Secondary Inorganic Aerosol Formation Research Articles

Sources and processes affecting the abundances of atmospheric NHx using δ15N over northwestern Indo-Gangetic plain

Ammonia (NH3) is the major constituent among all the reactive nitrogen species present in the atmosphere, and the most essential species for secondary inorganic aerosol formation. Recent satellite-based observations have identified the Indo-Gangetic Plain (IGP) as a major hotspot of global NH3 emission; however, the major sources and atmospheric processes affecting its abundance are poorly understood. The present study aims to understand the wintertime sources of NH3 over a semi-urban site (Patiala, 30.3°N, 76.4°E, 249 m amsl) located in the IGP using species specific δ15N in PM2.5. A distinct diurnal variation in the stable isotopic signature of total nitrogen (δ15N-TN) and ammonium (δ15N–NH4+) were observed; although, average day and night time concentrations of TN and NH4+ were similar. Mixing model results using δ15N–NH3 reveal the dominance of non-agricultural emissions (NH3 slip: 47 ± 24%) over agricultural emissions (24 ± 11%), combustion sources (19 ± 14 %), and biomass burning (10 ± 8%) for atmospheric NH3. Diurnal variability in source contributions to NH3 was insignificant. Further, significantly negative correlations of δ15N–NH4+ with ambient relative humidity (RH) and daytime NO3−-N concentration were observed, and attributed to the possibility of NH4NO3 volatilization during day-time owing to lower RH and higher temperature, resulting in isotopic enrichment of the remaining NH4+ in aerosol phase. This study, a first of its type from India, highlights the importance of non-agricultural NH3 emissions over the agriculture dominated IGP region, and the role of local meteorology on the isotopic fractionation of δ15N in aerosol NH4+.

Size-resolved water-soluble organic carbon and its significant contribution to aerosol liquid water

Size-segregated aerosols collected in Beijing from 2021 to 2022 were used to investigate the contribution of organic aerosols to the aerosol liquid water content (ALWC), the influencing factors of ALWC, and the concentrations and size distribution characteristics of water-soluble organic carbon (WSOC) after clean air actions. The results showed that the concentration of WSOC in particulate matter (PM)1.8 was 3.52 ± 2.43 μg/m3 during the sampling period. Obvious changes were observed in the size distribution of WSOC after clean air actions, which may be attributed to the enhancement of atmospheric oxidation capacity and the decrease in PM concentration. The contribution of organic aerosols to the ALWC in fine PM was 18.1 % during the sampling period, which was more significant at lower particles concentration and smaller particle size ranges. The ambient relative humidity (RH) and the ratio of NO3−/SO42− had an apparent influence on ALWC. The continuous increase in the nitrate proportion significantly reduced the deliquescence point of the aerosols, making them prone to hygroscopic growth at lower RH. Analysis of the relation among nitrogen oxidation ratio (sulfur oxidation ratio), ALWC and PM1.8 mass concentrations suggests that organic matter has a significant effect on the formation of secondary inorganic aerosols in the initial phase of pollution formation and plays a crucial role in aerosol pollution formation in Beijing. These results are conducive to understanding the formation mechanism of aerosols and provide scientific data and theoretical support for the formulation of more effective emission-reduction measures.

Insights into atmospheric trace gases, aerosols, and transport processes at a high-altitude station (2623 m a.s.l.) in Northeast Asia

