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.

Ammonium Chloride Associated Aerosol Liquid Water Enhances Haze in Delhi, India.

The interaction between water vapor and atmospheric aerosol leads to enhancement in aerosol water content, which facilitates haze development, but its concentrations, sources, and impacts remain largely unknown in polluted urban environments. Here, we show that the Indian capital, Delhi, which tops the list of polluted capital cities, also experiences the highest aerosol water yet reported worldwide. This high aerosol water promotes secondary formation of aerosols and worsens air pollution. We report that severe pollution events are commonly associated with high aerosol water which enhances light scattering and reduces visibility by 70%. Strong light scattering also suppresses the boundary layer height on winter mornings in Delhi, inhibiting dispersal of pollutants and further exacerbating morning pollution peaks. We provide evidence that ammonium chloride is the largest contributor to aerosol water in Delhi, making up 40% on average, and we highlight that regulation of chlorine-containing precursors should be considered in mitigation strategies.

Characteristics, formation, and sources of PM2.5 in 2020 in Suzhou, Yangtze River Delta, China.

Here we present seasonal chemical characteristics, formations, sources of PM2.5 in the year 2020 in Suzhou, Yangtze River Delta, China. Expectedly, organic matter (OM) found to be the most dominant component of PM2.5, with a year-average value of 10.3 ± 5.5 µg m-3, followed by NO3- (6.7 ± 6.5 µg m-3), SO42- (3.3 ± 2.5 µg m-3), NH4+ (3.2 ± 2.8 µg m-3), EC (1.1 ± 1.3 µg m-3), Cl- (0.57 ± 0.56 µg m-3), Ca2+ (0.55 ± 0.91 µg m-3), K+ (0.2 ± 1.0 µg m-3), Na+ (0.18 ± 0.45 µg m-3), and Mg2+ (0.09 ± 0.15 µg m-3). Seasonal variations of PM2.5 showed the highest average value in spring, followed by winter, fall, and summer. Meanwhile, the formation mechanisms of the major PM2.5 species (NO3-, SO42-, and OM) varied in seasons. Interestingly, NO2 may have the highest conversion rate to NO3- in spring, which might be linked with the nighttime chemistry due to the high relative humidity. Moreover, OM in summer was mainly produced by the daytime oxidation of volatile organic compounds, while local primary organic aerosols might play a significant role in other seasons. Source apportionment showed that the more-aged PM2.5 contributed significantly to the PM2.5 mass (42%), followed by the dust-related PM2.5 (38%) and the less-aged PM2.5 (21%). Potential contribution source function (PSCF) results indicated that aged PM2.5 were less affected by transportation than dust-related PM2.5.

[Characteristics of Secondary Inorganic Ions in PM2.5 and Its Influencing Factors in Summer in Zhengzhou].

Nitrate (NO3-), sulfate (SO42-), and ammonium (NH4+) are important components of PM2.5, and studying their characteristics and influencing factors is essential for the continuous improvement of air quality. A series of online instruments were used to analyze the chemical components of PM2.5 in Zhengzhou in the summer of 2020. The results showed that the average ρ(PM2.5) was (28 ±13) µg·m-3, showing a daily variation characteristic of high at night and low during the day. The main concentrations of NO3-, SO42-, and NH4+ were (7.8 ±6.7), (7.2 ±3.7), and (5.5 ±3.1) µg·m-3, accounting for 22%, 21%, and 16% in PM2.5, respectively. The proportions of NO3- (27%) and SO42- (23%) in PM2.5, respectively, increased with the increase in PM2.5 and O3 concentration. In addition, the proportions of NO3- and NH4+ increased under low wind speed, high humidity, low temperature, and rainfall conditions. Moreover, the proportion of NO3- showed a daily variation characteristic of high at night and low during the day, whereas the opposite was true for SO42-. The gas-particle partitioning process of NH4NO3 was the main factor affecting the concentrations of NO3- and NH4+ in PM2.5. Low temperature, high humidity, and high aerosol water content concentrations favored the partitioning of HNO3 and NH3 to the particulate phase. High pH also favored the partitioning of gas-phase HNO3 to NO3-; however, it was not conducive to the partition of NH3 to NH4+. These trends partially explained the increase in the concentration and proportion of NO3- in PM2.5 under different scenarios.

HONO chemistry and its impact on the atmospheric oxidizing capacity over the Indo-Gangetic Plain.

