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The Past, Present, and Future Trends of Biosorption

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DOI: 10.1007/s12257-009-0199-4

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Biotechnology and Bioprocess Engineering 2010, 15: 86-102
DOI/10.1007/s12257-009-0199-4

The Past, Present, and Future Trends

of Biosorption
=
Donghee Park1, Yeoung-Sang Yun2, and Jong Moon Park3*
1
Department of Environmental Engineering, Kyungpook National University, Daegu 702-701, Korea
2
Environmental Biotechnology National Research Lab, School of Chemical Engineering,
Research Institute of Industrial Technology, Chonbuk National University, Jeonju 561-756, Korea
3
Advanced Environmental Biotechnology Research Center, Department of Chemical Engineering,
School of Environmental Science and Engineering, Pohang University of Science and Technology, Pohang 790-784, Korea=

Abstract The discovery and further development of biosorption phenomena provide a basis for a whole new technology aimed
at the removal of various pollutants or the recovery of valuable resources from aqueous systems. Today, biosorption
is one of the main components of environmental and bioresource technology. Since the status of scientific develop-
ment of a technology can be reflected through analyses of the literatures pertaining to it, in this review, we qualita-
tively examine almost all aspects of biosorption research. A range of subjects are covered, including the initial history,
raw materials, mechanisms, instrumental tools, process factors, modification and immobilization methods, recovery
and regeneration, continuous processes, commercial application, and modeling studies of biosorption. Finally, we
summarized the important considerations of the current research on biosorption, as well as the suggestions for its fu-
ture directions. We believe that this review will prove to be useful for scientists and engineers in the performance of
their research into biosorption. © KSBB

hÉóïçêÇëW=~ÇëçêÄÉåíI=ÄáçëçêÄÉåíI=ÄáçëçêéíáçåI=ÜÉ~îó=ãÉí~äëI=ÇóÉëI=éêÉÅáçìë=ãÉí~äë=
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INTRODUCTION wastes, such as ash, or natural inorganic materials like clay,
synthetic materials like zeolite, as well as, living or nonliving
Rapid industrialization and urbanization have resulted in biomass/biomaterials, have been investigated as cheap ad-
the generation of large quantities of aqueous effluents, many sorbents capable of replacing the well-known, but more ex-
of which contain high levels of toxic pollutants [1,2]. Vari- pressive ones [8-15]. Considering their cost and efficiency,
ous physicochemical and biological processes are usually biomass-based adsorbents or biosorbents as they are com-
employed to remove pollutants from industrial wastewaters monly called, are the most attractive alternatives to ion-
before discharge into the environment [3]. In the case of exchange resins and activated carbons [2].
treatment of adsorptive pollutants like heavy metals and The use of biosorbents for the removal of toxic pollutants
ionic dyes, however, most of the conventional treatment or for the recovery of valuable resources from aqueous
processes, especially chemical precipitation or coagulation, wastewaters, is one of the most recent developments in envi-
become less effective and more expensive when the adsor- ronmental or bioresource technology [2,7,16,17]. The major
bates are in a low concentration range [5-7]. Although ion- advantages of this technology over conventional ones in-
exchange resins and activated carbons have long been rec- clude not only its low cost, but also its high efficiency, the
ognized as effective commercial adsorbents for treating in- minimization of chemical or biological sludges, the ability to
dustrial wastewaters containing adsorptive pollutants, their regenerate biosorbents, and the possibility of metal recovery
high cost and low efficiency have limited their commercial following adsorption [7].
use in actual industrial scenarios [2]. Although biosorption of heavy metals or dyes has become
Since any type of solid material has the capacity to adsorb a popular environmentally driven research topic, it represents
pollutants to some degree, a number of industrial inorganic only one particular application of the sorption process. In his
recent review paper, Bohumil Volesky, a pioneer in the field,
*Corresponding author defined ‘biosorption’ as the property of certain biomolecules
Tel: +82-54-279-2275 Fax: +82-54-279-2699 (or types of biomass) to bind and concentrate selected ions or
e-mail: [email protected] other molecules from aqueous solutions [7]. As opposed to a
 Biotechnol. Bioprocess Eng. 87=

much more complex phenomenon of bioaccumulation based biosorption technology for monitoring trace heavy metals in
on active metabolic transport, biosorption by dead biomass the environment [29]. Neufeld and Hermann (1975) studied
(or by some molecules and/or their active groups) is passive the kinetics of biosorption by activated sludge and reported
and occurs primarily due to the ‘affinity’ between the bio- rapid uptakes of Cd, Hg, and Zn in the first few min, fol-
sorbent and adsorbate [7]. lowed by a slow uptake over the next 3 h [30]. Friedmann
Since Hecker first reported a quantitative study on the and Dugan (1968) used a pure culture of Zoogloea for a
copper uptake by fungal spores of Trilletia tritici and Usti- metal-binding study [31]. Extensive screening of microor-
lago crameri in 1902 [18,19], over 3,000 research articles on ganisms for metal uptake had been carried out by A. Naka-
biosorption have been published in various journals in many jima and his coworkers (1978), who reported that the ability
countries. In addition, about 70 review papers and some of microorganisms to accumulate uranium ions was in the
books have appeared that deal with biosorption phenomena, order of: actinomycetes > bacteria > yeast > fungi [32,33].
equilibrium and kinetic modeling, reactor operation, and Gould and Genetelli (1984) examined the competition be-
application to real industries [20-22]. However, for general tween metal ions for binding sites of anaerobic sludge, and
readers, access to these special books or perusal of the large reported a binding affinity order of: Cu > Cd > Zn > Ni [34].
number of papers available on this topic is challenging. Y. Chiu and his coworkers (1976) analyzed biological sorp-
The aim of this review, therefore, is to summarize and en- tion of uranium on mycelia of Penicillium C-1 [35], while M.
capsulate the past and present trends in biosorption research, Tsezos and B. Volesky (1981) focused on biosorptive re-
by examining the primary subjects pertaining to biosorption moval of uranium and thorium by dead fungal biomass of
research. Finally, we discuss future directions of biosorption, Rhizopus arrhizus [36]. Steen and Karickhoff (1981) re-
as mentioned by specialists in this area, and presented our ported uptake of hydrophobic organic pollutants by mixed
own opinions on the prospects of this research area. microbial populations [37].
At this point, it should be noted that there was some con-
fusion prevalent in the literature regarding the use of terms
FUNDAMENTAL REVIEW ‘bioaccumulation’ and ‘biosorption’, based on the state of
the biomass used in this research at the time [2]. The early
The Initial History of Biosorption studies prior to 1980 have been reviewed in detail by Mura-
leedharan et al. [19]. As pioneers in this area, B. Volesky
Although the ability of living microorganisms to take up and M. Tsezos also provide their viewpoints on the initial
metals from aqueous solution was investigated as early as history of biosorption research in their special review papers
18th and 19th centuries [23], it is only during the last 3 dec- [7,38].
ades that living or non-living microorganisms have been
used as adsorbents for removal and recovery of materials Types of Biomass or Biomaterials
from aqueous solutions. The earliest technological applica-
tions of biosorption techniques involved sewage and waste Adsorptive pollutants like metals and dyes can be removed
treatment [24]. It was also investigated for use in renovating by living microorganisms, but can also be removed by dead
wastewater generated by the chemical industry [25]. The biological material [39]. Feasibility studies for large-scale
first patent for a biosorption apparatus used for biological applications have demonstrated that biosorptive processes
treatment of wastewater was registered by the Ames Crosta using non-living biomass are in fact more applicable than the
Mills & Company Ltd. in 1973 [26]. Scientists in life sci- bioaccumulative processes that use living microorganisms,
ences primarily focused on the toxicological effects and ac- since the latter require a nutrient supply and complicated
cumulation of heavy metals in microorganisms, while envi- bioreactor systems [2]. In addition, maintenance of a healthy
ronmental scientists and engineers used this capability of microbial population is difficult due to toxicity of the pollut-
microorganisms as a means of monitoring heavy metal pol- ants being extracted, and other unsuitable environmental
lution, as well as, for removal/recovery of metals from factors like temperature and pH of the solution being treated.
metal-bearing wastewaters [19]. Recovery of valuable metals is also limited in living cells
Some review papers have reported that the first quantita- since these may be bound intracellularly. For these reasons,
tive study on metal biosorption was done by L. Hecke, who attention has been focused on the use of non-living biomass
reported on the copper uptake by fungal spores of T. tritici as biosorbents [2,23].
and U. crameri in 1902 [18,19]. Similar studies were also As mentioned above, dead biomass has advantages over
reported by F. Pichler and A. Wobler in 1922, in which up- living microorganisms. However, many attributes of living
take of Ag, Cu, Ce, and Hg by corn smut were evaluated microorganisms remain unexploited in an industrial context
[19]. Ruchloft first reported that activated sludge efficiently and are all worthy of further attention since they may be of
removed even radioactive metals like plutonium-239 from use for specific applications [39,40]. A. Malik mentioned
contaminated domestic wastewater in 1949 [27], and the first that, when pure biosorptive metal removal is not feasible,
patent on the use of biosorption technology for removing application of a judicious consortium of growing metal-
uranium or thorium ions from aqueous suspension/solution resistant cells can ensure better removal through a combina-
was granted to B. Volesky and M. Tsezos in 1982 [28]. tion of bioprecipitation, biosorption, and continuous uptake
Goodman and Roberts (1971) reported the practical use of of metals after physical adsorption [40]. This type of ap-
88

