Journal of Environmental Chemical Engineering 2 (2014) 239–259

Contents lists available at ScienceDirect

Journal of Environmental Chemical Engineering
journal homepage: www.elsevier.com/locate/jece

Biomass-derived biosorbents for metal ions sequestration: Adsorbent
modification and activation methods and adsorbent regeneration
Ravindra Kumar Gautam a, Ackmez Mudhoo b, Giusy Lofrano c, Mahesh Chandra Chattopadhyaya a,*
a

Environmental Chemistry Research Laboratory, Department of Chemistry, University of Allahabad, Allahabad 211 002, India
Department of Chemical and Environmental Engineering, Faculty of Engineering, University of Mauritius, Re´duit, Mauritius
c
Department of Environment, Salerno Province, 84132 Fisciano, SA, Italy
b

A R T I C L E I N F O

A B S T R A C T

Article history:
Received 29 October 2013
Accepted 20 December 2013

Heavy metals released from industrial activities pose a significant threat to the environment and public
health due to their reported toxicity even at trace levels. Although there are several available methods to
treat or remove heavy metals from water and wastewater, the research focuses on development of
technological solutions which sound environmental friendly and economically feasible, able to reduce
the costs and maximize the efficiency. In this framework, the biosorption process, which uses cheap and
non-pollutant materials, may be considered as an alternative, viable and promising, technology for
heavy metal and metalloid ions sequestration and ultimately removal technology in the waste water
treatment. However, there is as yet little data on full-scale applications for the design and testing of
adsorption units using single biosorbents and their combinations to sequester heavy metal ions from
multi-metal systems. Immediate research and development is hence earnestly required in this specific
direction to further make progress this blooming technology and widen its scope of application to real
situations needing heavy metal pollution remediation. This review provides a comprehensive appraisal
of the equilibrium modeling of a number of biosorption processes as well as the structural, chemical and
morphological modifications and activation of biosorbents. Further the relative merits of the methods
used to recover sequestered heavy metal ions and regenerate biosorbents through desorption routes and
their future applications are discussed.
ß 2013 Elsevier Ltd. All rights reserved.

Keywords:
Biosorbent
Metal ions
Sequestration
Surface modification
Desorption
Recovery

Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Modeling of equilibrium biosorption processes .
Equilibrium adsorption isotherms . . . . . .
Kinetic studies and models . . . . . . . . . . .
Pseudo-first-order models. . . . .
Pseudo-second-order model . . .
Thermodynamic analyses . . . . . . . . . . . . . . . . . .
Biomass and biosorption of metal ions. . . . . . . .
Agro biosorbents . . . . . . . . . . . . . . . . . . . .
Organometallic compounds biosorption .
Weed . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Medicinal herbs . . . . . . . . . . . . . . . . . . . .
Non-timber products . . . . . . . . . . . . . . . .
Modifications and activation of biosorbents. . . .
Modification techniques . . . . . . . . . . . . . .

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* Corresponding author. Tel.: +91 9307663844; fax: +91 532 2541786.
E-mail addresses: ravindragautam1987@gmail.com (R.K. Gautam), ackmezchem@yahoo.co.uk (A. Mudhoo), glofrano@unisa.it (G. Lofrano),
mcchattopadhyaya@gmail.com (M.C. Chattopadhyaya).
2213-3437/$ – see front matter ß 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.jece.2013.12.019

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R.K. Gautam et al. / Journal of Environmental Chemical Engineering 2 (2014) 239–259

240

Activation of adsorbents . . . . . . . . . . . . . . . . . . . . . . . . . . .
Activated carbon . . . . . . . . . . . . . . . . . . . . . . . . .
Activated seaweed. . . . . . . . . . . . . . . . . . . . . . . .
Activated sawdust . . . . . . . . . . . . . . . . . . . . . . . .
Activated bagasse . . . . . . . . . . . . . . . . . . . . . . . .
Activated carbon from agro-waste . . . . . . . . . . .
New activated biosorbents . . . . . . . . . . . . . . . . .
Recovery of metals, regeneration and desorption of biosorbents
Outlooks and discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Concluding notes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

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Introduction
Heavy metal contamination of aqueous media and industrial
effluents is one of the significant environmental problems due to
the toxic nature and accumulation of these metal ions in the
food chain, because they are non-biodegradable [1,2]. Although
several adverse health effects of heavy metals have been known
for a long time, exposure to heavy metals continues, and is even
increasing in some parts of the world, in particular in less
developed countries, though emissions have declined in most
developed countries over the last 100 years. For example,
mercury is still used in gold mining in many parts of Latin
America. Arsenic is still common in wood preservatives, and
tetraethyl lead remains a common additive to petrol, although
this use has decreased dramatically in the developed countries.
Heavy metal contamination exists in wastewater of many
industries such as metal plating, mining operations, surface
finishing industry, tanneries, paper and pulp industries, chloralkali, fertilizer and pesticide industry, radiator manufacturing,
smelting, energy and fuel production, aerospace and atomic
energy installation, alloy industries, electroplating and batteries
industries [3–11].
While many of the heavy metals are needed by biological
systems at the micronutrient level, higher concentrations are
known to produce a range of toxic effects. A high exposure to lead
(Pb) causes encephalopathy, cognitive impairment, behavioral
disturbances, kidney damage, anemia and toxicity to the reproductive system [12]. Chromium (Cr) is widely accepted to exert
toxic effects in its hexavalent form due to its strong oxidation
properties [13,14]. Human exposure to Cr(VI) compounds is
associated with a higher incidence of respiratory cancers [15,16].
After it reaches the blood stream, it damages the kidneys, causes
irritation and corrosion of skin, the liver and blood cells through
oxidation reactions [17]. Cadmium (Cd) has been established as a
very toxic heavy metal. Due to its acute toxicity, Cd has recently
joined lead and mercury in the most toxic ‘‘Big Three’’ category of

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255

heavy metals with the greatest potential hazard to humans and the
environment [18]. Symptoms of acute poisoning include headaches, nausea, vomiting, weakness, pulmonary edema and
diarrhea. A disease known as ‘‘Itai–Itai’’ in Japan is specifically
associated with cadmium poisoning, resulting in multiple fractures
arising from osteomalacia. High dose of copper (Cu) concentrations
can lead to weakness, lethargy, anorexia and damage to the
gastrointestinal tract [19]. Human exposure to highly nickel (Ni)
polluted environments can cause skin allergies, lung fibrosis, and
cancer of the respiratory tract [20,21]. The exact mechanisms of
nickel-induced carcinogenesis are not known and have been the
subject of various epidemiologic and experimental investigations.
Table 1 summarizes the anthropogenic sources of heavy metals in
the environment.
There are several methods for removing heavy metal ions from
aqueous solutions and mainly consist of physical, chemical and
biological techniques and technologies. Conventional methods for
removing toxic metal ions from aqueous solution have been
recommended, such as chemical precipitation [37], filtration [38],
ion exchange [39], electrochemical treatment [40], membrane
technologies [41], floatation [42,43], adsorption on activated
carbon [44,45], evaporation and photocatalysis [46–48,50].
Table 2 shows the treatment technologies for the removal of
heavy metals from wastewaters and related advantages and
disadvantages.
However, chemical precipitation and electrochemical treatment are ineffective, especially when metal ion concentrations in
aqueous solution are low, and also alongside these removal
techniques produce large quantity of sludge which require further
treatment [10]. Ion exchange, membrane technologies and
activated carbon adsorption process are extremely expensive
when treating large amount of industrial effluent and wastewater
containing heavy metal ions in low concentration, they cannot be
used at large industrial scale. Despite its extensive use in the water
and wastewater treatment technologies, activated carbon remains
an expensive material.

Table 1
Significant anthropogenic sources of heavy metal in the environment.
Industry

Metals

Pollution arising

References

Electroplating
Batteries
Paints and pigments
Landfill leachate
Electronics
Metalliferous mining
Fertilizers
Manures sewage sludge
Specialist alloys and steels
Paper and pulp

Cr, Ni, Zn, Cu
Pb, Sb, Zn, Cd, Ni, Hg
Pb, Cr, As, Ti, Ba, Zn
Zn, Cu, Cd, Pb, Ni, Cr, Hg
Pb, Cd, Hg, Pt, Au, Cr, As, Ni, Mn
Cd, Cu, Ni, Cr, Co, Zn, As
Cd, Cr, Mo, Pb, U, V, Zn
Zn, Cu, Ni, Pb, Cd, Cr, As, Hg
Pb, Mo, Ni, Cu, Cd, As, Te, U, Zn
Zn, Cu, Cd, Pb, Ni, Fe, Mn

Liquid effluents from plating processes
Waste battery fluid, contamination of soil and groundwater
Aqueous waste from manufacture, old paint deterioration and soil pollution
Landfill leachate, contamination of ground and surface water
Aqueous and solid metallic waste from manufacturing and recycling process
Acid mine drainage, tailings, slag heaps
Run-off, surface and groundwater contamination, plant bioaccumulation
Land spreading threat to ground and surface water
Manufacture, disposal and recycling of metals. Tailings and slag heaps
Wastewater effluents

[22,23]
[24]
[25]
[26,27]
[28]
[29,30]
[31,32]
[31,33]
[34,35]
[36]

