Bioresource Technology 160 (2014) 191–202

Contents lists available at ScienceDirect

Bioresource Technology
journal homepage: www.elsevier.com/locate/biortech

Organic and inorganic contaminants removal from water with biochar, a

renewable, low cost and sustainable adsorbent – A critical review
Dinesh Mohan a,⇑, Ankur Sarswat a, Yong Sik Ok b, Charles U. Pittman Jr. c
a
School of Environmental Sciences, Jawaharlal Nehru University, New Delhi 110067, India
b
Korea Biochar Research Center & Department of Biological Environment, Kangwon National University, Chuncheon 200-701, Republic of Korea
c
Department of Chemistry, Mississippi State University, Mississippi State, MS 39762, USA

h i g h l i g h t s g r a p h i c a l a b s t r a c t

 Biochar water and wastewater

treatment is reviewed for the first
time.
 Applications of slow and fast
pyrolysis biochars in water treatment
are reviewed.
 Adsorption capacities for organic and
inorganic contaminants by biochars
are summarized and compared.
 Recommendations for further
research are made.

a r t i c l e i n f o a b s t r a c t

Article history: Biochar is used for soil conditioning, remediation, carbon sequestration and water remediation. Biochar
Received 1 November 2013 application to water and wastewater has never been reviewed previously. This review focuses on recent
Received in revised form 28 January 2014 applications of biochars, produced from biomass pyrolysis (slow and fast), in water and wastewater treat-
Accepted 30 January 2014
ment. Slow and fast pyrolysis biochar production is briefly discussed. The literature on sorption of organic
Available online 8 February 2014
and inorganic contaminants by biochars is surveyed and reviewed. Adsorption capacities for organic and
inorganic contaminants by different biochars under different operating conditions are summarized and,
Keywords:
where possible, compared. Mechanisms responsible for contaminant remediation are briefly discussed.
Biochar
Fast pyrolysis
Finally, a few recommendations for further research have been made in the area of biochar development
Slow pyrolysis for application to water filtration.
Contaminants removal Ó 2014 Elsevier Ltd. All rights reserved.
Adsorption

1. Introduction variety of biochars for use as fuel and adsorbents. Biochar may be
added as a modifier or carbon sink to reduce greenhouse CO2 emis-
Biochar is the ‘‘charred organic matter, produced with the intent sions from decaying biomass. Biochar has appreciable carbon
to deliberately apply to soils to sequester C and improve soil sequestration value. Biochar has a long history as a soil amendment
properties (Lehmann and Joseph, 2009). The International Biochar in Japanese horticulture and carbon black exists from wildfires in
Initiative (IBI) (http://www.biochar-international.org/biochar), Terra Preta sites throughout the Central Amazon (Brewer et al.,
states ‘‘biochar is a solid material obtained from the carbonization 2009; Lehmann, 2007; Lehmann et al., 2011). Biochar use in soil
of biomass. Various degrees of carbonization produces an infinite remediation, carbon sequestration, climate change mitigation, and
carbon farming have been critically reviewed (Ahmad et al.,
⇑ Corresponding author. Tel./fax: +91 11 26704616. 2013b; Lehmann, 2007; Lehmann et al., 2006; Sohi et al., 2009).
E-mail address: [email protected] (D. Mohan). Biochar sequestration does not require a fundamental scientific

http://dx.doi.org/10.1016/j.biortech.2014.01.120
0960-8524/Ó 2014 Elsevier Ltd. All rights reserved.
192 D. Mohan et al. / Bioresource Technology 160 (2014) 191–202

advance. The production technology is robust, simple and appropri- steam, or air. Gasification converts biomass into syngas by careful
ate for many regions of the world but optimization and economic control of the oxygen amount present. Pyrolysis covers a range of
evaluation of large scale development are required. Biochar gener- thermal decomposition processes and is difficult to precisely define.
ally increases (1) nutrient availability (2) microbial activity (3) soil The older literature equates pyrolysis to carbonization where char
organic matter (4) water retention and (4) crop yields in soils, while (charcoal) is the principal product (Fig. 1, Table 1). Today, pyrolysis
decreasing its (1) fertilizer needs (2) greenhouse gas emissions (3) often describes processes in which liquids (biooils) are preferred
nutrient leaching and (4) erosion (Sohi et al., 2009; Woolf et al., products. Liquid production is favored in short pyrolysis times (fast
2010). pyrolysis). Conventional (slow) or fast (flash) pyrolysis depend
Pyrolysis dates back at least to ancient Egypt when tar for upon the operating conditions used (temperature, heating rate
caulking boats and certain embalming agents were made using and vapor residence time) (Czernik and Bridgwater, 2004; Mohan
pyrolysis (Mohan et al., 2006). Pyrolysis processes have been con- et al., 2006). The feed’s heating rate, residence time and pyrolysis
tinuously improved and are widely used for coke and charcoal pro- temperature distinguish the pyrolysis processes. Conventional
duction. In the 1980s, plant pyrolysis liquid yields were increased pyrolysis is slow. The terms slow and fast pyrolysis are somewhat
by employing ‘‘fast pyrolysis’’ where the biomass is heated at a arbitrary and not precisely defined. Many pyrolyses have been per-
rapid rate (in a few seconds) to 400–500 °C producing chars, formed at rates that are not ‘‘fast’’ or ‘‘slow’’ but are in a broad range
gases and vapor/aerosol that is condensed rapidly to ‘‘biooil between these extremes. A key point is whether or not vapors and
(Mohan et al., 2006). aerosol components are rapidly removed to optimize liquid forma-
This review focuses only on use and opportunities for biochar in tion (fast pyrolysis, flash vacuum pyrolysis) or remain in contact
water treatment. Metal ions, organics and anions from industrial with the solid, undergoing secondary reactions which produce
effluents have been removed by chemical and biological methods. added carbonaceous solids. Operating parameters for slow and fast
Chemical precipitation is the most commonly used method. Pre- pyrolysis to biochars are briefly discussed below.
cipitations employ hydroxide, sulfide, carbonate, and phosphate,
but sludge production becomes a disposal problem. Adsorption 3.1. Conventional/slow pyrolysis
has evolved as a front line of defense for pollutants which are hard
to remove by other methods. Selective adsorption by biological Slow pyrolysis has been employed for thousands of years to pro-
materials, mineral oxides, activated carbon, or polymer resins, duce charcoal. Production and charcoal property knowledge accu-
has generated excitement. Activated carbon, often thought of as a mulated over the past 38 millenia have been reviewed (Antal and
universal adsorbent for water treatment, is frequently made from Grønli, 2003). Biomass is heated slowly to about 500 °C in absence
biomass or coal (Mohan and Pittman, 2007). Activated carbon is of air. Vapor residence times vary from 5 to 30 min. Vapors in con-
ideal for removing contaminants from water but costly to make. ventional pyrolysis do not escape rapidly unlike in fast pyrolysis.
On the other hand, ‘‘sustainable’’ biochar requires less investment.
Typical biochar is less carbonized than activated carbon. More 3.2. Fast pyrolysis
hydrogen and oxygen remain in its structure along with the ash
originating from the biomass. Biochars absorb hydrocarbons, other Fast pyrolysis requires dry feedstock (<10 wt% moisture), rapid
organics, and some inorganic metal ions (Hale et al., 2012; Mohan heat transfer, fast temperature increase by heating small biomass
et al., 2012), exhibiting potential for water purification and soil particles (1–2 mm) to 400–500 °C and vapor residence times of 1
amelioration. Biochar could replace coal-, coconut shell-, and s (maximum 5 s) (Lima et al., 2010). Fast pyrolysis differs funda-
wood-based activated carbons as a low cost sorbent for contami- mentally from slow pyrolysis.
nants and pathogens. Biochar might be used for removing contam-
inants from water while also being loaded with nutrients for 3.3. Gasification
subsequent use as a soil amendment, providing long-term sorption
capacity and a fertilizer (Bernd et al., 2013). Gasification produces a gas fuel that can be used for direct heat
This review covers the use of slow and fast pyrolysis biochars generation or electricity generation. Gasification is a partial
for removing contaminants from water, emphasizing publications combustion of solid. The product mix (gas, liquid and solid) is con-
mainly from the last 5 years. Efforts are also made to differentiate trolled by altering temperature, particle size, residence time, pres-
among biochars from slow pyrolysis, fast pyrolysis, gasification sure, gas composition under which the biomass is treated and the
and hydothermal carbonization (HTC). catalyst’s identity if one is used. Brewer et al. characterized the
chars from fast pyrolysis and gasification of switchgrass and corn
2. Biomass conversion technologies stover (Brewer et al., 2009). Higher char aromaticity was obtained
in slow pyrolysis than in fast pyrolysis or gasification. Fused aro-
A number of conversion schemes have been developed to capi- matic ring compound sizes in fast and slow pyrolysis chars were
talize on biomass feed properties and reviewed (Czernik and Bridg- similar (7–8 rings per compound) while gasification char was
water, 2004; Mohan et al., 2006). Both biological (anaerobic more highly condensed (17 rings per compound) (Brewer et al.,
digestion, hydrolysis and fermentation) and thermal (combustion, 2009).
pyrolysis, liquefaction, torrifaction and gasification) methods are
used for biomass conversion into fuel and byproducts. Only 3.4. Hydrochar
thermal processes to produce adsorbent chars are covered here.
Biochar from thermal treatment also has a high energy density It is important to differentiate biochars from hydrochars.
(typically >28 kJ/g). Hydrochars form by hydrothermal carbonization (HTC) of biomass
at high temperature and pressure in water, producing a char–
3. Biomass prolysis water–slurry (Libra et al., 2011). The solid char is easily separated.
Its chemical and physical properties differ significantly from the
Pyrolysis is the thermal decomposition of materials in the ab- starting biomass. Conversely, biochars are produced by pyrolysis
sence of oxygen or when significantly less oxygen is present than (slow or fast) or gasification at various temperatures, pressures
required for complete combustion (Fig. 1, Table 1). Pyrolysis should and carbonization times. Hydrochars from agricultural residues
be differentiated from gasification where biomass is reacted with were characterized and used for water and soil remediation
 D. Mohan et al. / Bioresource Technology 160 (2014) 191–202 193

