Transitional Adsorption and Partition of Nonpolar and Polar Aromatic ...
1
Environmental Science and Technology
2
Supporting Information
3 4
Transitional Adsorption and Partition of Nonpolar and Polar Aromatic
5
Contaminants by Bio-chars of Pine Needles with Different Pyrolytic
6
Temperatures
7 8
Baoliang Chen*, Dandan Zhou, and Lizhong Zhu
9
Department of Environmental Science, Zhejiang University, Hangzhou, Zhejiang 310028, China
10 11 12
* Corresponding Author E-mail: [email protected] Manuscript No. : es-2008-002684
13 14
Supporting Information consists of ten pages, including this one.
15
There are Batch Sorption Experiment, two Tables and six Figures.
16 17 18
May 2, 2008
19 20 21 22 23 24 25 S1
26
Batch Sorption Experiment. Naphthalene (NAPH), nitrobenzene (NB), and m-dinitro-
27
benzene (m-DNB) were chosen as model sorbates due to their different molecular polarities and
28
dimensions. Naphthalene were purchased from Aldrich Chemical Co. with a purity >98%, and
29
nitrobenzene and m-dinitrobenzene from Shanghai Chemical Co with a purity > 99%. These
30
compounds were used as received. The physico-chemical properties of selected sorbates are
31
shown in Table S-1 and the associated molecular dimensions determined from their van der Waals
32
radii are given in Figure S-1. All sorption isotherms were obtained in 0.01 mol/L CaCl2 to simulate
33
environmental water, with 200 mg/L NaN3 added to inhibit the degradation by incidental bacteria.
34
Relative initial-concentrations (Ci/CS) ranged from 0.03 to 0.94 for NAPH, 0.01~0.83 for NB, and
35
0.02~0.87 for m-DNB to saturate potential adsorption. For NB and m-DNB, a given amount of
36
sorbent (100, 50, 50, 20, 10, 10, 10, 7, and 2.5 mg for P100-P700 and AC, respectively) were
37
mixed with 8 mL solution. For NAPH, the added amount of P100-P600 to 8-mL vials were 15, 9,
38
7.5, 7.5, 2.5, 3, and 4 mg, respectively; and 4 mg of P700 and 1 mg of AC were mixed with 40 mL
39
solution. Isotherms consisted of ten concentration points; each point, including the blank and
40
calibration control, was run in duplicate. The vials were placed on a rotating shaker and agitated in
41
the dark at 20 rpm for 3 d. Preliminary tests indicated that apparent equilibrium was achieved in
42
less than 48 h (see Figure S-2 for more detail), which is consistent with previously kinetic studies
43
about wood and crop chars (12 and therein). The solution was separated from solids by
44
centrifugation at 4000 rpm for 15 min. The equilibrium concentrations were measured by using a
45
UV-2550 spectrophotometer at wavelength of 275 nm (NAPH), 268 nm (NB) and 260 nm
46
(m-DNB) with the detection limit of 0.1 mg/L (S/N=3). Because of a minimal sorption by the vials
47
and no biodegradation observed, the amount sorbed by sorbent was calculated by the sorbate mass
48
difference in solution.
49 50
S2
Table S-1. Selected Properties of Naphthalene (NAPH), Nitrobenzene (NB), and m-Dinitrobenzene (m-DNB). Organic compounds NAPH
Formula
Structural
C10H8
MW, g/mol
S, µg/mL
Kow
Density, g/cm3
MA, nm2
MV, nm3
128.2
32.05
1950
0.997
0.732
0.252
123.1
1936
71
1.196
0.620
0.213
168.1
574.9
31
1.600
0.839
0.289
NO 2
NB
C6H5NO2
O2N
m-DNB
C6H4N2O4
NO2
MW: molecular weight, g/mol; S: aqueous solubility at room temperature, µg/mL; Kow octanol-water partition coefficient; MA: molecular area, nm2; MV: molecular volume, nm3.
S3
Table S-2.
