Environmental Pollution 233 (2018) 64e70

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Environmental Pollution
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Correlations and adsorption mechanisms of aromatic compounds on

biochars produced from various biomass at 700
C*
Kun Yang a, b, c, *, Yuan Jiang a, b, c, Jingjing Yang a, b, c, Daohui Lin a, b, c
a
Department of Environmental Science, Zhejiang University, Hangzhou 310058, China
b
Key Laboratory of Environmental Pollution and Ecological Health of Ministry of Education, Hangzhou 310058, China
c
Zhejiang Provincial Key Laboratory of Organic Pollution Process and Control, Hangzhou 310058, China

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

Article history: Knowledge of adsorption behavior of organic contaminants on high heat temperature treated biochars is
Received 2 August 2017 essential for application of biochars as adsorbents in wastewater treatment and soil remediation. In this
Received in revised form study, isotherms of 25 aromatic compounds adsorption on biochars pyrolyzed at 700
C from biomass
3 October 2017
including wood chips, rice straw, bamboo chips, cellulose, lignin and chitin were investigated to establish
Accepted 9 October 2017
correlations between adsorption behavior and physicochemical properties of biochars. Isotherms were
well fitted by Polanyi theory-based Dubinin-Ashtakhov (DA) model with three parameters, i.e.,
adsorption capacity (Q0) and adsorption affinity (E and b). Besides the negative correlation of Q0 with
Keywords:
Biochar
molecular maximum cross-sectional areas (s) of organic compounds, positive correlations of Q0 with
Various biomass total pore volume (Vtotal) and average diameter of micropore (D) of biochars were observed, indicating
Aromatic compounds that adsorption by biochars is captured by the pore-filling mechanism with molecular sieving effect in
Adsorption biochar pores. Linear solvation energy relationships (LSERs) of adsorption affinity (E) with sol-
Correlation vatochromic parameters of organic compounds (i. e., am and p*) were established, suggesting that hy-
drophobic effect, p-p interaction and hydrogen-bonding interaction are the main forces responsible for
adsorption. The regression coefficient (p1) and intercept (C) of obtained LSERs are correlated with bio-
char H/C and Rmicro, respectively, implying that biochars with higher aromaticity and more micropores
have stronger p-p bonding potential and hydrophobic effect potential with aromatic molecule, respec-
tively. However, hydrogen-bonding potential of biochars for organic molecules is not changed signifi-
cantly with properties of biochars. A negative correlation of b with biochar H/C is also obtained. These
correlations could be used to predict the adsorption behavior of organic compounds on high heat
temperature treated biochars from various biomass for the application of biochars as sorbents and for the
estimating of environmental risks of organic compounds in the present of biochars.
© 2017 Elsevier Ltd. All rights reserved.

1. Introduction capability to organic contaminants because of their large surface

Biochar is a type of charcoal produced by heating crop wastes,
wood or other biomass in oxygen-limited condition, which has
been extensively studied because of the potential applications in
soil improvement, climate change mitigation, waste management
and energy production (Lehmann, 2007; Chai et al., 2012; Yao et al.,
2013). Studies have shown that the high heat temperature treated
biochars produced at 600e700
C have superior adsorption
*
This paper has been recommended for acceptance by Baoshan Xing.
* Corresponding author. Department of Environmental Science, Zhejiang Uni-
versity, Hangzhou 310058, China.
E-mail address: kyang@zju.edu.cn (K. Yang).
area, fine microporosity and highly aromatic structure (Chen et al.,
2008; Lattao et al., 2014; Srinivasan and Sarmah, 2015). Therefore,
they were widely interested for their applications as potential
sorbents in soil remediation and wastewater treatment
(Pingnatello et al., 2006; Chen et al., 2008; Keiluweit et al., 2010;
Lattao et al., 2014; Jin et al., 2016). They were also interested for
their alternating on the fate, transport and bioavailability of organic
contaminants in the environment by adsorption once they are
released into the environment in their production, transportation,
storage, disposal and especially use in soil improvement (Kwon and
Pignatello, 2005; Beesley et al., 2010).
Correlations capable of predicting adsorption behaviors of
organic compounds on high heat temperature treated biochars are