proach may lead to simultaneous removal of toxic metals, Table 1. Types of native biomass that have been used for pre-
organic pollutants, and other inorganic impurities [40]. To paring biosorbents
control the size of the current review, however, we have Category Examples
chosen to focus on single biosorption processes in this re-
view and to avoid discussion of hybrid processes combined Bacteria Gram-positive bacteria (_~Åáääìë sp., `çêóåÉÄ~ÅíÉJ
with biosorption. êáìã sp., ÉíÅK), gram-negative bacteria EbëJ
The first major challenge faced by biosorption researchers ÅÜÉêáÅÜá~ sp., mëÉìÇçãçå~ë sp., ÉíÅK), cyanobac-
was to select the most promising types of biomass from an teria (^å~Ä~Éå~ sp., póåÉÅÜçÅóëíáë sp., ÉíÅK)
extremely large pool of readily available and inexpensive Fungi Molds (^ëéÉêÖáääìë sp., oÜáòçéìë sp., ÉíÅK), mush-
biomaterials [41]. When choosing biomass, for large-scale rooms (^Ö~êáÅìë sp., qêáÅÜ~éíìã sp., ÉíÅK), and
industrial uses, the main factor to be taken into account is its yeast (p~ÅÅÜ~êçãóÅÉë sp., `~åÇáÇ~ sp., ÉíÅ.)
availability and cheapness [6,42,43]. Considering these fac-
Algae Micro-algae (`äçêÉää~ sp., `Üä~ãóÇçãçå~ë sp.,
tors, native biomass can come from (i) industrial wastes,
ÉíÅK), macro-algae (green seaweed (båíÉêçãçêJ
which should be available free of charge; (ii) organisms eas-
éÜ~ sp., `çÇáìã sp., ÉíÅK), brown seaweed (p~êJ
ily obtainable in large amounts in nature; and (iii) organisms
Ö~ëëìã sp., bÅâäçåá~ sp., ÉíÅK), and red seaweed
that can be grown quickly or specially cultivated or propa-
(dÉáäÇáìã sp., mçêéÜóê~=sp., ÉíÅK))
gated for biosorption purposes [6,43]. A broad range of bio-
mass types have been tested for their biosorptive capacities Industrial Fermentation wastes, food/beverage wastes, acti-
under various conditions at this point in time, but there are wastes vated sludges, anaerobic sludges, ÉíÅK
no limits to exploration of new biomass types having low Agricultural Fruit/vegetable wastes, rice straws, wheat bran,
cost and high efficiency. Biosorptive capacities of various wastes soybean hulls, ÉíÅK
biomass types have been quantitatively compared in many Natural residues Plant residues, sawdust, tree barks, weeds, ÉíÅK
review papers [2,16,43-56]. In some cases, the uptake of
Others Chitosan-driven materials, cellulose-driven materi-
heavy metals by biomass reached as high as 50% of its dry
als, ÉíÅK
weight [6,42].
Biosorbents primarily fall into the following categories:
bacteria, fungi, algae, industrial wastes, agricultural wastes,
natural residues, and other biomaterials (Table 1). Since it is [67]. Wang and Chen compared biosorptive capacities of a
impossible to quantitatively compare the hundreds of biosor- given amount of biomass from Saccharomyces cerevisiae,
bents reported thus far in the literature, we instead introduce according to species of heavy metals [68]. It should be noted
useful review papers that have done these types of compari- that the biosorptive capacity of a certain type of biosorbent
sons of biosorptive capacities of various biosorbents for depends on its pretreatment methods, as well as, on experi-
various pollutants as part of their aims and scope. For exam- mental conditions like pH and temperature. When comparing
ple, extensive comparisons of biosorptive capacities of vari- biosorptive capacities of biosorbents for a target pollutant,
ous types of bacterial biosorbents have been done by Malik therefore, the experimental data of each researcher should be
[40], Veglio and Beolchini [53], Vijayaraghavan and Yun carefully considered in light of these factors.
[2], and Volesky and Holan [43]. Mehta and Gaur compared After choosing a form of cheap and abundant biomass, the
biosorptive capacities of algae for heavy metals [51]. Wilde biosorbent capability for removing a target pollutant can be
and Benemann summarized biosorptive capacities of micro- derived through simple chemical and/or physical method(s).
algae [55], while Romera et al. summarized those of macro- Although simple cutting and/or grinding of dried biomass
algae (i.e., seaweed) [56]. In the case of fungi, Sağ compre- may yield stable biosorbent particles, some types of biomass
hensively summarized biosorptive capacities of fungi and have to be either immobilized in a synthetic polymer matrix
fungal cellular components like chitin and chitosan [52]. and/or grafted onto an inorganic support material like silica
Varma et al. [57] and Gerente et al. [58] also summarized to yield particles with the required mechanical properties
the biosorptive capacities of chitin/chitosan and its many [41]. New biosorbents can be manipulated for better effi-
derivatives. Some researchers briefly compared the biosorp- ciency and for multiple reuses to increase their economic
tive capacities of agricultural wastes for heavy metals [59- attractiveness, compared with conventional adsorbents like
63]. The utilization of plant-derived biomass as adsorbents ion-exchange resins or activated carbons [6]. Fig. 1 shows
was also reviewed in the literature [44,54]. Crini reviewed alternative process pathways to produce biosorbent materials
the use of polysaccharide-based materials as adsorbents [5], that are effective and durable in repeated long-term applica-
while O’Connell et al. reviewed cellulose-based adsorbents tions, which was suggested by Vieira and Volesky [6].
[64]. Some researchers have extensively compared various
biosorbents for specific heavy metals such as cadmium [48], Mechanisms of Pollutants Removal by Biosorbents
copper [65], or uranium [66]. Mack et al. reviewed the use
of biosorbents for recovery of precious metals like gold, As shown in Table 1, there are many types of biosorbents
platinum, and palladium [49]. Andrès et al. reviewed micro- derived from various forms of raw biomass, including bacte-
bial biosorbents as a means of concentrating rare earth ele- ria, fungi, yeasts, and algae. The complex structure of raw
ments like europium, lanthanum, scandium, and ytterbium biomass implies that there are many ways, by which these
 Biotechnol. Bioprocess Eng. 89=

Fig. 2. Biosorption mechanisms as classified by Veglio and

Beolchini [53]. (A) Classified according to the depend-
ence on the cellular metabolism. (B) Classified according
to the location where biosorption occurs.

