Properties of the plant- and manure-derived biochars and
their sorption of dibutyl phthalate and phenanthrene
Mengyi Qiu1, Ke Sun1,*, Jie Jin1, Bo Gao2, Yu Yan1, Lanfang Han1, Fengchang Wu3,
Baoshan Xing4
1
State Key Laboratory of Water Environment Simulation, School of Environment,
Beijing Normal University, Beijing 100875, China
2
State Key Laboratory of Simulation and Regulation of Water Cycle in River Basin,
China Institute of Water Resources and Hydropower Research, Beijing 100038,
China
3
State Key Laboratory of Environmental Criteria and Risk Assessment, Chinese
Research Academy of Environmental Sciences, Beijing 100012, China
4
Stockbridge School of Agriculture, University of Massachusetts, Amherst,
Massachusetts 01003, United States
Table numbers: 5
Figure numbers: 4
*Corresponding author. Tel: 86-10-58807493; Fax: 86-10-58807493; E-mail:
sunke@bnu.edu.cn (K. Sun).
Table S1. Surface composition and the percentages of C group functionalities of biochars.
biochars
Total C
(%)
C-Ca(%)
C-Oa(%)
C=Oa(%)
COOHa(%)
Total C (100%)
O-containing
groups (%)
O (%)
N (%)
Si (%)
Ca (%)
surface
(O+N)/C
CO300
77.5
79.64
11.31
3.62
5.43
20.36
18.0
1.64
1.97
0.94
0.19
PO300
70.8
81.91
9.05
7.04
2.01
18.1
18.1
3.29
1.97
3.76
0.23
LE300
69.7
80.54
9.05
7.24
3.17
19.46
17.8
4.40
2.94
3.35
0.25
RI300
67.2
78.93
11.76
6.14
3.17
21.07
22.3
2.24
5.76
ndb
0.28
WH300
68.4
76.27
15.08
6.13
2.52
23.73
20.7
1.06
2.13
nd
0.24
MA300
75.6
79.51
11.89
4.92
3.69
20.5
19.8
1.73
2.89
nd
0.22
NU300
65.7
80.71
13.20
2.54
3.55
19.29
21.2
0.92
4.31
2.64
0.25
WD300
76.0
77.20
16.06
3.11
3.63
22.8
20.8
0.36
2.85
nd
0.21
CH300
33.4
78.23
9.68
10.48
1.61
21.77
30.2
2.91
13.08
4.84
0.75
SW300
61.4
89.90
8.59
1.52
0.00
10.11
19.6
2.90
1.74
5.80
0.28
CO450
79.40
69.35
21.89
4.63
4.13
30.65
18.82
1.79
0.00
0.00
0.20
PO450
72.17
80.75
16.82
0.00
2.43
19.25
19.72
8.11
0.00
0.00
0.30
LE450
73.78
72.92
26.07
0.00
1.01
27.08
20.88
5.34
0.00
0.00
0.27
RI450
63.38
89.49
2.73
5.23
2.54
10.51
21.52
3.14
11.96
0.00
0.30
WH450
68.73
82.09
15.10
2.38
0.43
17.91
17.65
2.27
11.35
0.00
0.22
MA450
73.69
78.51
5.58
9.37
6.53
21.49
15.97
2.06
8.28
0.00
0.19
NU450
81.59
75.77
7.00
8.11
9.12
24.23
18.41
0.00
0.00
0.00
0.17
WD450
74.58
89.62
0.68
7.10
2.60
10.38
18.84
0.00
6.58
0.00
0.19
CH450
40.23
91.95
6.49
0.00
1.56
8.05
35.95
3.50
20.32
0.00
0.74
SW450
48.48
75.71
21.23
0.57
2.50
24.29
25.68
4.55
12.32
8.97
0.48
a
Surface elemental composition of the biochars were measured with XPS. The C1s binding energy levels were assigned as following: 284.9 ev to C-C, 286.5 ev to
C-O, 287.9 ev to C=O, and 289.4 ev to COO. bNot detected.CO, PO, LE, RI, WH, MA, NU, WD, CH and SW refer to the biochars produced from plant residues of
cotton straw, potato straw, leaf , rice straw, wheat straw, maize straw, nut, wood dust (PLABs) and manures of chicken and swine (ANIBs). The numbers of 300 and
450 were represented to the heating treatment temperatures of the biochars (e.g., 300 and 450 oC).
Table S2. Functional group assignments corresponding to biochar samples as determined by FTIR analysis
wavenumber (cm−1)
3400
2927, 2856, 1446, and 1370
1734
a broad band centered at 1700
1613
1514
1270
1160
1160-1030
885,815 and 750
1.
2.
3.
4.
5.
6.
