system [113].
In our previous studies and in agreement with many
authors we have reported that basically, the removal rate of
sorbate is rapid, but it gradually decreases with time until it
reaches equilibrium. The rate of percent metal removal is
higher in the beginning due to a larger surface area of the
adsorbent being available for the adsorption of the metals. The
metal uptake by the sorbent surface will be rapid initially,
slowing down as the competition for decreasing availability of
active sites intensifies by the metal ions remaining in solution
[114].
The equilibrium time for metal ions biosorption onto

various types of biomass recently reported in literature are
summarized in Table 2.
Fig.4b: Effect of biosorbent dose on metal uptake and
percentage metal removal (adopted from reference [110])
TABLE 2. EQUILIBRIUM TIME ACHIEVED FOR METAL
Experiments were carried out by Venugopal and Mohanty IONS BIOSORPTION ONTO DIFFERENT BIOMASSES
[110] to find the effect of biosorbent dose on Cr(VI) uptake Biosorbent Metal ion
Equilibrium time
Reference
(min.)
and percentage adsorption by Parthenium (P. hysterophorus
Grapefruit peel Cd (II), Ni (II) 60 [30]
L.) weed biomass . The results revealed that percentage Rice straw Cd (II) 5 [16]
removal of Cr(VI) increased from 61.28 to 80.81 with increase A. leucocephala bark Cu (II), Cd (II) 180 [22]
in adsorbent dose from 0.1 to 1.0 g which is the expected trend and Pb (II)
as more actives sites were available with increase in the Sugarcane bagasse Ni(II) 120 [10]
Peanut shell Cu(II) and 20 [17]
biosorbent dose. However, at the same dose the uptake Cr(III)
capacity of Cr(VI) decreased from 9.43 to 0.37 mg g−1 due to Cucumis melo Pb(II) 180 [9]
the increased metal-to-biosorbent ratio which decreased with Spirogyra and Pb(II), Cu(II) 30 [49]
Cladophora
increasing the biosorbent dose. filamentous
Similar trend of biomass effect was reported for the macroalgae
Green algae waste Pb(II), Cd(II), 180 [52]
biosorption of nickel by algal biomass of Oedogonium hatei biomass and Co(II),
[48], cadmium by Streptomyces lunalinharesii [70], copper Rhodococcus opacus Al(III) 5 [64]
and zinc by Streptomyces lunalinharesii [74],cadmium by
fungus Rhizopus cohnii [79], copper by cashew nut shell Pseudomonas Zn(II) 30 [62]
[106], cadmium by Lessonia kelps [111], lead and cadmium aeruginosa and
Bacillus cereus
by Chondracanthus chamissoi [112], etc. Punica granatum L. Pb(II) 50 [31]
According to Boschi et al. [111], the sorbent dosage peels
influences the density of reactive groups available for metal Castor leaf powder Pb(II) 30 [26]
binding and on the external surface area of the sorbent.
Red macroalgae Co(II), Cd(II), 60 [45]
Varying the sorbent dosage could thus influence the initial Cr(III) Pb(II)
slope of the curve (resistance to film diffusion) and the
equilibrium concentration. Additionally, it may affect the
ISSN:2278-5299 33
Biosorbent Metal ion

Equilibrium
Reference Elovich’s equation assumes that the actual solid surfaces are
time (min.)
Cladophora Se(IV) 60 [97]
energetically heterogeneous and that neither desorption nor
hutchinsiae biomass interactions between the adsorbed species could substantially
Citrus paradisi L. Cd(II) 30 [32] affect the kinetics of adsorption at low surface coverage [117].
biomass
Bacillus strains Pb(II) 80 [65]
Elovich’s equation is given as: qt = (1/b) ln (ab) + (1/b) ln (t);
where a (mg/g.min) is the initial sorption rate and b (g/mg) is
Chlamydomonas Cu(II), 100 [50] related to the extent of surface coverage and activation energy
reinhardtii algeal Pb(II)
cells
for chemisorption.
Waste biomaterial Pb(II) 80 [9] The criteria upon which the suitability of the model to fit the
of Cucumis melo experimental data is determined include both the correlation
Garden grass Cu(II) 400 [21] coefficient (R2) and the calculated qe value. When the model’s
Brown algae Ni(II) 120 [44]
R2 approaches unity and its qe calculated is equal to qe
experimental, then the model gives the best fit to the
Oil palm shell Cu(II), 480 [27] experimental data.
Pb(II)
Green bean husk Sb(III) 60 [4]
The kinetics of metal ions biosorption on various sorbents
Gooseberry fruit Cu(II) 60 [15] reported in many previous works mostly followed the pseudo-
waste second order kinetics. The applicability of the pseudo-second
Acacia Cu(II), 180 [22] order model to explain the kinetics of metal ions biosorption
leucocephala bark Cd(II) and suggests that the rate limiting step in adsorption of metal ions
powder Pb(II)
could be chemisorption involving valence forces through the
exchange of electrons between sorbent and sorbate,
complexation, coordination and/or chelation [109].
4. Biosorption Kinetics
The prediction of the biosorption rate gives important

