scholarly journals Direct contribution of ammonia to <i>α</i>-pinene secondary organic aerosol formation

2020 ◽  
Vol 20 (22) ◽  
pp. 14393-14405
Author(s):  
Liqing Hao ◽  
Eetu Kari ◽  
Ari Leskinen ◽  
Douglas R. Worsnop ◽  
Annele Virtanen
Keyword(s):  
Chemical Composition ◽  
High Resolution ◽  
Organic Acids ◽  
Gas Phase ◽  
Mass Spectrometer ◽  
Mass Concentration ◽  
Organic Aerosol ◽  
Particle Phase ◽  
Resolution Time ◽  
Aerosol Mass

Abstract. Ammonia (NH3), a gaseous compound ubiquitously present in the atmosphere, is involved in the formation of secondary organic aerosol (SOA), but the exact mechanism is still not well known. This study presents the results of SOA experiments from the photooxidation of α-pinene in the presence of NH3 in the reaction chamber. SOA was formed in in nucleation experiments and in seeded experiments with ammonium sulfate particles as seeds. The chemical composition and time series of compounds in the gas and particle phase were characterized by an online high-resolution time-of-flight proton-transfer-reaction mass spectrometer (HR-ToF-PTRMS) and a high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS), respectively. Our results show that the mass concentration of ammonium (NH4+) was still rising even after the mass concentration of the organic component started to decrease due to aerosol wall deposition and evaporation, implying the continuous new formation of particle-phase ammonium in the process. Stoichiometric neutralization analysis of aerosol indicates that organic acids have a central role in the formation of particle-phase ammonium. Our measurements show a good correlation between the gas-phase organic mono- and dicarboxylic acids formed in the photooxidation of α-pinene and the ammonium in the particle phase, thus highlighting the contribution of gas-phase organic acids to the ammonium formation. The work shows that the gas-phase organic acids contribute to the SOA formation by forming organic ammonium salts through acid–base reaction. The changes in aerosol mass, particle size and chemical composition resulting from the NH3–SOA interaction can potentially alter the aerosol direct and indirect forcing and therefore alter its impact on climate change.

scholarly journals Direct contribution of ammonia to CCN-size alpha-pinene secondary organic aerosol formation

2020 ◽  
Author(s):  
Liqing Hao ◽  
Eetu Kari ◽  
Ari Leskinen ◽  
Douglas R. Worsnop ◽  
Annele Virtanen
Keyword(s):  
Chemical Composition ◽  
High Resolution ◽  
Organic Acids ◽  
Gas Phase ◽  
Mass Spectrometer ◽  
Mass Concentration ◽  
Organic Aerosol ◽  
Particle Phase ◽  
Resolution Time ◽  
Aerosol Mass

Abstract. Ammonia (NH3), a gasous compound ubiquitiously present in the atmosphere, is involved in the formation of secondary organic aerosol (SOA), but the exact mechanisum is still not well known. This study presents the results of SOA experiments from the photooxidation of α-pinene in the presence of NH3 in the reaction chamber. SOA was formed in nucleation experiment and in seeded experiment with ammonium sulfate particles as seeds. The chemical composition and time-series of compounds in the gas- and particle- phase were characterized by an on-line high-resolution time-of-flight proton transfer reaction mass spectrometer (HR-ToF-PTRMS) and a high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS), respectively. Our results show that for the aerosol particles in cloud condensation nuclei (CCN) size, the mass concentration of ammonium (NH4+) was still rising even after the mass concentration of organic component started to decrease due to aerosol wall deposition and evaporation, implying the continuous new formation of particle phase ammonium in the process. Stoichiometric neutralization analysis of aerosol indicates that organic acids have a central role in the formation of particle phase ammonium. Our measurements show a good correlation between the gas phase organic mono- and di-carboxylic acids formed in the photooxidation of α-pinene and the ammonium in the particle phase, thus highlighting the contribution of gas-phase organic acids to the ammonium formation in the CCN-size SOA particles. The work shows that the gas-phase organic acids contribute to the SOA formation by forming ammonium salts through acid-base reaction. The changes in aerosol mass, particle size and chemical composition resulting from the NH3-SOA interaction can potentially alter the aerosol direct and indirect forcing and therefore alter its impact on climate change.

scholarly journals Chemical characterization of oxygenated organic compounds in the gas phase and particle phase using iodide CIMS with FIGAERO in urban air