Materials such as various bacteria. as well as on the particle size and magnetic properties.52] Ion exchange Coagulation–flocculation Flotation Membrane filtration Electrochemical treatment Magnetic separation and purification technique Adsorption Wide variety of target pollutants High capacity Fast kinetics Possibly selective depending on adsorbent Recently.K. With time.64]. Over the past decades. a lot of them have gone into operation and a great number of papers have been published in this field. Some empirical models for single solute systems are listed in Table 3. Equilibrium isotherm model equations such as Langmuir [61] and Freundlich [62] are used to describe experimental adsorption data in batch mode [63. The methodology of studying biosorption is based on an interdisciplinary approach to it. biosorption has become a promising technique for metal removal. whereby the phenomenon can be studied. Modeling of equilibrium biosorption processes Assessment of a solid–liquid sorption system is usually based on two types of investigations: equilibrium batch sorption tests and dynamic continuous-flow sorption studies. yeast. The mechanistic models are based on mechanism of metal ion biosorption. . / Journal of Environmental Chemical Engineering 2 (2014) 239–259 241 Table 2 Treatment technologies for the removal of heavy metals from wastewaters and associated advantages and disadvantages. In recent years. biosorption by dead biomass is passive and based mainly on the ‘‘affinity’’ between the sorbent and sorbate.58]. chemical engineers as well as by environmentalists.54] [55] [56] this review will help provide a better understanding and orientation in the important and interesting field of ‘‘biomass based activated biosorbents and biosorption of heavy metals’’. Technology Advantages Disadvantages References Chemical precipitation Process simplicity Not metal selective Inexpensive capital cost Metal selective Limited pH tolerance High regeneration Bacterial inactivation capability Good sludge settling and dewatering Characteristics Metal selective Low retention times Removal of small particles Low solid waste generation Low chemical consumption Small space requirement Possible to be metal selective No chemical required can be engineered to tolerate suspended solids Moderately metal selective Induced separation and purification of magnetically influenced contaminants Large amount of sludge containing metals Sludge disposal cost High maintenance costs High initial capital cost High maintenance cost [49] Chemical consumption Increased sludge volume generation [49] High initial capital cost High maintenance and operation costs [42] High initial capital cost High maintenance and operation costs Membrane fouling Limited flow-rates High initial capital cost Production of hydrogen (with some processes) Filtration process for flocs The collection of particles depends strongly on the creation of large magnetic field gradients. and has gradually become a keystone in environmental remediation. The Brunauer–Emmett– Teller (BET) model [70] describes the multi-layer adsorption at the biosorbent surface and assumes that the Langmuir isotherm applies to each layer. applying the biosorption technology in controlling and removing heavy metal pollution has been rewarded much attention. algae. Biosorption has been defined as the ‘property of certain biomolecules to bind and concentrate selected ions or other molecules from aqueous solutions’ [18]. chitin and chitosan have been used to prepare several types of biosorbents. As opposed to a much more complex phenomenon of bioaccumulation based on active metabolic transport. The Langmuir model (based on monolayer adsorption of solute) and the Freundlich model (developed for heterogeneous surfaces) are the most widely accepted and used in literatures [65–69]. Findings of studies on the development and potential use of different biosorbents have revealed the merits of biosorption as an effective technique for cleaning toxic metal ion-bearing effluents [60]. It is important to find best-fit isotherm to evaluate the efficacy of the prepared adsorbent to develop suitable industrial adsorption system designs. Langmuir adsorption isotherms are widely used to describe the relationship between the amount of adsorbate adsorbed on adsorbent and its equilibrium concentration in aqueous solution. We hope that [39] [53. examined and analyzed from different angles and perspectives – by chemists. and heavy metal and metalloid ions removal. Performance depends on type of adsorbent Physical or chemical activation to improve its sorption capacity [51. Gautam et al.R. Equilibrium adsorption isotherms Equilibrium isotherm models are usually classified into the empirical equations and the mechanistic models. fungi. Biosorption of heavy metal ions has become a popular environmentally driven research topic and it represents only one particular type of a concentration-removal aspect of the sorption process [10]. These materials however have a limited application in the removal of heavy metal ions because of their magnetic properties. which are able not only to represent but also to explain and predict the experimental behavior. Since environmental protection and stewardship is becoming an important global concern and urging one and all to develop greener remediation techniques and pollutant sequestration and/ or degradation routes. magnetic nanoparticles have been investigated for their potential to remove heavy metal ions from aqueous solutions [57. Polyrhodanine-coated g-Fe2O3 magnetic nanoparticles have been synthesized by one-step chemical oxidation polymerization and were applied to the process of removal of heavy metal ions from aqueous solution [59]. These models can provide information of metal uptake capacity and difference in metal uptake between various species. the demand of safe drinking water and need of economical methods for the elimination of heavy metals from wastewater has dictated research interest toward the production of low cost alternative bio-based adsorbents in preference to commercially available activated carbon. many new processes have been tested successfully.

[73] have studied the removal of Cr(VI) and Ni(II) from aqueous solution using bagasse and fly ash as low-cost potential adsorbents. Both simple basic models (Langmuir and Freundlich models) also do not incorporate the effects of any external variable environmental factors. whereas others can have more than two parameters Redlich–Paterson [79] and Sips isotherms [80]. first-order equation of Bhattacharya and Venkobachar. Freundlich and Bhattacharya and Venkobachar adsorption models. for the removal of aqueous cadmium and zinc from wastewater. i. These include pseudo-first and -second-order rate model.. temperature. as the system’s kinetics determines adsorbate residence time and the reactor dimensions [72]. Larger value of n (smaller value of 1/n) implies stronger interaction between biosorbent and heavy metal while 1/n equal to 1 indicates linear adsorption leading to identical adsorption energies for all sites [72].00 (mg g1).07 (mg g1). The Freundlich and Langmuir constants obtained at 40 8C for Cd(II) and Zn(II) were 5. The mechanistic conclusions from the good fit of the models alone should be avoided. although they are capable of describing many biosorption isotherms in most cases.and second-order kinetic models are the most well liked model to . ¼ VS  C e h K RP C e qe  Simple expression i  1 VS  ln C e Approaches Freundlich at high concentration Does not have Henry law and no saturation limit. Freundlich frequently describes the data better. It has been mentioned that the results from empirical models cannot be extrapolated and no predictive conclusions can be find out for biosorption of heavy metals from aqueous solutions operating under different environmental conditions [10]. these empirical models do not reflect any mechanisms of sorbate uptake and hardly have a meaningful physical interpretation for biosorption. This equation is one among the most widely used isotherms for the explanation of adsorption equilibrium.6% and 100%. In some cases the isotherm model such as Langmuir or Freundlich fails to describe the biosorption behavior of metal ions from aqueous solutions onto the biosorbent. At lower concentrations. In spite of this. Flory– Huggins [77]. In addition.43 (mg g1).04 (mg g1). Some other workers have given details about these models [60.75]. Adam–Bohart–Thomas relation. Predicting the rate of adsorption for a given system is among the most important factors in adsorption system design. The adsorption studies were carried out both in single. monolayer adsorption [71. pH of solution. more than one model have been applied to illustrate the biosorption mechanism. not applicable over wide range of concentration No special advantages Rao et al. and 6.1 N CH3COOH before its application. Several models initially developed for gas phase adsorption can be implemented to correlate heavy metals biosorption processes [74. and Dubinin–Raduskevich equations [78]. Isotherm Functional form Langmuir qe ¼ qm K L C e 1þK L C e Freundlich qe ¼ K F Ce ln qe ¼ ln K F þ 1n ln C e ln qe = VS  ln Ce Temkin qe ¼ RT lnðK T C e Þ b qe ¼ RT ln K T þ RT ln C e b b qeVS  ln Ce Redlich– Peterson (R–P) qe ¼ 1=n K RP C e b 1þaRP Ce Linear form Plot Advantages Disadvantages Ce qe Ce qe Has Henry law and finite saturation limit so valid over a wide range of concentration Simple expression and has parameter for surface heterogeneity Based on monolayer assumption ln 1 K L qm ¼ h K RP C e qe þ  1 qm Ce i  1 ¼ ln aRP þ b ln C e ln Langmuir equation relates the coverage of molecules on a solid surface to concentration of a medium above the solid surface at a fixed temperature. As previously noted that various factors govern the adsorption capacity. Equilibrium isotherms had been used to obtain the thermodynamic parameters and the obtained result showed that the adsorption was endothermic in nature.K. The Freundlich isotherm is an empirical equation. Langmuir isotherms are based on three assumptions: (i) the surface of the adsorbent is in contact with a solution containing an adsorbate which is strongly attracted to the surface. The pseudo-first. respectively. heavy metals nature. respectively. Freundlich isotherm is capable of describing the adsorption of heavy metals on a wide variety of biosorbents.and multicomponent systems. 54. Moreover. first-order reversible reaction model.and multicomponent systems. Kinetic models have been exploited to evaluate the mechanisms of biosorption of heavy metals and its potential rate-controlling steps that include mass transport and chemical reaction processes [82]. a kinetic model is only concerned with the effect of observable parameters on the overall rate. biosorbent particle size.72. it is also necessary to identify the adsorption mechanism type in a given system. a waste product in sugar refining industry. not structured. Gautam et al. The data were better fitted by the Freundlich isotherm as compared to Langmuir in both the single. The efficiencies of adsorbent materials for the removal of Cr(VI) and Ni(II) were found to be between 56. Several adsorption kinetic models have been established to understand the adsorption kinetics and rate-limiting step.72]. Some of these equations contain two fitting parameters such as Temkin isotherm [76]. and in most cases. biosorption isotherms may exhibit an irregular pattern due to the complex nature of both the biosorbents and its varied multiple active sites. It does not have correct Henry law limit and finite saturation limit. (iii) the adsorption involves the attachment of only one layer of molecules to the surface. (ii) the surface has a specific number of sites where the solute molecules can be adsorbed. Elovich’s model and Ritchie’s equation. Kinetic studies and models Adsorption equilibria studies are important to conclude the efficacy of adsorption. On average.1 N NaOH followed by 0. information on the kinetics of metal uptake is required to select the optimum condition for full-scale batch metal removal processes. initial heavy metals concentration. Weber and Morris sorption kinetic model. For instance Mohan and Singh [44] evaluated the behavior of modified bagasse.e. The equilibrium sorption data were correlated with Langmuir. Sometimes. an alternate isotherm developed by Herbert F.2% and 83. a favorable adsorption tends to have Freundlich constant n between 1 and 10. i.e. Raw bagasse was pretreated with 0. not applicable over wide range of concentration Same as Freundlich. external mass transfer model.2% and 96. 49.81]. as well as the complex solution chemistry of some metallic compounds.R. / Journal of Environmental Chemical Engineering 2 (2014) 239–259 242 Table 3 Summary of widely used isotherms for biosorption systems with their advantages and disadvantages.

