High-resolution Aerosol Mass Spectrometer Research Articles

Examination of the Influence of Alternative Fuels on Particulate Matter Properties Emitted from a Non-Proprietary Combustor

The aviation sector, like most other sectors, is moving towards becoming net zero. In the medium to long term, this will mean an increase in the use of sustainable aviation fuels. Research exists on the impact of fuel composition on non-volatile particulate matter (nvPM) emissions. However, there is more sparsity when considering the impact on volatile particulate matter (vPM) emissions. Here, nine different fuels were tested using an open-source design combustor rig. An aerosol mass spectrometer (AMS) was used to examine the mass-loading and composition of vPM, with a simple linear regression algorithm used to compare relative mass spectrum similarity. The diaromatic, cycloalkane and aromatic contents of the fuels were observed to correlate with the measured total number concentration and nvPM mass concentrations, resulting in an inverse correlation with increasing hydrogen content. The impacts of fuel properties on other physical properties within the combustion process and how they might impact the particulate matter (PM) are considered for future research. Unlike previous studies, fuel had a very limited impact on the organic aerosol’s composition at the combustor exit measurement location. Using a novel combination of Positive Matrix Factorization (PMF) and high-resolution AMS analysis, new insight has been provided into the organic composition. Both the alkane organic aerosol (AlkOA) and quenched organic aerosol (QOA) factors contained CnH2n+1, CnH2n−1 and CnH2n ion series, implying alkanes and alkenes in both, and approximately 12% oxygenated species in the QOA factor. These results highlight the emerging differences in the vPM compositional data observed between combustor rigs and full engines.

Enhancing characterization of organic nitrogen components in aerosols and droplets using high-resolution aerosol mass spectrometry

Abstract. This study aims to enhance the understanding and application of the Aerodyne high-resolution aerosol mass spectrometer (HR-AMS) for the comprehensive characterization of organic nitrogen (ON) compounds in aerosol particles and atmospheric droplets. To achieve this goal, we analyzed 75 N-containing organic compounds, representing a diverse range of ambient non-organonitrate ON (NOON) types, including amines, amides, amino acids, N heterocycles, protein, and humic acids. Our results show that NOON compounds can produce significant levels of NHx+ and NOx+ ion fragments, which are typically recognized as ions representative of inorganic nitrogen species. We also identified the presence of CH2N+ at m/z = 28.0187, an ion fragment rarely quantified in ambient datasets due to substantial interference from N2+. As a result, the utilization of an updated calibration factor of 0.79 is necessary for accurate NOON quantification via the HR-AMS. We also assessed the relative ionization efficiencies (RIEs) for various NOON species and found that the average RIE for NOON compounds (1.52 ± 0.58) aligns with the commonly used default value of 1.40 for organic aerosol. Moreover, through a careful examination of the HR-AMS mass spectral features of various NOON types, we propose fingerprint ion series that can aid the NOON speciation analysis. For instance, the presence of CnH2n+2N+ ions is closely linked with amines, with CH4N+ indicating primary amines, C2H6N+ suggesting secondary amines, and C3H8N+ representing tertiary amines. CnH2nNO+ ions (especially for n values of 1–4) are very likely derived from amides. The co-existence of three ions, C2H4NO2+, C2H3NO+, and CH4NO+, serves as an indicator for the presence of amino acids. Additionally, the presence of CxHyN2+ ions indicates the occurrence of 2N-heterocyclic compounds. Notably, an elevated abundance of NH4+ is a distinct signature for amines and amino acids, as inorganic ammonium salts produce only negligible amounts of NH4+ in the HR-AMS. Finally, we quantified the NOON contents in submicron particles (PM1) and fog water in Fresno, California, and PM1 in New York City (NYC). Our results revealed the substantial presence of amino compounds in both Fresno and NYC aerosols, whereas concurrently collected fog water in Fresno contained a broader range of NOON species, including N-containing aromatic heterocycle (e.g., imidazoles) and amides. These findings highlight the significant potential of employing the widespread HR-AMS measurements of ambient aerosols and droplets to enhance our understanding of the sources, transformation processes, and environmental impacts associated with NOON compounds in the atmosphere.

