Molecular characterization of nitrogen-containing organic compounds in fractionated atmospheric humic-like substances (HULIS) and its relationship with optical properties

Abstract

Diverse nitrogen-containing organics are important components of humic-like substances (HULIS) in the atmosphere. In this study, organic components in particulate matter (PM) samples representing multiple sources were separated by successive solvent fractionation, which were then analyzed by mass spectrometric and optical instruments. The CHON compounds were eluted and clustered into the Low-polar, Medium-polar, and High-polar fractions, and discrepancies of the polar-fractions were particularly reflected by molecular descriptors such as aromaticity, oxygen content and molecular weight. In addition, the results from the light-absorbing parameters (i.e., MAE₃₆₅ and SUVA₂₅₄) underscored the importance of the Low-polar and High-polar fractions on optical absorption properties. The Low-polar fraction accounted for 40% of the cumulative SUVA₂₅₄ values, suggesting significant content of ultraviolet-absorbing organics. The High-polar fraction contributed 52% of the cumulative MAE₃₆₅ values, indicating abundant light absorption capacity and efficiency. Significant improvements were made on statistical analysis of multidimensional data by a combination of the molecular descriptors and optical parameters. Molecular structures, including condensed aromatic, lignin-like, and aliphatic compounds observed in distinct electrospray ionization modes, were found as main contributors to the light absorption capacity and the abundances of fluorophores in individual polar-fractions. Differential contributions of molecular characteristics on types and abundances of fluorophores were further found among the samples of multiple sources. Conclusions obtained from this successive solvent fractionation experiment could promote development of the pretreatment method for exploring the potential light-absorbing organics, which also provide insights into the emission sources of organics that are related to specific light absorption and fluorescence properties.

Keywords: Fractionation; HULIS; Nitrogen-containing organic compounds; Optical properties; Particulate matter.