Fig. 1. Schematic diagram for processing different types of na-

tive biomass into biosorbents. This diagram was modified Instrumentation for Biosorption Research
from that suggested by Vieira and Volesky [6].
Information on the active sites involved in the binding of
pollutants can be obtained through use of a number of so-
biosorbents remove various pollutants, but these are not yet phisticated analytical tools, including infrared absorption
fully understood. For example, the structure and functional spectroscopy or Fourier transformed infrared spectroscopy
aspects of extracellular polymeric substances (EPS) of mi- (IR or FTIR), scanning electron microscopy (SEM), trans-
croorganisms are related with their roles in metal biosorption mission electron microscopy (TEM), energy dispersive X-
[69]. Thus, there are many chemical/functional groups that ray spectroscopy (EDS), X-ray diffraction (XRD) analysis,
can attract and sequester pollutants, depending on the choice electron spin resonance spectroscopy (ESR), nuclear mag-
of biosorbent. These can consist of amide, amine, carbonyl, netic resonance (NMR), X-ray photoelectron spectroscopy
carboxyl, hydroxyl, imine, imidazole, sulfonate, sulfhydryl, (XPS), X-ray absorption spectroscopy (XAS), thermogra-
thioether, phenolic, phosphate, and phosphodiester groups vimetric analysis (TGA), and differential scanning calo-
[6,62,70]. However, the presence of some functional groups rimetry (DSC), among others [46,57,68]. Table 2 shows a
does not guarantee successful biosorption of pollutants, as brief summary of the analytical techniques available in bio-
steric, conformational, or other barriers may also be present sorption research.
[42]. The importance of any given group for biosorption of a Many of these analytical techniques require costly equip-
certain pollutant by a certain biomass depends on various ment and are very expensive to carry out as routine meas-
factors, including the number of reactive sites in the biosor- urements. In addition, the type of information that they yield
bent, accessibility of the sites, chemical state of the sites (i.e. may not always be what is necessary for understanding and
availability), and affinity between the sites and the particular evaluating the biosorption phenomenon of interest [7]. How-
pollutant of interest (i.e. binding strength) [6]. ever, different techniques can often provide distinctive, but
The understanding of the mechanisms by which biosor- complementary, information on biosorption of a target pol-
bents remove pollutants is very important for the develop- lutant; thus, combining different techniques can optimize the
ment of biosorption processes for the concentration, removal, exploration of biosorption mechanisms [68].
and recovery of the pollutants from aqueous solutions [19].
When the chemical or physiological reactions occurring dur- Process Factors Influencing Biosorption
ing biosorption are known, the rate, quantity, and specificity
of the pollutant uptake can be manipulated through the speci- For the industrial application of biosorption technology
fication and control of process parameters. Biosorption of for pollutant removal, it is very important to investigate the
metals or dyes occurs mainly through interactions such as removal efficiency of a given biosorbent for the target pol-
ion exchange, complexation, adsorption by physical forces, lutant. Pollutant uptake can involve different types of bio-
precipitation and entrapment in inner spaces [62]. Fig. 2 sorption processes that will be affected by various physical
shows biosorption mechanisms classified by Veglio and and chemical factors, and these factors will determine the
Beolchini according to their metabolic dependency or the overall biosorption performance of a given biosorbent, (i.e.
site of biosorption [53]. its uptake rate, its specificity for the target, and the quantity
of target removed). For this reason, the first step of almost all
research has been to examine the individual and/or coopera-
90

Table 2. Analytical techniques used in biosorption research Table 3. Effects of batch processing factors on biosorptive re-
moval of adsorptive pollutants, such as metals or dyes
Analytical techniques Remarks
Atomic absorption Determine metal concentration in Process factors Effects on biosorption of pollutants
spectroscopy (AAS) aqueous phase Solution pH ↑ It enhances biosorptive removal of cationic
Inductively coupled plasma Determine metal concentration in metals or basic dyes, but reduces that of ani-
(ICP) aqueous phase onic metals or acidic dyes.
Temperature ↑ It usually enhances biosorptive removal of
UV-Vis spectrophotometer Determine metal or dye concen-
adsorptive pollutant by increasing surface
tration in aqueous phase by
activity and kinetic energy of the adsorbate,
measuring its color intensity
but may damage physical structure of biosor-
Scanning electron microscope Visual confirmation of surface bent.
(SEM) morphology of the biosorbent
Ionic strength ↑ It reduces biosorptive removal of adsorptive
Transmission electron Visual confirmation of inner morpho- pollutant by competing with the adsorbate for
microscope (TEM) logy of biomass, especially cells binding sites of biosorbent.
Energy dispersive X-ray Element analysis and chemical Initial pollutant conc. ↑ It increases the quantity of biosorbed pollutant
spectroscopy (EDS) characterization of metal bound on per unit weight of biosorbent, but decreases
the biosorbent its removal efficiency.
Crystallographic structure and Biosorbent dosage ↑ It decreases the quantity of biosorbed pollut-
X-ray diffraction (XRD)
chemical composition of metal ant per unit weight of biosorbent, but in-
analysis
bound on the biosorbent creases its removal efficiency.
Electron spin resonance Determine active sites of the Biosorbent size ↓ It is favorable for batch process due to higher
spectroscopy (ESR) biosorbent surface area of the biosorbent, but not for
Nuclear magnetic resonance Determine active sites of the column process due to its low mechanical
(NMR) biosorbent strength and clogging of the column.
Agitation speed ↑ It enhances biosorptive removal rate of ad-
Fourier transformed infrared Determine active sites of the
sorptive pollutant by minimizing its mass
spectroscopy (FT-IR) biosorbent
transfer resistance, but may damage physical
Potentiometric titration Determine active sites of the structure of biosorbent.
biosorbent and its amounts
Other pollutant conc. ↑ If coexisting pollutant competes with a target
X-ray photoelectron Determine oxidation state of metal pollutant for binding sites or forms any com-
spectroscopy (XPS) bound on the biosorbent and its plex with it, higher concentration of other pol-
ligand effects lutant(s) will reduce biosorptive removal of
X-ray absorption spectroscopy Determine oxidation state of metal the target pollutant.
(XAS) bound on biosorbent and its
coordination environment
Thermogravimetric analysis Characterize thermal stability of the or basic dyes is enhanced, while that of anionic metals or
(TGA) biosorbent acidic dyes is reduced. In some cases, a higher pH will cause
precipitation of cationic metals, making neutral conditions
Differential scanning Characterize thermal stability of the
essential in this case. Temperature seems to affect biosorp-
calorimetry (DSC) biosorbent
tion to a lesser extent within the range from 20 to 35oC [53].
Biosorptive removal of most adsorptive pollutants is endo-
thermic, thus higher temperature usually enhances biosorp-
tive effect(s) of various factors on biosorption [23,46,48,51, tive removal of the adsorbate through increases in its surface
71,72]. activity and kinetic energy [2]. However, higher temperature
In the case of batch biosorption processes for removing can also cause physical damage to the biosorbent; thus, room
adsorptive pollutants such as ionic metals or dyes, the impor- temperature is usually desirable for the biosorption processes.
tant factors include solution pH, temperature, ionic strength, Unlike controlled laboratory conditions, industrial efflu-
initial pollutant concentration, biosorbent dosage, biosorbent ents contain various pollutants including the target, one of
size, agitation speed, and also the coexistence of other pol- interest. Thus there is need for investigation of the inhibitory
lutants. Of these factors, the pH appears to be the most im- effects of ionic strength and competing ions. These factors
portant regulator of the biosorptive process. The pH affects influence biosorptive removal of a target pollutant by com-
the solution chemistry of the pollutants themselves, the ac- peting with the adsorbate for binding sites, by changing its
tivity of functional groups in the biosorbents, and the compe- activity, or by forming complexes with it [2]. The effects of
tition with coexisting ions in solution [2]. In general, as solu- other process factors on the biosorptive removal of adsorp-
tion pH increases, the biosorptive removal of cationic metals tive pollutants are briefly summarized in Table 3.
 Biotechnol. Bioprocess Eng. 91=