Several researchers pointed out that the highest correlation
information for designing batch biosorption systems.
coefficients for the sorption data were obtained for the pseudo-
Information on the kinetics of pollutant uptake is required for
second-order model for the biosorption of metal ions onto
selecting optimum operating conditions for full-scale batch
various biomasses. Examples include: the biosorption of
process [97].The sorption kinetics is significant in the
Cu(II) by gooseberry fruit waste [15], Ni(II) by Moringa
treatment of wastewater, as it provides valuable insights into
oleifera bark [23], Ni(II) by brown algae [44], Cd(II) and
the reaction pathways and mechanisms of sorption reactions
Pb(II) by castor leaf [26], Cr(VI) by mango and neem sawdust
[48].
[5], Pb(II) by Punica granatum peels [31], Cu(II) and Cr(III)
Several kinetic models have been applied to fit the
by peanut shell biomass [17], As(III) by Maugeotia genuflexa
biosorption data of different metal ions onto various
algae biomass [3], Cd(II) by rice straw [16], Ni(II) by
biosorbents. These models include the pseudo-first order,
sugarcane bagasse [10], Cu(II) and Pb(II) by oil palm shell
pseudo-second order, Elovich, intraparticle diffusion, etc.
[27], Sb(III) by various plant residues [4], Cr(VI) by brown
The pseudo-first-order kinetic model (Lagergren model)
seaweed Sargassum muticum [54], Ni(II) by Saccharum
assumes that metal ion binds only to one sorption site on the
bengalense biomass [119], Cd(II), Pb(II) and Zn(II) by Agave
sorbent surface [115]. In Lagergren model, the rate of
salmiana bagasse [120], U(VI) by rice husk [121], Cu(II),
occupation of biosorption sites is proportional to the number
Zn(II) and Ni(II) by wheat straw [122], Ni(II) by Litchi
of unoccupied sites [115]. The model is represented by: ln
chinensis seeds [18], Co(II), Cu(II), Ni(II), Pb(II) and Zn(II)
(qe−qt) = ln qe−K1t [116].
by Trichoderma reesei [115], Zn(II) and Cd(II) by Undaria
Where K1 (min−1) is the pseudo first order adsorption rate pinnatifid [123].
coefficient, qe and qt are the values of amount adsorbed per According to Ho [124] an expression of second-order rate
unit mass at equilibrium and at any time t. The values of K1 based on solid capacity has been presented for the kinetics of
and the calculated qe can be obtained respectively from the adsorption of divalent metal ions onto peat biomass. The
slope and intercept of the linear plot of ln (qe−qt) versus (t). biomass contains polar functional groups such as aldehydes,
The second order kinetic model assumes that the rate- ketones, acids, and phenolics which can be involved in
limiting step is most likely to involve chemical interactions chemical bonding and are responsible for the cation exchange
leading to binding of the ions to the surface by bonding as capacity of peat. Thus as an example, the peat- copper
strong as covalent bonding [117].The pseudo-second-order biosorption reaction may be represented in two ways as: 2P-
equation [118] based on equilibrium adsorption is expressed +Cu2+↔ CuP2 and 2HP + Cu2+↔ CuP2 +2H+ , where P-
as: t/q= 1/ K2q2e + t /qe; where K2 (g/mg min.) is the rate and HP are polar sites on the peat surface.
constant of second-order adsorption. Plots of (t/qt) versus (t) Going deeply into the biosorption mechanism, many
give the values of 1/qe as the slope and 1/K2qe2 as the intercept. researchers studied the application of the intraparticle
diffusion model for their biosorption data. The overall rate of
ISSN:2278-5299 34
adsorption can be described by the following three steps: (1)