2021 ◽  
Vol 21 (11) ◽  
pp. 8455-8478
Author(s):  
Chenshuo Ye ◽  
Bin Yuan ◽  
Yi Lin ◽  
Zelong Wang ◽  
Weiwei Hu ◽  
...  
Keyword(s):  
Organic Acids ◽  
Gas Phase ◽  
Organic Compounds ◽  
Mass Spectrometer ◽  
Organic Aerosol ◽  
Urban Site ◽  
Organic Nitrates ◽  
Particle Phase ◽  
Aerosol Mass

Abstract. The atmospheric processes under polluted environments involving interactions of anthropogenic pollutants and natural emissions lead to the formation of various and complex secondary products. Therefore, the characterization of oxygenated organic compounds in urban areas remains a pivotal issue in our understanding of the evolution of organic carbon. Here, we describe measurements of an iodide chemical ionization time-of-flight mass spectrometer installed with a Filter Inlet for Gases and AEROsols (FIGAERO-I-CIMS) in both the gas phase and the particle phase at an urban site in Guangzhou, a typical megacity in southern China, during the autumn of 2018. Abundant oxygenated organic compounds containing two to five oxygen atoms were observed, including organic acids, multi-functional organic compounds typically emitted from biomass burning, oxidation products of biogenic hydrocarbons and aromatics. Photochemistry played dominant roles in the formation of gaseous organic acids and isoprene-derived organic nitrates, while nighttime chemistry contributed significantly to the formation of monoterpene-derived organic nitrates and inorganics. Nitrogen-containing organic compounds occupied a significant fraction of the total signal in both the gas and particle phases, with elevated fractions at higher molecular weights. Measurements of organic compounds in the particle phase by FIGAERO-I-CIMS explained 24 ± 0.8 % of the total organic aerosol mass measured by aerosol mass spectrometer (AMS), and the fraction increased for more aged organic aerosol. The systematical interpretation of mass spectra of the FIGAERO-I-CIMS in the urban area of Guangzhou provides a holistic view of numerous oxygenated organic compounds in the urban atmosphere, which can serve as a reference for the future field measurements by FIGAERO-I-CIMS in polluted urban regions.

scholarly journals Chemical characterization of oxygenated organic compounds in gas-phase and particle-phase using iodide-CIMS with FIGAERO in urban air

2020 ◽  
Author(s):  
Chenshuo Ye ◽  
Bin Yuan ◽  
Yi Lin ◽  
Zelong Wang ◽  
Weiwei Hu ◽  
...  
Keyword(s):  
Organic Acids ◽  
Gas Phase ◽  
Organic Compounds ◽  
Mass Spectrometer ◽  
Organic Aerosol ◽  
Urban Site ◽  
Organic Nitrates ◽  
Particle Phase ◽  
Aerosol Mass

Abstract. The characterization of oxygenated organic compounds in urban areas remains a pivotal gap in our understanding of the evolution of organic carbon under polluted environments, as the atmospheric processes involving interactions between organics and inorganics, anthropogenic pollutants and natural emissions lead to formation of various and complex secondary products. Here, we describe measurements of an iodide chemical ionization time-of-flight mass spectrometer installed with a Filter Inlet for Gases and AEROsols (FIGAERO-I-CIMS) in both gas-phase and particle-phase at an urban site in Guangzhou, a typical mega-city in southern China, during the autumn of 2018. Abundant oxygenated organic compounds containing 2~5 oxygen atoms were observed, including organic acids, multi-functional organics typically emitted form biomass burning, oxidation products of biogenic hydrocarbons and aromatics. Photochemistry played dominant roles in the formation of gaseous organic acids and isoprene-derived organic nitrates, while nighttime chemistry contributed significantly to the formation monoterpene-derived organic nitrates and inorganics. Nitrogen-containing organic compounds occupied a significant fraction of the total signal in both gas and particle phases, with elevated fractions at higher molecular weights. Measurements of organic compounds in particle phase by FIGAERO-I-CIMS explained 24 % of the total organic aerosol mass measured by aerosol mass spectrometer (AMS), and the fraction increased for more aged organic aerosol. The systematically interpretation of mass spectra of the FIGAERO-I-CIMS in urban of Guangzhou provides a holistic view of numerous oxygenated organic compounds in the urban atmosphere, which can serve as a reference for the future field measurements by FIGAERO-I-CIMS in polluted urban regions.

scholarly journals Investigations of primary and secondary particulate matter of different wood combustion appliances with a high-resolution time-of-flight aerosol mass spectrometer

2011 ◽  
Vol 11 (12) ◽  
pp. 5945-5957 ◽  
Author(s):  
M. F. Heringa ◽  
P. F. DeCarlo ◽  
R. Chirico ◽  
T. Tritscher ◽  
J. Dommen ◽  
...  
Keyword(s):  
High Resolution ◽  
Mass Spectrometer ◽  
Organic Aerosol ◽  
Smog Chamber ◽  
Resolution Time ◽  
Aerosol Mass Spectrometer ◽  
Aerosol Mass ◽  
Wood Burning ◽  
Primary Emissions ◽  
Stable Burning