Chemical processes involving nitrous acid (HONO) play a pivotal role as it is a notable source of hydroxyl (∙OH) radicals, influencing the oxidation capacity of the atmosphere. We conduct a comprehensive investigation into the temporal dynamics of HONO, other gases (nitrogen oxides (NOx), ozone (O3), ammonia (NH3), sulphur dioxide (SO2), and nitric acid (HNO3)), particulate matter (PM2.5), and meteorological parameters using measurements that took place during the Winter Fog Experiment (WiFEx) campaign in Delhi, India, during the winter of 2017-2018. Remarkable day-to-day variations in HONO concentrations are observed, with the peak value reaching 54.5 µg m-3 during a fog event. This coincides with elevated levels of sulfate and nitrate in aerosols, underscoring the significant role of heterogeneous fog chemistry in HONO production. We investigated HONO sources and sinks during fog periods by using a photochemical box model. The model shows that the gas-phased chemistry of HONO predicts concentrations lower by an order of magnitude compared to observations (peaking at 0.60 µg m-3 compared to the average observed value of 7.00 µg m-3). The calculated production rates of HONO from observations for daytime to nighttime peaks are 3.10 µg m-3 h-1 (1.1 × 107 molecules cm3 s-1) and 2.00 µg m-3 h-1 (7.1 × 106 molecules cm3 s-1), respectively. This shows the existence of an undefined heterogeneous reaction pathway for HONO production. At the peak of HONO concentration, we estimated an ∙OH formation rate of 9.4 × 107 molecules cm3 s-1 due to the photolysis of HONO, which is much higher than the production of HONO from the reaction of O1D with H2O. This underscores the predominant role of HONO photolysis as the primary source of ∙OH radicals compared to other pathways and highlights the significant role of HONO chemistry in influencing atmospheric oxidation capacity.

Improvement of model simulation for summer PM2.5 and O3 through coupling with two new potential HONO sources in the North China Plain.

A large fraction of fine particulate matter (PM2.5) and ozone (O3) in the troposphere originates from secondary formation through photochemical processes, which remarkably contributes to the deterioration of regional air quality in China. The photochemical reactions initiated by hydroxyl radicals (OH) play vital roles in secondary PM2.5 and O3 formation. In contrast, the OH levels in polluted areas are underestimated by current chemical transport models (CTMs) because of the strongly unknown daytime sources of tropospheric nitric acid (HONO), which has been recognized as the dominant source of primary OH in polluted areas of China. In this study, the atmospheric HONO levels at two urban sites were found to be significantly underestimated by the WRF-Chem model based on available information on HONO sources. The HONO levels could be well reproduced by the WRF-Chem model after incorporating two new potential HONO sources from the photochemical reactions of NOx, as proposed in our previous study based on chamber experiment results. Comparing the simulations with available information of HONO sources, the simulated levels of atmospheric OH, secondary inorganic and organic aerosols (SIA and SOA), PM2.5 and daily maximum 8-h average (MDA8) O3 were evidently elevated or were closer to the observations over the North China Plain (NCP), with elevation percentages of 0.48-20.1 %, and a decrement percentage of -5.79 % for pNO3-. Additionally, the compensating errors in modeling PM2.5 and the gap in MDA8 O3 levels between observation and simulation in 2 + 26 cities became evidently smaller. The results of this study indicated that the empirical parameterization of two new potential HONO sources through photochemical reactions of NOx improved the model performance in modeling PM2.5 and O3 by narrowing the gap in daytime HONO levels between simulation and observation, although their detailed chemical mechanisms are still unknown and should be further investigated and explicitly parameterized.

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.

[Characteristics and Cause of PM2.5 During Haze Pollution in Winter 2022 in Zhoukou, China].

