Beruflich Dokumente
Kultur Dokumente
Technology
Mandu I. Inyang, Bin Gao, Ying Yao, Yingwen Xue, Andrew Zimmerman,
Ahmed Mosa, Pratap Pullammanappallil, Yong Sik Ok & Xinde Cao
To cite this article: Mandu I. Inyang, Bin Gao, Ying Yao, Yingwen Xue, Andrew Zimmerman,
Ahmed Mosa, Pratap Pullammanappallil, Yong Sik Ok & Xinde Cao (2016) A review of biochar as
a low-cost adsorbent for aqueous heavy metal removal, Critical Reviews in Environmental Science
and Technology, 46:4, 406-433, DOI: 10.1080/10643389.2015.1096880
Download by: [GGS Indraprastha University] Date: 21 August 2017, At: 00:03
CRITICAL REVIEWS IN ENVIRONMENTAL SCIENCE AND TECHNOLOGY
2016, VOL. 46, NO. 4, 406433
http://dx.doi.org/10.1080/10643389.2015.1096880
ABSTRACT KEYWORDS
As a low-cost adsorbent, biochar can be used as a low-cost Black carbon; charcoal; trace
adsorbent for wastewater treatment, particularly with respect to element; wastewater;
treating heavy metals in wastewater. A number of studies have pyrogenic carbon
demonstrated effective removal of heavy metals from aqueous
solutions by biochar and, in some cases, proven the superiority
of biochars to activated carbons. Among several factors
affecting the sorption ability of biochars, feedstock materials
play a signicant role. This review incorporates existing literature
to understand the overall sorption behavior of heavy metals on
biochar adsorbents. Depending on the biochar type, heavy
metal can be removed by different mechanisms such as
complexation, physical sorption, precipitation and electrostatic
interactions. Mathematical sorption models can be used to
understand the efciency of biochar at removing heavy metals,
and promote the application of biochar technology in water
treatment.
1. Introduction
Biochar is pyrogenic black carbon derived from thermal degradation (e.g., pyrolysis) of
carbon-rich biomass in an oxygen-limited environment. In recent years, biochar has
received increasing attention due to its multifunctionality including carbon sequestra-
tion and soil fertility enhancement (Laird et al., 2010), bioenergy production (Field et
al., 2013), and environmental remediation (Mohan et al., 2014a). Several recent publi-
cations have provided evidences of biochars excellent ability to immobilize organic
(Inyang et al., 2014; Lattao et al., 2014; Rajapaksha et al., 2014) and inorganic pollutants
(Meng et al., 2014; Mohan et al., 2014b; Yao et al., 2011a) in soil and water systems.
CONTACT Bin Gao bg55@u.edu Department of Agricultural and Biological Engineering, University of Flor-
ida, Gainesville, FL 32611, USA.
Color versions of one or more of the gures in the article can be found online at www.tandfonline.com/best.
2016 Taylor & Francis Group, LLC
CRITICAL REVIEWS IN ENVIRONMENTAL SCIENCE AND TECHNOLOGY 407
While most organic pollutants are biodegradable, inorganic pollutants, mainly heavy
metals, are nonbiodegradable and may be passed along the food chain through bioaccu-
mulation. Biochar is increasingly being considered as an alternative agent in water treat-
ment technologies for metal removal.
The presence of elevated concentrations of heavy metals in waste streams poses
challenges in environmental remediation. Table 1 summarizes several heavy metals
ranked in order of their toxicity by the Comprehensive Environmental Response
Compensation and Liability Act (Srivastava and Majumder, 2008). It also lists the
current maximum allowable contaminant levels (MCLs) provided by the Environ-
mental Protection Agency (EPA) for these metals. To meet the EPA standards, vari-
ous removal techniques (e.g., ion exchange, precipitation, electrocoagulation,
activated carbon adsorption, packed bed ltration) have been employed in wastewater
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treatment facilities. Most of these techniques, however, are expensive and there is a
need to develop more cost-effective technologies with low-cost adsorbents (Kailash et
al., 2010).