Fig. 1. Thermochemical conversion of biomass into biooil, biochar and gases.

Table 1
Thermochemical processes, reactions, residence time and primary products (modified) (Brewer, 2012).

Thermochemical process Temp. range (°C) Heating rate Pressure Residence time Desired product
Slow pyrolysis 350–800 Slow, (<10 °C/min) Atmospheric Hours–seconds Biochar
Torrefaction 200–300 Slow, (<10 °C/min) Atmospheric Minutes–hours Stabilized friable biomass
Fast pyrolysis 400–600 Very fast (1000 °C/s) Vacuum–atmospheric Seconds Biooil
Gasification 700–1500 Moderate-very fast Atmospheric–elevated Seconds–minutes Syngas/producer gas
HTC 175–250 Slow – Hours Hydrochar

(Wiedner et al., 2013). Chemical properties of biochars from 5. Characterization of biochars

gasification or pyrolysis were compared to hydrochars from HTC
(Wiedner et al., 2013). Hydrochars are less stable (dominated by al- Biochar physical, chemical and mechanical properties can vary
kyl moieties) than biochars (dominated by aromatics). Hydrochars with production conditions, making it challenging to engineer
are not included in the ‘‘European Biochar Certificate’’ (EBC) stan- biochars that are simultaneously optimized for carbon sequestra-
dardization due to their different chemical properties (Wiedner tion, nutrient storage, water-holding capacity and adsorption (Sun
et al., 2013). et al., 2012). The IBI has graded biochar into three classes based
on carbon content (http://www.biochar-international.org/sites/
default/files/Guidelines_for_Biochar_That_Is_Used_in_Soil_Final.pdf).
3.5. Torrefaction and retification These include, Class 1 biochar (contains 60% carbon or more), Class
2 biochar (between 30 and 60% carbon) and Class 3 biochar (be-
Wood ‘‘retification’’ takes place at 230–250 °C. The wood color tween 10% and 30% carbon). Thermal conversion of charcoal, de-
becomes reddish brown/chocolate. This product is considered to be rived from fluidized-bed fast pyrolysis oil production of
resistant towards biological attack. Similarly, torrefaction occurs switchgrass, has been reported (Boateng, 2007). Biochars pyrolyzed
between 250–280 °C at low heating rates, and creates a brown under several highly controlled conditions from corn stover and ap-
or black product with little strength. Torrefied wood yields range ple wood were characterized. Particle size, pyrolysis heating rate,
from 67% to 84% with energy yields of 77–90% (Antal and Grønli, and residence time had significant effects on biochar chemical com-
2003). Torrefaction increases the biomass energy density, greatly position, aromaticity, and pore structure (Sun et al., 2012). In fast
reduces weight, enhances hydrophobic nature and improves pyrolysis, the shorter the vapor residence time, less important are
wood’s commercial use for energy production by reducing trans- the secondary reactions of vapor with the developing char. Thus,
portation costs. Typically, torrefaction and retification do not reactions in the vapor and aerosol phases mainly influence chemi-
create adsorbent chars since only partial biomass decomposition cal composition of the biooil liquid phase and the gases produced.
occurs to prevent rot and induce some water loss. In slow pyrolysis, the vapors are confined and react extensively
with the solid phase. More mass ends up as char. Increasing both
pyrolysis time and temperature increases the %C in the char and de-
4. Development of biochars creases both the %O and surface hydrophilicity. The effect of these
parameters on adsorption is discussed in subsequent paragraphs.
Different feeds and reactors are employed to make biochars by
pyrolysis (slow or fast), gasification or HTC. Important feedstocks 6. Applications of biochars in water remediation
and operating conditions are listed in the Supplementary material
(Table SM1). Commonly used reactors include auger (Mohan et al., Biochar applications have been divided into subsections on
2014; Mohan et al., 2007; Mohan et al., 2011; Mohan et al., 2012), organics (6.1) and inorganics remediation (6.2). Organics are di-
well-swept fixed-bed, bench-scale fixed bed (Ates and Un, 2013), vided into (a) dyes (b) phenolics, pesticides, polynucelar aromatics
vertical tubular (Hameed and El-Khaiary, 2008), and fluidized and antibiotics removal. Inorganics are divided into (a) cations and
bed types (Han et al., 2013b). Feed stock pyrolyses into biochars (b) anions removal. Table 2 briefly summarizes example adsorp-
have been conducted on debarked loblolly pine (Pinus taeda) chips tions of inorganic species on various biochars while a comprehen-
(Park et al., 2013) oak wood, pine wood, oak bark and pine bark sive listing is given in Supplementary Material (Table SM2). The
(Mohan et al., 2007b), pine needles (Ahmad et al., 2013a), corn sto- first column of Table SM2 lists the biochar type employed while
ver and apple wood (Sun et al., 2012) among many others. column four gives the adsorbed species. This organization is
194 D. Mohan et al. / Bioresource Technology 160 (2014) 191–202

Table 2
Adsorption capacities of different biochars for removing metal ions from watera.