Cooking emissions are a major source of racial-ethnic air pollution exposure disparities in the United States

Racial-ethnic minority populations in the US are disproportionately exposed to airborne fine particulate matter (PM2.5), but few national studies have focused individually on the sources that contribute to these disparities. We address this gap by conducting a comprehensive analysis of PM2.5 exposure disparities by race-ethnicity in the US, focusing on three source-categories: mobile-sources, cooking, and all other sources combined. Our approach is based on high-resolution, national land-use regression estimates of source-resolved PM2.5 components, derived from high-resolution aerosol mass spectrometer measurements. We find that each of these sources contributes approximately one-third of the overall PM2.5 exposure disparities by race-ethnicity. While the importance of mobile-source tailpipe emissions is well recognized, our study underscores the significance of cooking emissions in creating PM2.5 exposure disparities. This finding represents a potentially significant opportunity to reduce these disparities, as cooking emissions are currently largely unregulated. It has important implications for policymakers and public health advocates aiming to address the persistent issue of racial-ethnic disparities in air pollution.

Volatilization and partitioning of residual electronic cigarette emissions to particulate matter

The growing prevalence of electronic cigarettes (e-cigs) prompts investigation of their impact on indoor air quality. While the investigation of residual cigarette smoke, also known as third-hand smoke (THS), has been increasing, there is minimal literature on similar residue from e-cig emissions. Lab generated ammonium sulfate aerosol was introduced into a stainless-steel chamber which previously contained JUUL electronic cigarette vape. Aerosol composition was monitored using a high-resolution aerosol mass spectrometer. This was performed in the same chamber 3 times over 5 days. Species from electronic cigarette residue (nicotine and vegetable glycerin) were found to partition to particles with decreasing concentration over the multiple experiments while maintaining a consistent chemical signature. This signature matches closely to that of the primary electronic cigarette vape with notable exclusions of propylene glycol, benzoic acid, and cadmium. Electronic cigarette vape can deposit onto surfaces and act as a long-term source of gas phase nicotine which can concentrate on aerosols and increase human exposure. The chemical processing of vape residue observed here is less substantial than has been previously presented for residual cigarette smoke. While our experiments were performed under controlled conditions, they highlight the importance of understanding indoor electronic cigarette use and unintended routes of exposure.Copyright © 2023 American Association for Aerosol Research

Real time measurements of the secondary organic aerosol formation and aging from ambient air using an oxidation flow reactor in seoul during winter

Herein, the formation and aging processes of organic aerosol (OA) in urban Seoul, Korea, during winter were investigated using a high-resolution aerosol mass spectrometer (HR-ToF-AMS) and an oxidation flow reactor (OFR). The results demonstrated that the highest secondary OA (SOA) production (ΔOA = 3.44 μg m−3 with a relative OA enhancement ratio (EROA) = 1.40) occurred at ∼2 eq. days of OH exposure. Particularly, higher SOA production was observed under the following atmospheric conditions: high relative humidity (RH) (>70%) and high PM1 mass concentration (>50 μg m−3), demonstrating that oxidation capacity, heterogeneous and aqueous phase reactions are important for further oxidation. Additionally, increased SOA formation occurs under both higher hydrocarbon-like OA and more oxidized OOA conditions. Further oxidation of both freshly emitted and aged and/or transported OA can be a remarkable further source of SOA in winter in Seoul and further downwind areas. In particular, the high mass concentration of MO-OOA in high total PM1 would be an important indication that SOA formation could be accelerated by a heterogeneous reaction, necessitating additional investigations on the haze formation process.

Insights into the compositional differences of PM1 and PM2.5 from aerosol mass spectrometer measurements in Beijing, China

Aerosol mass spectrometers (AMS) have been widely used for characterization of submicron aerosol (PM1) species in the world. However, the chemical differences between PM1 and fine particles (PM2.5) in megacities are poorly understood. Here a PM1 high-resolution AMS with standard vaporizer (SV) and a PM2.5 time-of-flight aerosol chemical speciation monitor (ToF-ACSM) with capture vaporizer (CV) were deployed simultaneously in summer and winter in Beijing, China, and the chemical differences of non-refractory aerosol species between PM1 and PM2.5 were characterized. Our results showed that aerosol species in PM2.5 were overall highly correlated with those in PM1 (r2 > 0.8), yet the PM1/PM2.5 ratios varied largely for different aerosol species. Nitrate existed dominantly in PM1 (80–90%), while a considerable fraction of sulfate (30–45%) was observed in the range of 1–2.5 μm (PM1–2.5). Comparatively, PM1 organics showed higher fractions in PM2.5 in summer than winter (∼70%). The changes in PM1/PM2.5 ratios of secondary inorganic aerosol (SIA) depended strongly on relative humidity (RH) in summer with considerable decreases as the increase of RH, while such a RH dependence of PM1/PM2.5 ratios was not significant in winter due to the absence of high RH data. We further compared the source apportionment results of organic aerosol (OA) between PM1 and PM2.5. Similar to previous studies, the SV AMS reported ubiquitously higher primary OA than the CV ToF-ACSM, nearly by a factor of 2 for cooking OA, and the difference in secondary OA composition can be substantial, particularly in winter. With the simultaneous measurements of AMS and ACSM, a parameterized relationship between oxygen-to-carbon (O/C) ratio and CV f44 (fraction of m/z 44 in OA) in summer and winter was developed, which has a potential implication for studying the oxidation and hygroscopicity properties of OA considering the rapid increases in CV ToF-ACSM measurements worldwide.