film or surface diffusion where the sorbate is transported from On the other hand, Hossain et al. [21] in their study for the
the bulk solution to the external surface of sorbent, (2) biosorption of copper onto garden grass observed two clear
intraparticle or pore diffusion, where sorbate molecules move steps visible in the plots of qt against t0.5 (Fig.5b). The first
into the interior of sorbent particles, and (3) adsorption on the stage may be attributed to the boundary layer diffusion effect,
interior sites of the sorbent [125]. while the second stage may be due to intra-particle diffusion
The Weber and Morris intraparticle diffusion model effects.
assumes three stages: external mass transfer and the stages of
intraparticle diffusion in larger and smaller pores till the
saturation of the surface [25]. The intraparticle diffusion
mechanism suggests proportionality between the adsoption
capacity and the square root of the time [126].
The model’s equation is expressed by: qt = K(i) t0.5 + Cb(i) ;
where qt is the adsorbed quantity of phenol, Ki is the
intraparticle diffusion parameter, and Cb(i) is the thickness of
the boundary layer at stage (i) [127].
The shape of the plots of qt against t0.5 gives much

information about the biosorption mechanism. These plots are
either presented by “one single line” or “multiple lines”. If the
Weber–Morris plot of qt versus t0.5 gives a straight line, then
the adsorption process is controlled by intraparticle diffusion
only [105]. If the regression of qt versus t0.5 is linear and
passes through the origin, then intraparticle diffusion is the
sole rate-limiting step [106]. However, if the data exhibit Fig. 5b: Plots of intra-particle diffusion kinetic model for the
multi-linear plots, then two or more steps influence the biosorption of copper by garden grass (Reference [21]).
adsorption–sorption processes [105]. The intercept of these
plots reflects also the boundary layer effect. Larger the
intercept, greater is the contribution of the surface sorption in Another qt against t0.5plot shape was reported by Ofomaja
the rate controlling step [106]. [128] for the biosorption of lead onto mansonia wood sawdust
where the plots showed three linear parts indicating the
When studying the mechanism of copper biosorption onto involvement of three steps in the biosorption process (Fig.5c).
cashew nut shell Senthilkumar et al. [106] obtained linear The first, sharper stage can be attributed to the diffusion of
plots at each of the tested concentrations (Fig.5a). These biosorbate through the solution to the external surface of the
authors also found that the obtained plots did not pass through biosorbent or the boundary layer diffusion of the biosorbate
the origin. This deviation from the origin was attributed to the molecules. The second stage describes the gradual biosorption,
difference in the rate of mass transfer in the initial and final where intraparticle diffusion is rate-limiting and the third stage
stages of the adsorption. This is indicative of some degree of is attributed to the final equilibrium for which the intraparticle
boundary layer control and this further showed that the diffusion starts to slow down due to extremely low biosorbate
intraparticle diffusion was not the only rate-limiting step, but concentration left in solution. The three stages in the plot
also be controlling the rate of sorption or all may be operating suggest that the biosorption process occurs by surface
simultaneously. biosorption and intraparticle diffusion (meso- and
micropores).
Fig. 5a: Intraparticle diffusion model for adsorption of