https://doi.org/10.1016/j.envpol.2017.10.035
0269-7491/© 2017 Elsevier Ltd. All rights reserved.
 K. Yang et al. / Environmental Pollution 233 (2018) 64e70
of great importance for their selected applications as potential
sorbents and for the fate, transport and bioavailability of organic
contaminants in the environment (Crittenden et al., 1999; Yang
et al., 2016). In the previous study (Yang et al., 2016), we
observed that isotherms of 25 aromatic compounds, including
polycyclic aromatic hydrocarbons (PAHs), nitrobezenes, phenols,
and anilines, on a bamboo biochar (Ba700) produced from bamboo
chips at 700
C were fitted well with the Polanyi-theory based
Dubinin-Ashtakhov (DA) model. A negative relationship of DA
model fitted Q0 parameter (adsorption capacity) of organic com-
pounds with their molecular cross-sectional areas (s) were estab-
lished, indicating that adsorption is captured by the pore filling
mechanism. A liner solvation energy relationship (LSER) of DA
model fitted E parameter (adsorption affinity) of organic com-
pounds with their solvatochromic parameters (i.e., polarity/polar-
izability parameter p* and hydrogen-bonding donor parameter am
in Table S1) were also established, indicating that adsorption on the
biochar is derived from the hydrophobic effects of organic com-
pounds and the forming of p-p EDA and hydrogen bonding in-
teractions of organic molecules with biochar surface sites. These
correlations would be useful for quantitative estimating the
adsorption of organic compounds on Ba700 from their commonly
physiochemical properties including p*, am and s. However,
whether these correlations established for Ba700 could be appli-
cable for biochar produced from other biomass is unclear yet and
need to be examined.
Besides the physiochemical properties of organic compounds,
the structural and surface properties such as surface area, pore
volume, pore size, surface oxygen-containing groups and aroma-
ticity of biochars may also play crucial roles in the adsorption. For
example, adsorption of simazine on biochar prepared by corn straw
increased with the increasing of surface area (Zhang et al., 2011).
Adsorption of biochar to organic contaminants was observed
enhanced with the increasing of aromaticity of biochar, as
increased aromatic rings can promote the p-p electron accepting
ability of biochar to form stronger p-p bonds with aromatic mol-
ecules (Zhu et al., 2005; Chen and Chen, 2009; Lattao et al., 2014;
Xie et al., 2014). Oxygen-containing groups on biochar surface
can suppress adsorption of organic compounds, especially hydro-
phobic organic compounds, because oxygen-containing groups are
hydrophilic and can form strong hydrogen-bonds with water
molecules (Zhu et al., 2005). Biochars, made from different biomass
such as plant tissue, crop residue, animal remains and biopolymers,
are commonly with various structural and surface properties and
thus having various adsorption for organic compounds (Fernandes
et al., 2003; James et al., 2005; Nguyen et al., 2007; Kearns et al.,
2014; Mandal et al., 2017). Therefore, it is critical to examine the
adsorption on high heat temperature treated biochars produced
from various biomass and to establish the correlations of adsorp-
tion capacity and affinity with structural and surface properties of
biochars, for predicting adsorption behaviors of organic com-
pounds on biochars and for exploring the underlying mechanisms.
In this study, adsorption of 25 aromatic compounds, the same
chemicals (i.e., PAHs, phenols, anilines and nitrobenzenes) inves-
tigated for Ba700 in our previous study (Yang et al., 2016), on 5
biochars produced from different biomass including wood chips,
rice straw, cellulose, lignin and chitin at 700
C, were investigated
by isotherm fitted using DA model to examine whether the corre-
lations established for Ba700 (Yang et al., 2016) are applicable for