As part of the efforts to understand long-range air pollution transport in Northeast Asia, a comprehensive field measurement campaign was conducted at the top of Changbai Mountain (2623 m a.s.l.) from 25th July to 21st August in 2021. The ambient concentrations of trace gases and chemical characteristics of fine particulate matter (PM2.5) were comparable to those at background or free tropospheric locations in China, but exceeded levels at corresponding sites in Europe and the United States. Well-defined diurnal variations were evident in most air pollutants, including carbon monoxide (CO), sulfur dioxide (SO2), and nitrogen oxide (NOx), reflecting the influence of boundary layer development and local anthropogenic activities. Ozone (O3) exhibited a unique diurnal distribution, with lower concentrations during the daytime and higher levels at nighttime, indicating a pronounced impact of downward transport of O3-rich air from the upper troposphere during the nighttime. During the campaign, organic carbon (OC) constituted the predominant component of PM2.5, comprising 43% of the total, while sulfate (SO42−) was the most abundant secondary inorganic component in PM2.5, accounting for 26%. Combining the analysis of air mass backward trajectories, we found that Changbai Mountain is primarily influenced by air masses originating from North Korea and the Sea of Japan, constituting 62% of the total, and local vegetation biological emissions and anthropogenic emissions in North Korea notably affect the observation site. Conversely, the secondary aerosol components were most abundant in marine air mass originating from the marginal seas of China and the strait between the Korean peninsula and southern Japan. Utilizing the Lagrangian photochemical trajectory model (LPTM), a significant increase in particulate SO42− concentrations was observed when air mass passed through the marginal seas of China, primarily due to SO2 oxidation reaction. This study contributes to an improved understanding of the atmospheric chemistry in the high-altitude regions of Northeast Asia and underscores the substantial role of secondary inorganic aerosol formation during the transport of marine air masses.

Monitoring ammonia concentrations in more than 10 stations in the Po Valley for the period 2007–2022 in relation to the evolution of different sources

Regarding secondary aerosols, in addition to the significant contribution of anthropogenic gases such as NOx and SO2, atmospheric ammonia (NH3) plays a crucial role as the primary basic gaseous species capable of neutralizing acidic compounds. This acid–base reaction is responsible for the formation of ammonium nitrate (NH4NO3), constituting up to 60% of PM10 within the Po River basin in Italy. Ion chromatographic analyses performed on offline samples indicate that this secondary inorganic species exhibits minimal concentration variability over the Po Valley because of limited air circulation due to orography and mesoscale air circulation. Therefore, investigating gaseous precursors becomes crucial. From the northern to the southern part of Lombardy—the region at the center of the basin—NH3 emission amounts account for 2.5, 11.1, and 27.7 t/y/km2, mainly due to agriculture and livestock activities (∼97%). To study NH3 temporal and spatial variability, the Environmental Protection Agency of Lombardy Region has been monitoring NH3 concentrations across its territory since 2007, with 10 active monitoring sites. Annual and seasonal cycles are presented, along with a focus on different stations, including urban, low-mountain background, high-impact livestock, and rural background, highlighting the impact of various sources. Measurements indicate that within the Po basin, NH3 concentrations can reach up to 700 µg/m3 (as an hourly average) in proximity to the main gaseous NH3 source. Instrument intercomparisons among online monitors and passive vials, as well as different online monitors, are presented. Therefore, this paper provides crucial data to understand the formation of secondary inorganic aerosols in one of the most important hotspot sites for air pollution.

Observational insights into the environmental effect for secondary inorganic aerosol formation in the Northeast China: Influence of biomass burning

Secondary inorganic aerosols (SIA), as one of the main ubiquitous components of PM2.5, still have unclear impacts on their formation in the ambient environment, especially under extremely cold weather conditions. To explore the effects of open biomass burning (OBB) source emissions and meteorological factors on SIA formation, biomass burning tracer, i.e., levoglucosan (LG), was observed along with SIA were analyzed during the heating season at the Longfengshan (LFS) background of Northeast China. Based on the LG/OC ratio and fire hotspots, the entire sampling campaign was divided into OBB and non-open biomass burning (NBB) periods.It was found that OBB emissions had little effect on sulfate formation but a significant impact on nitrate formation. High relative humidity (RH) conditions played a crucial role in SIA formation, with both SO42−/EC and NO3−/EC increasing as RH elevated at temperatures below −10 °C. Furthermore, the temperature dependence of SO42−/EC and NO3−/EC indicated that temperature could enhance the activity of either aqueous-phase production or gas-phase reactions, subsequently promoting the formation of SO42− and NO3− in the ambient environment. Additionally, positive matrix factorization (PMF) analysis was used to scientifically separate the sources of ambient aerosols during OBB and NBB periods.