copper(II) ions onto cashew nut shell at 30 °C (Reference
[106])
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Fig. 5c: Intraparticle diffusion treatment of lead(II) onto unfavourable [114], The adsorption process as a function of
mansonia wood sawdust at various initial lead(II) RL may be described as: Unfavorable when RL > 1; Linear
concentrations. Biosorbent dose: 2 g dm−3; solution pH: 5.0; when RL = 1; Favorable when 0 < RL <1; Irreversible
agitation speed: 200 rpm; temperature: 299 K (Reference when RL = 0.
[128]).
This kind of multi-linearity in the shape of the intraparticle
diffusion plot was also observed for the biosorption of copper 5.2. Freundlich isotherm
ions onto sunflower hulls [25], the biosorption of Cu(II),
Cd(II) and Pb(II) by Phormidium sp.-dominated mat [108], The Freundlich isotherm model applies to adsorption on
Cd(II) biosorption by native grapefruit biomass [32], the heterogeneous surfaces with the interaction between adsorbed
biosorption of Cu(II), Cd(II) and Pb(II) onto Acacia molecules, and the application of the Freundlich equation also
leucocephala bark powder [22], etc. suggests that sorption energy exponentially decreases on
completion of the sorption centers of an adsorbent [28]. The
empirical Freundlich equation [131] based on sorption on a
5. Biosorption equilibrium isotherms heterogeneous surface is given as: log Q = log Kf + (1/n) log
Ce; where (Kf) and (n) are the Freundlich constants
The equilibrium relationships between adsorbent and characteristic of the system and are indicators of adsorption
adsorbate are best explained by sorption isotherms [129]. The capacity and adsorption intensity, respectively [114].
biosorption isotherms describe the relationship between the The Freundlich equilibrium constants are usually
mass of the adsorbed component per biosorbent mass and the determined from the plots of log Qeq versus log Ceq. The n
concentration of this component in the solution. Determination value indicates the degree of nonlinearity between solution
of equilibrium parameters provides important information that concentration and adsorption as follows: if n = 1, then
allows for future design of adsorption systems [17]. adsorption is linear; if n < 1, then adsorption is a chemical
Biosorption isotherms are characterized by definite process; if n >1, then adsorption is a physical process [28].
parameters, which express the surface properties and affinity
of the biosorbent and can also be used to compare the
biosorptive capacities of the biosorbent for different pollutants 5.3.Temkin isotherm
[52] and [97].
Several equilibrium isotherm models were employed The Temkin isotherm model [121, 132] suggests an equal
to fit the biosorption experimental data in order to study the distribution of binding energies over a number of exchange
nature of adsorption process. These include two parameters sites on the surface. The linear form of the Temkin isotherm
isotherms such as the Langmuir, Freundlich, Temkin,
can be written as [132]: qe= B ln A + B ln Ce; where B is
Dubinin-Radushkevich and three parameters isotherms such as
the Sips and Redlich–Peterson. equal to RT/b with R being the universal gas constant
(8.314 J mol−1 K−1) and T being the absolute temperature in
Kelvin. A is the equilibrium binding constant and B
5.1.Langmuir isotherm corresponds to the heat of sorption.
The Langmuir isotherm model assumes a surface with

homogeneous binding sites, equivalent sorption energies, and 5.4.Dubinin-Radushkevich (D-R) isotherm
no interaction between sorbed species [48]. In this model once
a site is filled, no further sorption can take place at that site. The D–R isotherm model is a semi-empirical
As such, the surface will eventually reach a saturation point equation where adsorption follows a pore filling mechanism. It
where the maximum adsorption of the surface will be achieved assumes that the adsorption has a multilayer character,
[28]. The Langmuir equation developed by Irving Langmuir in involves van der Waals forces and is applicable for physical
1916 [130] is represented by: Ceq / Qeq = 1 /b Qmax + adsorption processes [125, 133]. The linear form of D–R
Ceq / Qmax; where Qmax (mg/g) is the maximum amount of isotherm model is expressed as: ln qe=ln qd−âå2,where qd is the
metal ion per unit weight of biosorbent to form a complete D–R constant (mg g−1), â is the constant related to free energy
monolayer on the surface bound at high Ceq, and b (l/ mg) is and ɛ is the Polanyi potential which is defined as: å = RT
the Langmuir constant related to the energy of adsorption. The ln[1+1/Ce] noting that the universal gas constant
Qmax and b can be determined from the linear plot of Ceq/ Qeq (8.314 J mol−1 K−1) and T being the absolute temperature in
versus Ceq [114]. Kelvin..
The essential characteristic of the Langmuir isotherm may 5.5.Sips isotherm

