Environ Sci Pollut Res
DOI 10.1007/s11356-015-4849-0
RESEARCH ARTICLE
Characterization of potassium hydroxide (KOH) modified
hydrochars from different feedstocks for enhanced removal
of heavy metals from water
Kejing Sun 1 & Jingchun Tang 1,2,3 & Yanyan Gong 1,2,3 & Hairong Zhang 1
Received: 30 December 2014 / Accepted: 5 June 2015
# Springer-Verlag Berlin Heidelberg 2015
Abstract Hydrochars produced from different feedstocks
(sawdust, wheat straw, and corn stalk) via hydrothermal car-
bonization (HTC) and KOH modification were used as alter-
native adsorbents for aqueous heavy metals remediation. The
chemical and physical properties of the hydrochars and KOH-
treated hydrochars were characterized, and the ability of
hydrochars for removal of heavy metals from aqueous solu-
tions as a function of reaction time, pH, and initial contami-
nant concentration was tested. The results showed that KOH
modification of hydrochars might have increased the aromatic
and oxygen-containing functional groups, such as carboxyl
groups, resulting in about 2–3 times increase of cadmium
sorption capacity (30.40–40.78 mg/g) compared to that of
unmodified hydrochars (13.92–14.52 mg/g). The sorption
ability among different feedstocks after modification was as
the following: sawdust>wheat straw>corn stack. Cadmium
sorption kinetics on modified hydrochars could be interpreted
with a pseudo-second order, and sorption isotherm was simu-
lated with Langmuir adsorption model. High cadmium uptake
on modified hydrochars was observed over the pH range of
Responsible editor: Hailong Wang
Electronic supplementary material The online version of this article
(doi:10.1007/s11356-015-4849-0) contains supplementary material,
which is available to authorized users.
* Jingchun Tang
tangjch@nankai.edu.cn
1
College of Environmental Science and Engineering, Nankai
University, Tianjin 300071, China
2
Tianjin Engineering Centre of Environmental Diagnosis and
Contamination Remediation, Tianjin 300071, China
3
Key Laboratory of Pollution Processes and Environmental Criteria
(Ministry of Education), Tianjin 300071, China
4.0–8.0, while for other heavy metals (Pb2+, Cu2+, and Zn2+)
the range was 4.0–6.0. In a multi-metal system, the sorption
capacity of heavy metals by modified hydrochars was also
higher than that by unmodified ones and followed the order
of Pb(II)>Cu(II)>Cd(II)>Zn(II). The results suggest that
KOH-modified hydrochars can be used as a low cost, envi-
ronmental-friendly, and effective adsorbent for heavy metal
removal from aqueous solutions.
Keywords Hydrochar . Hydrothermal carbonization .
Sorption . Heavy metal . Modification
Introduction
In recent years, biochar derived from pyrolysis of organic
materials (mainly agricultural residues, forest wastes, and ma-
nures) has been widely investigated for environmental appli-
cations (Karaosmanoglu et al. 2000; Keiluweit et al. 2010;
Cao et al. 2009). Due to its high degree of porosity and large
specific surface area, biochar may act as an effective adsorbent
for both organic and inorganic pollutants (Shrestha et al. 2010;
Wang et al. 2011). Moreover, biochar with high organic car-
bon content has the potential to serve as a soil amendment for
improving soil physicochemical and biological properties
(Chan et al. 2008; Sohi et al. 2010). However, the ability
of biochar to adsorb pollutants and improve soil proper-
ties depends on its chemical properties, which change
greatly with different pyrolysis conditions and various
sources of feedstocks (Bourke et al. 2007; Novak et al.
2009). Generally, biochar produced at low temperature
(523–673 K) shows low adsorption capacity whereas
the one produced at high temperature (673–973 K) has
greater surface area, high microporosity, and higher sorp-
tion capacity (Chen and Chen 2009).

