Mingqiang Huang

Experimental study of particulate products for aging of 1,3,5–trimethylbenzene secondary organic aerosol

Secondary organic aerosol (SOA) from the photooxidation of aromatic compounds is a very complex mixture containing products with a different chemical nature that are dependent on aging processes. In this study, we focus on the chemical characterization of major products that are formed from the OH–initiated oxidation of 1,3,5–trimethylbenzene and subsequent aging through OH–initiated reactions in the presence of NOx.The chemical composition of aged particles were measured in real–time by an aerosol laser time of flight mass spectrometer (ALTOFMS) coupled with Fuzzy C–Means (FCM) clustering algorithm. Experimental results demonstrated that methyl glyoxylic acid, 2–methyl–4–oxo–2–pentenoic acid, 3,5–dimethylbenzoic acid, 2–methyl–2,3–dihydroxyl–4–oxo–pentanoic acid, dimethyl–nitrophenol, 3,4–dimethyl–2–hydroxy–3–oxo–pentandioic acid, 2,4–dimethyl–2,3–dihydroxy–6–oxo–4–heptenoic acid, 2,4–dimethyl–4–hydroxy–2,3–epoxy– heptylic acid, 2,4–dimethyl–2,3,4–trihydroxy–5,6–dioxo–heptylic acid, and oligomer components were the predominant products in the aging particles. The possible reaction mechanisms leading to these aged products were also discussed and proposed.

Chemical analysis of aged benzene secondary organic aerosol using aerosol laser time-of-flight mass spectrometer

Secondary organic aerosol (SOA) from the photooxidation of aromatic compounds is a very complex mixture containing products with a different chemical nature that are dependent on aging processes. Aging of SOA particles formed from OH-initiated oxidation of benzene was investigated in a home-made smog chamber in this study. The chemical composition of aged benzene SOA particles were measured using aerosol laser time-of-flight mass spectrometer (ALTOFMS) coupled with Fuzzy C-Means (FCM) clustering algorithm. Experimental results showed that nitrophenol, dinitrophenol, nitrocatechol, dinitrocatechol, 6-oxo-2,4-hexadienoic acid, 2,4-hexadiendioic acid, 2,3-dihydroxy-6-oxo-4-hexenoic acid, 2,3-epoxy-4-hexendioic acid, 2,3-epoxy-4,5-dihydroxy-hexanedioic acid and high-molecular-weight (HMW) components were the predominant products in the aged particles. Compared to offline method such as liquid chromatography mass spectrometry (LC-MS) measurement, the real-time ALTOFMS detection approach coupled with the FCM data processing algorithm can make cluster analysis of SOA successfully and provide more information of products. The present results also indicate that benzene SOA aging proceeds through the oxidation of the internal double bond of ring-opened products, phenolic compounds, and acid-catalyzed heterogeneous reactions of carbonyl products. The possible reaction mechanisms leading to these aged products were also discussed and proposed.

Mass spectrometric study of aged benzene secondary organic aerosol in the presence of dry ammonium sulfate

Inorganic seed particles have relatively large surface area, and play an important role in the formation and aging of secondary organic aerosol (SOA). The effects of dry (NH4)2SO4 which is the most commonly found in urban atmosphere on the aged benzene SOA were qualitatively studied utilizing aerosol laser time-of-flight mass spectrometer (ALTOFMS) coupled with Fuzzy C-Means (FCM) clustering algorithm in this study. Experimental results indicated that nitrophenol, oxocarboxylic acid, epoxide products are the predominant components in the aged benzene SOA in the presence of low concentration (about 10xa0μgxa0m−3) of dry (NH4)2SO4. These aged products are the same as the previously obtained aged benzene SOA without (NH4)2SO4 seed aerosol, indicating that low concentration of dry (NH4)2SO4 acts just as the nucleation or condensation center of the SOA, and do not affect the chemical composition of SOA. However, 1xa0H-imidazole, 1xa0H-imidazole-2-carbaldehyde, hydrated 1xa0H-imidazole-2-carbaldehyde, 2,2′-biimidazole, hydrated N-glyoxal substituted 1xa0H-imidazole, N-glyoxal substituted hydrated 1xa0H-imidazole-2- carbaldehyde, hydrated mono glyoxal substituted hydrated 1xa0H-imidazole-2-carboxaldehyde, mono glyoxal substituted 2,2-biimidazole and hydrated glyoxal dimer substituted imidazole which are formed from ammonium ion reaction with glyoxal are the major particulate products in the aged benzene SOA in the presence of high concentration (about 100xa0μgxa0m−3) of dry (NH4)2SO4. The retention of water on the dry (NH4)2SO4 particles creates ammonium ion, which can promote the formation of high-molecular-weight (HMW) products through multiphase reactions such as hydration and polymerization of aldehydes form from OH-initiated oxidation of benzene.