Type of Biochars Metal Adsorption capacity References Type of Biochars Metal Adsorption capacity References
Ions (mg/g) Ions (mg/g)
Pine wood char Pb2+ 4.13 Mohan et al. Buffalo weed biochar Pb2+ 333.33 Yakkala et al.
Pine wood char Cd2+ – (2007) Cd2+ 11.63 (2013)
Pine wood char As3+ 1.20 Sugar beet tailing biochar Cr6+ 123 Dong et al. (2011)
Oak wood char Pb2+ 2.62 Soybean Stalk-Based Hg2+ 0.67 Kong et al. (2011)
Biochar
Oak wood char Cd2+ 0.37 Empty fruit branch Zn2+ 1.18 Mubarak et al.
magnetic biochar (2013)
Oak wood char As3+ 5.85 Oak Wood char Cr6+ 3.03 Mohan et al.
Pine bark char Pb2+ 3.00 Cr6+ 4.08 (2011)
Pine bark char Cd2+ 0.34 Cr6+ 4.93
Pine bark char As3+ 12.15 Oak Bark char Cr6+ 4.62
Oak bark char Pb2+ 13.10 Cr6+ 7.43
Oak bark char Cd2+ 5.40 Cr6+ 7.52
Oak bark char As3+ 7.40 Rice straw biochar Cd2+ 34.13 Han et al. (2013a)
Hard wood char Cu2+ 6.79 Chen et al. Pinewood biochar Cu2+ 4.46 Liu et al. (2010)
Hard wood char Zn2+ 4.54 (2011b) Cu2+ 2.75
Corn straw char Cu2+ 12.52 Dairy manure biochar Cu2+ 48.41 Xu et al. (2013)
Corn straw char Zn2+ 11.00 Zn2+ 32.95
Peanut straw char Cu2+ 0.09 Tong et al. Cd2+ 32.03
Peanut straw char Cu2+ 0.05 (2011) Cu2+ 51.46
Soybean straw char Cu2+ 0.05 Zn2+ 31.84
Soybean straw char Cu2+ 0.03 Cd2+ 54.63
Canola straw char Cu2+ 0.04 Pig manure biochar Cu2+ 78.36 Kołodyńska et al.
Canola straw char Cu2+ 0.03 Zn2+ 62.13 (2012)
Rice husks Cu2+ 6.26 Pellera et al. Cd2+ 107.08
Cu2+ 3.49 (2012) Pb2+ 175.44
Cu2+ 4.57 Cu2+ 88.23
Cu2+ 0.27 Zn2+ 79.62
Dried olive pomace Cu2+ 7.07 Cd2+ 117.01
Cu2+ 1.44 Pb2+ 230.70
Cu2+ 5.12 Cow manure biochar Cu2+ 76.12
Cu2+ 0.66 Zn2+ 58.11
Orange waste Cu2+ 10.26 Cd2+ 114.75
Cu2+ 5.81 Pb2+ 212.77
Cu2+ 4.92 Cu2+ 88.50
Cu2+ 0.42 Zn2+ 61.91
Compost Cu2+ 10.14 Cd2+ 118.40
Cu2+ 7.72 Pb2+ 219.34
Cu2+ 7.94 Cu2+ 81.50
Cu2+ 3.38 Zn2+ 49.06
Dairy manure biochar Pb2+ 109.40 Cao et al. Cd2+ 78.19
Pb2+ 132.81 (2009) Pb2+ 151.52
Pb2+ 93.65 Cu2+ 83.97
Pinewood biochar Pb2+ 3.89 Liu and Zhang Zn2+ 51.28
Pinewood biochar Pb2+ 4.03 (2009) Cd2+ 82.30
Pinewood biochar Pb2+ 4.25 Pb2+ 154.60
Rice husk biochar Pb2+ 1.84 Digested dairy waste Pb2+ 51.38 Inyang et al.
biochar (2012)
Rice husk biochar Pb2+ 2.25 Digested sugar beet Pb2+ 51.38
biochar
Rice husk biochar Pb2+ 2.40
Digested sugarcane Pb2+ 135.40 Inyang et al.
bagasse biochar (2011)
Raw sugarcane bagasse Pb2+ 81.90
biochar

a
Complete table is available in Supplementary Material as Table SM2.

somewhat arbitrary because the same general biochar types were conventional waste treatment methods since they are stable to
prepared in different ways by different authors. Also, several differ- light, oxidizing agents, and resist aerobic digestion. Biochars from
ent adsorbates were targeted for adsorption by the same biochar straw (Hameed and El-Khaiary, 2008; Qiu et al., 2009; Xu et al.,
types made by different research groups. 2011), and bamboo (Mui et al., 2010; Yang et al., 2013) were
developed to remove dyes from water and wastewater.
6.1. Biochar applications in organics remediation Slow pyrolysis rice straw-biochar was applied to malachite
green (MG) adsorption (Hameed and El-Khaiary, 2008). Rice straw
6.1.1. Color/dye removal biochar was made in a vertical tubular reactor for 2 h from
The disposal of dye industry wastewater poses major problems, 20–700 °C under nitrogen. Maximum MG was removed at pH 5
because effluents contain acids or bases, dissolved solids, toxic at 30 °C. About 95% of the MG was removed within 40 min from
compounds, and they have color. Color is instantly recognized a solution with 25 mg/L of initial MG. Kinetics fitted best to a pseu-
because it is visible. Many textile dyes are difficult to destroy by do first order model, suggesting the adsorption rate is initially
 D. Mohan et al. / Bioresource Technology 160 (2014) 191–202 195

