Molecular Characterization of Water-Soluble Humic like Substances in Smoke Particles Emitted from Combustion of Biomass Materials and Coal Using Ultrahigh-Resolution Electrospray Ionization Fourier Transform Ion Cyclotron Resonance Mass Spectrometry

Abstract

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.

Composition and mass size distribution of nitrated and oxygenated aromatic compounds in ambient particulate matter from southern and central Europe – implications for the origin

“…Some of the OPAHs with a single O atom, namely OBAT, BaOFLN, and BbOFLN, originate from primary sources (i.e. combustion of fossil fuels and biomass; Albinet et al, 2007;Karavalakis et al, 2010;Shen et al, 2013b;Souza et al, 2014;Huang et al, 2014;Tomaz et al, 2016;Vicente et al, 2016), whereas some quinones, such as 9,10-O 2 ANT and 1,2-O 2 BAA, are associated with both primary and secondary sources (Kojima et al, 2010;Souza et al, 2014;Lin et al, 2015;Zhuo et al, 2017). The presence of 3-NFLT and 1-NPYR at TK indicates the influence of primary sources at that site (Bandowe and Meusel, 2017); notably, these two NPAHs were not found in MZ samples.…”

“…Some NPAHs have distinct sources; for instance, 3nitrofluoranthene (3-NFLT) and 1-nitropyrene (1-NPYR) are specifically associated with combustion sources, whereas 2nitrofluoranthene (2-NFLT) and 2-nitropyrene (2-NPYR) are produced through the oxidation of their parent species in the atmosphere (Bandowe and Meusel, 2017). Similarly, OPAHs benzanthrone (OBAT), benz(a)fluorenone (BaOFLN), and benz(b)fluorenone (BbOFLN) have been associated with primary sources, whereas 9,10-anthraquinone (9,10-O 2 ANT), 1,2-benzanthraquinone (1,2-O 2 BAA), and 9-fluorenone (9-OFLN) have been attributed to both source types (Kojima et al, 2010;Souza et al, 2014;Lin et al, 2015;Zhuo et al, 2017). The primary sources dominate in wintertime with residential heating surpassing traffic emission (Lin et al, 2015).…”

Molecular characterization of organic aerosol in the Himalayas: insight from ultra-high-resolution mass spectrometry

“…Considering the high influence of biomass burning emission in the Himalayas (X. , the CHON compounds in our study were probably related to biomass burning emissions. Recent studies have proven that burning of mixed biomass fuels in Nepal could emit amounts of nitrogen species such as NH 3 , NO x , HCN, benzene, and organics, and the emission factors for these species are higher than for wood (Stockwell et al, 2016;Jayarathne et al, 2018). In addition, it is likely that smoldering burning of bio-fuels in high elevation areas is also re- sponsible for the presence of many nitrogen-containing compounds in BBOA .…”

“…Many studies show that biomass burning is an important source of brown carbon (e.g., Saleh et al, 2014;Washenfelder et al, 2015), which is very common in developing regions in the southern Himalayas. In comparison with other regions, high elevation and mixed biomass fuels in the southern Himalayas could make the evolution and chemical composition of OA from biomass burning emission more complicated (Stockwell et al, 2016;Fleming et al, 2018;Jayarathne et al, 2018).…”

Molecular Absorption and Evolution Mechanisms of PM2.5Brown Carbon Revealed by Electrospray Ionization Fourier Transform–Ion Cyclotron Resonance Mass Spectrometry During a Severe Winter Pollution Episode in Xi'an, China

“…ESI is a soft ionization technique that ionizes intact chemical species through multiple charging and capable of analyzing both small and large molecules of various polarities in a complex mixture (Banerjee & Mazumdar, 2012). Negative ESI‐FT‐ICR MS was applied to characterize molecules in ambient aerosols and smoke particles (Brege et al, 2018; Jiang et al, 2016; Mazzoleni et al, 2012; Song et al, 2018, Zhang et al, 2018). However, direct applications of ESI FT–ICR MS on studying BrC optical properties, such as exploring the relationship between absorption and molecules, are still very limited (Laskin et al, 2018; Li et al, 2019).…”