Moisture-induced secondary inorganic aerosol formation dominated the light absorption enhancement of refractory black carbon at an urban site in northwest China

Reducing the uncertainty in aerosol radiative forcing requires a comprehensive understanding of the factors affecting black carbon (BC) light absorption. In this study, the characteristics and influencing factors of light absorption enhancement (Eabs) of refractory BC (rBC) were investigated by conducting intensive measurements at an urban site in northwest China during the early summer of 2018. On average, the absorption of rBC was enhanced by 34% as a result of the internal mixing of rBC with other aerosol components. Secondary inorganic aerosols (SIAs) were found to have considerable effects on the Eabs of rBC. The Eabs showed a robust linear relationship with the bulk nitrate/rBC mass ratio in fine particles, with an increase of 3% per nitrate/rBC ratio unit. A notable increase in Eabs from dusk to the next morning was observed, in accordance with the diurnal variations in nitrate and sulfate, indicating the excellent contribution of non-photochemical formation of SIAs to Eabs. This fact was further supported by the positive correlation of the nitrate/rBC and sulfate/rBC ratios with relative humidity (RH) rather than photochemical indicators. This study indicates that the aqueous and/or heterogeneous formation of SIAs is likely the dominant aging pathway leading to the high Eabs of rBC.

Diurnal source apportionment of organic and inorganic atmospheric particulate matter at a high-altitude mountain site under summer conditions (Sierra Nevada; Spain)

High-altitude mountain areas are sentinel ecosystems for global environmental changes such as anthropogenic pollution. In this study, we report a source apportionment of particulate material with an aerodynamic diameter smaller than 10 μm (PM10) in a high-altitude site in southern Europe (Sierra Nevada Station; SNS (2500 m a.s.l.)) during summer 2021. The emission sources and atmospheric secondary processes that determine the composition of aerosol particles in Sierra Nevada National Park (Spain) are identified from the concentrations of organic carbon (OC), elemental carbon (EC), 12 major inorganic compounds, 18 trace elements and 44 organic molecular tracer compounds in PM10 filter samples collected during day- and nighttime. The multivariate analysis of the joint dataset resolved five main PM10 sources: 1) Saharan dust, 2) advection from the urbanized valley, 3) local combustion, 4) smoke from a fire-event, and 5) aerosol from regional recirculation with high contribution of particles from secondary inorganic and organic aerosol formation processes. PM sources were clearly associated with synoptic meteorological conditions, and day- and nighttime circulation patterns typical of mountainous areas. Although a local pollution source was identified, the contribution of this source to PM10, OC and EC was small. Our results evidence the strong influence of middle- and long-range transport of aerosols, mainly from anthropogenic origin, on the aerosol chemical composition at this remote site.

Establishing an emission inventory for ammonia, a key driver of haze formation in the southern North China plain during the COVID-19 pandemic

Despite the significant reduction in atmospheric pollutant levels during the COVID-19 lockdown, the presence of haze in the North China Plain remained a frequent occurrence owing to the enhanced formation of secondary inorganic aerosols under ammonia-rich conditions. Quantifying the increase or decrease in atmospheric ammonia (NH3) emissions is a key step in exploring the causes of the COVID-19 haze. Historic activity levels of anthropogenic NH3 emissions were collected through various yearbooks and studies, an anthropogenic NH3 emission inventory for Henan Province for 2020 was established, and the variations in NH3 emissions from different sources between COVID-19 and non-COVID-19 years were investigated. The validity of the NH3 emission inventory was further evaluated through comparison with previous studies and uncertainty analysis from Monte Carlo simulations. Results showed that the total NH3 emissions gradually increased from north-west to south-east, totalling 751.80 kt in 2020. Compared to the non-COVID-19 year of 2019, the total NH3 emissions were reduced by approximately 4 %, with traffic sources, waste disposal and biomass burning serving as the sources with the top three largest reductions, approximately 33 %, 9.97 % and 6.19 %, respectively. Emissions from humans and fuel combustion slightly increased. Meanwhile, livestock waste emissions decreased by only 3.72 %, and other agricultural emissions experienced insignificant change. Non-agricultural sources were more severely influenced by the COVID-19 lockdown than agricultural sources; nevertheless, agricultural activities contributed 84.35 % of the total NH3 emissions in 2020. These results show that haze treatment should be focused on reducing NH3, particularly controlling agricultural NH3 emissions.