Table 4. Modification methods for converting raw biomass into better biosorbents
Category Detailed methods
Physical modification Autoclaving, steam, thermal drying, lyophilization, cutting, grinding, ÉíÅK
Chemical modification Pretreatment Acids (HCl, H2SO4, HNO3, H3PO4, citric acid, ÉíÅK), Alkalis (NaOH, KOH, NH4OH, Ca(OH)2, ÉíÅK),
(washing) Organic solvents (methanol, ethanol, acetone, toluene, formaldehyde, epichlorohydrin, salicylic
acid, NTA, EDTA, SDS, L-cysteine, Triton X-100, ÉíÅK), and Other chemicals (NaCl, CaCl2, ZnCl2,
Na2CO3, NaHCO3, K2CO3, (NH4)2SO4, H2O2, NH4CH3COO, ÉíÅK)
Enhancement of Amination of hydroxyl group, carboxylation of hydroxyl group, phosphorylation of hydroxyl group,
binding groups carboxylation of amine group, amination of carboxyl group, saponification of ester group, sulfona-
tion, xanthanation, thiolation, halogenation, oxidation, ÉíÅK
Elimination of Decarboxylation/elimination of carboxyl group, deamination/elimination of amine group, ÉíÅK=
inhibiting groups
Graft polymerization High energy radiation grafting (using γ-irradiation, microwave radiation, electro-magnetic radiation,
ÉíÅK); Photochemical grafting (with/without sensitizers like benzoin ethyl ether, acrylated azo dye
and aromatic ketones under UV light); and Chemical initiation grafting (using ceric ion, perman-
ganate ion, ferrous ammonium nitrate/H2O2, KMnO4/citric acid, ÉíÅK)
Cell modification Culture optimization Optimization of culture conditions for enhancing biosorptive capacity of cells
(during growth) Genetic engineering Over-expression of cysteine-rich peptides (glutathione, phytochelatins, metallothioneins, ÉíÅK); and
Expression of hybrid proteins on the surface of cells

Modification of Biomass for Better Biosorbency groups that inhibit biosorption of a target pollutant; thus,
chemical elimination of the inhibiting groups will produce a
As the biosorption process primarily occurs on the surface better biosorbent [2]. Another efficient way to introduce
of the biomass, its surface modification can greatly alter its binding groups onto the surface of a biosorbent is the graft-
biosorptive capacity and function [2,54,70]. A number of ing of long polymer chains onto the surface of raw biomass,
chemical, physical, and other modification methods have via direct grafting or through polymerization of monomers,
been employed for this objective in the literature. In some such as acrylic acid, acrylamide, acrylonitrile, ethylenedia-
cases, a target chemical group present in a form of biomass mine, hydroxylamine, glycidyl monomers, and urea [64].
will be chemically modified to characterize the biosorption According to the methodology for creating active sites (free
mechanism connected with that group. A good example of radical or ionic chemical groups) for initiating polymeriza-
this would be the physical and/or chemical activation of raw tion reactions, there are 3 types of typical initiation methods
biomass for conversion into chars or activated carbons that have been used, including high energy radiation, and
[73,74], but further detail is beyond the aims and scope of photochemical and chemical initiation grafting (Table 4). In
this review. fact, since many researchers in this area (i.e. graft copoly-
Table 4 shows a number of modification methods that can merization) have preferred to use terms ‘adsorption’ and
be found in the literature for preparing better biosorbents. ‘adsorbent’ instead of ‘biosorption’ and ‘biosorbent’, infor-
Normally, physical modification is very simple and inexpen- mation regarding these types of modification has been
sive, but is generally less effective than chemical modifica- missed by researchers who search for the latter terms. Exten-
tion. Among various chemical modification methods, chemi- sive and detailed information concerning graft copolymeri-
cal pretreatment (washing) has been preferred due to its sim- zation has been presented in a recent review by O’Connell et
plicity and efficiency [2]. In many cases, acid-washing can al. [64].
enhance the capacity of biosorbents for cationic metals or Lastly, in the cases that utilize microbial biomass, the bio-
basic dyes, through extraction of soluble organic or inor- sorptive capacity can be enhanced by optimizing culture
ganic components from raw biomass and/or by changing its conditions or by using genetic engineering techniques at
biochemistry. However, some chemicals can cause serious some stage of cultivation. Genetic modification would be
mass losses of the biosorbent (i.e. structural damage), as well feasible especially when genetically-engineered microorgan-
as a drop in the biosorptive capacity. ism have been used in a fermentation process [2].
Vast improvements in the biosorptive capacity of a bio- In summary, excellent biosorbents can be prepared from
sorbent can be obtained through enhancement or modifica- various raw biomass forms using the above-mentioned tech-
tion of its functional groups [2,54]. Amine, carboxyl, hy- niques. However, modifications increase the commercial
droxyl, sulfonate, thiol, and phosphonate groups are known cost of the biosorbents, bringing these closer to the price
binding sites for metals or dyes; thus, these groups can be range of man-made ion-exchange resins. It should not be
newly formed, or their amounts increased, to enhance bio- forgotten that the major advantage of biosorbents is their low
sorptive capacity [54]. Raw biomass may also have certain cost relative to commercial adsorbents like ion-exchange
92

Table 5. Immobilization methods of biomass for use in process specific stages of its cultivation [50,53]. If living cells are
application directly used for a biosorption process, these can be easily
Category Detailed methods
immobilized within the process, in situ, and other pollutants
may be removed simultaneously [39,76]. Small particles or
Cell immobilization Immobilization of living cells on inert supports powders of biomass can be easily immobilized within vari-
(on inert support (sand, glass bead, paper or textile-making ous polymeric matrixes [50,53]. This entrapment method has
material) fibers, polymers, activated carbon, ÉíÅK) in a some benefits, including the control of particle size, high
stage of cultivation; fåJëáíì immobilization of biomass loading, minimal clogging, and easy liquid separa-
living biosorbents on inert supports within bio- tion and regeneration of the biosorbent [2]. Among various
sorption process reactors polymeric matrixes, alginate gel and polyacrylamide gel
Entrapment (within Alginate, polyacrylamide, polyethylenine, poly- have been the most extensively used in laboratory studies,
polymeric matrix) sulfone, polyurethane, polyhydroxyethylmetha- owing to their simple and rapid experimental protocols for
acrylate, ÉíÅK encapsulation [50,51,67]. Cross-linking techniques employ-
ing chemical linkers have been also used by many research-
Cross-linking (using Formaldehyde, glutaralhehyde, glutaric dialde-
ers and these have sometimes resulted in the favorable modi-
chemical linker) hyde, divinylsulfone, formaldehyde-urea mix-
fication of functionality of biosorbents [53,57,71].
tures, epichlorohydrin (EPI), ethylene glycol
Together with the cost of modifying raw biomass, the cost
diglycidiyl ether (EGDE), iminodiacetic acid,
of its immobilization (if required) is an important factor in
nitriloacetic acid, vinylketones, epoxides, or-
determining the overall cost of the commercial biosorbent
ganic diisocyanates, genipin, ÉíÅK
produced. Various strategies for reducing/minimizing these
steps have to be developed in order for these to be applied
successfully and economically in industrial applications.
resins or activated carbons.
The Biosorption Process
Immobilization of Biomass for Process Application
The application of biosorption in continuous processes has
Although some biosorbents have been shown to have received increasing attention from researchers because of its
greater adsorptive capacity than conventional ion-exchange potential industrial roles [67]. In fact, the decision of whether
resins, their uses in industrial applications are hinden by to use batch or continuous processes is a function of hydrau-
problems associated with the physical character of the bio- lic flow, physical characters of the biosorbent(s), the types of
sorbents [2,23,50]. Microbial biosorbents are particularly target pollutant(s), space availability, and invested capital. If
problematic as they are such small particles, with low den- the flow rate is low, a simple manual batch process is the
sity, poor mechanical strength, and little rigidity. When used most economical [77]. Many different types of process con-
in column processes, difficulty in solid-liquid separation, figurations, such as stirred tank reactors, up-flow or down-
possible biomass swelling, clogging, poor regeneration/reuse, flow packed bed reactors, fluidized bed reactors, rotating
and development of high pressure drop all can occur [2,53]. contactors, trickle filters and air-lift reactors, have been pro-
Fortunately, however, many of these problems can be over- posed and investigated for their industrial practicality
come by use of immobilization techniques [50,53,67,71,75]. [40,75,77]. Most of these have been used in applications that
In addition, the immobilization procedure converts the bio- employ living microorganisms for removal of metal con-
mass into a spherical shape, allowing it to be used like con- taminants from complex industrial wastewaters [40,78].
ventional adsorbents. Sizes ranges from 0.5 to 1.5 mm, with Among the continuous biosorption reactors, the down-flow
a good external porosity, and chemical and physical resis- packed bed reactor should theoretically be the most cost ef-
tance, can generally be achieved for commercial adsorbent fective system, due to its complete dependence upon gravita-
particles [67]. Immobilization of biomass is required for its tional forces to transfer the water body through the bed.
use in conventional reactor technology in larger systems, However, it is less easy to control effluent retention times
especially in packed or fluidized bed reactors [75]. Of course, within this type of reactor [77]. Consequently, the up-flow
there are a few exceptions; such as when highly rigid and packed bed reactor, commonly called a column reactor, has
efficient biomass (e.g. seaweeds) is available, in which case been more extensively used in laboratory study, owing to its
a raw/unprocessed form may be used in a biosorption proc- high operational yield and the relative ease of scaling up
ess without any prior immobilization step [2]. The use of procedures to industrial capacities [2,7]. In fact, column bio-
flotation for separation of metal-loaded biomass from aque- sorption reactor is a simple and reproducible method, and is
ous suspensions may also overcome the need for immobili- commonly used to assess the pollutant removal perform-
zation [76]. ances of a biosorbent operating in a continuous mode. B.
Various techniques have been used for the immobilization Volesky and his coworkers have long studied this type of
of biomass (Table 5), and in general can be divided into 3 biosorption reactor and detailed information has been de-
categories; cell immobilization on inert supports, entrapment scribed several times in their papers [7,41,43,79].
within a polymeric matrix, and cross-linking. Microbial Stirred tank reactors may be operated in combination with
biomass can be immobilized on various inert supports at a membrane system for liquid-solid separation. Fluidized
 Biotechnol. Bioprocess Eng. 93=