There are several examples where the pseudo-second-order model was best fitted for the biosorption of metal ions onto biosorbents. ii. the equilibrium sorption capacity. possibly due to a boundary layer or external resistance controlling at the beginning of the sorption process [105]. The pseudo-second-order kinetic model has been the most widely celebrated model for the biosorption of metal ions from aqueous solutions [112]. / Journal of Environmental Chemical Engineering 2 (2014) 239–259 study the biosorption kinetics of heavy metals and quantify the extent of uptake in biosorption kinetics. approximately. Nevertheless. it is necessary to use trial and error to obtain the equilibrium sorption capacity. However.113. gives lnðqe  qÞ ¼ ln qe  k1 t which can be represented as follows: q ¼ qe ð1  expðk1 tÞÞ or it can be expressed as: logðqe  qt Þ ¼ logðqe Þ  k1 t 2:303 The equation applicable to experimental results generally differs from a true first-order equation mainly in two ways [84]. The pseudo-first andsecond-order rate expressions have been and still in wide-use for studying the biosorption of heavy metals from aqueous solutions. copper [109. and compare this with a model where involving a second-order or higher process seems more likely. The main disadvantages of this model are (i) that the linear equation does not give theoretical qe values that agree with experimental qe values.123]. A more logical approach would be to analyze the likely mechanism of a first-order metal ion sorption uptake process on biosorbents. Fe(II) on wollastonite. The main deficiency of this extremely . results in 1 1 ¼ þ k2 t qe  q qe This equation can be expressed as t t 1 ¼ þ q qe k2 q2e where k2 is the equilibrium rate constant of pseudo-secondorder adsorption (g mg1 min1). The pseudo-second-order rate constants can be determined experimentally by plotting t/q versus t. This time lag is difficult to quantify and does little to help rationalize the differences in experimental and theoretical qe values. in comparison to pseudo-first-order kinetic this model is considered more appropriate to represent the kinetic data in biosorption systems [72]. No mechanisms have been proposed for this stage by any authors. For this reason. Cu(II) and for Cu(II). Furthermore. the amount sorbed is still significantly smaller than the equilibrium amount. k1 is the rate constant of adsorption (l min1). it should be noted that the limited model by Lagergren is generally restricted to only the initial 20% to 40% of the adsorption capacity. or Cd(II) and Ni(II) on peanut hull carbon by copper-coated moss [117].110. and lead [124].122]. and at t = t. Pseudo-second-order model Pseudo-second-order model is derived on the basis of the sorption capacity of the solid phase. qe. Various authors have made proposals for these deviations. q = q.112. Several researchers [109–113] have tested the Lagergren pseudo-first-order reaction model for Cu(II).106–108]. The pseudo-first-order kinetic model has been used extensively to describe the sorption of metal ions onto biosorbents [85–104]. Gautam et al. there are several examples of the use of the pseudo-first-order kinetic analysis for other systems. The equation needs further modification for longer sorption times and higher fractional surface coverages. when the experimental data are inspected several sets of results have very few data points in the initial 20–40% period and therefore the rejection of a pseudofirst-order reaction model on the grounds of poor model fitting may not be the correct reason. Pb(II). In chemisorption process. In terms of the short time correlation between experimental and theoretical data for the pseudo-first-order model. i. the pseudofirst-order equation of Lagergren does not fit well for the whole range of contact time and is generally applicable over the initial 20–30 min of the sorption process [84]. qe. t (min) and at equilibrium. most of the fits are moderate to poor. q = 0. q = 0. As such. i. cadmium [114–116. the pseudo-second order is superior to pseudo-first order model as it takes into account the interaction of adsorbent–adsorbate through their valency forces [72].. whereas in a true first-order sorption reaction log(qe) should be equal to the intercept of a plot of log(qe  qt) against t. In studies on the sorption of cadmium by chitosan the pseudo-second-order kinetic model was much more successful [114–116].e. All the literature fits using this method for chitosan–metal ion systems provide an exceptionally high degree of correlation between the model results and the experimental data over the whole range of the sorption uptake capacity. such as. Cr(VI) and Cu(II). In general.118– 120. In order to fit above equation to experimental data.252]: dq ¼ k2 ðqe  qÞ2 dt Integration of above equation with the boundary conditions t = 0.K. Integration of the above equation with the boundary conditions: t = 0. Hence.R. expressed as [111. The parameter log(qe) is an adjustable parameter which is often not found equal to the intercept of a plot of log(qe  qt) against t. it has been proposed that another first-order reaction supersedes the first or 243 another reaction of another order becomes predominant [83. q = q. Beyond this initial 30 min period the experimental and theoretical data do not correlate well. one has to find some means of extrapolating the experimental data to t = 1 or treat qe as an adjustable parameter to be determined by trial and error. One suggestion for the differences in the qe values is that there is a time lag. Pseudo-first-order models The Lagergren first-order rate expression based on solid capacity is generally expressed as follows [83]: dq ¼ k1 ðqe  qÞ dt where q and qe are amounts of adsorbate adsorbed (mg g1) at time. respectively. in order to analyze the pseudo-first-order model kinetics. must be known. The parameter k1(qe  qt) does not represent the number of available sites. and t = t. In most cases in the literature. and (ii) that the plots are only linear over the first 30 min. In many cases qe is unknown and as chemisorption tends to become unmeasurably slow.

and entropy (DS) were determined by using the following equation [130–132]: DG ¼ DH  T DS where C and Csi is the liquid phase concentration of sorbate in the bulk solution at time t and concentration of sorbate in the inner pore of sorbent.e. and 2071. DS. / Journal of Environmental Chemical Engineering 2 (2014) 239–259 useful model stems from the fact that it is a pseudo-kinetic model. papaya biosorbent was an exothermic process. Cd(II). The intraparticle diffusion can be estimated with D¼  2 d p K WM 8640 qe p where D and dp is the intraparticle diffusion coefficient and mean particle diameter. and Ni2+ ions at temperatures 25. which were displaced by the adsorbate species. yeasts. 2104. However. 29. and the negative value of DH shows that the reaction is exothermic [15.56 mg g1 for an increase in solution temperature from 293 to 323 K. Equilibrium kinetics was achieved within 30–90 min. 2547.80. and KL and A is the liquid–solid mass transfer coefficient and specific surface area of biomass.01. They observed that the external mass transfer coefficients can be ordered from high to low values as Cu(II) > Pb(II) > Zn(II) > CCd(II). The free energy of adsorption (DG) can be related with the Langmuir equilibrium constant by the following expression [129]: Of the many types of biosorbents (i. Pb(II).244 R. Ht represents the square root of time t. That was a clear indication that the biosorption of Hg2+ on C. depending upon particle size. and KWM and qe is the amount adsorbed at time t and amount of solute adsorbed at equilibrium condition. intraparticle diffusion and external mass transfer. Cd2+. 1914. thus allowing the prevalence of randomness in the system. 24. for example. Cu2+. Positive values of DH suggested the endothermic nature of the adsorption and the negative values of DG indicated the spontaneous nature of the adsorption process.K. Cr6+. low-cost biomass have proven to be highly effective as well as reliable and predictable in the removal of.72. According to their studies pectin-rich fruit materials and citrus peels were found to be most suitable for cadmium biosorption. 7879. 1699.65. enthalpy (DH). i. p q ¼ K WM t where q and KWM are the amount adsorbed at time t.03.40.00502 L mg1. 2077. The equation can be expressed as: energy (DG).84. Cd2+. Isotherm studies showed as the data were well fitted to Langmuir model.62 to 119. DH is used to identify the nature of adsorption [127]. fungi.60. 45 and 60 8C were 1675.11. and Zn2+ ions from aqueous solutions.00812 to 0. bacteria. as temperature was varied from 293 to 323 K. Gautam et al. It was also observed that the metal uptake decreased with decreasing pH. respectively. respectively. The Weber and Morris sorption kinetic model [125] was initially employed by Pasavant et al. and industrial and agricultural wastes) recently investigated for their ability to sequester heavy metal ions. The thermodynamic parameters such as changes in standard free Agro biosorbents Recently Schiewer and Patil [96]. Cd2+. [134] reported that the sorption of Hg2+ onto sunflower stem was exothermic and they observed DH value of 32 kJ mol1. investigated pectin-rich fruit wastes as biosorbents for heavy metal ion removal. Cd2+. Malik et al. so a specific but different rate constant is obtained for each change in system variable [84]. respectively. A positive value of DH indicates the reaction is endothermic. The slope and the intercept of the plot of DG versus T were used to determine the DS and DH values [133].33. The positive values of DS showed the increased randomness at the solid–solution interface during the adsorption process [136]. weeds. Conversely. A pseudo-second-order model was found to be more suitable than a first-order model to describe the kinetics. and Ni2+ at temperature 45 8C were 11. The negative entropy change. indicating competition of protons for binding to acidic sites. According to them.. [126]. and Weber and Morris intraparticle diffusion rate constant. Pb2+. 1024. a plot of ln KL versus 1/T should be a straight line.43. 1503. Uptake of metals by different low-cost biosorbents is summarized in Table 4. change in enthalpy (DH).e. It was stated that the adsorbed water molecules. So it is important to develop an equation for correlating the pseudo-rate constant with each variable [122]. The external mass transfer process was determined by dq ¼ K 0L AðC  Csi Þ dt DG ¼ RT ln K L Enthalpy and entropy changes are also related to the Langmuir equilibrium constant by the following expression: ln K L ¼ DS R  DH RT Thus. Negative DG indicates the spontaneity of the adsorption process. while the intraparticle diffusion coefficients were as follows: Cd(II) > Zn(II) > Cu(II) > Pb(II).38.76 and 1696. The saturated monolayer biosorption capacity. the negative values of DG with an increase in temperature indicated that the spontaneous nature of adsorption was inversely proportional to the temperature. was found to decrease from 185. A positive value of DS indicates increased randomness of adsorbate molecules on the solid surface than in solution [128]. respectively.55. respectively. the biosorption by Caulerpa lentillifera biomass for Cu(II). DH and DS values could be obtained from the slope and intercept of this plot. qmax. confirmed the decreased randomness at the solid– solution interface during biosorption and reversibility of mercury biosorption [135]. The values of DS (calmol1 K) and DH (calmol1) for Pb2+. Batch adsorption experiments were performed by Dhir and Kumar (2010) [143] to study adsorption potential of agricultural . and Zn(II)was regulated by two main mechanisms.30. The enhancement of adsorption at higher temperatures may be attributed to the enlargement of pore size and/or activation of the adsorbent surface [137]. Yasemin and Zek [130] have calculated the values of standard free energy (DG) for the biosorption of Pb2+. and change in entropy (DS). gain more transitional energy than was lost by the adsorbate ions.127]. and Ni2+ onto sawdust of walnut. 5479. the Langmuir isotherm constant decreased from 0. Thermodynamic analyses Biomass and biosorption of metal ions Gibbs free energy (DG). The results showed that the biosorption capacity of Carica papaya for Hg2+ decreased with increase in temperature. The values of DG (calmol1) for biosorption of Pb2+.