Development of biochar technology provides opportunities to satisfy the need of
low-cost adsorbents for aqueous heavy metals. Mohan et al. (2007) noted that
removal efciencies of lead (Pb) and cadmium (Cd) by oak bark char are compara-
ble to that of Calgon F-400, a commercial activated carbon. Chen et al. (2011)
reported that biochar produced from wood or corn straw can effectively adsorb
copper (Cu) and zinc (Zn) in aqueous solutions. Similarly, Kong et al. (2011)
reported 7587% removal of mercury from aqueous solution by soybean stalk bio-
char. Further, the application of different engineering methods in biochar produc-
tion, such as pretreatment of feedstocks or modication of char surfaces, has
resulted in many high efciency and cost-effective engineered biochars with
adsorption capacities comparable to or even surpassing some commercial activated
carbons. For instance, previous studies (Inyang et al., 2011, 2012) showed that bio-
chars produced from anaerobic digested biomass have a much higher Pb sorption
capacity than commercial activated carbon. Physical treatment of the feedstock, by
pulverization prior to pyrolysis, can also greatly enhance the sorption ability of the
biochars to Cu in aqueous solution (Tong et al., 2011).
Table 1. Top heavy metals and their maximum allowable contaminant level.
Heavy metals Rank (CERCLA) Maximum contaminant level by EPA (mg/l)
Lead 2 0.015
Mercury 3 0.002
Cadmium 7 0.005
Chromium 17 0.1
Cobalt 52
Nickel 57
Zinc 75 5.0
Uranium 97
Copper 125 1.3
Manganese 140 0.05
Note. Maximum contaminant level was derived from goals from CERCLAs 2011 list of priority hazardous substances
and EPAs drinking water standards (Srivastava and Majumder, 2008).
408 M. I. INYANG ET AL.
Many aspects of biochar including its production, physical and biological proper-
ties, stability, and its applications have been assembled in a book, Biochar for Environ-
mental Management: Science and Technology (Lehmann, 2012). A recent study by
Laird et al. (2009) also reviewed the process of pyrolysis as a practical and effective
platform for producing renewable bioenergy products, bio-oil and biochar, as well as
simultaneously controlling greenhouse emissions. As for biochars applications, there
are several good reviews about the potential environmental applications of biochar to
immobilizing contaminants, including metals and organics, in soils (Beesley et al.,
2011; Kookana, 2010; Mohan and Pittman, 2007). Recently, two comprehensive
reviews (Ahmad et al., 2014; Mohan et al., 2014a) were published on several aspects
of biochar production and heavy metal sorption, but certain aspects such as heavy
metal sorption kinetic and thermodynamic behaviors on different biochar types are
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Parent Biomass
Pinewood 300 4.3 (Liu and Zhang, 2009)
Rice husk 300 2.4 (Liu and Zhang, 2009)
Corn straw 600 12.5 11.0 (Chen et al., 2011)
Hardwood 450 6.8 4.5 (Chen et al., 2011)
Switch grass 300 2.1 (Kumar et al., 2011)
Pine wood 400/450 4.1 (Mohan et al., 2007)
Oak wood 400/450 0.4 2.6 (Mohan et al., 2007)
Pine bark 400/450 0.3 3.0 (Mohan et al., 2007)
Oak bark 400/450 5.4 13.1 (Mohan et al., 2007)
Sugar beet tailings 300 123.0 (Dong et al., 2011)
Soybean stalk 700 0.7 (Kong et al., 2011)
Flax shive 160 14.3 21.1 19.2 87.0 31.6 18.2 17.3 (El-Shafey et al., 2002)
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200 25.5 39.1 33.4 147.1 52.1 32.5 31.2 (El-Shafey et al.,
2002)
Oak wood 400450 3.0 (Mohan et al., 2011)
Oak bark 400450 4.6 (Mohan et al., 2011)
Rice husk 300 4.6 (Pellera et al., 2012)
600 0.3 (Pellera et al., 2012)
Olive pomace 300 5.1 (Pellera et al., 2012)
600 0.7 (Pellera et al., 2012)
Orange waste 300 4.9 (Pellera et al., 2012)
600 0.4 (Pellera et al., 2012)
Compost 300 7.9 (Pellera et al., 2012)
600 3.4 (Pellera et al., 2012)
Sugarcane bagasse 600 6.5 (Inyang et al., 2011)
Dairy manure 200 140.9 (Cao et al., 2009)
350 101.7 (Cao et al., 2009)
Industrial by-products
Sewage sludge 550 30.88 (Lu et al., 2012)
Anaerobically digested 600 135.5 (Inyang et al., 2011)
sugarcane bagasse
Anaerobically digested 600 40.8
whole sugar beet
Anaerobically digested 600 51.4 (Inyang et al., 2012)
animal waste
Dried sewage sludge 650 3.00 40.30 6.70 (Otero et al., 2009)
Chemically activated
materials
H2O2 Peanut hull 300 22.8 (Xue et al., 2012)
H2SO4 Corn stalk 220 36.4 (Youssef et al., 2004)
ZnCl2 Corn stalk 600 32.4 (Youssef et al., 2004)
H3PO4/HNO3 Peanut shell 550 35.5 (Xu and Liu, 2008)
Nonconventional
materials
Waste tire rubber ash 500 22.4 34.4 (Mousavi et al., 2010)
Bone char 500 47.6 34.7 (Cheung et al., 2000a)
feedstock for the production of biochar due to their ease of collection from residen-
tial collection services and wood mills.