Table 6. Desorption methods for regeneration of biosorbenets Table 7. Published patents related to biosorption
and recovery of metals or dyes Pub.
Title of the invention Pub. Num.
Category Detailed methods Date

Physical microwaving, heating, ÉíÅK Apparatus for the biological treatment of GB1324358 1973.07
waste water by the biosorption process
Non- Acids (HCl, H2SO4, HNO3, H3PO4, acetic acid,
Separation of uranium by biosorption UP4320093 1982.03
destructive Chemical ÉíÅK); Alkalis (NaOH, NH4OH, ÉíÅK); Organic sol-
vents (methanol, ethanol, acetone, ÉíÅK) Others Process for the separation of metals from UP4701261 1987.10
(CaCl2, KSCN, Na2CO3, KHCO3, EDTA, ÉíÅK) aqueous media

incineration, dissolution into strong acids or Removal of contaminants UP4732681 1988.03

Destructive Biosorbent for gold UP4769223 1988.09
alkalis, ÉíÅK
Metal recovery UP4898827 1990.02
Recovery of heavy and precious metals from WO9007468 1990.07
bed reactors have low mass transfer limitation relative to aqueous solutions
packed bed reactors. However, these reactors have been very Removal of metal ions with immobilized metal UP5055402 1991.10
rarely used for the purpose of biosorption using dead bio- ion-binding microorganisms
mass. To achieve simple liquid-solid separation, some hybrid Process and apparatus for removing heavy metals EP0475542 1992.03
processes have been suggested in the literature. K. A. Matis from aqueous media by means of a bioadsorber
and A. I. Zouboulis have studied the ‘biosorptive flotation’
Ionic binding of microbial biomass WO9413782 1994.06
process since 1993 [80,81]. Most recently, a biosorption
process using bio-functional magnetic beads has been pro- Polyaminosaccharide phosphate biosorbent GB2306493 1997.05
posed by a few researchers [82]. Method for production of adsorption material UP5648313 1997.07
Biosorption system WO9826851 1998.06
Recovery and Regeneration Biosorbent for heavy metals prepared from biomass UP5789204 1998.08
Bacteria expressing metallothionein gene into UP5824512 1998.10
One of the important industrial applications of biosorption
the periplasmic space, and method of using
is recovery of loaded pollutants (especially valuable metals)
such bacteria in environment cleanup
from the biosorbent and simultaneous regeneration of the
biosorbent for reuse. In fact, the usefulness of a specific Biosorption agents for metal ions and method WO9848933 1998.11
biomass as a biosorbent depends not only on its biosorptive for the production thereof
capacity, but also on the ease of its regeneration and reuse Hydrophilic urethane binder immobilizing US5976847 1999.11
[45]. However, most researchers have tended to focus only organisms having active sites for binding
on the biosorptive capacity of biosorbent tested, without noxious materials
consideration of the regeneration required for industrial ap-
Process for producing chitosan-glucan complexes, US6333399 2001.12
plications [2].
compounds producible therefrom and their use
The adsorbate bound onto the surface of a biosorbent
through metabolism-independent biosorption may be easily Bioadsorption process for the removal of WO0242228 2002.05
desorbed by simple non-destructive physical/chemical meth- colour from textile effluent
ods using chemical eluants, but intracellularly bound adsor- Heavy metal adsorbent composition WO04022728 2004.03
bate through metabolism-dependent bioaccumulation can be A novel process for decolorization of colored WO06059348 2006.06
only released by destructive methods like incineration or effluents
dissolution into strong acids or alkalis [39,75]. If cheap bio-
Process for the removal of metals by biosorption US7326344 2008.02
mass is used as a biosorbent for recovering rare and/or valu-
from mining or industrial effluents
able metals, then destructive recovery would be economi-
cally feasible [50]. However, most attention to date has fo-
cused on non-destructive desorption from the loaded biosor-
bent [2,23]. For this reason, the choice between living or times heating or microwaving can aid desorption with an
dead biomass systems is important because of the implica- eluant or mixture solution [84]. As well, as previously men-
tion for later metal recovery [39]. As shown in Table 6, vari- tioned, the solution pH will have a strong influence on bio-
ous chemical eluants have been tested for desorption of tar- sorption of a target pollutant; thus, simple manipulation of
get materials from biosorbents. In many cases, dilute mineral the pH of the desorbing solution should theoretically be a
acids or alkalis allow efficient desorption from the biosor- good method for regeneration of the biosorbent and recovery
bent, but they also cause serious structural damage to the of the pollutant.
biosorbent itself, resulting in a drop in the biosorptive capac-
ity of the biosorbent following regeneration [2]. Organic Commercial Applications of Biosorption Technology
solvents such as ethanol can be also used for desorbing or-
ganic pollutants such as dyes from the biosorbent [83]. Some- As many specialists in this area have frequently mentioned,
94

