Distribution, chemical, and molecular composition of high and low molecular weight humic-like substances in ambient aerosols

Abstract

Abstract. Humic-like substances (HULIS) encompass a continuum of molecular weight (MW) ranges, yet our understanding of how HULIS characteristics vary with MW is still limited and not well established. In this study, a combination of ultrafiltration and solid-phase extraction protocols was employed to fractionate the high MW (HMW; > 1 kDa) and low MW (LMW; < 1 kDa) HULIS fractions from ambient aerosols collected during summer and winter at a rural site. Subsequently, comprehensive characterization using total organic carbon, high-performance size exclusion chromatography (HPSEC), UV-visible (UV-vis) and fluorescence spectroscopy, Fourier transform infrared spectroscopy (FTIR), and negative electrospray ionization high-resolution mass spectrometry (ESI–HRMS) were conducted. The results revealed that HMW HULIS were dominated by larger-sized chromophores, substantially constituting a higher fraction of total organic carbon and UV absorption at 254 nm than LMW HULIS. While both HMW and LMW HULIS shared similar fluorophore types and functional groups, the former exhibited higher levels of humification and a greater presence of polar functional groups (e.g., −COOH; > C=O). HRMS analysis further unveiled that molecular formulas within HMW HULIS generally featured smaller sizes but higher degrees of unsaturation and aromaticity compared to those within LMW HULIS fractions. This observation suggests the possibility of small molecules assembling to form the HMW HULIS through intermolecular weak forces. Moreover, HMW HULIS contained a higher proportion of CHON but fewer CHO compounds than LMW HULIS. In both HMW and LMW HULIS, the unique molecular formulas were primarily characterized by lignin-like species, yet the former displayed a prevalence of N-enriched and highly aromatic species. Additionally, HMW HULIS contained more unique lipid-like compounds, while LMW HULIS exhibited a distinct presence of tannin-like compounds. These findings provide valuable insights into the distribution, optical properties, and molecular-level characteristics of HULIS in atmospheric aerosols, thereby advancing our understanding of their sources, composition, and environmental implications.