0 – 2. (residue from fermentation industry) Cystoseira baccata Spirulina sp.3 Pb Pb Algae Plants 303 264–297 5 5.5–1. then treated with 0.6 204 4 4 5. ground and passed through 125 mm screen Treated with 0.0 mm in size.1. and oven dried at 343 K for 24 h.5–6.0 Immobilized beads of a tropical tree fruit native to India Ground into particles.1 111–132 5.Table 4 Recently reported biosorption studies of biomass materials for the removal of heavy metals and metalloids.2 Hg Cd Cd Cd Cd Algae Bacteria Fungi (yeast) Fungi (yeast) Fungi 329 99.3 2.3 5–6.1. The biomass was mixed with urea in 1:2 by mass and irradiated in a microwave oven for a period of 12 min The huge biomass generated from Spirodela polyrhiza can be successfully utilized for wastewater treatment Protonation was carried out by suspending the sorbent material in 0.2 72 0. rinsing.1 2 1 Penicillium oxalicum var.5 1 Orange peels Pb Plants 1.2 5.0 6.0 7 4 – 6.0 Ulva onoi Ulva onoi Cd Cd Algae Algae 61.5 M NaOH.4 5 72 0.1 M HNO3 for 3 h.) Schleiden biomass Cd Aquatic plant 36. Pb Algae 266 2–7 2 4 [150] Treated with 10 M NaOH under boiling. then washed with 1 M HCl The rice husk ash obtained from burning of rice husk in electrical oven at 700 8C for 3 h Magnetically modified Brewer’s yeast cells Hg Fungi 269.5 24 2.2 Hg Fungi 161. activated by alkali and CaCl2/MgCl2/NaCl (2:1:1. experiments conducted at 10–40 8C Ground and passed through 90 mm screen.7 7. [152] [153] [154] [155] [156] [151] [158] [159] [160] [161] [146] [251] [255] [162] [163] [164] [154] [165] R. Armeniaca (residue from fermentation industry) Tolypocladium sp.0 4 0.5 1 2 1 2.5 6 10 1 2 Phragmites australis shoot Pb Plants 17.0 1 1.3 6. Recovery of 82% Cd(II) in the solution of 0.3 5 5.K.1.5 3 0.7 mm was selected for use in the sorption studies. (commercially available) Saccharomyces cerevisiae (waste brewer’s yeast) Baker’s yeast (lab cultured) Phomopsis sp.2% formaldehyde 2. then ground and passed through 1–4 mm screen Ground and sieved (0.1 M NaOH was used in granulated form The brown seaweed Sargassum sp.5–1 mm screen Lyophilized bacterial cells Ground and passed through 150 mm screen Modified by crosslinking cystine with glutaraldehyde Mycelium boiled with 0.0 1–10 [148] [149] [138] Saccharomyces cerevisiae (brewer’s yeast) (from brewery) Penicillium oxalicum var. 0. optimal pH for adsorption: near neutral Weed can be utilized for the treatment of Cd(II).5 15. was harvested from the sea.1 M NaOH. (lab cultured) Hg Fungi (yeast) 133. 0.5 0.22 4. dried at 60 8C. molar ratio).51 2–8 0.41 85.9 90.0  0. / Journal of Environmental Chemical Engineering 2 (2014) 239–259 [157] [157] [151] [166] [160] [161] [167] [168] 245 .0 120 0.1 Orange peels Pb Plants 400 3–5 0.1 M HCl had been obtained Dried rice straw was grinded and sieved to pass 40–60 mesh.0 mm in size. ground and passed through 125 mm screen Ground and passed through 125 mm screen [151] Ground and passed through 0. 0. 0. experiments conducted at 10–40 8C Ground and passed through 90 mm screen.5 3 6 0.8 12 12 1 1 Gelidium sesquipedale Olive pomace Azolla filiculoides Cd Cd Cd Algae Plants Plants 18.0 7 72 0. Dried biomass was cut and sieved.2  0. ground and washed by distilled water 2.5 24 100 5 2.63 29  1 6.1 M NaOH for 1 h. Armeniaca (residue from fermentation industry) Sargassum sp. activated by alkali and CaCl2/MgCl2/NaCl (2:1:1.8 7. Gautam et al.333 10 Oryza sativa Cd Plants 20. ground and passed through 100 mm screen Ground and passed through 1–4 mm screen Soaked in 0.4 11. different concentrations of citric acid and different temperatures on the preparation of orange peel biosorbents were investigated Lyophilized cells with capsular polysaccharide (CPS) Ground and passed through 150 mm screen Modified with polyethylenimine and crosslinked with glutaraldehyde Treated with 10 M NaOH under boiling.007 6 2.5 1 – 10 2 10 2 Phragmites australis shoot Cd Plants 10.2 – 3 1 Streptomyces rimosus Pb Bacteria 135 2–4 3 3 Sargassum sp.2.25–1 mm in size) Dried.5  0.166 16 Spirodela polyrhiza (L. washed with distilled water to remove particulate material. Azolla filiculoides Pb Fungi 47.11 8. and drying for 12 h at 40 8C Effects of alkaline saponification.3 – 3 1 Parthenium hysterophorous Cd Weed 27 3–4 0. Biomass material Metal Biomass type Biosorption capacity (mg g1) pH Reaction time (h) Adsorbent concentration (g L1) Remarks References Garcinia cambogia Waste crab shells Rice husk ash As As Se Plants Animal Crop 704.70 6 0.67 Gloeocapsa gelatinosa Saccharomyces cerevisiae (waste brewer’s yeast) Penicillium chrysogenum (lab cultured) Pb Pb Pb Bacteria Fungi (yeast) Fungi 256.3–0. molar ratio). The fraction with 0.1 M NaOH Streptomyces rimosus biomass treated with 0. then treated with 0.

3  0.92  0.09 Oedogonium hatei Cr Empty food branch Algae 31.246 Table 4 (Continued ) Biomass material Metal Biomass type Biosorption capacity (mg g1) pH Reaction time (h) Adsorbent concentration (g L1) Remarks References Spirodela polyrhiza (L.1–1 Spirulina sp. Gautam et al.8 91. activated by alkali and CaCl2/MgCl2/NaCl (2:1:1. experiments conducted at 10–40 8C Ground and passed through 90 mm screen. then treated with 0.17–2.8 12 1 Azolla filiculoides Zn Plants 64.0 mm in size. then ground and passed through 1–4 mm screen 2.5 Modified with polyethylenimine and crosslinked with glutaraldehyde Treated with 0.0 mm in size.34 4 3 2 The huge biomass generated from Spirodela polyrhiza can be successfully utilized for wastewater treatment Ground and passed through 150 mm screen Ni Fungi 55  1 5.75–1.5  0.75  0. dried at 60 8C. Lyophilized cells Lyophilized cells Treated with 1% formalin.91  0. Azolla filiculoides Ni Ni Algae Plants 71. particles (0.) Schleiden biomass Pb Aquatic plant 137 4.5 1 Spirulina sp. centrifuged.06 7 6 6 5 5 – 0.588 2–8 1 1–10 Phomopsis sp. then treated with 0.5 Algal biomass was washed in running tap water followed by Milli-Q water 4–5 times.2 1–4 0. (lab cultured) Zn Fungi 10.2 10 2 Phragmites australis shoot Zn Plants 5. molar ratio).5  0.1 [255] Saccharomyces cerevisiae (waste brewer’s yeast) Penicillium chrysogenum (lab cultured) Ni Fungi (yeast) 6.0 120 0. Lyophilized cells Ground and passed through 150 mm screen Available in tropical countries.1 M NaOH for 1 h. experiments conducted at 10–40 8C Ground and passed through 90 mm screen.2% formaldehyde Dried.5 2 1. washed with the physiological saline solution and dried in an oven at 60 8C. ground and passed through 100 mm screen Soaked in 0. then sun dried for four days followed by drying in an oven at 70 8C for 24 h Raw biomass of Oedogonium hatei was treated with 0. activated by alkali and CaCl2/MgCl2/NaCl (2:1:1.67 0.1 M NaOH. Olive pomace Phragmites australis shoot Cu Cu Cu Cu Cu Cu Bacteria Bacteria Fungi Algae Plants Plants 196 60 26 87. Mycelium boiled with 0.1 M NaOH. then treated with 0.0 1–4 0.5 24 2 – 3 1 3 2 1 10 1 Acrylic acid functionalized poly(N isopropylacrylamide) hydrogel Quercus coccifera shell Cu Biomass based material 67.4 5.5 18 5 24 1 2 10 10 Sugarcane bagasse Cr Plants 103  9 3 24 10 Corn stover Cr Plants 84  10 3 24 10 Mucor hiemalis Cr Fungi 53. dried at 105 8C for 24 h Modified by crosslinking with dimethyloldihydroxyethylene urea and quaternary amine Modified by crosslinking with dimethyloldihydroxyethylene urea and quaternary amine Modified by crosslinking with dimethyloldihydroxyethylene urea and quaternary amine M.1 N HCl was added to the biomass to obtained formaldehyde treated biomass [154] .2 6 10 1 2 Phragmites australis shoot Ni Plants 7. hiemalis was cultured in potato dextrose broth and the biomass was harvested after 7 days. kept on a filter paper to reduce the water content.07 – 3 1 Magnetic biochar Zn 1.4 10 2 0. Sphaerotilus natans Aspergillus niger Sargassum sp. Saccharomyces cerevisiae (waste brewer’s yeast) Bengal gram (Cicer arientinum) seed husk Soybean hulls Cr Cr Cr Cr Bacteria Fungi (yeast) Plants Plants 185 12. / Journal of Environmental Chemical Engineering 2 (2014) 239–259 A mixture of formalin 30% and 0.3 5 24 2 Ulva onoi Zn Algae 74. optimal pH for adsorption Empty food branch was grinded to 150 mm and treated by ferric chloride with impregnation ratio of 0.5 4 [166] [160] [161] [138] [156] [157] [160] [161] [250] [169] [169] [153] [154] [170] [171] [171] [171] [15] [153] [172] [173] [166] [159] [161] [256] [174] R.1 M NaOH The rice husk ash obtained from burning of rice husk in electrical oven at 700 8C for 3 h.6 70.1–84.K.5 6 1 [165] Sargassum sp.25 5.67 0. molar ratio).06 – 3 1 Rice husk ash Zn Crop 9.64 58  2 7 4 2.1 5 5. Harvested biomass was washed thoroughly and was killed by autoclaving at 121 8C and a pressure of 15 lb.6 7.0 – 0.2% formaldehyde 2. ground and washed by distilled water Ground and passed through 90 mm screen.5 M NaOH.0 3 0.0 mm in size) Treated with 0.1 M HCl and then stirred the mixture at 200 rpm for 8.0 h. optimal pH for adsorption Poly(N isopropylacrylamide-co-acrylic acid) hydrogels can be utilized for copper ion adsorption from aqueous solutions Co Plants 33 3–11 1.5 0.1–1 Oedogonium hatei Cr Algae 35.3–80.17–2.1 10  1 9.