Fluorescence of solvent-extractable organics in sub-micrometer forest aerosols in Hokkaido, Japan

Excitation–emission matrix (EEM) fluorescence spectroscopy is an analytical method for obtaining the properties, components, and sources of chromophores of atmospheric organic aerosols (OA). Most studies have been limited to water-soluble OA; the chemical structures of OA associated with chromophores and the sources of chromophores are still not well understood. In this study, the fluorescence properties of solvent-extractable organic components, fractionated based on their polarity in sub-micrometer forest aerosols in Hokkaido, Japan, were characterized on the basis of their EEMs in combination with chemical structural characterization from offline aerosol mass spectrometry. The fluorescence volume normalized by the mass concentration (NFV) and the fluorescence volume (FV) corresponding to the atmospheric abundance for water-insoluble organic matter (WISOM) were higher than those of other OA fractions and highest in the winter. Correlation analyses between the NFVs and the relative intensities of ion groups from the mass spectra from a high-resolution aerosol mass spectrometer suggest that organic compounds containing O and N contributed to the fluorescence of the OA fractions. Although the fluorescence indices used to characterize aquatic dissolved organic matter exhibited comparable values for water-soluble organic matter (WSOM) in this study and in previous studies, they are not applicable in explaining the types or sources of other OA fractions. A parallel factor (PARAFAC) analysis for EEM profiles identified five components. Four components had fluorescence characteristics similar to those associated with humic-like substances (HULIS), and one had fluorescence characteristics associated with protein-like compounds (PLOM). The chromophores commonly associated with HULIS with oxygenated structures contributed significantly to respective OA fractions; this implies that for fluorescence measurements, such as the detection of primary biological aerosol particles (PBAP), contributions from oxygenated organics should be considered in the forest region.

Characteristics and Oxidative Potential of Ambient PM2.5 in the Yangtze River Delta Region: Pollution Level and Source Apportionment

Fine particulate matter (PM2.5) is a major contributor to the degree of air pollution, and it is associated with a range of adverse health impacts. Moreover, the oxidative potential (OP, as a tracer of oxidative stress) of PM2.5 has been thought to be a possible determinant of its health impact. In this study, the OP of 136 fine aerosol filter samples collected in Changzhou in two seasons (spring and summer) were determined using a dithiothreitol (DTT) assay. Source apportionments of the PM2.5 and DTT activity were further performed. Our results showed that the daily average ± standard deviation of the DTTv (volume-normalized DTT activity) in the PM2.5 was 1.16 ± 0.58 nmol/min/m3 and 0.85 ± 0.16 nmol/min/m3 in the spring and summer, respectively, and the DTTm (mass-normalized DTT activity) was 13.56 ± 5.45 pmol/min/μg and 19.97 ± 6.54 pmol/min/μg in the spring and summer, respectively. The DTTv was higher in the spring compared to the summer while the opposite was true for the DTTm. Most of the detected components (including the organic component, element component, NH4+, Mn, Cu, Zn, etc.) exhibited a moderately positive correlation with the DTTv, but the opposite was found with the DTTm. An aerodyne high-resolution aerosol mass spectrometer (HP-AMS) was deployed to probe the chemical properties of the water-soluble organic matter (WSOA). Positive matrix factorization (PMF) coupled with multiple linear regression was used to obtain the relative source contributions to the DTT activity for the WSOA in the PM2.5. The results showed that the sensitivity sequences of the DTTv to the WSOA sources were oxygenated organic aerosol (OOA) > biomass burning OA (BBOA) > hydrocarbon-like OA (HOA) in the spring and HOA > nitrogen-enriched OA (NOA) > OOA in the summer. The PMF suggested the highest contribution from traffic emissions to the DTTv of the PM2.5 in both seasons. Our findings point to the importance of both organic components from secondary formation and transition metals to adverse health effects in this region. This study can provide an important reference for adopting appropriate public health policies regarding the detrimental outcomes of exposure to PM2.5.