controlled by external mass transfer. Intraparticle diffusion was Optimum adsorption occurred at pH 2.0 on all chars. Adsorption
controlling at a later stage. The monolayer Langmuir adsorption capacity was highest on the char made at 800 °C.
capacity was 149 mg/g at 30 °C (Hameed and El-Khaiary, 2008)
(Table SM2). Straw biochar was acid-treated (0.1 M HCl) to remove 6.1.2. Phenols removal
metals, followed by demineralization using HCl-HF (Qiu et al., Phenolic compounds are manufactured for plastics, dyes, drugs,
2009) according to Chun’s method (Chun et al., 2004). This biochar antioxidants, and pesticides. They pose serious danger when enter-
(BC) and a commercial activated carbon (Darco G-60, Sigma Al- ing the food chain as water pollutants. Phenols affect the taste and
drich) (AC) were used to remove reactive brilliant blue (KNR) and odor of fish and drinking water at very low concentration. Also,
rhodamine B (RB) dyes from water. Surprisingly, the BC surface nitrophenols and chlorophenols are priority pollutants. Poly(acryl-
area (1057 m2/g) was higher than the AC’s (970 m2g1) amide)-chicken, wood, and tire biochars (p(AAm)-CB), (p(AAm)-
(Table SM2). BC was less carbonized than AC as evidenced by its WB), and (p(AAm)-TB) were developed as hydrogel composites
high surface acidity. Biochar (at pH 6.5) adsorbed more RB than using acrylamide (AAm) monomer with N,N0 -methylenebisacryla-
the commercial AC (at pH 3) because the dye molecules more eas- mide (MBA) as crosslinker and ammonium persulfate (APS) as ini-
ily accessed the larger micropores of BC than the fine pores of AC. tiator. P(AAm)-CB, p(AAm)-WB, and p(AAm)-TB were utilized for
KNR adsorption increased as its concentration increased (at pH 6.5) aqueous phenol removal (Karakoyun et al., 2011).
due to negative surface charge neutralization by Na+ cations of the High sorption capacity rice husk and corncob biochars were
dye. Two main IR bands observed after dye adsorption suggest prepared at fixed temperatures and different residence times. Bio-
intermolecular hydrogen bonding between O atoms of char func- char prepared within 1.6 s exhibited a higher phenol adsorption
tional groups and AOH groups of the dye. High RB adsorption capacity (589 mg g1). Adsorption via acid–base interaction and
(pH 3) with increasing ionic strength was possibly due to the for- hydrogen binding between phenol and the functional groups was
mation of RB dimers. Also, C@O and AOH groups participated in di- proposed to explain the process (Liu et al., 2011). Catechol adsorp-
pole–dipole attractions between RB and BC. tion on oak, pine, and grass biochars prepared at 250, 400, and
Canola straw (CS), peanut straw (PS), soybean straw (SS), and 650 °C was reported. Catechol sorption capacity increased with rise
rice hulls (RH) were each slowly pyrolyzed for 4 h at 350 °C in a in biochar pyrolysis temperature (Kasozi et al., 2010).
muffle furnace, generating their respective biochars (Xu et al.,
2011). The ramp heating rate was 20 °C/min. These biochars re- 6.1.3. Pesticides and polynuclear aromatics removal
moved methyl violet from water. Sorption capacities followed Pesticide and PAH remediation has attracted great attention.
the order CS > PS > SS > RH which was parallel to their respective They are introduced into the environment from economic produc-
cation exchange capacities. Methyl violet at higher concentrations tion and wide application in agriculture. Important pesticide reme-
adsorbed on biochar due to its low water solubility. Zeta potentials diation targets include organophoshorous, organochlorine,
of the CS and PS chars showed their surfaces were acidic. Changes carbamate, triazine and chlorophenoxy acid compounds.
in the FT-IR phenolic AOH stretching and carboxylate asymmetric Dibromochloropropane, a soil fumigant used to control nema-
stretching peaks of methyl violet occur after adsorption. A drop in todes, was adsorbed from well waters onto almond shell activated
band intensities at 1065 and 1045 cm1 indicated the char’s sur- biochars (Klasson et al., 2013). Almond shells were slowly pyrolyzed
face carbonates interacted with methyl violet. Monolayer adsorp- at 650 °C for 1 h under N2 in a Lyndberg furnace with a retort. Further
tion capacities of 256, 179, and 124 mg/g were obtained for PS, steam activation at 800 °C for 45 min gave a specific surface area of
SS, and RH chars, respectively. 344 m2/g. The maximum adsorption capacity was 102 mg/g. Field
Slow pyrolysis of waste bamboo scaffolding under N2 for 1–4 h studies were also carried out successfully (Klasson et al., 2013).
at 400–900 °C gave biochars (Mui et al., 2010). Char yields Orange peel biochars from slow pyrolysis ranging from 150 to
decreased with increasing temperature. Specifically, a sharp yield 700 °C (OP150–OP700) were used for naphthalene and 1-naphthol
decrease from 400 to 500 °C was due to lignin and hemicelluloses adsorption (Chen and Chen, 2009). Maximum 1-naphthol and
partial gasification. The char H/C ratios decreased versus O/C in naphthalene uptake was achieved by OP200 and OP700, respec-
van Krevlen plots, showing high pyrolysis temperatures caused tively. Naphthalene adsorption was controlled by surface coverage
progressive aromatization. Surface area increased with higher and partition whereas 1-naphthnol adsorption was controlled by
pyrolysis temperatures, reaching 327 m2/g at 900 °C. Char yields partition, surface coverage, and surface interactions. Raw orange
and %H and %O dropped on longer pyrolysis times, whereas surface peels underwent large weight loses from 150 to 400 °C. The O/C ra-
area increased. High heating rates resulted in lower surface areas, tio decreased with a rise in pyrolysis temperature. Chun et al. re-
pore volumes, and yields due to rapid depolymerization at char sur- ported a similar trend (Chun et al., 2004).
faces. Acid blue 25 (AB25), acid yellow 117 (AY117), and methylene
blue (MB) adsorption occurred. This bamboo char had a higher 6.1.4. Solvents removal
adsorption capacity for MB than AY117 and AB25. Bamboo biochar Biochars (WC-300, WC-400, WC-500, WC-600, and WC-700)
also adsorbs metal complex dye acid black 172 (Yang et al., 2013). were generated by pyrolyzing a wheat residue (Triticum aestivum
Kenaf (Hibiscus cannabinus) fiber char (KFC) supplied by Kenaf L.) for 6 h between 300 °C and 700 °C and analyzing for their elemen-
Fiber Industries Sdn. Bhd., Malaysia was slowly pyrolyzed to tal compositions, surface areas, and surface functional groups (Chun
acid-treated biochar (HKFC) at 1000 °C (Mahmoud et al., 2012). et al., 2004). These chars removed benzene and nitrobenzene from
This HKFC adsorbed methylene blue (MB) in a honeycomb pore water. The samples made at 500–700 °C were well carbonized with
network observed by SEM. Char surface area increased on acid high surface areas (>300 m2/g), little organic matter (<3%), and low
treatment. HKFC, a mesoporous solid (average pore dia. 3 nm), oxygen content (610%). Chars formed at 300–400 °C were only
had almost double the fixed carbon and a higher oxygen content partially carbonized and exhibited <200 m2/g surface areas,
than KFC. HKFC had a higher MB removal efficiency than KFC. 40–50% organic carbon, and >20% oxygen (Chun et al., 2004). High-
The Langmuir adsorption capacity at pH 6–7 was 22.7 mg/g at temperature chars acted via adsorption on their carbonized surfaces,
50 °C (MB conc. of 100 mg/L). Sorption followed pseudo second or- Low-temperature char sorption occurred by surface adsorption and
der kinetics. Both intraparticle diffusion and boundary layer diffu- some concurrent partition into the residual organic-matter. Nitro-
sion controlled adsorption. Hornbeam sawdust biochars were benzene had higher surface affinities than nonpolar benzene. Char
made in a fixed bed reactor at 500, 600, 700, and 800 °C under WC-700 was highly carbonized (low H/C and low O/C) versus chars
an inert atmosphere to adsorb orange 30 (Ates and Un, 2013). formed at lower temperatures. Maximum surface area was achieved
196 D. Mohan et al. / Bioresource Technology 160 (2014) 191–202