The characteristics and main factors of causes of haze in Zhoukou in January 2022 were analyzed. Six air pollutants, water-soluble ions, elements, OC, EC, and other parameters in fine particulate matter were monitored and analyzed using a set of online high-time-resolution instruments in an urban area. The results showed that the secondary inorganic aerosols(SNA), carbonaceous aerosols(CA, including organic carbon OC and inorganic carbon EC), and reconstructed crustal materials(CM, such as Al2O3, SiO2, CaO, and Fe2O3, etc.) were the three main components, accounting for 61.3%, 24.3%, and 9.72% in PM2.5, respectively. The concentrations of SNA, CA, CM, and SOA were increased, accompanied with higher AQI. The sulfur oxidation rate(SOR) and nitrogen oxidation rate(NOR) in January were 0.53 and 0.46, respectively. The growth rates[µg·(m3·h)] of sulfate and nitrate were 0.027(-5.89-9.47, range) and 0.051(-23.1-12.4), respectively. During the haze period, the growth rates of sulfate and nitrate were 0.13 µg·(m3·h)-1and 0.24 µg·(m3·h)-1, which were 4.8 and 4.7 times higher than the average value of January, respectively. Although the sulfur oxidation rate was greater than the nitrogen oxidation rate, the growth rate of nitrate was approximately 1.8 times that of sulfate owing to the difference in the concentration of gaseous precursors and the influence of relative humidity. The growth rates of nitrate in SNA were significantly higher than those of sulfate on heavily polluted days. The values of SOR, NOR, and concentrations of SNA and SOA during higher AQI and humidity periods were higher than those in lower AQI and humidity periods. The Ox(NO2+O3) decreased with the increase in relative humidity. The SOA was higher at nighttime, increasing faster with the humidity than that in daytime. Under the situation of lower temperature, higher humidity, and lower wind speed, the emission of gaseous precursors of SNA requires further attention in Zhoukou in winter. Advanced control strategies of emissions of SO2 and NO2, such as mobile sources and coal-burning sources, could reduce the peak of haze in winter efficiently.

Elevated particle acidity enhanced the sulfate formation during the COVID-19 pandemic in Zhengzhou, China.

The significant reduction in PM2.5 mass concentration after the outbreak of COVID-19 provided a unique opportunity further to study the formation mechanism of secondary inorganic aerosols. Hourly data of chemical components in PM2.5, gaseous pollutants, and meteorological data were obtained from January 1 to 23, 2020 (pre-lockdown) and January 24 to February 17, 2020 (COVID-lockdown) in Zhengzhou, China. Sulfate, nitrate, and ammonium were the main components of PM2.5 during both the pre-lockdown and COVID-lockdown periods. Compared with the pre-lockdown period, even though the concentration and proportion of nitrate decreased, nitrate was the dominant component in PM2.5 during the COVID-lockdown period. Moreover, nitrate production was enhanced by the elevated O3 concentration, which was favorable for the homogeneous and hydrolysis nitrate formation despite the drastic decrease of NO2. The proportion of sulfate during the COVID-lockdown period was higher than that before. Aqueous-phase reactions of H2O2 and transition metal (TMI) catalyzed oxidations were the major pathways for sulfate formation. During the COVID-lockdown period, TMI-catalyzed oxidation became the dominant pathway for aqueous-phase sulfate formation because the elevated acidity favored the dissolution of TMI. Therefore, the enhanced TMI-catalyzed oxidation affected by the elevated particle acidity dominated the sulfate formation, resulting in the slight increase of sulfate concentration during the COVID-lockdown period in Zhengzhou.

Formation pathway of secondary inorganic aerosol and its influencing factors in Northern China: Comparison between urban and rural sites.

Secondary inorganic aerosol, including sulfate, nitrate, and ammonium (SNA), is a significant source of PM2.5 during haze episodes in Northern China. A series of high-time-resolution instruments were used in collecting PM2.5 chemical components and gaseous pollutants during a regional heavy pollution process from January 12-25, 2018, at urban and rural sites. SNA, accounting for >50% of PM2.5 at both sites, had greater importance on haze formation. Gas-phase and N2O5 hydrolysis reactions were the main formation pathways of nitrate during the daytime and nighttime, respectively. The OH radical was the primary factor for gas-phase reactions. HONO photolysis played a more critical role in OH radical formation when O3 concentration decreased during the haze episode. N2O5 hydrolysis reaction was mainly affected by O3 and aerosol water content. High relative humidity, aerosol water content, and N2O5 concentrations at the urban site enhanced the hydrolysis reactions more than those at the rural site. The aqueous-phase reactions dominated the sulfate formation with the highest rate of transition metal ion catalytic and H2O2 oxidation reactions at the urban and rural sites, respectively. Elevated relative humidity and particle acidity at the urban site resulted in a higher formation rate of aqueous-phase sulfate than at the rural site. The gas-particle partition coefficient of NH3 had a negative correlation with the particle pH, and the presence of NH3 could promote the increase of SNA concentration. Thus, more attention should be paid to the differences in SNA formation between urban and rural regions when formulating air quality policies.