Table 8. Commercialized biosorbents Table 9. Guiding questions to be considered for commercial

application of biosorption
Products Remarks
AlgaSORB
TM
Biosorbent manufactured from a fresh water alga, Category Remarks
`ÜäçêÉää~=îìäÖ~êáë, by being immobilized on silica Effluent Effluent volume, types of target pollutant and other con-
B.V. Sorbex Biosorbent manufactured from a variety of sources taminants, solution chemistry, pH, temperature, ÉíÅK
Biosorbent including the algae p~êÖ~ëëìã= å~í~åë, ^ëÅçéÜóäJ Biosorbent Availability, overall manufacturing cost, regenerability
äìã= åçÇçëìã, e~äáãÉÇ~= çéìåíá~, m~äãóê~= é~ã~J and reusability, pollutant specificity, biosorptive capacity
Ç~, `ÜçåÇêìë=ÅêáëéìëI and `K=îìäÖ~êáë and rate, mechanical stability, ÉíÅK
TM
AMT-Bioclaim Biosorbent manufactured from _~Åáääìë sp. by being Process Types of process, connection with other processes,
immobilized with polyethyleneimine and glutaral- operator’s skill, ÉíÅK
dehyde
Capital Land space, construction cost, operating cost, ÉíÅK
Bio-Fix Biosorbent manufactured from a variety of sources Others Disposal of exhausted biosorbent, recovery/reuse of
including algae by being immobilized in porous metals in eluants, ÉíÅK
polypropylene beads
RAHCO Biosorbent prepared from a variety of sources in-
Bio-Beads cluding peat moss by being immobilized within an mechanisms, analyzing experimental data, predicting an-
organic polymer swers to operational condition changes, and optimizing
processes. In the field of biosorption, many researchers have
developed/used various models for predicting/describing
biosorption is a potent alternative technique for treating in- batch equilibria, batch kinetics and reactor operational data.
dustrial wastewaters containing metals and/or dyes [2,7,16, Some useful review papers that focus on the modeling of
17]. The potential of biosorption is very great; for example, biosorption are available in the literature [2,16,58,71,85-87].
it may be used for the purification and recovery of rare pro-
teins, steroids, pharmaceuticals, and drugs that are valued in Modeling of Batch Equilibrium Isotherms
thousands of dollars per gram [7]. For this reason, many
biosorption processes are under development or have been The biosorption process involves a solid phase (sorbent)
developed and patented for commercial applications, as and a liquid phase (solvent, normally water) containing the
shown in Table 7. Pilot installations and a few commercial- dissolved species to be adsorbed (adsorbate). Quantification
scale units have been constructed in the USA and Canada of adsorbate-adsorbent interactions is fundamental for the
[38]. Through a pilot installation, M. Tsezos has confirmed evaluation of potential implementation strategies. To com-
the applicability of biosorption as the basis for sequestering pare pollutant uptake capacities of different types of biosor-
or removing pollutants (especially uranium), but also found bents, adsorption phenomena can be expressed as batch equi-
some limitations of this technique, i.e. difficulty in obtaining librium isotherm curves. These can be modeled by mecha-
a reliable supply of inexpensive raw biomass, difficulty in nistic or empirical equations; the former can explain, repre-
regeneration and reuse of the biomass, and negative effects sent, and predict the experimental behavior, while the latter
of co-existing ions on biosorptive capacity [38]. Although do not reflect the mechanism, but can reflect the experimen-
some biosorbents have been commercialized as adsorbents tal curves [2]. As shown in Table 10, empirical models in-
for removing/sequestering metals from aqueous solutions volving 2, 3, or even 4 parameters have been used to fit
(Table 8), to the best of our knowledge, no industrial facility batch equilibrium isotherm curves to biosorbents. Among
yet exists that uses these adsorbents at the present time. Thus, these, the Langmuir and Freundlich models have been most
biosorption is not yet a proven technology, given its market commonly used, with a high rate of success. There are no
history [2,38]. critical reasons to use more complex models if the two-
Recently, some researchers have highlighted questions parameter models can fit the experimental data reasonably
that should be considered when evaluating the feasibility of a well [87].
potential biosorbent for the removal of metals or dyes from Since many industrial wastewaters contain several com-
industrial effluents [1,7,38,77]. These include the effluent ponents to be bound onto the biosorbent, a very judicious use
characteristics, biosorbent characteristics, the biosorption is necessary for practical applications of effective multi-
process itself, and capital characteristics (Table 9). More component biosorption models [87]. Single component iso-
information regarding the R&D work in the field of biosorp- therm models have frequently been extended to the forma-
tion is available in a special volume published by B. Volesky, tion of multi-component ones (Table 10). Among these, in
owner of BV Sorbex, Inc. [7,22]. many cases, the extended Langmuir equation is found to fit
the experimental data reasonably well. To characterize the
competitive adsorption of biosorbents, a few researchers
BIOSORPTION MODELLING have successfully employed the Ideal Adsorbed Solution
(IAS) theory using only single-component isotherm parame-
Appropriate models are useful for understanding process ters [2].
 Biotechnol. Bioprocess Eng. 95=

Table 10. Equilibrium isotherm models Table 11. Thermodynamic equations and their parameters
System Expression Equation form Remarks (Crini and Badot, 2008)

Langmuir q bC Monolayer Expression Equation form Parameters

q= m e
[88] 1 + bCe sorption E Apparent activation
Freundlich Simple Arrhenius ln kabs = − a + ln ka
q = KCe1/ n RT energy
[89] expression
Temkin RT Considering ⎛q ⎞
q= ln(aCe ) ΔG = − RT ln ⎜ e ⎟
[90] b temperature Gibbs Free energy change
⎡ 2
⎤
⎝ Ce ⎠
Dubinnin- ⎪⎧ ⎛ 1 ⎞⎪⎫
Radush- q = qD exp ⎢−BD ⎨RT ln ⎜1+ ⎟⎬ ⎥ Considering
kevich [91] ⎢ ⎪
⎩ ⎝ Ce ⎠⎪⎭ ⎥ temperature ⎛q ⎞ ΔH ΔS Enthalpy change
⎣ ⎦ van’t Hoff ln ⎜ e ⎟ = − +
Langmuir- qmbC 1/ n C
⎝ e⎠ RT R Entropy change
Freundlich q =
e
1/ n Combination
[92] 1 + bC Clausius- − RT1T2
( ln C2 − ln C1 )
e
Approaches ΔH = Enthalpy change
Redlich- aCe clapeyron T2 − T2
Single q= Freundlich
Peterson
component [93] 1 + bCen at high con-
centration
aCen but also the solubility of the adsorbate molecules (especially
Sips [92] q= Complicated
1 + bCen in the case of dye biosoprtion) [71]. The adsorption charac-
Radke- arCen teristics of a material can be expressed in thermodynamic
Prausnitz q = Complicated parameters such as ΔG (Gibbs free energy change), ΔH (en-
[94] a + rCen −1
qmbCe thalpy change), and ΔS (entropy change). These parameters
Khan [95] q= Complicated can be calculated by using the thermodynamic equilibrium
(1 + bCe )n
coefficient obtained at different temperatures and concentra-
qm bCe
Toth [96] q= Complicated tions (Table 11), and their evaluation gives an insight into
{(1 + (bC ) } e
1/ n n
the possible mechanisms of adsorption [71]. At constant
Brunnauer q = qmBCe Multilayer
temperature and pressure, the ΔG value is the fundamental
(BET) [97] {
( Cs −Ce ) 1+ ( B −1)( Ce / Cs ) } sorption criterion of spontaneity. If this value is negative, then ad-
qmi bi Ci
sorption would take place, indicating the spontaneity of the
Langmuir qi = N reaction. By using the equilibrium constant obtained from
Competitive
[88] 1 + ∑ ( bi Ci ) the Langmuir model at each temperature, ΔG can be easily
i =1
1/ ni
calculated according to the Gibbs expression, while ΔH and
Langmuir- q = qmi bi Ci ΔS can be determined using the van’t Hoff plot (Table 11). It
Multi-
Freundlich i N
Competitive
component
[92] 1+ ∑(
bi Ci1/ ni ) is important to note that the ΔG can be estimated from the
i =1 equilibrium adsorption data under the assumption that the
Redlich- ai Ci adsorption of a molecule is reversible and that an equilib-
qi = N
Peterson
(
1 + ∑ bi Cini ) Competitive rium condition is established in the batch system [71]. In
[93]
i =1 addition, it should be also noted that, theoretically, the con-
centration of adsorbate used in the Langmuir isotherm equa-
tion must be expressed as its molar concentration [86,98].
Based on preliminary biomass characterization, with the However, in the literature of biosorption research, the volu-
formulation of a set of hypothesized reactions between the metric concentration of adsorbate has been commonly used
sorbent sites and solutes, some mechanistic models have in the Langmuir isotherm equation without any theoretical
been proposed and used to describe equilibrium data of consideration. This has eventually led to misapplication of
metal biosorption in a single, binary, or multi-component the Langmuir isotherm equation in calculating the ΔG in
system(s) [2]. These models revealed the complexity of bio- thermodynamic studies [98,99].
sorption phenomenon and also showed good agreement with
experimental data. Although mechanical modeling requires Modeling of Batch Kinetics
titration or other biomass characterization data, in addition to
the solution chemistry, this approach would be useful for the Batch kinetic modeling is necessary to describe the re-
understanding and isolation of the operating binding mecha- sponse of the biosorption system to changes caused by varia-
nisms, as well as the proper and true representation of ex- tions in the experimental conditions and the properties of
perimental sets [2]. biosorbents, as well as, the parametric sensitivity of the
model to process parameters [23,71,85,86]. The model re-
Thermodynamics Study sults can be affected by biosorbent size, initial pollutant con-
centration, the maximum uptake capacity of biosorbent,
An increase in temperature affects not only diffusion rate mass transfer coefficients, and solute diffusivity. Thus, kinet-
of adsorbate molecules from the solution to the adsorbent, ics studies give detailed information on adsorbate uptake
96