be expressed in terms of dimensionless separation parameter
RL =1/ (1 + b C0), which is indicative of the isotherm shape Sips [64,134] proposed an empirical isotherm equation, also
that predicts whether an adsorption system is favourable or kwon as Langmuir–Freundlich isotherm, which is often
ISSN:2278-5299 36
expressed as: qe=KsCens / 1+aSCenS, where KS is the Sips measurements and the data were found to fit well with the
constant (Lmg−1), aS is the affinity coefficient (Lmg−1) and ns Langmuir model [68].
is the heterogeneity coefficient. At low sorbate concentrations The experimental data for the biosorption of Ni(II) ions
it effectively reduces to a Freundlich isotherm and thus does onto sugarcane bagasse turned out good fits with Langmuir
not obey Henry’s law. At high sorbate concentrations, it isotherm (R2 > 0.99). Therefore a chemisorption controlled
predicts a monolayer adsorption capacity characteristic of the mechanism can be postulated as the mechanism governing the
Langmuir isotherm. biosorption process [10]. The Langmuir model fitted the
equilibrium data for palladium(Pd(II)) and platinum (Pt(IV))
biosorption onto Indian almond leaf biomass (Terminalia
5.6. Redlich–Peterson isotherm catappa L.) better than the Freundlich isotherm [34].
The three parameters R-P isotherm incorporate three