Characterization of brown carbon constituents of benzene secondary organic aerosol aged with ammonia

Nitrogen-containing organic compounds (NOC) formed from secondary organic aerosols (SOA) age via reaction with reduced nitrogen species are a vital class of brown carbon compounds. NOC compounds from ammonia (NH3) gas-aging of benzene SOA were investigated in present study, and the experiments were performed by irradiating benzene/CH3ONO/NO/NH3 air mixtures in a home-made smog chamber. The particulate NOC products of aged benzene SOA in the presence of NH3 were measured by UV-Vis spectrophotometer, attenuated total reflectance-Fourier transform infrared (ATR-FTIR), and aerosol laser time-of-flight mass spectrometer (ALTOFMS) coupled with Fuzzy C-Means (FCM) clustering algorithm, respectively. Experimental results demonstrated that NH3 has significant promotion effect on benzene SOA formation. Organic ammonium salts, such as ammonium glyoxylate, ammonium 6-oxo-2,4-hexadienoiclate, which are formed from NH3 reactions with gaseous organic acids were detected as the major particulate NOC products of NH3-aged benzene SOA. 1H–imidazole, 1H–imidazole-2-carbaldehyde and other imidazole products via the heterogeneous reactions between NH3 and dialdehydes of benzene SOA were successfully detected as important brown carbon constituents. The formation of imidazole products suggests that some ambient particles contained organonitrogen compounds may be come from this mechanism. The results of this study may provide valuable information for discussing NH3 deposition and SOA aging mechanisms.

Characterization of particulate products for aging of ethylbenzene secondary organic aerosol in the presence of ammonium sulfate seed aerosol

Aging of secondary organic aerosol (SOA) particles formed from OH- initiated oxidation of ethylbenzene in the presence of high mass (100-300μg/m(3)) concentrations of (NH4)2SO4 seed aerosol was investigated in a home-made smog chamber in this study. The chemical composition of aged ethylbenzene SOA particles was measured using an aerosol laser time-of-flight mass spectrometer (ALTOFMS) coupled with a Fuzzy C-Means (FCM) clustering algorithm. Experimental results showed that nitrophenol, ethyl-nitrophenol, 2,4-dinitrophenol, methyl glyoxylic acid, 5-ethyl-6-oxo-2,4-hexadienoic acid, 2-ethyl-2,4-hexadiendioic acid, 2,3-dihydroxy-5-ethyl-6-oxo-4-hexenoic acid, 1H-imidazole, hydrated N-glyoxal substituted 1H-imidazole, hydrated glyoxal dimer substituted imidazole, 1H-imidazole-2-carbaldehyde, N-glyoxal substituted hydrated 1H-imidazole-2-carbaldehyde and high-molecular-weight (HMW) components were the predominant products in the aged particles. Compared to the previous aromatic SOA aging studies, imidazole compounds, which can absorb solar radiation effectively, were newly detected in aged ethylbenzene SOA in the presence of high concentrations of (NH4)2SO4 seed aerosol. These findings provide new information for discussing aromatic SOA aging mechanisms.