Recently, hydrothermal carbonization (HTC) has been pro-
posed as a promising method to prepare biochar in the presence
of water and received much attention. During the HTC process,
biomass (such as agricultural residues, lignocellulosic biomass,
and algae) are converted into carbon-rich materials (i.e.,
hydrochar) under relatively mild conditions (423–623 K)
(Mumme et al. 2011; Xiao et al. 2012; Pham et al. 2013).
Hydrochar typically has higher concentrations of oxygen-
containing functional groups and lower carbon content than
pyrolysis biochar, making it act as an alternative lower-cost
adsorbent to remove environmental contaminants (Libra et al.
2011; Sevilla et al. 2011). By comparing the sorption capacities
of organic pollutions on hydrothermal and thermal biochars,
Sun et al. demonstrated that hydrochars exhibited higher uptake
of both polar and nonpolar organic contaminants, namely 17α-
ethinyl estradiol (EE2), bisphenol A (BPA), and phenanthrene
(Phe), than thermal biochar under otherwise identical condi-
tions (Sun et al. 2011). In addition, various studies have been
carried out to investigate the sorption of heavy metals by
hydrochars. For example, Liu and Zhang (2009) investigated
the sorption efficiency of lead on hydrochars produced from
pinewood (P300) and rice husk (R300). The results showed that
the maximum lead adsorption capacities were 4.25 and
2.40 mg/g for hydrochars produced from P300 and R300 at
318 K, respectively. However, as hydrothermal process is gen-
erally conducted under lower temperatures of less than 523 K,
which may result in a low adsorption ability of hydrochar on
heavy metals as compared to activated carbon.
To enhance the adsorption capability of hydrochar, modi-
fication turned out to be an effective method. Recently, Regmi
et al. (2012) compared the sorption capacities of HTC biochar
and alkali activated HTC biochar (HTCB) for removing cop-
per and cadmium from aqueous solution. They found that with
an initial metal concentration of 40 mg/L at pH 5.0 and a
contact time of 24 h, about 100 % of copper and cadmium
were removed by HTCB at 2 g/L, while HTC biochar only
removed 16 % of copper and 5.6 % of cadium. Similarly,
batch and column experiments were conducted to study the
removal of lead and multi-metals from aqueous solutions by
hydrochar and H2O2-treated hydrochar (Xue et al. 2012). The
modified hydrochar enhanced lead sorption ability with a val-
ue of 22.82 mg/g, which was more than 20 times of that of
untreated hydrochar (0.88 mg/g). The modification process
may increase the oxygen-containing functional groups on
hydrochar surface and improve the sorption capacities. So
far, only few studies have examined the sorption of multiple
heavy metals on hydrochars, particularly on modified
hydrochars and compared the sorption capacities of modified
hydrochars from different raw materials.
This study presented a novel and simple methodology to
fabricate hydrochars from different feedstocks (sawdust,
wheat straw, and corn stalk) via KOH modification. The over-
all goal of this research was to investigate the sorption ability
Environ Sci Pollut Res
of hydrochars (HCs) and KOH-modified hydrochars (mHCs)
derived from different raw materials to remove cadmium and
multi-metals (Pb(II), Cd(II), Cu(II), and Zn(II)) from aqueous
solutions. The specific objectives are as follows: (1) prepare
and characterize unmodified and KOH-modified hydrochars
from different feedstocks; (2) compare the sorption capacities
of these hydrochars to remove single and multiple heavy
metals from aqueous solutions; (3) examine the effects of
initial heavy metal concentration, contact time, and pH, on
the effectiveness of heavy metals removal; and (4) acquire
further insights into the sorption mechanisms.
Materials and methods
Materials
The feedstocks (sawdust, wheat straw, and corn stalk) were
collected from a suburb of Tianjin, China. All chemical re-
agents used in this study were of analytical grade. The stock
solutions of Pb(II), Cd(II), Cu(II), and Zn(II) were prepared by
dissolving their nitrate salts (Sinopharm Chemical Reagent
Co., Beijing, China) in a 0.01 M NaNO3 solution.
Preparation and modification of hydrochars
Hydrochars were produced following a typical HTC process
(Mumme et al. 2011; Oliveira et al. 2013). Briefly, 5 g (dry
weight) of three different biomass (sawdust, wheat straw, or
corn stalk,) and 60 mL of water were loaded into 100-mL
autoclaves, which was heated up to 473 K and maintained
for 20 h under oxygen limiting condition. After cooling to
room temperature (295 K), the mixture was extracted with
50 mL acetone to obtain tarry materials. The resultant solids
were rinsed several times with distilled water and dried at 378
±0.5 K for 12 h. The dried hydrochars (designated as H-SD,
H-WS, and H-CS for sawdust, wheat straw, and corn stalk,
respectively) were gently ground and homogenized to pass
through a 300 μm sieve and stored in a desiccator for later use.
To make the modified hydrochar, 2 g of the hydrochars
were mixed with 500 mL of 2 N KOH solution for 1 h (Regmi
et al. 2012). After washing with distilled water and drying
overnight in an oven at 378 K, the modified hydrochars (des-
ignated as mH-SD, mH-WS, and mH-CS) were ground and
passed through a 300 μm sieve for characterization and sorp-
tion experiments.