7.
assignment
the hydrogen bonded O-H stretching vibration
the aliphatic CH2 stretching in biopolymers
the C=O stretching vibrations of ester bonds
the carbonyl/carboxylic acid C=O stretch
the C=C and C=O stretching vibrations in the aromatic rings
the C=C ring stretching vibration of lignin
the aromatic CO- and phenolic C-OH stretch associated with ligneous guaiacyl units
the C-O stretching vibrations of ester bonds
the aliphatic C-O-C and alcohol-OH symbolize oxygenated functional groups of cellulose
the aromatic C-H out-of-plane deformations
refs
1
2
1
3
4
4
5
1
6
1, 7
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237-260 (1999).
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Geol. 37, 29-53 (1998).
Table S3. Functional groups from the 13C-NMR spectra.
biochars
alkyl
0-45 ppm
methoxyl
45-63 ppm
carbohydrate
63-93 ppm
aryl
93-148 ppm
o-aryl
148-165 ppm
carboxyl
165-187 ppm
carbonyl
187-220 ppm
aromaticitya
(%)
CO300
20.4
5.7
1.8
53.3
10.2
5.3
3.3
69.4
PO300
31.9
5.4
1.0
44.3
8.3
8.6
0.6
57.9
LE300
35.5
1.8
0.4
50.4
5.7
5.7
0.7
59.9
RI300
22.4
7.8
10.7
43.8
8.1
3.8
3.4
55.9
WH300
18.1
8.3
12.1
47.1
7.6
4.3
2.5
58.7
MA300
12.9
8.5
10.6
57.9
6.8
0.4
3.0
67.0
NU300
14.2
8.5
21.5
45.3
6.0
2.6
2.0
53.7
WD300
14.4
9.6
12.1
48.9
8.0
3.9
3.2
61.3
CH300
22.9
6.2
6.4
47.0
9.2
5.7
2.5
61.3
SW300
14.3
9.3
11.4
51.4
7.9
2.9
3.0
62.9
CO450
5.9
0.8
2.6
72.0
12.3
3.3
3.1
90.1
PO450
8.1
0.7
2.0
79.6
5.5
2.5
1.5
88.6
LE450
8.4
2.0
1.4
79.2
5.7
1.7
1.7
87.8
RI450
7.9
0.3
0.4
71.6
8.9
4.8
6.2
90.3
WH450
9.4
2.3
0.2
72.0
9.6
4.3
2.3
87.4
MA450
8.9
2.4
1.0
76.0
9.7
1.9
0.1
87.4
NU450
5.8
1.9
1.7
76.0
8.6
3.6
2.5
90.1
WD450
6.2
1.8
0.3
70.4
13.2
3.9
4.1
90.9
CH450
26.2
5.5
0.8
55.2
7.9
2.9
1.6
66.0
SW450
10.9
1.0
0.8
75.2
7.6
2.6
2.0
86.8
a
Aromaticiy =100 × aromatic C (93-165 ppm)/[aromatic C (93-165 ppm) + aliphatic C (0-93 ppm)].CO, PO, LE, RI, WH, MA, NU, WD, CH and SW represented the
biochars obtained from cotton straw, potato straw, leaf , rice straw, wheat straw, maize straw, nut, wood dust and manures of chicken and swine, respectively. The
numbers of 300 and 450 were represented to the heating treatment temperatures of the biochars (e.g., 300 and 450 oC).
Table S4. Freundlich isotherm parameters and calculated results of dibutyl phthalate
(DBP) sorption on biochars.