Changes in primary and secondary aerosols during a controlled Chinese New Year

Large reductions in anthropogenic emissions during the Chinese New Year (CNY) holiday in Beijing have been well reported. However, the changes during the CNY of 2021 are different because most people stayed in Beijing to control the spread of coronavirus disease (COVID-19). Here a high-resolution aerosol mass spectrometer (HR-AMS) was deployed for characterization of the changes in size-resolved aerosol composition and sources during the CNY. We found that the reductions in traffic-related NOx and fossil fuel-related organic aerosol (OA), and cooking OA (1.3–12.7%) during the CNY of 2021 were much smaller than those in previous CNY holidays of 2013, 2015, and 2020. In contrast, the mass concentrations of secondary aerosol species except nitrate showed ubiquitous increases (17.6–30.4%) during the CNY of 2021 mainly due to a 4-day severe haze episode. OA composition also changed substantially during the CNY of 2021. In particular, we observed a large increase by nearly a factor of 2 in oxidized primary OA likely from biomass burning, and a decrease of 50.1% in aqueous-phase secondary OA. A further analysis of the severe haze episode during the CNY illustrated a rapid transition of secondary formation from photochemical to aqueous-phase processing followed by a scavenging process, leading to significant changes in aerosol composition, size distributions, and oxidation degree of OA. A parameterization relationship between oxygen-to-carbon (O/C) and f44 (fraction of m/z 44 in OA) from a collocated capture vaporizer aerosol chemical speciation monitor (CV-ACSM) was developed, which has a significant implication for characterization of OA evolution and the impacts on hygroscopicity due to the rapidly increased deployments of CV-ACSM worldwide.

Abundance, chemical structure, and light absorption properties of humic-like substances (HULIS) and other organic fractions of forest aerosols in Hokkaido

Atmospheric organic aerosol (OA) are considered as a significant contributor to the light absorption of OA, but its relationship with abundance, composition and sources are not understood well. In this study, the abundance, chemical structural characteristics, and light absorption property of HULIS and other low-to-high polar organics in PM0.95 collected in Tomakomai Experimental Forest (TOEF) were investigated with consideration of their possible sources. HULIS were the most abundant (51%), and correlation analysis revealed that biogenic secondary organic aerosols significantly contribute to HULIS. The mass spectra obtained using a high-resolution aerosol mass spectrometer (HR-AMS) showed that HULIS and highly polar water-soluble organic matter (HP-WSOM) were substantially oxygenated organic aerosol fractions, whereas water-insoluble organic matter (WISOM) had a low O/C ratio and more hydrocarbon-like structures. The WISOM fraction was the predominant light-absorbing organics. HULIS and WISOM showed a noticeable seasonal change in mass absorption efficiency (MAE365), which was highest in winter. Further, HULIS were shown to be less absorbing than those reported for urban sites. The findings in this study provide insights into the contribution of biogenic secondary OA on aerosol property and radiative forcing under varying contributions from other types of OA.

Sources and processes of water-soluble and water-insoluble organic aerosol in cold season in Beijing, China

Abstract. Water-soluble and water-insoluble organic aerosol (WSOA and WIOA) constitute a large fraction of fine particles in winter in northern China, yet our understanding of their sources and processes are still limited. Here we have a comprehensive characterization of WSOA in cold season in Beijing. Particularly, we present the first mass spectral characterization of WIOA by integrating online and offline organic aerosol measurements from high-resolution aerosol mass spectrometer. Our results showed that WSOA on average accounted for 59 % of the total OA and comprised dominantly secondary OA (SOA, 69 %). The WSOA composition showed significant changes during the transition season from autumn to winter. While the photochemical-related SOA dominated WSOA (51 %) in early November, the oxidized SOA from biomass burning increased substantially from 8 % to 29 % during the heating season. Comparatively, local primary OA dominantly from cooking aerosol contributed the major fraction of WSOA during clean periods. WIOA showed largely different spectral patterns from WSOA which were characterized by prominent hydrocarbon ions series and low oxygen-to-carbon (O/C = 0.19) and organic mass-to-organic carbon (OM/OC = 1.39) ratios. The nighttime WIOA showed less oxidized properties (O/C = 0.16 vs. 0.24) with more pronounced polycyclic aromatic hydrocarbons (PAHs) signals than daytime, indicating the impacts of enhanced coal combustion emissions on WIOA. The evolution process of WSOA and WIOA was further demonstrated by the triangle plot of f44 (fraction of m/z 44 in OA) vs. f43, f44 vs. f60, and the Van Krevelen diagram (H/C vs. O/C). We also found more oxidized WSOA and an increased contribution of SOA in WSOA compared with previous winter studies in Beijing, indicating that the changes in OA composition due to clean air act have affected the sources and properties of WSOA.

