Molecular Characterization of Nitrogen-Containing Compounds in Humic-like Substances Emitted from Biomass Burning and Coal Combustion

Abstract

N-containing organic compounds (NOCs) in humic-like substances (HULIS) emitted from biomass burning (BB) and coal combustion (CC) were characterized by ultrahigh-resolution mass spectrometry in the positive electrospray ionization mode. Our results indicate that NOCs include CHON+ and CHN+ groups, which are detected as a substantial fraction in both BB- and CC-derived HULIS, and suggest that not only BB but also CC is the potential important source of NOCs in the atmosphere. The CHON+ compounds mainly consist of reduced nitrogen compounds with other oxygenated functional groups, and straw- and coal-smoke HULIS exhibit a lower degree of oxidation than pine-smoke HULIS. In addition, the NOCs with higher N atoms (N₂ and/or N₃) generally bear higher modified aromaticity index (AI_mod) values and are mainly contained in BB HULIS, especially in straw-smoke HULIS, whereas the NOCs with a lower N atom (N₁) always have relatively lower AI_mod values and are the dominant NOCs in CC HULIS. These findings imply that the primary emission from CC may be a significant source of N₁ compounds, whereas high N number (e.g., N_2-3) compounds could be associated with burning of biomass materials. Further study is warranted to distinguish the NOCs from more sources.