Role of oxygen-containing functional groups in forest fire-generated and pyrolytic chars for immobilization of copper...

Char as a carbon-rich material, can be produced under pyrolytic conditions, wildfires or prescribed burn offs for fire management. The objective of this study was to elucidate mechanistic interactions of copper (Cu²⁺) and nickel (Ni²⁺) with different chars produced by pyrolysis (green waste, GW; blue-Mallee, BM) and forest fires (fresh-burnt by prescribed fire, FC; aged char produced by wild fire, AC). The pyrolytic chars were more effective sorbents of Cu²⁺ (∼11 times) and Ni²⁺ (∼5 times) compared with the forest fire chars. Both cross-polarization (CPMAS-NMR) and Bloch decay (BDMAS-NMR) ¹³C NMR spectroscopies showed that forest fire chars have higher woody components (aromatic functional groups) and lower polar groups (e.g. O-alkyl C) compared with the pyrolytic chars. The polarity index was greater in the pyrolytic chars (0.99-1.34) than in the fire-generated chars (0.98-1.15), while aromaticity was lower in the former than in the latter. Fourier transform infrared (FTIR) and Raman spectroscopies indicated the binding of carbonate and phosphate with both Cu²⁺ and Ni²⁺ in all chars, but with a greater extent in pyrolytic than forest fire-generated chars. These findings have demonstrated the key role of char's oxygen-containing functional groups in determining their sorption capacity for the Cu²⁺ and Ni²⁺ in contaminated lands.