Simulating wildfire emissions and plume rise using geostationary satellite fire radiative power measurements: a case study of the 2019 Williams Flats fire

Abstract. We use the Weather Research and Forecasting with Chemistry (WRF-Chem) model with new implementations of GOES-16 wildfire emissions and plume rise based on fire radiative power (FRP) to interpret aerosol observations during the 2019 NASA-NOAA FIREX-AQ field campaign and perform model evaluations. We compare simulated aerosol concentrations and optical properties against observations of black carbon aerosol from the NOAA Single Particle Soot Photometer (NOAA-SP2), organic aerosol from the CU High-Resolution Aerosol Mass Spectrometer (HR-AMS), and aerosol backscatter coefficients from the high-spectral-resolution lidar (HSRL) system. This study focuses on the Williams Flats fire in Washington, which was repeatedly sampled during four science flights by the NASA DC-8 (3–8 August 2019). The emissions and plume-rise methodologies are implemented following NOAA's operational High-Resolution Rapid Refresh coupled with Smoke (HRRR-Smoke) forecasting model. In addition, new GOES-16 FRP-based diurnal cycle functions are developed and incorporated into WRF-Chem. The FIREX-AQ observations represented a diverse set of sampled environments ranging from fresh/aged smoke from the Williams Flats fire to remnants of plumes transported over long distances. The Williams Flats fire resulted in significant aerosol enhancements during 3–8 August 2019, which were substantially underestimated by the standard version of WRF-Chem. The simulated black carbon (BC) and organic carbon (OC) concentrations increased between a factor of 92–125 (BC) and a factor of 28–78 (OC) with the new implementation compared to the standard WRF-Chem version. These increases resulted in better agreement with the FIREX-AQ airborne observations for BC and OC concentrations (particularly for fresh smoke sampling phases) and aerosol backscatter coefficients. The model still showed a low bias in simulating the aerosol loadings observed in aged plumes from Williams Flats. WRF-Chem with the FRP-based plume rise simulated similar plume heights to the standard plume-rise model in WRF-Chem. The simulated plume heights (for both versions) compared well with estimated plume heights using the HSRL measurements. Therefore, the better agreement with observations was mainly driven by the higher emissions in the FRP-based version. The model evaluations also highlighted the importance of accurately accounting for the wildfire diurnal cycle and including adequate representation of the underlying chemical mechanisms, both of which could significantly impact model forecasting performance.

Highly time-resolved chemical speciation and source apportionment of organic aerosol components in Delhi, India, using extractive electrospray ionization mass spectrometry

Abstract. In recent years, the Indian capital city of Delhi has been impacted by very high levels of air pollution, especially during winter. Comprehensive knowledge of the composition and sources of the organic aerosol (OA), which constitutes a substantial fraction of total particulate mass (PM) in Delhi, is central to formulating effective public health policies. Previous source apportionment studies in Delhi identified key sources of primary OA (POA) and showed that secondary OA (SOA) played a major role but were unable to resolve specific SOA sources. We address the latter through the first field deployment of an extractive electrospray ionization time-of-flight mass spectrometer (EESI-TOF) in Delhi, together with a high-resolution aerosol mass spectrometer (AMS). Measurements were conducted during the winter of 2018/19, and positive matrix factorization (PMF) was used separately on AMS and EESI-TOF datasets to apportion the sources of OA. AMS PMF analysis yielded three primary and two secondary factors which were attributed to hydrocarbon-like OA (HOA), biomass burning OA (BBOA-1 and BBOA-2), more oxidized oxygenated OA (MO-OOA), and less oxidized oxygenated OA (LO-OOA). On average, 40 % of the total OA mass was apportioned to the secondary factors. The SOA contribution to total OA mass varied greatly between the daytime (76.8 %, 10:00–16:00 local time (LT)) and nighttime (31.0 %, 21:00–04:00 LT). The higher chemical resolution of EESI-TOF data allowed identification of individual SOA sources. The EESI-TOF PMF analysis in total yielded six factors, two of which were primary factors (primary biomass burning and cooking-related OA). The remaining four factors were predominantly of secondary origin: aromatic SOA, biogenic SOA, aged biomass burning SOA, and mixed urban SOA. Due to the uncertainties in the EESI-TOF ion sensitivities, mass concentrations of EESI-TOF SOA-dominated factors were related to the total AMS SOA (i.e. MO-OOA + LO-OOA) by multiple linear regression (MLR). Aromatic SOA was the major SOA component during the daytime, with a 55.2 % contribution to total SOA mass (42.4 % contribution to total OA). Its contribution to total SOA, however, decreased to 25.4 % (7.9 % of total OA) during the nighttime. This factor was attributed to the oxidation of light aromatic compounds emitted mostly from traffic. Biogenic SOA accounted for 18.4 % of total SOA mass (14.2 % of total OA) during the daytime and 36.1 % of total SOA mass (11.2 % of total OA) during the nighttime. Aged biomass burning and mixed urban SOA accounted for 15.2 % and 11.0 % of total SOA mass (11.7 % and 8.5 % of total OA mass), respectively, during the daytime and 15.4 % and 22.9 % of total SOA mass (4.8 % and 7.1 % of total OA mass), respectively, during the nighttime. A simple dilution–partitioning model was applied on all EESI-TOF factors to estimate the fraction of observed daytime concentrations resulting from local photochemical production (SOA) or emissions (POA). Aromatic SOA, aged biomass burning, and mixed urban SOA were all found to be dominated by local photochemical production, likely from the oxidation of locally emitted volatile organic compounds (VOCs). In contrast, biogenic SOA was related to the oxidation of diffuse regional emissions of isoprene and monoterpenes. The findings of this study show that in Delhi, the nighttime high concentrations are caused by POA emissions led by traffic and biomass burning and the daytime OA is dominated by SOA, with aromatic SOA accounting for the largest fraction. Because aromatic SOA is possibly more toxic than biogenic SOA and primary OA, its dominance during the daytime suggests an increased OA toxicity and health-related consequences for the general public.