Regression Parameters of Isotherms of Organic Pollutants to Bio-chars and an
Activated Carbon from Aqueous Solution. Solutes
Samples
NAPH
NB
m-DNB
Freundlich 1)
Linear over high relative conc. 2)
N
logKf
R2
P100
1.107 ± 0.021
2.342 ± 0.017
0.995
Q = 295.4 Ce
0.993
P200
0.874 ± 0.010
3.036 ± 0.007
0.998
Q = 782.8 Ce + 329.4
0.997
P250
0.777 ± 0.007
3.212 ± 0.005
0.999
Q = 783.8 Ce + 1724
0.991
P300
0.589 ± 0.007
3.494 ± 0.005
0.998
Q = 785.0 Ce + 4006
0.994
P400
0.332 ± 0.012
4.222 ± 0.010
0.980
Q = 748.3 Ce + 25690
0.914
P500
0.207 ± 0.010
4.286 ± 0.009
0.972
Q = 299.5 Ce +27400
0.914
P600
0.17 4 ± 0.010
4.097 ± 0.009
0.957
Q = 274.2 Ce + 15140
0.901
P700
0.124 ± 0.080
5.085 ± 0.007
0.964
Q = 1086 Ce + 136800
0.875
AC
0.147 ± 0.011
5.340 ± 0.018
0.838
Q = 314300
Linear equation
R2
-
P100
0.971 ± 0.019
1.446 ± 0.045
0.994
Q = 24.58 Ce
0.991
P200
0.800 ± 0.009
2.486 ± 0.021
0.998
Q = 72.60 Ce + 5908
0.993
P250
0.701 ± 0.008
2.890 ± 0.017
0.998
Q = 94.34 Ce + 10080
0.994
P300
0.513 ± 0.007
3.701 ± 0.015
0.997
Q = 129.6 Ce + 51140
0.966
P400
0.271 ± 0.007
4.367 ± 0.015
0.990
Q = 71.04 Ce + 79710
0.995
P500
0.179 ± 0.007
4.592 ± 0.016
0.974
Q = 29.58 Ce + 96630
0.948
P600
0.114 ± 0.005
4.720 ± 0.013
0.968
Q = 19.93 Ce + 91690
0.920
P700
0.111 ± 0.008
5.091 ± 0.020
0.938
Q = 85.97 Ce + 181200
0.976
AC
0.208 ± 0.009
5.058 ± 0.022
0.968
Q = 44.41 Ce + 386300
0.982
P100
0.983 ± 0.016
1.538 ± 0.029
0.996
Q = 30.99 Ce
0.994
P200
0.745 ± 0.011
2.675 ± 0.021
0.997
Q = 88.61 Ce + 5655
0.991
P250
0.684 ± 0.009
2.891 ± 0.015
0.997
Q = 99.26 Ce + 7534
0.993
P300
0.488 ± 0.007
3.486 ± 0.012
0.997
Q = 109.7 Ce + 17090
0.985
P400
0.233 ± 0.006
4.346 ± 0.011
0.991
Q = 66.57 Ce + 60010
0.961
P500
0.115 ± 0.004
4.519 ± 0.007
0.987
Q = 25.11 Ce + 55230
0.706
P600
0.084 ± 0.003
4.353 ± 0.007
0.973
Q = 35830
-
P700
0.076 ± 0.003
5.180 ± 0.007
0.980
Q = 70.86 Ce + 208000
0.941
AC
0.214 ± 0.014
5.178 ± 0.025
0.938
Q = 21.58 Ce + 424500
0.987
1) The Freundlich parameters (Kf and N) were calculated using the logarithmic form of the equation Q= Kf CeN, where Q is the amount sorbed per unit weight of sorbent, mg/kg; Ce is the equilibrium concentration, mg/L; Kf [(mg/kg)/(mg/L)N] is the Freundlich capacity coefficient, and N (dimensionless) describes the isotherm curvature. R2 is regression coefficient. 2) Linear isotherms over high relative concentration range (i.e., Ce/CS= 0.1-0.7) were regressed, and the slope and y-axis intercept of the linear equation were used to calculate partition coefficient (KP) and the maximum adsorption capacity ( Q Amax , mg/g, 19, 22), respectively.
S4
H
H
H
H
H
H
0.9517nm
0.9517nm
H
H
0.7688nm
0.7688nm
(A) Naphthalene (Molecular area =0.732 nm2, Molecular Volume =0.252 nm3 ) O
+
O
-
N H
H
0.8928nm
0.8928nm H
H H
0.6948nm
0.6948nm
(B) Nitrobenzene (Molecular area =0.620 nm2, Molecular Volume =0.213 nm3 )
O
-
H
O +
+
N
N
O
O
-
0.8124nm H
H
0.8124nm
H
1.033nm
1.033nm
(C) m-Dinitrobenzene (Molecular area =0.839 nm2, Molecular Volume =0.289 nm3 )
Figure S-1.