Characterization of unmodified and KOH-modified
hydrochars
The elemental (carbon, C; hydrogen, H; and nitrogen, N) com-
positions were analyzed with an elemental analyzer (Vario EL
cube, Elementar Analysensysteme GmbH, Hanau, Germany).
Environ Sci Pollut Res
The amount of ash was measured by heating the samples at
1023 K for 6 h, and the O content was calculated based on the
mass difference (Sun et al. 2011).
The pore structure characteristics of the samples were de-
termined by N2 adsorption at 77 K using a surface area ana-
lyzer (ASAP 2020/Tristar 3000, Micromeritics Instrument
Corp., Georgia, USA). The specific surface area was calculat-
ed following the multipoint N2-Brunauer-Emmett-Teller
(BET) adsorption method. The volume and surface area of
the micropores were obtained using the t-plot method.
The functional groups of the samples were examined using
Fourier transform infrared spectroscopy (FTIR, FTS6000,
Bio-Rad Corp., California, USA) in the wavenumber range
of 4000–400 cm−1. Oxygen-containing functional groups
were determined by Boehm titration method (Boehm 1966;
Bandosz et al. 1993).
The crystalline compositions were identified by X-ray dif-
fraction (XRD) using a Bruker D8 FOCUS diffractometer
(Bruker AXS GmbH, Karlsruhe, Germany) with Cu Kα radi-
ation (λ=1.5406 Å) at a scan speed of 4°/min and a step size of
0.02° in the 2θ range of 10∼35°. The morphology of the
samples was determined through scanning electron microsco-
py (SEM, S-3000 N, Hitachi Ltd., Tokyo, Japan).
Sorption kinetic and isotherm tests of cadmium
Batch kinetic experiments of cadmium sorption by unmodi-
fied or KOH-modified hydrochars were carried out in 100 mL
stoppered reagent glass bottles. The initial concentrations of
cadmium and the dose of HCs or mHCs were set at 20 mg/L
and 2 g/L, respectively. The pH of the mixture was adjusted to
6.0 with NaOH (0.1 M) or HNO3 (0.1 M). 0.01 M NaNO3 was
added in the suspensions to maintain constant ionic strength.
The bottles were then sealed and agitated on an incubator
shaker (HNY-2102C, Honour Instrument Co. Ltd., Tianjin,
China) at 150 rpm at 303±1 K. At predetermined time inter-
vals, the solid adsorbent was separated from the liquid phase
by centrifugation at 5000 rpm for 10 min, and the supernatant
was subjected to filtration through a 0.22 μm membrane filter
and then analyzed for cadmium concentration in the filtrates
by an atomic absorption spectroscopy (SpectrAA240FS,
Varian Inc., California, USA). The adsorption experiments
were performed in duplicates. Controls without hydrochars
were also included under the same experimental conditions.
The adsorption isotherm experiments were performed in
100 mL stoppered reagent glass bottles with 0.06 g of the
hydrochars (HCs or mHCs) and 30 mL of the cadmium solu-
tion. Experimental conditions were NaNO3 =0.01 M and ini-
tial cadmium concentration=5∼300 mg/L. The bottles were
equilibrated at 303±1 K for 24 h in the same manner as in the
kinetic tests. The pH of solution was adjusted with NaOH
(0.1 M) or HNO3 (0.1 M) to 6.0. And controls without
hydrochars were also included in the same experiments.
The effect of pH on cadmium removal by HCs and mHCs
was conducted at the adsorbent dose (2 g/L), initial metal con-
centration (20 mg/L), and reaction temperature (303±1 K) for
24 h. The initial pH of solution was 2.0∼10.0 and adjusted with
NaOH (0.1 M) or HNO3 (0.1 M). Controls without adsorbents
were also included in the same experiments.
Sorption of mixed heavy metals
A mixture solution of four heavy metals was prepared with
lead nitrate, cadmium nitrate, copper nitrate, and zinc nitrate.
The initial concentration of these metals were in the range of
5∼300 mg/L. Other conditions were same as the cadmium
sorption isotherm tests. Similar adsorption experiments as
above were used to test the removal of the four heavy metals
on the adsorbent (HCs or mHCs). And controls without ad-
sorbents were also included in the same experiments. Heavy
metal concentrations were determined with the ICP-OES
(IRIS Intrepid II XSP, Thermo Electron Corp., Wisconsin,
USA).
Data analysis
Adsorption kinetics is important in the prediction of the rate at
which the contaminants can be removed by the hydrochars. In
this work, the sorption kinetics data were fitted by a pseudo-
second-order kinetics equation (Ho and McKay 1998):
t 1 t
¼ þ ð1Þ
Qt k 2 Qe 2 Qe
where t is the adsorption time, Qt (mg/g) is the amount of
heavy metals adsorbed onto the composite at time t, Qe (mg/
g) is the amount of heavy metals adsorbed at equilibrium, and
k2 (g/mg·min) is the rate constant of pseudo-second-order
adsorption.
The equilibrium cadmium uptake was calculated based on
the difference between the initial and final concentrations of
aqueous cadmium. Freundlich and Langmuir isotherm models
were used to fit the equilibrium sorption isotherm data (Lang-
muir 1918; Freundlich 1906).
Freundlich model : Qe ¼ K f C e =n
1
ð2Þ
Ce 1 Ce
Langmuir model : ¼ þ ð3Þ
Qe bQm Qm
where Qe (mg/g) and Ce (mg/L) represent the equilibrium
sorbed and aqueous concentrations, respectively. Kf (mg/g/
(mg/L)1/n) and n are Freundlich coefficients related to the ad-
sorption capacity and adsorption intensity, respectively. Qm
(mg/g) denotes the maximum adsorption capacity, and b
(L/mg) is the Langmuir constant.
 Environ Sci Pollut Res