Estimation and variation analysis of secondary inorganic aerosols across the Greater Bay Area in 2005 and 2015.

As the concentrations of primary components of fine particulate matter (PM2.5) have substantially decreased, the contribution of secondary inorganic aerosols to PM2.5 pollution has become more prominent. Therefore, understanding the variations in and characteristics of secondary inorganic aerosols is vital to further reducing PM2.5 concentrations in the future. In this study, an ensemble back-propagation neural network model was built by combining 3D numerical models, observation data, and machine learning methods, to estimate the concentrations of secondary inorganic aerosols (SO2-4, NO-3, and NH+4) across the Greater Bay Area (GBA) in 2005 and 2015. The ensemble model provided a better estimation than the 3D numerical air quality model, with higher correlation coefficients (approximately 0.85) and lower root mean square errors. The model revealed that the concentrations of the SO2-4, NO-3, and NH+4 decreased by 1.91, 0.20, and 0.49 µg/m3, respectively, from 2005 to 2015. To investigate the oxidation and acidy of sulfate, the sulfur oxidation ratio (SOR), degree of sulfate neutralization (DSN), and particle neutralization ratio (PNR) were calculated and analyzed for 2005 and 2015 across the GBA region. The SOR slightly increased in summer, but decreased in other seasons in 2015, indicating the overall weaker sulfate chemical formation due to sulfur emission control measures. The increasing DSN and PNR indicated that more sulfate was neutralized due to reduced sulfur emission and increased ammonia availability. Our study suggests that more effort is needed to control ammonia emission to further reduce the concentrations of SO2-4, NO-3, and NH+4 across the GBA region in the future.

Incorporation and improvement of a heterogeneous chemistry mechanism in the atmospheric chemistry model GRAPES_Meso5.1/CUACE and its impacts on secondary inorganic aerosol and PM2.5 simulations in Middle-Eastern China.

Heterogeneous chemistry is considered one of the critical pathways of secondary inorganic aerosol (SIA) productions. In this study, a heterogeneous chemistry mechanism is incorporated into the atmospheric chemistry model GRAPES_Meso5.1/CUACE. Varying uptake coefficient schemes of SO2 and NO2 are compared and the equivalent ratio of inorganic aerosol (ER)-dependent scheme for SO2 and relative humidity (RH)/ER-dependent scheme for NO2 are used to form the improved heterogeneous chemistry. Focusing on a severe haze episode in Middle-Eastern China, the impacts of heterogeneous mechanism on SIA and PM2.5 composition are investigated based on the updated model. Study results show that the differences in RH or ER uptake coefficients result in obvious differences in sulfate and nitrate concentrations, especially during the severe pollution period, because the ER schemes restrict the excessive production of sulfate and nitrate under high RH effectively by including the self-limitation of heterogeneous reactions, which shows better performance in capturing the magnitude and temporal variations of surface SIA and PM2.5. Normalized mean bias of sulfate, nitrate, ammonium, and PM2.5 in megacity Beijing decreases from -27.0, -28.3, -58.2, and -26.3 to 1.0, -2.2, -47.2, and -16.5 %, respectively. And the fractions of sulfate, nitrate, ammonium, and organics during the polluted period change from 13.7, 19.3, 6.9, and 60.1 to 16.5, 23.0, 7.6, and 52.9 %, respectively, which is more consistent with the observation (16.0, 23.2, 14.1, and 46.7 %). SIA and PM2.5 simulations in another megacity Shanghai have the similar improvements. The modeled SIA by heterogeneous processes contributes 11.7 % of total PM2.5 in Beijing and 22.5 % in Shanghai. That is 13.5 % in the Chinese megalopolis Beijing-Tianjin-Hebei and 19.8 % in Yangtze-River-Delta, indicating a considerable contribution of heterogeneous pathways to haze pollution. This work indicates the importance of detailed and reasonable heterogeneous schemes for better SIA and haze/fog prediction in the atmospheric chemistry model.

Model vs. observation discrepancy in aerosol characteristics during a half-year long campaign in Northeast China: The role of biomass burning.