Schematic of molecular structures and dimensions of the tested organic compounds based on van der Waals radii.
S5
90
45
80
40
70
Removal Efficiency, %
Removal Efficiency, %
50
35 30 25 20 15 10
(A) P100-NAPH
60 50 40 30 20
(B) P700-NAPH
10
5 0
0
0
12
24
36
48
60
72
84
96
108
0
12
24
36
Time, h
60
72
84
96
108
Time, h
40
25
Removal Efficiency, %
20 Removal Efficiency, %
48
15
10
5
30
20
10 (D) P700-NB
(C) P100-NB
0
0 0
12
24
36
48
60
72
84
0
96 108
12
24
36
48
60
72
84
96
108
Time, h
Time, h
Figure S-2. Selected sorption kinetic curves for naphthalene (NAPH) and nitrobenzene (NB) to bio-chars of P100 and P700. The initial concentrations are 22.6 mg/L and 550 mg/L for NAPH and NB, respectively. Uptake of NOCs by bio-chars reaches apparent equilibrium within 48 h, which is consistent with previous kinetic studies about wood and crop chars (Chun, 2004; Kranfil, 1999; and Paulsen, 1999). Chun, Y.; Sheng, G. Y.; Chiou, C. T.; Xing, B. S. Compositions and sorptive properties of crop residue-derived chars. Environ. Sci. Technol. 2004, 38, 4649–4655. Karanfil, T.; Kilduff, J. E. Role of granular activated carbon surface chemistry on the adsorption of organic compounds. 1. Priority pollutants. Environ. Sci. Technol. 1999, 33 (18), 3217-3224. Paulsen, P. D.; Moore, B. C.; Cannon, F. S. Applicability of adsorption equations to argon, nitrogen, and volatile organic compound adsorption onto activated carbon. Carbon 1999, 37(11), 1843-1853.
S6
40000
360000
(A) NAPH
(B) NAPH
320000 280000
30000
Amount sorbed, mg/kg
Amount sorbed, mg/kg
35000
25000 20000 15000 10000
240000 200000 160000 120000 80000
5000
40000
0
0 0
5
10
15
20
0
5
10
Equilibrium Concentration, mg/L P100
P200
P250
P300
P400
P500
P500
90000
20
25
P600
P700
400
500
AC
500000
(C) m-DNB
80000
(D) m-DNB
450000 400000 Amount Sorbed, mg/kg
70000 Amount sorbed, mg/kg
15
Equilibrium Concentration, mg/L
60000 50000 40000 30000
350000 300000 250000 200000 150000
20000
100000
10000
50000
0
0
0
100
200
300
400
500
P100
Figure S-3.
P200
P250
P300
P400
0
100
200
300
Equilibrium Concentration, mg/mL
Equilibrium Concentration, mg/L
P500
P500
P600
P700
AC
Sorption isotherms of naphthalene (NAPH) and m-dinitrobenzene (m-DNB) to the bio-chars (P100-P700) and an activated carbon (AC) sample in aqueous solution.
S7
Pyrolytic Temperature, ˚C 700 600 500 400
1.2
250 200
100
Naphthalene Nitrobenzen × m-Dinitrobenzene
1.0 0.8 N Value
300
0.6 0.4 0.2 0.0 0.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
1.6
H/C Atomic Ratio
Pyrolytic Temperature, ˚C 700 600 500 400
6.0
300
250 200
100
5.0
log K f
4.0 3.0 2.0
Naphthalene Nitrobenzen × m-Dinitrobenzene
1.0 0.0 0.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
1.6
H/C Atomic Ratio
Figure S-4.
Linear relationships of sorption regression parameters (i.e., N and logKf) of
solutes with bio-char’s aromaticities (i.e., H/C atomic ratio).