at 600 °C. Total acidity decreased as pyrolysis temperature rose. limited oxygen at 300 and 600 °C for 6 h was followed by deminer-
Soybean stover, peanut shells and pine needles were pyrolyzed alization by acid. HTC produced chars in a high pressure reactor by
(Ahmad et al., 2012, 2013a). Soybean stover and peanut shells were heating to 300 °C for 30 min, followed by acetone extraction to re-
charred at 300° (SBC300, PBC300) and 700 °C (SBC700, PBC700) and move oils (Pellera et al., 2012). Slow 600 °C pyrolysis chars were less
used to remove trichloroethylene (TCE) from water. Chars produced efficient for Cu2+ removal than those produced at 300 °C, but slow
at 700 °C had higher surface areas (420 and 448 m2/g) than those at pyrolysis chars removed more Cu2+ than the hydrothermal chars
300 °C (6 and 3 m2/g). SBC700 and PBC700 had higher maximum (Pellera et al., 2012) (Table 2 and Table SM2). Peanut, canola, and
adsorption capacities (32.02 mg/g for PBC700) than the other chars. soybean straw biochars, prepared in a 400 °C muffle furnace (ramp
TCE adsorption correlated well with high carbon contents and rate of 20 °C/min) for 3.75 h under limited oxygen, were also used
negatively with higher oxygen content (Table SM2). for Cu2+ adsorption (Tong et al., 2011). All three biochars had higher
adsorption capacities than commercial activated carbon at pH
6.1.5. Miscellaneous 3.5–5.0. Cu2+ sorption involved electrostatic and non-electrostatic
Poultry litter (T-PL) and wheat straw (T-WS) biochars, produced adsorption. Cu2+ sorption capacity rose as pH went up as strong com-
at 400 °C over 120–420 min and hydrothermal poultry litter and plexes formed between CuAOH and char surface functions (AOH
swine solids chars at 250 °C under autogenic pressures for 20 h and ACOOH). Higher phosphate contents of soybean and canola
were made to remove phenanthrene (Phen), bisphenol A (BPA), straw chars versus peanut straw char caused Cu-phosphate forma-
and 17a-ethinyl esteradiol (EE2) from water (Sun et al., 2011). tion and precipitation (Tong et al., 2011). Desorption rates were
Lower H/C and O/C ratios were reported for the thermal biochars, canola straw > soybean straw > peanut straw. Leguminous (peanut
indicating more carbonization than in the hydrothermal chars. and soybean straw) chars had higher capacities than that of non-
Thermal biochars were more hydrophobic than hydrothermal leguminous canola straw char. Peanut straw char had a maximum
chars (Sun et al., 2011) and exhibited mostly aromatic (sp2) car- Cu2+ capacity of 1.4 mol/kg at pH 5.0 (Tong et al., 2011). Each of these
bons with small amounts of alkyl (sp3) carbons. Hydrothermal three straw feeds were also pyrolyzed at 300, 400, and 500 °C for use
chars had carboxyl, methoxyl, O-aryl, and alkyl carbons in their to remove Cu2+ from water (Tong et al., 2011). Cu2+ adsorption rates
13
C nuclear magnetic resonance spectra. More EE2 and BPA was ad- followed the order: peanut straw char > soybean straw char > cano-
sorbed onto hydrothermal biochars prepared at 250 °C than onto la straw char > rice straw char. Biochars formed at 400 °C gave the
thermal biochars. The oxygen-containing polar functional groups best sorption. The sorption occurred by both adsorption and surface
of hydrothermal biochars hydrogen-bond to EE2 and BPA. Organic precipitation (Tong et al., 2011) (Tables 2 and SM2).
carbon-normalized distribution coefficients (log Koc) of the hydro- Fast and slow pyrolyzed hardwood and corn straw biochars
thermal biochars were higher than for thermal biochars. Log Koc were reported (Chen et al., 2011b). Fast hardwood pyrolysis
values of Phen, EE2, and BPA followed the same order as their (HW450) was made at 450 °C in a <5 s residence time at Dynamo-
hydrophobicities: Phen > EE2 > BPA. BPA possesses two phenol tive Inc., Vancouver, Canada. Slow pyrolysis biochars (CS600) were
rings. Hence weak p-H-bonding with the char and phenolic hydro- made at 600 °C (residence time 2 h) at BEST Energies Inc., Madison,
xyl hydrogen bonding with the hydrothermal char’s oxygen func- Wisconsin, USA. HW450 was acidic due to organic acids and phe-
tions occurs. Phen adsorption on chars occurs by extensive p–p nolic compounds. Above 300 °C, alkali salts separate, raising the
interactions (Sun et al., 2011). char’s pH. High H/C ratios of these biochars indicate lower carbon-
ization and aromaticity than activated carbon. HW450 had a great-
6.2. Biochar applications in inorganic remediation er O/C ratio and higher polarity than CS600. CS600 possesses a
higher surface area (13.08 m2/g) than HW450 (0.43 m2/g). Com-
6.2.1. Metal ion removal paring surface areas of many biochars illustrated that feed compo-
Heavy metals pose serious health threats even at very low con- sition can play as an important role in surface area as the synthetic
centrations. Some are cumulative poisons, capable of assimilation, technique employed. Surface area plays a critical role. SA can dom-
storage and concentration by organisms exposed long periods to inate, as confirmed by the higher Cu2+ and Zn2+ uptake by CS600
low concentrations. Eventual metal built-up in tissues can cause verses highly surface-functiminalized HW450. Maximum Lang-
harmful physiological effects. The heavy metals appear among the muir adsorption capacities of 12.52 mg/g for Cu2+ and 11.0 mg/g
main pollutants in this century (Davydova, 1999). Discharged heavy for Zn2+ were achieved using CS600 char (Tables 2 and SM2).
metals present a serious threat to human health and natural waters. Pig and cow manure biochars were made at 400 and 600 °C at
Important biochar adsorption studies have been made with Cr, Cu, ambient pressure under nitrogen followed by chemical and
Pb, Cd, Hg, Fe, Zn, and As ions. Activated carbon has long been used mechanical treatments (Kołodyńska et al., 2012). The chemically
to remove metal ions, but only a few milligrams of metal ions are treated 600 °C pig manure char had the highest surface area
typically adsorbed per gram of activated carbon. Regeneration prob- (15.89 m2/g). These chars were used for Cu2+, Zn2+, Cd2+, and Pb2+
lems also exist. This makes activated carbon expensive for treating removal. Optimum pH values were 5.0 for Cu2+ and Zn2+ and 6.0
wastewater, so its use in developing countries is more problematic. for Cd2+ and Pb2+ adsorption. Sorption kinetics for Cu2+ and Pb2+
Low cost locally available materials with adsorption capacities com- was a complex combination of intraparticle pore diffusion, external
parable to activated carbon are needed. Solid biomass-derived waste mass transfer, and sorption processes (Kołodyńska et al., 2012)
is also a vexing problem. Recycling requires a suitable recycled prod- (Table 2 and Table SM2). Metal ion sorption was governed by
uct quality if possible. Lignocellulosic wastes have fuel value, so inner-sphere ion complexation with surface functional groups
complete combustion, fast pyrolysis to biooil or gasification to syn (Kołodyńska et al., 2012). Competitive adsorption of Cu2+ and
gas are options. Biochar is a byproduct of biooil production in Pb2+ was adversely affected by the presence of Cd2+ and Zn2+.
15–25% yields. If biooil production becomes widespread, its result- Zn2+, Cu2+ and phenol adsorption was studied on switchgrass
ing char would be widely available for water remediation use. Slow (SG), hardwood (HW), and softwood (SW) derived slow and fast
pyrolysis to biochars also converts lignocellulosic wastes to bioch- pyrolysis biochars (Han et al., 2013b). Fast pyrolysis was carried
ars. Industrial wastewater and ground/surface waters could then out at in a fluidized bed reactor at 500 °C. Slow pyrolysis was done
be widely treated with biochars to decrease metal ion removal costs. at 500 and 700 °C for 1 and 2 h, respectively. Chars made at 500 °C
Biochars from slow pyrolysis and hydrothermal treating of rice were steam-activated at 800 °C for 45 min using N2 as a carrier gas.
husks, olive pomace, orange wastes, and compost were used for Surface areas of steam-activated slow pyrolysis chars (168, 344,
Cu2+ remediation (Pellera et al., 2012). Slow pyrolysis under 384 m2/g for SG, HW, and SW chars, respectively) were higher than
 D. Mohan et al. / Bioresource Technology 160 (2014) 191–202 197