The process was endothermic and spontaneous in nature. and 3. Therefore. The adsorption process was found to be endothermic and spontaneous in nature. wheat straw. Mean free energies at different temperatures were in between 7. baccifera raw carbon and M. protonated peels.45 and 28. Fe(III). [138] as a function of contact time. pore volume and presence of surface functional groups influence the adsorption capacity of adsorbents prior to their modification. native orange peels.87.485. Heavy metal removal efficiency was more at low metal concentration (35 mg L1). Langmuir. respectively. Biosorption followed Freundlich isotherm at 50 8C. The biosorption was maximum (92%) at pH 4. but were the same when non–linear method was used.49 to 9.999. Weed The efficiency of Parthenium hysterophorous weed for the removal and recovery of Cd(II) ions from wastewater have been studied by Ajmal et al.999. Fe(III) and Zn(II) metallic ions from aqueous solutions. wheat straw and Salvinia plant biomass for removal of heavy metals such as Cr. and Zn(II). pore-size distribution. and extracted pectic acid.9 mg g1 for Cr(III). and 107. respectively and the experimental qe values were also agreed well with the calculated qe values. depectinated peels. respectively. the data were best fitted to Sips isotherm models. [141] reported the feasibility of pecan nutshell (Carya illinoensis) as an biosorbent to remove Cr(III).723 and 27. Organometallic compounds biosorption Modifications and activation of biosorbents A few biosorbents have been reported for the adsorption of heavy metals not only in the form of metallic ions but also organometallic compounds. Schiewer and Iqbal [140] investigated the role of pectin in Cd2+ metal binding by citrus peels.91. 247 affinity of CH3HgCl > C2H5HgCl > Hg2+. Ni. Langmuir isotherm model provided the best fit. Five kinetic models were tested. Metal binding kinetics was better described by the first-order model than by the second-order model. Mostly. by chemical treatment and used in various experiments to test its functions as adsorbents for removal of Ni(II) and Zn(II) from aqueous solution. so that they may be tailored to have the desired . and Redlich–Peterson. Its adsorption capability and adsorption rate were considerably higher and faster for Zn(II) ions than for Se(IV) ions. The magnitude of the negative surface charge determined from potentiometric titrations decreased in the order PP > PrP > DP > NP. with the maximum sorption capacities of 79. and 61 mg g1. and Cd. / Journal of Environmental Chemical Engineering 2 (2014) 239–259 residues viz. respectively. Salvinia biomass possessed higher efficiency for removing heavy metals such as Cr. Freundlich. Similarly.3. [147] have tested the biosorption potential of Fennel biomass (Foeniculum vulgari) a medicinal herb for the effective removal of Cd(II) ions. 40 and 50 8C temperatures were 21. baccifera activated carbon for Ni(II) and Zn (II) and the calculated qe values from pseudo-second-order kinetics were agreed well with the experimental qe values than the pseudo-first-order. The authors reported that the kinetics data for the adsorption process obeyed second-order rate equation. Taking into account a statistical error function. 40. Medicinal herbs Rao et al. Equilibrium adsorption of Zn(II) and Se(IV) ions by rice husk ash followed typical adsorption isotherms and fits both the Langmuir. The biosorption of Cd(II) was concentration dependent and increased from 0. Saglam et al. 52.R.01. the correlation coefficients (R2) of Zn(II) for the pseudo-second-order kinetics model onto M.999 and 0. respectively and the experimental qe values were agreed well with the calculated qe values. The biosorption process was spontaneous and exothermic process in nature. Kinetic experiments showed that equilibrium was achieved in 1 h. [121] have applied activated charcoal prepared from Melocanna baccifera raw charcoal.987 and 0. 24 and 30 mg g1. baccifera activated carbon were 0. the adsorption kinetics being the better fitted one to the fractionary-order kinetic model. baccifera raw carbon and M. The effects of several parameters. and Temkin adsorption isotherms. The affinity of Rice husk ash for Zn(II) ions was greater than that for Se(IV) ions.01. Langmuir isotherm parameters obtained from the four Langmuir linear equations by using linear method were not similar.1 and 11. respectively. an agricultural waste. Freundlich.3 mg g1 with increase in concentration from 5 to 100 mg L1. and pH at 25 8C. The adsorption potential of pecan nutshell to remove these metallic ions was investigated by using batch mode. Zn(II) removal was found fast reaching equilibrium within 1 h while Se(IV) adsorption was slow reaching equilibrium within 100 h. Ho and Ofomaja [139] used coconut copra meal. [142] have prepared the biosorbents by the biomass of Phanerochaete chrysosporium which adsorbed inorganic mercury and alkylmercury species with an Various factors such as specific surface area.1 M HCl solution was used as eluent. Non-timber products Lalhruaitluang et al.K.95 kJ mol1 indicating chemical nature of biosorption process. The maximum biosorption capacity of pecan nutshell were 93. rice straw. The desorption studies confirmed 82% recovery of Cd(II) when 0. 76. 9. Gautam et al. They examined a comparison of linear least-squares method and a trial and error non-linear method of three widely used isotherms. as an adsorbent of Zn(II) and Se(IV) from their aqueous solution was carried out by El-Said et al.59.7% in the pH range 3–4. showing that carboxyl groups of pectin was a major contributor to the surface charge. On the other hand. it had been concluded that the adsorption system followed a pseudo-second-order reaction rather than pseudo-first-order reaction. metal binding experiments have been carried out at optimized pH 5. Vaghetti et al. The maximum adsorption capacity of Cd(II) ions was 99. 4. Kinetics studies showed that pseudo second order kinetics model was applicable to the data. [146]. such as pH and the biosorbent dosage on the adsorption capacities of pecan nutshell were studied. An attempt at the use of rice husk ash. Recently. Salvinia biomass) were taken together in comparison to other combinations. the spontaneity of the process increases with increase in temperature. The authors used the Bangham equation to express the mechanism of adsorption. The correlation coefficients (R2) of Ni(II) for the pseudo-second-order kinetics model onto M. Ni and Cd followed by a combination where three materials (rice straw. the most abundant and economically important non-timber product in the tropical countries. adsorbent dose. The adsorption of metal ions increased with an increase in the biosorbent dosage from 1 to 10 g L1 and with a decrease in initial metal ions concentrations. metal ion concentration. the correlation coefficients of the pseudo-first-order kinetics model were lower than the pseudo-second-order kinetics model in M. baccifera raw carbon and M.53. 67. baccifera activated carbon were 0. Freundlich and Langmuir isotherms constants (mg g1) for the adsorption of Ni(II) and Zn(II) onto Melocanna baccifera raw carbon and M. Maximum biosorption capacities of Cd(II) at 30.93. baccifera activated carbon were 2. a waste product of coconut industry for its potential use as a biosorbent for cadmium ions from aqueous solution.

activated carbons are mainly microporous. The other is that the global yield of the chemical activation tends to be greater since burn off char is not required.178]. [(Fig.K. such as acid and caustic. boiling or heating. 1. Activated carbon Activated carbon biosorbents constitutes one of the most important types of industrial carbon and is prepared by modification and activation of a large number of raw biomass. Basically. Modification Treatment Advantages Disadvantages Chemical characteristics Acidic Increases acidic functional groups on activated carbon surface enhances chelation ability with metal species Enhances uptake of organics May decrease BET surface area and pore volume Basic Physical characteristics Biological characteristics Impregnation of foreign materials Heat Bioadsorption Enhances in-built catalytic oxidation capability Increases BET surface area and pore volume Prolongs activated carbon bed life by rapid oxidation of organics by bacteria before the material can occupy adsorption sites May. the modification of cell wall can greatly alter the binding of metal ions. Biosorbents preparation routes from biomass using chemical and physical methods. Because of its high adsorption capacity it is used extensively in environmental applications for the removal of impurities from gases and liquids. and pore size distribution [179–181]. One is the lower temperature in which the process is accomplished. Among these three methods. in some cases. Most of the activated carbons are produced by a two-stage process carbonization followed by activation [124]. formaldehyde. which are very important in facilitating access of the adsorbate molecules to the interior of the carbon particle and in many of the adsorption applications in liquid phase [182]._1)TD$IG] Activation of adsorbents Fig. acid or alkali treatment. meso-. Generally. / Journal of Environmental Chemical Engineering 2 (2014) 239–259 248 Table 5 Technical advantages and disadvantages of existing modification techniques. while pore size and micropore distribution are closely related to the composition of the adsorbents and the type of biomass raw material supplied for their synthesis [175]. etc. methanol. only studies on modification with chemical compounds of activated carbons have been visited in this review. Physical methods include vacuum and freeze-drying. The high adsorptive capacities of activated carbons are mainly associated with their internal pore properties such as pore surface area. autoclaving and mechanical disruption. it needs to possess a well developed pore structure. Table 5 lists and compares the advantages and disadvantages of existing modification techniques with regard to technical aspects. which is recognized to be the most important property of activated carbon [177. the activations are two different processes for the preparation of activated carbon: physical activation and chemical activation. 1 shows the sequence of steps in the preparation of different types of biosorbents from biomass sources. modification with chemical compounds has been more frequently employed to increase the adsorption and hence removal capacity of activated carbon or similar biosorbents. As the biosorption process involves sequestration of metal ions on the cell surface. but in addition to micropores they contain meso and macropores. The pretreatments could modify the surface characteristics/groups either by removing or masking the groups or by exposing more metal binding sites [176]. The various chemical treatments used for raw biomaterials modification include washing the biomaterial with detergents. In order to facilitate a more focused discussion. drying and lyophilization. There are two important advantages of chemical activation in comparison to physical activation. A number of methods have been employed for cell wall modification of microbial cells in order to enhance the metal binding capacity of biomass and to elucidate the mechanism of biosorption. and macropores.R. decrease the uptake of metal ions May decrease BET surface area and pore volume Decreases oxygen surface functional Groups Thick biofilm encapsulating activated carbon may impede diffusion of adsorbate species Carbon surface can be modified to develop desirable physicochemical properties by adequate choice of activation procedures. Usually. The structure and volume of micropores and transitional pores developed during activation physical and chemical attributes to enhance their affinities toward metal ion uptake from aqueous solutions. The first step is to enrich the carbon content and to create an initial porosity and the activation process helps in enhancing the pore structure. The physical treatments include heating/boiling. physical and biological characteristics. freezing/thawing. The techniques of modification of carbon/activated carbon can be categorized into three broad groups: modification of chemical. It is even possible to prepare carbons with designated proportions of micro-. Chemical methods include treatment with various organic and inorganic compounds. Gautam et al. Modification techniques . pore volume. Fig. adsorption capacity increases with increase in specific surface area due to the availability of a number of adsorption sites.