logKOCd (mL g-1)
KOC/KHWf
e
0.01Sw
0.1Sw 1Sw Ce=0.01Sw
CO300
1.86
0.519±0.016 20 0.989 2.72
4.05
3.57
3.09
1.74
PO300
1.85
0.657±0.026 20 0.982 2.59
4.38
4.03
3.69
3.72
2.70
LE300
1.90
0.630± 0.022 20 0.986
4.34
3.97
3.60
3.39
RI300
2.03
0.513±0.016 18 0.989 2.37
4.28
3.80
3.31
2.95
WH300
1.79
0.588±0.017 20 0.990 2.62
4.14
3.73
3.32
2.14
MA300
1.73
0.506±0.024 20 0.973 2.49
3.91
3.42
2.92
1.26
NU300
0.72
0.827±0.034 18 0.986 2.18
3.58
3.41
3.24
0.59
WD300
1.60
0.496± 0.028 20 0.962 2.45
3.75
3.25
2.74
0.87
CH300
1.66
0.531± 0.023 18 0.978 0.47
4.70
4.23
3.76
7.76
SW300
1.88
0.519± 0.026 18 0.969 1.58
4.34
3.86
3.38
3.39
CO450
1.47
0.717± 0.030 20 0.984 2.89
4.03
3.75
3.46
1.66
PO450
1.80
0.720± 0.017 20 0.994 2.75
4.44
4.16
3.88
4.27
LE450
1.46
0.778± 0.035 18 0.983 2.66
4.20
3.98
3.76
2.45
RI450
1.47
0.727± 0.036 18 0.977 2.40
4.14
3.87
3.60
2.14
WH450
1.43
0.757± 0.018 20 0.994 2.87
4.09
3.84
3.60
1.91
MA450
1.55
0.689± 0.028 18 0.987 3.00
4.04
3.73
3.42
1.70
NU450
0.59
0.845± 0.038 20 0.984 2.65
3.38
3.22
3.07
0.37
WD450
1.28
0.787± 0.041 19 0.975 3.01
3.96
3.75
3.54
1.41
CH450
0.69
0.897± 0.022 20 0.994 0.44
4.49
4.39
4.29
4.79
SW450
1.40
0.732± 0.023 20 0.990 1.46
4.32
4.06
3.79
3.24
a
n b
-1
-1
KF is the sorption capacity coefficient with unit of (µg g )/(µg L ) . Number of data points. cKd
is the sorption capacity coefficient (Kd) with unit of (mL g-1). dKoc is the concentration-dependent
organic carbon (OC)-normalized sorption distribution coefficient. eSW, solubility of DBP in water,
11.2 mg L-1. fKHW is hexadecane-water partition coefficient, logKHW = 3.81 for DBP. CO, PO, LE,
RI, WH, MA, NU, WD, CH and SW refer to the biochars produced from plant residues of cotton
straw, potato straw, leaf , rice straw, wheat straw, maize straw, nut, wood dust (PLABs) and
manures of chicken and swine (ANIBs). The numbers of 300 and 450 were represented to the
heating treatment temperatures of the biochars (e.g., 300 and 450 oC).
biochars
logKFa
n
Nb
r2
log
Kdc
Table S5. Freundlich isotherm parameters and calculated results of phenanthrene
(PHE) sorption on biochars.
logKOCd (mL g-1)
KOC/KHWf
e
0.01Sw
0.1Sw 1Sw Ce=0.01Sw
CO300
2.16 0.644±0.022 f 20 0.992 3.33
4.96
4.61 4.25
1.74
PO300
2.49
0.658±0.018 20 0.994 3.17
5.36
5.02 4.68
4.37
LE300
2.26
0.785±0.049 20 0.976 3.26
5.25
5.03 4.82
3.39
RI300
2.48
0.552±0.024 20 0.986 2.91
5.26
4.82 4.37
3.47
WH300
2.27
0.648±0.015 20 0.996 3.23
5.10
4.75 4.40
2.40
MA300
2.17
0.633±0.020 20 0.992 3.18
4.98
4.61 4.24
1.82
NU300
1.69
0.709±0.012 20 0.998 2.80
4.60
4.31 4.02
0.76
WD300
1.93
0.629±0.125 20 0.997 3.09
4.72
4.35 3.98
1.00
CH300
1.94
0.584±0.031 20 0.978 0.55
5.51
5.09 4.67
6.17
SW300
2.45
0.500±0.024 18 0.982 1.96
5.37
4.87 4.37
4.47
CO450
2.74
0.412±0.009 20 0.995 3.77
5.27
4.68 4.10
3.55
PO450
2.83
0.514±0.024 20 0.984 3.42
5.53
5.05 4.56
6.46
LE450
2.79
0.487±0.015 20 0.993 3.46
5.45
4.94 4.43
5.37
3.09
RI450
2.67
0.447±0.016 20 0.988
5.33
4.77 4.22
4.07
WH450
2.57
0.512±0.015 20 0.993 3.66
5.21
4.72 4.23
3.09
MA450
2.63
0.427±0.014 20 0.989 3.84
5.16
4.59 4.01
2.75
NU450
1.78
0.554±0.018 20 0.992 3.47
4.42
3.98 3.53
0.50
WD450
2.59
0.540±0.019 20 0.989 3.96
5.22
4.76 4.30
3.16
CH450
1.95
0.527±0.017 20 0.991 0.53
5.47
4.99 4.52
5.62
SW450
2.50
0.495±0.024 20 0.981 1.83
5.44
4.93 4.43
5.25
a
KF is the sorption capacity coefficient with unit of (µg g-1)/(µg L-1)n. bNumber of data points. cKd
is the sorption capacity coefficient (Kd) with unit of (mL g-1). dKoc is the concentration-dependent
organic carbon (OC)-normalized sorption distribution coefficient. eSW, solubility of PHE in water,
1.12 mg L-1. fKHW is hexadecane-water partition coefficient, KHW = 4.74 for PHE. CO, PO, LE, RI,
WH, MA, NU, WD, CH and SW refer to the biochars produced from plant residues of cotton
straw, potato straw, leaf , rice straw, wheat straw, maize straw, nut, wood dust (PLABs) and
manures of chicken and swine (ANIBs). The numbers of 300 and 450 were represented to the
heating treatment temperatures of the biochars (e.g., 300 and 450 oC).