Chemical compositions and possible transportation of PM2.5 during two haze periods in a coastal city of the North China Plain

Although numerous studies have been carried out to study haze formation in the North China Plain (NCP) and Northeastern Plain (NP), little is known about the chemical compositions and haze formations in Qinhuangdao city, which is located in the northeast edge of the NCP and adjacent to the NP. In this study, water‐soluble inorganic ions, organic carbon and elemental carbon (EC) were analysed offline during two haze periods from October 29 to November 7, 2021. The results showed that NO3− and organic matter (OM) accounted for 34.81% and 21.15% of total PM2.5 mass concentration, respectively, followed by NH4+ (14.06%) and SO42− (12.33%). The sulphur oxidation ratio and nitrogen oxidation ratio as well as OM/EC ratio on haze days were higher than those on non‐haze days, suggesting both high secondary inorganic and organic aerosol formation on haze days under high relative humidity. Source apportionment results showed that marine aerosols contributed small of total aerosol particle loads, while the combustion‐related sources were the most, possibly coal combustion, biomass burning and vehicle emissions. Air masses during haze periods mainly came from southwest and west directions in this case. Further calculated meteorological data of 2018–2021 showed high PM2.5 mass in Qinhuangdao were mainly affected by low‐speed southwest wind in autumn. The results highlighted the important role of long‐range transport of air pollutants from the NCP instead of the NP on haze formation in autumn in Qinhuangdao.

Trends of inorganic sulfur and nitrogen species at an urban site in western Canada (2004–2018)

A 15-year (2004–2018) record of measurement data of gaseous and particulate sulfur and nitrogen pollutants in air collected at an urban site in Burnaby in western Canada was analyzed for generating their decadal trends using three different methods, including linear regression, Mann-Kendall test and Theil-Sen trend estimator (MK-TS), and ensemble empirical mode decomposition (EEMD). Annual mean concentration of SO2 and SO42− decreased by about 59% and 42%, respectively, during the 15-year period. The slower decreases of SO42− than SO2 were mainly caused by the increased O3 concentration and temperature in spring and summer, which promoted conversion of SO2 to SO42− through gas-phase reaction, and by the increased aerosol pH value and availability of H2O2 in winter, which enhanced aqueous-phase SO42− formation. Accordingly, the sulfur oxidation ratio (SOR) increased by 23% or more in spring, summer, and winter during the 15-year period. Annual mean concentrations of NO2 and NO3− declined by 36% and 38%, respectively, during this period. On seasonal basis, NO3− decreased faster than NO2 in autumn and slower in winter. The non-linear responses of NO3− to NO2 concentration decreases were more evident in winter than the other seasons, partly due to the increased particulate NO3− fraction caused by decreased temperature, increased aerosol pH value, and enhanced NO3− formation caused by increased O3 concentrations. Annual mean concentration of NH3 showed small increases due to stable NH3 emission and reduced conversion of NH3 to NH4+. NH4+ concentration decreased by 51% during the 15-year period. These results suggest that reduced oxidants levels are likely responsible for weakened formation of secondary inorganic aerosols, besides emission reductions for SO2 and NO2.

Measurement report: The 4-year variability and influence of the Winter Olympics and other special events on air quality in urban Beijing during wintertime

