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

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 (Cu) and nickel (Ni) 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 Cu (∼11 times) and Ni (∼5 times) compared with the forest fire chars. Both cross-polarization (CPMAS-NMR) and Bloch decay (BDMAS-NMR) C 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 Cu and Ni 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 Cu and Ni in contaminated lands.