biochar produced from other biomass. Moreover, based on the
observed negative relationships of DA model fitted Q0 with s and
the LSERs of DA model fitted E with solvatochromic parameters (i.e.,
p* and am) of aromatic compounds on these 5 biochars in this study
65
and the relationships on Ba700 reported in our previous study
(Yang et al., 2016), the correlations capable of predicting adsorption
were established. 25 organic compounds (i.e., PAHs, phenols, ani-
lines and nitrobenzenes) were employed in this study, because they
have significant difference in functional groups, solubility, melting
points, solvatochromic parameters (i.e., VI/100, p*, am and bm) and
molecule size (Table S1). For example, the solubility is in a range
from 0.135 mg/L to 80190 mg/L, varied in 7 orders of magnitude. In
previous studies (Yang et al., 2008, 2016; Wu et al., 2016), we have
gotten expected correlations with significance of statistical analysis
using these 25 chemicals. These compounds are widely found in
the effluents from dyestuffs, pesticides, petrochemicals, pharma-
ceuticals and other industries (Castilla, 2004; Laszlo et al., 2007;
Zhang et al., 2007), which brought serious environmental pollu-
tion and risks for human's health and safety and have been listed as
priority pollutants by US Environmental Protection Agencies
(Castilla, 2004; Laszlo et al., 2007; Zhang et al., 2007). The biomass
investigated in this study such as wood chips, bamboo chips and
rice straw are ubiquitous in the environment and frequently-used
plant biomass and crop residue. Lignin and cellulose were the vi-
tal components of plants. Chitin, widely exists in crab and shrimp
shells, is the second most abundant polysaccharide after cellulose
(Wang and Xing, 2007).
2. Materials and methods
2.1. Biochars and chemicals
Wood chips and rice straw were collected from Zhejiang, China.
Cellulose, lignin (dealkaline) and chitin were purchased from J&K
Scientific, Tokyo Chemical Industry and Aladdin Reagent Corpora-
tion, respectively. Biochars were prepared by heated biomass under
oxygen-limited conditions in a muffle furnace at 700
C for 6 h, as
was described in detail in our previous study (Yang et al., 2016). The
biochars prepared from wood chips, rice straw, cellulose, lignin and
chitin were labeled as W700, S700, Ce700, Li700 and Ch700,
respectively.
Twenty five aromatic chemicals, including 3 PAHs, 8 phenols, 7
anilines, 7 nitrobenzenes, the same chemicals used in our previous
study (Yang et al., 2016) were employed in this study. Selected
properties of these chemicals, including purity, water solubility
(Cs), density (r), melting points (MP), cross-sectional areas (s) and
Kamlet-Taft solvatochromic parameters, including polarity/polar-
izability parameter (p*), intrinsic molar volume (V1), hydrogen-
bonding acceptor parameter (bm) and hydrogen-bonding donor
parameter (am), are listed in Table S1 (Yang et al., 2008, 2016).
2.2. Characterization of biochars
N2 sorption-desorption isotherms of biochars at 77 K were
determined by a physisorption analyzer (Quantachrome, AUTO-
SORB AS-1) to calculate the surface area, pore volume and pore size
of biochars. Specific surface area (SA) was calculated by multipoint
Brunaer-Emmett-Teller (BET) method in the relative pressure (p/p0)
region of 0.05e0.3. Micropore surface area (Amicro) was calculated
by t-plot method. Total pore volume (Vtotal) was estimated at p/p0 of
about 0.99. The Density Functional Theory (DFT) method (El-
Merraoui et al., 2000) was employed to calculate micropore vol-
ume (Vmicro). Average diameter of micropore (D, nm) was calculated
by ratio of a quadruple micropore volume to surface area (Gregg
and Sing, 1982). C, H and N contents of biochars were detected
using a elemental analyzer (Thermo Finningan, Flash EA 1112 CHN).
Ash content was measured by heating biochars at 800
C for 1 h,
66 K. Yang et al. / Environmental Pollution 233 (2018) 64e70