Evolution of source attributed organic aerosols and gases in a megacity of central China

Abstract. The secondary production of oxygenated organic aerosol (OOA) impacts air quality, climate, and human health. The importance of various sources in contributing to the OOA loading and associated different ageing mechanisms remains to be elucidated. Here we present a concurrent observation and factorization analysis on the mass spectra of organic aerosol (OA) by a high-resolution aerosol mass spectrometer and volatile organic compounds (VOCs) by a proton transfer reaction mass spectrometer in Wuhan, a megacity in central China, during autumn. The full mass spectra of organics with two principle anthropogenic sources were identified as the traffic and cooking sources, for their primary emission profiles in aerosol and gas phases, the evolutions, and their respective roles in producing OOA and secondary VOCs. Primary emissions in gas and aerosol phases both contributed to the production of OOA. The photooxidation of traffic sources from the morning rush hour caused a 2.5 fold increase in OOA mass in a higher oxidation state (oxygen-to-carbon ratio as O/C =0.72), co-producing gas phase carboxylic acids, while, at night, cooking aerosols and VOCs (particularly acrolein and hexanal) importantly caused the nocturnal formation of oxygenated intermediate VOCs, increasing OOA mass by a factor of 1.7 (O/C =0.42). The daytime and nighttime formation of secondary aerosols, as contributed by different sources, was found to be modulated by solar radiation and air moisture, respectively. The environmental policy should, therefore, consider the primary emissions and their respective ageing mechanisms influenced by meteorological conditions.

Chemical composition, sources and optical properties of nitrated aromatic compounds in fine particulate matter during winter foggy days in Nanjing, China

Functionalized aromatic compounds are one of the most important light-absorbing organic chromophores – so-called brown carbon (BrC) – in fine particulate matter (PM2.5). In this study, we conducted a wintertime field campaign to measure eight nitrated aromatic compounds (NACs) in PM2.5 with offline analysis techniques, including liquid chromatograph mass spectrometer (LC-MS) and aerodyne high-resolution aerosol mass spectrometer (AMS) measurements, during foggy and nonfoggy days in suburban Nanjing in the Yangtze River Delta region, China. On average, 4-nitrophenol could be one of the most important light absorbing materials in the observed BrC, which accounted for over 40% of the mass concentration of identified chromophores. The mass concentration of 2-methyl-4-nitrophenol and 2,6-dimethyl-4-nitrophenol were evidently increased during foggy days, contribution of which to total NACs were increased by 10% and 5%, respectively. Positive matrix factorization analysis of combining LC-MS and AMS dataset was performed to identify the primary and secondary sources of NACs. Primary sources, e.g., traffic and solid-fuel combustion, accounted for 71% of the sum of 4-nitrophenol, 2,6-dimethyl-4-nitrophenol and 3-nitrosalicylic acid, suggesting important contribution of primary emissions to these NACs. The contribution of secondary sources, associated with two oxygenated organic aerosols, could contribute 66% to 4-nitrophenol, reflecting the link of such nitrated aromatic compounds to secondary organic aerosol source. Together with optical measurements, 4-nitrophenol presented a high contribution (>50%) to the identified BrC absorbance in the light range 250 and 550 nm was observed. This could highlight an important role of such NACs in ambient BrC light absorption, despite its mass contribution to total organic carbon was negligible. Our work could improve the understanding of the links between optical properties and chemical composition of BrC, and the difference between BrC chromophores from nonfoggy days and foggy days under the typical polluted atmospheric conditions.