Complex air pollutant sources and distinct meteorological conditions resulted in unique wintertime haze pollution in the Harbin-Changchun (HC) metropolitan area, China's only national-level city cluster located in the severe cold climate region. In this study, field observation and air quality modeling were combined to investigate fine particulate matter (PM2.5) pollution during a six-month long heating season in HC's central city (Harbin). The model significantly underpredicted PM2.5 and organic carbon (by up to ∼230 µg/m3 and 110 µgC/m3, respectively, in terms of daily average) when levoglucosan concentrations were above 0.5 µg/m3. Based on a synthesis of levoglucosan concentrations and fire counts, the large gaps were attributed to underestimation of open burning emissions by the model. However, the model tended to overpredict elemental carbon (more significantly at higher NO2), likely pointing to an overestimation of vehicle emissions. With increasing levoglucosan, the difference between observed and simulated nitrate (nitrateobs ‒ nitratemod, i.e., Δnitrate) showed a transition from negative to positive values. The positive Δnitrate were attributed to underprediction of the open-burning related nitrate, whereas the negative Δnitrate were likely caused by overprediction of nitrate from other sources (presumably vehicle emissions). The dependence of Δnitrate on levoglucosan indicated that with stronger impact of open burning, the overprediction effect was gradually offset and finally overwhelmed. Influence of open burning on sulfate formation was evident as well, but less apparent compared to nitrate. This study illustrates how the uncertainties in open burning emissions will influence PM2.5 simulation, on not only primary components but also secondary species.

Role of ammonia in secondary inorganic aerosols formation at an ammonia-rich city in winter in north China: A comparative study among industry, urban, and rural sites.

Ammonia is essential for the generation of secondary inorganic aerosols (SIA) in particulate matter, which affects severely the air quality in north China. In this study, PM2.5 sampling was conducted as well as gaseous pollutant concentration and meteorological parameters were measured from November 2017 to January 2018. PM2.5 concentration was highest in the industrial site (94.8 ± 41.7 µg m-3), followed by urban (40.9 ± 24.1 µg m-3) and rural (35.6 ± 20.3 µg m-3) sites. The mass ratio of NO3-/SO42- exhibited clear site variations, with the highest average value of 1.2 was found at the urban site, likely due to the dense traffic volume resulting in higher emissions of NO2, and the lowest value of 0.9 at the industry site. The presence of Excess-NHx (E-NHx), raising the pH 24 by 1.4, 1.3, and 1.4 units in industry, urban, and rural sites, respectively, might be vital for raising the aerosol pH. Correlation coefficients of Nitrogen oxidation rate (NOR, NOR = [NO3-]/[NO3-] + [NO2]) vs. Photochemical oxidants (Ox, NO2 +O3 in our study) and NOR vs. aerosol water content (AWC) at three sites were implied that both homogeneous and heterogeneous reactions occurred for nitrate formation in industry site, while heterogeneous reactions were dominant in urban and rural sites. Oxidation rates were most sensitive to the variation of E-NHx concentration at rural site, followed by the urban and industry sites, which was shown by the fact that the increase in E-NHx concentration by 1.0 µg m-3 increased the SIA concentration by 1.21, 1.02, and 0.37 µg m-3 at rural, urban, and industry sites, respectively. With the increase in NHx emissions at present, the role of NHx in SIA formation at ammonia-rich atmosphere requires more attention, especially in the less-noticed rural areas.

Pollution severity-dependent aerosol light scattering enhanced by inorganic species formation in Beijing haze.

The dependence of aerosol optical properties on the chemical composition and size of particles in haze in Beijing was studied. We measured the scattering coefficient of dehydrated PM2.5 aerosols (σsp_dry) and analyzed the chemical composition of PM2.5. We also monitored the size distribution of particles in the range of ~10-700 nm to observe the particle growth (PGsize). Results showed that the concentrations of secondary inorganic aerosols (SIAs) and the mean size of PM2.5 particles (scattering Ångström exponent decreasing) increased with the deterioration of the air quality and increase in relative humidity (RH) which enhanced mass scattering efficiency and increased PM2.5. Thus, the increase in σsp_dry was particularly dramatic and highly sensitive to the ambient RH in severe haze stages. When the ratio of SIAs to PM2.5 (MSIAs) exceeded 0.35 during the polluted environment, the water content, PGsize, and σsp_dry showed distinct increases, indicating that the formation of SIAs enhanced water vapor condensation and particle growth. This finding revealed the existence of a critical value for MSIAs in terms of describing the correlation of σsp_dry variation with pollution severity. The estimation of the respective contributions of individual components to σsp_dry with the IMPROVE formula revealed that ammonium nitrate and ammonium sulfate were the two largest contributors. These results indicate that the rapid formation of SIAs and PGsize under humid conditions are the key factors contributing to the increased σsp_dry via enhanced mass scattering efficiency and increased PM2.5 in the severe haze observed in this study.

