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Frontiers of Environmental Science & Engineering

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Front. Environ. Sci. Eng.    2020, Vol. 14 Issue (3) : 48    https://doi.org/10.1007/s11783-020-1225-1
RESEARCH ARTICLE
Ammonia and phosphorus removal from agricultural runoff using cash crop waste-derived biochars
Alisa Salimova1, Jian’e Zuo1(), Fenglin Liu1,2, Yajiao Wang1, Sike Wang1, Konstantin Verichev3
1. State Key Joint Laboratory of Environmental Simulation and Pollution Control, School of Environment, Tsinghua University, Beijing 100084, China
2. Beijing JingYi Air Protection & Technology Company, Wanda Plaza, 93 Jianguo Road, Chaoyang District, Beijing 100022, China
3. Institute of Civil Engineering, Faculty of Engineering Sciences, Universidad Austral de Chile, Valdivia 5090000, Chile
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Abstract

• Orange tree residuals biochar had a better ability to adsorb ammonia.

• Modified tea tree residuals biochar had a stronger ability to remove phosphorus.

• Partially-modified biochar could remove ammonia and phosphorus at the same time.

• The real runoff experiment showed an ammonia nitrogen removal rate of about 80%.

• The removal rate of total phosphorus in real runoff experiment was about 95%.