The strong sorption ability of biochars produced from agricultural and forest
residues may be attributed to their surface properties originating from the feed-
stock materials (Sun et al., 2014; Wang et al., 2015a). For example, the abundance
of oxygen containing groups (CDO, C O, OH) in oak bark biochars originat-
ing from polyphenolic tannins, avonoids, and suberin contents in the partially
410 M. I. INYANG ET AL.
aromatized bark materials provided negatively charged surface sites (COO and
OH) for the attraction of Pb2C(Mohan et al., 2007). Kumar et al. (2011) reported
that volatilization of large amounts of cellulose from switch grass during pyrolysis
creates porous carbon materials with surface functional groups strongly afliated
to aqueous U (VI). Pyrolysis of other agricultural residues, such as sugar beet tail-
ings, may also yield electron donor functional groups (C-OH, C-O, C-O-R)
because the feedstocks have complex heteropolysaccharides containing galactur-
onic acid, arabinose, galactose, and several pectin substances (Aksu and Isoglu,
2005). These oxygen functional groups can promote the sorption of aqueous chro-
mium, Cr (VI) on biochar by reducing Cr (VI) to Cr (III) to facilitate surface
adsorption (Dong et al., 2011). It has also been reported that elevated levels of cat-
ionic nutrients, such as Na, K, and Mg, in oak and pine wood feedstock materials
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can also increase the cation exchange capacities of the corresponding biochars and
enhance their sorption of Pb through ion exchange process under acidic pH condi-
tions (Mohan et al., 2007).
Domesticated animal wastes are another abundant source of potential biochar
feedstock. Biochars produced from animal wastes such as poultry litter (including
bedding materials, spilled feed, and feathers) and dairy manure generally have
high amounts of ash and inorganic components that can bind heavy metals (Cao
et al., 2011; Duku et al., 2011; Uchimiya et al., 2010). Multiple mechanisms, includ-
ing precipitation and surface complexation, have been reported to be responsible
for the strong afliations between animal waste-derived biochar and aqueous
heavy metals (Cao et al., 2011; Uchimiya et al., 2010).
Gupta, 2010; Rhee and Park, 2010) have also been explored for producing carbon
sorbents. In particular, the use of waste tires as feedstock for biochar production is
attractive because waste tires are abundant, and pyrolysis of waste tires reduces the
risk and operation cost of waste tire disposal. Several studies have also shown that
pyrolyzed waste tire is an effective sorbent for heavy metals, such as Pb in aqueous
solutions (Mousavi et al., 2010), partly due to electrostatic interactions between the
positively charged cations and negatively charged biochar surface. Bone biochars
are heterogeneous sorbent materials derived from the combustion of crushed and
distilled animal bones (Pan et al., 2009). Cheung et al. (2000a) showed strong
uptake of Cu and Zn by bone biochars and suggested that high amounts of calcium
hydroxyapatite and calcium carbonate in the bone biochars promote ion-exchange
reactions between heavy metals (Cu, Zn) in solution and lattice Ca2C ions of the
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apatite within the biochar (Cheung et al., 2000a; Pan et al., 2009).