fast pyrolysis chars (3.07, 5.50, and 6.72 m2/g for SG, HW, and SW, et al., 2007b). These chars have very small (5–25 m2/g) surface
respectively). Biochars adsorbed more Cu2+ (pH 4.8) than Zn2+ (pH areas versus the high commercial activated carbon values
7.0). Adsorption capacities reflected char surface areas and avail- (400–1000 m2/g) but remove the metal ions well. Ion exchange
ability of surface functional groups. Sorption by metals at pH 7.0 dominated the metal ion adsorption mode (Mohan et al., 2007b)
decreased in the order: 500 °C steam activated char > 700 °C (Table 2 and SM2).
char > 500 °C char > fast pyrolysis char (Table SM2). Alamo switch- Sugarcane pulp residue biochar from slow pyrolysis (2–3 h) at
grass biochar was produced via hydrothermal carbonization at 500 °C under N2 gave maximum Cr3+ uptake (15.9 mg/g) at pH
300 °C in a high pressure batch-reactor (Regmi et al., 2012). This 5.0 (Zhi-hui et al., 2013) (Table SM2). Slow pyrolysis (300 °C, 2 h)
biochar (HTB) was activated (HTCB) using KOH to enhance porosity in nitrogen of oven-dried sugar beet tailings in a muffle furnace
and clear its partially blocked pores. HTB and HTCB removed Cu2+ gave chars used for Cr6+ removal (Dong et al., 2011). A maximum
and Cd2+ from aqueous solutions. Almost complete removal of Langmuir adsorption capacity (123 mg/g) was achieved at pH 2.0
Cu2+/Cd2+ was achieved at pH 5.0 from an initial Cu2+/Cd2+ concen- (Tables 2 and SM2).
tration of 40 mg/L. HTCB showed higher Cd2+affinity (34 mg/g) Oak wood and bark chars from fast pyrolysis in an auger
than HTB (31 mg/g), whereas HTB showed greater affinity biooil reactor at 400-500 °C were characterized and used for aque-
(4.0 mg/g) for Cu2+ than for HTBC (1.5 mg/g) (Table SM2). Buffalo ous Cr6+ remediation (Mohan et al., 2011). Maximum chromium
weed biochars were prepared at 300, 500, and 700 °C by 4 h of slow capacity (Q0) occurred at pH 2.0. Cr6+ removal increased with
pyrolysis under N2 for Cd2+ and Pb2+ removal (Yakkala et al., 2013). rising temperature (Q 0Oak wood : 25 °C = 3.03 mg/g; 35 °C = 4.08 mg/g;
The BET surface area was far higher (279.8 m2/g) for 700 °C char 45 °C = 4.93 mg/g and Q 0oak bark : 25 °C = 4.61 mg/g; 35 °C = 7.43 mg/
than the other two (1.35 and 4.83 m2/g for 300 and 500 °C chars, g; 45 °C = 7.51 mg/g). More chromium was removed with bark than
respectively) (Yakkala et al., 2013). More surface availability for wood char. Remarkably, oak chars (SBET: 1–3 m2/g) removed simi-
complexation and cation exchange leads to a high Langmuir lar amounts of Cr6+ as activated carbon (SBET: 1000 m2/g) (Mohan
adsorption capacities by the 700 °C biochar (11.63 and 333 mg/g et al., 2011) (Tables 2 and SM2). Water swelled these chars, creat-
for Cd2+ and Pb2+), respectively. Ion exchange and metal ion surface ing more internal char/water contact. Functional groups within the
complexation dominated the mechanism (Yakkala et al., 2013) swollen solid volume can complex or react with Cr6+ leading to
(Tables 2 and SM2). greater adsorption capacity. Char successfully remediated chro-
Lead adsorption by slow (600 °C) pyrolysis biochars from raw mium from contaminated surface water with dissolved interfering
(BC) and anaerobically digested sugarcane bagasse (DBC) was stud- ions. These pyrolytic chars readily reduce Cr6+ and bind Cr3+. Aro-
ied (Inyang et al., 2011). These biochars possessed far lower surface matic ortho- and para-dihydroxy compounds reduce Cr6+ to Cr3+
areas than activated carbon. However, DBC’s sorption capacity while being oxidized to ortho- or para-quinones, respectively. Sub-
(653.9 mmol/kg) was twice that of AC (395.3 mmol/kg) and twenty sequent chelation of Cr3+ occurs (Mohan et al., 2011).
times higher than BC (31.3 mmol/kg) (Tables 2 and SM2). DBC had
higher cation and anion exchange capacities than BC and activated 6.2.2. Anion removal
carbon. Negative zeta potentials indicated these adsorbents had Low cost pine wood and pine bark chars, by-products from fast
strong negatively charged surfaces. Lead minerals (hydrocerrusite pyrolysis in an auger bio-oil production reactor at 400 and 450 °C,
and cerrusite) detected on DBC by XRD after sorption confirmed were used, as-received, for water defluoridation (Mohan et al.,
lead precipitation. Disappearance of ACOO carbonyl IR peaks after 2012). Pine chars successfully treated fluoride-contaminated
adsorption suggested insoluble lead carboxylates formed on DBC ground water at pH 2.0. All chars swelled in water due to their high
surfaces. BC surface hydroxyl oxygens coordinate with lead oxygen content (8–11%), opening new internal pore volume (Mo-
cations, forming AOAPb bonds and a proton is released. han et al., 2012). Fluoride also diffused into the chars’ subsurface
Anaerobically digested dairy waste residue (DAWC) and solid volume promoting further adsorption. Ion exchange and me-
digested whole sugar beets (DWSBC) were lowly pyrolyzed to tal fluoride precipitation (from ash components) are adsorption
biochars at 600 °C for 2 h under N2 (Inyang et al., 2012) (Tables 2 modes. Remarkably, these low surface area chars (SBET: 1–3 m2/g)
and SM2). DAWC possessed higher surface area (161.2 m2/g) than can remove similar amounts or more fluoride than activated car-
DWSBC (48.6 m2/g). Pb2+ sorption capacities were 197 (DWSBC) bon (SBET:1000 m2/g). More water imbibed in the chars than is
and 248 (DAWC) mmol/kg, so DWSBC was 4 times better a sor- possible by filling only the measured pore volume of dry adsor-
bent per unit of surface area. Aerobically composted swine manure bent. Weight loss on removing imbibed water from pine wood char
was converted to slow pyrolysis biochars at 400 and 700 °C for was 0.37–0.38 g/g of char and from pine bark char was 0.26–
Cu2+ removal (Meng et al., 2013). A higher char yield occurred at 0.57 g/g of char (Mohan et al., 2012). Thus, water occupied about
400 °C, because more cellulose and hemicellulose carbonized at 0.37–0.38 cc/g and 0.26–0.57 cc/g of these two chars. Some of this
700 °C. Surface areas and pore sizes decreased from 400 to 700 °C volume was due to diffusion into pore walls and by expansion of
due to the pore blockage by inorganic components of the high internal pore structure. This swelling contrasts with the behavior
ash content. During pyrolysis, alkali salts separate and increase of almost fully carbonized carbon blacks. The char has 8–12%
biochar pH. H/C, O/C, and (O + N)/C ratios decreased at 700 °C. by wt. oxygen throughout its chemical structure, so it is more
The maximum Cu2+ uptake was 20.11 mg/g (Table SM2). Pine hygroscopic than carbon black (Mohan et al., 2012). During fast
wood and rice husk hydrothermal biochars formed at 300 °C gave pyrolytic decomposition, gases and steam rapidly generated inside
maximum aqueous lead removal capacities of 4.25 and 2.40 mg/g, the wood or bark particles are ‘‘exploded’’ outward. As these es-
respectively (Liu and Zhang, 2009). Capacity increased on raising cape from the pyrolyzing/decomposing particles, more porosity is
adsorption temperature (Tables 2 and SM2). generated. These internal pore networks partially collapse or close
Biproduct chars from pine wood, pine bark, oak wood and oak on cooling (Mohan et al., 2012).
bark fast pyrolysis in an auger-fed reactor at 400 and 450 °C, dur- Slow pyrolysis chars prepared from orange peels and water
ing bio-oil production, were characterized (Mohan et al., 2007b). treatment sludge at 400, 600, and 700 °C were also used for fluo-
Without activation they successfully remediate aqueous Pb2+, ride uptake (Oh et al., 2012). Sludge chars had high ash (76–90%)
Cd2+, and As3+. Oak bark char offers great potential for Pb2+, Cd2+ and low carbon contents (6–8%). H/C and O/C ratios decreased with
and As3+ adsorption. The significantly higher adsorption on oak increased pyrolysis temperatures. Orange peel biochars made at
bark char versus pine wood, oak wood and pine bark chars was 600 and 700 °C adsorbed more fluoride than those made at
partially due to its higher surface area and pore volume (Mohan 400 °C (pH 2.0–3.3). Sludge-based chars had maximum fluoride
198 D. Mohan et al. / Bioresource Technology 160 (2014) 191–202