Particulate air pollution from different sources and mortality in 7.5 million adults - The Dutch Environmental Longitudinal Study (DUELS).

BACKGROUND: Long-term exposure to particulate air pollution has been associated with mortality in urban cohort studies. Few studies have investigated the association between emission contributions from different particle sources and mortality in large-scale population registries, including non-urban populations. OBJECTIVES: The aim of the study was to evaluate the associations between long-term exposure to particulate air pollution from different source categories and non-accidental mortality in the Netherlands based on existing national databases. METHODS: We used existing Dutch national databases on mortality, individual characteristics, residence history, neighbourhood characteristics and modelled air pollution concentrations from different sources and air pollution components: particulate matter PM10, primary particulate matter PM10 (PPM10), particulate matter PM2.5, primary particulate matter PM2.5 (PPM2.5), elemental carbon (EC), nitrogen dioxide (NO2) and secondary inorganic aerosol (SIA) in PM10 (SIA10) or in PM2.5 (SIA2.5). We established a cohort of 7.5 million individuals 30 years or older. We followed the cohort for eight years (2008-2015). We applied Cox proportional hazard regression models adjusting for potential individual and area-specific confounders. RESULTS: We found statistically significant associations between total and primary particulate matter (PM10 and PM2.5), elemental carbon and mortality. Adjustment for nitrogen dioxide did not change the associations. Secondary inorganic aerosol showed less consistent associations. All primary PM sources were associated with mortality, except agricultural emissions and, depending on the statistical model, industrial PM emissions. CONCLUSIONS: We could not identify one or more specific source categories of particulate air pollution as main determinants of the mortality effects found in this and in a previous study. This suggests that present policy measures should be focussed on the wider spectrum of air pollution sources instead of on specific sources.

Chemical characteristics, sources and evolution processes of fine particles in Lin'an, Yangtze River Delta, China.

In this study, daily PM2.5 mass and chemical composition were measure in Lin'an Reginal Background Station, Yangzte River Delta, from March 1, 2018, to February 28, 2019. Organic matter (OM) was found to be the most dominant component in four seasons. The proportions of nitrate in PM2.5 presented dramatically lowest in warm seasons but highest in winter, indicating that NO3- was maily driven by thermodynamics. Regional transportation in winter plays a strong impact on PM2.5 concentration, which showed the highest average mass of 60.1 µg m-3. Sulfate occupied a significant portion of PM2.5 in summer (19%), followed by spring (17%), fall (15%), and winter (12%), respectively, suggesting photochemical processes may play a dominant role in the sulfate formation. Secondary inorganic aerosol (SIA) was the dominant component (70%) in the highest polluted periods (PM2.5 > 75 µg m-3), whereas OM decreased into the lowest fraction (22%) of PM2.5. Nitrate was the most important component in SIA in the highest polluted periods with regarding winter. Source apportionment results shown that winter haze was likely strongly dominated by SIA, which was mainly affected by air masses from the North China Plain and Shang-Hangzhou direction. PM2.5 is known to play an important role in sunlight absorption and reversing to human health, continuous observation on PM2.5 species in a background site can help us to evaluate the control policy, and promote our insights to lifetime, formation pathways, health effects of PM2.5.

Fossil-driven secondary inorganic PM2.5 enhancement in the North China Plain: Evidence from carbon and nitrogen isotopes.