Abstract. A series of photo-oxidation smog chamber experiments were performed to investigate the primary emissions and secondary aerosol formation from two different log wood burners and a residential pellet burner under different burning conditions: starting and flaming phase. Emissions were sampled from the chimney and injected into the smog chamber leading to primary organic aerosol (POA) concentrations comparable to ambient levels. The composition of the aerosol was measured by an Aerodyne high resolution time-of-flight aerosol mass spectrometer (HR-TOF-AMS) and black carbon (BC) instrumentation. The primary emissions were then exposed to xenon light to initiate photo-chemistry and subsequent secondary organic aerosol (SOA) production. After correcting for wall losses, the average increase in organic matter (OM) concentrations by SOA formation for the starting and flaming phase experiments with the two log wood burners was found to be a factor of 4.1±1.4 after five hours of aging. No SOA formation was observed for the stable burning phase of the pellet burner. The startup emissions of the pellet burner showed an increase in OM concentration by a factor of 3.3. Including the measured SOA formation potential, average emission factors of BC+POA+SOA, calculated from CO2 emission, were found to be in the range of 0.04 to 3.9 g/kg wood for the stable burning pellet burner and an old log wood burner during startup respectively. SOA contributed significantly to the ion C2H4O2+ at mass to charge ratio m/z 60, a commonly used marker for primary emissions of wood burning. This contribution at m/z 60 can overcompensate for the degradation of levoglucosan leading to an overestimation of the contribution of wood burning or biomass burning to the total OM. The primary organic emissions from the three different burners showed a wide range in O:C atomic ratio (0.19−0.60) for the starting and flaming conditions, which also increased during aging. Primary wood burning emissions have a rather low relative contribution at m/z 43 (f 43) to the total organic mass spectrum. The non-oxidized fragment C3H7+ has a considerable contribution at m/z 43 for the fresh OA with an increasing contribution of the oxygenated ion C2H3O+ during aging. After five hours of aging, the OA has a rather low C2H3O+ signal for a given CO2+ fraction, possibly indicating a higher ratio of acid to non-acid oxygenated compounds in wood burning OA compared to other oxygenated organic aerosol (OOA).

scholarly journals Chemical characteristics of submicron particles at the central Tibetan Plateau: insights from aerosol mass spectrometry

2018 ◽  
Vol 18 (1) ◽  
pp. 427-443 ◽  
Author(s):  
Jianzhong Xu ◽  
Qi Zhang ◽  
Jinsen Shi ◽  
Xinlei Ge ◽  
Conghui Xie ◽  
...  
Keyword(s):  
Chemical Composition ◽  
High Resolution ◽  
Tibetan Plateau ◽  
Mass Transport ◽  
Mass Concentration ◽  
Organic Aerosol ◽  
Early Morning ◽  
Monsoon Period ◽  
Air Mass ◽  
Aerosol Mass

Abstract. Recent studies have revealed a significant influx of anthropogenic aerosol from South Asia to the Himalayas and Tibetan Plateau (TP) during pre-monsoon period. In order to characterize the chemical composition, sources, and transport processes of aerosol in this area, we carried out a field study during June 2015 by deploying a suite of online instruments including an Aerodyne high-resolution time-of-flight aerosol mass spectrometer (HR-AMS) and a multi-angle absorption photometer (MAAP) at Nam Co station (90∘57′ E, 30∘46′ N; 4730 m a.s.l.) at the central of the TP. The measurements were made at a period when the transition from pre-monsoon to monsoon occurred. The average ambient mass concentration of submicron particulate matter (PM1) over the whole campaign was ∼ 2.0 µg m−3, with organics accounting for 68 %, followed by sulfate (15 %), black carbon (8 %), ammonium (7 %), and nitrate (2 %). Relatively higher aerosol mass concentration episodes were observed during the pre-monsoon period, whereas persistently low aerosol concentrations were observed during the monsoon period. However, the chemical composition of aerosol during the higher aerosol concentration episodes in the pre-monsoon season was on a case-by-case basis, depending on the prevailing meteorological conditions and air mass transport routes. Most of the chemical species exhibited significant diurnal variations with higher values occurring during afternoon and lower values during early morning, whereas nitrate peaked during early morning in association with higher relative humidity and lower air temperature. Organic aerosol (OA), with an oxygen-to-carbon ratio (O ∕ C) of 0.94, was more oxidized during the pre-monsoon period than during monsoon (average O ∕ C ratio of 0.72), and an average O ∕ C was 0.88 over the entire campaign period, suggesting overall highly oxygenated aerosol in the central TP. Positive matrix factorization of the high-resolution mass spectra of OA identified two oxygenated organic aerosol (OOA) factors: a less oxidized OOA (LO-OOA) and a more oxidized OOA (MO-OOA). The MO-OOA dominated during the pre-monsoon period, whereas LO-OOA dominated during monsoon. The sensitivity of air mass transport during pre-monsoon with synoptic process was also evaluated with a 3-D chemical transport model.