S8
90000
(A) P100
30000
Amount sorbed, mg/kg
Amount sorbed, mg/kg
35000
25000 20000 15000 10000 5000
(B) P200
80000 70000 60000 50000 40000 30000 20000 10000
0
0 0
300
600
900
1200
1500
0
300
Equilibrium Concentration, mg/L
100000 80000 60000 40000 20000 0
1200
(D) P300 200000 150000 100000 50000 0
0
200
400
600
800
1000
1200
0
300
Equilibrium Concentration, mg/L 200000 180000
600
900
1200
1500
Equilibrium Concentration, mg/L 160000
(E) P400
Amount sorbed, mg/kg
Amount sorbed, mg/kg
900
250000
(C) P250
Amount sorbed, mg/kg
Amount sorbed, mg/kg
120000
160000 140000 120000 100000 80000 60000 40000
(F) P500
140000 120000 100000 80000 60000 40000 20000
20000 0
0 0
300
600
900
1200
1500
1800
0
300
Equilibrium Concentration, mg/L
600
900
1200
1500
1800
1500
1800
Equilibrium Concentration, mg/L
140000
350000
(G) P600
120000
Amount sorbed, mg/kg
Amount sorbed, mg/kg
600
Equilibrium Concentration, mg/L
100000 80000 60000 40000 20000
(H) P700
300000 250000 200000 150000 100000 50000
0
0
0
300
600
900
1200
1500
1800
0
Equilibrium Concentration, mg/L
300
600
900
1200
Equilibrium Concentration, mg/L
Figure S-5. Quantitative contribution of partition ( ) and adsorption (×) to total sorption ( ) of nitrobenzene onto bio-chars (P100-P700).
S9
Pyrolytic Temperature, ˚C 700 600 500 400
1200
300
250
200
100
1000
KPom , mL/g K , mL/g
800 600 400
(A) Naphthalene
200 0 0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
(O+N)/C Atomic Ratio
Pyrolytic Temperature, ˚C 700 600 500 400
140
300
250
200
100
120
KKP,ommL/g , mL/g
100 80 60 40
(B) Nitrobenzene
20 0 0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
(O+N)/C Atomic Ratio
Pyrolytic Temperature, ˚C 700 600 500 400
300
250
200
100
120 100
KKPom , mL/g , mL/g
80 60 40
(C) m-Dinitrobenzene
20 0 0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
(O+N)/C Atomic Ratio
Figure S-6. Relationships of partition coefficient (KP) of the tested solute with bio-char’s
polarity indexes (i.e., (O+N)/C)
S10
Environmental Science and Technology
2
Supporting Information
3 4
Transitional Adsorption and Partition of Nonpolar and Polar Aromatic
5
Contaminants by Bio-chars of Pine Needles with Different Pyrolytic
6
Temperatures
7 8
Baoliang Chen*, Dandan Zhou, and Lizhong Zhu
9
Department of Environmental Science, Zhejiang University, Hangzhou, Zhejiang 310028, China
10 11 12
* Corresponding Author E-mail: [email protected] Manuscript No. : es-2008-002684
13 14
Supporting Information consists of ten pages, including this one.
15
There are Batch Sorption Experiment, two Tables and six Figures.
16 17 18
May 2, 2008
19 20 21 22 23 24 25 S1
26
Batch Sorption Experiment. Naphthalene (NAPH), nitrobenzene (NB), and m-dinitro-
27
benzene (m-DNB) were chosen as model sorbates due to their different molecular polarities and
28
dimensions. Naphthalene were purchased from Aldrich Chemical Co. with a purity >98%, and
29
nitrobenzene and m-dinitrobenzene from Shanghai Chemical Co with a purity > 99%. These
30
compounds were used as received. The physico-chemical properties of selected sorbates are
31
shown in Table S-1 and the associated molecular dimensions determined from their van der Waals
32
radii are given in Figure S-1. All sorption isotherms were obtained in 0.01 mol/L CaCl2 to simulate
33
environmental water, with 200 mg/L NaN3 added to inhibit the degradation by incidental bacteria.