Cotton seed hull 350 Cd, Cu, Ni, and Pb Complexation of metals by (Uchimiya et al.,
char oxygen functional groups 2011)
Rice husk carbon 175180 Hg, Zn Ion exchange between HC and (El-Shafey, 2010)
Zn2C and Hg2C
Flax shive 200 Cd Ion exchange between HC and (El-Shafey et al.,
carbon Cd2C 2002)
Beech wood 550 Cu Complexation of Cu by carboxyl (Borchard et al.,
char functional groups 2012)
Wheat and rice open eld burning Pb Electrostatic interaction (Qiu et al., 2008)
char between Pb2C and
negatively charged
functional groups on biochar
Sugar beet 300 Cr Electrostatic attraction between (Dong et al.,
tailings char Cr(VI) and biochar and 2011)
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et al., 2009; Inyang et al., 2011; 2012). Table 3 summarizes the governing mecha-
nisms for the immobilization of aqueous metallic species by various biochars.
2010). Animal bone chars were also reported (Choy and McKay, 2005) to
retain Cd (53.6 mg/g), Cu (45.04 mg/g), and Zn (33.03 mg/g) in their pore
networks, and their sorption data was well described by lm pore diffusion
controlled model.
3.4 Complexation
Complexation (outer- and innersphere) involves the formation of multiatom structures
(i.e., complexes) with specic metal-ligand interactions. This binding mechanism is
likely important for metals, such as transition metals with partially lled d-orbitals, hav-
ing a high afnity for ligands (Crabtree, 2009). In particular, oxygen functional groups
(carboxyl, phenolic, and lactonic) in low-temperature biochars have been demonstrated
to effectively bind with heavy metals (Liu and Zhang, 2009; Mohan et al., 2007). Oxygen
content of biochars has also been shown to increase over time, likely due to oxidation of
biochar surface and the formation of carboxyl group (Harvey et al., 2011), thus, metal
complexation may increase over time.
From Table 3, it can be inferred that complexation of metallic species is more popular
with plant-derived than animal-derived biochars. As a result, plant-derived chars readily
bind with several heavy metals, such as Cd, Cu, Ni, and Pb to precipitate phenolic and
carboxylic-metal complexes on the chars. Similarly, some animal derived chars in partic-
ular, dairy manure and chicken litter carbons can also bind metals such as Pb with phos-
phate ligands which originate from the nutrient rich, feeds to form metallic complexes
such as pyromorphite (Cao et al., 2009; Guo et al., 2010).
3.5 Precipitation
Precipitation is the formation of solid(s), either in solution or on a surface, during
the sorption processes. Precipitation has been commonly cited as one of the main
mechanisms responsible for the immobilization of heavy metals by biochar sorb-
ents. Metals and rare earth elements with intermediate ionization potentials
between 2.5 and 9.5 (e.g., Cu, Zn, Ni, Pb) are more likely to precipitate (Krauskopf,
1967) on biochar surfaces than other elements. The thermal degradation of cellu-
lose and hemicellulose in plant biomass at relatively high temperatures (>300 C)
often produces alkaline biochars (Cao and Harris, 2010). When in solution, these
biochars may trigger the precipitation of metallic species. For instance, previous
study had showed that digested bagasse biochar (pH of 10.93) was able to
CRITICAL REVIEWS IN ENVIRONMENTAL SCIENCE AND TECHNOLOGY 415
and Harris (2010) suggested that soluble forms of these phases also exist in low tem-
perature biochars (<200 C), and can directly react with heavy metal species to form
insoluble metallic precipitates such as pyromorphite [Pb5(PO4)3Cl] (Cao et al., 2009).
Less soluble forms of these mineral phases exist at higher temperatures (350600 C),
and are more likely to be slowly released during sorption reactions with heavy metals
to form precipitates on biochar surfaces (Inyang et al., 2011).