parameters and can be applied either in homogenous or The applicability of Langmuir model in the study of [20] for
heterogeneous systems [135,136]. The linear form of this fitting the experimental data of the simultaneous biosorption
isotherm is presented by: ln [(ACe/qe) -1] = g ln(Ce)+ln(B), of Co2+, Cu2+, Ni2+, Pb2+ and Zn2+ ions onto Trichoderma
where A, B and g (0 < g < 1) are the three isotherm constants. reesei showed that the biosorption follows this model.
For a high concentration, the isotherm equation reduces to the The experimental data obtained for the biosorption of
Freundlich isotherm. In the case that g= 1, it will reduce to the copper(II), zinc(II), cadmium(II) and lead(II) from aqueous
Langmuir equation. solutions by dead Avena fatua biomass were best described by
When reviewing the applicability of the different isotherms the Langmuir model [29]. Langmuir model exhibited the best
to fit the metal ions biosorption data, we have found that there fit to experimental data of nickel biosorption by Litchi
is no general or even almost general trend. While some chinensis seeds [18].The Langmuir sorption isotherm model
authors agreed for the better use of Langmuir model in correlated best with the U(IV) biosorption equilibrium data
describing metal ions biosorption [5, 49, 68, 97] other authors using rice husk for the 10–100 mg/ L concentration range
disagreed with this and found that the Freundlich model was [121].
the best [27, 30, 53]. Sometimes it was also noticed that some The suitability of the Langmuir model for fitting the
researchers suggested the applicability of more than one biosorption data of metal ions in the was attributed according
isotherm model [21, 119]. From the articles published to Meena et al. [138] attributed to three main causes: (i) the
between 2010 and 2013 we summarized the different trends formation of monolayer coverage on the surface of biosorbent
reported by the researchers examining the isothermal with minimal interaction among molecules of substrate, (ii)
modeling of their biosorption data. immobile and localized adsorption, and (iii) all sites having
equal adsorption energies.
Tuzen and Sarý, [97] found that the coefficient of In contrary to those researchers that have proposed the good
determination (R2) for the biosorption of selenium using green fit of the Langmuir model to the biosorption data of metal ions
algae (Cladophora hutchinsiae) was 0.9956 indicating that the onto various biomasses, other researchers reported the
biosorption of the selenium ions onto C. hutchinsiae biomass Freundlich isotherm to best fit their biosorption data.
fitted well the Langmuir model. These authors stated that in Pang et al. [81] found that the adsorption process of
other words, the sorption of selenium using C. hutchinsiae was uranium onto non-living biomass of Penicillium citrinum
taken place at the functional groups/binding sites on the could be well defined by both the Langmuir and Freundlich
surface of the biomass which is regarded as monolayer isotherms, however, Freundlich isotherm displayed a better
biosorption. Biosorption isotherm data of chromium onto fitting model than Langmuir isotherm. Chong et al., [27]
mango and neem sawdust at various initial metal found that the adsorption of Cu(II) and Pb(II) ions by oil palm
concentrations were in good agreement with the Langmuir shell showed a slightly better fit with the Freundlich compared
isotherm [5]. The Langmuir model fitted well the biosorption to Langmuir. The Freundlich isotherm also had the best fit for
of lead and copper ions onto the green algae species, cadmium biosorption using citrus peels [139]; cadmium and
Spirogyra and Cladophora [49]. The biosorption of Cu2+,Cd2+ nickel biosorption onto grapefruit peel [30]; Cd(II) and Pb(II)
and Pb2+ on Caulerpa lentillifera biomass correlated well with biosorption onto the biomass of the blue green alga Anabaena
the Langmuir isotherm (R2>0.99) [137]. sphaerica [53].
In the work of Bulgariu and Bulgariu, [52], the Langmuir Other authors confirmed the more adequacy of the three
model best-fitted the equilibrium data for the biosorption of parameters isotherms to explain their biosorption data.
Pb(II), Cd(II), and Co(II)) on green algae waste biomass. Hossain et al. [21] found that both the SIP and Redlich–
These authors also found that the maximum biosorption Peterson isotherms better fitted with the experimental data of
capacity, which is a measure of the adsorption capacity to copper (II) removal by garden grass than the Langmuir and
form a monolayer, increase in the order: Pb(II) > Cd(II) > Freundlich models. The sorption data of lead on Aspergillus
Co(II). Cobalt and cadmium biosorption performance by versicolor biomass were found to be best fitted to the Redlich–
freeze-dried cells of R. leguminosarum bv. viciae STDF- Peterson model indicating that the adsorption mechanism is a
Egypt19 biomass was estimated using biosorption equilibrium hybrid one and does not follow the ideal monolayer adsorption
ISSN:2278-5299 37
behavior [80]. The equilibrium sorption data for the removal industrial effluents of electroplating. The results revealed that
of Ni(II) ions by Saccharum bengalense plant biomass were single metal removal efficiencies by the fungal biomass were
better fitted to Langmuir and Sips isotherm model than any 46.01, 59.22, 9.1 and 9.4% for Cu(II), Ni(II), Zn(II) and
other model [119].The Sip’s isotherm (Langmuir-Freundlich Cr(VI), respectively.
model) provided the closest fit to the equilibrium experimental
data of cadmium biosorption using Acidiphilium symbioticum Bairagi et al. [80] determined the efficiency of Aspergillus
indicating that both physical and chemical sorption takes place versicolor biomass to remove lead from an actual system
simultaneously [140]. Sips isotherm was most accurately fitted using effluent from battery industries located in Northern
to the equilibrium data of the biosorption of Cr(III) and Cu(II) region of Kolkata, India. The percentage removal of lead from
by using soybean meal waste [141]. The best fit of this industrial effluent was 86% after adjusting the solution pH to
combined isotherm model confirms that metal biosorption 5.
continues beyond the first layer, there is a significant vertical
interaction between the biosorbent and metal ions, resulting in The efficacy of sugarcane bagasse for the removal of
overlapping multi-layer biosorption [142]. chromium from tannery wastewater was evaluated by Ullah et