The importance of hydroxymethanesulfonate (HMS) in winter haze episodes in North China Plain

Hydroxymethanesulfonate (HMS), a key marker species of aqueous-phase processing, plays a significant role in sulfur budget in atmosphere. Here we have a comprehensive characterization of HMS at urban and rural sites in North China Plain (NCP) by using the real-time measurements from a high-resolution aerosol mass spectrometer (AMS) and a single-particle AMS together with offline filter analysis. Our results showed much higher winter concentration of HMS at the rural site (average±1σ: 2.58 ± 2.56 μg m−3) than that (1.70 ± 2.68 μg m−3) in Beijing due to the more frequent fog events, low particle acidity and high concentration of precursors. The HMS on average contributed 6.3% and 5.2% to organic aerosol (OA), and 16% and 12% to the total particulate sulfur, at the rural and urban sites, respectively. HMS was highly correlated with aqueous-phase secondary OA and sulfate, and its contribution to the total particulate sulfur increased significantly as a function of relative humidity demonstrating the effective HMS production from aqueous-phase processing. Single-particle analysis showed that HMS-containing particles were mainly mixed with amine-related compounds. In addition, we found that organosulfur compounds (OS) estimated from sulfur-containing fragments of AMS correlated well with HMS at both urban and rural sites. While OS at the rural site was dominated by HMS, other types of OS were also important in urban area. The high HMS also affected the estimation of particle acidity using the AMS measured and predicted ammonium, particularly during severe haze episodes. Overall, our results demonstrated the importance of HMS in winter in NCP, and it could be more important in total particulate sulfur budget as the continuous decrease in sulfate in the future.

Secondary organic aerosol formation and aging from ambient air in an oxidation flow reactor during wintertime in Beijing, China

Secondary organic aerosols (SOA) constitute a large fraction of atmospheric aerosols, yet our knowledge of the formation and aging processes of SOA in megacities of China is still limited. In this work, the formation and aging processes of SOA in winter in Beijing was investigated using a high-resolution aerosol mass spectrometer (AMS) and an oxidation flow reactor (OFR). Our results showed that the OA enhancement from OH aging peaked at ∼3.9 equivalent days with an average enhancement of 0.9 (±0.3) μg m−3. Positive matrix factorization analysis of AMS-OFR data identified three primary OA (POA) and two SOA factors. While the concentrations of POA factors decreased as a function of photochemical age, the two SOA factors showed clear enhancements by 2.5 and 4.3 μg m−3 at ∼3.9 and ∼2.6 days of equivalent photochemical age, respectively. The average contribution of SOA to the total OA was 47% in ambient air and 87% in OFR-oxidized ambient air. The elevated oxygen-to-carbon (O/C) ratio from 0.49 to 0.77–0.82 and the decreased hydrogen-to-carbon (H/C) from 1.37 to ∼1.1 highlighted the formation of more oxidized SOA during photochemical aging in winter in Beijing. The ubiquitous SOA enhancement as a function of OA levels indicated the significant formation potential of SOA in winter, and it varied differently among different episodes. In particular, we observed a maximum SOA enhancement of 38.6 μg m−3 during a biomass burning event. This result demonstrates that photochemical oxidation of ubiquitous biomass burning emissions can be a large source of SOA in winter in North China Plain.

Constraining the response factors of an extractive electrospray ionization mass spectrometer for near-molecular aerosol speciation