Abstract. Comprehensive measurements are vital to obtain big enough datasets for better understanding the complex atmosphere and further improving the air quality. To investigate the 4-year variation of air quality and the influences of special events (Beijing Winter Olympics, COVID lockdown and Chinese New Year) on it during the wintertime in polluted urban air, we conducted comprehensive observations in Beijing, China, during 1 January–20 February, in the years from 2019 to 2022. The mass concentration of PM2.5 and its composition (organics, nitrate, sulfate, ammonium, chloride and black carbon) and the number size distributions of particles (down to ∼1 nm) and ions, gaseous pollutants (CO, NOx, SO2, O3) and condensable vapors (sulfuric acid and oxygenated organic molecules), as well as meteorological parameters, were simultaneously measured. The days before 22 January without any special events in each year were selected to investigate the 4-year variability of air quality. We found that the concentrations of CO, NOx, total oxygenated organic molecules (OOMs), total PM2.5, organics, chloride and black carbon and the number concentration of sub-3 nm particles (N1.3−3) showed similar variations, decreasing from 2019 to 2021 and then increasing in 2022. For SO2, however, its concentration decreased year by year due to the significant emission reduction, further leading to the decrease of gaseous sulfuric acid and particulate sulfate from 2019 to 2022. O3 concentration showed an opposite 4-year variation compared with NOx. Meanwhile, both the oxygen and nitrogen contents of oxygenated organic molecules increased year by year, implying that not only the oxidation state of those compounds increased, but also NOx was involved more efficiently in their formation processes. With higher sulfuric acid concentrations and new particle formation (NPF) frequencies in 2021 than in 2022, and with the lowest concentrations of background aerosols and the lowest ambient temperatures in 2021, N1.3−3 was still the lowest in 2021. Unlike N1.3−3, the ion concentrations in both 0.8–2 and 2–4 nm size ranges were higher in 2021 than in the other years. Then, the days after 4 February were chosen to explore the influence of special events. The non-event days within this date range in 2019 and 2021 were chosen as the reference period. Due to the favorable meteorological conditions together with reductions in anthropogenic emissions, there were basically no haze events during the Olympics. Therefore, CO, NOx, SO2, total OOMs, accumulation-mode particles (N100−1000), and total PM2.5 and its composition were much lower, while ion concentrations were much higher compared with the reference period. Although there was also emission reduction during COVID, especially for NOx, the enhancement of secondary inorganic aerosol formation, together with unfavorable meteorological conditions, caused severe haze events during this period. Hence, CO, total OOMs and all PM2.5 compositions during COVID increased dramatically compared with the reference period. Influenced by SO2, condensation sink and sunlight, sulfuric acid concentration was found to be comparable between the Olympics and the reference period but was lower during COVID and Chinese New Year. Additionally, N1.3−3 was almost at the same level during different periods, indicating that the special events only had little impact on the NPF processes. These results provide useful information to the development of more targeted pollution control plans.

Elaborations of the influencing factors on the formation of secondary inorganic aerosols in a heavily polluted urban area of China

In this study, online water-soluble inorganic ions were detected to deduce the formation mechanism of secondary inorganic aerosol in Xianyang, China during wintertime. The dominant inorganic ions of sulfate (SO42−), nitrate (NO3−), and ammonium (NH4+) (the sum of those is abbreviated as SNA) accounted for 17%, 21%, and 12% of PM2.5 mass, respectively. While the air quality deteriorated from excellent to poor grades, the precursor gas sulfur dioxide (SO2) of SO42- increased and then decreased with a fluctuation, while nitrogen dioxide (NO2) and ammonia (NH3), precursors of NO3− and NH4+, and SNA show increasing trends. Meteorological factors including boundary layer height (BLH), temperature, and wind speed also show decline trends, except relative humidity (RH). Meanwhile, the secondary conversion ratio shows a remarkable increasing trend, indicating that there was a strong secondary transformation. From the perspective of chemical mechanisms, RH is positively correlated with sulfur oxidation ratios (SOR), nitrogen oxidation ratios (NOR), and ammonia conversion ratios, representing that the increase of humidity could promote the generation of SNA. Notably, SOR and NOR were also positively related to the ammonia. On the one hand, the low wind speed and BLH led to the accumulation of pollutants. On the other hand, the increases of RH and ammonia promoted more formations of SNA and PM2.5. The results advance our identification of the contributors to the haze episodes and assist to establish more efficient emission controls in Xianyang, in addition to other cities with similar emission and geographical characteristics.

Impact of primary emission variations on secondary inorganic aerosol formation: Prospective from COVID-19 lockdown in a typical northern China city

Hourly observations in northern China city of Taiyuan were performed to compare secondary inorganic aerosol (SIA) reaction mechanisms, and emission effects on SIA during the pre-lock and COVID-19 lock days. Emission control implemented and meteorological conditions during lock days both caused beneficial impact on air quality. NO2 showed the highest decrease ratio of −49.5%, while the relative fraction of NO3− in PM2.5 increased the most (2.7%). Source apportionment revealed the top three contributors to PM2.5 were secondary formation (SF), coal combustion (CC), and vehicle exhaust (VE) during both pre-lock and lock days. EC lock/pre were all lower than 1, suggesting the overall reduction of primary emissions during lock days, while the higher ratio of (SIA/EC) lock/pre (1.01–1.36) indicated the enhanced secondary formation in lock days. The ratio of SIA of pollution to clean days during lock periods considerably higher by 23.7% compared with that in pre-lock periods, which was indicated SIA secondary formation was more pronounced and contributed great to pollution days in lock periods though secondary formation existed in pre-lock and lock periods. Enhanced secondary formation of NO3− and SO42− during lock days might be mainly due to the increased in aqueous and gas-phase reactions, respectively. Except for SF, high contribution of VE and CC were also important for high SIA concentration in pre-lock and lock days, respectively. The decreased contribution of VE weakens its contribution to SIA formation, indicating the effectiveness of VE emission control, as confirmed during the COVID-19 pandemic. This study highlights the aqueous and gas-phase reactions for nitrate and sulfate, respectively, which contributed to heavy pollution, as well as indicated the important role of VE on SIA formation, suggesting the urgent need to further strengthen controls on vehicle emissions.