2.4
Results and discussion
2.2
2.0 Carbohydrates
Characterization of hydrochar adsorbents
1.8 Proteins
Lipids
1.6
Chemical properties of hydrochars Basic properties of
1.4 dehydration
hydrochar samples were summarized in Table 1. Weight-

H/C
1.2 SD
based production yields of hydrochars were 47.1–54.7 %, Unsaturated
hydrocarbons WS
1.0 Lignins
which are similar to previously reported values for hydrother- CS
0.8 H-SD
mal conversion of agricultural residues (Oliveira et al. 2013). H-WS
0.6
There was almost no weight loss after the KOH modification, Condensed aromatic structures
H-CS
0.4 mH-SD
and the yields of mHCs were very high (83–94.8 %), suggest- mH-WS
0.2
ing that the KOH treatment had little impact on the yields of mH-CS
0.0
mHCs. The pH value of the hydrochars was in an acidic rage 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 1.1 1.2
from 3.4 to 3.9, which are lower than that of other hydrother- O/C
mal products prepared at lower temperature (200 °C, pH Fig. 1 The van Krevelen plot of elemental ratios for unmodified and
around 6.0) (Libra et al. 2011). However, pH of the modified KOH-modified hydrochars and feedstocks
hydrochars was much higher (8.1–9.3), which could be attrib-
uted to the carboxyl functional groups formed on the surface contents of mHCs (38.5–39.5 %) were higher than that of
after the KOH treatment. HCs (31.5–34.9 %), resulting in higher O/C and H/C ratios
Elemental compositions of the feedstocks showed that all for mHCs, which made them better adsorbents for aqueous
of these materials contained high carbon contents (43.1– contaminants (Libra et al. 2011; Regmi et al. 2012). Higher O/
45.2 %) (Table 1). After the HTC process, the elemental anal- C ratio also suggests that oxygen-containing functional groups
ysis results showed that hydrochars had higher carbon content may play an important role for mHCs as absorbent materials.
and lower oxygen content than feedstocks. The elemental The molecular composition of the feedstocks and
composition analysis also showed that KOH treatment had hydrochar samples is illustrated by a van Krevelen diagram
little impact on the nitrogen contents of the two hydrochars. on the basis of molar H/C and O/C ratios (Fig. 1). Based on the
However, the carbon contents of mHCs (48.9–51.5 %) were data given by Ohno et al. (2010), clusters within defined re-
lower than that of HCs (54.8–61.5 %), and the oxygen gions of H/C versus O/C are given for characteristic

Table 1 Yield, pH, and elemental compositions of feedstocks, unmodified and KOH-modified hydrochar samples

Sample Yield (%)a pH Elemental composition (%, mass based)b Ash (%)d O/Ce H/Cf

C H N Oc

Feedstock
SD – – 43.13 6.62 0.17 49.14 0.94 0.85 1.84
WS – – 44.75 7.3 0.43 43.89 3.63 0.74 1.96
CS – – 45.18 7.08 0.53 45.85 1.36 0.76 1.88
Hydrochar
H-SD 54.7 3.45 61.46 5.83 0.08 31.6 1.03 0.38 1.14
H-WS 47.1 3.94 55.28 7.19 0.27 31.47 5.79 0.43 1.56
H-CS 48.4 3.58 54.76 6.9 0.3 34.88 3.16 0.48 1.51
Modified hydrochar
mH-SD 83.0 8.13 51.48 6.49 0.07 38.47 3.49 0.56 1.51
mH-WS 94.8 9.34 48.87 6.55 0.23 39.46 4.89 0.60 1.61
mH-CS 83.5 8.19 50.33 6.48 0.25 39.14 3.8 0.58 1.54

feestock weight  100%; modified hydrochar yield (%) =

Yields are on a water-free basis; hydrochar yield (%) = hydrochar  100%
a weight modi f ied hydrochar weight
hydrochar weight
b
Elemental compositions and atomic ratios are on a total dry weight basis
c
Oxygen content is estimated as follows: O=100−(C+H+N+ash)
d
Ash are on a water-free basis
e
O/C: atomic ratio of oxygen to carbon
f
H/C: atomic ratio of hydrogen to carbon
Environ Sci Pollut Res

Table 2 Surface area, pore volume, and pore size parameters for hydrochar samples

Samples SBET (m2/g)a Smic (m2/g)b Smic/SBET (%) Vt (cm3/g)c Vmic (cm3/g)d Vmic/Vt (%) Pore size (d, nm)e

Hydrochar
H-SD 4.4139 3.3016 74.80 0.01273 0.001491 11.72 11.53
H-WS 9.1428 0.7297 7.98 0.04127 0.000128 0.31 18.06
H-CS 8.5805 3.1137 36.29 0.03394 0.001331 3.92 15.82
Modified hydrochar
mH-SD 0.6887 0.4059 58.94 0.002352 0.000210 8.93 13.66
mH-WS 0.4204 1.0158 241.63 0.003488 0.000514 14.74 33.19
mH-CS 1.8367 0.0792 4.31 0.005871 0.000033 0.56 12.79
a
Measured using N2 adsorption with the Brunauer-Emmett-Teller (BET) method
b
Micropore surface area calculated using the t-plot method
c
Total pore volume determined at P/P0 =0.99
d
Micropore volume calculated using the t-plot method
e
Pore size in diameter means average values