uptake at pH 5. Fluoride forms complexes to oxidized aluminum 7.2. Chemically modified biochars
and iron species on sludge char surfaces. Fluoroaluminates are re-
leased into solution at low pH, decreasing the sludge char’s sorp- Nanocomposites containing MgO were made by pyrolyzing
tion efficiency. Bench-scale slow pyrolysis (600 °C, 2 h, under N2) (600 °C, N2) MgCl2 with biomass feedstocks (sugar beet tailings,
of anaerobically digested and undigested sugar beet tailings gave sugarcane bagasse, cottonwoods, pine woods, and peanut shells)
45% (DSTC) and 36% char yields respectively (Yao et al., 2011). (Zhang et al., 2012a). MgO particles were well dispersed over the
The DSTC surface (336 m2/g) was negatively charged. Magnesium, biochar surface. Micropores predominated. These nanocomposites
silicon, and calcium were present. DSTC removed significantly were used to remove phosphate and nitrate from water. An
more phosphate than many adsorbents. In most natural aqueous adsorption capacity of 835 mg/g (phosphate) was achieved by su-
conditions, positive MgO surfaces (high pHZPC) actively bind nega- gar beet tailing composites. Peanut shell/MgO biochar adsorbed
tive phosphate, forming mono and polynuclear complexes. Surface 12% nitrate from water, highest among these chars, with an
diffusion in DSTC’s large mesopores is important with phosphate. adsorption capacity of 94 mg/g. These high nitrate and phosphate
The Langmuir sorption capacity was 133 mg/g at pH 5.2 (Tables capacities may be due to surface area and porosity enhancement
2 and SM2). by introducing MgO (Zhang et al., 2012a).
Hybrid multi-walled carbon nanotube (CNT)-coated biochars
were made by dip-coating biomass into varying concentrations of
7. Modified biochars for water filtration carboxyl-functionalized CNT solutions (0.01% and 1% w/w) prior
to slow pyrolysis (tubular furnace) at 600 °C/1 h at 10 °C/min under
7.1. Magnetic biochars N2 (Inyang et al., 2014). Untreated hickory (HC) and bagasse bioch-
ars (BC) and CNT–biochar composites (HC–CNT and BC–CNT) were
Innovations incorporating engineered nanoparticles into bio- characterized and used for methylene blue (MB) adsorption. CNT
char production could improve biochar functioning in soil fertility addition significantly enhanced the HC–CNT-1% and BC–CNT-1%
enhancement, carbon sequestration and wastewater treatment thermal stabilities, surface areas (351 and 390 m2/g), and pore vol-
applications (Inyang et al., 2014). Adsorbent magnetization is an umes (0.14 and 0.22 cc g1, respectively) (Inyang et al., 2014). Elec-
emerging water remediation area to overcome filtration problems trostatic attraction dominated MB sorption and diffusion controlled
of non-magnetic adsorbents. Magnetic adsorbents can easily be MB’s adsorption rate (Inyang et al., 2014).
recovered from contaminated water containing suspended solids, A comparative study of the adsorption capacity of functional-
oil and grease using low strength external magnetic fields. Impuri- ized carbon nanotubes (CNTs) and magnetic biochar from empty
ties may cause adsorbent fouling requiring frequent separation/ fruit branches for Zn2+ removal was reported (Mubarak et al.,
regeneration. Magnetic separation simplifies isolation and wash- 2013). Maximum Zn2+ adsorption capacities were 1.05 and
ing, followed by redispersion. Few papers have appeared where 1.18 mg/g for functionalized CNT and magnetic biochar, respec-
fast or slow pyrolysis biochars were magnetized, characterized tively (Mubarak et al., 2013) (Tables 2 and SM2). A biochar/AlOOH
and use to treat water. nano-flake nanocomposite was fabricated from AlCl3-pretreated
Magnetic oak wood (MOWBC) and oak bark (MOBBC) biochars biomass through slow pyrolysis in N2 at 600 °C for 1 h (Zhang
were obtained by fast pyrolysis (400 and 450 °C) during bio-oil pro- and Gao, 2013). This was a highly effective adsorbent to remove ar-
duction in an auger-fed reactor and used for aqueous Cd2+ and Pb2+ senic, methylene blue, and phosphate. The Langmuir capacity of
remediation (Mohan et al., 2014). Aqueous biochar suspensions methylene blue adsorption on the biochar/AlOOH (85000 mg/
were magnetized by mixing with aqueous Fe3+/Fe2+ solutions, kg) was 10 times higher than that of the corresponding biochar
followed by NaOH, causing mixed iron oxides to nucleate and bind. without aluminum treatment (8000 mg/kg) (Zhang et al., 2012b).
The SBET of the magnetic oak wood and bark chars were 6.1 and The Langmuir adsorption capacity of phosphate and arsenic on
8.8 m2/g, respectively. Magnetic chars remediated Pb2+ and Cd2+ the biochar/AlOOH was 135,000 and 17410 mg/kg, respectively
better [Q 0MOWBC (Pb2+:30.2 & Cd2+: 7.4 mg/g), Q 0MOBBC (Pb2+ 10.13 & (Zhang and Gao, 2013). Magnetic aerobically digested sewage
2.87 mg/g)] than the nonmagnetic biochars [Q 0OWBC (Pb2+:2.62 & sludge [SBET 188 m2/g] and magnetic undigested sewage sludge
Cd2+: 0.37 mg/g); Q 0OBBC (Pb2+ 13.10 & 5.40 mg/g)] previously [SBET 375 m2/g] biochars were prepared in a horizontal furnace at
reported (Mohan et al., 2007b) (Tables 2 and SM2). More adsorp- a 10 °C/min heating rate for 2 h at 600 °C under N2 and successfully
tion occurred than expected based on the chars’ SBET values applied to for 1-diazo-2-naphthol-4-sulfonic acid adsorption (Gu
(Mohan et al., 2014). Adsorption of Pb2+ and Cd2+ was largest at et al., 2013). Another magnetic (saturation magnetization of 69.2
the highest pH values because carboxylic acids anhydrides, and emu/g) biochar, with colloidal or nanosized c-Fe2O3 particles
phenols become carboxylate and phenoxide anions. Columbic embedded in the porous matrix, was fabricated via FeCl3-treated
attractions bound free Pb2+ and Cd2+ and other hydrated Pb and cottonwood pyrolysis at 600 °C in N2 environment for 1 h (Zhang
Cd cations. et al., 2013). A large quantity of c-Fe2O3 particles with sizes from
Three magnetic biochars (MOP250, MOP400, MOP700) were hundreds of nanometers to several micrometers grew within the
formed by chemical co-precipitation of Fe3+/Fe2+ on orange peel porous biochar. Its sorption capacity for As(V) removal was
powder and subsequest 250, 400 and 700 °C pyrolysis (Chen 3,147 mg/kg (Zhang et al., 2013) (Tables 2 and SM2).
et al., 2011a). Iron oxide (magnetite) formation occurred in one-
step magnetic biochar preparation. These were applied to aqueous 7.3. Biochar as an activated carbon precursor
phosphate, naphthalene and p-nitrotoluene remediation. A higher
organic content remained in the magnetic versus nonmagnetic Biochar is a high heating value solid fuel commonly used in
biochars after pyrolysis. Iron oxide in the char did not contribute kilns and boilers. It was evaluated as a feed to produce activated
to naphthalene or p-nitrotoluene sorption (Chen et al., 2011a). carbons at 535 °C (Azargohar and Dalai, 2006). Activated carbons
Naphthalene and p-nitrotoluene sorption on magnetic biochars in- that resulted had internal surface areas >500 m2/g versus 10 m2/g
creased with higher pyrolysis temperatures. Sorption was a combi- for the precursor biochar. This activated carbon was highly micro-
nation of adsorption and partition. Magnetic orange peel biochars porous, confirmed by SEM analysis. FT-IR spectroscopy proved
had higher phosphate sorption efficiencies than their nonmagnetic aromatization had occurred. The BET surface area of Luscar char in-
analogs, indicating bound iron oxide aggregates assisted in phos- creased more than 10-fold upon steam activation (Azargohar and
phate removal (Chen et al., 2011a). Dalai, 2005). This adsorbent’s high micropore to mesopore area,
 D. Mohan et al. / Bioresource Technology 160 (2014) 191–202 199