Table 1
Elemental composition, surface area, and porosity of biochars.

biochars Yield (%) C (%) N (%) H (%) O (%) Ash (%)a H/C O/C (N þ O)/C SA Amicro Vtotal Vmicro Rmicro Db
(m2/g) (m2/g) (cm3/g) (cm3/g) (%) (Å)

W-700 19 84.7 0.32 1.46 12.1 1.45 0.21 0.11 0.11 557 453 0.33 0.24 81 17.24
S-700 27 53.4 0.95 0.89 6.76 38.0 0.20 0.09 0.11 195 158 0.15 0.09 81 18.46
Ce-700 15 92.5 0.00 1.28 5.66 0.61 0.17 0.05 0.05 430 335 0.32 0.17 78 15.81
Li-700 13 63.9 0.00 1.01 9.35 25.8 0.19 0.11 0.11 306 239 0.20 0.14 78 18.30
Ch-700 13 69.7 7.71 2.04 14.6 5.98 0.35 0.16 0.25 334 186 0.27 0.14 56 16.77
Ba-700c / 87.2 0.50 1.40 7.40 3.50 0.19 0.06 0.07 511 445 0.26 0.21 87 16.44

H/C: atomic ratio of hydrogen to carbon. O/C: atomic ratio of oxygen to carbon. (NþO)/C: atomic ratio of the sum of nitrogen and oxygen to carbon. SA: surface area (m2/g);
Amicro: micropore surface area (m2/g); Vtotal: total pore volume (cm3/g); Vmicro: micropore volume (cm3/g); Rmicro: the ratio of micropore surface area to specific surface area;
D: the average diameter of micropore (nm).
a
Ash measured by heating samples at 800
C for 1 h.
b
D: were calculated by ratio of a quadruple Vmicro to SA.
c
Ba-700: data obtained from Yang et al. (2016).

and O content was calculated by mass difference. The measured (Crittenden et al., 1999).
properties of the prepared 5 biochars in this study and Ba700 re- vffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
uP  
ported in our previous study (Yang et al., 2016) were listed in u Wcal Wexp 2
Table 1. Cross-sectional transmission electron microscope (TEM, t Wexp
SDEV ¼  100 (2)
JEM1230) was employed to observe the pore morphology directly. v
Before TEM observation, biochars were embedded in the spurr
resin (mixture with 10 g ERL 4221, 8 g DER 736, 25 g NSA and 0.3 g where v is the degree of freedom (v ¼ N- k), N is the number of
DMAE, purchased from SPI-Chem Supplies), heated at 70
C for experimental values, k is the number of predictors (for example,
10 h, and then cut into sections about 90 nm by ultramicrotome k ¼ 3 for DA model, k ¼ 2 for linear regression).
(Leica, EMUC7).

