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
1State Key Laboratory of Water Environment Simulation, School of Environment, Beijing Normal University, Beijing 100875, China
2State Key Laboratory of Simulation and Regulation of Water Cycle in River Basin, China Institute of Water Resources and Hydropower Research, Beijing 100038, China
3State Key Laboratory of Environmental Criteria and Risk Assessment, Chinese Research Academy of Environmental Sciences, Beijing 100012, China
4Stockbridge 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: (K. Sun).
biochars / Total C
(%) / C-Ca(%) / C-Oa(%) / C=Oa(%) / COOHa(%) / O-containing groups (%) / O (%) / N (%) / Si (%) / Ca (%) / surface (O+N)/C
Total C (100%)
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
aSurface 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) / assignment / refs
3400 / the hydrogen bonded O-H stretching vibration / 1
2927, 2856, 1446, and 1370 / the aliphatic CH2 stretching in biopolymers / 2
1734 / the C=O stretching vibrations of ester bonds / 1
a broad band centered at 1700 / the carbonyl/carboxylic acid C=O stretch / 3
1613 / the C=C and C=O stretching vibrations in the aromatic rings / 4
1514 / the C=C ring stretching vibration of lignin / 4
1270 / the aromatic CO- and phenolic C-OH stretch associated with ligneous guaiacyl units / 5
1160 / the C-O stretching vibrations of ester bonds / 1
1160-1030 / the aliphatic C-O-C and alcohol-OH symbolize oxygenated functional groups of cellulose / 6
885,815 and 750 / the aromatic C-H out-of-plane deformations / 1, 7
1. Chen, B., Zhou, D., & Zhu, L. Transitional adsorption and partition of nonpolar and polar aromatic contaminants by biochars of pine needles with different pyrolytic temperatures. Environ. Sci. Technol.42, 5137-5143 (2008).
2. Chen, B., Johnson, E. J., Chefetz, B., Zhu, L. & Xing, B., Sorption of polar and nonpolar aromatic organic contaminants by plant cuticular materials: role of polarity and accessibility. Environ. Sci. Technol. 39, 6138-6146 (2005).
3. Pan, B. et al. The opposite impacts of Cu and Mg cations on dissolved organic matter-ofloxacin interaction. Environ. Pollut. 161, 76-82 (2012).
4. Bustin, R. Guo, Y., Abrupt changes (jumps) in reflectance values and chemical compositions of artificial charcoals and inertinite in coals. Int. J. Coal. Geol. 38, 237-260 (1999).
5. Trivedi, P. Vasudevan, D. Spectroscopic investigation of ciprofloxacin speciation at the goethite-water interface. Environ. Sci. Technol. 41, 3153-3158 (2007).
6. Zhu, L. Chen, B. Sorption behavior of p-nitrophenol on the interface between anion-cation organobentonite and water. Environ. Sci. Technol. 34, 2997-3002 (2000).
7. Guo, Y. Bustin, R. M. FTIR spectroscopy and reflectance of modern charcoals and fungal decayed woods: implications for studies of inertinite in coals. Int. J. Coal. 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
aAromaticiy =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.
biochars / logKFa / n / Nb / r2 / log Kdc / logKOCd (mL g-1) / KOC/KHWf
Ce=0.01Sw
0.01Swe / 0.1Sw / 1Sw
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
LE300 / 1.90 / 0.630± 0.022 / 20 / 0.986 / 2.70 / 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
aKF 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 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).
Table S5. Freundlich isotherm parameters and calculated results of phenanthrene (PHE) sorption on biochars.
biochars / logKFa / n / Nb / r2 / log Kdc / logKOCd (mL g-1) / KOC/KHWf
Ce=0.01Sw
0.01Swe / 0.1Sw / 1Sw
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
RI450 / 2.67 / 0.447±0.016 / 20 / 0.988 / 3.09 / 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
aKF 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).
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).
Figure S2. Cross polarization magic angle spinning 13C-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 oC).
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).