Abstract. Humic-like substances (HULIS) in smoke fine particulate matter (PM 2.5 ) emitted from the combustion of biomass materials (rice straw, corn straw, and pine branch) and fossil fuels (lignite coal and diesel fuel) were comprehensively studied in this work. The HULIS fractions were first isolated with a one-step solid-phase extraction method, and were then investigated with a series of analytical techniques: elemental analysis, total organic carbon analysis, UV-vis (ultraviolet-visible) spectroscopy, excitationemission matrix (EEM) fluorescence spectroscopy, Fourier transform infrared spectroscopy, and 1 H-nuclear magnetic resonance spectroscopy. The results show that HULIS account for 11.2-23.4 and 5.3 % of PM 2.5 emitted from biomass burning (BB) and coal combustion, respectively. In addition, contributions of HULIS-C to total carbon and water-soluble carbon in smoke PM 2.5 emitted from BB are 8.0-21.7 and 56.9-66.1 %, respectively. The corresponding contributions in smoke PM 2.5 from coal combustion are 5.2 and 45.5 %, respectively. These results suggest that BB and coal combustion are both important sources of HULIS in atmospheric aerosols. However, HULIS in diesel soot only accounted for ∼ 0.8 % of the soot particles, suggesting that vehicular exhaust may not be a significant primary source of HULIS. Primary HULIS and atmospheric HULIS display many similar chemical characteristics, as indicated by the instrumental analytical characterization, while some distinct features were also apparent. A high spectral absorbance in the UV-vis spectra, a distinct band at λ ex /λ em ≈ 280/350 nm in EEM spectra, lower H / C and O / C molar ratios, and a high content of [Ar-H] were observed for primary HULIS. These results suggest that primary HULIS contain more aromatic structures, and have a lower content of aliphatic and oxygen-containing groups than atmospheric HULIS. Among the four primary sources of HULIS, HULIS from BB had the highest O / C molar ratios (0.43-0.54) and [H-C-O] content (10-19 %), indicating that HULIS from this source mainly consisted of carbohydrate-and phenolic-like structures. HULIS from coal combustion had a lower O / C molar ratio (0.27) and a higher content of [Ar-H] (31 %), suggesting that aromatic compounds were extremely abundant in HULIS from this source. Moreover, the absorption Ångström exponents of primary HULIS from BB and coal combustion were 6.7-8.2 and 13.6, respectively. The mass absorption efficiencies of primary HULIS from BB and coal combustion at 365 nm (MAE 365 ) were 0.97-2.09 and 0.63 m 2 gC −1 , respectively. Noticeably higher MAE 365 values for primary HULIS from BB than coal combustion indicate that the former has a stronger contribution to the light-absorbing properties of aerosols in the atmospheric environment.

Water-soluble humic like substances (HULIS) in smoke particles emitted from combustion of biomass materials and coal were characterized by ultrahigh-resolution Fourier transform ion cyclotron resonance mass spectrometry. The formulas identified were classified into four main groups: CHO, CHON, CHOS, and CHONS. The average H/C and O/C ratios are 1.13-1.33, 1.01-1.13, 1.26-1.48, 1.09-1.24 and 0.21-0.41, 0.27-0.45, 0.41-0.46, 0.44-0.61 for the CHO, CHON, CHOS, and CHONS groups, respectively. The CHO compound was the predominant component (43%-72%) of the smoke HULIS from biomass burning (BB) and coal combustion, followed by the CHON group for BB-smoke HULIS and the S-containing groups (i.e., CHOS and CHONS) for coal-smoke HULIS. These results indicate that the primary HULIS emitted from biomass burning contain a high abundance of CHON species, which appear to be made up mainly of oxidized nitrogen functional groups such as nitro compounds and/or organonitrates. The coal-smoke HULIS contained more compounds with relatively low molecular weight and high aromaticity index (AI). They were significantly enriched in S-containing compounds with high double bond equivalent (≥4), and O/S ratios suggest that they are most likely made up of aromatic organosulfates and nitrooxy organosulfates that are usually found in polluted atmospheres. These findings imply that the primary emissions from combustion of biomass and coal fuels are potential sources of water-soluble HULIS in an atmospheric matrix and that coal combustion is an especially important source of sulfate compounds.