Measuring isotopic ratios in aerosol particles is a powerful tool for identifying major sources, particularly in separating fossil from non-fossil sources and investigating aerosol formation processes. We measured the radiocarbon, stable carbon, and stable nitrogen isotopic composition of PM2.5 in Beijing (BJ) and Changdao (CD) in the North China Plain (NCP) from May to mid-June 2016. The mean PM2.5 concentrations were 48.6 ± 28.2 µg m-3 and 71.2 ± 29.0 µg m-3 in BJ and CD, respectively, with a high contribution (∼66%) from secondary inorganic aerosol (SIA; NO3-, NH4+, and SO42-). The mean δ13C of total carbon (TC) and δ15N of total nitrogen (TN) values differed significantly between the two sites (p-value of <0.001): -25.1 ± 0.3‰ in BJ and -24.5 ± 0.4‰ in CD and 10.6 ± 1.8‰ in BJ and 5.0 ± 3.1‰ in CD, respectively. In BJ, the average δ15N (NH4+) and δ15N (NO3-) values were 12.9 ± 2.3‰ and 5.2 ± 3.5‰, respectively. The ionic molar ratios and isotopic ratios suggest that NO3- in BJ was formed through the phase-equilibrium reaction of NH4NO3 under sufficient NH3 (g) conditions, promoted by fossil-derived NH3 (g) transported with southerly winds. In BJ, fossil fuel sources comprised 52 ± 7% of TC and 45 ± 28% of NH4+ on average, estimated from radiocarbon (14C) analysis and the δ15N and isotope mixing model, respectively. These multiple-isotopic composition results emphasize that PM2.5 enhancement is derived from fossil sources, in which vehicle emissions are a key contributor. The impact of the coal source was sporadically noticeable. Under regional influences, the fossil fuel-driven SIA led to the PM2.5 enhancements. Our findings demonstrate that the multiple-isotope approach is highly advantageous to elucidate the key sources and limiting factors of secondary inorganic PM2.5 aerosols.

Pollution characteristics of bioaerosols in PM2.5 during the winter heating season in a coastal city of northern China.

Frequent heavy air pollution occurred during the winter heating season of northern China. In this study, PM2.5 (particles with an aerodynamic diameter less than 2.5 µm) was collected from a coastal city of China during the winter heating season from January 1 to March 31, 2018, and the soluble ions, organic carbon (OC), elemental carbon (EC), bacterial, endotoxin, and fungal concentration in PM2.5 were analyzed. During the winter heating season, PM2.5 and bioaerosols increased on polluted days, and the secondary inorganic ions, including NO3-, NH4+, and SO42-, increased significantly. Meteorological factors, such as wind direction and wind speed, had major impacts on the distributions of PM2.5 and bioaerosols. Pollutant concentration was high when there was a westerly wind with the speed of 3-6 m/s from inland area. Using the air mass backward trajectories and principal component analysis, we elucidate the potential origins of bioaerosol in PM2.5. The backward trajectory suggested that air mass for polluted samples (PM2.5 > 75 µg/m3) commonly originated from continent (9.62%), whereas air masses for clean samples (PM2.5 < 35 µg/m3) were mainly from marine (56.73%). The interregional transport of pollutants from continental area contributed most to PM2.5. Principal component analysis of the water-soluble ions and bioaerosol indicated that air pollution of the coastal city was greatly affected by coal combustion, biomass burning, and regional transmission of high-intensity pollutants from continent. Among that, interregional transport, biomass burning, and dust from soil and plants were main sources of bioaerosol. Our findings provide important insights into the origins and characteristics of bioaerosol in PM2.5 during the winter heating season of the coastal city in northern China.

Source assessment of atmospheric fine particulate matter in a Chinese megacity: Insights from long-term, high-time resolution chemical composition measurements from Shanghai flagship monitoring supersite.

Here we present a long-term, hourly resolution dataset (from January 2014 to April 2015) of secondary inorganic aerosol (SIA) matter, organic matter (OM) and black carbon (BC) as PM2.5 chemical components in China. Seasonally differentiated weekly diurnal profiles of major particulate species were investigated in conjunction with potential source contribution function (PSCF) analysis. The average concentration of PM2.5 was 48.3 ± 35.1 µg m-3, in which OM was the major constituent (29.7 ± 13.9%), followed by sulfate (25.1 ± 8.1%), nitrate (18.5 ± 8.3%), ammonium (13.3 ± 3.8%), and other trace species (6.8 ± 4.0%). Interestingly, unlike other PM species, OM concentrations kept very similar level among different seasons, indicating on-road traffic is a stable source of PM2.5. Besides, a persistently strong particulate OM pollution belt was found along the lower reaches of Yangtze River. Significant enhancement of SIA (mainly nitrate) was coincided with high PM2.5 mass loading. Source apportionment were conducted and found the overwhelming dominance of long-range transport of the pollutants from north China. Using a case study, we further integrate Weather Research and Forecasting (WRF) meteorological modeling and lidar observation to better understand the evolution process of a typical pollution episode. Our assessment of the extremely large datasets derived from Shanghai supersite demonstrated the online instrumentation as a robust and credible alternative to filter-based sampling techniques for long-term PM2.5 monitoring and characterization in heavily polluted areas.