1. Using Biochar as a Soil Amendment for Sustainable Agriculture Biochar Symposium Illinois Sustainable Technology Center (ISTC) June 9, 2011 W. Zheng B.K. Sharma K. Rajagopalan

2. Using Biochar as a Soil Amendment for Sustainable Agriculture Illinois Sustainable Technology Center (ISTC) Sustainable Agriculture Grant Program by Illinois Department of Agriculture Grant #: SA 09-37 (2009-2010)

3. Project Goal The objective of this project was to examine the potential use of biochar as a soil amendment in a typical corn field in Illinois as part of a larger goal of promoting sustainable agricultural practice. To achieve this goal, three tasks were undertaken in the project:  Biochar production and characterization: Biochar production through a low-temperature slow pyrolysis technique from a variety of waste biomass.  Removal of nutrients by biochar: The sorption kinetics and mechanisms of NH 4 + and PO 4 3- removal by biochar were investigated.  Field trial to demonstrate the efficacy of biochar as a simple soil amendment as measured by crop yields and lowered fertilizer use in Illinois, which attempted to investigate if the use of biochar as a soil amendment could reduce chemical fertilizer use while at the same time maintaining or increasing crop yields.

4. Feedstock The feedstocks used for biochar production in this study focused on three kinds of waste biomass:  Agricultural residues corn cobs corn stover;  Yard wastes walnut shells and wood chips;  By-products from bioenergy defatted dried distiller grains (DDGs)

5. Pyrolysis Syngas H 2, CO, CO 2 Waste Biomass Pyrolysis Bio-oil Biochar Pyrolysis is a most common thermochemical conversion process where biomass is heated in the absence of oxygen to yield a series of bioproducts: syngas; bio-oil; and biochar.

6. Schematic Diagram for Biochar Production in a Slow Pyrolyzer

7. . ISTC Sustainable Biochar

8. Effect of Selected Feedstocks and Pyrolysis Conditions on Yields of Bioproducts BiocharFeedstockBiochar (%)Bio-oil (%)Syngas (%) ZW-1Corn cob32.2 %45.6 %22.2% ZW-2Corn stover39.0 %42.8 %18.2 % ZW-3Defatted DDG45.8 %40.3 %14.9 % ZW-4Pine cone38.0 %44.4 %17.6 % ZW-5America chestnut shell 42.2 %45.6 %12.2 % ZW-6-1*Wood chip35.0 %42.0 %23.0 % ZW-6-2*Wood chip35.0 %42.1 %22.9 % ZW-6-3*Wood chip35.1 %42.1 %22.8 % The yields of three bio-products produced from selected feedstocks under oxygen-limited condition for 60 min at 400 o C. *ZW-6-1, 2, and 3 refer to the feedstock pyrolyzed under 0, 2, and 5 L/min nitrogen flow.

9. Effect of Pyrolysis Temperature on the Yields of Bioproducts

10. Biochar Characterization on Physicochemical Properties Feedstock Pyrolysis Temperature SSA (m 2 /g) % C% H% N% O(O+N)/CO/CH/C % Moisture % Ash Corn cob250 O C 1.86 61.164.960.82 27.820.3530.3410.9731.323.92 Corn cob300 O C 2.42 70.544.190.81 19.060.2130.2030.7131.34.1 Corn cob350 O C 3.36 72.923.790.79 16.860.1830.1730.6241.294.35 Corn cob400 O C 4.70 75.233.370.82 14.110.1500.1410.5381.355.12 Corn cob450 O C 7.79 77.842.950.86 11.450.1200.1100.4551.355.55 Corn cob500 O C 17.08 80.852.50.97 8.870.0930.0820.3711.255.56 Corn cob550 O C 30.57 82.622.250.84 7.430.0760.0670.3271.285.58 Wood pellet750 O C 105.3 81.991.140.52 3.040.0330.0280.1674.568.75 Wood chip450 O C 12.96 70.442.671.11 13.860.1610.1480.4551.6910.23 Defatted DDG400 O C 1.98 64.433.767.44 10.140.2170.1180.7001.4512.78 Corn stover400 O C 4.69 55.983.40.43 18.160.2500.2430.7291.2820.75 Pine cone400 O C 17.92 73.883.211.33 15.310.1710.1550.5211.324.95 Activated carbon 988.4 91.10.90.285.710.0500.0470.1191.120.89