K. The lamella remains apart causing porosity and yielding high surface area carbon [203]. CaO has a low charge to radius ratio and can provide strong basic sites to the surface of the adsorbent [200]. Calcium oxide have been used as activating agents for preparation of activated carbon biosorbents and used as a nonconventional adsorbent for the removal of Cu(II) and Ni(II) ions from aqueous solutions [199]. increased surface area. Thus during activation with KOH.Ethanol–water extraction . 3 shows the SEM images of raw and activated biomass based biosorbents. in situ. Among the numerous dehydrating agents. NMR. The KOH concentration of 50% and 60% treatment showed highest adsorption of Ni(II) and Zn(II) from aqueous solutions.Lignin peroxidase. The purpose of activation of charcoal is to create pores and develop larger surface area in the carbon material and thereby increase the adsorptive capacity. Action of pretreatment on biomass materials for the production of biosorbents. The reaction between KOH and carbon precursor can result in the formation of functional groups such as –OK using oxygen of the alkali salt. BET surface area analyzer.257].144. NH3. laccase . Alkaline treatments on biomass have been reported to enhance the metal ion adsorption capacity in many cases [192–198]. Fig.Extrusion .Butanol–water extraction Fungi and actinomycetes: . 4). FTIR. zinc chloride in particular is the widely used chemical agent in the preparation of activated carbon for the removal of metal ions from aquatic environment [124.Ball milling . creating interlayer voids. manganese peroxidase. the lamellas of the crystallite were disturbed from their normal form into a slightly wrinkled or folded or puckered form. SO2.Pyrolysis Explosion: . HCl. HNO3 and HCl could increase the total amount of acidic functional groups on biomass surface [157.Benzene–water extraction . have applied for the characterization of biomass activated biosorbents. (NH4)2SO3 Acid: . IR spectroscopy.204.O3 -Wet oxidation Solvent extraction of lignin: .Hammer milling Irradiation: . At the same time. amorphous carbon as well as silica are removed from the carbon precursor resulting in porous structure and a corresponding increase in the surface area. intercalates in to the lamella of the crystallite. TGA–DTA.H2SO4.205]. Physical methods Chemical and Physicochemical methods Biological methods Milling: .High pressure steaming . the yields of carbon are usually high [185].202]. Among the alkali metal salts. Surface functional groups can be created at the edges of the lamella. Several sophisticated instruments such as SEM.Steam.247. Element analyzer. HNO3 and H3PO4 acids Gas: . Gautam et al. 2. sulfuric acid in 1:1 ratio (Fig. The introduction of alkali or alkaline earth metals on the surface of the adsorbent provides basic sites that have a high affinity for adsorption. SO2 Oxidizing agents: . pore size. Chemical activation by zinc chloride improves the pore development in the carbon structure. It is worthwhile to mention that every treatment for improving surface chemistry of activated carbon may change its textural characteristics [197]. and because of the effect of chemicals.ClO2.H2O2 . Acids Alkali: ._2)TD$IG] Fig.Gamma-ray irradiation . XRD.Ultrasound irradiation .Hydrothermal . respectively. Activate carbon [(Fig. impregnation of urea may enhance the development of carbon . The oxidative treatment in an oxidized gas atmosphere or a reaction with strong acid such as H2SO4.CaO. and surface area during activation of various types of carbon have been reviewed by several authors [183]. Table 6 shows the classification of pretreatment methods for the production of activated biosorbents.184]. AFM. For example.145. The presence of such potassium and oxygen bond in the char leads to the oxidation of cross linking carbon atoms in the adjacent lamella during the process of activation. Ammonia. / Journal of Environmental Chemical Engineering 2 (2014) 239–259 249 Table 6 The classification of pretreatment methods for the production of activated biosorbents. 2 shows the pretreatment action on the biomaterials. TEM. partial hydrolysis of hemicelluloses etc.White-rot and brown-rot fungi depend upon the nature of the starting material and the conditions of activation. NaOH. NO2. [121]. The adsorption capacity of chemically activated charcoal biomass from Bamboo with various concentrations of KOH had been investigated by Lalhruaitluang et al. As a result of removal of cross linking between adjacent lamella and also the formation of new functional groups on individual lamella.Two-roll milling . [129. Fig. have been developed by treating raw mustard husk with conc. CO2. Pretreatment action may results in modification of the structure.Microwave irradiation Others: . Data has been compiled from Refs. Also the potassium metal produced in the process of activation. Knowledge of different variables during the activation process is very important in developing the porosity of carbon sought for a given application. increased pore sizes. XPS. etc. ZnCl2.Electron-beam irradiation . KOH is the most effective activating agent in producing activated carbon materials.186–191.R. The changes that occur in micropore volume. The KOH activation was reported to be effective for increasing micropore volume [201. DSC. the lamella cannot return to their original state. Extensive drying of the lignocellulosic materials should be avoided because it may results to pore shrinking which may leads to limits the diffusion of metal ions.

The prepared biomass material was applied for the adsorption of Cd from aqueous solution in batch mode. Both SBET and surface chemistry were changed dramatically due to acid and acid–base treatment.K. the dried biomass was soaked in 0. SEM images of biomass based biosorbents.5. 4. It has been showed that treated Ulva have excellent ability for adsorption of heavy metals. In the case of the alkalipretreated material. which resulted in extremely different adsorption preference [197]. Formaldehyde treated sawdust of Pinus sylvestris have been studied for the removal of Cd(II) and Pb(II) from aqueous solutions [211]. 3. (B) activated mustard husk. The experimental data showed that the pseudo-second-order model was the best fitted kinetic model for description of biosorption of Cd(II) ions on treated Mulberry sawdust. and (D) activated Ficus fruit. The biosorption of Cd(II) ions was pH dependent and maximum biosorption was achieved at pH 6 after 30 min shaking. and rinsed with distilled water until the pH of the rinsing water was less than 10. (C) activated Pinus cone.0 mol L1 HCl solutions for 24 h. [157] have removed the heavy metals from aqueous solution by non-living Ulva seaweed as biosorbent.[(Fig.1 M NaOH for 1 h. All the activated carbon had been obtained by treating concentrated sulfuric acid (ratio of biomass with conc. Fig. The isotherm model was well fitted to most celebrated monolayer Langmuir model with sorption capacity of 60–90 mg g1. sulfuric acid was 1:1). Activated seaweed The adsorption capacity for metal ions was significantly improved with acid–base modification [157. The sorption characteristics of sawdust strongly depend on its charging status controlled by the types and numbers of functional groups on its surface [253]. / Journal of Environmental Chemical Engineering 2 (2014) 239–259 porosity [206].208]. Activated sawdust Sawdust is one of the promising materials which can be used to adsorb heavy metals. and oxidation may decrease specific surface area and pore volume [207.209.1 M HCl for 1 h and rinsed with distilled water until the pH of the rinsing water was more than 4. The mustard husk was activated by applying concentrated sulfuric acid and the ratio of mustard husk with concentrated sulfuric acid was 1:1. Suzuki et al. The same authors have reported that they have [(Fig. FTIR image of activated mustard husk. Gautam et al. The Mulberry sawdust was chemically treated with 1.73 (mg g1) for Cd(II) ions._4)TD$IG] Fig. The dried biomass was pretreated with 0._3)TD$IG] 250 R. which showed a great adsorption capacity of the treated biomass. . Biosorption of cadmium from aqueous solution using Mulberry wood sawdust treated with hydrochloric acid has been studied [205]. The maximum biosorption capacity of chemically treated sawdust obtained from Langmuir isotherm was 403. (A) raw mustard husk.210].