biomolecules alongside. The major compositions of feed-
stocks were carbohydrates, while hydrochars were plotted in
an area near proteins and lignins. The van Krevelen diagram
also showed that the HTC is a decarboxylation and dehydra-
tion process.
BET analysis The hydrochar materials possess hardly any
porosity; the sawdust derived hydrochar had a surface area
of 4.4 m2/g, and the wheat and corn stalk derived hydrochars
exhibited surface area of 8.6 and 9.1 m2/g, respectively
(Table 2). These surface area values match well with the ex-
ternal surface area determined by the t-plot technique (Sevilla
and Fuertes 2009). Therefore, the hydrochar materials possess
virtually no framework-confined pores, and their surface area
arises mainly from interparticle voids. Notably, these porous
textural characteristics of hydrochars were common for bio-
chars produced at low temperature (220 °C) (Novak et al.
2009; Sevilla et al. 2011). Previous studies have found that
temperature and feedstock play an important role in hydrochar
surface area by controlling creation of pores and creaking in
the hydrochar basal-structural sheets (Mumme et al. 2011;
Lehmann and Joseph 2009). However, after treatment with
KOH, all the hydrochar materials presented low apparent
BET surface area (0.4∼1.8 m2/g) and pore volume (0.002∼
0.006 cm3/g), which can be related to pore blockage due to the
organic compounds that was not transferred to the liquid phase
during the KOH treatment (Román et al. 2013).
The N 2 adsorption − desorption isotherms for the
hydrochars and modified hydrochars are shown in
Figure S1. It can be seen that all of the adsorption isotherms
of hydrochars, regardless of the modification, showed type III
isotherms, indicating the presence of large fractions of
mesopores. From the point of the formation of hysteresis loop,
the N2 adsorption isotherms in Figure S1a showed H3
hysteresis loop, indicating the type of hydrochars should be-
long to the slit aperture formed by the accumulation of flake
particles (Rouquerol et al. 1994). After KOH modification, the
hysteresis loop disappeared (Figure S1b).
The mesopore size distribution of the hydrochars and mod-
ified hydrochars exhibited different results (Figure S1c). Nev-
ertheless, almost all of the mesopores in the hydrochars and
modified hydrochars had a diameter in the range of 0 ∼
180 nm, which confirmed that the hydrochars contained main-
ly mesoporous structures.
Functional group analysis on hydrochar samples Figure 2
presents FTIR spectra of hydrochars produced from the three
feedstocks. And the band assignments for Fig. 2 are summa-
rized in Table S1 (Uchimiya et al. 2011a, b). The spectra
suggested that several oxygen functional groups, namely, O-
H stretching at 3300–3500 cm−1, aromatic C=O stretching of
conjugated ketones and quinones (1500–1600 cm−1), and
symmetric C-O stretching (1058 and 1065 cm−1) were identi-
fied in both feedstocks and hydrochars. In an earlier study,
Kumar et al. (2011) confirmed the presence of several oxygen
functional groups (carboxylic, hydroxyl/phenolic, carbonyl)
in HTC biochar using FTIR spectra. In our study, corn stalk
and its hydrochars had similar peaks for most of the
wavenumbers such as O-H stretching (3337 cm−1), C-H
stretchings (2907 cm−1), and C-O stretching (1058 cm−1)
(Fig. 2c); while the peaks at 3330–3350, 2900–2920, 1500–
1600, and 1065 cm−1 of the hydrochars made from sawdust
and wheat straw were stronger than that of feedstocks, partic-
ularly after further alkalization (Fig. 2a, b). Regmi et al.
(2012) found that functional groups such as C=O dem-
onstrated high coordination with heavy metal. The fact
that mH-SD and mH-WS had stronger peaks at 3330–
3350, 2900–2920, 1500–1600, 1065, and 610–902 cm−1
 Environ Sci Pollut Res

Carboxyl C=O 1702.8

100 a O-H, N-H
3342.8 -CH2-,-CH3-
Aromatic C-O, C-O-C
1064.9 C-H bending mostly increased during activation with
2906.7 C=C, C=O
Aromatic C-H
90
1592.3
1507.2 895.6 609.5 KOH.
Transmittance (%, arbitary units)

Phenolic O-H
1272.9 The hydrochar samples were further analyzed for
80
oxygen-containing functional groups content using Boehm
70 titration (see Fig. 3). Functional groups determined were
60 mainly oxygen-containing functional groups (phenolic hy-
droxyl, lactone, carboxylic) with a few alkaline groups
50
such as amino. As shown in Fig. 3, the oxygen-
SD
40
H-SD containing functional groups, especially the carboxylic
30
mH-SD (−COOH) of hydrochars (0.37, 0.46, and 0.75 mmol/g for
H-SD, H-WS, and H-CS, respectively) became higher with
20
4000 3500 3000 2500 2000 1500 1000 500 the KOH modification (corresponding 1.13, 1.04, and
Wavenumber (cm )
-1 0.94 mmol/g). It was reported that hydrochars showed im-
proved sorption capability for heavy metals as the oxygen-
containing functional groups increased (Liu and Zhang
100 b O-H, N-H Carboxyl C=O1709.0
Aromatic C-O, C-O-C
3336.6 -CH2-,-CH3-
2919.8
C=C, C=O
1064.9 2009; Chen et al. 2011c). This was consistent with results
1599.4 Aromatic C-H
90 1514.2 901.8 615.7 analyzed in FTIR. In addition, the oxygen-containing func-
Phenolic O-H
tional groups of activated hydrochars were much higher
Transmittance (%, arbitary units)

1371.1
80
than other reported hydrochars (Kang et al. 2012). The
70 result indicated that KOH treatment improved the content
60 of oxygen-containing functional groups and is an impor-
tant factor for adsorptive hydrochar production.
50
WS
40 H-WS XRD analysis The XRD patterns of feedstocks and
mH-WS hydrochar samples obtained in the 2θ range of 10∼35°
30
are shown in Fig. 4. Sharp and strong peaks in the feed-
20 stocks and hydrochars especially for feedstocks and HCs
4000 3500 3000 2500 2000 1500 1000 500
-1
at 2θ = 22.06∼ 22.68° indicated that miscellaneous inor-
Wavenumber (cm )
ganic components are mainly composed of quartz (such
as the sharp quartz peak at 2θ=22.49°). Peak spacings of
100 c O-H, N-H -CH2-,-CH3-
Carboxyl C=O1702.8
Aromatic C-O, C-O-C 0.60, 0.53, 0.404, and 0.259 nm were assigned to (101),
1058.0
3336.6 2906.7 C=C, C=O (110), (200), and (004) of completely ordered (i.e., crys-
1598.4 Aromatic C-H
90 1514.2 895.6 609.5 talline) regions of cellulose, respectively (Keiluweit et al.
Phenolic O-H 2010). The feedstocks and HCs showed strong peaks from
Transmittance (%, arbitary units)