Adsorption of biochars (BC) produced from cash crop residuals is an economical and practical technology for removing nutrients from agricultural runoff. In this study, BC made of orange tree trunks and tea tree twigs from the Laoguanhe Basin were produced and modified by aluminum chloride (Al-modified) and ferric sulfate solutions (Fe-modified) under various pyrolysis temperatures (200°C–600°C) and residence times (2–5 h). All produced and modified BC were further analyzed for their abilities to adsorb ammonia and phosphorus with initial concentrations of 10–40 mg/L and 4–12 mg/L, respectively. Fe-modified Tea Tree BC 2h/400°C showed the highest phosphorus adsorption capacity of 0.56 mg/g. Al-modified Orange Tree BC 3h/500°C showed the best performance for ammonia removal with an adsorption capacity of 1.72 mg/g. FTIR characterization showed that P = O bonds were formed after the adsorption of phosphorus by modified BC, N-H bonds were formed after ammonia adsorption. XPS analysis revealed that the key process of ammonia adsorption was the ion exchange between K+ and NH4+. Phosphorus adsorption was related to oxidation and interaction between PO43– and Fe3+. According to XRD results, ammonia was found in the form of potassium amide, while phosphorus was found in the form of iron hydrogen phosphates. The sorption isotherms showed that the Freundlich equation fits better for phosphorus adsorption, while the Langmuir equation fits better for ammonia adsorption. The simulated runoff infiltration experiment showed that 97.3% of ammonia was removed by Al-modified Orange tree BC 3h/500°C, and 92.9% of phosphorus was removed by Fe-modified Tea tree BC 2h/400°C.
Keywords Biochar      Adsorption      Ammonia removal      Phosphorus removal      Agricultural runoff     
Corresponding Author(s): Jian’e Zuo   
Issue Date: 16 March 2020
 Cite this article:   
Alisa Salimova,Jian’e Zuo,Fenglin Liu, et al. Ammonia and phosphorus removal from agricultural runoff using cash crop waste-derived biochars[J]. Front. Environ. Sci. Eng., 2020, 14(3): 48.
 URL:  
https://academic.hep.com.cn/fese/EN/10.1007/s11783-020-1225-1
https://academic.hep.com.cn/fese/EN/Y2020/V14/I3/48
Fig.1  SEM image of: (a) non-modified Orange Tree BC, (b) Al-modified Orange Tree BC after adsorption of phosphorus, (c) Fe-modified Tea Tree BC before phosphorus adsorption, (d) Fe-modified Tea Tree BC after phosphorus adsorption, (e) Al-modified Orange tree BC before adsorption, (f) Al-modified Orange tree BC before adsorption negative color image.
Fig.2  FTIR spectrum of (a) Al-modified Orange Tree BC 3h/500°C before and after the adsorption of ammonia and phosphorus, (b) Fe-modified Tea Tree 2h/400°C before and after the adsorption of phosphorus.
Fig.3  Atomic mass percentage of chosen BC elemental composition before and after the adsorption of ammonia and phosphorus (a) N, P, K, Fe, Al, (b) O, C.
Fig.4  XRD comparison of (a) Non-modified Orange Tree BC 3h/500°C and Al-modified OTBC 3h/500°C before and after phosphorus adsorption, (b) of Non-modified Orange Tree BC 5h/400°C before and after ammonia adsorption, (c) Non-modified Tea Tree BC 2h/400°C and Fe-modified Tea Tree BC before and after phosphorus adsorption, (d) Non-modified Tea Tree BC 3h/400°C before and after ammonia adsorption.
Fig.5  Removal efficiency of (a) Orange Tree BC after ammonia adsorption, (b) Orange Tree BC after phosphorus adsorption, (c) Tea Tree BC after ammonia adsorption, (d) Tea Tree BC after phosphorus adsorption.
Fig.6  The best performance BC in (a) ammonia adsorption, (b) phosphorus adsorption.
(a) Ammonia adsorption capacity
Initial Temp. 300°C 400°C 500°C 600°C
conc. duration a) b) c) a) b) c) a) b) c) a) b) c)
10 mg/L 2h 0.46 0.36 0.13 0.50 0.24 0.22 0.45 0.49 0.27 0.29 0.26 0.15
3h 0.30 0.34 0.44 0.58 0.52 0.32 0.45 0.65 0.25 0.12 0.17 0.34
4h 0.43 0.28 0.38 0.44 0.56 0.16 0.56 0.44 0.25 0.30 0.06 0.29
5h 0.41 0.27 0.45 0.66 0.38 0.34 0.50 0.37 0.37 0.29 0.13 0.31
20 mg/L 2h 0.83 0.45 0.28 1.08 0.37 0.49 0.90 0.89 0.74 0.47 0.49 0.49
3h 0.63 0.53 0.72 1.00 0.84 0.64 0.74 1.03 0.58 0.26 0.38 0.67
4h 0.85 0.47 0.52 0.91 0.76 0.33 0.99 0.70 0.33 0.55 0.14 0.33
5h 0.87 0.59 0.56 0.92 0.47 0.53 0.80 0.54 0.46 0.40 0.31 0.45
40 mg/L 2h 1.26 0.63 0.36 1.47 0.49 0.76 1.40 1.49 1.14 0.86 0.58 1.15
3h 0.85 0.85 1.01 1.54 1.51 0.94 1.15 1.72 0.88 0.58 0.63 0.96
4h 1.43 0.72 0.70 1.48 1.32 0.52 1.56 1.21 0.55 1.00 0.43 0.57
5h 1.42 1.21 0.92 1.60 1.04 0.86 1.02 0.68 0.85 0.41 0.75 0.83
(b) Phosphorus adsorption capacity
Initial Temp. 300°C 400°C 500°C 600°C
conc. duration d) e) f) d) e) f) d) e) f) d) e) f)
4 mg/L 2h 0.03 0.07 0.13 0.00 0.01 0.27 0.00 0.02 0.16 0.00 0.04 0.11
3h 0.02 0.07 0.13 0.04 0.01 0.21 0.01 0.04 0.06 0.00 0.07 0.03
4h 0.00 0.03 0.13 0.00 0.03 0.19 0.00 0.05 0.18 0.00 0.07 0.16
5h 0.01 0.02 0.12 0.00 0.11 0.19 0.00 0.08 0.14 0.00 0.05 0.08
8 mg/L 2h 0.02 0.07 0.13 0.00 0.03 0.49 0.00 0.04 0.18 0.00 0.10 0.12
3h 0.02 0.10 0.14 0.05 0.01 0.37 0.01 0.06 0.08 0.00 0.10 0.06
4h 0.00 0.03 0.14 0.00 0.03 0.35 0.00 0.07 0.20 0.00 0.10 0.18
5h 0.01 0.04 0.12 0.00 0.12 0.29 0.02 0.09 0.22 0.00 0.07 0.09
12 mg/L 2h 0.02 0.07 0.14 0.00 0.05 0.56 0.00 0.06 0.20 0.00 0.12 0.12
3h 0.03 0.17 0.16 0.06 0.00 0.42 0.02 0.10 0.09 0.01 0.14 0.08
4h 0.00 0.03 0.16 0.00 0.03 0.41 0.00 0.07 0.31 0.00 0.11 0.20
5h 0.00 0.06 0.13 0.00 0.13 0.35 0.03 0.10 0.26 0.00 0.07 0.10
Tab.1  Ammonia and phosphorus adsorption capacity of all BC samples (mg/g)
(a) Ammonia removal speed by Orange Tree BC
Initial conc.(mg/L) 1 h 2 h 3 h 6 h 12 h 24 h 48 h
10.00 7.32 7.04 6.68 5.33 4.84 3.46 3.45
20.00 16.42 14.66 12.97 12.74 11.78 10.81 10.82
40.00 35.02 33.49 30.66 29.52 26.11 23.94 23.95
(b) Phosphorus removal speed by Tea Tree BC
Initial conc. 5 min 15 min 30 min 1 h 3 h 6 h 12 h
4.00 3.31 2.21 1.52 1.31 1.30 1.31 1.31
8.00 6.68 4.42 3.54 3.14 3.15 3.14 3.14
12.00 10.10 7.51 6.91 6.43 6.42 6.44 6.43
Tab.2  Ammonia and phosphorus adsorption kinetics by selected BC (mg/L)
BC sample Langmuir equation Freundlich equation
B (L/mg) Q (mg/g) R2 K (mg/g) n R2
Non-modified TTBC 3h/400 °C I 0.06 1.52 0.99 0.12 1.62 0.98
Al-modified Orange Tree BC 3h/500 °C I 0.22 1.77 0.98 2.66 2.24 0.98
Fe-modified Tea Tree 2h/400 °C II 0.96 0.58 0.95 0.25 2.15 0.98
Al-modified Tea Tree BC 3h/500 °C II 0.14 0.37 0.98 0.14 0.37 0.98
Tab.3  Ammonia and phosphorus adsorption characteristics for the selected BC
BC sample Runoff volume (L) Influent concentration (mg/L) Effluent concentration (mg/L) Removal efficiency (%)
Non-modified TTBC 3h/400 °C I 45 1.11 0.0 92.8
Al-modified Orange Tree BC 3h/500 °C I 45 1.11 0.03 97.3
Fe-modified Tea Tree 2h/400 °C II 45 0.56 0.04 92.9
Al-modified Tea Tree BC 3h/500 °C II 45 0.56 0.09 83.9
Tab.4  Ammonia and phosphorus removal efficiency in the column leaching experiment
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