and 6.45.72. Cd2+. and Pb2+ [215. and carboxymethyl [225. The sugarcane bagasse has been modified with succinic anhydride to introduce carboxylic functions to sugarcane bagasse and the chemical introduction of commercial linear polyamine via the formation of amide functions [212]. MMSCB 3 and 5 were synthesized from MMSCB 1 using two different methods. Maximum adsorption capacities of MMSCB 3 and 5 for Cu2+.66 mg g1 and 7. In contrast to most other plants which need to grow for 10–100 years. However. But when the pH was >4. respectively. The pHzpc for coconut shell carbon (CSC). aluminum hydroxyl and some low densities of sulfhydryl and phosphoryl groups. 2. The analysis of surface properties showed that high proton affinity sites were mainly composed of phenolic and alcohol hydroxyl. baccifera activated charcoal pH 5.5. Several authors have been used hen egg shell as adsorbent for heavy metal sequestration or as activating agent for carbon surface [219]. and ammonia persulfate treated coconut shell carbon (CSCA) were 7. baccifera was found to be more suitable Fig.5 the adsorption capacity declined simultaneously. EABC was synthesized by amination with diethylenetriamine on bacterial cellulose. Gautam et al.4. and amidoxime [221].5 mol L1 HCl solution. Then. thiolate [223]. carboxy [224]. Additionally. respectively.730 mg g1. and Pb2+ from aqueous single metal ion solutions was evaluated at different contact times. the activated biosorbents of M. derived from succinylated twice-mercerized sugarcane bagasse (MMSCB 1). Activated carbon from agro-waste Sorption of Cu(II) and Ni(II) ions from aqueous solutions using calcium oxide activated date (Phoenix dactylifera) stone carbon have been performed by Danish et al. 86.226]. and 53. baccifera raw charcoal and M. Vasu et al. baccifera for the development of an efficient adsorbent for the removal of Pb(II) from aqueous solutions. It has been well established that polyamines have powerful chelating properties. mainly toward ions such as Cu2+. The hen egg shells had been applied as an activating agent for commercial carbon via modification of their surface chemistry [219]. contact time 120 min. baccifera activated charcoal were 10. which becomes mature in 4–6 years. and initial metal ion concentrations.4.79%) from loaded biosorbent by using 1. and adsorption isotherm was well described by the Langmuir model. The Langmuir and Freundlich adsorption capacity of Pb(II) onto M. pH. 6. Adsorption isotherms were well fitted by Langmuir model. A vast array of functional groups such as carboxylates. the obtained carbon was oxidized with concentrated nitric acid.K. which resulted in a slightly higher adsorption capacity for Cu(II) than Ni(II). In the first method. the wood processing in industrial and agricultural production often generates a massive amount of sawdust that needs to be reused. The purpose of the oxidizing agent modification of the carbon surface was to enhance the density of the surface functional groups (Fig. hydrogen peroxide treated coconut shell carbon (CSCH). or an ionic moiety such as phosphate [222]. while low proton affinity sites mainly consisted of carboxylic acid.[(Fig. and Pb2+ were found to be 59. The results revealed that calcium oxide activated date stone has a honeycomb like surface morphology with large mesoporous surface area (645.0–6. [199]. 158. Cd2+. and carbonyl groups in biomaterials have the ability to adsorb metal ions. baccifera Roxburgh (bamboo). To enhance the heavy metal ion adsorption of biomass. This was due to the protonation of the amino groups at the acidic conditions. baccifera raw charcoal and M.76. MMSCB 1 was activated with 1. Activated bagasse Adsorption of heavy metal ion from aqueous solution by modified sugarcane bagasse has been well recognized [212–214]. hydrogen peroxide treated coconut shell carbon (CSCH). The results showed that the adsorption rate was well fitted by pseudo-second-order rate model. [190] have synthesized the activated carbon by carbonizing the coconut shells in a muffle furnace at a temperature of 400 8C for 1 h. 5). nitric acid treated coconut shell carbon (CSCN). contact time (15–360 min) and metal ion concentrations (50–90 mg L1). silicon hydroxyl. The trend of adsorption amount of Cu(II) and Ni(II) was appeared same at the equilibrium.0). However.2 mg g1. MMSCB 3 and 5. [227]. 5.254] as a raw adsorbent to remove heavy metal in water. They have conducted batch experiments for under varying range of pH (2.40. phenolic and aliphatic hydroxyls. the biomaterial was chemically modified by introducing different complexing groups such as aminoalkyl [220]. For keeping in mind the practical . nitric acid treated coconut shell carbon (CSCN). Gurgel and Gil [217] have described the preparation of two new chelating materials.7 and 222. than raw biosorbent of M. Natural bamboo sawdust with cellulose–lignin polymeric structure was used by Zhao et al. New activated biosorbents Adsorption of Pb(II) and Cu(II) onto diethylenetriaminebacterial cellulose (EABC) was performed by Shen et al. Zn2+. bamboo is a fast-growing and renewable resource.2 and 106. respectively. The optimum conditions for Pb(II) biosorption were almost same for M.216].0. In this experiment the adsorption uptake of metal ions was good but it takes a too longer contact time. / Journal of Environmental Chemical Engineering 2 (2014) 239–259 251 recovered maximum cadmium (92. 6. hydrogen peroxide and ammonium persulfate._5)TD$IG] R.2-diaminoethyl. and ammonia persulfate treated coconut shell carbon (CSCA) [190]. The amount of adsorption of Pb(II) and Cu(II) onto EABC was maximum in acidic medium at pH 4.5 and 69. the adsorption capacity of raw hen egg shell was very low.32 mg g1.5 cm3 g1) for adsorption and removal of copper and nickel was followed the pseudo-second-order kinetics and Langmuir model of isotherms. [218] have performed the removal of Pb(II) adsorption from aqueous solutions by raw and activated charcoals of M. and both ions adsorption increased as the initial metal ion concentration increased. The greater electronegativity of Cu(II) have been given the reason to enhance the binding capacity of copper toward the negatively charged adsorbent surface. [253.3-diisopropylcarbodiimide and in the second with acetic anhydride and later both were reacted with triethylenetetramine in order to obtain MMSCB 3 and 5.76 mg g1 and 46. Lalhruaitluanga et al. The capacity of MMSCB 3 and 5 to adsorb Cu2+. Effect of oxidation on the surface charges of coconut shell carbon (CSC).

Co2+ and Ni2+ removal onto HApC was 12.04. Konjac glucomannan (KGM) is a neutral polysaccharide which consists of mannose and glucose in a molar ratio of 1. The partially saturated agro-waste materials were efficiently regenerated by an EDTA solution at 55 8C without apparent modifications on the biosorbents. CH3COOH proved to be the best for recovery of Se(IV). The regeneration of the sorbent was accomplished with very little loss in metal removal efficiency for both single and multi-metal systems. The desorption efficiency of EDTA was quite high (99%) in comparison of HCl (90%) solution. and the biosorbents color change. Ni(II) and Al(III).1 M EDTA and HCl solutions. and HNO3 showed almost equal and higher recovery efficiency 27% for Zn(II). El-Said et al. HNO3.1 M HCl was selected due to its high metal desorption properties and its lower cost of operation [236–240]. 122% and 91% were achieved for Zn(II).K. Acid and alkaline solutions attacked the carboxyl groups conversely to EDTA solutions. Pb2+. contact time. The KGM showed a high adsorption capacity for Cu2+ and Pb2+ ions. Equilibrium data were fitted well in the Langmuir and Freundlich isotherm models. respectively. Regeneration and reuse of a seaweed-based biosorbent in single and multi-metal systems have been performed by Bakir et al. 10. [241] have studied the sorption and desorption of Cr(III) by agro-waste biosorbents such as sorghum straw. or complexation (EDTA-Cr (III)). HCl. and CH3COOH of known concentration was contacted with metal-loaded Rice husk ash (0. respectively. Gautam et al. several studies have shown that it would also decrease metal adsorption abilities of the regenerated biosorbents because of hydrolysis of the polysaccharides on the biomass surface as metal binding sites [233. The adsorption isotherm data was well described by Langmuir model and the kinetic data were fitted well to pseudosecond-order rate model. The adsorption process followed pseudo-second order kinetics and intraparticle diffusion model. For desorption experiments. [230] chemically modified the KGM by crosslinking agent to overcome this problem and functionalized with carboxymethyl groups for removal heavy metal ions from aqueous solutions. Niu et al.0 M EDTA obtained at 55 8C suggested that the interaction Cr(III)-EDTA involved a chelate formation and an increase in temperature facilitated the chemical interaction between EDTA and Cr(III). In addition. Because of low degree of substitution of carboxymethyl groups on crosslinked KGM. the mixture was centrifuged and the supernatant was analyzed for metal ions released into the solvent. regeneration and desorption of biosorbents In favor of material cycling and safe post-treatment of metal loaded biosorbent. for subsequent metal loading cycles. 96% and 94% removal efficiency were achieved for Zn(II).252 R. HCl. 35 8C.. NaOH (1. The regeneration of the biosorbent using an acid wash resulted in the release of high metal concentrations during multiple desorption cycles. Recovery of metals.1 M HCl solution at 25 mL min1 for 180 min.1 M or 0. [81] have studied the removal of Zn(II) by untreated and anionic surfactant treated dead biomass of isolated yeast . The Increase in adsorption capacity with increase in equilibrium metal ion concentration for different metal ions was in the order Pb2+ > Co2+ > Ni2+.4-linkage. In addition. its dissolution is very high in water showing increased water absorbency [229]. Co2+ and Ni2+ adsorption capacities of HApC increased with increase of equilibrium concentration. Recent research on recovery of metals from metal-loaded biosorbents using chemical reagents and regeneration of the biosorbents are summarized in Table 7. Then after. The effect of different concentration of Pb2+. H2SO4. the metal loaded biomass was exposed to a continuous feed of a 0. Ni(II) and Al(III). This limitation prevents the KGM for being used as adsorbent in separation science. respectively. However. The mixtures were agitated at 100 rpm for 5 h in the orbital shaker. between H+ and Na+ with Cr(III) species. H2SO4. Ni(II) and Al(III). Bernardo et al. HCl. based on the chromium desorbed and the initial weight lost. adsorbent dose. although it is less effective as compared with dilute acids. Co2+ and Ni2+ by hydroxyapatite/chitosan composite from aqueous solution [232]. alkaline and acid regeneration produced hydrolysis of the agro-waste materials confirmed by the initial weight lost. Desorption of Zn(II) and Se(IV) using of mineral acids. Even though HCl has a very high capacity to desorb metals.1 N).0 N or 0. [231] synthesized carboxylic acid functionalized deacetylated konjac glucomannan by free radical graft copolymerization of methyl acrylate (MA) and methylmethacrylate (MMA) onto the backbone of deacetylated konjac glucomannan with subsequent chemical activation of the ester groups in the side chains of the resulting graft copolymer by sodium hydroxide. [138] have conducted batch desorption experiments and the desorption efficiencies were compared. The Cr(III) loaded biosorbents were added to 100 mL of HNO3 (1. 82% and 82% for Zn(II). HNO3. at 25 8C and 35 8C. 0. [235]. and 55 8C). Heavy metals and metalloids can be effectively removed from metal-laden biosorbents using dilute acids (e. mineral acids. On the other hand. They have investigated the effect of various physicochemical parameters such as pH.05 M) solutions at different concentrations and temperatures (25 8C.54 mg L1. and H2SO4).5 g) at 25  1 8C. These eluents were selected aiming at an ion exchange process. for the 5th sorption cycle in single metal aqueous solutions. derived from the tubers of Amorphophallus konjac [228]. On the other hand.g. It was clear that Pb2+.0 N or 0. Values of 92%.63 and 8. respectively. The maximum adsorption capacity onto carboxylic acid functionalized deacetylated konjac glucomannan was found to 64. and agave bagasse. Co2+ and Ni2+ on the adsorption had been investigated at 303 K.1 M EDTA was much lower (0–9%) than what was obtained when 1. the initial weight lost of acid-washed materials due to the regeneration with 0. Co2+ and Ni2+ adsorption capacities of HApC were given as a function of equilibrium concentration. The Langmuir constant for Pb2+. Liu et al.5 mg g1 and 191. H2SO4. / Journal of Environmental Chemical Engineering 2 (2014) 239–259 applications of synthesized biomaterial the same authors have performed desorption experiments and regeneration of adsorbent by using 0. EDTA can be used as an eluent of metal cations. initial metal ion concentration and temperature on adsorption of metal ions onto HApC composite. The metals adsorbed on the surface of biosorbents can be recovered by desorption with adequate eluents. EDTA was the best option to regenerate the chromium-loaded agro-waste materials.1 N) or EDTA (0. significantly exceeding the desorption rates observed for conventional sorbents. a series of 250 mL Erlenmeyer flasks containing 50 mL of aqueous solution of HCl.6:1 with a b1.0 N HNO3 or 1. it is necessary to remove and recover metals from the metal-loaded biomass that has been used in the treatment of metal-contaminated wastewater. the removal capacity of crosslinked carboxymethyl KGM biomaterial for heavy metal ions was not high. Hydroxyapatite/chitosan (HApC) composite was synthesized by precipitation method for the adsorptive removal of Pb2+. A slight decrease was observed for the same metals in multi-metal systems with maximum removal efficiencies of 85%. Das et al. oats straw.0 N NaOH was used as eluent. The higher chromium desorption with 1.234]. This fact suggested that EDTA solutions produced fewer structural modifications in the biosorbents than the acid or the alkaline solutions. and HNO3 compared with CH3COOH acid showed maximum desorption efficiency of 27% for Zn(II) and 10% for Se(IV).3 mg g1 for Cu2+ and Pb2+ ions. respectively. Biosorption capacity for Cr(III) uptake were conducted in batch experiments at pH 3 and 4. Maximum desorption efficiencies of 183%. Therefore.

