Implications of Pyrolytic Gas Dynamic Evolution on Dissolved Black Carbon Formed During Production of Biochar from Nitrogen-Rich Feedstock.

Gases and dissolved black carbon (DBC) formed during pyrolysis of nitrogen-rich feedstock would affect atmospheric and aquatic environments. Yet, the mechanisms driving biomass gas evolution and DBC formation are poorly understood. Using thermogravimetric-Fourier transform infrared spectrometry and two-dimensional correlation spectroscopy, we correlated the temperature-dependent primary noncondensable gas release sequence (HO → CO → HCN, NH → CH → CO) with specific defunctionalization stages in the order: dehydration, decarboxylation, denitrogenation, demethylation, and decarbonylation. Our results revealed that proteins in feedstock mainly contributed to gas releases, and low-volatile pyrolytic products contributed to DBC. Combining mass difference analysis with Fourier transform ion cyclotron resonance mass spectrometry, we showed that 44-60% of DBC molecular compositions were correlated with primary gas-releasing reactions. Dehydration (-HO), with lower reaction energy barrier, contributed to DBC formation most at 350 and 450 °C, whereas decarboxylation (-CO) and deamidization (-HCNO) prevailed in contributing to DBC formation at 550 °C. The aromaticity changes of DBC products formed via gas emissions were deduced. Compared to their precursors, dehydration increased DBC aromaticity, while deamidization reduced the aromaticity of DBC products. These insights on pyrolytic byproducts help predict and tune DBC properties via changing gas formed during biochar production, minimizing their negative environmental impacts.