3. Results and discussion

2.3. Adsorption experiments, isotherm fitting and regression
analysis
All the isotherms were conducted by the batch technique at
25 ± 1
C in 8, 20, 40, 100 or 250 mL glass vials equipped with screw
caps, as described in our previous study (Yang et al., 2016). A brief
description of the batch experiments was given in the Supporting
Information. Isotherms of organic compounds on biochars were
fitted by the DA model (equation (1)).
Log qe ¼ Log Q0 e (ε/E)b
where qe [mg/g] is the adsorbed amount of compounds in equi-
librium; Q0 [mg/g] is the adsorption capacity of compounds; ε [KJ/
mol], ε ¼ RTln(Cs/Ce) is the effective adsorption potential; Ce [mg/L]
is the equilibrium concentration of compounds in aqueous phase;
Cs [mg/L] is the water solubility of compounds; R [8.314  103 KJ/
(mol$K)] is the universal gas constant; T [K] is the absolute tem-
perature; E [KJ/mol] and b are parameters that can be used to
identify the adsorption affinity of compounds (Yang and Xing,
2010). Freundlich model and Langmuir model, which have been
widely used in fitting isotherms of organic compounds on carbo-
naceous adsorbents including biochars, are the special forms of DA
model (Yang and Xing, 2010).
Isotherm fitting and regression analysis were carried out by a
commercial software program (SPSS 16.0). Linear regression or
multiple linear regression was conducted to establish the correla-
tions of DA model fitted adsorption capacity (Q0) and affinity (E and
b) with physiochemical properties of organic compounds and bio-
chars. The stepwise method was employed for variable selection in
multiple linear regression to establish the LSERs between E values
of organic compounds and solvatochromic parameters (Yang et al.,
2016). Percent sample deviation (SDEV, %) in equation (2), based on
the relative error between experimental value (Wexp) and the
calculated value (Wcal), significance of F test and correlation co-
efficients (r2) were used to evaluate the goodness of the fitting
results and the established correlations by regression analysis
Isotherms of 25 aromatic compounds on W700, S700, Ce700,
Li700 and Ch700 are significantly nonlinear (Fig. S1). The amounts
of chemicals adsorbed on biochars increased sharply at low con-
centrations, and then reached a plateau at the equilibrium con-
centrations of about 0.01e0.02 Ce/Cs (Fig. S1). These isotherms were
well fitted with DA model (Fig. S1, Table S2), as indicated by the low
SDEV values (<6%), the significance of F test (P < 0.001), and the
good correlation coefficient values (r2 close to 1) (Table S2). Similar
isotherms of 25 aromatic compounds on Ba700 were observed in
(1) our previous study (Yang et al., 2016). These isotherm fitting results
suggested that aqueous adsorption of organic compounds on high
temperature treated biochars was captured by Polanyi theory, as
was also reported by other researchers (Nguyen et al., 2007; Zheng
et al., 2013).
The negative correlation (equation (3), Fig. S2) between DA
model fitted adsorption capacity (Q0, cm3/g) of 25 aromatic com-
pounds (Table S2) and their molecular cross-sectional areas (s,
nm2) (Table S1), observed on Ba700 (Yang et al., 2016), were also
observed on the investigated biochars (i.e., W700, S700, Ce700,
Li700 and Ch700) in this study (Table 2).
Q0 ¼ a1  s þ Q* (3)
where a1 is the slope and Q* (cm3/g) is the intercept. These negative
correlations could be attributed to the size exclusion effect of pore-
filling mechanism, i.e., the organic molecules were largely
restricted to access into the biochar pores those diameters are
smaller than the molecule diameters (Dobruskin, 1998; Zhu et al.,
2005; Nguyen et al., 2007; Yang et al., 2016). This pore-filling
mechanism was also supported by the abundant slit-shaped
pores in TEM images of the investigated biochars (Fig. S3) and the
changes of these slit-shaped pores after adsorption (Fig. S4). For
example, the number of slit-shaped pores, in total of 20 TEM im-
ages with area of 8780 mm2, of W700 fell to 358 from 637 when
W700 adsorbed with 2-CA (Fig. 1). Moreover, the slit-shaped pores
of W700 was narrowed down when W700 adsorbed with 2-CA
 K. Yang et al. / Environmental Pollution 233 (2018) 64e70 67

Table 2
Linear regression results of Q0 with molecular cross-sectional areas.a

biochars Q*(cm3/g) a1 N r2 F p SDb SEDV, %

W 700 0.302(±0.023) 0.225(±0.034) 25 0.653 43 <0.001 0.017 15.0

S 700 0.181(±0.009) 0.172(±0.013) 25 0.880 169 <0.001 0.008 22.1
Ce700 0.313(±0.019) 0.321(±0.028) 25 0.851 131 <0.001 0.016 19.3
Li700 0.215(±0.013) 0.217(±0.019) 25 0.845 126 <0.001 0.011 17.9
Ch700 0.271(±0.025) 0.247(±0.036) 25 0.667 46 <0.001 0.021 24.9
Ba700c 0.303(±0.015) 0.286(±0.022) 25 0.885 156 <0.001 0.013 15.3
a
All estimated parameter values and their standard deviations were obtained by a commercial software program (SPSS 16.0).
b
SD: standard deviation.
c
Data obtained from Yang et al. (2016).