The shifting of secondary inorganic aerosol formation mechanisms during haze aggravation: the decisive role of aerosol liquid water

Abstract. Although many considerable efforts have been done to reveal the driving factors on haze aggravation, however, the roles of aerosol liquid water (ALW) in secondary inorganic aerosol (SIA) formation were mainly focused on the condition of aerosol liquid water content (ALWC) < 100 µg m−3. Based on the in situ high-resolution field observations, this work studied the decisive roles and the shifting of secondary inorganic aerosol formation mechanisms during haze aggravation, revealing the different roles of ALWC on a broader scale (∼500 µg m−3) in nitrate and sulfate formation induced by aqueous chemistry in the ammonia-rich atmosphere. The results showed that chemical domains of perturbation gas limiting the generation of secondary particulate matter presented obvious shifts from a HNO3-sensitive to a HNO3- and NH3-co-sensitive regime with the haze aggravation, indicating the powerful driving effects of ammonia in the ammonia-rich atmosphere. When ALWC < 75 µg m−3, the sulfate generation was preferentially triggered by the high ammonia utilization and then accelerated by nitrogen oxide oxidation from clean to moderate pollution stages, characterized by nitrogen oxidation ratio (NOR) < 0.3, sulfur oxidation ratio (SOR) < 0.4, ammonia transition ratio (NTR) < 0.7 and the moral ratio of NO3-/SO42-=2:1. When ALWC > 75 µg m−3, the aqueous-phase chemistry reaction of SO2 and NH3 in ALW became the prerequisite for SIA formation driven by Henry's law in the ammonia-rich atmosphere during heavy and serious stages, characterized by high SOR (0.5–0.9), NOR (0.3–0.5) and NTR (>0.7), as well as the high moral ratio of NO3-/SO42-=1:1. A positive feedback of sulfate on nitrate production was also observed in this work due to the shift in ammonia partitioning induced by the ALWC variation during haze aggravation. It implies the target controlling of haze should not simply focus on SO2 and NO2, but more attention should be paid to gaseous precursors (e.g., SO2, NO2, NH3) and aerosol chemical constitution during different haze stages.

A Box-Model Simulation of the Formation of Inorganic Ionic Particulate Species and Their Air Quality Implications in Republic of Korea

The Observation-Constrained Atmospheric BOX model (OCABOX) was used to analyze the formation of secondary inorganic PM species in the Seoul Metropolitan Area (SMA), South Korea. The measurement data of the ionic components of PM2.5 and their gaseous precursors made at the Olympic Park ground site (37.53°N, 127.12°E) during the Korea-United States Air Quality field campaign were used to run OCABOX in observation-based mode and compare the simulation results. The use of the HNO3 concentrations measured at a marine background site as the boundary conditions appeared to increase the accuracy of the model prediction of HNO3 and particulate NO3− concentrations. For the primary precursors emitted considerably throughout the SMA, such as NOx and NH3, using the data measured inside the SMA as the boundary conditions could lead to more accurate predictions. OCABOX was shown to be a reliable tool to analyze the formation of secondary inorganic aerosol in the SMA if used with appropriate regional background concentrations and observation-based constraints

Atmospheric ammonia in the rural North China Plain during wintertime: Variations, sources, and implications for HONO heterogeneous formation