1371.1
80 cellulose especially at 0.60 and 0.404 nm, suggested that
the hydrothermal carbonization did not change the crystal
70

60 2.5
OH Alkaline group
50 C=O
2.0 COOH
40 CS
Functional group (mmol/g)

H-CS
30 mH-CS 1.5

20
4000 3500 3000 2500 2000 1500 1000 500 1.0
-1
Wavenumber (cm )
Fig. 2 FTIR spectra of hydrochar samples and feedstocks
0.5

than H-SD and H-WS indicated that the functional

0.0
groups for O-H stretching, C-H stretchings, aromatic H-SD H-WS H-CS mH-SD mH-WS mH-CS
C=C and C=O stretching, C-O stretching, and aromatic Fig. 3 Functional groups in hydrochar samples
Environ Sci Pollut Res

600
a previous research found the existence of an amorphous
SD
C in the activated carbon prepared from coconut coir
H-SD
500 mH-SD (Sharma and Gode 2010). Generally, amorphous materials
Intensity (%, arbitary units)

as adsorbents would be better due to their high specific

400 surface area and more active sites on their surfaces
(Tchomgui-Kamga et al. 2010).
300

200
SEM analysis Scanning electron microscope (SEM) im-
ages of hydrochar samples are shown to illustrate the
100 physical changes of the hydrochar following KOH acti-
vation (Fig. 5). For the SEM images of hydrochar mate-
0 rials, H-WS had a surface with porous characteristics and
10 15 20 25 30 35
impurities (Fig. 5c) while the surface of H-SD and H-CS
2Theta (degree)
are all fragments without porous structures (Fig. 5a, e).
Because of the high temperature and long residence time
b WS of the reaction conditions during HTC process, the po-
400
H-WS rous structure of hydrochar appeared partially blocked as
mH-WS
a result of the repolymerization/recondensation of water
Intensity (%, arbitary units)

300 soluble compounds (Kumar et al. 2011). The SEM im-

ages of mH-SD and mH-WS were completely different
with a surface that was clearly regular and porous
200 (Figs. 4f and 5b), whereas mH-WS had a surface with
irregular and porous characteristics (Fig. 5d). Since KOH
has cleaning effect on hydrochars, it is possible that the
100 impurities on surface or blocks might be washed out by
KOH.

0
10 15 20 25 30 35
Cadmium sorption on HCs and mHCs: sorption kinetics,
2Theta (degree)
sorption isotherm, and effects of pH

Sorption kinetics For both HCs and mHCs, it took about

600 c
CS 2 h for cadmium sorption to reach apparent equilibrium
H-CS
(Fig. 6a). However, removals of cadmium on mHCs (more
500 mH-CS
than 80 %) were much higher than that on HCs (less than
Intensity (%, arbitary units)

10 %), suggesting KOH modification could enhance the

400
removal of cadmium by the hydrochars. Figure 6b presents
both the experimental data and the pseudo-second-order
300
model, with the plots of t/Qt versus t giving straight lines.
The results are also shown in Table 3. The second-order
200
model fitted well for both the mH-SD and mH-CS (R2 =
0.99), but it did not for mH-WS (R2 =0.90). There is no
100
difference among different mHCs for Cd adsorption. It is
possible that the rate limiting step in adsorption of mHCs
0
10 15 20 25 30 35
for Cd(II) is a chemical adsorption process rather than dif-
2Theta (degree) fusion (Bai et al. 2011).
Fig. 4 X-ray diffraction plots of hydrochar samples and feedstocks
Sorption isotherm Figure 7 presents cadmium sorption
isotherms for unmodified and KOH-modified hydrochars.
structure of cellulose. After the alkalized treatment, the Classical Langmuir and Freundlich sorption isotherm
peaks at 0.60 and 0.404 nm progressively lose intensity models were tested to fit the isotherm data. The fitting
and become broader, indicating a gradual decrease in cel- parameters are summarized in Table 4. The result showed
lulose crystallinity. That means that the organic C of the that the Langmuir model fitted the mH-SD, mH-WS, and
modified hydrochars would be amorphous. In addition, mH-CS (R2 =0.98, 0.88, and 0.89, respectively) sorption