Q* ¼ 0.735 (±0.131)  Vtotal þ 0.077 (±0.035)

N ¼ 6, R2 ¼ 0.887, F ¼ 31.3, P < 0.005, SDEV ¼ 7.0% (4)

a1 ¼ 0.476 (±0.084)  D e 1.061 (±0.144)

N ¼ 6, R2 ¼ 0.889, F ¼ 32.0, P < 0.005, SDEV ¼ 8.7% (5)

The LSERs (equation (6)) between adsorption affinity (E) of ar-

Fig. 1. Pore sizes in 20 TEM images (total area of 8780 mm2) of W700 and W700
adsorbed with 2-chloroaniline (2-CA), sequenced by the order from big pore size to
small one.
omatic compounds and their solvatochromic parameters (i.e., po-
larity/polarizability parameter p* and hydrogen-bonding donor
parameter am in Table S1), observed for Ba700 (Yang et al., 2016),
were also observed for biochars investigated in this study, indi-
cating that adsorption of aromatic compounds on high temperature
treated biochars is mainly induced by hydrophobic effect, p-p
interaction and hydrogen bonding interaction (Yang and Xing,
2010; Yang et al., 2016). The multiple linear regression results of E
with chemical solvatochromic parameters are listed in Table 3. The
E values of aromatic compounds on biochars, calculated using
equation (6) from chemical solvatochromic parameters (i.e., p* and
am) listed in Table S1 and the regression coefficients (i.e., p1, b1 and
C) listed in Table 3, are well agreed with the experimental E values
(Fig. S6), as indicated by the low SDEV values (<6%), the significance
of F test (P < 0.001), and the good correlation coefficient values (r2
close to 1) (Table 3).

E ¼ p1  p* þ b1  am þ C (6)

(Fig. 1), e.g., the maximum pore diameter of W700 narrowed down
from 160 nm to 120 nm (Fig. 1). Intercepts of these equations (Q*,
cm3/g) are the adsorption capacity of aromatic compounds with
molecular cross-sectional areas closing to 0. A significant linear
relationship between Q* (Table 2) and total pore volume (Vtotal,
cm3/g) of biochars (Table 1) was observed (equation (4), Fig. 2A).
Moreover, positively linear relationship between the slope a1 in
Table 2 and the average diameter (D) of biochar micropores
(0  D  2, nm) (Table 1) was also observed (equation (5), Fig. 2B).
This positive relationship suggests that the negative influence of
molecular size on adsorption (i.e., the molecular sieving effect) is
much significant for biochars with smaller micropores. For
example, when diameter (D) of biochar micropores increased to
2 nm, a1 will approach to 0 according to equation (5), implying that
the molecular sieving effect on adsorption could be largely
neglected in biochar pores with diameter larger than 2 nm. With
equations (3)e(5), one can directly calculate the adsorption ca-
pacity (Q0) of aromatic compounds on high temperature treated
biochars from the cross-sectional areas (s) of aromatic molecules,
the average diameter of biochar micropores (D) and the total pore
volume (Vtotal) of biochars. The calculated Q0 values of the inves-
tigated 25 aromatic compounds on 6 biochars, using equations
(3)e(5), are well agreed with the experimental Q0 values (Fig. S5),
suggesting the usefulness of equations (3)e(5) for Q0 predicting.
The obtained intercept C, regression coefficients p1 and b1 of
equation (6) can be used to identify the potential ability of a given
adsorbent to form hydrophobic effect, p-p interaction and
hydrogen-bonding interaction with organic molecule, respectively.
With equation (6), one can calculate the relative contribution of
hydrophobic effect, p-p interaction and hydrogen-bonding inter-
action to the overall adsorption force of aromatic compounds on
biochars (Yang and Xing, 2010; Yang et al., 2016), respectively. For
example, the percent contribution of hydrophobic effects,
hydrogen-bonding interaction and p-p interaction to the adsorp-
tion affinity E for 3-nitrophenol on W700 is 58%, 27.1% and 14.9%,
respectively. The percent contribution of three interactions to
adsorption calculated for individual compounds on 6 biochars are
listed in Table S3. The LSERs (equation (6)) of E with chemical
solvatochromic parameters for adsorption of aromatic compounds
on 10 carbon nanotubes (CNTs), including one single-walled CNTs
(SWCNTs) and 9 multi-walled CNTs (MWCNTs), were also observed
in our previous study (Wu et al., 2016). Bigger p1 values were re-
ported for adsorption of aromatic compounds on CNTs (Wu et al.,
2016) than that on biochars (Table 3). A negative correlation of
the regression coefficient p1 of aromatic compounds on 6 biochars
(Table 3) and 10 CNTs (Wu et al., 2016) with the H/C of biochars
(Table 1) and CNTs (Wu et al., 2016) was observed (equation (7),
Fig. 3A), suggesting that increasing aromaticity of biochars will
68 K. Yang et al. / Environmental Pollution 233 (2018) 64e70