scholarly journals Seasonal characteristics of organic aerosol chemical composition and volatility in Stuttgart, Germany

2019 ◽  
Vol 19 (18) ◽  
pp. 11687-11700 ◽  
Author(s):  
Wei Huang ◽  
Harald Saathoff ◽  
Xiaoli Shen ◽  
Ramakrishna Ramisetty ◽  
Thomas Leisner ◽  
...  
Keyword(s):  
Chemical Composition ◽  
High Resolution ◽  
Organic Compounds ◽  
Mass Spectrometer ◽  
Time Of Flight ◽  
Organic Aerosol ◽  
Molecular Composition ◽  
Winter Period ◽  
Ionization Mass ◽  
Resolution Time

Abstract. The chemical composition and volatility of organic aerosol (OA) particles were investigated during July–August 2017 and February–March 2018 in the city of Stuttgart, one of the most polluted cities in Germany. Total non-refractory particle mass was measured with a high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS; hereafter AMS). Aerosol particles were collected on filters and analyzed in the laboratory with a filter inlet for gases and aerosols coupled to a high-resolution time-of-flight chemical ionization mass spectrometer (FIGAERO-HR-ToF-CIMS; hereafter CIMS), yielding the molecular composition of oxygenated OA (OOA) compounds. While the average organic mass loadings are lower in the summer period (5.1±3.2 µg m−3) than in the winter period (8.4±5.6 µg m−3), we find relatively larger mass contributions of organics measured by AMS in summer (68.8±13.4 %) compared to winter (34.8±9.5 %). CIMS mass spectra show OOA compounds in summer have O : C of 0.82±0.02 and are more influenced by biogenic emissions, while OOA compounds in winter have O : C of 0.89±0.06 and are more influenced by biomass burning emissions. Volatility parametrization analysis shows that OOA in winter is less volatile with higher contributions of low-volatility organic compounds (LVOCs) and extremely low-volatility organic compounds (ELVOCs). We partially explain this by the higher contributions of compounds with shorter carbon chain lengths and a higher number of oxygen atoms, i.e., higher O : C in winter. Organic compounds desorbing from the particles deposited on the filter samples also exhibit a shift of signal to higher desorption temperatures (i.e., lower apparent volatility) in winter. This is consistent with the relatively higher O : C in winter but may also be related to higher particle viscosity due to the higher contributions of larger-molecular-weight LVOCs and ELVOCs, interactions between different species and/or particles (particle matrix), and/or thermal decomposition of larger molecules. The results suggest that whereas lower temperature in winter may lead to increased partitioning of semi-volatile organic compounds (SVOCs) into the particle phase, this does not result in a higher overall volatility of OOA in winter and that the difference in sources and/or chemistry between the seasons plays a more important role. Our study provides insights into the seasonal variation of the molecular composition and volatility of ambient OA particles and into their potential sources.

scholarly journals Evaluating the degree of oxygenation of organic aerosol during foggy and hazy days in Hong Kong using high-resolution time-of-flight aerosol mass spectrometry (HR-ToF-AMS)

2013 ◽  
Vol 13 (2) ◽  
pp. 3533-3573 ◽  
Author(s):  
Y. J. Li ◽  
B. Y. L. Lee ◽  
J. Z. Yu ◽  
N. L. Ng ◽  
C. K. Chan
Keyword(s):  
Mass Spectrometry ◽  
Hong Kong ◽  
High Resolution ◽  
Time Of Flight ◽  
Organic Aerosol ◽  
Present Observation ◽  
Particle Phase ◽  
Resolution Time ◽  
Aerosol Mass ◽  
Aerosol Mass Spectrometry