4. Mathematical modeling
4.1 Adsorption thermodynamics
Thermodynamic models are powerful tools to describe metal sorption processes and to
explore governing mechanisms. Thermodynamic parameters of metal sorption on bio-
chars reported in the literatures have been summarized in Table 4. The thermodynamic
behavior of heavy metal sorption on biochars can be described as either exothermic
(sorption decreases with increasing temperature) or endothermic sorption processes
(sorption increases with increasing temperature). Three thermodynamic parameters are
often used to characterize the thermodynamics: (a) enthalpy, DH ; (b) entropy, DS ; and
(c) Gibbs free energy, DG . According to Chen et al. (2011), these thermodynamic
parameters can be computed from the following equations:
qe
Ke D (1)
Ce
DG0 D RTlnKe (2)
B
DG D DH TDS
0
(3)
DS 0
DH 0
lnKe D (4)
R R
where qe (mg/g) is the amount of heavy metals adsorbed on biochar at equilibrium,
Ce (mg/l) is the equilibrium concentration of heavy metals in the solution, R (J/
mol_K) is the gas constant (8.314), T (K) is the absolute temperature, and Ke (l/g) is
the adsorption equilibrium constant. By plotting ln Ke against 1/T, the values of
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416
Table 4. Summary of thermodynamic parameters by biochar-based sorbents.
Thermodynamics parameters
Biochar (temperature [ C]) Metal Temperature (K) DG0 (KJ/mol) DH0 (KJ/mol) DS0 (J/mol K) Sorption type Reference
Pine wood (300) Pb 298 14.68 41.1 187.15 Endothermic, spontaneous (Liu and Zhang, 2009)
308 16.55
318 18.42
Rice husk (300) Pb 298 13.20 37.13 168.88 Endothermic, spontaneous (Liu and Zhang, 2009)
308 14.89
318 16.58
Corn straw (600) Cu 295 -0.80 25.27 88.21 Endothermic, spontaneous (Chen et al., 2011)
303 1.39
310 2.13
Zn 295 1.45 30.94 99.85 Endothermic (Chen et al., 2011)
303 0.68
310 0.05
Hard wood (450) Cu 295 5.38 9.22 13.09 Endothermic, non spontaneous (Chen et al., 2011)
303 5.2
310 5.19
Zn 295 6.39 7.55 3.99 Endothermic, nonspontaneous (Chen et al., 2011)
303 6.31
310 6.34
Barrabus barkcarbon Fea 303 2.59 0.92 5.42 Endothermic, spontaneous (Arivoli et al., 2008)
313 2.81
323 3
333 3.18
Coa 303 1.8 2.16 8.82 Endothermic, spontaneous (Arivoli et al., 2008)
313 2.21
323 2.52
333 2.74
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Table 4. (Continued ).
Thermodynamics parameters
Biochar (temperature [ C]) Metal Temperature (K) DG0 (KJ/mol) DH0 (KJ/mol) DS0 (J/mol K) Sorption type Reference
a
Ni 303 0.615 1.15 5.21 Endothermic, spontaneous (Arivoli et al., 2008)
313 0.655
323 0.708
333 0.77
Oxidized peanut shell carbon Cr(VI) 293 28.38 0.04 0.1 Endothermic and spontaneous (Al-Othman et al., 2012)
303 29.39
313 30.32
Unoxidized peanut shell carbon Cr(VI) 293 11.73 0.02 0.04 Endothermic, spontaneous (Al-Othman et al., 2012)
303 11.13
313 12.53
a
Thermodynamic parameter values were obtained at a concentration of 30 mg/l.
417
418 M. I. INYANG ET AL.
DH and DS can be determined from the slopes and intercepts, respectively. The
values of DG can then be calculated from the corresponding values of DH and
DS . Positive DH values indicate that the sorption reaction is endothermic, sup-
ported by an increase in qe (mg/g) with increasing temperature. On the other hand,
negative DG values suggest a spontaneous sorption process with increasing metal
sorption at higher temperatures. Positive values of DS may reect an afnity of the
carbon sorbent for the metal ions (Lu et al., 2009). Free energy, DG (KJ/mol) could
also provide information to distinguish physical sorption (DG , 20 to 0 KJ/mol)
from chemisorption (DG , 400 to 80 KJ/mol) processes (Liu and Zhang, 2009).
Traditionally, thermodynamics of biochar sorption to heavy metals have been
investigated in conjunction with exploring the effect of temperature on the sorption
capacity of biochar. For instance, adsorption studies by Liu and Zhang (2009) with
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where qt (mmol kg1) and qe (mmol kg1) are the amounts of metal sorbed at time
t and at equilibrium respectively; k1 (h1) and k2 (kg mmol1 h1) are the rst-
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419
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420
Table 5. (Continued ).