Table 12. Adsorption kinetic models for biosorption

Expression Equation form Remarks
Early applied sec-
Second-order rate 1 1 ond-order rate
= kt +
equation [85] Ct C0 equation in
solid/liquid system
Lagergren equation
(
[101] (Pseudo first- qt = qe 1 − e
− kt
) Based on adsorp-
tion capacity
order model)

Elovich equation ⎛ 2.3 ⎞ ⎛ 2.3 ⎞

q = ⎜ ⎟ log ( t + t0 ) − ⎜ ⎟ log t0 Chemisorption
[102] ⎝α ⎠ ⎝α ⎠
Webber-Morris
qt = kt1/ 2 + C Intra-diffusion
equation [100]
Fig. 3. Model selection criteria in sorption studies, suggested by
Ho equation [85] t 1 1 Gerente Éí=~äK [58].
= + t Based on adsorp-
(Pseudo second-
qt k2 qe2 qe tion capacity
order model)
General rate raw dλt Non-fixed reaction Modeling of a Continuous Biosorption Process
− = k λtn
equation [103] dt order
The model development of a continuous biosorption proc-
ess would be helpful for evaluating the biosorptive perform-
ance of an industrial-scale process, based on data from labo-
rates and on rate-controlling steps such as external mass ratory-scale experiments. Good models cannot only help in
transfer, intraparticle mass transfer, and biosorptive reac- analyzing and interpreting experimental data, but they also
tion(s) [23]. Intraparticle diffusion has often been shown to aid in predicting the response of the systems to changing
be an important factor in determining the attainment of equi- conditions [41]. Due to its simple/reproducible method and
librium in immobilized biosorbents [2]. To identify its in- the relative ease of scaling up the procedures, as mentioned
volvement, batch kinetic data is fitted to an intraparticle dif- before, an up-flow packed bed column reactor has been ex-
fusion plot, as suggested by Weber and Morris; i.e. qt = kt1/2 tensively used for laboratory study. Thus, almost all model-
[100]. If this plot passes through the origin, then intraparticle ing of continuous biosorption process have been done with
diffusion is the rate-determining step. Various intra- or extra- continuous operation of a column reactor [2]. The perform-
mass transfer models in sorption studies have been well ance of continuous column operation is described through
summarized in the literature [58]. However, it should be the concept of the breakthrough concentration curve of a
noted that the effects of transport phenomena and biosorp- target pollutant, which is typically S-shaped. Various pa-
tive reaction(s) are often experimentally inseparable [48]. rameters have been examined for its characterization, includ-
Over 25 models have been introduced in attempts to quan- ing the length of the sorption zone, uptake, removal effi-
titatively describe kinetic behavior during the adsorption ciency, and slope of the breakthrough curve [2]. Flow rate,
process, but each model has its own limitations [2]. Table 12 initial solute concentration, and the amount of biosorbent
shows representative kinetic models for a biosorptive reac- loaded also influence the biosorption performance of the
tion. Derivation of these equations as well as their physical column. Good biosorbents for the column reactor process are
meaning has been summarized in the literature [85,86]. In regarded as ones that show a delayed breakthrough, earlier
most cases, both pseudo-first- and second-order kinetic exhaustion, a shorted mass transfer zone, high uptake, steep
equations have been commonly employed in parallel, and breakthrough curve, and high removal efficiency [2,7].
one was often claimed to be better than the other, according The breakthrough curves of a column reactor could be
to marginal differences in the correlation coefficient [85]. In modeled using mathematical models or statistical approaches
general, the pseudo-second-order equation has been success- like neural networks, but the former have been preferred in
fully applied to the biosorption of metal ions, dyes, herbi- this field. Table 13 shows typical models that have been
cides, oils, and organic substances from aqueous solutions tested for a packed-bed biosorption column; i.e. the Bohart-
[86]. Due to the complexity of the biosorption mechanism, Adams, Thomas, Wolborska, Yoon-Nelson, Modified dose-
however, Y. Liu comments that, in theory, the order of a response, and Clark models. These models have primarily
biosorption process must be determined by the general rate originated from research on activated carbon sorption, ion
law equation, rather than preset-order kinetic equations exchange, or chromatographic applications [2,7].
[86,103]. He also comments that selection of a kinetic equa- As a matter of course, reliable prediction of the concentra-
tion should be based on the mechanism since a good curve tion-time profile or effluent breakthrough curve is required
fitting cannot guarantee the physical meaning of the equation for the successful design of a column biosorption process [7].
used. Fig. 3 shows model selection criteria in sorption stud- Among the column models, the Bohart-Adams and Thomas
ies, suggested by Gerente and his coworkers [58]. models have been found to fulfill this purpose and thus have
 Biotechnol. Bioprocess Eng. 97=