biochars
logKFa
n
Nb
r2
log
Kdc
aliphatic C-H
O-H (H bonded)
Absorbance
CO300
PO300
lignin
aromatic
aromatic C=C
C-H
C=C and ring
C=O
C=C,C=O,
C-O,C-H
carbonyl/
carboxylic
acid C=O
aliphatic C-H
O-H (H bonded)
CO450
PO450
LE300
RI300
WH300
MA300
LE450
RI450
WH450
MA450
NU300
WD300
NU4500
WD450
CH300
SW300
CH450
SW450
4000
3500
3000
2000 1500 1000 500
4000 3500
Wavenumber (cm-1)
lignin
aromatic C=C
aromatic
C=C and ring
C-H
C=O
C=C,C=O,
C-O,C-H
carbonyl/
carboxylic
acid C=O
3000
2000 1500 1000
500
Figure S1. FTIR spectroscopy spectra of 20 biochars. CO, PO, LE, RI, WH, MA, NU, WD, CH and SW represented the biochars obtained from
cotton straw, potato straw, leaf , rice straw, wheat straw, maize straw, nut, wood dust and manures of chicken and swine, respectively. The
numbers of 300 and 450 were represented to the heating treatment temperatures of the biochars (e.g., 300 and 450 oC).
COOH Aromatic C Aliphatic C
C=O (93-165)
(0-93)
(165-220)
Paraffinic C
(0-45)
CO300
COOH Aromatic CAliphatic C
C=O (93-165) (0-93)
(165-220)
Paraffinic C
(0-45)
CO450
PO300
LE300
PO450
LE450
RI300
RI450
WH300
WH450
MA300
MA450
NU300
NU450
WD300
WD450
CH300
CH450
SW300
SW450
250 200
150
100
50
0
-50 250 200
ppm
Figure S2. Cross polarization magic angle spinning
13
150
100
50
0
C-NMR spectra. CO, PO, LE,
RI, WH, MA, NU, WD, CH and SW represented the biochars obtained from cotton
straw, potato straw, leaf , rice straw, wheat straw, maize straw, nut, wood dust and
manures of chicken and swine, respectively. The numbers of 300 and 450 were
represented to the heating treatment temperatures of the biochars (e.g., 300 and 450
o
C).
-50
104 DBP-Biochars (300)
104 PHE-Biochars (300)
qe (μg g-1)
103
102
102
103
104
104 DBP-Biocahrs (450)
103
CO 103
PO
LE
2
RI 10
WH
MA
100
101
102
NU
WD 104 PHE-Biochars (450)
CH
SW
103
103
102
2
10
102
103
104
100
101
102
103
Ce (μg L-1)
Figure S3. Freundlich isotherms of dibutyl phthalate (DBP) and phenanthrene (PHE),
respectively, by 20 biochars. The nonlinear coefficients (n) derived from Freundlich
modeling were significantly smaller than 1 (p < 0.01). The qe (μg g-1) and Ce (μg L-1)
are DBP solid-phase and liquid-phase concentrations, respectively. CO, PO, LE, RI,
WH, MA, NU, WD, CH and SW represented the biochars obtained from cotton straw,
potato straw, leaf , rice straw, wheat straw, maize straw, nut, wood dust and manures
of chicken and swine, respectively. The numbers of 300 and 450 were represented to
the heating treatment temperatures of the biochars (e.g., 300 and 450 oC).
0.10
0.05
0.00
-1
0.5
-1
0.15
0.6
0.4
3
-1
0.20
CO300
PO300
LE300
RI300
WH300
MA300
NU300
WD300
CH300
SW300
dV (w) (cm g nm )
-1
0.25
3
dV (w) (cm g nm )
0.30
0.3
CO450
PO450
LE450
RI450
WH450
MA450
NU450
WD450
CH450
SW450
0.2
0.1
0.0
0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6
0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6
Pore width (nm)
Pore width (nm)
Figure S4. Pore size distributions of 20 biochars measured by CO2 adsorption. CO,
PO, LE, RI, WH, MA, NU, WD, CH and SW represented the biochars obtained from
cotton straw, potato straw, leaf , rice straw, wheat straw, maize straw, nut, wood dust
and manures of chicken and swine, respectively. The numbers of 300 and 450 were
represented to the heating treatment temperatures of the biochars (e.g., 300 and 450
o
C).