Biochar type
(temperature
[ C]) Metal Model Parameter 1 Parameter 2 Parameter 3 Parameter 4 Reference
Table 5. (Continued ).
Biochar type
(temperature
[ C]) Metal Model Parameter 1 Parameter 2 Parameter 3 Parameter 4 Reference
1
Compost (300) Cu(II) First order k1 (min ) D 0.003 qe (mg/g) D 0.543
Second order k2 (g mg1 min1) D 0.107 qe (mg/g) D 3.630
Langmuir K (l/mg) D 0.359 Smax (mg/g) D 7.937
Freundlich Kf (l/g) D 1.701 n D 1.744
Intraparticle diffusion
Kd (mg g1min1/2) D 0.018 C (mg/g) D 3.0078
Sludge (650) Hg(II) Langmuir K (l/mg) D 0.044 Smax (mg/g) D 64.9 (Otero et al., 2009)
Pb(II) K (l/mg) D 0.019 Smax (mg/g) D 40.3
Cu(II) K (l/mg) D 0.022 Smax (mg/g) D 6.7
Cr(III) K (l/mg) D 0.015 Smax (mg/g) D 3.0
Oak bark (400/ Cr(VI) First order k1 (h1) D 1.49 qe (mg/g) D 1.49 (Mohan et al., 2011)
450) Second order k2 (g mg1 h1) D 1.63 qe (mg/g) D 1.63
Langmuir K (l/mg) D 0.073 Smax (mg/g) D 4.619
Freundlich Kf (l/g) D 0.523 n D 2.016
Langmuir-Freundlich KL-F (l/g) D 0.182 aL-F (l/mg) D 0.048 nL-F D 1.461
Dairy manure Pb (II) Langmuir K (l/mmol) D 61.3 Smax (mmol/kg) D 452 (Cao et al., 2009)
(350) Double Langmuir K1 (l/mmol) D 0.91 Smax1 (mmol/kg) D 78.3 K2 (l/mmol) D 69.3 Smax2 (mmol/kg) D 413
421
422 M. I. INYANG ET AL.
The pseudo rst-order adsorption rate coefcient, k1 (h1), can be evaluated as the
slope from the plot of ln (qeqt) versus ln qe. The value of qe is unknown and the
amount sorbed is signicantly smaller than the actual equilibrium amount (Gerente
et al., 2007). As such, the pseudo rst-order may only apply for the initial 2030 min
of most sorption processes, after which, the model may not t the whole sorption
data within the entire range of contact times (Gupta and Bhattacharyya, 2011). When
this occurs, the plot of ln (qe qt) versus ln qe ceases to be linear and an accurate
representation of the sorption data would require a more complex model, such as the
second order kinetic model. Despite limitations of the pseudo rst order model, this
model has been successfully applied to describe the sorption kinetics of heavy metals
on various biochar sorbents (Table 5). For instance, Zuo et al. (2012) reported that
the pseudo rst-order model closely reproduced data from the sorption of Cu, Cd,
and Zn by carbonized mulch. Plotted kinetic curves for Cd, Zn, and Cu on the car-
bonized mulch, revealed a rapid sorption of these metals for the initial 30 min (typical
for rst order reactions). However, as more adsorption sites progressively lled up,
the sorption rate gradually reduced until equilibrium.
A plot of t/qt against t gives a linear relationship, from which values of qe and k2
can be determined from the slope and intercept of the plot, respectively. Typically,
the rate of the second order reaction depends on the amount of adsorbate (metal
ion) on the surface of the adsorbent (biochar) and the amount of adsorbate in
CRITICAL REVIEWS IN ENVIRONMENTAL SCIENCE AND TECHNOLOGY 423
solution at equilibrium (Ho, 2006). The pseudo second-order kinetic model has
been used to effectively correlate sorption data for the removal of Cu and Zn by
corn straw and hardwood biochars with coefcients of determination above 0.98
(R2 > 0.98; Table 5; Chen et al., 2011). The close t of the pseudo second-order
model to the adsorption data suggests that the model could be applied to the whole
time range of the sorption process with chemisorption being the rate-limiting
mechanism for the retention of Cu (II) and Zn (II) on the biochars. Other reported
pseudo second-order model parameters of heavy metal sorption on biochars are
summarized in Table 5.