11. Project Goal The objective of this project was to examine the potential use of biochar as a soil amendment in a typical corn field in Illinois as part of a larger goal of promoting sustainable agricultural practice. To achieve this goal, three tasks were undertaken in the project:  Biochar production and characterization: Biochar production through a low- temperature slow pyrolysis technique from a variety of waste biomass.  Removal of nutrients by biochar: The sorption kinetics and mechanisms of NH 4 + and PO 4 3- removal by biochar were investigated.  Field trial to demonstrate the efficacy of biochar as a simple soil amendment as measured by crop yields and lowered fertilizer use in Illinois, which attempted to investigate if the use of biochar as a soil amendment could reduce chemical fertilizer use while at the same time maintaining or increasing crop yields.

12. Sorption Capacities of NH 4 + and PO 4 3- on Selected Biochars and a Commercial Activated Carbon NH 4 + PO 4 3-

13. Sorption Kinetics NH 4 + PO 4 3-

14. Sorption Kinetics To investigate the controlling mechanisms of sorption processes, e.g., mass transfer and chemical reaction, the data obtained from this study were analyzed using two kinetic equations: the pseudo- first order equation and the pseudo-second order equation: where Q e and Q t are the amounts of nutrients sorbed (mmol/g) at equilibrium and at time t (h), k 1 and k 2 are sorption rate constants of pseudo-first order and pseudo-second order, respectively. The fit of these two models was checked by the linear plot of log (Q e -Q t ) versus t and t/Q t versus t, respectively, and by comparison to the regression coefficients for each expression.

15. Pseudo-first orderPseudo-second order k 1 (h -1 ) Q e (cal) (mmol/g) R2R2 k 2 (mmol/g) -1 h -1 Q e (cal) (mmol/g) R2R2 NH 4 + Biochar-750 0.115 7.87 x 10 -3 0.95968.6 2.44 x 10 -2 0.999 Biochar-450 0.105 1.41 x 10 -2 0.99228.9 3.14 x 10 -2 0.995 PO 4 3- Biochar-750 0.119 6.05 x 10 -2 0.9841.23 8.61 x 10 -2 0.932 Biochar-450 0.097 5.79 x 10 -2 0.9900.013 4.81 x 10 -1 0.006 Sorption Kinetics Pseudo-first order and pseudo-second order sorption rate constants of NH 4 + and PO 4 3- on two selected biochars

16. Sorption Isotherms of NH 4 + and PO 4 3- on Selected Biochars NH 4 + PO 4 3-

17. Sorption Isotherm Freundlich isotherm log C s = log K f + 1/n log C e Langmuir isotherm C e /Q e = 1/(bQ 0 ) + C e /Q 0 K f (mmol/g) (mmo/L) -n 1/nR2R2 Q 0 (mmol/g) b (L/mmol) R2R2 NH 4 + Biochar-7502.56 x 10 -2 0.650 0.9710.2460.1080.933 Biochar-4504.12 x 10 -2 0.516 0.9810.2340.1900.974 PO 4 3- Biochar-7505.74 x 10 -2 0.795 0.8950.5760.1400.835 Biochar-4503.60 x 10 -2 0.933 0.8730.7870.0470.270

18. Removal Mechanisms of Phosphate & Ammonium by Biochar Analyte Units Biochar after DI H 2 O washingBiochar no washing mg/L Sodium*< 0.6 Potassium*7.715 Calcium*2.83.8 Beryllium< 0.002 Boron0.0890.094 Magnesium1.52.3 Aluminum0.0750.084 Silicon2.01.0 Titanium0.00270.0022 Vanadium< 0.001 Chromium0.00320.0033 Manganese0.00770.0055 Iron*< 0.10.11 Zeta potential (ζ)-21.9±3.8-22.3±6.9 Ca 2+ + PO 4 3- +. xH 2 0 → Ca 3 (PO 4 ) 2. xH 2 0  Precipitation process  Surface sorption Biochar with negatively charged surface