Fig. 5 SEM images of hydrochar
materials derived from a H-SD, c
H-WS, e H-CS, and modified
hydrochars b mH-SD, d mH-WS,
f mH-CS
isotherm better than the Freundlich model (R 2 = 0.94,
0.82, and 0.85, respectively). Usually, the Langmuir
model better describes adsorption on homogeneous sur-
faces, while the Freundlich model is better for heteroge-
neous surfaces (Xue et al. 2012). Thus, the modeling
results confirmed that the surfaces of mHCs were more
homogeneous than that of HCs. It is notable that the
m a x i m u m a d so rp ti o n c a p a c i t y o f t h e m o d i f i e d
hydrochars was higher than that of not activated
hydrochars (Fig. 7a) and other various reported biochars
(Chen et al. 2011a; Han et al. 2013; Yakkala et al. 2013).
In this work, the maximum sorption capacities of mH-SD,
mH-WS, and mH-CS to remove Cd2+ were 40.78, 38.75,
and 30.40 mg/g, respectively, which were about 2–3 times
of that of the untreated corresponding hydrochars. Previous
studies showed that the removal of heavy metals by biochars,
including hydrochar, is directly correlated with the amount of
oxygen-containing functional groups (Uchimiya et al. 2011a).
Thus, the enhanced Cd(II) removal by the KOH-modified
hydrochar could be attributed to the increase of surface func-
tional groups.
Environ Sci Pollut Res
Effects of pH The pH value is an important parameter in the
sorption process optimization. It affects not only the surface
charge of the adsorbent but also the degree of ionization and
speciation of the metal ions in solution (Kołodyńska et al.
2012). Effects of pH on cadmium adsorption were investigat-
ed in an initial pH range between 2.0 and 10.0 (Fig. 8). The
removal efficiency of cadmium by mHCs increased dramati-
cally as pH was increased from 2.0 to 4.0, remained at 90–
98 % from pH 4.0 to 8.0, and decreased slightly at pH 10.0. At
pH lower than 4, the surface functional groups (mainly
oxygen-containing groups) linked to the H+, making these
groups inaccessible for Cd2+. With the increase of pH value,
the deprotonation of functional groups provided the chance to
coordinate with cadmium ions resulting in a higher removal
rate (Kula et al. 2008). However, the removal of cadmium
onto HCs was only 1–7 % at pH below 8.0 and increased with
the increase of pH, reaching a plateau value (74–83 %) at
pH 10.0. The wider range of pH with high removal efficiency
of cadmium in mHCs suggests that the mechanism of the
enhanced adsorption by mHCs may be related to greater avail-
able sites for surface complexation.
Environ Sci Pollut Res

45
100
a a
40
mH-SD
80 35 mH-WS
mH-CS
30 H-SD
mH-SD H-WS
Removal (%)

60
mH-WS

Q(mg/g)
25 H-CS
mH-CS
H-SD 20
40 H-WS
H-CS 15

10
20
5

0 0
0 1 2 3 4 5 6
0 50 100 150 200 250 300 350
Time (h)
Ce(mg/L)
12
b
pseudo-second-order kinetic model 50
b Freundlich model
10

40
8
t/Qt (h·g/mg)

30
Qe(mg/g)
6

mH-SD
20
4 mH-WS
mH-SD
mH-CS
mH-WS
mH-CS 10
2

0
0

0 50 100 150 200 250 300

0 1 2 3 4 5 6
Ce(mg/L)
time (h)
Fig. 6 a Kinetic adsorption curves of HCs and mHCs for Cd(II): 45
hydrochar dose, 2 g/L; temperature, 30 °C; C0 =20 mg/L; pH=6. b The c Langmuir model
40
simulated pseudo-second-order kinetics of mHCs for Cd(II)
35

30
Notably, at pH 10, the removal efficiency of mHCs for
Qe(mg/g)

25
Cd(II) was similar to that of HCs, indicating that at pH
20 mH-SD
higher than 8.0, the decreasing trend for mHCs and the mH-WS
15 mH-CS
increasing trend for HCs was caused by the formation of
insoluble hydroxyl complexes (Blázquez et al. 2005). In 10

Table 3 Parameters of pseudo-second-order kinetic model for Cd(II) 0 50 100 15 0 200 25 0 30 0

adsorption onto modified hydrochar Ce(mg/L)

Adsorbent Second-order rate constants Fig. 7 a Adsorption isotherms of HCs and mHCs for Cd(II): adsorption
time, 24 h; hydrochar dose, 2 g/L; temperature, 30 °C; pH=6. b The
K2 (g/mg·min) Qe(mg/g) R2 Freundlich model of mHCs for Cd(II). c The Langmuir Model of mHCs
for Cd(II)
mH-SD 12.8131±5.8299 0.597±0.022 0.9915
mH-WS 0.9935±0.2526 0.856±0.002 0.8951
other words, when pH higher than 8.0, the increasing
mH-CS 11.6348±4.7395 0.608±0.020 0.9920
trend for HCs might be due to the OH activation. There-
Qe (mg/g) is the amount of biochars adsorbed at equilibrium, and k2 fore, all the other experiments in this study were carried
(g/mg·min) is the rate constant of pseudo-second-order adsorption out at an optimum initial pH 6.0.
 Environ Sci Pollut Res

Table 4 Related constants and

linear regression coefficients of Adsorbent Freundlich model Langmuir model
Langmuir and Freundlich fitting
for Cd(II) adsorption onto Kf (mg/g) n R2 Qm (mg/g) b (L/mg) R2
modified hydrochar
mH-SD 9.1499±1.2505 3.5264±0.3545 0.9405 40.78±0.67 0.1014±0.0115 0.9803
mH-WS 7.7928±1.8685 3.2728±0.5523 0.8159 38.75±0.56 0.1091±0.0247 0.8810
mH-CS 10.2033±1.5195 4.8142±0.7480 0.8470 30.40±1.13 0.3719±0.0979 0.8996

Kf (mg/g/(mg/L)1/n ) and n are Freundlich coefficients related to the adsorption capacity and adsorption intensity,
respectively. Qm (mg/g) denotes the maximum adsorption capacity, and b (L/mg) is the Langmuir constant