34
Relative initial-concentrations (Ci/CS) ranged from 0.03 to 0.94 for NAPH, 0.01~0.83 for NB, and
35
0.02~0.87 for m-DNB to saturate potential adsorption. For NB and m-DNB, a given amount of
36
sorbent (100, 50, 50, 20, 10, 10, 10, 7, and 2.5 mg for P100-P700 and AC, respectively) were
37
mixed with 8 mL solution. For NAPH, the added amount of P100-P600 to 8-mL vials were 15, 9,
38
7.5, 7.5, 2.5, 3, and 4 mg, respectively; and 4 mg of P700 and 1 mg of AC were mixed with 40 mL
39
solution. Isotherms consisted of ten concentration points; each point, including the blank and
40
calibration control, was run in duplicate. The vials were placed on a rotating shaker and agitated in
41
the dark at 20 rpm for 3 d. Preliminary tests indicated that apparent equilibrium was achieved in
42
less than 48 h (see Figure S-2 for more detail), which is consistent with previously kinetic studies
43
about wood and crop chars (12 and therein). The solution was separated from solids by
44
centrifugation at 4000 rpm for 15 min. The equilibrium concentrations were measured by using a
45
UV-2550 spectrophotometer at wavelength of 275 nm (NAPH), 268 nm (NB) and 260 nm
46
(m-DNB) with the detection limit of 0.1 mg/L (S/N=3). Because of a minimal sorption by the vials
47
and no biodegradation observed, the amount sorbed by sorbent was calculated by the sorbate mass
48
difference in solution.
49 50
S2
Table S-1. Selected Properties of Naphthalene (NAPH), Nitrobenzene (NB), and m-Dinitrobenzene (m-DNB). Organic compounds NAPH
Formula
Structural
C10H8
MW, g/mol
S, µg/mL
Kow
Density, g/cm3
MA, nm2
MV, nm3
128.2
32.05
1950
0.997
0.732
0.252
123.1
1936
71
1.196
0.620
0.213
168.1
574.9
31
1.600
0.839
0.289
NO 2
NB
C6H5NO2
O2N
m-DNB
C6H4N2O4
NO2
MW: molecular weight, g/mol; S: aqueous solubility at room temperature, µg/mL; Kow octanol-water partition coefficient; MA: molecular area, nm2; MV: molecular volume, nm3.
S3
Table S-2.
Regression Parameters of Isotherms of Organic Pollutants to Bio-chars and an
Activated Carbon from Aqueous Solution. Solutes
Samples
NAPH
NB
m-DNB
Freundlich 1)
Linear over high relative conc. 2)
N
logKf
R2
P100
1.107 ± 0.021
2.342 ± 0.017
0.995
Q = 295.4 Ce
0.993
P200
0.874 ± 0.010
3.036 ± 0.007
0.998
Q = 782.8 Ce + 329.4
0.997
P250
0.777 ± 0.007
3.212 ± 0.005
0.999
Q = 783.8 Ce + 1724
0.991
P300
0.589 ± 0.007
3.494 ± 0.005
0.998
Q = 785.0 Ce + 4006
0.994
P400
0.332 ± 0.012
4.222 ± 0.010
0.980
Q = 748.3 Ce + 25690
0.914
P500
0.207 ± 0.010
4.286 ± 0.009
0.972
Q = 299.5 Ce +27400
0.914
P600
0.17 4 ± 0.010
4.097 ± 0.009
0.957
Q = 274.2 Ce + 15140
0.901
P700
0.124 ± 0.080
5.085 ± 0.007
0.964
Q = 1086 Ce + 136800
0.875
AC
0.147 ± 0.011
5.340 ± 0.018
0.838
Q = 314300
Linear equation
R2
-
P100
0.971 ± 0.019
1.446 ± 0.045
0.994
Q = 24.58 Ce
0.991
P200
0.800 ± 0.009
2.486 ± 0.021
0.998
Q = 72.60 Ce + 5908
0.993
P250
0.701 ± 0.008
2.890 ± 0.017
0.998
Q = 94.34 Ce + 10080
0.994
P300
0.513 ± 0.007
3.701 ± 0.015
0.997
Q = 129.6 Ce + 51140
0.966
P400
0.271 ± 0.007
4.367 ± 0.015
0.990
Q = 71.04 Ce + 79710
0.995
P500
0.179 ± 0.007
4.592 ± 0.016
0.974
Q = 29.58 Ce + 96630
0.948
P600
0.114 ± 0.005
4.720 ± 0.013
0.968
Q = 19.93 Ce + 91690
0.920
P700
0.111 ± 0.008