Atmospheric ammonia (NH3) plays an important role in secondary inorganic aerosol formation. Understanding the temporal variations, sources, and environmental influences of NH3 is conducive to better formulate PM2.5 pollution control strategies for policy-makers. Here, we performed a comprehensive field campaign with the measurements of NH3 and related parameters at a rural site of the North China Plain (NCP) in winter of 2017. The results showed that residential coal combustion contributed dominantly to NH3 during the entire observation period, resulting in the obviously high average concentration of NH3 (31.2 ± 24.6 ppbv). The sensitivity tests of pH-NHx during the three different pollution periods suggested that the rural site was always in the NHx-rich atmosphere where high levels of NHx increased the particle pH inefficiently. Nevertheless, the particle pH still elevated by 1.5–2.2 units at the excessive NHx levels during the three pollution periods. In addition, the HONO/NO2 ratios were found to correlate linearly with NH3 concentrations, implying the acceleration effect of NH3 on HONO production from NO2 heterogeneous reactions. After considering the NH3-enhanced uptake coefficient of NO2 in the nocturnal HONO budget, the unknown source of HONO could be fully explained. Therefore, more attentions should be given for effective emission control of NH3 to improve air quality throughout the NCP, especially in the rural areas.

Ammonia Cycling and Emerging Secondary Aerosols from Arable Agriculture: A European and Irish Perspective

Ammonia (NH3) is a naturally occurring, highly reactive and soluble alkaline trace gas, originating from both natural and anthropogenic sources. It is present throughout the biosphere, yet plays a complicated role in atmospheric acid–base reactions resulting in the formation of inorganic secondary inorganic aerosols (SIAs). While the general mechanisms are recognised, factors controlling the reactions leading to SIA formation are less explored. This review summarises the current knowledge of NH3 sources, emission and deposition processes and atmospheric reactions leading to the formation of SIA. Brief summaries of NH3 and SIA long-range transport and trans-boundary pollution, a discussion of precursor species to SIAs (other than NH3), abiotic and biotic controls and state-of-the-art methods of measurement and modelling of pollutants are also included. In Ireland, NH3 concentrations remained below National and European Union limits, until 2016 when a rise in emissions was seen due to agricultural expansion. However, due to a lack of continuous monitoring, source and receptor relationships are difficult to establish, including the appointment of precursor gases and aerosols to source regions and industries. Additionally, the lack of continuous monitoring leads to over- and underestimations of precursor gases present, resulting in inaccuracies of the estimated importance of NH3 as a precursor gas for SIA. These gaps in data can hinder the accuracy and precision of forecasting models. Deposition measurements and the modelling of NH3 present another challenge. Direct source measurements are required for the parameterization of bi-directional fluxes; however, high-quality data inputs can be limited by local micrometeorological conditions, or the types of instrumentation used. Long-term measurements remain challenging for both aerosols and precursor gases over larger areas or arduous terrains.

PM2.5-bound Inorganic and Nonpolar Organic Compounds in Chuncheon, Korea

In this study, major chemical components of PM2.5 including nitrate, sulfate, organic carbon (OC), and elemental carbon (EC) were measured in Chuncheon, South Korea in May–June, 2021. Average PM2.5 concentration was 16.4±9.7 µg m−3, and OC was the largest contributor of PM2.5 mass concentration. High concentration episodes (HCEs), defined when PM2.5 concentration exceeded 30 µg m−3, were caused by Asian dust, secondary inorganic aerosol (SIA) formation, and primary OC emission. NH4+ was determined to be a limiting factor for SIA formation based on neutralization ratio. There was statistically significant correlation between n-alkanes and PM2.5, and odd alkanes including C27, C29, and C31, which are generally emitted from biogenic sources, were abundant species, suggesting the importance of natural sources over fossil fuel combustion. Polycyclic aromatic hydrocarbons (PAHs) concentrations were significantly lower than those measured at the same sampling site in 2014–2015. Based on the diagnostic ratios of PAHs, vehicular emission, rather than solid fuel emission, were significant for PAHs. Detailed characterization of chemical composition of PM2.5 reported in this study can be of great help in establishing an appropriate abatement policy to reduce PM2.5 concentrations.