al. [100]. In this respect, wastewater sample was obtained
from a local tanning plant (Kasur, Pakistan). At the optimum
6. Application of biosorption for real wastewater conditions pre-determined during the batch biosorption
treatment: case studies studies; the maximum chromium removal from wastewater
was 73%. Natural adsorbents including rice straw, rice husk,
Several authors attempted to apply their pilot biosorption rice bran and water hyacinth roots were tested for their
experimental results to real wastewater samples in order to capability of removing copper ions from electroplating
move from the experiment to the application in real world. We wastewater collected from Kolkata, west India. Under
are summarizing the wastewater sampling protocols as well as optimum batch conditions the results indicated that all
some case studies describing the successful application of biosorbents were effective in reducing the Cu(II) ions
biosorption process to treat polluted water. concentration with hyacinth roots being the most suitable
[143].
In order to demonstrate the practical application of the
biosorption process, Vinodhini et al. [5] performed column Conclusions
experiment using neem sawdust to treat raw tannery
wastewater sample collected from a common effluent In the present work we aimed to highlight the
treatment plant in India. The results showed that a dose of 20 g “biosorption” process through the review of the recently
biosorbent was sufficient to achieve 99% chromium removal published studies concerning the use of natural biomasses for
from wastewater volume of 1.5 L. metal ions removal from aqueous solutions:
 Waste biomasses from agricultural, fungal, bacterial
In order to determine the effectiveness of gooseberry fruit and algal origins could be developed onto costly effective and
(emblica officinalis) biomass to remove copper ions from real environmental friendly biosorbents for metal ions removal
wastewater; Rao and Ikram [15] collected electroplating from aqueous solutions.
wastewater from a local electroplating plant in Aligarh city. The biomass materials were proven to contain many
The results showed that 65% removal of Cu(II) could be “effective” functional groups that positively contribute to the
achieved in batch mode and 97.6% in column process. metal ions biosorption process.
 Several experimental operating parameters have been
Ay et al. [31] evaluated the potential performance of the found to influence the biosorption process including the
biomass of Punica granatum L. peels for the removal of lead solution pH, contact time, biosorbent dose and metal ion
(II) ions from real wastewater samples collected from metal concentration.
processing factories in Turkey. The removal lead (II) ions at  The pH of the solution was proven to be one of the
the optimum experimental conditions obtained during the most important factors affecting metal ions biosorption. The
batch experiment was found to be 98.07%. solution pH affects metal ion solubility as well as biosorbent
total charge. The removal of metal ions is almost negligible at
Effluent samples were collected from El-Fayoum-Egypt for
highly acidic pH values and increases by increasing the
chemical production company to evaluate the efficiency of
solution pH up to a certain limit.
four algal biomasses to remove metal ions from wastewater
[45]. The efficiencies of C. mediterranea, G. oblongata, J.  It has been generally found that the biosorption
rubens, and P. capillacea biomasses to remove metal ions capacity increases as the initial metal ion concentration in the
ranged from 57% to 94% at a biomass dosage 10 g/L, pH 5 solution increases and on the other hand it is reduced when the
biomass dosage increases.
and contact time 60 min.
 The kinetics of metal ions biosorption usually was
Javaid et al. [76] studied the potential use of Pleurotus found to be best described by the “pseudo-second order”
ostreatus biomass for the removal of heavy metals from real
ISSN:2278-5299 38
model suggesting that the rate limiting step in adsorption of updated on June 2013.
Available from: http://water.epa.gov/drink/contaminants/index.cfm
metal ions could be chemisorption.
 The intraparticle diffusion mechanism was generally [15] Rao RAK, Ikram S. Sorption studies of Cu(II) on gooseberry fruit
(emblica officinalis) and its removal from electroplating wastewater.
accepted to describe the mechanism of metal ions biosorption. Desalination 2011;277:390–8.
 The isothermal models including the Langmuir, [16] Ding Y, Jing D, Gong H, Zhou L, Yang X. Biosorption of aquatic
Freundlich, Temkin, Sips, R-D and others have been widely cadmium(II) by unmodified rice straw. Bioresour Technol
employed for modeling the biosorption process. 2012;114:20–5.
 Several case studies have been reported for [17] Witek-Krowiak A, Szafran RG, Modelski S. Biosorption of heavy
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Urbina E. Biosorption of Ni(II) from aqueous solutions by Litchi
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[19] Kelly-Vargas K, Cerro-Lopez M, Reyna-Tellez S, Bandala ER,
Sanchez-Salas JL. Biosorption of heavy metals in polluted water,
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International Journal of Latest Research in Science and Technology ISSN (Online):2278-5299

Volume 3, Issue 1: Page No.24-42 ,January-February 2014

BIOSORPTION FOR METAL IONS REMOVAL

In many countries, more strict legislations have been

Fig. 2a: Effect of pH on Cd(II) biosorption capacity using

Luo et al. [79] attributed that to the biosorption capacities of

As a rule, increasing the initial metal concentration

The removal efficiency of the ions by the biosorbent

of different initial ions concentrations on the biosorption of

3.3. Effect of biomass dosage

Biomass provides binding sites for the sorption of metal

3.4. Effect of contact time

The equilibrium time for metal ions biosorption onto

Biosorbent Metal ion

The prediction of the biosorption rate gives important

adsorption can be described by the following three steps: (1)

The shape of the plots of qt against t0.5 gives much

Fig. 5a: Intraparticle diffusion model for adsorption of

The Langmuir isotherm model assumes a surface with

The essential characteristic of the Langmuir isotherm may 5.5.Sips isotherm

The three parameters R-P isotherm incorporate three

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