5.091 ± 0.020
0.938
Q = 85.97 Ce + 181200
0.976
AC
0.208 ± 0.009
5.058 ± 0.022
0.968
Q = 44.41 Ce + 386300
0.982
P100
0.983 ± 0.016
1.538 ± 0.029
0.996
Q = 30.99 Ce
0.994
P200
0.745 ± 0.011
2.675 ± 0.021
0.997
Q = 88.61 Ce + 5655
0.991
P250
0.684 ± 0.009
2.891 ± 0.015
0.997
Q = 99.26 Ce + 7534
0.993
P300
0.488 ± 0.007
3.486 ± 0.012
0.997
Q = 109.7 Ce + 17090
0.985
P400
0.233 ± 0.006
4.346 ± 0.011
0.991
Q = 66.57 Ce + 60010
0.961
P500
0.115 ± 0.004
4.519 ± 0.007
0.987
Q = 25.11 Ce + 55230
0.706
P600
0.084 ± 0.003
4.353 ± 0.007
0.973
Q = 35830
-
P700
0.076 ± 0.003
5.180 ± 0.007
0.980
Q = 70.86 Ce + 208000
0.941
AC
0.214 ± 0.014
5.178 ± 0.025
0.938
Q = 21.58 Ce + 424500
0.987
1) The Freundlich parameters (Kf and N) were calculated using the logarithmic form of the equation Q= Kf CeN, where Q is the amount sorbed per unit weight of sorbent, mg/kg; Ce is the equilibrium concentration, mg/L; Kf [(mg/kg)/(mg/L)N] is the Freundlich capacity coefficient, and N (dimensionless) describes the isotherm curvature. R2 is regression coefficient. 2) Linear isotherms over high relative concentration range (i.e., Ce/CS= 0.1-0.7) were regressed, and the slope and y-axis intercept of the linear equation were used to calculate partition coefficient (KP) and the maximum adsorption capacity ( Q Amax , mg/g, 19, 22), respectively.
S4
H
H
H
H
H
H
0.9517nm
0.9517nm
H
H
0.7688nm
0.7688nm
(A) Naphthalene (Molecular area =0.732 nm2, Molecular Volume =0.252 nm3 ) O
+
O
-
N H
H
0.8928nm
0.8928nm H
H H
0.6948nm
0.6948nm
(B) Nitrobenzene (Molecular area =0.620 nm2, Molecular Volume =0.213 nm3 )
O
-
H
O +
+
N
N
O
O
-
0.8124nm H
H
0.8124nm
H
1.033nm
1.033nm
(C) m-Dinitrobenzene (Molecular area =0.839 nm2, Molecular Volume =0.289 nm3 )
Figure S-1.
Schematic of molecular structures and dimensions of the tested organic compounds based on van der Waals radii.
S5
90
45
80
40
70
Removal Efficiency, %
Removal Efficiency, %
50
35 30 25 20 15 10
(A) P100-NAPH
60 50 40 30 20
(B) P700-NAPH
10
5 0
0
0
12
24
36
48
60
72
84
96
108
0
12
24
36
Time, h
60
72
84
96
108
Time, h
40
25
Removal Efficiency, %
20 Removal Efficiency, %
48
15
10
5
30
20
10 (D) P700-NB
(C) P100-NB
0
0 0
12
24
36
48
60
72
84
0
96 108
12
24
36
48
60
72
84
96
108
Time, h
Time, h
Figure S-2. Selected sorption kinetic curves for naphthalene (NAPH) and nitrobenzene (NB) to bio-chars of P100 and P700. The initial concentrations are 22.6 mg/L and 550 mg/L for NAPH and NB, respectively. Uptake of NOCs by bio-chars reaches apparent equilibrium within 48 h, which is consistent with previous kinetic studies about wood and crop chars (Chun, 2004; Kranfil, 1999; and Paulsen, 1999). Chun, Y.; Sheng, G. Y.; Chiou, C. T.; Xing, B. S. Compositions and sorptive properties of crop residue-derived chars. Environ. Sci. Technol. 2004, 38, 4649–4655. Karanfil, T.; Kilduff, J. E. Role of granular activated carbon surface chemistry on the adsorption of organic compounds. 1. Priority pollutants. Environ. Sci. Technol. 1999, 33 (18), 3217-3224. Paulsen, P. D.; Moore, B. C.; Cannon, F. S. Applicability of adsorption equations to argon, nitrogen, and volatile organic compound adsorption onto activated carbon. Carbon 1999, 37(11), 1843-1853.