Abstract. The chemical characteristics of organic aerosol (OA) are still poorly constrained. Here we present observation results of the degree of oxygenation of OA based on high-resolution time-of-flight aerosol mass spectrometry (HR-ToF-AMS) measurements made at a coastal site in Hong Kong from late April to the end of May in 2011. Two foggy periods and one hazy period were chosen for detailed analysis to compare the changes in the degree of oxygenation of OA due to different processes. The Extended Aerosol Inorganic Model (E-AIM) predicted a fine particle liquid water content (LWCfp) up to 85 μg m−3 during the foggy days. Particle concentration as measured by HR-ToF-AMS was up to 60 μg m−3 during the hazy days and up to 30 μg m−3 during the foggy days. The degree of oxygenation of OA, as indicated by several parameters including the fraction of m/z 44 in organic mass spectra (f44), the elemental ratio of oxygen to carbon (O : C), and the carbon oxidation state (OSc), was evaluated against the odd oxygen (Ox) concentration, LWCfp, ionic strength (IS), and in-situ pH (pHis). Results suggest that the high concentration of OA (on average 11 μg m−3) and the high degree of oxygenation (f44 = 0.15, O : C = 0.51, and OSc = −0.31) during the hazy period were mainly due to gas-phase oxidation. During the foggy periods with low photochemical activities, the degree of oxygenation of OA was almost as high as that on the hazy days and significantly higher than that during non-foggy/non-hazy days. However, the OA evolved quite differently in the two foggy periods. The first foggy period in late April saw a larger LWCfp and a lower Ox concentration and the OA was made up of ~ 20% semi-volatile oxygenated organic aerosol (SVOOA) as resolved by positive matrix factorization (PMF). In the second foggy period in mid-May, higher Ox concentration and lower LWCfp were observed, and the OA was found to contain >50% low-volatility oxygenated organic aerosols (LVOOA). An examination of the particle-phase constituents suggests that partitioning may have been the dominating process through which oxygenated species were incorporated into the particle phase during the first foggy period, while oxidation in the aqueous phase may have been the dominating process during the second foggy period. Both physical and chemical processes were found to be important for oxygenated OA formation.

scholarly journals Seasonal characteristics of organic aerosol chemical composition and volatility in Stuttgart, Germany

2019 ◽  
Author(s):  
Wei Huang ◽  
Harald Saathoff ◽  
Xiaoli Shen ◽  
Ramakrishna Ramisetty ◽  
Thomas Leisner ◽  
...  
Keyword(s):  
Chemical Composition ◽  
High Resolution ◽  
Volatile Organic Compounds ◽  
Organic Compounds ◽  
Mass Spectrometer ◽  
Time Of Flight ◽  
Organic Aerosol ◽  
Molecular Composition ◽  
Resolution Time ◽  
Volatile Organic

Abstract. Chemical composition and volatility of organic aerosol (OA) particles were investigated during July–August 2017 and February–March 2018 in the city of Stuttgart, one of the most polluted cities in Germany. Total non-refractory particle mass was measured with a high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS; hereafter AMS). Aerosol particles were collected on filters and analyzed in the laboratory with a filter inlet for gases and aerosols coupled to a high-resolution time-of-flight chemical ionization mass spectrometer (FIGAERO-HR-ToF-CIMS; hereafter CIMS), yielding the molecular composition of oxygenated OA (OOA) compounds. While the average organic mass loadings are lower in the summer period (5.1 ± 3.2 µg m−3) than in the winter period (8.4 ± 5.6 µg m−3), we find relatively larger mass contributions of organics measured by AMS in summer (68.8 ± 13.4 %) compared to winter (34.8 ± 9.5 %). CIMS mass spectra show OOA compounds in summer have O : C ratios of 0.82 ± 0.02 and are more influenced by biogenic emissions, while OOA compounds in winter have O : C ratios of 0.89 ± 0.06 and are more influenced by biomass burning emissions. Volatility parametrization analysis shows that OOA in winter is less volatile with higher contributions of low volatile organic compounds (LVOC) and extremely low volatile organic compounds (ELVOC). We partially explain this by the higher contributions of compounds with shorter carbon chain lengths and higher number of oxygen atoms, i.e. higher O : C ratios in winter. Organic compounds desorbing from the particles deposited on the filter samples also exhibit a shift of signal to higher desorption temperatures (i.e. lower apparent volatility) in winter. This is consistent with the relatively higher O : C ratios in winter, but may also be related to higher particle viscosity due to the higher contributions of larger molecular-weight LVOC and ELVOC, interactions between different species and/or particles (particle matrix), and/or thermal decomposition of larger molecules. The results suggest that whereas lower temperature in winter may lead to increased partitioning of semi-volatile organic compounds (SVOC) into the particle phase, this does not result in a higher overall volatility of OOA in winter, and that the difference in sources and/or chemistry between the seasons plays a more important role. Our study provides insights into the seasonal variation of molecular composition and volatility of ambient OA particles, and into their potential sources.

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