19. Sorption Mechanism of Phosphate by Biochar XAD patterns of before and after PO 4 3- adsorption by biochar Ca 3 (PO 4 ) 2. xH 2 0 Ca 2+ + PO 4 3- +. xH 2 0 → Ca 3 (PO 4 ) 2. xH 2 0

20. Project Goal The objective of this project was to examine the potential use of biochar as a soil amendment in a typical corn field in Illinois as part of a larger goal of promoting sustainable agricultural practice. To achieve this goal, three tasks were undertaken in the project:  Biochar production and characterization: Biochar production through a low- temperature slow pyrolysis technique from a variety of waste biomass.  Removal of nutrients by biochar: The sorption kinetics and mechanisms of NH 4 + and PO 4 3- removal by biochar were investigated.  Field trial to demonstrate the efficacy of biochar as a simple soil amendment as measured by crop yields and lowered fertilizer use in Illinois, which attempted to investigate if the use of biochar as a soil amendment could reduce the application rates of chemical fertilizer while at the same time maintaining or increasing crop yields.

21. 2010 Biochar Field Experiment Design 90 Feet and 36 rows 60 Feet No FertilizerHalf FertilizerFull FertilizerNo FertilizerHalf FertilizerFull Fertilizer 10 feet x 0.66 feet used for biochar treatments

22. Biochar Application in a Corn Field

24. Biochar Application in Corn Field

26. Standard corn growing practices

29. http://www.istc.illinois.edu/research/biochar.cfm ISTC Biochar Website

30. Biochar Application in Corn Field Nitrogen Fertilizer 050 %100 % No Biochar 139.3 a 174.3 a 173.0 a Biochar-A 164.6 b 213.7 b 239.8 b Biochar-B 170.9 b 194.2 b 201.3 a

31. Treatments Soil Organic Matter (%) Phosphorus Neutral Ammonium Acetate (exchangeable) pH Cation Exchange Capacity (CEC) meq/100g Nitrate-N mg/kg P1 mg/kg P1 mg/kg K mg/kg Mg mg/kg Ca mg/kg Before experiment No fertilizer and no biochar3.2152220634519535.816.319 No fertilizer with biochar-A3.6192332627418085.715.439 No fertilizer with biochar-B4.1202821834920465.717.335 50% fertilizer and no biochar4.2193218043823405.620.732 50% fertilizer with biochar-A4.7274235840624745.619.033 50% fertilizer with biochar-B4.0213125136219865.220.867 100% fertilizer and no biochar4.6121717252726176.021.134 100%fertilizer with biochar-A4.6224319544924225.919.775 100% fertilizer with biochar-B3.3152414934518785.417.674 After experiment (at harvest) No fertilizer and no biochar3.9203019831019065.415.221 No fertilizer with biochar-A5.0334625931821056.116.112 No fertilizer with biochar-B4.5193116632919155.820.121 50% fertilizer and no biochar4.5223817636622345.518.332 50% fertilizer with biochar-A5.5407434231322986.219.029 50% fertilizer with biochar-B4.8294717932420776.121.325 100% fertilizer and no biochar4.2142117545623985.817.758 100%fertilizer with biochar-A5.1356023940323086.522.613 100% fertilizer with biochar-B4.9273922137622475.920.956 Selected Soil Properties Before and After Experiments

32. Colleagues  Dr. Rajagopanlan, K.  Dr. Kulkarni, M.  Dr. Marlin, J.  Monte Wilcoxon  Joe Pickowitz  Ed Zaborski  Dr. Sharma, B.K.  John Scott  Dr. Li, X.  Christie Teausant  Nancy Holm  Brent Panno Acknowledgments This study is being supported by Illinois Department of Agriculture’s Sustainable Agriculture Grant Program

33. Questions Stay on the Stage