S6
40000
360000
(A) NAPH
(B) NAPH
320000 280000
30000
Amount sorbed, mg/kg
Amount sorbed, mg/kg
35000
25000 20000 15000 10000
240000 200000 160000 120000 80000
5000
40000
0
0 0
5
10
15
20
0
5
10
Equilibrium Concentration, mg/L P100
P200
P250
P300
P400
P500
P500
90000
20
25
P600
P700
400
500
AC
500000
(C) m-DNB
80000
(D) m-DNB
450000 400000 Amount Sorbed, mg/kg
70000 Amount sorbed, mg/kg
15
Equilibrium Concentration, mg/L
60000 50000 40000 30000
350000 300000 250000 200000 150000
20000
100000
10000
50000
0
0
0
100
200
300
400
500
P100
Figure S-3.
P200
P250
P300
P400
0
100
200
300
Equilibrium Concentration, mg/mL
Equilibrium Concentration, mg/L
P500
P500
P600
P700
AC
Sorption isotherms of naphthalene (NAPH) and m-dinitrobenzene (m-DNB) to the bio-chars (P100-P700) and an activated carbon (AC) sample in aqueous solution.
S7
Pyrolytic Temperature, ˚C 700 600 500 400
1.2
250 200
100
Naphthalene Nitrobenzen × m-Dinitrobenzene
1.0 0.8 N Value
300
0.6 0.4 0.2 0.0 0.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
1.6
H/C Atomic Ratio
Pyrolytic Temperature, ˚C 700 600 500 400
6.0
300
250 200
100
5.0
log K f
4.0 3.0 2.0
Naphthalene Nitrobenzen × m-Dinitrobenzene
1.0 0.0 0.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
1.6
H/C Atomic Ratio
Figure S-4.
Linear relationships of sorption regression parameters (i.e., N and logKf) of
solutes with bio-char’s aromaticities (i.e., H/C atomic ratio).
S8
90000
(A) P100
30000
Amount sorbed, mg/kg
Amount sorbed, mg/kg
35000
25000 20000 15000 10000 5000
(B) P200
80000 70000 60000 50000 40000 30000 20000 10000
0
0 0
300
600
900
1200
1500
0
300
Equilibrium Concentration, mg/L
100000 80000 60000 40000 20000 0
1200
(D) P300 200000 150000 100000 50000 0
0
200
400
600
800
1000
1200
0
300
Equilibrium Concentration, mg/L 200000 180000
600
900
1200
1500
Equilibrium Concentration, mg/L 160000
(E) P400
Amount sorbed, mg/kg
Amount sorbed, mg/kg
900
250000
(C) P250
Amount sorbed, mg/kg
Amount sorbed, mg/kg
120000
160000 140000 120000 100000 80000 60000 40000
(F) P500
140000 120000 100000 80000 60000 40000 20000
20000 0
0 0
300
600
900
1200
1500
1800
0
300
Equilibrium Concentration, mg/L
600
900
1200
1500
1800
1500
1800
Equilibrium Concentration, mg/L
140000
350000
(G) P600
120000
Amount sorbed, mg/kg
Amount sorbed, mg/kg
600
Equilibrium Concentration, mg/L
100000 80000 60000 40000 20000
(H) P700
300000 250000 200000 150000 100000 50000
0
0
0
300
600
900
1200
1500
1800
0
Equilibrium Concentration, mg/L
300
600
900
1200
Equilibrium Concentration, mg/L
Figure S-5. Quantitative contribution of partition ( ) and adsorption (×) to total sorption ( ) of nitrobenzene onto bio-chars (P100-P700).
S9
Pyrolytic Temperature, ˚C 700 600 500 400
1200
300
250
200
100
1000
KPom , mL/g K , mL/g
800 600 400
(A) Naphthalene
200 0 0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
(O+N)/C Atomic Ratio
Pyrolytic Temperature, ˚C 700 600 500 400
140
300
250
200
100
120
KKP,ommL/g , mL/g
100 80 60 40
(B) Nitrobenzene
20 0 0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
(O+N)/C Atomic Ratio
Pyrolytic Temperature, ˚C 700 600 500 400
300
250
200
100
120 100
KKPom , mL/g , mL/g
80 60 40
(C) m-Dinitrobenzene
20 0 0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
(O+N)/C Atomic Ratio
Figure S-6. Relationships of partition coefficient (KP) of the tested solute with bio-char’s
polarity indexes (i.e., (O+N)/C)
S10
