Fundamental and molecular composition characteristics of biochars produced from sugarcane and rice crop residues and by-products

• Pyrolysis temperature at 550 °C yields stable biochar characteristics and maximum CEC.
• Lignin decarboxylation and demethoxylation at 450 °C and dehydroxylation at above 550 °C.
• Biochars are dominated with 20-nm pores and high temperatures increased both smaller and larger than 50 nm pores.
• Lower WHC of rice husk biochar dominated with higher hydrophobic composition of BTX and PAH than other biochars.

Biochar conversion of sugarcane and rice harvest residues provides an alternative for managing these crop residues that are traditionally burned in open field. Sugarcane leaves, bagasse, rice straw and husk were converted to biochar at four pyrolysis temperatures (PTs) of 450 °C, 550 °C, 650 °C, and 750 °C and evaluated for various elemental, molecular and surface properties. The carbon content of biochars was highest for those produced at 650–750 °C. Biochars produced at 550 °C showed the characteristics of biochar that are commonly interpreted as being stable in soil, with low H/C and O/C ratios and pyrolysis fingerprints dominated by aromatic and polyaromatic hydrocarbons. At 550 °C, all biochars also exhibited maximum CEC values with sugarcane leaves biochar (SLB) > sugarcane bagasse biochar (SBB) > rice straw biochar (RSB) > rice husk biochar (RHB). The pore size distribution of biochars was dominated by pores of 20 nm and high PT increased both smaller and larger than 50 nm pores. Water holding capacity of biochars increased with PT but the magnitude of the increase was limited by feedstock types, likely related to the hydrophobicity of biochars as evident by molecular composition, besides pore volume properties of biochars. Py-GC/MS analysis revealed a clear destruction of lignin with decarboxylation and demethoxylation at 450 °C and dehydroxylation at above 550 °C. Overall, biochar molecular compositions became similar as PT increased, and the biochars produced at 550 °C demonstrated characteristics that have potential benefit as soil amendment for improving both C sequestration and nutrient dynamics.