Abstract. Online characterization of aerosol composition at the near-molecular level is key to understanding chemical reaction mechanisms, kinetics, and sources under various atmospheric conditions. The recently developed extractive electrospray ionization time-of-flight mass spectrometer (EESI-TOF) is capable of detecting a wide range of organic oxidation products in the particle phase in real time with minimal fragmentation. Quantification can sometimes be hindered by a lack of available commercial standards for aerosol constituents, however. Good correlations between the EESI-TOF and other aerosol speciation techniques have been reported, though no attempts have yet been made to parameterize the EESI-TOF response factor for different chemical species. Here, we report the first parameterization of the EESI-TOF response factor for secondary organic aerosol (SOA) at the near-molecular level based on its elemental composition. SOA was formed by ozonolysis of monoterpene or OH oxidation of aromatics inside an oxidation flow reactor (OFR) using ammonium nitrate as seed particles. A Vocus proton-transfer reaction mass spectrometer (Vocus-PTR) and a high-resolution aerosol mass spectrometer (AMS) were used to determine the gas-phase molecular composition and the particle-phase bulk chemical composition, respectively. The EESI response factors towards bulk SOA coating and the inorganic seed particle core were constrained by intercomparison with the AMS. The highest bulk EESI response factor was observed for SOA produced from 1,3,5-trimethylbenzene, followed by those produced from d-limonene and o-cresol, consistent with previous findings. The near-molecular EESI response factors were derived from intercomparisons with Vocus-PTR measurements and were found to vary from 103 to 106 ion counts s−1 ppb−1, mostly within ±1 order of magnitude of their geometric mean of 104.6 ion counts s−1 ppb−1. For aromatic SOA components, the EESI response factors correlated with molecular weight and oxygen content and inversely correlated with volatility. The near-molecular response factors mostly agreed within a factor of 20 for isomers observed across the aromatics and biogenic systems. Parameterization of the near-molecular response factors based on the measured elemental formulae could reproduce the empirically determined response factor for a single volatile organic compound (VOC) system to within a factor of 5 for the configuration of our mass spectrometers. The results demonstrate that standard-free quantification using the EESI-TOF is possible.

Large Emissions of Low-Volatility Siloxanes during Residential Oven Use

Cooking is a source of airborne particles indoors and outdoors. A field study at a residential test house (HOMEChem) included two Thanksgiving-style cooking experiments involving prolonged use of an oven with a light use history. Large enhancements of airborne low-volatility siloxanes were observed by three in situ particle-phase instruments: a high-resolution aerosol mass spectrometer, a semivolatile thermal desorption aerosol gas chromatograph, and an extractive electrospray ionization mass spectrometer. The combination of these instruments permits the quantitative analysis of time-dependent processes and fates over a wide volatility range with high chemical specificity. Cumulatively, 17 and 8.5 mg of bulk siloxane material were emitted indoors and observed in airborne particles during the first and second Thanksgiving experiments, respectively; a peak 5 min average siloxane concentration of 58 μg/m3 was measured. Cyclic siloxanes D10–D18 were quantified, and D17 and D16 were the most abundant. We infer that heating of silicone materials inside the oven caused volatilization of cyclic siloxanes and cooler temperatures away from the oven resulted in condensation. Low-volatility siloxanes comprised a surprisingly large fraction of the total emitted submicrometer particle mass: 18% and 9% during the first and second Thanksgiving experiments, respectively. We estimate ∼75% of the low-volatility siloxane mass was ventilated outdoors.

Insights into aqueous-phase and photochemical formation of secondary organic aerosol in the winter of Beijing

Haze pollution has become a major public concern of China in recent years, especially in Beijing and surrounding areas, and in the fall and winter seasons. Implementation of Clean Air Action Plan in 2013 targeted the distinct improvement of air quality in Beijing since 2017. However, there is the absence of detailed investigation of SOA evolutionary processes in winter 2017. Here we deployed an Aerodyne high-resolution aerosol mass spectrometer during winter 2017 in Beijing. Our results show that PM1 average mass concentrations decreased from 81.7 μg/m3 in 2013 to 24.5 μg/m3 in 2017. OA was the most abundant component in PM1, accounting for 37%. Five OA factors, including two SOA factors, less-oxidized oxygenated OA (LO-OOA) and more-oxidized oxygenated OA (MO-OOA), were resolved using positive matrix factorization analysis. The mass fraction of SOA in OA was higher than 58%, underlining the important role of secondary formation in OA pollution. The contribution of MO-OOA to OA increased from ~20% to more than 40% as a function of relative humidity and odd oxygen (OX=O3+NO2), indicating the promotion of aqueous-phase processing and photochemical oxidation on SOA formation. O/CSOA ratio also presented similar trends, increasing from ~0.8 to around 1.0. Comparison of SOA evolution at daytime and nighttime shows that SOA aging at daytime was more active than that at nighttime, implying the potential of aqueous photoformation. Further analysis of the joint influence of RH and OX indicates that aqueous-phase processing was more significant than photochemical formation in MO-OOA formation and SOA aging. This study helps better understand the rapid decrease of PM1 with increasing contribution of SOA in Beijing winter. SummaryThis work focused on the detailed characteristics of SOA formation in Beijing winter, and found the potential significance of the intense photochemical aqueous-phase oxidation on SOA formation.