(Wu et al., 2009a), and has been proposed for modeling sorption processes of
adsorbents with heterogeneous surfaces (Cheung et al., 2000b). The model can be
used as a combination of two or more simultaneous rst order kinetic equations to
describe experimental data that is not accurately described by a single rst-order
equation (Chien and Clayton, 1980). It is also a powerful tool in evaluating homo-
geneity of adsorbent surfaces during the whole course of sorption reaction time.
Thus, any deviations in linearity of the linearized Elovich equation would reect
changes in surface reactivity (Chien and Clayton, 1980). There have been some
attempts at interpreting experimental data from the sorption of heavy metals by
biochars with the Elovich model (Table 5). For instance, Pb sorption kinetics study
showed that the Elovich model reproduced experimental data of Pb sorption on
digested whole sugar beet biochar much better than either the rst- or second-
order models (Inyang et al., 2012).
Wu et al., 2009b). Previous study (Inyang et al., 2011) noted that intraparticle dif-
fusion may more likely occur in microporous than in macroporous adsorbents. In
addition, this study reported that pre-equilibrium sorption of lead on bagasse bio-
char had a strong linear dependency on the square of time.
Equilibrium models and sorption isotherms are used to explore how an adsorbate
interacts with an adsorbent (Ai et al., 2011). Common equilibrium models used to
describe isotherms of metal sorption on biochars include Langmuir, Freundlich,
Langmuir-Freundlich, and double Langmuir model, which are expressed as the fol-
lowing:
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Smax KC
Langmuir S D (11)
1 C KC
Freundlich S D Kf C n (12)
Smax .KC/n
Langmuir Freundlich S D (13)
1 C .KC/n
Smax1 K1 C Smax2 K2 C
Double Langmuir S D C (14)
1 C K1 C 1 C K2 C
where S (mmol/kg) is the amount of metal adsorbed and Smax (mmol/kg) is the
maximum amount of metal adsorbed in mmol/kg; Smax1 (mmol/kg) and Smax2
(mmol/kg) are the maximum amounts of metal adsorbed related to the sorption
and precipitation processes, respectively; K (l/mmol) is the Langmuir adsorption
constant related to the interaction bonding energy; Kf (mmol(1n)Ln/kg) is the
Freundlich equilibrium constant in l/mmol; K1 and K2 are the Langmuir bonding
terms related to sorption and precipitation energies in l/mmol, respectively; C is
the equilibrium solution concentration in mmol/l of the sorbate; and n is the
Freundlich linearity constant.
describe the sorption isotherms for Pb sorption on bagasse biochars (Inyang et al.,
2011).
summation of adsorption on all sites (each site having its own bond energy) and
the energy distribution of the sorption sites exponentially decays, up until the com-
pletion of the adsorption process (Foo and Hameed, 2010; Gerente et al., 2007).
The Freundlich equation has been successfully applied to describe the sorption iso-
therms of heavy metals such as Cu, Zn, and Pb on various biochars (Table 5).
Figure 2. (a) Comparison of breakthrough curve data for the sorption of lead on modied peanut
hull hydrochar and unmodied peanut hull hydrochar (PHHC) and (b) breakthrough curve data for
sorption of multicomponent sorption of Cd, Ni, Cu, and Pb on modied peanut hull hydrochar
(mPHHC (Xue et al., 2012)).
Elsevier. Reproduced by permission of Elsevier. Permission to reuse must be obtained from the
rightsholder.
CRITICAL REVIEWS IN ENVIRONMENTAL SCIENCE AND TECHNOLOGY 427
@Cw @ 2 Cw @Cw
DD 2 v S (15)
@t @z @z
where Cw is the heavy metal concentration in pore water (mg l1); D is the disper-
sion coefcient (cm2 min1); v is the velocity of pore water (cm min1); and S is
the sink term, which reects the removal rate in the biochar column. Presently,
there is still a paucity of studies being conducted to study the ltration of heavy
metals by biochars in xed-bed settings. Xue et al. (2012) reported effective
removal of Pb, Cd, Ni, and Cu by laboratory ltration columns packed with hydro-
chars. They found that the ADE model can accurately predict the ltration and
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transport of four heavy metals both in single- and mixture-metal mode (Figure 2).
Funding
This research was partially supported by the NSF through grants: CBET-1054405.
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