Molecular Tracer Characterization during COVID-19 Pandemic in Shanghai: Changes in the Aerosol Aqueous Environment and Implications for Secondary Organic Aerosol Formation

The COVID-19 lockdown has opened a unique window for investigating aerosol formation and evolution with controlled anthropogenic emissions in urban areas. Here, variations of PM2.5 chemical compositions, gaseous pollutants, meteorological conditions, and secondary organic aerosol (SOA) molecular tracers were monitored during three stages at an urban site (Pudong) and a suburban site (Qingpu) in Shanghai, which were defined as pre-COVID lockdown (PL), during COVID lockdown (DL), and after COVID lockdown (AL) in 2020. Abundances of pollutants during the same periods back in 2019 were also analyzed for a more comprehensive intercomparison and evaluation of the impact of the 2020 COVID-19 lockdown on regional air quality. With the sudden cessation of anthropogenic activities during the lockdown, significant reductions in PM2.5 were observed compared to both PL in 2020 (32% in Pudong and 36% in Qingpu) and the DL period back in 2019 (31% in Pudong and 35% in Qingpu), which was accompanied by the significantly reduced PM2.5 components (29–44% and 14–44% reductions in sulfate, nitrate, ammonium, organic carbon, and elemental carbon for Pudong and Qingpu, respectively). In particular, with the reduced secondary inorganic aerosol (SIA), the time series of SOA molecular tracers also underwent significant reduction that was characteristic to the lockdown. Amid the uncontrolled biogenic emissions and even slightly enhanced atmospheric oxidation capacity during the 2020 DL period, controlling anthropogenic emissions exhibits synergistic effects on the reduction of SIA and SOA, which could be further attributed to the changes in the aerosol aqueous-phase environment, such as aerosol liquid water content (ALWC), ionic strength, sulfate content, and particulate NH4+. Based on thermodynamic modeling, greatly reduced ALWC was observed during 2020 DL, which can prevent the partitioning of oxygenated organics into the condensed phase as well as the aqueous-phase formation of SOA. Higher ionic strength in 2020 DL may have a “salting-out” effect on gas–particle partitioning of oxygenated organics. The reduced SOA during 2020 DL at both sites can generally be reflected by the predicted heterogeneous reaction kinetics (γ) of the isoprene SOA formation pathway. Overall, our study showed a synergistic effect in suppressing SIA and SOA formation upon the reduction of anthropogenic emissions during the COVID-19 lockdown, which shed light on the importance of controlling anthropogenic emissions in regulating secondary aerosol formation in typical urban areas of East China.

Transboundary haze from peatland fires and local source-derived PM2.5 in Southern Thailand

This study characterizes impacts on PM2.5 of transboundary haze from peatland fires in Indonesia and local emission sources during 2019–2020 to a large and densely populated city, Hat Yai in southern Thailand. Organic carbon (OC), elemental carbon (EC), water soluble organic carbon (WSOC), water soluble ions (WSI: Cl−, NO3−, SO42− and NH4+), element tracers (K, Na, Mg and Ca), heavy metals (Cr, Co, Pb, Cd, Ni, Mn) and As, and 16 polycyclic aromatic hydrocarbon (PAHs) components from PM2.5 samples (n = 18) were measured to identify local and regional emission sources using a chemical mass balance (CMB) model. We used a combination of air mass backward trajectories and CMB source apportionment to identify PM2.5 sources. An increase of PM2.5 and chemical component concentrations, during the transboundary haze period, were clearly influenced by aerosols from open biomass burning in Indonesia: PAH concentrations were 2 times higher and OC concentrations, 5 times higher. Secondary organic carbons were predominant during transboundary haze periods, accounting for 52–58% of total OC, indicating higher secondary organic aerosol formation. High K levels demonstrated that the dominant source during this period was biomass burning. Whereas a high level of Ca in the background air came from urban road dust, as well as local biomass burning. Moreover, the increased concentration of SO42−, NH4+ and NO3− during the wet season, as well as transboundary haze periods, was mainly derived the secondary inorganic aerosol formation. Effect on PM2.5 concentration from a volcanic eruption near the air mass trajectory during the sampling period was minimal. However, it may have contributed slightly to an increase of SO42− concentration in PM2.5. Sources of PM2.5 in Hat Yai were clearly influenced by local emission sources, e.g. diesel combustion and biomass burning (rubber wood and rice straw), transboundary haze and also secondary organic and inorganic aerosols.