Multi-heavy metal sorption on HCs and mHCs
Maximum adsorption capacities (Qmax) of four heavy metals
on hydrochars and modified hydrochars were compared in
Fig. 9. Their Qmax generally followed a trend of Pb(II)>
Cu(II)>Cd(II)>Zn(II), which coincided with the reverse order
of hydrated ionic radius (Table S2). Similar results were also
reported in the sorption of these metals by sediment-derived
biochars (Dong et al. 2014), broiler litter-derived biochars
(Uchimiya et al. 2010), and H2O2 modified hydrochar (Xue
et al. 2012).
The Qmax of heavy metals on KOH-treated hydrochars
were higher than untreated ones, which may be explained by
the increased binding sites associated with oxygen-containing
functional groups, such as hydroxyl and carboxyl groups. In
addition, the sorption capacities of the four different heavy
metals increased with the increasing equilibrium concentra-
tion of metal ion (Figure S3b, d, f). In contrast, the sorption
capacities of heavy metals onto mHCs increased with the in-
creasing initial concentration to specific values (lower than
10 mg/L for Cd2+ and Zn2+, 20 mg/L for Cu2+), and their
sorption capacities decreased after the specific values
(Figure S3a, c, e). Pb(II) with small hydrated ionic radius
may easily diffuse into the pores and form cation-π bond with
the hydrochar samples (Wu et al. 2012). However, cadmium
100
sorption capacities on mHCs were only 4.18∼4.73 mg/g in the
multi-metal experiment, which was much lower than that in
the single-metal system (30.40∼40.78 mg/g), indicating the
competition for surface adsorption sites from other heavy
metals in solution. Because Cd(II) sorption on hydrochar sam-
ples mainly depends on complexation with surface functional
groups, particularly carboxyl groups (Xue et al. 2012), other
heavy metals may also react with the same groups to form
complexes. The competition from Pb(II) might reduce the
sorption of other heavy metals which result in the reduction
of sorption capacities even with the increase of initial concen-
tration in modified hydrochars.
In addition, effects of pH on multi-metal system were also
investigated in an initial pH range between 3.0 and 7.0
(Figure S2). As follows from the speciation distribution of
the metal ions (Hydrochemical Equilibrium Constant Data-
base, Royal Institute of Technology, Sweden) in the pH range
1.0–8.0, almost 100 % of cadmium is present in the Cd(II)
form. For Cu(II), this range is equal to 1.0–5.0, for Zn(II) 1.0–
7.0, and for Pb(II) 1.0–5.5. At pH higher than 6.0, it occurs
precipitation for the metal ions, while at lower pHs, as pH
increases, the competition of M(II) ions and protons for
25
Cd
Cu
20 Pb
Zn

80
Q max (mg/g)

15
Removal (%)

60 mH-SD
mH-WS 10
mH-CS
40 H-SD
H-WS
H-CS 5

20

0
0 mH-SD H-SD mH-WS H-WS mH-CS H-CS
2 4 6 8 10
Fig. 9 Sorption capacities of Cd(II), Cu(II), Pb(II), and Zn(II) on mHCs
pH and HCs: adsorption time, 24 h; hydrochar dose, 2 g/L; temperature,
Fig. 8 Effects of pH on the removal efficiency of Cd(II): hydrochar dose, 30 °C; pH=6. The bar charts presented in the figure are maximum ad-
2 g/L; temperature, 30 °C; C0 =20 mg/L sorption capacities
Environ Sci Pollut Res
binding sites decreases and more binding sites are released,
which results in the increase of removal effectiveness. Similar
results were obtained in other study (Kołodyńska et al. 2012;
Chen et al. 2011b).
Conclusions
In this paper, it was found that KOH modification can activate
the sorption ability of hydrochars produced by hydrothermal
carbonization of sawdust, wheat straw, and corn stalk. FTIR,
BET, and XRD analysis showed that KOH modification in-
creased the aromatic and oxygen-containing functional
groups, such as carboxyl groups. At the same time, the mod-
ification of hydrochars greatly enhanced the ability to remove
heavy metals from water. After KOH modification, the sorp-
tion capacity of cadmium was improved 2–3 times at pH 6.0
and 303 K for 24 h. The pH value, concentration of solutions,
and contact time affect the adsorption process. The optimum
pH for adsorption was at the range of 4.0∼8.0 for modified
hydrochars. Cadmium removal on modified hydrochars was
effective in batch experiments, and adsorption data were
strongly correlated with the Langmuir adsorption isotherm
and the pseudo-second-order kinetic equation. In addition,
Cu(II), Zn(II), Cd(II), and Pb(II) removal in the mixed solu-
tion were greatly enhanced by the activation of hydrochars.
Thus, KOH-treated hydrochars can be used as an effective
sorbent to remove heavy metals from water. Because
hydrochar can be derived from various organic biomass
(e.g., agricultural and forest residues) with low cost, it is ex-
pected that the simple modification method can also be ap-
plied to other hydrothermal and thermal biochars to produce
alternative and more effective sorbent for environmental
applications.
Acknowledgments This work was supported by (1) National Natural
Science Foundation of China (31270544, 41473070), (2) 863 Major Pro-
gram (2013AA06A205), and (3) Research Fund for the Doctoral Program
of Higher Education.
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