Table 13. Mathematical models for continuous biosorption proc- serious drawback for long-term applications in adsorption
esses processes, in particular, in dynamic systems using fixed-bed
Process Expression Equation form
columns [71]. The low thermal stability of biomass and its
degradation resulting from desorbing agents are other impor-
Reversible mass dC j dq tant criteria that need to be taken into account.
CSTR V = v0C j 0 − v0C j − j Vxi
transfer model [104] dt dt The cost of producing/cultivating microorganisms for the
sole purpose of transformation into biosorbents has been
Bohart-Adams model C ⎛ Z ⎞ shown to be too expensive. Furthermore, the continuous
= exp ⎜ kABC0t − kAB N 0 ⎟
[105] C0 ⎝ U0 ⎠ supply of biomass cannot be assured, which has a huge im-
pact on its successful application in an actual industrial set-
Thomas model C0 ⎛k ⎞
= 1 + exp ⎜ TH ( Q0 M − C0Veff ) ⎟ ting [2,38]. Quite a few researchers have been suggesting the
[106] C ⎝ F ⎠ use of their microbial biomass systems without adequately
⎛β C considering this point.
Wolborska model C β Z⎞
= exp ⎜ a 0 t − a ⎟ Some researchers have reported useless case studies intro-
[107] C0 ⎝ N0 U0 ⎠ ducing new microbial or waste biomass systems that have
Packed-
Yoon-Nelson model C exp ( kYN t − τ kYN ) very poor biosorptive capacity for heavy metals (even below
bed R. = 10 mg/g). Factors other than simply the availability and
[108] C0 1 + exp ( kYN t − τ kYN )
cheapness of biomass, especially the biosorptive capacity,
Modified dose-res- C 1 need to be considered when selection of biomass is made.
= 1− a
ponse model [109] C0 1 + (Veff / bmdr ) mdr
Batch Experiment
1/ n −1
⎛ ⎞
Clark model C ⎜
⎜
1
⎟
⎟
It is relatively simple and easy to obtain laboratory equi-
= librium biosorption data for a single adsorbate. Unfortu-
[110] C0 ⎜ ⎛ C0 n −1
⎞ ⎟
⎜⎜ 1 + ⎜ n −1 − 1⎟ exp ( rtbreak − rt ) ⎟⎟ nately, however, quite a few researchers err when obtaining
⎝ ⎝ Cbreak ⎠ ⎠
data points for equilibrium isotherms. A general experimen-
tal procedure for this has been kindly described in a review
paper [7], in which the importance of controlling environ-
been widely applied to determine the characteristic parame- mental parameters (especially pH) at the given value over
ters during the biosorption of a target pollutant [2,7]. Besides the entire period of contact time, until the sorption reaches its
the typical models, mechanistic models that take mass trans- equilibrium state, was stressed.
fer and/or diffusion into consideration have also been used to In studying biosorption behavior, we always have to avoid
describe the column biosorption process [52,87]. In particu- micro-precipitation phenomena and their contribution to the
lar, B. Volesky and his coworkers have developed a good uptake of metals, by maintaining the pH of the sorption
column model that can predict breakthrough curves of each process [7].
element even in a mixture system [7,41,87]. However, many Unfortunately, the effect of pH on the biosorption capacity
column modeling work needs to be done to allow industrial of a given biosorbent is not always presented in the literature.
scale applications of biosorption. It should not be forgotten that the neglect of a possible pH
effect may lead to serious deviation in experimental results
[16].
COMMENTS AND SUGGESTIONS Although the solution pH changes during the course of an
adsorption experiment, some researchers examine the pH
Many researchers have made valuable comments and/or effect only in terms of the initial pH of the aqueous solution
suggestions on biosorption in their review papers and/or in before adding biosorbent [111,112]. Except in special cases,
supplemental publications such as notes or letters. We have the solution pH should be constantly maintained at a given
summarized these comments and suggestions, and have value during the course of a biosorption experiment by using
added our own ideas regarding the current status of biosorp- acids/alkalis or buffer solutions.
tion research.
Modeling Work
Selection of Potential Biomass
G. McKay and his coworkers indicated common mistakes
The application of untreated plant wastes as adsorbents in equilibrium and kinetic modeling as follows [65]: many
can bring about a serious release of soluble organic com- researchers failed to test experimental equilibrium data using
pounds contained within the plant materials [54]. Thus, re- several models and did not determine the best-fit model by
searchers have to consider this point when screening raw error analysis or by postulating sorption mechanism(s). In
biomass for potential use in biosorption processes. addition, the application of more than one kinetic model is
Normally, biomass and biomass-driven biosorbents are extremely rare. They also indicated little information on the
biodegradable or decomposable. This property may be a characteristics of biosorbents tested, such as surface area,
98

pore size distribution, surface activity, particle size, hardness skills of authors, duplicated or repeated work already per-
or attrition rates, and influence of pH. These are the key fac- formed by other researchers have been published, occasion-
tors that need to be known in order to develop and design ally even in well-known journals. Some researchers have
industrial biosorption systems. written “Salami slice” papers of low scientific quality, look-
Due to the complexity of biosorption mechanism, Y. Liu ing at experimental batch data combined with a fully-
commented that, in theory, the order of the biosorption proc- researched adsorbate and a fully-researched biosorbent. Re-
ess must be determined by the general rate law equation, searchers should make an effort to publish more valuable
rather than the preset-order kinetic equations [86,103]. He and/or useful papers that make significant contributions to
also commented that selection of kinetic equation should be new knowledge in this area.
based on the mechanism, since a good curve fitting cannot
guarantee the physical meaning of the equation used.
Although, theoretically, the concentration of adsorbate FUTURE DIRECTION
used in the Langmuir isotherm equation must be expressed
as its molar concentration, the volumetric concentration of Biosorption is in its developmental stages and further im-
adsorbate has been commonly used in the biosorption re- provement in both performance and costs can be expected in
search literature [86,98]. This has eventually led to misappli- future. We have summarized future directions of biosorption
cation of the Langmuir isotherm equation in calculating the research, mentioned by other researchers in this area and also
ΔG in thermodynamic studies [98,99]. added our opinions.
We must continue fundamental research to better under-
Modification Studies for Better Biosorbent stand the mechanisms of biosorption and on what drives the
selectivity of biosorptive and bioaccumulatory processes
Although modification methods can cause mass loss of [38]. Various high techniques like XAS will be helpful in
raw biomass, many researchers have evaluated these meth- this area.
ods according to the biosorptive capacity of the modified More comprehensive or specific models for equilibria or
biosorbent, without consideration of its overall mass yield. kinetic studies should be developed that can simulate more
Together with the biosorptive capacities of raw biomass and complex biosorption systems, such as hybrid biosorption
the modified biosorbent, researchers also need to measure system [68].
the weights of the biomass before and after the modification Unlike laboratory solutions, industrial effluents contain
methods. various pollutants including those of interest. Thus, there is a
In order for raw biomass to have enhanced sorption capac- need to investigate the simultaneous removal of many coex-
ity, researchers may try to add the binding sites to and/or isting pollutants. It is desirable to develop general-purpose
remove some interfering sites from the raw biomass or bio- biosorbents that can remove a variety of pollutants. One such
material. Once the chemically modified biosorbents are ob- possibility would be the use of ‘combo’ biosorbents consist-
tained, researchers should verify if the biomass are success- ing more than one type of biomass [23]. Although ‘combo’
fully modified. For this, instrumental analyses such as FTIR, biosorbents would tend to further complicate characteriza-
XPS, and so on should be provided as evidences along with tion of these biosorption systems, it may represent a more
the experimental data indicating the enhanced uptake. realistic approach to the design of biosorbent systems [50].
Pretreatment of biomass increases the cost of biosorbents To date, there are no systematic or comparative studies
preparation. However, the enhanced sorption performance taking into account the physicochemical properties of the
may compensate for the cost of modification steps. Therfore, different kinds of pollutant dyes. A more detailed study ap-
cost aspects should be discussed with the effect of modifica- pears to be necessary to show how the chemical structure of
tion on the performace enhancement. a dye affects not only its adsorption capacitie, but also the
understanding of the adsorption phenomena involved for that
Process Study dye. Thus, more investigation should be focused on studying
the influence of the chemical structure of dyes on their bio-
Many researchers have proposed the suitability of bacte- sorption capacity [71].
rial biomass for industrial applications, based on batch ex- Although chemical pretreatment methods significantly
perimental results. However, a continuous mode of operation enhance biosorptive capacity and specificity of the biomass,
is preferred for most industrial applications. Thus, only care- these are not cost effective at large scale [5]. Further study is
ful and systematic investigation of biosorbent performance therefore required to drop the overall cost for pretreatments
in a column mode will ensure its applicability to real situa- or to develop new methods that are both cheap and effective.
tions [2]. The use of immobilized biomass, rather than native bio-
mass, has been recommended for large-scale application of
Paper Publication biosorption process. Immobilization techniques increase the
overall cost of biosorbents, and decrease their biosorptive
These days, a large number of manuscripts have been sub- rates and capacities. Thus, more attention needs to be paid to
mitted to peer-reviewed international journals. As a result of this point. In addition, more work needs to be done to under-
the excessive work of editorial reviewers, as well as writing stand the effect of various immobilization techniques on the
 Biotechnol. Bioprocess Eng. 99=

rate and equilibrium uptake of pollutant by immobilized second phase of the Brain Korea 21 Program in 2009 at
biomass. Kyungpook National University. This work was also sup-
Biosorption processes are still at the stage of laboratory- ported by the KOSEF through the AEBRC at POSTECH
scale study in spite of unquestionable progress. Thus, much and by the KOSEF NRL Program grant funded by the Korea
work in this area is necessary to demonstrate its possibilities government (MEST) (No. R0A-2008-000-20117-0).
on an industrial scale [71].
So far, biosorption research has mainly aimed for the re-
moval of pollutants such as heavy metals and organics. Received August 3, 2009; accepted September 12, 2009
However, precious metal resources are getting paid attention
because of their price increases and limited deposits. For the
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