0. Gautam et al. 0.K. optimal pH for adsorption: near neutral Pyrolyzed at 500 8C.1 M NaOH. >95 lead ions was recovered by Na2EDTA Raw biomass of Oedogonium hatei was treated with 0. then treated with 0.9 Baker’s yeast Gloeocapsa gelatinosa Fungi (yeast) Bacteria 0.1 M NaOH. recovery of metal was repeated 3 times Ground and passed through 90 mm screen.0–91. mixed with clay as a binder (pyrolyzed coffee residue:clay = 80:20 [in weight]).0).10 M HCl. 4 mm in diameter) Modified by crosslinking cystine with glutaraldehyde Lyophilized cells with capsular polysaccharide (CPS).1 M NaOH 5 Batch 1 75 Cr Mucor hiemalis Fungi 0.10 M HNO3.01 M EDTA >6 – Batch Batch 1 0.5 Pyrolyzed coffee residue Plants Distilled water 5 Batch 0.10 M Na2EDTA – Batch – >95 Cr Oedogonium hatei Algae 0.25  3 95 49.05 M HCl. in eluate as compared with the original Cd solution. 0.1 N NaOH 5 Batch 1.5 99 50-fold increase in Cd conc.05 M Na2EDTA.1 M HCl and then stirred the mixture at 200 rpm for 8.1 M HCl >3 Batch 1 90.5 Sargassum sp.5 88. Pb [155] [161] [249] [155] [164] [161] [168] [169] [15] R.1 M HCl 0. Desorption data showed that nearly 99% of the Cr(VI) adsorbed on M.Table 7 Recovery of heavy metals and metalloids from metal-loaded biosorbents reported recently. The regenerated material had a higher maximum adsorption capacity than the original one Modified by crosslinking cystine with glutaraldehyde Ground and passed through 90 mm screen. hiemalis was desorbed using 0. Biosorbent material Biosorbent type Eluent Number of adsorption– desorption cycles Elution mode Elution time (h) Recovery (%) Remarks References Cd Streptomyces clavuligerus Bacteria 1 M Na2SO4 (pH about 10) – Filtration – >95 [248] Baker’s yeast Phragmites australis shoot Fungi (yeast) Plants 0. glanular (10 mm in length. optimal pH for adsorption: near neutral High value of the conditional formation constant of the complex Pb(II)–EDTA (K0 f = 3. / Journal of Environmental Chemical Engineering 2 (2014) 239–259 Metal 253 . 0. then treated with 0. 0.05 M HNO3.1 N NaOH.1 M HCl >6 >3 Batch Batch 1 1 95 98.7 Phragmites australis shoot Plants 0. which favors the desorption of lead.0 h.1 M HCl 0. centrifuged.85  1011 at pH = 5. Algae 0. washed with the physiological saline solution and dried in an oven at 60 8C.

In particular. reactor. salt solutions. Pretreatments of raw biomass by physical or chemical methods have been also found to improve the metal adsorption performances of the biosorbents. These models play an important role in predictive modeling for analysis and design of adsorption systems. The costs for formulating biosorbents and operating the treatment systems are generally low. agriculture-based sorbents have demonstrated outstanding removal capabilities for certain metal ions in comparison to activated carbon. It is not necessary to feed any substrates or energy for propagation of the raw biomass of biosorbents if these microbial wastes and abundant biomass are to be utilized. The adsorption of metal cations on biosorbents would be also inhibited by inorganic and organic anions present in the solution due to complexation with the metal cations. despite a number of . and the biomass that exists abundantly such as exotic weeds can be utilized as cheap raw materials of biosorbents. The elution efficiency and percentage removal of Zn(II) were found to decrease in the successive cycles. three and four parameter isotherm models. and these metal ions would compete with each other for the binding sites on biosorbents. Inexpensive. to remove the poisoning of the metal ions from aqueous solutions.) used for the removal of heavy metals influence the sorption processes. Not only heavy metals but also Ca and Mg present in hard water and Al and Fe in most of industrial effluents and mine drainage may strongly obstruct biosorption of the target heavy metals [245]. or composts as fertilizer. the physical and chemical stability of the materials and the reproducibility of the sorption properties are of utmost importance. Freundlich isotherm model was well fitted for the adsorption of Zn(II) from aqueous system. Four cycles of desorption and sorption was performed to study the reusability of the biosorbent. etc. Biosorbents are basically biodegradable.0 in presence of 90 mg L1 Zn(II) at 30 8C in batch system for C. commonly known as adsorption isotherms. rugosa and C. such as the final wastewater treatment process to meet regulation standards of metals before being discharged to the environment. This property of biosorption would make it the most effective in treatment of voluminous water bodies containing low concentrations of metals. a wide range of non-conventional low-cost adsorbents has been presented. Undoubtedly biosorbents offer a lot of promising benefits for commercial purposes in the future. and (b) improve biosorption selectivity for target metals. Performances of biosorbents can be improved through various kinds of physical and chemical pretreatments. In this review. ionic strength. column. on the other hand the comparison of sorption performance depends not only the parameters related to the experimental conditions and the effluent.K. and suspended solids. biosorption can play a key enabling role. from the recent literature reviewed. However. coexisting ions. there is little information on this subject. Biosorption of metal ions is strongly affected by the properties of the water to be treated. such as pH. / Journal of Environmental Chemical Engineering 2 (2014) 239–259 species viz. It is generally easy to recover metals from metal-loaded biosorbents and regenerate the biosorbents for further adsorption–desorption cycles. Gautam et al. Several parameters (batch. thermal energy by combustion. The experimental data were analyzed using two. Concluding notes In the development of new separation and purification technologies. In view of industrial developments of the various kinds of sorbents described in the literature.4% and 54. Outlooks and discussion Several advantages in using low cost biosorbents for removal and recovery of heavy metals from aqueous solutions are discussed below together with the main drawbacks. Unfortunately. There is a little knowledge about the comparison studies of biosorbents for the removal of heavy metals from industrial effluents. such as removal of heavy metals. They are. a direct comparison of data obtained using different biosorbents is difficult because of inconsistencies in the data presentation [242. Biosorption treatment can be operated at a wide range of scales. and chelating agents such as ethylenediaminetetraacetic acid (EDTA) solution are reported to be effective in eluting metals from the metal-laden biosorbents. Desorption of the adsorbed metals with suitable acid or base results in the regeneration of biosorbents and the recovery of precious metals.243]. metal adsorption performance of biosorbents should be carefully evaluated in not only a single-metal solution system but also multi-metal solution systems prior to their practical applications [246]. and this system can be scaled up to the treatment of a large volume of acid mine drainage and industrial wastewater and scaled down to the removal of As from contaminated well water. This behavior is primarily due to continuous usage of the biosorbent. although this is not always the case. The design and efficient operation of adsorption processes also requires equilibrium adsorption data for use in kinetic and mass transfer models [244]. A breakthrough in sorbents development is needed to solve the critical problem of removal and recovery of metal ions. and they will take additional costs according to the reagents and equipments used for the modifications. locally available and effective materials could be used in place of commercial activated carbon for the removal of heavy metals from industrial effluents. Candida rugosa and Candida laurentii in both batch and column mode. if the complete (if not. Therefore. Remarkable increase in Zn(II) removal was noted using dead yeast biomass treated with anionic surfactant sodium dodecyl sulfate (SDS). acidic pH favors biosorption of metal anions. However. A packed bed column reactor configuration is considered to be the most effective mode of the biosorption process. and their adsorbed amounts would decrease as solution pH is lowered because of diminishing of negatively charged sites on the biosorbents due to protonation. Additional work on this subject can boost up the zeal of the biosorption of heavy metals. This evaluation would clarify at the same time the selectivity of the biosorbents in metal binding. Thus. Optimal pH for biosorption of metal cations is generally around neutral. agricultural byproducts. Dilute acid and alkaline solutions. especially waste bacteria and fungi from various fermentation industries. sufficient) removal of adsorbed metals from the biosorbents is secured. The main purposes of modification of raw biosorbent materials are to (a) shape and impart mechanical strength and resistance to chemical and microbial degradation. The metal ions removal rates from aqueous solution by biosorption are generally faster than those by other metabolically mediated processes. there is need for the further development of newer biosorbents of highest removal capacity. A decreased breakthrough time and exhaustion time were observed as the regeneration cycles progressed. A special attention should be paid on reuse aspects. Mine drainage and industrial wastewater usually contain more than one heavy metal species. On the other hand. The maximum removal was 65. and the exhausted biosorbents that consist mainly of degradable organic matter could be converted into energy fuels through fermentation processes. often required to receive some modifications before introduction into the real wastewater treatment systems. however. There is a lack of data concerning the reproducibility of the adsorption properties and the equilibrium data.254 R. laurentii.8% of Zn at pH 6.

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