Fig. 2. Correlation of Q* with total pore volume (Vtotal, cm3/g) of biochars (A) and correlation of a1 with the average micropore diameter (D, nm) of biochars (B). Data of Ba700
obtained from Yang et al. (2016).

Table 3
Multiple linear regression results of E with chemical solvatochromic parameters.a

Biochars p1 b1 C N r2 F p SDb SEDV, %

W 700 6.49(±1.93) 15.32(±1.50) 26.90(±2.08) 25 0.826 52 <0.001 2.19 5.9

S 700 5.09(±1.50) 13.40(±1.16) 25.27(±1.62) 25 0.858 67 <0.001 1.70 5.2
Ce700 7.06(±1.67) 13.35(±1.70) 26.92(±2.36) 25 0.828 53 <0.001 1.91 5.7
Li700 6.12(±1.60) 11.54(±1.24) 28.05(±1.73) 25 0.797 43 <0.001 1.82 5.0
Ch700 2.98(±1.01) 13.30(±0.79) 23.93(±1.10) 25 0.930 147 <0.001 1.16 3.0
Ba700c 6.11(±1.86) 14.98(±1.45) 25.47(±2.01) 25 0.830 54 <0.001 2.13 6.0
a
All estimated parameter values and their standard deviations were obtained by a commercial software program (SPSS 16.0).
b
SD: standard deviation.
c
Data obtained from Yang et al. (2016).

Fig. 3. Correlation of coefficient p1 with H/C of biochars and CNTs (A) and correlation of intercept C with Rmicro of biochars and CNTs (B). Data of Ba700 and CNTs obtained from Yang
et al. (2016) and Wu et al. (2016), respectively.