its methylene blue adsorption number, pore volume and average processing requirements, pyrolysis conditions, reactor availability,
pore diameter demonstrated a broad potential. Operating condi- recycling and lifetime issues. These are not in the literature. Costs
tions for biochar activation were investigated using a central com- for biochars vary in different countries. Costs will depend on
posite design (CCD) study (Azargohar and Dalai, 2008). The whether pyrolysis is part of an existing biorefinery and if value-
relationship between biochar-based activated carbon’s physico- added coproducts are produced. The biochar could be the major
chemical properties and phenanthrene adsorption was investi- targeted product or simply a byproduct as in the case of biorefin-
gated (Park et al., 2013). Steam-activation’s ability to add value eries. One economic analysis of Fischer–Tropsch (FT) liquid fuel
to fast-pyrolysis bio-chars was studied (Lima et al., 2010). Broiler production including diesel fuel, from crop residues appeared
litter, alfalfa stems, switchgrass, corn cob, corn stover, guayule ba- (Manganaro and Lawal, 2012). This was thermochemical based,
gasse, guayule shrub, soybean straw were all converted to chars by involving fast pyrolysis, autothermal reforming (ATR) followed by
fast pyrolysis in a fluidized-bed. The surface areas of these biochars FT synthesis. A simple, transparent spreadsheet for estimating eco-
and their corresponding steam-activated counterparts were deter- nomics was presented. The sale of pyrolysis char byproduct for soil
mined. All were used for aqueous copper, cadmium, nickel and zinc enhancement at $500/t had a large favorable impact on the eco-
removal. Surface areas increased with steam activation from negli- nomics, reducing diesel price by $0.35/gal. The cost of biomass
gible to 136–793 m2/g with concomitant pore development. Metal (including its transport to pyrolysis site) is the largest single con-
ion adsorption varied with feedstock but always increased with tributor to the final price of biomass-derived fuel, becoming more
steam activation (Lima et al., 2010) (Tables 2 and SM2). so as plant capacity increases. This suggests the need to improve
methods of gathering and delivering biomass. For each $10/dry t
increase in biomass price, the sales price of FT fuel is estimated
8. Comparative evaluation of biochars
to increase by $0.20/gal. Pyrolyzer collectives 25 miles square
(mi2) on a side would reduce diesel price by $0.12/gal, as compared
Adsorption capacities of many biochars for different contami-
to those 14 mi2 on a side (Manganaro and Lawal, 2012). The cost
nants are summarized in Table 2 and the comprehensive
effects of using mobile pyrolyzers that could go to the biomass
Table SM2. It is very difficult to directly compare adsorption capac-
sources has not been carefully analyzed.
ities due to a lack of consistency in the literature data. Sorption
Based on the literature reviewed, following is recommended for
capacities were reported at different pHs, temperatures, adsorbate
future biochar research.
concentration ranges, biochar doses, particle sizes and surface
areas. The biochars have been used to treat ground water, drinking
1. Serious economic studies of biochar production in various sized
water, synthetic industrial wastewater and actual wastewater. The
biorefineries and at distributed minisources connected with
types and concentrations of interfering ions are different and sel-
agriculture and forestry.
dom documented. Some adsorption capacities were reported in
2. Economic studies of how biochar costs would be impacted by
batch experiments and others in column modes. These cannot be
both energy crop growth and large scale char uses for carbon
readily compared. In batch sorption experiments, the sorption
sequestration.
capacities were computed by the Langmuir or Freundlich isotherms
3. How large scale char production could use arid and other lands
or experimentally. This makes comparisons more complicated to
poorly productive for traditional agriculture. What are water
pursue. Recycling studies after desorption steps are largely missing
and fertilizer/mineral needs for large scale char production?
in the literature. In other words, direct comparisons of the tested
This is not a big issue for adsorbent use only, but it is critical
adsorbents are largely impossible. Keeping these caveats in mind,
when coupled to energy fuels (char-byproducts) and C seques-
some of the best biochars having high capacities for selected con-
tration on large scales.
taminants were chosen and compared using a bar diagram (Fig. 2).
4. Major biochars made by fast or slow pyrolysis with systemati-
Of the biochars compared in this review, bamboo char was best
cally varied %O and % carbonization from major crop precursors
for removing methylene blue dye. Cow manure, pig manure, peanut
each need to be studied for many adsorption/remediation uses.
straw biochars offered excellent adsorption capacity (>88 mg/g) for
Some chars will serve only a small number of uses while some
Cu2+ (Fig. 2). Maximum lead (219 mg/g) was removed by cow man-
may have wide applicability. Detailed knowledge is needed to
ure biochar (Fig. 2). Surprisingly very high zinc adsorption capacity
compare with other adsorbents.
(256 mg/g) was achieved by softwood biochar (Fig. 2). Cow manure
5. Low cost activation studies are needed. How do high, medium,
and pig manure biochars also performed better versus other bioch-
and lower %O chars function? Adsorption responses should be
ars. Maximum Cr6+ and Cr3+ removal was achieved with sugar beet
analyzed versus costs. Activation versus non-activation should
tailing biochar and sugar pulp biochars, respectively (Tables 2 and
be better understood.
SM2). Highest fluoride removal (>20 mg/g) occurred with pine bark
6. More understanding of the 3-D aspects of biochar adsorption
biochar. No single biochar removed all the contaminants from
is needed (low surface area but large capacities). What does
water but the conditions employed in those studies can be simu-
swelling actually do or allow? What role does it play in
lated for large-scale applications for drinking water purification
kinetics? How are various types of adsorbates distributed
(Table 2 and SM2).
throughout the biochars on all dimensional levels (pore,
Another reason of biochar adsorbents are hard to compare is
inside and below pore surfaces, throughout the solid mate-
that they are often prepared under different conditions (tempera-
rial, etc.)?
ture, time, atmosphere etc.). Studies of biochar preparation by sev-
7. Stripping pollutants/contaminants from biochar adsorbents fol-
eral methods from the same feedstock, followed by adsorption of
lowed by recycling needs to be far more widely studied. One
the same adsorbents are rare. Likewise, identical biochar prepara-
important advantage of really low cost biochar adsorbents
tions from the same feed followed by adsorption studies of the
could be the ability to use them once and then dispose of them
same adsorbents are needed to assess reproducibility.
without stripping. Could be used only a few times?. Disposal
could involve combustion to use their fuel value, depending
9. Cost estimation on what had been adsorbed. Many metals would end up as
oxide ash and many organic adsorbates would simply burn.
Cost studies of biochars from different precursors rarely appear. However, chlorinated organics or volatile metal products would
Individual biochar costs depend on local precursor availability, require more care.
200 D. Mohan et al. / Bioresource Technology 160 (2014) 191–202

No. Biochar Types Reference

100
1 Corn straw biochar (Chen et al., 2011b)
2 Orange waste biochar (Pellera et al., 2012)
80
3 Rice husk biochar
Adsorption capacity (mg/g)

4 Olive pomace biochar

60 Cu2+
5 Compost biochar
6 Cow manure biochar (Kołodyńska et al., 2012)
40
7 Pig manure biochar
8 Dairy manure biochar (Xu et al., 2013)
20 9 Hardwood biochar (Chen et al., 2011b)
10 Peanut straw biochar (Tong et al., 2011)
0 11 Soybean straw biochar
0 2 4 6 8 10 12 14 16
12 Canola straw biochar
Biochar Types
13 Switchgrass biochar (Han et al., 2013b)
14 Softwood biochar
15 Pinewood biochar (Liu et al., 2010)

350

Pb2+
300 1 Sugarcane bagasse biochar (Inyang et al., 2011)
Adsorption capacity (mg/g)

2 Raw sugarcane bagasse biochar

250
3 Pig manure biochar (Kołodyńska et al.,
200 4 Cow manure biochar 2012)
5 Pinewood biochar (Mohan et al., 2007b)
150 6 Pinebark biochar
7 Oak wood biochar
100
8 Oak bark biochar
50
9 Magnetic oak bark biochar (Mohan et al., 2013)
10 Digested dairy waste char (Inyang et al., 2012)
0 11 Sugar beet biochar
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 12 Rice husk biochar (Liu & Zhang, 2009)
Biochar Types 13 Dairy manure biochar (Cao et al., 2009)
14 Buffalo weed biochar (Yakkala et al., 2013)

300
1 Corn straw biochar (Chen et al., 2011b)
2 Pig manure biochar (Kołodyńska et al., 2012)
Adsorption capacity (mg/g)

250
Zn2+ 3 Cow manure biochar
200 4 Fruit branch magnetic char (Mubarak et al., 2013)
5 Dairy manure biochar (Xu et al., 2013)
150
6 switchgrass biochar Han et al., 2013b)
100
7 hardwood biochar
8 Softwood biochar
50

0
1 2 3 4 5 6 7 8
Biochar Types

140
Adsorption capacity (mg/g)

120
Cd2+ 1 Dairy manure biochar (Xu et al., 2013)
100
2 Buffalo weed biochar (Yakkala et al., 2013)
80 3 Rice straw biochar (Han et al., 2013a)
60 4 Oak bark biochar (Mohan et al., 2007b)
5 Pig manure biochar Kołodyńska et al.,
40
6 Cow manure biochar 2012)
20

0
1 2 3 4 5 6
Biochar Types

Fig. 2. Comparative evaluation of adsorbents for Cu2+, Pb2+, Zn2+ and Cd2+.

10. Conclusions sustainable. Renewable bioenergy reduces greenhouse gas emis-

sions. Currently, bio-oil markets are economically limited due to
The pyrolysis platform for producing bio-oil and byproduct biooils modest heating value and upgrading requirements for
biochar from biomass is practical, effective, and environmentally transportation uses. Traditional charcoal production is polluting
 D. Mohan et al. / Bioresource Technology 160 (2014) 191–202 201

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