strengthen the p-p bonds of aromatic molecules on biochar surface
(Zhu et al., 2005; Chen and Chen, 2009; Lattao et al., 2014; Xie et al.,
2014). The bigger p1 values, reported for CNTs (Wu et al., 2016),
could be attributed to the higher aromaticity of CNTs and the
stronger p-p bonding potential of CNTs with aromatic molecule
than biochars. The regression coefficient b1 (Table 3) of aromatic
compounds on 6 biochars is almost constant, with a mean value of
13.65 ± 1.36, which is no significant difference with that of CNTs a
mean value of 11.11 ± 0.50, reported in our previous study (Wu
et al., 2016). The intercept C of 6 biochars is also almost constant,
 K. Yang et al. / Environmental Pollution 233 (2018) 64e70
with a mean value of 26.09 ± 1.48, which is much bigger than that
of SWCNTs (11.25 ± 2.27) and MWCNTs in a range from 5.01 ± 2.00
to 6.58 ± 1.58 reported in our previous study (Wu et al., 2016). A
positive correlation of C on 6 biochars (Table 3) and 10 CNTs (Wu
et al., 2016) with the ratio of micropore surface area to specific
surface area (Rmicro, %) were observed (equation (8), Fig. 3B). This
positive correlation indicates that hydrophobic effect on adsorption
of aromatic molecules is much significant in micropores than that
on surface of mesopores or macropores, as is captured by the
Polanyi theory, i.e., adsorption potential is highest in the narrowest
pores because of proximity to more adsorbent atoms (Dubinin and
Astakhov, 1971; Yang and Xing, 2010; Kasozi et al., 2011; Sun et al.,
2011; Yang et al., 2016). With the constant b1, equations (6)e(8),
one can directly calculate the adsorption affinity (E) of aromatic
compounds on high temperature treated biochars from the sol-
vatochromic parameters (i.e., p* and am) of aromatic molecules, the
H/C and Rmicro ratios of biochars (Fig. S7).
p1 ¼ 18.18 (±2.26)  (H/C) þ 9.55 (±0.32)
N ¼ 16, R2 ¼ 0.82, F ¼ 64, P < 0.001, SDEV ¼ 11.2% (7)
C ¼ 30.11 (±2.05)  Rmicro þ 1.90 (±1.02)
N ¼ 16, R2 ¼ 0.94, F ¼ 216, P < 0.001, SDEV ¼ 24.3% (8)
DA model fitted b is another paramater to describe adsorption
affinity (Yang and Xing, 2010). For a given biochar, b values of 25
aromatic compounds on the biochar were relatively constant
(Fig. S8). The average b values of W700, S700, Ce700, Li700 and
Ch700 were 1.77 ± 0.27, 1.95 ± 0.19, 2.13 ± 0.26, 1.93 ± 0.21 and
1.40 ± 0.18, respectively. The reported average b value of 25 aro-
matic compounds on Ba700 was 2.03 ± 0.21 (Yang et al., 2016). A
negative correlation between the average b values and H/C ratios of
biochars was observed (equation (9), Fig. 4), indicating that
adsorption affinity b is also depending on biochar aromaticity.
b ¼ 3.76 (±0.58)  (H/C) þ 2.69 (±0.13)
Fig. 4. Correlation of average b values of 6 biochars with biochar H/C. Data of Ba700
obtained from Yang et al. (2016).
69
N ¼ 6, R2 ¼ 0.91, F ¼ 42, P < 0.005, SDEV ¼ 5.0% (9)
4. Conclusion
Adsorption of aromatic compounds on biochars pyrolyzed at a
high heat temperature of 700
C from different biomass, including
wood chips, rice straw, bamboo chips, cellulose, lignin and chitin
were investigated in this study. Isotherms were well fitted by
Polanyi theory-based DA model with three parameters, i.e.,
adsorption capacity (Q0) and adsorption affinity (E and b). Besides
the negative correlation of Q0 with molecular maximum cross-
sectional areas (s) of organic compounds, positive correlations of
Q0 with total pore volume (Vtotal) and average diameter of micro-
pore (D) of biochars were established in this study, indicating that
adsorption on high heat temperature treated biochars is subjected
to molecular sieving effect. Moreover, adsorption on high heat
temperature treated biochars is mainly induced by three adsorp-
tion attractive forces including hydrophobic effect, p-p interaction
and hydrogen bonding interaction, as was indicated by the
observed LSERs of E with solvatochromic parameters of organic
compounds (i. e., am and p*). The intercept C, regression coefficients
p1 and b1 of obtained LSERs can be used to identify adsorption
potential by hydrophobic effect, p-p interaction and hydrogen-
bonding interaction of biochars for organic molecules, respec-
tively. The positive correlation of intercept C with biochar Rmicro
indicates that hydrophobic effect on adsorption of aromatic mole-
cules is much significant in biochar micropores than that on surface
of mesopores or macropores, while the negative correlation of p1
with biochar H/C indicates that biochars with higher aromaticity
have stronger p-p bonding potential with aromatic molecules.
However, the hydrogen-bonding potential of biochars for organic
molecules is not changed significantly with the properties of bio-
chars. Adsorption affinity parameter b is also depending on biochar
aromaticity and having a negative correlation with biochar H/C, but
independent of properties of organic compounds. The obtained
correlations could be used to quantitatively estimate the adsorption
behavior of aromatic compounds on high temperature treated
biochars from the physiochemical properties of both aromatic
compounds and biochars. The use of these predictive correlations
will greatly reduce the cost, time, and labor that are needed to
investigate the unknown adsorption behaviors of new organic
compounds and different types of biochars. They are also helpful to
make optimum selection in the applications of biochars as sorbents
in removal of organic contaminants from the environment.
Acknowledgements
This work was supported partly by the National Key Research
and Development Program of China (2017YFA0207001), the NSF of
China (21621005, 21777138 and 21322702), and the National Key
Basic Research Program of China (2014CB114403).
Appendix A. Supplementary data
Supplementary data related to this article can be found at
https://doi.org/10.1016/j.envpol.2017.10.035.
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